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Group 6 carbene complexes derived from lithiated azoles and the crystal structure of a molybdenum thiazolinylidene complex |
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| Authors: | Helgard G Raubenheimer Yolanda Stander Eugene K Marais Catharine Thompson Gert J Kruger Stephanie Cronje Maggel Deetlefs |
| Institution: | a Department of Chemistry, University of Stellenbosch, P/Bag X1, Matieland, 7602, South Africa b Department of Chemistry and Biochemistry, Rand Afrikaans University, PO Box 524, Aucklandpark, 2006, South Africa |
| Abstract: | 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 CF3SO3CH3. 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 CH3O(CH2)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. |
| Keywords: | Carbene complexes Group 6 metals Azolinylidene complexes Transmetallation |
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