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DOI: 10.1039/A708733K (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1998, 1097-1106

Synthesis, structure and reactivity of triosmium clusters derived from the reactions of [Os3(CO)10(µ-dppm)] (dppm = Ph2PCH2PPh2) and [Os3(µ-H)(CO)8{Ph2PCH2P(Ph)C6H4}] with PHPh2

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Kazi A. Azam, Michael B. Hursthouse, Md. Rafiqul Islam, Shariff E. Kabir, K. M. Abdul Malik, Rashid Miah, Claas Sudbrake and Heinrich Vahrenkamp

Abstract

The reaction of [Os3(CO)10(µ-dppm)] 1 with diphenylphosphine in refluxing toluene led to the substituted cluster [Os3(CO)9(µ-dppm)(PHPh2)] 3 and the phosphido-bridged dihydride [Os3H(µ-H)(CO)7(µ-dppm)(µ-PPh2)2] 4. The cluster 4 exists as three isomeric forms in solution. The 46-electron compound [Os3(µ-H)(CO)8{Ph2PCH2P(Ph)C6H4}] 2 reacted with an excess of PHPh2 at room temperature to yield [Os3(µ-H)(CO)8{Ph2PCH2P(Ph)C6H4}(PHPh2)] 5 and [Os3(CO)8(µ-dppm)(PHPh2)2] 6 in 16 and 62% yields respectively. Thermolysis of 6 in refluxing toluene gave 4 and two stereoisomeric compounds 7 and 8 with stoichiometry [Os3(µ-H)2(CO)6(µ-dppm)(µ-PPh2)2]. The cluster 3 decarbonylated at 110 °C to give the phosphido-bridged monohydride cluster [Os3(µ-H)(CO)8(µ-dppm)(µ-PPh2)] 9 which exists as two isomers in solution. Compound 4 converts into 7 and 8 on thermolysis in toluene. All the compounds have been characterized by infrared, 1H and 31P-{1H} NMR spectroscopy and elemental analysis and in the case of 3, 4, 6 and 7 also by X-ray crystallography.

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