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Synthesis and Characterization of 5‐Coordinate Tungsten Hydride Anions: [( t Bu 3 SiNH)( t Bu 3 SiN=) 2 HWR]M
Author(s) -
Schafer Daniel F.,
Wolczanski Peter T.,
Lobkovsky Emil B.,
MacMillan Samantha N.
Publication year - 2017
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.201700042
Subject(s) - chemistry , hydride , tungsten , medicinal chemistry , alkyl , stereochemistry , acetylide , crystallography , organic chemistry , hydrogen
Treatment of ( t Bu 3 SiNH)( t Bu 3 SiN=) 2 WH ( 1 ‐H) with small alkyl anions (RM) afforded tungsten alkyl hydride anions [( t Bu 3 SiNH)( t Bu 3 SiN=) 2 HWR)]M ( 3 ‐(R)M: R=CH 3 , M=Li; R= n Bu, M=Li; R= neo Pe, M=Li; R=CH 2 Ph (Bn), M=K (two isomers); R=CCH, M=Na; R=CH=CH 2 (Vy), M=Li). The saturated alkyl anions 3 ‐(R)M ( 3 ‐(R)M: R=CH 3 , M=Li; R= n Bu, M=Li; R= neo Pe, M=Li; R=CH 2 Ph (Bn), M=K) degraded via apparent 1,2‐RH‐elimination to produce the known [( t Bu 3 SiN=) 3 WH]M ( 2 ‐HM), but the acetylide ( 3 ‐(C 2 H)Na) and vinyl ( 3 ‐(Vy)Li) anions converted to their hydrogenated isomers, [( t Bu 3 SiN=) 3 WVy]Na ( 2 ‐VyNa) and [( t Bu 3 SiN=) 3 WEt]Li ( 2 ‐EtLi), respectively. The structure of 3 ‐( n Bu)Li is reported, and a discussion of tungsten‐hydride coupling constants in t Bu 3 SiX‐ligated (X=O, NH, N) systems is given.