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The Bis(pentafluoroethyl)germylene Trimethylphosphane Adduct (C 2 F 5 ) 2 Ge⋅PMe 3 : Characterization, Ligand Properties, and Reactivity
Author(s) -
Pelzer Stefanie,
Neumann Beate,
Stammler HansGeorg,
Ignat'ev Nikolai,
Hoge Berthold
Publication year - 2016
Publication title -
angewandte chemie international edition
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 1433-7851
DOI - 10.1002/anie.201601468
Subject(s) - chemistry , adduct , phosphonium , reactivity (psychology) , ligand (biochemistry) , dichloromethane , reductive elimination , ylide , x ray crystallography , bond length , crystallography , cycloaddition , medicinal chemistry , stereochemistry , diffraction , crystal structure , organic chemistry , catalysis , receptor , pathology , solvent , optics , medicine , biochemistry , physics , alternative medicine
The synthesis of the germylene phosphane adduct (C 2 F 5 ) 2 Ge⋅PMe 3 is described. Starting from (C 2 F 5 ) 3 GeH in an excess of PMe 3 , heating was applied, whereupon reductive elimination of C 2 F 5 H occurred. The molecular structure was ascertained by X‐ray diffraction and compared with information obtained by quantum chemical methods. The ligand properties were derived by studying the IR spectrum of the nickel(0) complex [Ni(CO) 3 {Ge(C 2 F 5 ) 2 (PMe 3 )}] in the CO region. (C 2 F 5 ) 2 Ge⋅PMe 3 turned out to be a π‐accepting ligand comparable to PMe 3 , in terms of Tolman's electronic parameter. Furthermore a [2+4] cycloaddition reaction with 2,3‐dimethyl‐1,3‐butadiene, and σ‐bond insertion reactions were recorded. Activation of the C−Cl bond in dichloromethane gives rise to the formation of the phosphonium ylide complex [(C 2 F 5 ) 2 Cl 2 Ge‐CH 2 PMe 3 ], which was fully characterized by X‐ray diffraction.