Issue 35, 2019

A dipyrromethane-based diphosphane–germylene as precursor to tetrahedral copper(i) and T-shaped silver(i) and gold(i) PGeP pincer complexes

Abstract

A six-membered ring N-heterocyclic germylene flanked by two CH2PiPr2 groups, Ge(pyrmPiPr2)2CMe2 (1; (HpyrmPiPr2)2CMe2 = 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(PPh3)]n (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{κ3P,Ge,P-GeCl(pyrmPiPr2)2CMe2}(PPh3)] (2) and [M{κ3P,Ge,P-GeCl(pyrmPiPr2)2CMe2}] (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.

Graphical abstract: A dipyrromethane-based diphosphane–germylene as precursor to tetrahedral copper(i) and T-shaped silver(i) and gold(i) PGeP pincer complexes

Supplementary files

Article information

Article type
Paper
Submitted
25 Jul 2019
Accepted
29 Jul 2019
First published
30 Jul 2019

Dalton Trans., 2019,48, 13273-13280

A dipyrromethane-based diphosphane–germylene as precursor to tetrahedral copper(I) and T-shaped silver(I) and gold(I) PGeP pincer complexes

J. A. Cabeza, I. Fernández, P. García-Álvarez and C. J. Laglera-Gándara, Dalton Trans., 2019, 48, 13273 DOI: 10.1039/C9DT03045J

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