Centro de Innovación en Química Avanzada (ORFEO-CINQA) and Departamento de Química Orgánica e Inorgánica, Universidad de Oviedo, 33071 Oviedo, Spain.
Centro de Innovación en Química Avanzada (ORFEO-CINQA) and Departamento de Química Orgánica I, Facultad de Ciencias Químicas, Universidad Complutense de Madrid, 28040 Madrid, Spain.
Dalton Trans. 2019 Sep 21;48(35):13273-13280. doi: 10.1039/c9dt03045j. Epub 2019 Aug 19.
A six-membered ring N-heterocyclic germylene flanked by two CHPPr groups, Ge(pyrmPPr)CMe (1; (HpyrmPPr)CMe = 5,5-dimethyl-1,9-bis(di-isopropylphosphanylmethyl)dipyrromethane), has been prepared in high yield. Upon treatment with group 11 metal precursors of the type [MCl(PPh)] (M = Cu (n = 4), Ag (n = 4), Au (n = 1)), germylene 1 easily forms a PGeP chloridogermyl ligand that is able to stabilize tetrahedral copper(i) and unusual T-shaped silver(i) and gold(i) PGeP pincer complexes, as has been demonstrated by the isolation of [Cu{κP,Ge,P-GeCl(pyrmPPr)CMe}(PPh)] (2) and [M{κP,Ge,P-GeCl(pyrmPPr)CMe}] (M = Ag (3), Au (4)). Theoretical calculations have shown that the Ge-M bonds of these complexes are weak and that their strength decreases in the series 2 > 3 > 4.
一个由两个 CHPPr 基团包围的六元环 N-杂环Germylene，Ge(pyrmPPr)CMe（1;（HpyrmPPr）CMe = 5,5-二甲基-1,9-双（二异丙基膦基甲基）二吡咯甲烷），以高产率制备。用类型[MCl（PPH）]的 11 族金属前体（M = Cu（n = 4），Ag（n = 4），Au（n = 1））处理后，Germylene 1 很容易形成能够稳定四面体铜（i）和不寻常的 T 形银（i）和金（i）PGeP 夹钳配合物的 PGeP 氯化Germyl 配体，这已经通过分离[Cu{κP，Ge，P-GeCl（pyrmPPr）CMe}（PPH）]（2）和[M{κP，Ge，P-GeCl（pyrmPPr）CMe}]（M = Ag（3），Au（4））得到证明。理论计算表明，这些配合物的 Ge-M 键较弱，其强度按 2 > 3 > 4 的顺序降低。
