ISSN:
0947-6539
Keywords:
carbon-carbon coupling
;
carbonyl complexes
;
hafnium complexes
;
ketenylidene complexes
;
zirconium complexes
;
Chemistry
;
General Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
The biscyclopentadienyldicarbonyl derivatives of zirconium(II) and hafnium(II) ([MCp2(CO)2]; M=Zr, Hf) promote the reductive coupling of coordinated carbon monoxide to give, in the presence of N,N-dialkylcarbamtes of the tetravalent metals [M(O2CNR2)4], the ketenylidene complexes [M3Cp2(μ2-CCO)-(μ3-O)(O2CNR2)6] (1 a: M=Zr, R=Et; 1 b: M=Zr, R=iPr; 2: M=Hf, R=iPr). The yields of the isolated zirconium complexes are as high as 60%, while that of the hafnium derivative is 40%. The X-ray crystal structure analysis of 1 b shows that it consists of trinuclear molecules, with the three zirconium atoms held together by the bidentate C2O ligand, by the tridentate bridging oxide and by the bidentate carbamato groups. Labelling experiments with [ZrCp2(13CO)2] show that the ketenylidene ligand originates from the coordinated CO groups. These ketenylidene complexes, which are rare examples of compounds containing a CCO but no CO ligand, are characterized by an intense IR band at about 2015 cm-1, associated with the bridging C2O ligand. The ketenylidene group of 1 b was readily removed and replaced by a bidentate μ-oxo ligand of the same hapticity by reaction with carbon dioxide or acetone or by thermal decomposition. The resulting product [Zr3Cp2(μ-O)(μ3-O)-(O2CNiPr2)6] (3) crystallizes in the same space group as 1 b and with similar cell constants and bond parameters.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/chem.19960020410
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