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Synthesis, Structure, and Reactivity of a Pyridine‐Stabilized Germanone
Author(s) -
Yao Shenglai,
Xiong Yun,
Wang Wenyuan,
Driess Matthias
Publication year - 2011
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.201003409
Subject(s) - pyridine , adduct , chemistry , reactivity (psychology) , aryl , yield (engineering) , ligand (biochemistry) , crystallography , germanium , crystal structure , medicinal chemistry , stereochemistry , alkyl , organic chemistry , materials science , medicine , alternative medicine , pathology , biochemistry , receptor , silicon , metallurgy
The first isolable pyridine‐stabilized germanone has been prepared and its reactivity toward trimethylaluminum has been investigated. The germanone adduct results from a stepwise conversion that starts from 4‐dimethylaminopyridine (DMAP) and the ylide‐like N‐heterocyclic germylene LGe: (L=CH{(CCH 2 )(CMe)[N(aryl)] 2 }, aryl=2,6‐ i Pr 2 C 6 H 3 ) ( 1 ) at room temperature, and gives the corresponding germylene–pyridine adduct L(DMAP)Ge: ( 2 ) in 91 % yield. The latter reacts with N 2 O at room temperature to form the desired germanone complex L(DMAP)GeO ( 3 ) in 73 % yield. The GeO distance of 1.646(2) Å in 3 is the shortest hitherto reported for a GeO species. The reaction of 3 with trimethylaluminum leads solely to the addition product LGe(Me)O[Al(DMAP)Me 2 ] ( 4 ). The latter results from insertion of the GeO subunit into an AlMe bond of AlMe 3 and concomitant migration of the DMAP ligand from germanium to the aluminum atom. Compounds 2 – 4 have been fully characterized by analytical and spectroscopic methods. Their molecular structures have been established by single‐crystal X‐ray crystallographic analysis.