Nitrosyl transfer reactions

Ungermann, Charles; Caulton, Kenneth G.

doi:10.1021/ja00429a022

Cited by 42 publications

(14 citation statements)

References 17 publications

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“…In many of these systems, the form of NO (NO·, NO + or NO − ) formally being transferred from the DNIC to the acceptor is dictated by the stability of the resulting nitrosylated or nitrosated product. Such dependence was noted previously in a study of NO-transfer from a cobalt nitrosyl to a variety of different metal complexes 63. The reactivity suggests that NO-transfer reactions are dictated by the thermodynamic requirements of the acceptor and that different forms of NO may be released or transferred from the DNIC depending on the nature of the acceptor.…”

Section: Discussionsupporting

confidence: 68%

Chemistry of Nitrosyliron Complexes Supported by a β-Diketiminate Ligand

et al. 2011

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Several nitrosyl complexes of Fe and Co have been prepared using the sterically hindered Ar-nacnac ligand (Ar-nacnac = anion of [(2,6-diisopropylphenyl)NC(Me)]2CH). The dinitrosyl iron complexes, [Fe(NO)2(Ar-nacnac)] (1) and (Bu4N)[Fe(NO)2(Ar-nacnac)] (2) react with [FeIII(TPP)Cl] (TPP = tetraphenylporphine dianion) to generate [FeII(TPP)(NO)] and the corresponding mononitrosyl iron complexes. The factors governing NO-transfer with DNICs 1 and 2 are evaluated, together with the chemistry of the related mononitrosyl iron complex, [Fe(NO)Br(Ar-nacnac)], 4. The synthesis and properties of the related cobalt dinitrosyl [Co(NO)2(Ar-nacnac)], 3, is also discussed for comparison to DNICs 1 and 2. The solid-state structures of several of these compounds as determined by X-ray crystallography are reported.

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Section: Discussionsupporting

confidence: 68%

Chemistry of Nitrosyliron Complexes Supported by a β-Diketiminate Ligand

et al. 2011

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“…In this regard, one of the early examples involves the acid-promoted intermolecular transfer of NO from Co II to Cr II , involving the formation of a labile aqua complex at lower pH. 5a In another case, protonation of an axial ligand transforms the geometry of coordinated NO toward a more bent conformation, allowing NO-transfer. 5b Caulton and co-workers undertook a detailed investigation of nitrosyl transfer from Co(NO)(dmgH) 2 (dmgH = monoanion of dimethylglyoxime (dmgH 2 )) to the various metal complexes of Fe, Co, Ni, and Ru.…”

Section: Introductionmentioning

confidence: 99%

“…5a In another case, protonation of an axial ligand transforms the geometry of coordinated NO toward a more bent conformation, allowing NO-transfer. 5b Caulton and co-workers undertook a detailed investigation of nitrosyl transfer from Co(NO)(dmgH) 2 (dmgH = monoanion of dimethylglyoxime (dmgH 2 )) to the various metal complexes of Fe, Co, Ni, and Ru. 5c For the first time, they suggested a μ -bridged nitrosyl formation prior to the transfer of NO.…”

Section: Introductionmentioning

confidence: 99%

“…5b Caulton and co-workers undertook a detailed investigation of nitrosyl transfer from Co(NO)(dmgH) 2 (dmgH = monoanion of dimethylglyoxime (dmgH 2 )) to the various metal complexes of Fe, Co, Ni, and Ru. 5c For the first time, they suggested a μ -bridged nitrosyl formation prior to the transfer of NO. A dissociative pathway of NO-transfer was described for a Co(NO)(dmgH) 2 complex in the presence of hemoglobin (Hb), with first dissociation of NO followed by formation of HbNO.…”

Section: Introductionmentioning

confidence: 99%

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Factors That Control the Reactivity of Cobalt(III)–Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation

Kumar

Lee

et al. 2016

J. Am. Chem. Soc.

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Metal–nitrosyl complexes are key intermediates involved in many biological and physiological processes of nitric oxide (NO) activation by metalloproteins. In this study, we report the reactivities of mononuclear cobalt(III)–nitrosyl complexes bearing N-tetramethylated cyclam (TMC) ligands, [(14-TMC)CoIII(NO)]2+ and [(12-TMC)CoIII(NO)]2+, in NO-transfer and dioxygenation reactions. The Co(III)–nitrosyl complex bearing 14-TMC ligand, [(14-TMC)CoIII(NO)]2+, transfers the bound nitrosyl ligand to [(12-TMC)CoII]2+ via a dissociative pathway, {[(14-TMC)CoIII(NO)]2+ → {(14-TMC)-Co⋯NO}2+}, thus affording [(12-TMC)CoIII(NO)]2+ and [(14-TMC)CoII]2+ as products. The dissociation of NO from the [(14-TMC)CoIII(NO)]2+ complex prior to NO-transfer is supported experimentally and theoretically. In contrast, the reverse reaction, which is the NO-transfer from [(12-TMC)CoIII(NO)]2+ to [(14-TMC)CoII]2+, does not occur. In addition to the NO-transfer reaction, dioxygenation of [(14-TMC)CoIII(NO)]2+ by O2 produces [(14-TMC)CoII(NO3)]+, which possesses an O,O-chelated nitrato ligand and where, based on an experiment using 18O-labeled O2, two of the three O-atoms in the [(14-TMC)CoII(NO3)]+ product derive from O2. The dioxygenation reaction is proposed to occur via a dissociative pathway, as proposed in the NO-transfer reaction, and via the formation of a Co(II)–peroxynitrite intermediate, based on the observation of phenol ring nitration. In contrast, [(12-TMC)CoIII(NO)]2+ does not react with O2. Thus, the present results demonstrate unambiguously that the NO-transfer/dioxygenation reactivity of the cobalt(III)–nitrosyl complexes bearing TMC ligands is significantly influenced by the ring size of the TMC ligands and/or the spin state of the cobalt ion.

