Jones Cameron, Rose Richard P, Stasch Andreas
School of Chemistry, PO Box 23, Monash University, VIC 3800, Australia.
Dalton Trans. 2008 Jun 7(21):2871-8. doi: 10.1039/b801168k. Epub 2008 Apr 17.
Reactions of lithium salts of the bulky guanidinate ligands, ArNC(NR2)NAr (NR2 = N(C6H11)2 (Giso-) and cis-NC5H8Me2-2,6 (Pipiso-); Ar = C6H3Pri2-2,6), with GeCl2.dioxane afforded the heteroleptic germylenes, [(Giso)GeCl] and [(Pipiso)GeCl], the former of which was structurally characterised. The further reactivity of these and the related complexes, [(Piso)GeCl] and [(Priso)GeCl] (Piso- = [ArNC(Bu(t))NAr]-, Priso- = [ArNC(NPri2)NAr]-) has been investigated. Salt elimination reactions have yielded the new monomeric complexes, [(Piso)Ge(NPri2)] and [(Piso)GeFeCp(CO)2], whilst a ligand displacement reaction afforded the heterometallic species, [(Piso)Ge(Cl)(W(CO)5)]. Chloride abstraction from [(Priso)GeCl] with GaCl3 has given the structurally characterised contact ion pair, [(Priso)Ge][GaCl4]. In addition, the inconclusive outcome of a number of attempts to reduce the germanium halide complexes are discussed.
位阻胍基配体[ArNC(NR₂)NAr]⁻（NR₂ = N(C₆H₁₁)₂ （Giso⁻）和顺式-NC₅H₈Me₂-2,6 （Pipiso⁻）；Ar = C₆H₃Pri₂-2,6）的锂盐与二氧六环合二氯化锗反应，得到了杂配型亚锗烯[(Giso)GeCl]和[(Pipiso)GeCl]，其中前者通过结构表征得以确定。对这些以及相关配合物[(Piso)GeCl]和[(Priso)GeCl]（Piso⁻ = [ArNC(Bu(t))NAr]⁻，Priso⁻ = [ArNC(NPri₂)NAr]⁻）的进一步反应活性进行了研究。消除盐反应生成了新的单体配合物[(Piso)Ge(NPri₂)]和[(Piso)GeFeCp(CO)₂]，而配体置换反应得到了异金属物种[(Piso)Ge(Cl)(W(CO)₅)]。用GaCl₃从[(Priso)GeCl]中提取氯离子，得到了经结构表征的接触离子对[(Priso)Ge][GaCl₄]。此外，还讨论了多次尝试还原卤化锗配合物但结果不确定的情况。
