@article{jeffers_shen_bissinger_khalil_gunnoe_roe_2014, title={Polymers for the stabilization and delivery of proteins topically and per os to the insect hemocoel through conjugation with aliphatic polyethylene glycol}, volume={115}, ISSN={["1095-9939"]}, DOI={10.1016/j.pestbp.2014.08.006}, abstractNote={Co-feeding of aliphatic polyethylene glycol (PEG), phospholipase A2, anionic and ionic detergents, and amphipathic glycoside with bovine serum albumin (BSA) as a model protein to fourth stadium tobacco budworms, Heliothis virescens, did not affect the levels of BSA in the hemolymph. Covalent conjugation of small proteins like the decapeptide trypsin modulating oostatic factor (TMOF) to polyethylene glycol was previously shown to protect the peptide from protease attack and enhance its accumulation in the insect hemocoel. Whether this polymer chemistry could do the same for larger proteins was examined. The chemistry for the synthesis of polydispersed aliphatic PEG350-insulin and monodispersed aliphatic PEG333-insulin are described herein. Insulin was used for this synthesis and not BSA to better control conjugation among the available free amine groups. When PEGylated insulin or free insulin were fed in artificial diet to fifth stadium budworms, greater concentrations of insulin using the PEGylated variants were found in the hemolymph than when free insulin was used (a 6.7 and 7.3-fold increase for the PEG350 and PEG333 conjugates, respectively). When insulin is topically applied to the dorsum of H. virescens, no insulin is found in the hemolymph. However, after topical application of the PEGylated insulins, PEG350-insulin and PEG333-insulin were detected in the hemolymph. After injections of insulin into the hemocoel of fourth stadium H. virescens, insulin is completely cleared from the hemolymph in 120 min. In comparison, PEG350-insulin and PEG333-insulin were present in the hemolymph for 300 and 240 min after injection, respectively, translating to a 3.3 and 2.7-fold increase in the length of time insulin remains in the hemolymph after injection.}, journal={PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY}, author={Jeffers, Laura A. and Shen, Hongyan and Bissinger, Brooke W. and Khalil, Sayed and Gunnoe, T. Brent and Roe, R. Michael}, year={2014}, month={Oct}, pages={58–66} } @article{jeffers_shen_khalil_bissinger_brandt_gunnoe_roe_2012, title={Enhanced activity of an insecticidal protein, trypsin modulating oostatic factor (TMOF), through conjugation with aliphatic polyethylene glycol}, volume={68}, ISSN={["1526-498X"]}, DOI={10.1002/ps.2219}, abstractNote={Abstract}, number={1}, journal={PEST MANAGEMENT SCIENCE}, author={Jeffers, Laura A. and Shen, Hongyan and Khalil, Sayed and Bissinger, Brooke W. and Brandt, Alan and Gunnoe, T. Brent and Roe, R. Michael}, year={2012}, month={Jan}, pages={49–59} } @article{delp_goj_pouy_munro-leighton_lee_gunnoe_cundari_petersen_2011, title={Well-Defined Copper(I) Amido Complex and Aryl Iodides Reacting to Form Aryl Amines}, volume={30}, ISSN={["1520-6041"]}, DOI={10.1021/om101084e}, abstractNote={The CuI complex (IPr)Cu(NHPh) {IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene} reacts with aryl iodides to form diaryl amine products and (IPr)Cu(I), which was confirmed by independent synthesis and characterization. For the reaction with iodobenzene, the products are diphenylamine and aniline. Protection of the hydrogen para to the iodo functionality with ortho-methyl groups results in quantitative conversion to diaryl amine. Combined computational and experimental studies suggest that C−N bond formation most likely occurs via an oxidative addition/reductive elimination sequence.}, number={1}, journal={ORGANOMETALLICS}, author={Delp, Samuel A. and Goj, Laurel A. and Pouy, Mark J. and Munro-Leighton, Colleen and Lee, John P. and Gunnoe, T. Brent and Cundari, Thomas R. and Petersen, Jeffrey L.}, year={2011}, month={Jan}, pages={55–57} } @article{foley_abernethy_gunnoe_hill_boyle_sabat_2009, title={Chlorination of Boron on a Ruthenium-Coordinated Hydridotris(pyrazolyl)borate (Tp) Ligand: A Caveat for the Use of TpRu(PPh3)(2)Cl}, volume={28}, ISSN={["1520-6041"]}, DOI={10.1021/om8008074}, abstractNote={A side-product that accompanies the synthesis of the widely utilized starting material TpRu(PPh3)2Cl (Tp = hydridotris(pyrazolyl)borate) has been identified as the complex ClTpRu(PPh3)2H (ClTp = chlorotris(pyrazolyl)borate), which provides a rare example of a boron-halogenated pyrazolylborate ligand. The reaction of ClTpRu(PPh3)2H with dichloromethane or chloroform quantitatively produce ClTpRu(PPh3)2Cl.}, number={1}, journal={ORGANOMETALLICS}, author={Foley, Nicholas A. and Abernethy, Robyn J. and Gunnoe, T. Brent and Hill, Anthony F. and Boyle, Paul D. and Sabat, Michal}, year={2009}, month={Jan}, pages={374–377} } @article{shen_brandt_witting-bissinger_gunnoe_roe_2009, title={Novel insecticide polymer chemistry to reduce the enzymatic digestion of a protein pesticide, trypsin modulating oostatic factor (TMOF)}, volume={93}, ISSN={["1095-9939"]}, DOI={10.1016/j.pestbp.2009.02.004}, abstractNote={A limiting factor in the use of proteins as insecticides, especially when the site of action is in the insect hemocoel, is protease degradation in the digestive system and hemolymph and movement across the midgut ventriculus. Trypsin modulating oostatic factor (TMOF) is a per os mosquito peptidic larvacide which moves across the digestive system and binds to receptors on the hemolymph side of the gut where the hormone inhibits protease synthesis and food utilization ultimately causing death. In the current study, the in vitro degradation of TMOF by the digestive enzyme, leucine aminopeptidase, was inhibited by conjugation of TMOF-K with aliphatic polyethylene glycol (PEG) polymers. Structure activity studies demonstrated a correlation between the molecular weight of the PEG polymer and resistance to digestion and show proof of concept that aliphatic-PEG protein polymerization can be used to prevent protease degradation of a protein insecticide.}, number={3}, journal={PESTICIDE BIOCHEMISTRY AND PHYSIOLOGY}, author={Shen, Hongyan and Brandt, Alan and Witting-Bissinger, Brooke E. and Gunnoe, T. Brent and Roe, R. Michael}, year={2009}, month={Mar}, pages={144–152} } @article{foley_gunnoe_cundari_boyle_petersen_2008, title={Activation of sp(3) carbon-hydrogen bonds complex and subsequent metal-mediated formation}, volume={47}, number={4}, journal={Angewandte Chemie [International Edition in English]}, author={Foley, N. A. and Gunnoe, T. B. and Cundari, T. R. and Boyle, P. D. and Petersen, J. L.}, year={2008}, pages={726–730} } @article{munro-leighton_delp_alsop_blue_gunnoe_2008, title={Anti-Markovnikov hydroamination and hydrothiolation of electron-deficient vinylarenes catalyzed by well-defined monomeric copper(I) amido and thiolate complexes}, ISSN={["1359-7345"]}, DOI={10.1039/b715507g}, abstractNote={Monomeric Cu(I) amido and thiolate complexes that are supported by the N-heterocyclic carbene ligand 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) catalyze the hydroamination and hydrothiolation of electron-deficient vinylarenes with reactivity patterns that are consistent with an intermolecular nucleophilic addition of the amido/thiolate ligand of (IPr)Cu(XR) (X = NH or S; R = Ph, CH2Ph) to free vinylarene.