Reversal of polarization in amidophosphines: neutral- and anionic-kappaP coordination vs. anionic-kappaP,N coordination and the formation of nickelaazaphosphiranes.

Nickel(ii) chloride reacts with the bis(tert-butylamino)diazadiphosphetidine {Bu(t)(H)NP(micro-NBu(t))(2)PN(H)Bu(t)} to form trans-[{Bu(t)(H)NP(micro-NBu(t))(2)PN(H)Bu(t)}(2)NiCl(2)]. In solution and the solid-state each heterocyclic ligand coordinates nickel through one phosphorus atom only. For comparison the solid-state structure of the known trans-[NiCl(2)(PEt(3))(2)] was also determined and it was found that the two complexes have almost identical bond parameters about nickel.

Synthesis and characterization of an air-stable gallium hydride, [t-Bu(H)Ga(mu-NEt(2))](2), and related chloride derivatives.

The synthesis of [t-Bu(H)Ga(mu-NEt(2))](2) (1) was accomplished by the addition of 4 t-BuLi to [Cl(2)Ga(mu-NEt(2))](2). Evidence suggests that two tert-butyl groups are lost as isobutylene and result in Ga-H bond formation. The gallium hydride 1 is remarkably stable toward ambient air, oxygen, photolysis, and moderate heating; however, in CHCl(3) the hydride is replaced by chloride, producing [t-Bu(Cl)Ga(mu-NEt(2))](2) (2).

Monomeric, Four-Coordinate Group 4 Metal Complexes with Chelating Bis(tert-butylamido)cyclodisilazane Ligands: Syntheses and Molecular Structures of {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MCl(2) and {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MMe(2), M = Zr, Hf.

The interaction of (MeSiN(t)Bu)(2)(N(t)BuLi)(2) with MCl(4) in hot toluene produces {(MeSiN(t)Bu)(2)(N(t)Bu)(2)}MCl(2,) M = Zr (1), Hf (2), in good yields. The light-yellow and colorless solids are isostructural and crystallize in the monoclinic crystal system, space group P2(1)/n, with four molecules in the unit cell. The unit cell dimensions for 1 (293 K) are a = 9.