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Two extremely bulky bis(aryl)amines, HN(Ar*)(Ph) (HLPh) and HN(Ar*)(Mes) (HLMes) (Ar* = C6H2{C(H)Ph2}2Me-2,6,4; Mes = mesityl), have been prepared by palladium-catalyzed cross-coupling reactions and structurally characterized. These have been utilized in the preparation of the amido-germanium(II) chlorides, [LPhGeCl] and [LMesGeCl]. Reactions of these, and the known complex, [L′GeCl] (L′ = −N(Ar*)(SiMe3)), with Na[CpMo(CO)3] have afforded the first examples of structurally characterized two-coordinate molybdenum substituted germylenes, [Cp(CO)3MoGeN(Ar*)(R)] (R = SiMe3 or Ph). The former readily eliminates a molecule of CO when heated or irradiated with UV light to give an unprecedented amino-germylyne complex, [Cp(CO)2Mo≡GeN(Ar*)(SiMe3)]. The spectroscopic and structural data for this complex, in combination with the results of computational studies, show that this compound is best viewed as having a bent Mo–Ge “triple” bond, with little multiple bond character to its Ge–N interaction. Computational stud...

The β-diketiminato germanium(II) chloride complex [(ButMesNacnac)GeCl] (ButMesNacnac = [{N(Mes)C(But)}2CH]−, Mes = mesityl) has been prepared and spectroscopically characterized. Treating this compound and a less bulky system, [(MeMesNacnac)GeCl] (MeMesNacnac = [{N(Mes)C(Me)}2CH]−), with K[HBEt3] led to differing outcomes, namely, the formation of the novel diamido germylene [(ButMesNacnacH)Ge:] (ButMesNacnacH = [N(Mes)C(H)(But)C(H)C(But)N(Mes)]2-) and the germanium(II) hydride [(MeMesNacnac)GeH], both of which were crystallographically characterized. The former product forms via a 1,3-hydrogen migration reaction involving [(ButMesNacnac)GeH] as an unstable reaction intermediate. Reactions of [(MeMesNacnac)GeH] with CO2 and P≡CBut proceed at or below ambient temperature, in the absence of a catalyst, to give the crystallographically characterized hydrogermylation products [(MeMesNacnac)GeOC(═O)H] and [(MeMesNacnac)GeC(But)═PH], with complete regioselectivity. When a solution of the latter was gently heate...

Decamethylgermanocene GeCp* 2 (1) (Cp* = Me 5 C 5 ) was synthesized starting from a solution of GeBr and was obtained as colorless crystals. The molecular structure of I was determined by X-ray diffraction, showing that 1 is monomeric in the solid state, featuring two pentahapto-bonded Cp* ligands in a bent configuration with a bending angle of 162°.