}, number={1}, journal={CHEMICAL COMMUNICATIONS}, author={Munro-Leighton, Colleen and Delp, Samuel A. and Alsop, Nikki M. and Blue, Elizabeth D. and Gunnoe, T. Brent}, year={2008}, pages={111–113} } @article{foley_ke_gunnoe_cundari_petersen_2008, title={Aromatic C-H activation and catalytic hydrophenylation of ethylene by TpRu{P(OCH2)(3)CEt}(NCMe)Ph}, volume={27}, ISSN={["1520-6041"]}, DOI={10.1021/om800275b}, abstractNote={The complexes TpRu{P(OCH2)3CEt}(L)R {L = PPh3 or NCMe; R = Cl, OTf (OTf = trifluoromethanesulfonate), or Ph; Tp = hydridotris(pyrazolyl)borate} and TpRu{P(OCH2)3CEt}(η3-C3H4Me) were synthesized and isolated. TpRu{P(OCH2)3CEt}(NCMe)Ph was found to initiate C−H activation of benzene and to catalyze the hydrophenylation of ethylene to produce ethylbenzene. Ethylene C−H activation to ultimately produce TpRu{P(OCH2)3CEt}(η3-C3H4Me) kinetically competes with the catalytic hydrophenylation of ethylene. Computational studies were undertaken on reactions in the proposed catalytic ethylene hydrophenylation cycle as well as key side reactions.}, number={13}, journal={ORGANOMETALLICS}, author={Foley, Nicholas A. and Ke, Zhuofeng and Gunnoe, T. Brent and Cundari, Thomas R. and Petersen, Jeffrey L.}, year={2008}, month={Jul}, pages={3007–3017} } @misc{lail_pittard_gunnoe_2008, title={Chemistry surrounding Group 7 complexes that possess Poly(pyrazolyl)borate ligands}, volume={56}, journal={Organotransition metal chemistry of poly(pyrazolyl)borates, pt 1}, author={Lail, M. and Pittard, K. A. and Gunnoe, T. B.}, year={2008}, pages={95–153} } @article{mckeown_foley_lee_gunnoe_2008, title={Hydroarylation of unactivated olefins catalyzed by platinum(II) complexes}, volume={27}, ISSN={["0276-7333"]}, DOI={10.1021/om8006008}, abstractNote={The Pt(II) complex [(tbpy)Pt(Ph)(THF)][BAr′4] catalyzes the hydroarylation of olefins utilizing unactivated substrates. Preliminary studies indicate that the reactions proceed via Pt-mediated C−H activation rather than a traditional Friedel−Crafts pathway.}, number={16}, journal={ORGANOMETALLICS}, author={McKeown, Bradley A. and Foley, Nicholas A. and Lee, John P. and Gunnoe, T. Brent}, year={2008}, month={Aug}, pages={4031–4033} } @article{munro-leighton_feng_zhang_alsop_gunnoe_boyle_petersen_2008, title={Preparation and reactivity of a monomeric octahedral platinum(IV) amido complex}, volume={47}, DOI={10.1021/icS00843b}, number={14}, journal={Inorganic Chemistry}, author={Munro-Leighton, C. and Feng, Y. and Zhang, J. and Alsop, N. M. and Gunnoe, T. B. and Boyle, P. D. and Petersen, J. L.}, year={2008}, pages={6124–6126} } @article{sumiyoshi_gunnoe_petersen_boyle_2008, title={Ruthenium(II) complexes possessing the eta(6)-p-cymene ligand}, volume={361}, ISSN={["1873-3255"]}, DOI={10.1016/j.ica.2007.10.012}, abstractNote={Complexes possessing a soft donor η6-arene and hard donor acetylacetonate ligand, [(η6-p-cymene)Ru(κ2-O,O-acac-μ-CH)]2[OTf]2 (1) (OTf = trifluoromethanesulfonate; acac = acetylacetonate) and [(η6-p-cymene)Ru(κ2-O,O-acac)(THF)][BAr4′](2) {Ar′ = 3,5-(CF3)–C6H3}, were prepared and fully characterized. The lability of the μ-CH linkage for complex 1 and the THF ligand of 2 allow access to the unsaturated cation [(η6-p-cymene)Ru(κ2-O,O-acac)]+. The reaction of [(η6-p-cymene)Ru(κ2-O,O-acac)(THF)][BAr4′](2) with KTp {Tp = hydridotris(pyrazolyl)borate} produces [TpRu(η6-p-cymene)][BAr4′](5). The azide complex [(η6-p-cymene)Ru(κ2-O,O-acac)(N3Ar)][BAr4′](6) forms upon reaction of [(η6-p-cymene)Ru(κ2-O,O-acac)(THF)][BAr4′](2)with N3Ar (Ar = p-tolyl), and reaction of [(η6-p-cymene)Ru(κ2-O,O-acac)(THF)][BAr4′](2) with CHCl3 at 100 °C yields the chloride-bridged binuclear complex [{(η6-p-cymene)Ru}2(μ-Cl)3][BAr4′](7). The details of solid-state structures of [(η6-p-cymene)Ru(κ2-O,O-acac-μ-CH)]2[OTf]2 (1), [TpRu(η6-p-cymene)][BAr4′](5) and [{(η6-p-cymene)Ru}2(μ-Cl)3][BAr4′](7) are disclosed.}, number={11}, journal={INORGANICA CHIMICA ACTA}, author={Sumiyoshi, Taisuke and Gunnoe, T. Brent and Petersen, Jeffrey L. and Boyle, Paul D.}, year={2008}, month={Jul}, pages={3254–3262} } @misc{cundari_grimes_gunnoe_2007, title={Activation of carbon-hydrogen bonds via 1,2-addition across M-X (X = OH or NH2) bonds of d(6) transition metals as a potential key step in hydrocarbon functionalization: A computational study}, volume={129}, ISSN={["0002-7863"]}, DOI={10.1021/ja074125g}, abstractNote={Recent reports of 1,2-addition of C-H bonds across Ru-X (X = amido, hydroxo) bonds of TpRu(PMe3)X fragments {Tp = hydridotris(pyrazolyl)borate} suggest opportunities for the development of new catalytic cycles for hydrocarbon functionalization. In order to enhance understanding of these transformations, computational examinations of the efficacy of model d6 transition metal complexes of the form [(Tab)M(PH3)2X]q (Tab = tris-azo-borate; X = OH, NH2; q = -1 to +2; M = TcI, Re(I), Ru(II), Co(III), Ir(III), Ni(IV), Pt(IV)) for the activation of benzene C-H bonds, as well as the potential for their incorporation into catalytic functionalization cycles, are presented. For the benzene C-H activation reaction steps, kite-shaped transition states were located and found to have relatively little metal-hydrogen interaction. The C-H activation process is best described as a metal-mediated proton transfer in which the metal center and ligand X function as an activating electrophile and intramolecular base, respectively. While the metal plays a primary role in controlling the kinetics and thermodynamics of the reaction coordinate for C-H activation/functionalization, the ligand X also influences the energetics. On the basis of three thermodynamic criteria characterizing salient energetic aspects of the proposed catalytic cycle and the detailed computational studies reported herein, late transition metal complexes (e.g., Pt, Co, etc.) in the d6 electron configuration {especially the TabCo(PH3)2(OH)+ complex and related Co(III) systems} are predicted to be the most promising for further catalyst investigation.