American Chemical Society
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Synthesis, Structure, and Electrochemistry of Acetylide and Oxo Incorporated Mixed Fe/Mo and Fe/W Chalcogen-Bridged Clusters

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journal contribution
posted on 2002-10-22, 00:00 authored by Pradeep Mathur, Sarbani Mukhopadhyay, Goutam K. Lahiri, Soma Chakraborty, Carsten Thöne
Thermolysis of a benzene solution containing [Fe2Mo(CO)103-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)103-S)2] (4) with [(η5-C5Me5)W(CO)3C⋮CPh] (2) in benzene leads to an oxygen-free mixed metal cluster [(η5-C5Me5)MoWFe43-S)34-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)63-S)2}2] (6), [(η5-C5Me5)WMo(O)2(μ-O)(μ-CCPh){Fe2(CO)63-S)2}] (7), and [(η5-C5Me5)Mo3(μ-O)2(μ-S)(μ3-CCPh){Fe2(CO)63-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.