Bimetallic complexes from amphoteric group 13/15 ligands: syntheses and X-ray crystal structures.

Bimetallic, pentel-bridged complexes of the type [(dmap)Me2M-E(SiMe3)2-M'(CO)n] (M=Al, Ga; E=P, As, Sb; M'=Cr, Fe, Ni; DMAP=4-(dimethylamino)pyridine) are formed by reactions of DMAP-coordinated monomeric Group 13/15 compounds [(dmap)Me2M-E(SiMe3)2] with the transition metal complexes [(Me3N)Cr(CO)5], [Fe3(CO)12], and [Ni(CO)4]. For the first time, this reaction offers a general pathway to compounds containing a Group 13 metal and a transition metal bridged by a pentel atom. Complexes prepared in this way were characterized by IR and multinuclear NMR spectroscopy and by single-crystal X-ray structure analysis.

1,3-Diphospholene-4-ylidene chromium (tungsten) pentacarbonyl complexes formed by CO insertion into the ring of a 1,3-diphosphacyclobutane-2,4-diyl-2-ide-complexes of a phosphanyl carbene or a phosphonium ylide?

Reaction of the 1,3-diphosphacyclobutane-2,4-diyl-2-ide 1 with chromium or tungsten hexacarbonyl afforded the anionic complexes [cyclo-[P(Mes*)-C(SiMe(3))-P(Mes*)-C(O)-C[M(CO)(5)]]](-) (3 a,b: M=Cr, W) by the formal insertion of CO into the four membered ring. Computational analysis suggests that this reaction proceeds via two intermediates that can be formulated as a cyclic metal acyl and an acyclic ketenyl complex. The anionic complexes 3 a,b further reacted with electrophiles to afford the neutral complexes [cyclo-(P(Mes*)-C(SiMe(3))-P(Mes*)-C(OR)-C[M(CO)(5)])] (4 a,b: M=Cr, W, R=Me; 5, 6: M=Cr, R=SiMe(3), H).

Reactions of Et Bi with tBu M (M=Al, Ga)-Synthesis of Complexes with a Bidentate Dibismuthane Ligand.

Functioning as a bidentate ligand toward Lewis acids, dibismuthane forms bisadducts of the type [R M] [Bi R$\rm{^{\prime }_{4}}$] with R M=tBu Al (1) and tBu Ga (2; structure depicted; R'=Et), which were characterized by single-crystal X-ray diffraction.

[Me AlBi(SiMe ) ] -The First Structurally Characterized Organometallic Compound Containing a Bond between an Element of Group 13 and Bi.

Dehydrosilylation of Bi(SiMe ) with Me AlH gave the title compound. This has a trimeric structure, the central unit of which is a six-membered Al Bi ring (see structure). In agreement with the VSEPR model the angles are greater at the Al centers and smaller at the Bi centers.

Synthesis and Crystal Structure of a P-Hydridophosphoraniminato-Zirconium Complex and Reaction to the First Tris(hydrido)cyclotriphosphazene.

The first oligomeric phosphazene in which each phosphorus center features a PH functionality (3) was obtained from the amidophosphane 1 or its zirconium complex 2.

Valence Isomerization in the Solid State: From 1,3-Diphosphacyclobutane-2,4-diyl to 1,2-Dihydro-1,2-diphosphete.

The butadiene-like phosphanylcarbene 2 is, according to ab initio calculations, the intermediate in the conversion of 1 into 3 in the solid state [Eq. (a)]; it is only 1.3 kJ mol higher in energy than 1.

Reactions of Bis(triphenylphosphonio)isophosphindolide Salts with Mercury(II) Compounds: Coordination Induced Addition and Oxidation Reactions and Synthesis of a Monomeric 1:1 Complex of the Type [R(2)(R'O)P]HgBr(2).

Bis(triphenylphosphonio)isophosphindolide triflate (1[CF(3)SO(3)]) reacted with HgCl(2) and H(2)O or MeOH to give a phosphinito complex which was converted with excess HgCl(2) into the dimercury complex 5. In contrast, methanolysis of 1[X] (X = CF(3)SO(3), Br) in the presence of Hg(OAc)(2) afforded the phosphonium cation 9. A mercury complex 8 was isolated for X = Br as a reaction intermediate.

X-ray Crystal Structure, ab Initio Calculations, and Reactivity of 1,3,2lambda(5)-Diazaphosphetes: A New Type of 4-pi-Electron 4-Membered Heterocycle.

The structure of P,P-bis(diisopropylamino)-4-phenyl-1,3,2lambda(5)-diazaphosphete, 1a, has been determined by a single-crystal X-ray diffraction study (C(19)H(33)N(4)P, monoclinic system, space group P2(1), a = 9.482(1) Å, b = 11.374(3) Å, c = 9.