Transition Metal Complexes with Sulfur Ligands. 117.¹A Reaction Cycle for Nickel Mediated Thioester Formation from Alkyl, CO, and Thiolate Groups Modeling the Acetyl-Coenzyme A Synthase Function of CO Dehydrogenase

Abstract

In quest of nickel complexes with sulfur ligation that model the acetyl-CoA synthase function of CO dehydrogenase (

The Synthesis and Electronic Structure of a Novel [Ni‘S4’Fe2(CO)6] Radical Cluster: Implications for the Active Site of the [NiFe] Hydrogenases

“…[26,27] The yields of these reactions were improved by the use of excess 1,3-dibromopropane in the synthetic procedure, which could be easily washed from the precipitated product with MeOH. The resolution of the 1 H NMR spectra for 3 a and 4 is consistent with the formulation of 3 a and 4 as diamagnetic Ni II S 4 centres possessing approximate squareplanar coordination geometries.…”

“…The resolution of the 1 H NMR spectra for 3 a and 4 is consistent with the formulation of 3 a and 4 as diamagnetic Ni II S 4 centres possessing approximate squareplanar coordination geometries. [26,27] After a mixture of 3 a and [Fe 3 (CO) 12 12 ] with thiols. [28] These reaction mixtures always contain [Fe(CO) 5 ], probably formed through an interaction of [Fe(CO) 4 ] fragments with CO produced during the reaction.…”

Genetic Construction of Truncated and Chimeric Metalloproteins Derived from the α Subunit of Acetyl-CoA Synthase from Clostridium thermoaceticum

“…16 This center has also been modeled by Holm, Riordan, Sellmann, and Pohl using nonproteinaceous ligands. [17][18][19][20] Although such constructs are catalytically inactive and lack the precise spectroscopic, redox, and substrate-binding characteristics of the A-cluster, they each represent outstanding progress towards this difficult modeling goal.A related approach, known as "redesign", alters existing protein structures by adding/modifying metal centers and/or regulatory elements. Caradonna et al used the DEZYMER algorithm to incorporate an Fe 4 S 4 synthetic cluster within the protein matrix of thioredoxin.…”

Synthesis, Structures, and Reactions of Sulfur-Rich Nickel and Platinum Complexes with [MS3] and [MNS2] Cores

“…Related structures are found in 276.3(3) pm [30] and 279.5(3) pm [31] have been assumed to indicate weak NiϪNi interactions. The trinuclear [Pt('S 3 ')] 3 [Pd(SC 2 H 4 SC 2 H 4 S)] 3 , [25b] [Ni('µ-S 2 C 3 Me 2 ') 3 ], [32] and [Ni('tBuS 4 ')] 3 . [33] (5) exhibits a cyclohexane-like [PtS] 3 six-membered ring [26] and exclude NiϪS bonding interactions.…”