ISSN:
0009-2940
Schlagwort(e):
Ruthenium clusters
;
Phosphorus ylides
;
Triply bridging organic ligands
;
Alkyne insertion
;
Chemistry
;
Inorganic Chemistry
Quelle:
Wiley InterScience Backfile Collection 1832-2000
Thema:
Chemie und Pharmazie
Notizen:
Reactivity of Derivatives of Phosphorus Ylides on Ru3 Clusters: Interconversions due to Alkyne InsertionThe Ru3 clusters with triply bridging organic ligands derived from phosphorus ylides undergo interconversions by insertion of alkynes. The phosphoniomethylidyne-bridged cluster H2Ru3(CO)9(μ31-C - PPh3) (1) inserts alkynes either into one Ru - H bond (HC=CSiMe3, EtC=CEt) forming μ21-vinyl-Ru3 complexes or into the Ru3-μ31-C unit (HC=CSiMe3, PhC=CPh) converting it into a μ31-allyl ligand, e.g. in Ru3(CO)8(PPh3)(μ31-Ph3P - C=CH=CSiMe3) (6). HC=CPh induces fragmentation of 1. The phosphonio enolate-bridged clusters HRu3(CO)9-(μ31-Ph3P - CH - CO) (2a) and HRu3(CO)8(PPh3)(μ31-Ph3P - CH - CO) (2b) insert alkynes (HC=CPh, PhC=CPh, HC=CSiMe3, EtC=CEt) into the Ru - H bond to form μ21-vinyl-bridged derivatives, e.g. Ru3(CO)8(μ31-Ph3P - CH - CO)(μ21-RC=CHR′) (9). In addition, the alkyne reactions of 2a induce cluster opening with concomitant CO and alkyne incorporation into the organic ligand and formation of an oxaruthenol-derived trinuclear complex 11, as proved by an X-ray structure determination of the PhC=CPh product 11b. For the cluster H2Ru3(CO)7(PPh3)(μ31-C6H4Ph2P - C(O)Me) (3) containing an ortho1-metalated phosphonio ketone ligand, only alkyne insertion into one or two Ru - H units is observed.
Zusätzliches Material:
1 Ill.
Materialart:
Digitale Medien
URL:
http://dx.doi.org/10.1002/cber.19931260213
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