}, number={43}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Cundari, Thomas R. and Grimes, Thomas V. and Gunnoe, T. Brent}, year={2007}, month={Oct}, pages={13172–13182} } @article{munro-leighton_delp_blue_gunnoe_2007, title={Addition of N-H and O-H bonds of amines and alcohols to electron-deficient olefins catalyzed by monomeric copper(I) systems: Reaction scope, mechanistic details, and comparison of catalyst efficiency}, volume={26}, ISSN={["1520-6041"]}, DOI={10.1021/om061133h}, abstractNote={Monomeric copper(I) amido, alkoxide, and aryloxide complexes catalyze the addition of N−H and O−H bonds of amines and alcohols, respectively, to electron-deficient olefins. The ancillary ligands of the active catalysts include the N-heterocyclic carbene (NHC) ligands IPr, IMes, and SIPr {IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene; IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene; SIPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene} as well as the chelating bisphosphine ligand dtbpe {dtbpe = 1,2-bis(di-tert-butylphosphino)ethane}. For the hydroamination and hydroalkoxylation of olefins, both aromatic and alkyl substituents can be incorporated into the nucleophile, and both primary and secondary amines are reactive. Monosubstituted and disubstituted olefins have been demonstrated to undergo reaction. For the addition of aniline to acrylonitrile, kinetic studies suggest a pathway that is dependent on the concentration of amine, olefin, and catalyst as well as inversely proportional t...}, number={6}, journal={ORGANOMETALLICS}, author={Munro-Leighton, Colleen and Delp, Samuel A. and Blue, Elizabeth D. and Gunnoe, T. Brent}, year={2007}, month={Mar}, pages={1483–1493} } @article{delp_munro-leighton_goj_ramirez_gunnoe_petersen_boyle_2007, title={Addition of s-h bonds across electron-deficient olefins catalyzed by well-defined copper(I) thiolate complexes}, volume={46}, ISSN={["1520-510X"]}, DOI={10.1021/ic070268s}, abstractNote={A series of monomeric (NHC)Cu(SR) (R = Ph or CH2Ph; NHC = N-heterocyclic carbene) complexes have been synthesized and fully characterized including single-crystal X-ray diffraction studies. These complexes catalyze the addition of S-H bonds across electron-deficient olefins to regioselectively produce "anti-Markovnikov" products.}, number={7}, journal={INORGANIC CHEMISTRY}, author={Delp, Samuel A. and Munro-Leighton, Colleen and Goj, Laurel A. and Ramirez, Magaly A. and Gunnoe, T. Brent and Petersen, Jeffrey L. and Boyle, Paul D.}, year={2007}, month={Apr}, pages={2365–2367} } @article{deyonker_foley_cundari_gunnoe_petersen_2007, title={Combined experimental and computational studies on the nature of aromatic C-H activation by octahedral ruthenium(II) complexes: Evidence for sigma-bond metathesis from Hammett studies}, volume={26}, ISSN={["1520-6041"]}, DOI={10.1021/om7009057}, abstractNote={Article discussing combined experimental and computational studies on the nature of aromatic C-H activation by octahedral ruthenium(II) complexes of the type TpRu(L)(NCMe)R [Tp = hydridotris(pyrazolyl)borate; R = alkyl or aryl; L = CO or PMe3].}, number={26}, journal={ORGANOMETALLICS}, author={DeYonker, Nathan J. and Foley, Nicholas A. and Cundari, Thomas R. and Gunnoe, T. Brent and Petersen, Jeffrey L.}, year={2007}, month={Dec}, pages={6604–6611} } @article{foley_lail_gunnoe_cundari_boyle_petersen_2007, title={Combined experimental and computational study of TpRu{P(pyr)(3)}(NCMe)Me (pyr = N-pyrrolyl): Inter- and intramolecular activation of C-H bonds and the impact of sterics on catalytic hydroarylation of olefins}, volume={26}, ISSN={["1520-6041"]}, DOI={10.1021/om700666y}, abstractNote={Complexes of the type TpRu{P(pyr)3}(L)R {L = PPh3 or NCMe; R = Cl, OTf (OTf = trifluoromethanesulfonate), Me, or Ph; Tp = hydridotris(pyrazolyl)borate; pyr = N-pyrrolyl} and TpRu{κ2-P,C-P(pyr)2(NC4H3)}NCMe have been synthesized and isolated. TpRu{P(pyr)3}(NCMe)Me initiates intermolecular C−H activation of benzene to form TpRu{P(pyr)3}(NCMe)Ph and, in the absence of benzene, intramolecular C−H activation of a pyrrolyl ring to form the cyclometalated species TpRu{κ2-P,C-P(pyr)2(NC4H3)}NCMe. TpRu{P(pyr)3}(NCMe)Ph catalyzes the hydrophenylation of ethylene in benzene to produce ethylbenzene in low yields. Experimental and computational analyses of the hydrophenylation of ethylene by TpRu{P(pyr)3}(NCMe)Ph suggest that inefficient catalysis is not due to difficulty in the C−H activation of benzene by the active catalyst species, but rather likely arises from the steric bulk of the tris-N-pyrrolyl phosphine ligand, which inhibits coordination of ethylene and thus thwarts C−C bond formation.}, number={23}, journal={ORGANOMETALLICS}, author={Foley, Nicholas A. and Lail, Marty and Gunnoe, T. Brent and Cundari, Thomas R. and Boyle, Paul D. and Petersen, Jeffrey L.}, year={2007}, month={Nov}, pages={5507–5516} } @article{foley_lail_lee_gunnoe_cundari_petersen_2007, title={Comparative reactivity of TpRu(L)(NCMe)Ph (L = CO or PMe3): Impact of ancillary ligand L on activation of carbon-hydrogen bonds including catalytic hydroarylation and hydrovinylation/oligomerization of ethylene}, volume={129}, ISSN={["1520-5126"]}, DOI={10.1021/ja068542p}, abstractNote={Complexes of the type TpRu(L)(NCMe)R [L = CO or PMe3; R = Ph or Me; Tp = hydridotris(pyrazolyl)borate] initiate C-H activation of benzene. Kinetic studies, isotopic labeling, and other experimental evidence suggest that the mechanism of benzene C-H activation involves reversible dissociation of acetonitrile, reversible benzene coordination, and rate-determining C-H activation of coordinated benzene. TpRu(PMe3)(NCMe)Ph initiates C-D activation of C6D6 at rates that are approximately 2-3 times more rapid than that for TpRu(CO)(NCMe)Ph (depending on substrate concentration); however, the catalytic hydrophenylation of ethylene using TpRu(PMe3)(NCMe)Ph is substantially less efficient than catalysis with TpRu(CO)(NCMe)Ph. For TpRu(PMe3)(NCMe)Ph, C-H activation of ethylene, to ultimately produce TpRu(PMe3)(eta3-C4H7), is found to kinetically compete with catalytic ethylene hydrophenylation. In THF solutions containing ethylene, TpRu(PMe3)(NCMe)Ph and TpRu(CO)(NCMe)Ph separately convert to TpRu(L)(eta3-C4H7) (L = PMe3 or CO, respectively) via initial Ru-mediated ethylene C-H activation. Heating mesitylene solutions of TpRu(L)(eta3-C4H7) under ethylene pressure results in the catalytic production of butenes (i.e., ethylene hydrovinylation) and hexenes.}, number={21}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Foley, Nicholas A. and Lail, Marty and Lee, John P. and Gunnoe, T. Brent and Cundari, Thomas R. and Petersen, Jeffrey L.}, year={2007}, month={May}, pages={6765–6781} } @article{lee_jimenez-halla_cundari_gunnoe_2007, title={Reactivity of TpRu(L)(NCMe)R (L = CO, PMe3; R = Me, Ph) systems with isonitriles: Experimental and computational studies toward the intra- and intermolecular hydroarylation of isonitriles}, volume={692}, ISSN={["1872-8561"]}, DOI={10.1016/j.jorganchem.2007.01.037}, abstractNote={The Ru(II) phenyl complex TpRu(PMe3)(NCMe)Ph {Tp = hydridotris(pyrazolyl)borate} reacts with isonitriles to form complexes of the type TpRu(PMe3)(CNR)Ph (R = tBu, CH2Ph, CH2CH2Ph). Neither thermal nor photolytic reactions of these systems with excess isonitrile and benzene resulted in the production of corresponding imines. DFT studies that probed the energetics of the desired catalytic transformations revealed that (Tab)Ru(PH3)(CNCH2CH2Ph)Ph {Tab = tris(azo)borate} is the most stable species in a proposed catalytic cycle. Exclusive of calculated transition states, the highest points on the calculated free energy surface are 34 kcal/mol, for (Tab)Ru(PH3)(o,η2-C,C-CNCH2CH2Ph)Ph {relative to the starting material (Tab)Ru(PH3)(CNCH2CH2Ph)Ph}, and 27 kcal/mol for the C–H activation product (Tab)Ru(PH3)(o-C6H4CH2CH2NC) and benzene. The substantial increases in free energy result primarily from the loss of the stable ruthenium–η1-isonitrile interaction.