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A Germylene Supported by Two 2‐Pyrrolylphosphane Groups as Precursor to PGeP Pincer Square‐Planar Group 10 Metal(II) and T‐Shaped Gold(I) Complexes
Author(s) -
Cabeza Javier A.,
Fernández Israel,
FernándezColinas José M.,
GarcíaÁlvarez Pablo,
LagleraGándara Carlos J.
Publication year - 2019
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201902784
Subject(s) - pincer movement , square (algebra) , planar , group (periodic table) , metal , crystallography , chemistry , combinatorics , materials science , mathematics , geometry , metallurgy , organic chemistry , computer science , catalysis , computer graphics (images)
An efficient synthesis of 2‐di‐ tert ‐butylphosphanylmethylpyrrole (HpyrmP t Bu 2 ), by treating 2‐dimethylaminomethylpyrrole (HpyrmNMe 2 ) with t Bu 2 PH at 135 °C in the absence of any solvent, has allowed the preparation of the new PGeP germylene Ge(pyrmP t Bu 2 ) 2 ( 1 ), by treating [GeCl 2 (dioxane)] with LipyrmP t Bu 2 , in which the Ge atom is stabilized by intramolecular interactions with one (solid state) or both (solution) of its phosphane groups. Reactions of germylene 1 with Group 10 metal dichlorido complexes containing easily displaceable ligands have led to [MCl{κ 3 P , Ge , P ‐GeCl(pyrmP t Bu 2 ) 2 }] [M=Ni ( 2 ), Pd ( 3 ), Pt ( 4 )], which have an unflawed square‐planar metal environment. Treatment of germylene 1 with [AuCl(tht)] (tht=tetrahydrothiophene) rendered [Au{κ 3 P , Ge , P ‐GeCl(pyrmP t Bu 2 ) 2 }] ( 5 ), which is a rare case of a T‐shaped gold(I) complex. The hydrolysis of 5 gave the linear gold(I) derivative [Au(κ P ‐HpyrmP t Bu 2 ) 2 ]Cl ( 6 ). Complexes 2 – 5 contain a PGeP pincer chloridogermyl ligand that arises from the insertion of the Ge atom of germylene 1 into a M−Cl bond of the corresponding metal reagent. The bonding in these molecules has been studied by DFT/NBO/QTAIM calculations. These results demonstrate that the great flexibility of germylene 1 makes it a better precursor to PGeP pincer complexes than the previously known germylenes of this type.