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A new synthesis and the molecular structure of trimethyl(silylmethylene)phosphorane in the gas phase, determined by electron diffraction
Author(s) -
Ebsworth E. A. V.,
Rankin David W. H.,
ZimmerGasser Beate,
Schmidbaur Hubert
Publication year - 1980
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19801130502
Subject(s) - chemistry , phosphorane , crystallography , methylene , molecule , bond length , electron diffraction , molecular geometry , double bond , stereochemistry , gas phase , single bond , diffraction , crystal structure , medicinal chemistry , alkyl , organic chemistry , physics , optics
Trimethyl(silylmethylene)phosphorane ( 1 ) has been prepared in a reaction of H 3 SiCH 2 CH 2 Cl and (CH 3 ) 3 PCH 2 in a molar ratio 1:2. C 2 H 4 is evolved in a β‐elimination process, followed by formation of [(CH 3 ) 4 P] + Cl − in a transylidation step. — The molecular structure of (CH 3 ) 3 PCHSiH 3 in the gas phase has been determined by electron diffraction. Principal bond lengths ( r a ) are: PC = 180.7(8), P = C = 165.3(11), SiC = 185.2(20) pm. The angles between the PC(methyl) bonds are 103.4(13)° and the SiCP angle is 123.4(8)°, consistent with a planar configuration of the methylene carbon atom. The molecule adopts a conformation in which the SiC bond is twisted 25° from a position in which it eclipses one PC bond, but there is a large amplitude torsional vibration about the PC bond.