Stuart T. Schwab

Mono-and di-nuclear phosphido and arsenido complexes of gallium; Ga(EBut2)3, Ga[PH(2,4,6-But3C6H2)]3 and [Ga(µ-EBut2)R2]2, (E = P, As; R = Me, Bun)

The reaction of GaCl3 with three equivalents of But2AsLi, But2AsLi, or ArP(H)Li (Ar = 2,4,6-But3C6H2) affords Ga(PBut2)3, Ga(AsBut2)3, and Ga[P(H)Ar]3, respectively, whilst the reaction of GaCl3 with one equivalent of But2ELi and two equivalents of RLi results in dimeric phosphido- or arsenido-bridged compounds of the type [Ga(µ-EBut2)R2]2(E = P, As; R = Me, Bun).

Synthesis of tert-butyl mercapto complexes of titanium(IV). X-ray crystal structure of Ti(diars)Cl2 (tBuS)2

Abstract The new class of tert-butyl mercapto compounds, Ti(L)Cl2(tBuS)2 (L = diars, dmpe, dppe), has been synthesized and characterized. The X-ray crystal structure of Ti(diars)Cl2(tBuS)2 (1) shows that the Ti(IV) atom has a distorted octahedral geometry with trans chlorides and cis tert-butyl mercapto units. The structures of the other complexes are similar based on spectroscopic (NMR, IR) evidence. Crystal data for (1): C18H34As2Cl2S2Ti, M = 583.24, trigonal space group P3121 (No. 152), a = b = 16.892(5) A, c = 8.492(2) A, U = 2098.4 A3, Z = 3, Dc = 1.389 gcm−3, μ = 29.841 cm−1, λ(MoKα) = 0.71069 A (graphite monochromator). Refinement of 948 observed (1371 unique measured; I > 3σ(I) reflections gave a final R = 0.0462 and Rw = 0.0597.

Synthesis and ligand substituion chemistry of dinuclear, phosphido-bridged complexes of manganese. X-ray crystal structures of Mn2(μ-H)(μ-Cy2P)(CO)7(PCy2H)(1) and Mn2(μ-H)(μ-Cy2P)(CO)6(PMe32

Abstract Reaction of Mn2 (CO)10 with two equivalents of dicyclohexylphosphine in toluene at 110° produces Mn2 (μ-H)(μ-Cy2P)(CO)7(PCy2H) (1) in 60% yield. Interaction of 1 with excess trimethylphosphine produces Mn2(μ-H)(μ-Cy2P)(CO)6 (PMe3)(2 (2) in 90% yield. The X-ray crystal structures of 1 and 2 have been determined. Both structures contain two Mn atoms bridged by a Cy2P group and a hydridge. In each case, the metal atoms exhibit distorted octahedral geometry, with the phosphines occupying positions trans to the P atom of the bridging dicyclohexylphosphine. A metal-metal distance of ca. 2.9 A separates the manganese atoms in both complexes.

Synthesis and x-ray structure of [Ni(μ-t-Bu2P)(CO)2]2(Ni-Ni), Spontaneous Loss Of Co To Give The Asymmetric Tricarbonyl Ni2(μ-t-Bu2P)2(CO)3

Abstract Reaction of t-Bu2PCl with Na2[Ni6(CO)12] (2:1) in THF at -78°C yields [Ni(μ-t-Bu2P)(CO)2]2 (1) in 65% yield. The structure of (1) as determined by X-ray crystallography consists of two Ni atoms (Ni-Ni = 2.509 (2) A) bridged by two di-tertbutylphosphido groups. Each Ni also bears two terminal CO ligands and has a roughly tetrahedral coordination geometry. The complex slowly loses CO (t1/2 · 24h in C6D6 ambient temperature) to give the thermodynamically stable tricarbonyl complex Ni2(μ-t-Bu2P)2(CO)3 in which one Ni now bears a single CO ligand and the other retains two. Crystal data (1): C20H36Ni2O4P4, M = 519.88, monoclinic, C2/M, a = 13.646 (2), b = 11.861 (2), c = 8.712 (3) A, β = 117.97 (2)°, U = 1245.3 (5) A3, Z = 2. Dc = 1.386 g cm−3. Methods: MULTAN, difference Fourier, full-matrix least-squares. Refinement on 913 reflections (I > 3°(I)) out of 1153 unique observed reflections (3° < 2° < 50°) gave R and Rw values of 0.030 and 0.033, respectively.