}, number={11}, journal={JOURNAL OF ORGANOMETALLIC CHEMISTRY}, author={Lee, John P. and Jimenez-Halla, Oscar C. and Cundari, Thomas R. and Gunnoe, T. Brent}, year={2007}, month={May}, pages={2175–2186} } @misc{gunnoe_2007, title={Reactivity of ruthenium(II) and copper(I) complexes that possess anionic heteroatomic ligands: Synthetic exploitation of nucleophilicity and basicity of amido, hydroxo, alkoxo, and aryloxo ligands for the activation of substrates that possess polar...}, number={9}, journal={European Journal of Inorganic Chemistry}, author={Gunnoe, T. B.}, year={2007}, pages={1185–1203} } @article{munro-leighton_blue_gunnoe_2006, title={Anti-Markovnikov N-H and O-H additions to electron-deficient olefins catalyzed by well-defined Cu(I) anilido, ethoxide, and phenoxide systems}, volume={128}, ISSN={["0002-7863"]}, DOI={10.1021/ja057622a}, abstractNote={The monomeric Cu(I) complexes (IPr)Cu(Z) (IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, Z = NHPh, OEt, or OPh) react with YH (Y = PhNH, PhCH2NH, EtO, or PhO) to catalytically add Y-H bonds across the C=C bond of electron-deficient olefins to yield anti-Markovnikov organic products. Catalytic activity has been observed for olefins CH2C(H)(X) with X = CN, C(O)Me, or CO2Me as well as crotononitrile. Preliminary studies implicate an intermediate in which the C-Y bond forms through a nucleophilic addition pathway.}, number={5}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Munro-Leighton, C and Blue, ED and Gunnoe, TB}, year={2006}, month={Feb}, pages={1446–1447} } @article{goj_blue_delp_gunnoe_cundari_pierpont_petersen_boyle_2006, title={Chemistry surrounding monomeric copper(I) methyl, phenyl, anilido, ethoxide, and phenoxide complexes supported by N-heterocyclic carbene ligands: Reactivity consistent with both early and late transition metal systems}, volume={45}, DOI={10.1021/ic0611995}, abstractNote={Monomeric copper(I) alkyl complexes that possess the N-heterocyclic carbene (NHC) ligands IPr, SIPr, and IMes [IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene, SIPr = 1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene, IMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene] react with amines or alcohols to release alkane and form the corresponding monomeric copper(I) amido, alkoxide, or aryloxide complexes. Thermal decomposition reactions of (NHC)Cu(I) methyl complexes at temperatures between 100 and 130 degrees C produce methane, ethane, and ethylene. The reactions of (NHC)Cu(NHPh) complexes with bromoethane reveal increasing nucleophilic reactivity at the anilido ligand in the order (SIPr)Cu(NHPh) < (IPr)Cu(NHPh) < (IMes)Cu(NHPh) < (dtbpe)Cu(NHPh) [dtbpe = 1,2-bis(di-tert-butylphosphino)ethane]. DFT calculations suggest that the HOMO for the series of Cu anilido complexes is localized primarily on the amido nitrogen with some ppi(anilido)-dpi(Cu) pi-character. [(IPr)Cu(mu-H)]2 and (IPr)Cu(Ph) react with aniline to quantitatively produce (IPr)Cu(NHPh)/dihydrogen and (IPr)Cu(NHPh)/benzene, respectively. Analysis of the DFT calculations reveals that the conversion of [(IPr)Cu(mu-H)]2 and aniline to (IPr)Cu(NHPh) and dihydrogen is favorable with DeltaH approximately -7 kcal/mol and DeltaG approximately -9 kcal/mol.}, number={22}, journal={Inorganic Chemistry}, author={Goj, L. A. and Blue, E. D. and Delp, S. A. and Gunnoe, T. B. and Cundari, T. R. and Pierpont, A. W. and Petersen, J. L. and Boyle, P. D.}, year={2006}, pages={9032–9045} } @article{feng_lail_foley_gunnoe_barakat_cundari_petersen_2006, title={Hydrogen-deuterium exchange between TpRu( PMe3)(L)X (L) = PMe3 and X = OH, OPh, Me, Ph, or NHPh; L = NCMe and X = Ph) and deuterated arene solvents: Evidence for metal-mediated processes}, volume={128}, ISSN={["1520-5126"]}, DOI={10.1021/ja0615775}, abstractNote={At elevated temperatures (90-130 degrees C), complexes of the type TpRu(PMe3)2X (X = OH, OPh, Me, Ph, or NHPh; Tp = hydridotris(pyrazolyl)borate) undergo regioselective hydrogen-deuterium (H/D) exchange with deuterated arenes. For X = OH or NHPh, H/D exchange occurs at hydroxide and anilido ligands, respectively. For X = OH, OPh, Me, Ph, or NHPh, isotopic exchange occurs at the Tp 4-positions with only minimal deuterium incorporation at the Tp 3- or 5-positions or PMe3 ligands. For TpRu(PMe3)(NCMe)Ph, the H/D exchange occurs at 60 degrees C at all three Tp positions and the phenyl ring. TpRu(PMe3)2Cl, TpRu(PMe3)2OTf (OTf = trifluoromethanesulfonate), and TpRu(PMe3)2SH do not initiate H/D exchange in C6D6 after extended periods of time at elevated temperatures. Mechanistic studies indicate that the likely pathway for the H/D exchange involves ligand dissociation (PMe3 or NCMe), Ru-mediated activation of an aromatic C-D bond, and deuteration of basic nondative ligand (hydroxide or anilido) or Tp positions via net D+ transfer.}, number={24}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Feng, Yuee and Lail, Marty and Foley, Nicholas A. and Gunnoe, T. Brent and Barakat, Khaldoon A. and Cundari, Thomas R. and Petersen, Jeffrey L.}, year={2006}, month={Jun}, pages={7982–7994} } @article{feng_gunnoe_grimes_cundari_2006, title={Octahedral [TpRu(PMe3)(2)OR](n+) complexes (Tp = hydridotris(pyrazolyl) borate; R = H or Ph; n=0 or 1): Reactions at Ru(II) and Ru(III) oxidation states with substrates that possess carbon-hydrogen bonds}, volume={25}, ISSN={["1520-6041"]}, DOI={10.1021/om0606385}, abstractNote={The Ru(II) complexes TpRu(PMe3)2OR (R = H or Ph) react with excess phenylacetylene at elevated temperatures to produce the phenylacetylide complex TpRu(PMe3)2(C⋮CPh). Kinetic studies indicate that the reaction of TpRu(PMe3)2OH and phenylacetylene likely proceeds through a pathway that involves TpRu(PMe3)2OTf as a catalyst. The reaction of TpRu(PMe3)2OH with 1,4-cyclohexadiene at elevated temperature forms benzene and TpRu(PMe3)2H, while TpRu(PMe3)2OPh does not react with 1,4-cyclohexadiene even after 20 days at 85 °C. The paramagnetic Ru(III) complex [TpRu(PMe3)2OH][OTf] is formed upon single-electron oxidation of TpRu(PMe3)2OH with AgOTf. Reactivity studies suggest that [TpRu(PMe3)2OH][OTf] initiates reactions, including hydrogen atom abstraction, with C−H bonds that have bond dissociation energy < 80 kcal/mol. Experimentally, the O−H bond strength of the Ru(II) cation [TpRu(PMe3)2(OH2)][OTf] is estimated to be between 82 and 85 kcal/mol, while computational studies yield a BDE of 84 kcal/mol, which are ...}, number={22}, journal={ORGANOMETALLICS}, author={Feng, Yuee and Gunnoe, T. Brent and Grimes, Thomas V. and Cundari, Thomas R.