A. Deeming, Despo M. Speel, M. Stchedroff
Dec 23, 1997
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0
Influential Citations
29
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Journal
Organometallics
Abstract
The cluster [Ru3(CO)12] normally reacts readily with tertiary phosphines and diphosphines in the presence of Me3NO to give simple phosphine-substituted derivatives by a reaction involving nucleophilic attack of the amine oxide at CO leading to CO2 formation. However, the corresponding reaction of [Ru3(CO)12] with (R)-BINAP [2,2‘-bis(diphenylphosphino)-1,1‘-binaphthyl] in the presence of Me3NO does not give [Ru3(CO)10(BINAP)], as expected, but instead an 80% yield of the dihydroxy complex [Ru3(μ-OH)2(CO)8{μ-(R)-BINAP}] (1) as the first example of a μ-BINAP complex. NMR coalescence effects are observed in the 1H NMR spectra, but by using a 13CO-enriched sample, we were able to show that the fluxionality is not cluster-centered since the 13C{1H} NMR spectrum for the CO ligands is invariant over a wide temperature range. COSY spectra were used to show that there is restricted rotation about two of the four P−Ph bonds while the other two are rotating freely. From a single-crystal XRD study it can be seen that ...