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β‐Diiminato Complexes of V III and Ti III – Formation and Structure of Stable Paramagnetic Dialkylmetal Compounds
Author(s) -
M. Budzelaar Peter H.,
van Oort A. Bart,
Orpen A. Guy
Publication year - 1998
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199810)1998:10<1485::aid-ejic1485>3.0.co;2-f
Subject(s) - chemistry , vanadium , aryl , crystal structure , catalysis , metal , olefin fiber , reagent , medicinal chemistry , stereochemistry , crystallography , inorganic chemistry , organic chemistry , alkyl
(Mono‐β‐diiminato)titanium(III) and ‐vanadium(III) dichlorides LMCl 2 [L = ArNC(R)CHC(R)NAr – ] are easily accessible from the metal trichlorides and LLi in THF. The crystal structures of LVCl 2 (Ar = 2,6‐ i Pr 2 C 6 H 3 , R = Me) and LTiCl 2 (Ar = 2,4,6‐Me 3 C 6 H 2 , R = Me and Ar = 2,4,6‐Me 3 C 6 H 2 , R = t Bu) reveal tetrahedral metal environments. Treatment of LVCl 2 with alkyllithium reagents affords surprisingly stable dialkylvanadium(III) compounds; the structure of LV( n Bu) 2 (Ar = 2,6‐ i Pr 2 C 6 H 3 , R = Me) is similar to that of the dichloride. The corresponding dialkyltitanium(III) compounds are less stable; only the dimethyl derivatives could be obtained in pure form (from LTiCl 2 and MeMgI), and only for ligands bearing 2,6‐disubstituted aryl groups. The structure of LTiMe 2 (Ar = 2,4,6‐Me 3 C 6 H 2 , R = Me) is also similar to that of the dichloride. Reaction of LTiMe 2 with B(C 6 F 5 ) 3 produces a catalyst for α‐olefin polymerization, but the corresponding V III derivatives are inactive.