}, year={2006}, month={Oct}, pages={5456–5465} } @article{blue_gunnoe_petersen_boyle_2006, title={Protonation of N-heterocyclic carbene ligand coordinated to copper(I): Coordination mode of imidazolium cation as a function of counterion as determined by solid-state structures}, volume={691}, ISSN={["1872-8561"]}, DOI={10.1016/j.jorganchem.2006.09.051}, abstractNote={Reactions of (IPr)Cu(X) (X = Cl or trifluoromethanesulfonate, IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) complexes with the strong acids HOTf or HCl result in protonation of the C2 carbon of the IPr ligand to form imidazolium cations. Coordination of the imidazolium to the resulting CuI system depends upon the identity of the two counterions (chloride or triflate). The copper complexes [(IPrH)Cu(OTf)(μ-OTf)]2 and [IPrH][CuCl2] as well as the imidazolium salt [IPrH][OTf] have been characterized by NMR spectroscopy and single crystal X-ray diffraction studies.}, number={26}, journal={JOURNAL OF ORGANOMETALLIC CHEMISTRY}, author={Blue, Elizabeth D. and Gunnoe, T. Brent and Petersen, Jeffrey L. and Boyle, Paul D.}, year={2006}, month={Dec}, pages={5988–5993} } @article{goj_lail_pittard_riley_gunnoe_petersen_2006, title={Reactions of TpRu(CO)(NCMe)(Ph) with electron-rich olefins: examples of stoichiometric C-S, C-O and C-H bond cleavage}, number={9}, journal={Chemical Communications (Cambridge, England)}, author={Goj, L. A. and Lail, M. and Pittard, K. A. and Riley, K. C. and Gunnoe, T. B. and Petersen, J. L.}, year={2006}, pages={982–984} } @article{lee_pittard_deyonker_cundari_gunnoe_petersen_2006, title={Reactions of a Ru(II) phenyl complex with substrates that possess C-N or C-O multiple bonds: C-C bond formation, N-H bond cleavage, and decarbonylation reactions}, volume={25}, ISSN={["1520-6041"]}, DOI={10.1021/om050967h}, abstractNote={Article on the reactions of an Ru(II) phenyl complex with substrates that possess C-N or C-O multiple bonds and C-C bond formation, N-H bond cleavage, and decarbonylation reactions.}, number={6}, journal={ORGANOMETALLICS}, author={Lee, JP and Pittard, KA and DeYonker, NJ and Cundari, TR and Gunnoe, TB and Petersen, JL}, year={2006}, month={Mar}, pages={1500–1510} } @article{goj_blue_delp_gunnoe_cundari_petersen_2006, title={Single-electron oxidation of monomeric copper(I) alkyl complexes: Evidence for reductive elimination through bimolecular formation of Alkanes}, volume={25}, ISSN={["1520-6041"]}, DOI={10.1021/om060409i}, abstractNote={Monomeric Cu(I) alkyl complexes (NHC)Cu(R) (NHC = N-heterocyclic carbene; R = Me or Et) and (dtbpe)Cu(Me) (dtbpe = 1,2-bis(di-tert-butylphosphino)ethane) have been prepared, isolated, and characterized. Single-electron oxidation of the Cu(I) alkyl complexes upon reaction with AgOTf to form putative Cu(II) intermediates of the type [(L)Cu(R)]+ (L = NHC or dtbpe, R = Me or Et) results in the rapid production of (L)Cu(X) (X = OTf) and R2. Experimental studies suggest that the reductive elimination of R2 from Cu(II) occurs through a nonradical bimolecular mechanism. Computational studies of the Cu−Cmethyl yield bond dissociation enthalpies of [(SIPr)Cu−CH3]n+ (80 kcal/mol for n = 0 {Cu(I)} and 38 kcal/mol for n = 1 {Cu(II)}).}, number={17}, journal={ORGANOMETALLICS}, author={Goj, Laurel A. and Blue, Elizabeth D. and Delp, Samuel A. and Gunnoe, T. Brent and Cundari, Thomas R. and Petersen, Jeffrey L.}, year={2006}, month={Aug}, pages={4097–4104} } @article{goj_blue_munro-leighton_gunnoe_petersen_2005, title={Cleavage of X-H bonds (X = N, O, or C) by copper(I) alkyl complexes to form monomeric two-coordinate copper(I) systems}, volume={44}, ISSN={["1520-510X"]}, DOI={10.1021/ic0517624}, abstractNote={The monomeric copper(I) alkyl complexes (IPr)Cu(R) [R = Me or Et; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene] react with substrates that possess N-H, O-H, and acidic C-H bonds to form monomeric systems of the type (IPr)Cu(X) (X = anilido, phenoxide, ethoxide, phenylacetylide, or N-pyrrolyl) and methane or ethane. Solid-state X-ray crystal structures of the anilido, ethoxide, and phenoxide complexes confirm that they are monomeric systems. Experimental studies on the reaction of (IPr)Cu(Me) and aniline to produce (IPr)Cu(NHPh) suggest that a likely reaction pathway is coordination of aniline to Cu(I) followed by proton transfer to produce methane and the copper(I) anilido complex.}, number={24}, journal={INORGANIC CHEMISTRY}, author={Goj, LA and Blue, ED and Munro-Leighton, C and Gunnoe, TB and Petersen, JL}, year={2005}, month={Nov}, pages={8647–8649} } @article{lail_gunnoe_barakat_cundari_2005, title={Conversions of ruthenium(III) alkyl complexes to ruthenium(II) through Ru-C-alkyl bond homolysis}, volume={24}, ISSN={["1520-6041"]}, DOI={10.1021/om049145v}, abstractNote={Single-electron oxidation of the Ru(II) complexes TpRu(L)(L‘)(R) (L = CO, L‘ = NCMe, and R = CH3 or CH2CH2Ph; L = L‘ = PMe3 and R = CH3) with AgOTf leads to alkyl elimination reactions that produce...}, number={6}, journal={ORGANOMETALLICS}, author={Lail, M and Gunnoe, TB and Barakat, KA and Cundari, TR}, year={2005}, month={Mar}, pages={1301–1305} } @article{goj_gunnoe_2005, title={Developments in catalytic aromatic C-H transformations: Promising tools for organic synthesis}, volume={9}, ISSN={["1875-5348"]}, DOI={10.2174/1385272053765051}, abstractNote={Catalytic carbon-carbon bond formation using transition metal complexes typically incorporates the use of an aryl halide or triflate compound (electrophile) in combination with an organometallic reagent (nucleophile). Versatile synthetic methods that allow C-C bond formation of aromatic compounds that proceed through transformation of C-H bonds would be of substantial value. Potential routes for C-C bond formation with aromatic substrates include the hydroarylation of unsaturated compounds (e.g., olefins or alkynes) and oxidative coupling of aromatic compounds and olefins or alkynes. Such reactions can proceed through metal-mediated transformation of C-H bonds. The range of reported catalysts and catalytic cycles for these classes of reactions have been reviewed herein. Keywords: transformations, carbon-hydrogen, carbonylation reactions, oxidative coupling, anti-markovnikov product, toluene, phenylation, palladium-catalyzed oxidative coupling, anilides}, number={7}, journal={CURRENT ORGANIC CHEMISTRY}, author={Goj, LA and Gunnoe, TB}, year={2005}, month={May}, pages={671–685} } @article{feng_lail_barakat_cundari_gunnoe_petersen_2005, title={Evidence for the net addition of arene C-H bonds across a Ru(II)-hydroxide bond}, volume={127}, ISSN={["0002-7863"]}, DOI={10.1021/ja054101e}, abstractNote={TpRu(PMe3)2(OH) (1) reacts with C6D6 to initiate H/D exchange between the hydroxide ligand and the deuterated benzene. In addition, complex 1 catalyzes H/D exchange between H2O and C6D6. Mechanistic and computational studies suggest that a likely reaction pathway for the H/D exchange involves loss of PMe3 to produce {TpRu(PMe3)(OH)}, followed by the net addition of a benzene C-H(D) bond across the Ru-OH bond to form the putative complex TpRu(PMe3)(OH2)(Ph).