Metalations of bis(diphenylthiophosphinoyl)methane, CH 2 (PPh 2 dS) 2 , with equimolar Bu n Li or Bu n 2 Mg in THF afforded [Li{(SdPPh 2 ) 2 CH}(THF)(Et 2 O)] (1) and [MgC(PPh 2 dS) 2 (THF)] 2(2), respectively. Compound 1 with a group 13 metal chloride MCl 3 (M = Al, Ga, In) gave the methanediide complex [MCl{C(PPh 2 dS) 2 }] 2 (M = Al (3), Ga (4), In ( 5)). Compounds 3-5 are believed to be formed by ligand transfer reaction followed by dehydrochlorination. X-ray structures of 1-5 have been determined. It was found that the magnesium complex 2 has a similar structure to the group 13 metal analogues 3-5.Supporting Information Available: Details on the X-ray crystal structures, including ORTEP diagrams and tables of crystal data and structure refinement, atomic coordinates, bond lengths and angles, and anisotropic displacement parameters for 1-5. This material is available free of charge via the Internet at http://pubs.acs.org.

The crystalline, hexane-soluble metal alkyls [Na(p-R)lm 1, [KR(pmedta)],, and [Rb(p-R)(pmdeta)12 2 [R = CH(SiMe&, pmdeta = (Me2NCH2CH2)2NMe] have been prepared from LiR with equimolar portions of NaOBut, KOBut + pmdeta, and Rb(OC6H2But2-2,6-Me-4) + pmdeta, respectively; 1 has chains of alternating cations and planar Ranions which are approximately orthogonal to the chains, (Na-C),, 2.555(10) A, (Na-C-H),, 76(3) and (Na-C-Na),, 152(1)", whereas 2 consists of discrete dimers, (Rb-C),, 3.412(9) A, Rb-C-Rb 75.3(2) and C-Rb-C 104.7(2)".

Bis(thiophosphinoyl)methane, CH 2 (PPh 2 dS) 2 , and its monolithium salt [Li{(SdPPh 2 ) 2 CH}-(THF)(Et 2 O)] (1) have been used to prepare a series of low-valent group 14 metal complexes. The reaction of lithium salt [Li{(SdPPh 2 ) 2 CH}(THF)(Et 2 O)] (1) with 1 equiv of MCl 2 (M=Ge, Sn) in diethyl ether afforded monomeric organometal(II) chlorides [MCl{CH(PPh 2 dS) 2 }] (M=Ge (2), Sn (3)). Treatment of CH 2 (PPh 2 dS) 2 with equimolar M{N(SiMe 3 ) 2 } 2 (M = Sn, Pb) afforded 1,3dimetallacyclobutanes [M{μ 2 -C(Ph 2 PdS) 2 }] 2 (M = Sn (4), Pb (5)), which are believed to be formed by the dimerization of the metallavinylidene intermediate. Compounds 2 and 5 further reacted with elemental chalcogens (S and Se) to give trans-dithiadigermetane [GeCl{CH(PPh 2 dS) 2 }(μ-S)] 2 (6) and lead(II) chalcogenates [PbE{C(PPh 2 dS) 2 }] (E = S (7), Se (8)), respectively. Compounds 2-8 have been determined by X-ray crystallography.

The reaction of [Ge{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (1) with LiBut or LiC⋮CPh in Et2O afforded substituted products [Ge(R){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}] [R = But (2) or C⋮CPh (3)], respectively. However, the one-pot reaction of 1 with PhC⋮CH and BunLi in Et2O afforded lithium germinate [{(PhC⋮C)3Ge}3GeLi(Et2O)3] (4). Compound 1 can also undergo ligand transfer reaction with LiAlH4 to give [AlH{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}2] (5). Treatment of 1 with excess NaBH4 in THF afforded germanium(II) hydride-borane adduct [Ge(BH3){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}H] (6). The reaction of 1 with MI (M = Cu and Au) gave the first examples of Ge(II)−M(I) adducts [Ge(CuI){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl]4 (7) and [Ge(AuI){N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}Cl] (8). Compounds 2−8 have been characterized by X-ray analysis.

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The lithium complex [HC(PPh2NSiMe3)2Li(THF)] (2) prepared by the reaction of BunLi with bis(iminophosphorano)methane reacts with GeCl2·dioxane in different stoichiometric ratios to afford [HC(PPh2NSiMe3)2GeCl] (3) and [(Me3SiNPPh2)2CGe→GeC(PPh2NSiMe3)2] (4), respectively. Bisgermavinylidene 4 can also be obtained by the reaction of 3 with [Ge{N(SiMe3)2}2] or 2. Further reaction of 4 with Me3NO afforded [(μ-NPh2P)(Me3SiNPh2P)CGe(OSiMe3)]2 (5), and direct reaction of elemental chalcogens (sulfur, selenium, and tellurium) with 4 afforded [(Me3SiNPPh2)2CGe(μ-E)]2 [E = S (6), Se (7), and Te (8)]. X-ray structures of compounds 2−8 have been determined.

The bisgermavinylidene [(Me3SiNPPh2)2CGe→GeC(PPh2NSiMe3)2] (1) has been used as the source of unstable germavinylidene for the synthesis of a series of metal−germavinylidene complexes. Treatment of 1 with M(PPh3)4 (M = Ni, Pd) afforded the metal−germavinylidene complexes [{(Me3SiNPPh2)2CGe}2Ni(PPh3)2] (2) and [{(Me3SiNPPh2)2CGe-μ2}Pd(PPh3)]2 (3), respectively. The germavinylidene moiety from 1 acts as a two-electron terminal and bridging ligand, respectively. Similar reaction of 1 with AgCl or AuI gave [(Me3SiNPPh2)2CGe(Ag)(Cl)]2 (5) and [(Me3SiNPPh2)2CGe(Au)(I)]2 (6), respectively. The result has shown that the germavinylidene moiety from 1 behaves as a Lewis base and undergoes an insertion reaction into the metal−halogen bond. X-ray structures of 2, 3, 5, and 6 have been determined.

The novel lithium complexes [Li{N(SiMe3)C(R2)C(R1)(C5H4N-2)}]2 (R1 = H, R2 = But (1b); R1 = SiMe3, R2 = Ph (1c)) were prepared from the insertion of R2CN into [Li{C(SiMe3)(R1)(C5H4N-2)}]2. Similarly, Li{N(SiMe3)C(Ph)C(R)(C9H6N-2)} (R = H or SiMe3) was prepared from PhCN and Li{C(SiMe3)(R)(C9H6N-2)}. X-ray data are provided for 1b, 1c, and [Li{N(SiMe3)C(Ph)C(SiMe3)(C5H4N-2)}(Et2O)(PhCN)] (1c‘). Compounds 1b and 1c are dimers in the solid state, whereas 1c‘ is monomeric.