Nickel complexes / Palladium complexes / S ligands / Exchange reactions / Azide / Sulfinylimide In order to obtain suitable precursors for nickel and [Ni(PR 3 )('S 3 ')] [R = Cy (7), Ph (8)], (NBu 4 )[Ni(Cl)('S 3 ')] (9), and (NBu 4 )[Ni(N 3 )('S 3 ')] (10). When treated with Me 3 SiX, the palladium complexes that model the reactivity of the active sites of hydrogenases and CO dehydrogenases, a series of StBu -ligand in (NBu 4 )[Ni(StBu)('S 3 ')] (3) was exchanged to give (NBu 4 )[Ni(X)('S 3 ')] [X = Cl -(9), N 3 -(10), NCS -(11), [M(L)('S 3 ')] complexes has been synthesized [M = Ni II , Pd II ; 'S 3 ' 2-= bis(2-mercaptophenyl)sulfide(2-)]. X-ray structure NSO -(12)]. The palladium complex [Pd('S 3 ')] 3 (2) could also be cleaved with StBu -, but the resulting determinations of [Ni('S 3 ')] 3 (1) and [Pd('S 3 ')] 3 (2) have revealed that the [M('S 3 ')] fragments trimerize to give six-(NBu 4 )[Pd(StBu)('S 3 ')] (13) proved inert towards exchange reactions with Me 3 SiX. All the mononuclear complexes have membered [MS] 3 rings, which exhibit chair conformations with alternating M II centers and thiolate bridging atoms. been characterized by standard spectroscopic techniques and by elemental analysis. The molecular structures of 3, 4, Reactions of the parent complex [Ni('S 3 ')] 3 (1) with nucleophiles L, such as thiolates SR -(R = tBu, Cy, Me, Ph), 6, 7, 8, 9, and 13 have been determined by X-ray crystallography. The [MS 3 L] core geometries of all the phosphanes PR 3 (R = Cy, Ph), chloride, or azide, have been found to yield the corresponding anionic or neutral complexes are non-planar, exhibiting a considerable tetrahedral distortion. [Ni(L)('S 3 ')] complexes, which were isolated as (NBu 4 )[Ni(SR)('S 3 ')] [R = tBu (3), Cy (4), Me (5), Ph (6)], [ ] Part 138: D. Sellmann, D. Häußinger, F. W. Heinemann, Eur.
derivatives are much more soluble than the parent com-J. Inorg. Chem.