}, number={41}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Feng, Y and Lail, M and Barakat, KA and Cundari, TR and Gunnoe, TB and Petersen, JL}, year={2005}, month={Oct}, pages={14174–14175} } @article{zhang_gunnoe_peterson_2005, title={Reactions of (PCP)Ru(CO)(NHPh)(PMe3) (PCP=2,6-((CH2PBu2)-Bu-t)(2)C6H3) with substrates that possess polar bonds}, volume={44}, ISSN={["1520-510X"]}, DOI={10.1021/ic0483592}, abstractNote={The Ru(II) amido complex (PCP)Ru(CO)(PMe(3))(NHPh) (1) (PCP = 2,6-(CH(2)P(t)Bu(2))(2)C(6)H(3)) reacts with compounds that possess polar C=N, C triple bond N, or C=O bonds (e.g., nitriles, carbodiimides, or isocyanates) to produce four-membered heterometallacycles that result from nucleophilic addition of the amido nitrogen to an unsaturated carbon of the organic substrate. Based on studies of the reaction of complex 1 with acetonitrile, the transformations are suggested to proceed by dissociation of trimethylphosphine, followed by coordination of the organic substrate and then intramolecular N-C bond formation. In the presence of ROH (R = H or Me), the fluorinated amidinate complex (PCP)Ru(CO)(N(Ph)C(C(6)F(5))NH) (6) reacts with excess pentafluorobenzonitrile to produce (PCP)Ru(CO)(F)(N(H)C(C(6)F(5))NHPh) (7). The reaction with MeOH also produces o-MeOC(6)F(4)CN (>90%) and p-MeOC(6)F(4)CN (<10%). Details of the solid-state structures of (PCP)Ru(CO)(F)(N(H)C(C(6)F(5))NHPh) (7), (PCP)Ru(CO)[PhNC{NH(hx)}N(hx)] (8), (PCP)Ru(CO){N(Ph)C(NHPh)O} (9), and (PCP)Ru(CO){OC(Ph)N(Ph)} (10) are reported.}, number={8}, journal={INORGANIC CHEMISTRY}, author={Zhang, JB and Gunnoe, TB and Peterson, JL}, year={2005}, month={Apr}, pages={2895–2907} } @article{pittard_cundari_gunnoe_day_petersen_2005, title={Ruthenium(II)-mediated carbon-carbon bond formation between acetonitrile and pyrrole: Combined experimental and computational study}, volume={24}, ISSN={["1520-6041"]}, DOI={10.1021/om0506668}, abstractNote={The reaction of TpRu(CO)(NCMe)(Me) (1) and pyrrole forms TpRu(CO){κ2-N,N-(H)NC(Me)(NC4H3)} (2). The formation of complex 2 involves the cleavage of the N−H bond and 2-position C−H bonds of pyrrole as well as a C−C bond forming step between pyrrole and the acetonitrile ligand of 1. Mechanistic studies indicate that the most likely reaction pathway involves initial metal-mediated N−H activation of pyrrole to produce TpRu(CO)(N-pyrrolyl)(NCMe) (3) followed by C−C bond formation and proton transfer. Complex 3 has been independently prepared and demonstrated to convert to 2. Computational studies support the suggested selectivity for initial N−H bond cleavage in preference to C−H bond activation.}, number={21}, journal={ORGANOMETALLICS}, author={Pittard, KA and Cundari, TR and Gunnoe, TB and Day, CS and Petersen, JL}, year={2005}, month={Oct}, pages={5015–5024} } @article{zhang_barakat_cundari_gunnoe_boyle_petersen_day_2005, title={Synthesis of the five-coordinate ruthenium(II) Complexes [(PCP)Ru(CO)(L)][BAr'(4)] {PCP=2,6-((CH2PBu2)-Bu-t)(2)C6H3, BAr'(4) 3,5-(CF3)(2)C6H3, L = eta(1)-ClCH2Cl, eta-N-2, or mu-Cl-Ru(PCP)(CO)}: Reactions with phenyldiazomethane and phenylacetylene}, volume={44}, DOI={10.1012/ic051074k}, number={23}, journal={Inorganic Chemistry}, author={Zhang, J. B. and Barakat, K. A. and Cundari, T. R. and Gunnoe, T. B. and Boyle, P. D. and Petersen, J. L. and Day, C. S.}, year={2005}, pages={8379–8390} } @article{lail_bell_conner_cundari_gunnoe_petersen_2004, title={Experimental and computational studies of ruthenium(II)-catalyzed addition of arene C-H bonds to olefins}, volume={23}, ISSN={["1520-6041"]}, DOI={10.1021/om049404g}, abstractNote={This article discusses experimental and computational studies of Ruthenium(II)-Catalyzed addition of arene C-H bonds to olefins.}, number={21}, journal={ORGANOMETALLICS}, author={Lail, M and Bell, CM and Conner, D and Cundari, TR and Gunnoe, TB and Petersen, JL}, year={2004}, month={Oct}, pages={5007–5020} } @article{pittard_lee_cundari_gunnoe_petersen_2004, title={Reactions of TpRu(CO)(NCMe)(Me) (Tp = hydridotris(pyrazolyl)borate) with heteroaromatic substrates: Stoichiometric and catalytic C-H activation}, volume={23}, ISSN={["1520-6041"]}, DOI={10.1021/om049508r}, abstractNote={The Ru(II) complex TpRu(CO)(NCMe)(Me) (Tp = hydridotris(pyrazolyl)borate) initiates carbon−hydrogen bond activation at the 2-position of furan and thiophene to produce methane and TpRu(CO)(NCMe)(aryl) (aryl = 2-furyl or 2-thienyl). Solid-state structures have been determined for TpRu(CO)(NCMe)(2-thienyl) and [TpRu(CO)(μ-C,S-thienyl)]2. The complex TpRu(CO)(NCMe)(2-furyl) serves as a catalyst for the formation of 2-ethylfuran from ethylene and furan. DFT calculations of the C−H activation of furan by {(Tab)Ru(CO)(Me)} (Tab = tris(azo)borate) indicate that the C−H activation sequence does not proceed through a Ru(IV) oxidative addition intermediate.}, number={23}, journal={ORGANOMETALLICS}, author={Pittard, KA and Lee, JP and Cundari, TR and Gunnoe, TB and Petersen, JL}, year={2004}, month={Nov}, pages={5514–5523} } @article{zhang_gunnoe_boyle_2004, title={Ruthenium(II) anilido complex containing a bisphosphine pincer ligand: Reversible formation of amidinate ligands via intramolecular C-N bond formation}, volume={23}, ISSN={["1520-6041"]}, DOI={10.1021/om0497543}, abstractNote={The reaction of the octahedral anilido complex (PCP)Ru(CO)(NHPh)(PMe3) with acetonitrile produces the amidinate complex (PCP)Ru(CO){N(H)C(Me)N(Ph)}. Mechanistic studies indicate that the reaction proceeds through coordination of the nitrile to the Ru(II) metal center, followed by intramolecular nucleophilic addition of the amido ligand.}, number={13}, journal={ORGANOMETALLICS}, author={Zhang, J and Gunnoe, TB and Boyle, PD}, year={2004}, month={Jun}, pages={3094–3097} } @article{conner_jayaprakash_cundari_gunnoe_2004, title={Synthesis and reactivity of a coordinatively unsaturated ruthenium(II) parent amido complex: Studies of X-H activation (X = H or C)}, volume={23}, ISSN={["1520-6041"]}, DOI={10.1021/om049836r}, abstractNote={Article discussing the synthesis and reactivity of a coordinatively unsaturated Ruthenium(II) parent amido complex and studies of X-H activation (X = H or C).}, number={11}, journal={ORGANOMETALLICS}, author={Conner, D and Jayaprakash, KN and Cundari, TR and Gunnoe, TB}, year={2004}, month={May}, pages={2724–2733} } @article{lail_arrowood_gunnoe_2003, title={Addition of arenes to ethylene and propene catalyzed by ruthenium}, volume={125}, ISSN={["1520-5126"]}, DOI={10.1021/ja035076k}, abstractNote={TpRuII(CO)(Me)(NCMe) (Tp = hydridotris(pyrazolyl)borate) serves as a catalyst precursor for the conversion of benzene and ethylene or propene to alkylaromatic products. The reaction proceeds via the formation of the active catalyst TpRu(CO)(Ph)(NCMe) and is mildly selective for linear propylbenzene over isopropylbenzene.