ISSN:
0009-2940
Keywords:
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Transition Metal Ketene Compounds, VI1) Transition Metal-Substituted Ketenes of Molybdenum and Tungsten - Preparation, Reactivity, and Spectroscopic InvestigationsMetal-substituted ketenes of molybdenum and tungsten (η5-C5H5)(CO)[P(CH3)3]2MC(CO)R 2d, 4a, b, e (R = CH3. 1-cyclopenten-1-yl, C6H4CH3-(4), Si(C6H5)3) are formed on treatment of dicarbonyl(η5-cyclopentadienyl)carbyne complexes 1d, 3a, b, e with trimethylphosphine. The cleavage of one phosphine ligand leads in a reversible reaction to η2-ketenyl] compounds (η5-C5H5)(CO)[P(CH3)3]M[O=C=C - R] 5d, 6a, b, e. They add carbon monoxide to give dicarbon] substituted η1ketenes(η5C5H5)(CO)2[P(CH3)3] MC(CO)R (7d. 8a-g. R = CH3. 1-cyclo-penten-1-yl, C6H5, C6H4CH3-(4), Si(C6H5)3 C5H4FeC5H5. C6H2(CH3)3-(2.4.6)). 7d and 8d are also available by direct carbonylation of (η5-C5H5)(CO)[P(CH3)3]M≡C—C6 H4 CH3-(4) The diamagnetic compounds, some of which arc very thermolabile, were characterized In IR. 1H, 13C, and 13P NMR spectroscopy.
Notes:
Metallsubstituierte Ketene von Molybdän und Wolfram (η5-CsH5)(CO)[P(CH3)32MC(CO)R 2d, 4a, b, e(R = CH3. 1-Cyclopenten-1-yl], C6H4CH3-(4), Si(C6H5)3)entstehen bei der Umsetzung der Dicarbonyl(η5-cyclopentadienyl)carbin-Komplexe 1d, 3a, b, e mil Trimethylphosphan. In einer reversiblen Reaktion spalten sie Phosphan ab und gehen hierbei in die η2-Ketenylverbindungen 5d, 6a, b, e über. Diese addieren Kohlenmonoxid, wobei sich dicarbonylsubstituierte η1-Ketene der allgemeinen Art (η5-C5H5)(CO)2[P(CH2)3]MC(CO)R (7d, 8a-g, R = CH3, 1-Cyclopenten-1-yl, C6H5, C6H4CH3-(4), Si(C6H5)3, C5H4FeC5H5,. C6H2(CH3)3-(2,4,6)) bilden. 7d und 8d sind ferner noch durch direkte Carbonylierung von (η5-C5H5)(CO)[P(CH3)3]M ≡C—C6H4CH3-(4) (9d und 10d) zugänglich. Die diamagnetischen, teilweise sehr thermolabilen Komplexe werden durch 1R-, 1H-, 13C- und 31P-NMR-Spektren gesichert.
Additional Material:
5 Tab.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19791121007
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