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Early transition‐metal complexes of α‐keto‐stabilized phosphorus ylides
Author(s) -
Spannenberg Anke,
Baumann Wolfgang,
Rosenthal Uwe
Publication year - 2000
Publication title -
applied organometallic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.53
H-Index - 71
eISSN - 1099-0739
pISSN - 0268-2605
DOI - 10.1002/1099-0739(200010)14:10<611::aid-aoc46>3.0.co;2-0
Subject(s) - chemistry , ylide , phosphonium , transition metal , bromide , medicinal chemistry , inorganic chemistry , trimethylsilyl , triphenylphosphine , crystal structure , metal , magnesium bromide , polymer chemistry , crystallography , organic chemistry , catalysis , magnesium
The complexation behaviour of the α‐keto‐stabilized phosphorus ylides Ph 3 PCHC(O)R (R = Ph, Me) towards the early transition metal ions titanium(IV), zirconium(IV) and niobium(III) was investigated. The complex [Ph 3 PCHC(Ph)O]TiBr 2 (NMe 2 ) 2 was obtained from the reaction of the phosphonium bromide [Ph 3 PCH 2 C(O)Ph]Br with Ti(NMe 2 ) 4 . The crystal structure of this complex is discussed. It is frequently observed that the complex formed from the ylide with the early transition metal is very unstable (not isolable) and stabilizes by migration of one NMe 2 group from the starting metal complex to the ylide. Thus the reaction of Ph 3 PCHC(O)Me with Ti(NMe 2 ) 4 provides an access to the novel ylide Ph 3 PCHC(NMe 2 )CH 2 . Niobium complexes of the α‐keto‐stabilized phosphorus ylides Ph 3 PCHC(O)R (R = Ph, Me) were obtained by reacting these ylides with NbCl 3 (TMSC≡CPh)·DME (TMS, trimethylsilyl; DME, dimethoxyethane) in CH 2 Cl 2 . A binuclear structure could be confirmed by X‐ray crystal structure analysis. Copyright © 2000 John Wiley & Sons, Ltd.