}, number={25}, journal={JOURNAL OF THE AMERICAN CHEMICAL SOCIETY}, author={Lail, M and Arrowood, BN and Gunnoe, TB}, year={2003}, month={Jun}, pages={7506–7507} } @article{bergman_cundari_gillespie_gunnoe_harman_klinckman_temple_white_2003, title={Computational study of methane activation by TpRe(CO)(2) and CpRe(CO)(2) with a stereoelectronic comparison of cyclopentadienyl and scorpionate ligands}, volume={22}, ISSN={["0276-7333"]}, DOI={10.1021/om021048j}, abstractNote={A computational investigation of metal-based C−H activation with complexes that possess scorpionate (i.e., tris(pyrazolyl)borate) and cyclopentadienyl ligands was reported. The model tris(azo)borate ligand (Tab; [HB(NNH)3]-) was created as an alternative to the parent tris(pyrazolyl)borate (Tp). The Tab ligand was found to closely reproduce the structure and energetics of Tp in Re-mediated C−H activation of methane. Relative to separated reactants oxidative addition of methane to CpRe(CO)2 was exothermic, while the same transformations with TpRe(CO)2 and (Tab)Re(CO)2 were endothermic. The differences between the Tp and Cp systems were attributed primarily to steric effects. The reactivity differences between Tp and Cp drew attention to how each system would respond, sterically and electronically, to ring substitutions. TpRe(CO)3 complexes consistently had a broader νCO (a measure of electronic properties) and cone angle (a measure of steric bulk) range in comparison to CpRe(CO)3 congeners. While Cp was mo...}, number={11}, journal={ORGANOMETALLICS}, author={Bergman, RG and Cundari, TR and Gillespie, AM and Gunnoe, TB and Harman, WD and Klinckman, TR and Temple, MD and White, DP}, year={2003}, month={May}, pages={2331–2337} } @article{conner_jayaprakash_wells_manzer_gunnoe_boyle_2003, title={Octahedral Ru(II) amido complexes TpRu(L)(L ')(NHR) (Tp = hydridotris(pyrazolyl)borate; L = L ' = P(OMe)(3) or PMe3 or L = CO and L ' = PPh3; R = H, Ph, or Bu-t): Synthesis, characterization, and reactions with weakly acidic C-H bonds}, volume={42}, ISSN={["1520-510X"]}, DOI={10.1021/ic034410a}, abstractNote={The octahedral Ru(II) amine complexes [TpRu(L)(L')(NH(2)R)][OTf] (L = L' = PMe(3), P(OMe)(3) or L = CO and L' = PPh(3); R = H or (t)Bu) have been synthesized and characterized. Deprotonation of the amine complexes [TpRu(L)(L')(NH(3))][OTf] or [TpRu(PMe(3))(2)(NH(2)(t)Bu)][OTf] yields the Ru(II) amido complexes TpRu(L)(L')(NH(2)) and TpRu(PMe(3))(2)(NH(t)Bu). Reactions of the parent amido complexes or TpRu(PMe(3))(2)(NH(t)Bu) with phenylacetylene at room temperature result in immediate deprotonation to form ruthenium-amine/phenylacetylide ion pairs, and heating a benzene solution of the [TpRu(PMe(3))(2)(NH(2)(t)Bu)][PhC(2)] ion pair results in the formation of the Ru(II) phenylacetylide complex TpRu(PMe(3))(2)(C[triple bond]CPh) in >90% yield. The observation that [TpRu(PMe(3))(2)(NH(2)(t)Bu)][PhC(2)] converts to the Ru(II) acetylide with good yield while heating the ion pairs [TpRu(L)(L')(NH(3))][PhC(2)] yields multiple products is attributed to reluctant dissociation of ammonia compared with the (t)butylamine ligand (i.e., different rates for acetylide/amine exchange). These results are consistent with ligand exchange reactions of Ru(II) amine complexes [TpRu(PMe(3))(2)(NH(2)R)][OTf] (R = H or (t)Bu) with acetonitrile. The previously reported phenyl amido complexes TpRuL(2)(NHPh) [L = PMe(3) or P(OMe)(3)] react with 10 equiv of phenylacetylene at elevated temperature to produce Ru(II) acetylide complexes TpRuL(2)(C[triple bond]CPh) in quantitative yields. Kinetic studies indicate that the reaction of TpRu(PMe(3))(2)(NHPh) with phenylacetylene occurs via a pathway that involves TpRu(PMe(3))(2)(OTf) or [TpRu(PMe(3))(2)(NH(2)Ph)][OTf] as catalyst. Reactions of 1,4-cyclohexadiene with the Ru(II) amido complexes TpRu(L)(L')(NH(2)) (L = L' = PMe(3) or L = CO and L' = PPh(3)) or TpRu(PMe(3))(2)(NH(t)Bu) at elevated temperatures result in the formation of benzene and Ru hydride complexes. TpRu(PMe(3))(2)(H), [Tp(PMe(3))(2)Ru[double bond]C[double bond]C(H)Ph][OTf], [Tp(PMe(3))(2)Ru=C(CH(2)Ph)[N(H)Ph]][OTf], and [TpRu(PMe(3))(3)][OTf] have been independently prepared and characterized. Results from solid-state X-ray diffraction studies of the complexes [TpRu(CO)(PPh(3))(NH(3))][OTf], [TpRu(PMe(3))(2)(NH(3))][OTf], and TpRu(CO)(PPh(3))(C[triple bond]CPh) are reported.}, number={15}, journal={INORGANIC CHEMISTRY}, author={Conner, D and Jayaprakash, KN and Wells, MB and Manzer, S and Gunnoe, TB and Boyle, PD}, year={2003}, month={Jul}, pages={4759–4772} } @article{arrowood_lail_gunnoe_boyle_2003, title={Radical polymerization of styrene and methyl methacrylate with Ruthenium(II) complexes}, volume={22}, ISSN={["0276-7333"]}, DOI={10.1021/om020871c}, abstractNote={Methylation of [TpRu(CO)2(THF)][PF6] yields the Ru(II) complex TpRu(CO)2(Me), and reaction of TpRu(CO)2(Me) with Me3NO in refluxing acetonitrile yields TpRu(CO)(CH3)(NCMe) (Tp = hydridotris(pyrazolyl)borate). Reactions of TpRu(CO)(CH3)(NCCH3) with CD3CN indicate that the bound acetonitrile ligand undergoes exchange to yield TpRu(CO)(CH3)(NCCD3), and the rates of the exchange reactions are independent of CD3CN concentration. At elevated temperatures catalytic quantities of TpRu(CO)(CH3)(NCMe) in the presence of styrene result in the production of polystyrene. The dependence of polystyrene molecular weight on benzene/cumene molar ratios indicates a radical polymerization mechanism. Styrene polymerization also occurs in the presence of carbon tetrachloride or methyl dichloroacetate. In addition, the polymerization of methyl methacrylate in the presence of TpRu(CO)(CH3)(NCMe) with carbon tetrachloride or methyl dichloroacetate has been observed at 90 °C.}, number={23}, journal={ORGANOMETALLICS}, author={Arrowood, BN and Lail, M and Gunnoe, TB and Boyle, PD}, year={2003}, month={Nov}, pages={4692–4698} } @article{zhang_gunnoe_2003, title={Reactions of ruthenium benzylidene complexes with cyclic and acyclic imines: Oligomerization of 1-pyrroline and metathesis via tautomerism}, volume={22}, ISSN={["0276-7333"]}, DOI={10.1021/om0301029}, abstractNote={At room temperature, NMR spectroscopy indicates that the ruthenium benzylidene complex (Cl)2(PCy3)2RuCHPh reacts with 1-pyrroline to yield (Cl)2(PCy3)(1-pyrroline)RuCHPh. Heating a solution of (Cl)2(PCy3)2RuCHPh with excess 1-pyrroline to 90 °C results in ring-opening oligomerization of the cyclic imine. The combination of ruthenium carbene complexes (Cl)2(PCy3)2RuCHPh and (Cl)2(PCy3)(H2IMes)RuCHPh (H2IMes = 1,3-dimesityl-4,5-dihydroimidazolylidene) with acyclic imines of the type (R)NCH(R‘) results in metathesis reactions when the imine possesses a C−H bond α to the imine carbon. Imines that lack C−H bonds α to the imine carbon do not react with (Cl)2(PCy3)2RuCHPh. The primary products from the reactions of (Cl)2(PCy3)2RuCHPh and (Cl)2(PCy3)(H2IMes)RuCHPh with acyclic imines are olefins and new Fischer carbene complexes of the type (Cl)2(L)(L‘)RuCH{N(H)R} (L = L‘ = PCy3; L = PCy3, L‘ = H2IMes). The ruthenium complex (Cl)2(PCy3)2RuCH{N(H)Pr} has been isolated from the reaction of (Cl)2(PCy3)2RuCHPh with (...