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“…O conjunto de dados cinéticos apresentados anteriormente somados aos dados da literatura [72][73][74]…”

Section: Identificação E Cálculos Ab Initio Do Intermediário Da Reaçãunclassified

Sobre a formação do ligante nitroxila e a reação de transferência de óxido nítrico em tetraaminas de rutênio

Metzker¹

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Ao Prof. Douglas pela orientação, amigável convivência, discussões e por sua fundamental contribuição em minha formação profissional. Aos Professores Benedito, Ubirajara e Daniel Rodrigues Cardoso pela amigável convivência e pelas valiosas discussões durante esses anos. Aos colegas do Laboratório de Química Inorgânica e Analítica, dos que já se "foram" aos aqui ainda presentes, pela prazerosa convivência, discussões e ajuda durante esses anos de jornada. Aos colegas do Laboratório da Química da Aguardente pela agradável convivência. Aos grandes amigos da "velha guarda" (Turma IQSC 2003) Pietro, Raphael e Bruno. A Veroneide pela sua eterna disposição em ajudar e pela amizade. A todo pessoal da Biblioteca, em especial a Bernadete, Eliana e Wilneide. A Silvia, Andreia e Gustavo, da Comissão de Pós-Graduação pelo auxílio e apoio. Aos todos os funcionários do IQSC (oficinas de apoio, CAQI, corpo administrativo) sem os quais este trabalho não teria condições de ser realizado. Ao CNPq pela bolsa concedida. Um agradecimento especial a minha "família ararense" (meu pai Antonio, minha mãe Carmen e ao meu irmão Fabrício) a minha tia Apparecida pelo seu grande apoio e incentivo durante todos os anos desta jornada e para minha "família são-carlense" (Natália, minha noiva e ao Bohr, nosso cachorro) pelo amor, carinho e compreensão. Epígrafe "Mantenha-se simples, bom, puro, sério, livre de afetação, amigo da justiça, temente aos deuses, gentil, apaixonado, vigoroso em todas as suas atitudes. Lute para viver como a filosofia gostaria que vivesse. Reverencie os deuses e ajude os homens. A vida é curta." Marcus Aurelius "Carefully watch your thoughts, for they become your words. Manage and watch your words, for they will become your actions. Consider and judge your actions, for they have become your habits. Acknowledge and watch your habits, for they shall become your values. Understand and embrace your values, for they become your destiny." Mahatma Gandhi Resumo Resumo Foram estudadas as reações de formação do NO-/ HNO, estados de spin e reatividade frente a redutores dos complexos trans-[Ru II (NO +)(NH 3) 4 (L)](X) n onde L = N-heterocíclicos (IsN, Nic e ImN) ou éster de fósforo (P(OEt) 3). O potencial para o par redox [Ru II (NO 0)] n+ / [Ru II (NO-)] (n-1)+ foi identificado somente para L = P(OEt) 3 com valor de E p =-0,41V. Cálculos DFT indicaram que após a redução, a espécie singleto coordenada (NO-) é formada por ser mais estável que forma tripleto (3 NO-), sendo imediatamente protonada, dando origem a espécie singleto protonada (1 HNO) não havendo, portanto proibição de spin para a reação de protonação do ligante, indicando comportamento diferente do observado para o ligante livre, onde a espécie 3 NOé a mais estável. Após a redução química por Zn(Hg), a espécie N 2 O, produto da dimerização do HNO, pôde ser identificada indicando a liberação de HNO pelo complexo trans-[Ru II (NO +)(NH 3) 4 (L)] n+. A reação de transferência de óxido nítrico entre os nitrosilo complexos onde L = IsN, Nic, ImN, P(OEt) 3 , P(OMe) 3 , P(OIsp...

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Nitrosyl transfer reactions

Cited by 42 publications

References 17 publications

Chemistry of Nitrosyliron Complexes Supported by a β-Diketiminate Ligand

Chemistry of Nitrosyliron Complexes Supported by a β-Diketiminate Ligand

Factors That Control the Reactivity of Cobalt(III)–Nitrosyl Complexes in Nitric Oxide Transfer and Dioxygenation Reactions: A Combined Experimental and Theoretical Investigation

Sobre a formação do ligante nitroxila e a reação de transferência de óxido nítrico em tetraaminas de rutênio

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