Synthesis and reactions of mono- and dinuclear Ni(I) thiolate complexes

The dinuclear and mononuclear nickel(I) thiolates, [Ni(PPh(3))(mu-SR)](2) (1a: R is 2,4,6-triisopropylphenyl (Tip), 1b: R is 1-adamantyl (Ad)), (DxpS)Ni(mu-SDxp)Ni(PPh(3)) (2) (Dxp is 2,6-dixylylphenyl), and Ni(SDmp)(PPh(3)) (3) (Dmp is 2,6-dimesitylphenyl), have been synthesized by the reaction of the nickel(I) amide Ni{N(SiMe(3))(2)}(PPh(3))(2) with the corresponding thiols. The two nickel centers of 1a and 1b are equivalent, and are linked by two thiolato sulfurs and a Ni-Ni bond, whereas the two inequivalent nickels of 2 are connected by a SDxp sulfur, a eta(2)/eta(3)-xylyl group of the other SDxp ligand, and a Ni-Ni bond. A slightly bulkier m-terphenyl thiolate, SDmp, prevents its nickel complex from forming a Ni-Ni bond, and the mononuclear nickel(I) center of 3 is bound to PPh(3) and SDmp through interactions with the sulfur and a eta(2)-mesityl. The coordinatively unsaturated nickel(I) complex 3 is reactive, and the reaction of 3 with TEMPO generated diamagnetic Ni(SDmp)(PPh(3))(O,N:eta(2)-TEMPO) (4). N-Heterocyclic carbenes, 1,3,4,5-tetramethylimidazolin-2-ylidene (IMe') and 1,3-bis-(2,4,6-trimethylphenyl)imidazolin-2-ylidene (IMes), also react with 3 to afford a dinuclear nickel(I) complex, [Ni(IMe')(mu-SDmp)](2) (5), and a mononuclear nickel(I) complex, Ni(SDmp)(IMes) (6), respectively. The reaction of 3 with 1 equiv of (t)BuNC afforded the dinuclear complex [Ni(CN(t)Bu)(mu-SDmp)](2) (7), whereas the analogous reaction with 1 equiv of CO resulted in a mixture of Ni(PPh(3))(2)(CO)(2) and Ni(CO)(SDmp)(2)(PPh(3)) (8).