Wiley InterScience Backfile Collection 1832-2000
Chemistry and Pharmacology
In order to obtain suitable precursors for nickel and palladium complexes that model the reactivity of the active sites of hydrogenases and CO dehydrogenases, a series of [M(L)(‘S3’)] complexes has been synthesized [M = NiII, PdII; ‘S3’2- = bis(2-mercaptophenyl)sulfide(2-)]. X-ray structure determinations of [Ni(‘S3’)]3 (1) and [Pd(‘S3’)]3 (2) have revealed that the [M(‘S3’)] fragments trimerize to give six-membered [MS]3 rings, which exhibit chair conformations with alternating MII centers and thiolate bridging atoms. Reactions of the parent complex [Ni(‘S3’)]3 (1) with nucleophiles L, such as thiolates SR- (R = tBu, Cy, Me, Ph), phosphanes PR3 (R = Cy, Ph), chloride, or azide, have been found to yield the corresponding anionic or neutral [Ni(L)(‘S3’)] complexes, which were isolated as (NBu4)[Ni(SR)(‘S3’)] [R = tBu (3), Cy (4), Me (5), Ph (6)], [Ni(PR3)(‘S3’)] [R = Cy (7), Ph (8)], (NBu4)[Ni(Cl)(‘S3’)] (9), and (NBu4)[Ni(N3)(‘S3’)] (10). When treated with Me3SiX, the StBu- ligand in (NBu4)[Ni(StBu)(‘S3’)] (3) was exchanged to give (NBu4)[Ni(X)(‘S3’)] [X = Cl- (9), N3- (10), NCS- (11), NSO- (12)]. The palladium complex [Pd(‘S3’)]3 (2) could also be cleaved with StBu-, but the resulting (NBu4)[Pd(StBu)(‘S3’)] (13) proved inert towards exchange reactions with Me3SiX. All the mononuclear complexes have been characterized by standard spectroscopic techniques and by elemental analysis. The molecular structures of 3, 4, 6, 7, 8, 9, and 13 have been determined by X-ray crystallography. The [MS3L] core geometries of all the complexes are non-planar, exhibiting a considerable tetrahedral distortion.
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