Nucleophilic attack on .eta.2-acetyl ligands. Structure of a bridging .eta.2-acetone complex

Martin, Bruce D.; Matchett, Stephen A.; Norton, Jack R.; Anderson, Oren P.

doi:10.1021/ja00312a025

Cited by 28 publications

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“…There are several examples of bimetallic catalvsts in the or~ano~netallic chemical 1i;erature. A hetGobi1netallic complex containing CH3-Zr and Mo-CO undergoes further carbonylation to form an acetyl complex(30). Reaction of meth~l -M n ( C 0 )~ with an Fe-carbonyl complex yields a heterobimetallic bridging acetyl co~nplex(31).…”

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confidence: 99%

A Methylnickel Intermediate in a Bimetallic Mechanism of Acetyl-Coenzyme A Synthesis by Anaerobic Bacteria

Kumar

Qiu

Spiro

et al. 1995

Science

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Resonance Raman (RR) spectroscopy was used to identify a methylnickel adduct (upsilon Ni-C = 422 wave numbers) of carbon monoxide dehydrogenase (CODH) from Clostridium thermoaceticum. Formed at a nickel/iron-sulfur cluster on CODH called center A, the methylnickel species is the precursor of the methyl group of acetyl-coenzyme A in an anaerobic pathway of carbon monoxide or carbon dioxide fixation. Rapid kinetic and RR studies demonstrated that methylation of nickel occurs by heterolysis of the methyl-cobalt bond (upsilon Co-C = 429 wave numbers) of a methylated corrinoid/iron-sulfur protein. In combination with the earlier finding of an iron-carbonyl adduct at center A, detection of the methylnickel intermediate establishes a bimetallic mechanism for acetyl-coenzyme A synthesis.

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confidence: 99%

A Methylnickel Intermediate in a Bimetallic Mechanism of Acetyl-Coenzyme A Synthesis by Anaerobic Bacteria

Kumar

Qiu

Spiro

et al. 1995

Science

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“…Several prior reports support our mechanistic proposal. Reports of acetone formation from reaction of metal-methyl groups with CO are legion: examples of such reactivity can be found for most of the early to mid transition metals, including Ti, Zr, , V, Nb, ,,, Ta, − , W, and Re . In these examples, the newly formed acetone either remains bound to the metal center as an η 2 -acetone ligand or dissociates to give a low valent metal center and free acetone.…”

Section: Resultsmentioning

confidence: 99%

A Diverse Array of C–C Bonds Formed at a Tantalum Metal Center

et al. 2021

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We demonstrate the formation of a diverse array of organic and organometallic products containing newly formed C−C bonds via successive methyl transfers from di-, tri-, and tetramethyl Ta(V) precursors to unsaturated small molecule substrates under mild conditions. The reactions of Ta(V) methyl complexes 1−X [H 2 B( Mes Im) 2 ]TaMe 3 X (X = Me, Cl; Im = imidazole, Mes = 2,4,6trimethylphenyl) with CO led to oxo enolate Ta(V) products, in which the enolate ligands were constructed from Ta-Me groups and two equivalents of CO. Similarly, the reaction of 1-Me with CNXyl yielded an imido enamine Ta(V) product. Surprisingly, 1-Cl reacted with CNXyl (1 equiv) at the borate backbone of the [H 2 B( Mes Im) 2 ] ligand with concomitant methyl transfer from the metal center to form a new, dianionic scorpionate ligand that supported a Ta(V) dimethyl chloro complex (6). Treatment of 1-Cl with further CNXyl led to an azaallyl scorpionate complex, and an imido isocyanide scorpionate complex, along with propene and xylyl ketenimine. Complex 6 reacted with CO to yield a pinacol scorpionate complex 10a new reaction pathway in early transition metal chemistry. Mechanistic studies revealed that this proceeded via migratory insertion of CO into a Ta-Me group, followed by methyl transfer to form an η 2 -acetone intermediate. Elimination of acetone furnished a CO-stabilized Ta(III) intermediate capable of rebinding and subsequently coupling two equivalents of CO-derived acetone to form the pinacol ligand in 10.

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“…AQESIZ (Mukherjee et al, 2011); AXIBOA (Boulho et al2016); BESGOW (Bolig & Chen, 2004); BODMIR (Helmstedt et al, 2008); BUHVAD (Xu et al, 2015); BUYSOD10 (Longato et al, 1985); CADRUU (Hunter et al, 1983); COHTEY (Waymouth et al, 1984); COPRII (Ho et al, 1984); DAGKAX and DAGKIF (Gambarotta et al, 1985); DITHAP (Martin et al, 1985); EHEFUT (Neu et al, 2011); EKEVEX, EKEVIB, EKEVOH, EKEVUN, EKEWAU and EKEWEY (Normand et al, 2016); ESISAA (Zuccaccia et al, 2004); GIPYUZ (Matchett et al, 1988); HEMCOR (Askham et al, 1994); HIKHUF and HIKJAN (Gurubasavaraj et al, 2007); HUVLAL (Fujdala et al, 2003); IGUDOD (Hü erlä nder et al, 2002); JITVAK and JITVEO (Mandal et al, 2007); JUGCIZ (Boulho et al, 2015); KEXYER (Erker et al, 1990); KODQAV (Koch et al, 2000); KUPQAP (Mariott & Chen, 2005); LEDBEB (Askham et al, 1993); LEPXAH (Mukherjee et al, 2013); MOJHEZ (Black et al, 2008); NAHYOL (Bai et al, 2005); NAPXUY (Pineda et al, 2005); NIMNOM (Johnson et al, 1997); ODOBIU, ODOBOA and ODOBUG (Frö mel et al, 2013); OKUFUX (Bestgen et al, 2016); OZUCAO (Kelsen et al, 2011); PEDFUA (Singh et al, 2006); QIZCEI ; REDTUQ (Cummings et al, 2006); TIWKUG (Yang, Schulz et al, 2008); TOWMUN (Breen & Stephan, 1996); VIBSOO (Waymouth et al, 1990); WAJLO...…”

Section: Figurementioning

confidence: 99%

(μ-Di-tert-butylsilanediolato)bis[bis(η⁵-cyclopentadienyl)methylzirconium]

et al. 2019

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Nucleophilic attack on .eta.2-acetyl ligands. Structure of a bridging .eta.2-acetone complex

Cited by 28 publications

References 0 publications

A Methylnickel Intermediate in a Bimetallic Mechanism of Acetyl-Coenzyme A Synthesis by Anaerobic Bacteria

A Methylnickel Intermediate in a Bimetallic Mechanism of Acetyl-Coenzyme A Synthesis by Anaerobic Bacteria

A Diverse Array of C–C Bonds Formed at a Tantalum Metal Center

(μ-Di-tert-butylsilanediolato)bis[bis(η⁵-cyclopentadienyl)methylzirconium]

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Nucleophilic attack on .eta.2-acetyl ligands. Structure of a bridging .eta.2-acetone complex

Cited by 28 publications

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A Methylnickel Intermediate in a Bimetallic Mechanism of Acetyl-Coenzyme A Synthesis by Anaerobic Bacteria

A Methylnickel Intermediate in a Bimetallic Mechanism of Acetyl-Coenzyme A Synthesis by Anaerobic Bacteria

A Diverse Array of C–C Bonds Formed at a Tantalum Metal Center

(μ-Di-tert-butylsilanediolato)bis[bis(η5-cyclopentadienyl)methylzirconium]

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(μ-Di-tert-butylsilanediolato)bis[bis(η⁵-cyclopentadienyl)methylzirconium]