Group 6 carbene complexes derived from lithiated azoles and the crystal structure of a molybdenum thiazolinylidene complex

Fischer-type (alkoxy)azolyl carbene complexes and Öfele–Lappert-type azolylinylidene complexes were synthesised by reaction of 1-phenylpyrazol-3-yllithium, 4-methylthiazol-2-yllithium, benzothiazol-2-yllithium, 1-methylimidazol-2-yllithium with M(CO) 5L (L=CO, THF or Cl −; M=Cr, Mo or W) and subsequ...

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Bibliographic Details
Published in:Journal of organometallic chemistry 1999-11, Vol.590 (2), p.158-168
Main Authors: Raubenheimer, Helgard G., Stander, Yolanda, Marais, Eugene K., Thompson, Catharine, Kruger, Gert J., Cronje, Stephanie, Deetlefs, Maggel
Format: Article
Language:English
Subjects:
Azolinylidene complexes
Carbene complexes
Group 6 metals
Transmetallation
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Summary:Fischer-type (alkoxy)azolyl carbene complexes and Öfele–Lappert-type azolylinylidene complexes were synthesised by reaction of 1-phenylpyrazol-3-yllithium, 4-methylthiazol-2-yllithium, benzothiazol-2-yllithium, 1-methylimidazol-2-yllithium with M(CO) 5L (L=CO, THF or Cl −; M=Cr, Mo or W) and subsequent alkylation with CF 3SO 3CH 3. The alkylation of Fischer-type carbene complexes containing an azolyl as the organic substituent proceeded via ring opening of tetrahydrofuran. When the alkylation is carried out in THF, the carbocation CH 3O(CH 2) 4 + acts as an electrophile. Protonation rather than alkylation of coordinated imidazolyl furnished cyclic imine complexes. Changing the donor atom of a coordinated thiazole from N to C by deprotonation and alkylation afforded a carbene complex.
ISSN:0022-328X
1872-8561
DOI:10.1016/S0022-328X(99)00445-3