Capture of NiII, CuIand ZnIIby thiolate sulfurs of an N2S2Ni complex: A role for a metallothiolate ligand in the acetyl-coenzyme A synthase active site

Golden, Melissa L.; Rampersad, Marilyn V.; Reibenspies, Joseph H.; Darensbourg, Marcetta Y.

doi:10.1039/b304884p

Cited by 54 publications

(49 citation statements)

References 22 publications

(30 reference statements)

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“…18 Since the publication of the first structure of ACS/CODH, several low molecular weight models of the ACS site have been synthesized and studied to determine the intrinsic properties of the metal-containing active site(s). [19][20][21][22][23][24][25] In these pursuits, researchers have focused mostly on the bimetallic M p -Ni d site of ACS and ignored the Fe 4 S 4 portion (unlikely site of substrate binding). For example, Rauchfuss and coworkers have synthesized the model complex [{Ni(CO) 2 }{NiS 2 N' 2 }] 2− (structure a, Figure 2) with two terminal CO ligands bound to the bridged Ni center in the 0 oxidation state.…”

Section: Introductionmentioning

confidence: 99%

Synthetic Analogues of the Active Site of the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase: Syntheses, Structures, and Reactions with CO

2006

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Two metallosynthons, namely (Et 4 N) 2 [Ni(NpPepS)] (1) and (Et 4 N) 2 [Ni(PhPepS)] (2) containing carboxamido-N and thiolato-S as donors have been used to model the bimetallic M p -Ni d subsite of the A-cluster of the enzyme ACS/CODH. A series of sulfurbridged Ni/Cu dinuclear and trinuclear complexes (3-10) have been synthesized to explore their redox properties and affinity of the metal centers toward CO. The structures of (Et 4 N) 2 (8), and [Ni(dppe)Ni(PhPepS)]•CH 2 Cl 2 (10•CH 2 Cl 2 ) have been determined by crystallography. The Ni d mimics 1 and 2 resist reduction and exhibit no affinity toward CO. In contrast, the sulfur-bridged Ni center (designated Ni C ) in the trinuclear models 5-8 are amenable to reduction and binds CO in the Ni(I) state. Also, the sulfurbridged Ni C center can be removed from the trimers (5-8) by treatment with 1,10-phenanthroline much like the "labile Ni" from the enzyme. The dinuclear Ni-Ni models 9 and 10 resemble the Ni p -Ni d subsite of the A-cluster more closely and only the modeled Ni p site of the dimers can be reduced. The Ni(I)-Ni(II) species display EPR spectra typical of a Ni(I) center in distorted trigonal bipyramidal and distorted tetrahedral geometries for 9 red and 10 red , respectively. Both species bind CO and the CO-adducts 9 red -CO and 10 red -CO display strong ν co at 2044 and 1997 cm -1 , respectively. The reduction of 10 is reversible. The CO-affinity of 10 in the reduced state and the ν co value of 10 red -CO closely resemble the CO-bound reduced A-cluster (ν co = 1996 cm -1 ).

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Section: Introductionmentioning

confidence: 99%

Synthetic Analogues of the Active Site of the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase: Syntheses, Structures, and Reactions with CO

2006

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“…Regarding the NiS 4 complexes as dithiolate ligands makes the novel octanuclear compound [{Ni-(bsms) 2 } 3 (CuI) 5 ] a [Cu 5 ("S 2 ") 3 ] cluster. Numerous Cu I thiolate clusters have been reported; however, only two clusters have been reported with a related Cu 5 (SR) 6 arrangement. [29] The copper centres in these complexes are also in a trigonal-bipyramidal array, each axial-equatorial edge of which is bridged by a thiolate sulfur atom.…”