}, number={11}, journal={ORGANOMETALLICS}, author={Zhang, JB and Gunnoe, TB}, year={2003}, month={May}, pages={2291–2297} } @article{conner_jayaprakash_gunnoe_boyle_2002, title={Influence of filled d pi-manifold and L/L ' ligands on the structure, basicity, and bond rotations of the octahedral and d(6) amido complexes TpRu(L)(L ')(NHPh) (Tp = hydridotris(pyrazolyl)borate; L= L ' = PMe3 or P(OMe)(3), or L = CO and L ' = PPh3): Solid-state structures of [TpRu(PMe3)(2)(NH2Ph)][OTf], [TpRu{P(OMe)(3)}(2)(NH2Ph)][OTf], and TpRu{P(OMe)(3)}(2)(NHPh)}, volume={41}, ISSN={["1520-510X"]}, DOI={10.1021/ic020163j}, abstractNote={It has been suggested that the reactivity of π-donating ligands bound to late-transition-metal complexes is heightened due to high d-electron counts. Herein, the synthesis and characterization of the Ru(II) amine and Ru(II) amido complexes [TpRuL2(NH2Ph)][OTf] (OTf = trifluoromethanesulfonate) and TpRuL2(NHPh) (L = PMe3 or P(OMe)3) are presented, including solid-state X-ray diffraction studies of [TpRu(PMe3)2(NH2Ph)][OTf], [TpRu{P(OMe)3}2(NH2Ph)][OTf], and TpRu{P(OMe)3}2(NHPh). The pKa's of the Ru(II) amine complexes and the previously reported [TpRu(CO)(PPh3)(NH2Ph)]+ have been estimated to be comparable to that of malononitrile in methylene chloride. In addition, the impact of the filled dπ-manifold (i.e., Ru(II) and d6 octahedral systems) on barriers to rotation of the Ru−NHPh moieties has been studied. For TpRu(PMe3)2(NHPh) and TpRu{P(OMe)3}2(NHPh), evidence for hindered rotation about the amido nitrogen and phenyl ipso carbon has been observed, and the relative N−C and Ru−N bond rotational barriers for the series of three amido complexes are discussed in terms of the π-conflict.}, number={11}, journal={INORGANIC CHEMISTRY}, author={Conner, D and Jayaprakash, KN and Gunnoe, TB and Boyle, PD}, year={2002}, month={Jun}, pages={3042–3049} } @article{conner_jayaprakash_gunnoe_boyle_2002, title={Ruthenium(II) anilido complexes TpRuL(2)(NHPh): Oxidative 4,4 '-aryl coupling reactions (Tp = hydridotris(pyrazolylborate); L = PMe3, P(OMe)(3), or CO)}, volume={21}, ISSN={["1520-6041"]}, DOI={10.1021/om0206406}, abstractNote={Reactions of the Ru(II) amido complexes TpRuL2(NHPh) (L = CO, PMe3, or P(OMe)3) with AgOTf (OTf = trifluoromethanesulfonate) yield the binuclear complexes [TpRuL2NH(C6H4−)]2[OTf]2 along with the Ru(II) amine complexes [TpRuL2(NH2Ph)][OTf] in an approximate 1:1 molar ratio. In these reactions, the two ruthenium fragments are coupled via C−H bond cleavage and C−C bond formation at the para position of anilido ligands. A resonance structure corresponding to Ru(II) metal centers linked by a diimine ligand contributes significantly to the bonding. Evidence for such a contribution comes from the diamagnetic nature of the binuclear complexes and a solid-state X-ray crystallographic study of [TpRu{P(OMe)3}2NH(C6H4−)]2[OTf]2. It is proposed that the coupled products are formed via initial single-electron oxidation followed by C−C bond formation. Variable-temperature NMR spectra of the aryl-coupled complexes are consistent with two geometrical isomers around the rigid HN−C6H4−C6H4NH bridges.}, number={24}, journal={ORGANOMETALLICS}, author={Conner, D and Jayaprakash, KN and Gunnoe, TB and Boyle, PD}, year={2002}, month={Nov}, pages={5265–5271} } @article{jayaprakash_gillepsie_gunnoe_white_2002, title={Synthesis of the Ru-IV amido complex [TpRu(CO)(PPh3)(NHPh)][OTf](2) (Tp = hydridotris(pyrazolyl)borate; OTf = trifluoromethanesulfonate) and deprotonation to form an octahedral and d(4) imido complex: computational study of Ru-IV-imido bonding}, DOI={10.1039/b110999e}, abstractNote={Deprotonation of [TpRu(CO)(PPh3)(NHPh)][OTf]2 yields the thermally unstable d4 imido complex [TpRu-(CO)(PPh3)(NPh)][OTf]; a computational study of the bonding of the imido complex provides a foundation for discussion of its instability in terms of pi-conflict.}, number={4}, journal={Chemical Communications (Cambridge, England)}, author={Jayaprakash, K. N. and Gillepsie, A. M. and Gunnoe, T. B. and White, D. P.}, year={2002}, pages={372–373} } @article{blue_gunnoe_brooks_2002, title={Synthesis, spectroscopy, and solid-state structural characterization of the hexanuclear copper macrocycle [Cu6Cl6(mu-PCHP)(6)]}, volume={41}, number={14}, journal={Angewandte Chemie [International Edition in English]}, author={Blue, E. D. and Gunnoe, T. B. and Brooks, N. R.}, year={2002}, pages={2571-} } @article{jayaprakash_gunnoe_boyle_2001, title={Preparation of the octahedral d(6) amido complex TpRu(CO)(PPh3)(NHPh) (Tp = hydridotris(pyrazolyl)borate): Solid-state structural characterization and reactivity}, volume={40}, ISSN={["0020-1669"]}, DOI={10.1021/ic010785p}, abstractNote={The reaction of TpRu(CO)(PPh(3))(OTf) (2) with LiNHPh affords the amido complex TpRu(CO)(PPh(3))(NHPh) (3) in 88% isolated yield. The amido complex 3 has been characterized by (1)H NMR, (13)C NMR, (31)P NMR, elemental analysis, cyclic voltammetry, and a solid-state X-ray diffraction study. Variable temperature NMR studies have revealed a rotational barrier around the ruthenium-amido nitrogen bond of 3 of 12 kcal/mol (transformation of the major isomer to the minor isomer). The solid-state structure of 3 discloses a pyramidal amido moiety. Heating benzene solutions of the amido complex 3 and 1,4-cyclohexadiene or 9,10-dihydroanthracene results in no observable reaction. Reaction of complex 2 with excess aniline yields [TpRu(CO)(PPh(3))(NH(2)Ph)][OTf] (4).}, number={25}, journal={INORGANIC CHEMISTRY}, author={Jayaprakash, KN and Gunnoe, TB and Boyle, PD}, year={2001}, month={Dec}, pages={6481–6486} } @article{jayaprakash_conner_gunnoe_2001, title={Synthesis and reactivity of the octahedral d(6) parent amido complexes TpRu(L)(L ')(NH2) (Tp = hydridotris(pyrazolyl)borate; L = L ' PMe3, P(OMe)(3); L = CO, L ' PPh3) and [TpRu(PPh3)(NH2)(2)][Li]}, volume={20}, ISSN={["0276-7333"]}, DOI={10.1021/om010739x}, abstractNote={A series of octahedral ruthenium(II) parent amido complexes of the type TpRu(L)(L‘)(NH2) (L/L‘ = neutral and two-electron-donor ligands) and [TpRu(PPh3)(NH2)2][Li] (Tp = hydridotris(pyrazolyl)borate) have been prepared. Preliminary reactivity studies indicate that the amido moieties are highly basic:  for example, TpRu(L)(L‘)(NH2) complexes deprotonate phenylacetylene at room temperature to form [TpRu(L)(L‘)(NH3)][PhC2] ion pairs, as determined by 1H NMR spectroscopy.}, number={25}, journal={ORGANOMETALLICS}, author={Jayaprakash, KN and Conner, D and Gunnoe, TB}, year={2001}, month={Dec}, pages={5254–5256} } @misc{tellers_skoog_bergman_gunnoe_harman_2000, title={Comparison of the relative electron-donating abilities of hydridotris(pyrazolyl)borate and cyclopentadienyl ligands: Different interactions with different transition metals}, volume={19}, ISSN={["1520-6041"]}, DOI={10.1021/om000043o}, abstractNote={A comparison of the electron-donating abilities of the hydridotris(pyrazolyl)borate ligand and cyclopentadienyl ligand toward transition metals is presented. These data demonstrate that there is no definitive trend in donor ability across the periodic table, and consequently generalizations about the relative donating abilities of the two ligands should be discouraged.}, number={13}, journal={ORGANOMETALLICS}, author={Tellers, DM and Skoog, SJ and Bergman, RG and Gunnoe, TB and Harman, WD}, year={2000}, month={Jun}, pages={2428–2432} }