2011
DOI: 10.1002/anie.201105281
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The Conversion of Nickel‐Bound CO into an Acetyl Thioester: Organometallic Chemistry Relevant to the Acetyl Coenzyme A Synthase Active Site

Abstract: When three become one: Within one nickel-based model system, the three reactants CO, MeI, and PhSH have been assembled to yield an acetyl thioester. The reactivity is of relevance for the functioning of the acetyl coenzyme A synthase active site and provides insights into possible binding sequences.

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Cited by 30 publications
(24 citation statements)
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“…The same coordination geometry is adopted in solution as confirmed by 1 H NMR spectroscopy of 2 dissolved in C 6 D 6 , which revealed signals for chemically non‐equivalent t Bu and i Pr groups on the β‐diketiminate ligand connected to a diamagnetic metal ion. For nickel in the +2 oxidation state, this is in accordance with a square‐planar coordination sphere with two different donor atoms beside the β‐diketiminate, just as in the case of the nickel acetyl complex [L t Bu NiC(O)Me] …”
Section: Figuresupporting
confidence: 54%
“…The same coordination geometry is adopted in solution as confirmed by 1 H NMR spectroscopy of 2 dissolved in C 6 D 6 , which revealed signals for chemically non‐equivalent t Bu and i Pr groups on the β‐diketiminate ligand connected to a diamagnetic metal ion. For nickel in the +2 oxidation state, this is in accordance with a square‐planar coordination sphere with two different donor atoms beside the β‐diketiminate, just as in the case of the nickel acetyl complex [L t Bu NiC(O)Me] …”
Section: Figuresupporting
confidence: 54%
“…One of the isomers is a dimer {[L t BuOO Ni II Cl][Na(OEt 2 )]} 2 [BAr F 4 ] 2 , 5(OEt 2 ) (Figure ), while the other, {[L t BuOO Ni II Cl][Na(OEt 2 )]} x [BAr F 4 ] x , 5(OEt 2 )′ , is polymeric. In dinuclear 5(OEt 2 ) , the planar [C 3 N 2 Ni] motif that is usually observed in nickel(II) complexes with β‐diketiminate ligands has given way to a boat conformation, as the O 2 reaction has converted it into a tridentate [L t BuOO ] ligand. That is, bidentate [L t Bu ] has transferred two electrons onto the O 2 moiety with formation of a C−O bond to the α‐carbon atom of the ligand.…”
Section: Methodsmentioning
confidence: 99%
“…It is also notable that the MTA yield decreased steeply as the NiS electroreduction potential was positively changed from -1.0 to -0.8 VSHE (Figure 2b to d) although -0.8 VSHE is still sufficient for the Ni 0 generation (Figure 1f). In light of reported chemical functions of Ni and other metals in organometallic analogues of ACS, [28,29] one possible interpretation is that the MTA synthesis involves at least two adjacent surface Ni 0 sites (Figure 2e (Table S3 and S4), where the resultant methyl converts to CH4 via protonation, while thiolysis of the methyl generates dimethyl sulfide. If a random Ni 0 distribution is assumed, a 12% conversion of Ni 2+ to Ni 0 achieved at -1.0 VSHE (Figure 1f) results in 1.4% occurrence of the adjacent Ni 0 -Ni 0 surface pair, while this percentage drops to 0.16% with a 4% conversion achieved at -0.8 VSHE.…”
Section: Co + 2ch3sh → Ch3cosch3 + H2smentioning
confidence: 99%