Syntheses and X-ray structures of the bridging and chelating isomers of Os3(CO)10(dmpe)

Author： Watson William   Poola Bhaskar   Richmond Michael  

Publisher： Springer Publishing Company

ISSN： 1074-1542

Source： Journal of Chemical Crystallography, Vol.36, Iss.2, 2006-02, pp. : 123-128

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Abstract

The substitution chemistry of the activated clusters Os3(CO)10(MeCN)2 (1) and Os3(CO)10(1,5-cod) (2) has been investigated with the bidentate ligand 1,2-bis(dimethylphosphino)ethane (dmpe). Both starting clusters react rapidly with dmpe at room temperature to give the corresponding substitution product Os3(CO)10(dmpe) (3), whose isomeric composition is shown to depend on the nature of the starting cluster. Whereas the bridged cluster 1,2-Os3(CO)10(dmpe) (3b) was formed almost exclusively upon reaction with Os3(CO)10(MeCN)2, a near statistical mixture of bridging (3b) and chelating (3c) isomers of Os3(CO)10(dmpe) was found in the reaction employing Os3(CO)10(1,5-cod). Both dmpe isomers have been characterized in solution by 3iP NMR spectroscopy and their solid-state structures established by X-ray crystallography. The bridged cluster 1,2-Os3(CO)10(dmpe) crystallizes in the monoclinic space group P21/n, a = 9.867(2) Å, b = 17.081(3) Å, c = 14.198(2) Å, β = 95.902(3)°, V = 2380.4(6) Å3, Z = 4, and d calc = 2.793 Mg/m3; R = 0.0435, R w = 0.0466 for 3519 reflections with I > 2σ(I). The chelated cluster 1,1-Os3(CO)10(dmpe) crystallizes in the orthorhombic space group c222(1), a = 8.329(3) Å, b = 19.028(6) Å, c = 15.008(5) Å, V = 2379(1) Å3, Z = 4, and d calc = 2.795 Mg/m3; R = 0.0390, R w = 0.0718 for 2360 reflections with I > 2σ(I).

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