Showing papers by "Antony J. Deeming published in 1973"

Some benzyne complexes of osmium derived from dimethylphenylphosphine or dimethylphenylarsine

Abstract: The complexes [Os3(CO)11(EMe2Ph)] or [Os3(CO)10(EMe2Ph)2](E = P or As) on heating give C6H4-bridged complexes [HOs3(C6H4)(EMe2)(CO)9], [HOs3(C6H4)(PMe2)(PMe2Ph)(CO)8]. [Os3(C6H4)(Eme2)2(CO)7], and [HOs3(Me2PC6H4C6H3)(PMe2)(CO)8]. When E = As, dimeric complexes containing bridging C6H4 are also obtained. Structures and mechanisms of the fluxional behaviour of these complexes are discussed in the light of n.m.r. spectra.

Hydrogenation and fluxional behaviour of H2Os3(CCH2)(CO)9, a vinylidene complex derived from ethylene

Abstract: Preliminary crystallographic data for the complex H2Os3(CCH2)(CO)9 derived from ethylene and Os3(CO)12 are given and the mechanisms of its fluxional behaviour and hydrogenation to give H3Os3(CCH3)(CO)9 are discussed.

Carbon–hydrogen cleavage reactions of some trimethyl- and triethyl-phosphine complexes of osmium

Abstract: A new type of metallation reaction is reported in which the complexes Os3(CO)11(PR3) or Os3(CO)10(PR3)2(R = Me or Et) on heating in refluxing n-nonane give the derivatives H2Os3(R2PCX)(CO)9 or H2Os3(R2PCX)(CO)8(PR3) where X = H or Me. The ligands R2PCX bridge the three metal atoms and the nonacarbonyl complexes show rapid exchange between hydrides as well as between R-groups. Isomerism observed for H2Os3(Me2PCH)(CO)8(PMe3) is probably due to the PMe3 occupying different co-ordination positions.

Some insertion reactions of platinum hydrido-complexes with olefins: hydrolysis of platinum–carbon σ-bonds

Abstract: The insertion of olefins into the Pt–H bond of trans-PtH(NO3)(PEt3)2 occurs via preliminary substitution of nitrate by olefin, and the intermediate trans-[PtH(C2H4)(PEt3)2]BPh4 has been isolated. Butadiene and allene give π-allylic complexes and cyclo-octa-1,5-diene and norbornadiene give enyl-systems. Whereas PhN:CH·CH:CHPh gives [PtH(PhN:CH·CH:CHPh)(PEt3)2]BPh4 with no insertion, CH2:CHCOMe gives [Pt(CH2·CH2·-COMe)(PEt3)2]BPh4, the Pt–C σ-bond of which is readily hydrolysed to give [Pt2(OH)2(PEt3)4]2+ and ethyl methyl ketone.

Some insertion reactions of platinum hydrido-complexes with olefins, hydrolysis of platinum-carbon sigma-bonds

Abstract: Die Einschiebung von Olefinen in die Pt-H-Bindung des trans-Pt-Komplexes (III) verlauft uber die Substitution des Nitratliganden durch das Olefin.