posted on 2002-10-22, 00:00authored byPradeep Mathur, Sarbani Mukhopadhyay, Goutam K. Lahiri, Soma Chakraborty, Carsten Thöne
Thermolysis of a benzene solution containing [Fe2Mo(CO)10(μ3-Se)2] (1) and [(η5-C5Me5)W(CO)3C⋮CPh] (2) under an optimum concentration of oxygen in the reaction medium yields
the cluster [(η5-C5Me5)MoWFe2(O)(μ3-Se)(μ4-Se)(CO)8(CCPh)] (3), containing a monooxygenated metal center. Under an argon atmosphere, thermolysis of [Fe2Mo(CO)10(μ3-S)2] (4) with
[(η5-C5Me5)W(CO)3C⋮CPh] (2) in benzene leads to an oxygen-free mixed metal cluster [(η5-C5Me5)MoWFe4(μ3-S)3(μ4-S)(CO)14(CCPh)] (9). Interestingly, on reacting a benzene solution
of 4 with 2 and [(η5-C5Me5)Mo(CO)3C⋮CPh] (5) under an increased concentration of oxygen
in the reaction medium gave way to clusters [(η5-C5Me5)WMo2(μ-O)2(μ-S)(μ3-CCPh){Fe2(CO)6(μ3-S)2}2] (6), [(η5-C5Me5)WMo(O)2(μ-O)(μ-CCPh){Fe2(CO)6(μ3-S)2}] (7), and [(η5-C5Me5)Mo3(μ-O)2(μ-S)(μ3-CCPh){Fe2(CO)6(μ3-S)2}2] (8) with higher oxygen content. The structures of
the newly formed clusters 3, 6, 7, 8, and 9 were established crystallographically and the
oxo-containing Mo and W clusters investigated electrochemically.