ISSN:
1434-1948
Schlagwort(e):
Nickel complexes
;
Platinum complexes
;
S ligands
;
C-S cleavage
;
Hydride complexes
;
Chemistry
;
General Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Nickel and platinum complexes with tridentate ligands, having [S3] or [NS2] donor sets were investigated in order to model active sites of enzymes such as hydrogenases or CO dehydrogenases. Starting from diphenyl sulfide, a preparative synthesis was developed for ‘S3’-H2 [‘S3’-H2 = bis(2-mercaptophenyl) sulfide]. Reactions of ‘S3’-H2 or anionic ‘S3’2- with nickel and platinum precursors resulted in the formation of binuclear [Ni(‘S3’)]2 (1) and trinuclear [Pt(‘S3’)]3 (5). Complex 1 was cleaved by PMe3 or CN- to give the mononuclear complexes [Ni(‘S3’)(PMe3)] (2) and NMe4[Ni(‘S3’)(CN)] (3). Attempts to coordinate hydride to the [Ni(‘S3’)] fragment led to C-S bond cleavage of the ligand and formation of (NMe4)2[{Ni(μ-SC6H5)(S2C6H4)}2] (4). Oxidative addition of Li[‘S3’-H] to [Pt(PPh3)4] afforded the platinum hydride complexes Li[Pt(H)(‘S3’)] and Li[Pt(H)(PPh3)(‘S3’)] which, however, could not be separated from each other and yielded [Pt(‘S3’)(PPh3)] (6) when treated with MeOH. In order to investigate electronic effects of the donor set, the ‘S3’ ligand was modified by alkylation of one thiol group to give ‘RS3’-H derivatives (R = Me, Et, Cy) and by replacing a mercaptophenyl unit by an amine in ‘Et2NS2’-H [‘Et2NS2’-H = N,N-diethyl-2-(2-mercaptothiophenyl)ethylamine]. Reactions of NiII or Ni0 compounds with these ligands in a 1:1 ratio yielded the 1:2 complexes [Ni(‘MeS3’)2] (7), [Ni(‘EtS3’)2] (9) and [Ni(‘CyS3’)2] (10), with ‘RS3’- acting as bidentate ligands only. Complex 7 reversibly reacted with PMe3 to form cis-[Ni(PMe3)2(‘MeS3’)2] (8), exhibiting monodentate ‘MeS3’ ligands. [Ni(‘Et2HNS2’)2]Br2 (11) reacted reversibly with bases to presumably give octahedral [Ni(‘Et2NS2’)2]. Complexes 7, 9 and 10 also did not yield any [Ni(‘RS3’)(H)] hydride complex when treated with hydride sources. Oxidative addition of ‘CyS3’-H to [Pt(PPh3)4] yielded the hydride complexes [Pt(H)(‘CyS3’)] and [Pt(H)(PPh3)(‘CyS3’)] which, however, formed an inseparable mixture and underwent C-S bond cleavage when heated, affording [Pt(o-S2C6H4)(PPh3)2]. The molecular structures of 1, 2, 3, 5, 6, 7, and 11 were determined by X-ray crystallography, revealing butterfly-like shapes for the [MS3L] cores of the complexes.
Zusätzliches Material:
4 Ill.
Materialart:
Digitale Medien
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