Section: Discussionmentioning

confidence: 99%

“…However, the resulting complex [{Ni(xbsms)CuI} 2 ] is obviously different and, as similar reaction conditions were applied in the two syntheses, the resulting dissimilar structures must be a consequence of packing effects. The reported [6,16] complex [{Ni(N 2 S 2 )} 3 (CuBr) 2 ] may be regarded as being derived from the present Ni 3 Cu 5 complex by removal of the three equatorial CuI units. Structures have been reported of [{Ni(N 2 S 2 )} 2 Cu 2 ] 2+ , which have the same nickel/copper ratio as [{Ni(xbsms)CuI} 2 ] but which do not contain coordinated halides and in which the sulfur binding is different.…”

Section: Discussionmentioning

confidence: 99%

“…A study [6] 5 ]. The complex [Ni 3 (xbsms) 2 (ZnBr 3 ) 2 ] does not show reactivity towards CuI, which may be related to the low solubility of this complex.…”

Section: Discussionmentioning

confidence: 99%

“…[1] However, due to the earlier reports of Cu-or Zn-containing structures, [2,3] attempts to synthesise structural models of the A-cluster have resulted in reports of several new heteronuclear clusters. [4][5][6][7][8][9][10][11] In most of these investigations, discrete mononuclear nickel complexes of tetradentate N 2 S 2 ligands have been used as building blocks, and their reactivity towards transition metals such as Fe, Ni, Cu, Zn, Ag, Pd and Hg have been studied. The nickel complexes can be considered to react as didentate S ligands.…”

Section: Introductionmentioning

confidence: 99%

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Nickel Thiolate Complexes as Ligands for Copper and Zinc: Novel Additions to a Library of Binding Modes

et al. 2006

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The reactivity of the two nickel complexes [Ni(xbsms)] and [Ni(bsms) 2 ] [H 2 xbsms = α,αЈ-bis(4-mercapto-3,3-dimethyl-2-thiabutyl)-o-xylene; Hbsms = 4-mercapto-3,3-dimethyl-1-phenyl-2-thiabutane] towards copper iodide and zinc bromide has been investigated. The reactions yield novel aggregates of higher nuclearity with topologies that are different from previous reports; the nickel complexes in all cases can be considered as didentate S ligands. The X-ray structure of the novel octanuclear cluster [{Ni(bsms) 2 } 3 (CuI) 5 ] shows a unique arrangement in which the cis-NiS 2 SЈ 2 units act as didentate ligands to a trigonal-bipyramidal array of five Cu I ions. The tetranuclear structure of [{Ni(xbsms)CuI} 2 ] shows unprecedented asymmetric bridging of the thiolate sulfur atoms, with one of the thiolate groups binding to one copper

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Nickel: Inorganic & Coordination Chemistry

Collinson

Schröder

2005

Encyclopedia of Inorganic Chemistry

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The general features and coordination chemistry of Ni 0 to Ni IV and complexation to cyanide, N‐, P‐, O‐, S‐, and halide‐donor ligands are detailed. The reactivity of Ni II complexes in the template synthesis of macrocycles and for the oligomerization and polymerization of alkenes are highlighted. The stabilization of radical Ni I and Ni III centers is related to the associated ligand types and metal‐ion stereochemistries. The supramolecular chemistry of Ni II includes the formation of aggregates, framework polymers, and receptors. The structures of a number of Ni‐containing enzymes have been elucidated and the formation of low‐molecular weight complex mimics is discussed.

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Capture of Ni^II, Cu^Iand Zn^IIby thiolate sulfurs of an N₂S₂Ni complex: A role for a metallothiolate ligand in the acetyl-coenzyme A synthase active site

Abstract: The metal binding affinity of an (N2S2)Ni bridging metallothiolate ligand (Zn2+ < Ni2+ < Cu+) gives precedent for the observed heterogeneity in ACS/CODH.

Cited by 54 publications

References 22 publications

Synthetic Analogues of the Active Site of the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase: Syntheses, Structures, and Reactions with CO

Synthetic Analogues of the Active Site of the A-Cluster of Acetyl Coenzyme A Synthase/CO Dehydrogenase: Syntheses, Structures, and Reactions with CO

Nickel Thiolate Complexes as Ligands for Copper and Zinc: Novel Additions to a Library of Binding Modes

Nickel: Inorganic & Coordination Chemistry

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