ISSN:
0009-2940
Keywords:
Ruthenium clusters
;
Phosphorus ylides
;
Oxidative addition
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Notes:
Three-Centre Oxidative Addition of Phosphorus Ylides to Ru3(CO)12Phosphorus ylides undergo oxidative addition to Ru3(CO)12 to yield a wide range of Ru3 clusters with triply bridging organic ligands derived from the ylides. Ph3P=CH2 forms HRu3(CO)9(μ31-Ph3P - CH - CO) (1) containing a phosphonio enolate. Ph3P=CH - CHO yields a product mixture containing the phosphonio enolate-bridged cluster and its PPh3 derivative 6, the phosphoniomethylidyne-bridged compound H2Ru3(CO)9(μ31-C - PPh3) (5), and the ketenylidene-bridged compound H2Ru3(CO)8(PPh3)(μ31-C - CO) (7). Thermal treatment converts the phosphonio enolate ligand (in 1) into the phosphoniomethylidyne ligand (in 5), and the latter into the ketenylidene ligand (in 7). With Ph3P=CH - C(O)Me and Ru3(CO)12 ortho1-metalated Ru3 derivatives 10, 11 of the phosphonio ketone R3P - C - C(O)Me are produced, and likewise with Ph3P=CH - COOEt the ortho1-metalated derivative 12 of the phosphonio ester R3P - C - CO2Et. Me3P=CH - COOtBu is oxidatively added to form HRu3(CO)9(μ31-Me3P - C - COOtBu) (13) bearing a phosphonio ester ligand. - The crystal structures of 6 and 13 are reported. The sequence of Ru3 clusters and the bonding modes of the μ3 ligands can be related to the surface reactions during Fischer-Tropsch catalysis.
Additional Material:
3 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/cber.19931260212
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