Organometallics p. 777 - 788 (1987)
Update date:2022-08-04
Topics:
Richmond
Kochi
The tetracobalt cluster Co4(CO)10(μ4-PPh)2 (I) undergoes facile reductive decarbonylation to afford the bridged hydride Co4(CO)9(PPh)2(μ-H)- in quantitative yields upon the treatment with various types of borohydrides at 25°C. However, when the reductions are carried out at -78°C, a transient intermediate can be detected and its structure shown to be the corresponding formyl derivative Co4(CO)9(PPh)2CHO- (III) from its IR spectrum and 1H and 13C NMR spectra. The formation of the formyl intermediate III is confirmed by deuterium-labeling studies, and its spontaneous decarbonylation to the μ-hydride is described. Nucleophilic addition to a CO ligand as a route to the formyl intermediate is demonstrated by the generation of the corresponding acyl analogues in excellent yields following the treatment of I with methyl- and n-butyllithium. The formyl and acetyl tetracobalt clusters are efficiently trapped by O-alkylation with methyl inflate to afford the carbene derivatives Co4(CO)9(PPh)2[μ-C(OMe)H] and Co4(CO)9(PPh)2[μ-C(OMe)Me], respectively. Nucleophilic addition to I followed by alkylation to afford these tetracobalt carbene derivatives is thus analogous to the behavior of the triosmium cluster Os3(CO)12 recently reported by Kaesz and co-workers. The acid-catalyzed 1,2-elimination of methanol from the carbene cluster Co4(CO)9(PPh)2[μ-C(OMe)Me] yields the vinylidene cluster Co4(CO)9(PPh)2(μ-C=CH2), which is also produced in high yields when the acetyl cluster is treated with trifluoroacetic anhydride. The molecular structpres of Co4(CO)9(PPh)2[μ-C(OMe)Me] and the vinylidene derivative are established by X-ray crystallography. Co4(CO)9(PPh)2[μ-C(OMe)Me] crystallizes in the monoclinic space group P21/c with a = 16.465 (2) A?, b = 23.987 (3) A?, c = 15.775 (2) A?, β = 112.61 (1)°, V = 5752 A?3, and Z = 8. Co4(CO)9(PPh)2(μ-C=CH2) crystallizes in the monoclinic space group P21/n with a = 9.954 (1) A?, b = 12.865 (3) A?, c = 10.270 (1) A?, β = 98.88 (1)°, V = 1299 A?3, and Z = 2. Reactivity studies of the formyl and the various carbene ligands bound to the tetracobalt cluster are described.
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Doi:10.1021/jo00382a008
(1987)Doi:10.1021/ja020052j
(2002)Doi:10.1246/cl.1986.1385
(1986)Doi:10.1016/S0040-4039(00)82124-3
(1988)Doi:10.1016/S0022-328X(00)99669-4
(1986)Doi:10.1021/jo00383a042
(1987)
