Synthesis, structure and electrochemistry of acetylide-bridged mixed metal cluster [Fe2(CO)6(μ3-S)2W{(η5-C5H5)W(CO)3(CCPh)}2]

Synthesis, Structure, and Reactivity of Mixed-Metal Clusters Bearing η1-Acetylide Groups, (η5-C5H5)MFe2(μ3-E)2(CO)6(η1-CCPh) (M = Mo or W and E = Se or Te)

“…Our previous attempts at preparation of mixed Fe/Mo or Fe/W clusters bearing uncoupled, η 1 -acetylide moieties have been unsuccessful; under anaerobic conditions, either dimerization of the mononuclear acetylide complexes takes place or clusters bearing coupled acetylide units are formed . Under aerobic and mild thermolytic reaction conditions, oxo-bridged mixed-metal complexes are obtained in which the acetylide units remain uncloupled, but are π-bonded, and hence the acetylide triple bond is unutilizable for further reactions. − We report here on the first example of a mixed-metal cluster bearing a η 1 -bound acetylide group in which the C⋮C triple bond remains intact and, hence, susceptible to attack by electrophiles.…”

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

“…We became interested in oxo-containing complexes after a serendipitous discovery of the complex [(η 5 -C 5 H 5 ) 2 Mo 2 WFe 2 (O) 2 (S) 2 (CO) 9 (CCPh) 2 ] during our work on acetylide-bridged cluster complexes. − In our efforts to systematize the synthesis of other chalcogen-stabilized mixed metal clusters containing both the acetylide and the oxo groups, we have isolated a number of such species, formation of which takes place only under limited concentration of oxygen in the reaction medium. We hereby report on the reactions of [Fe 2 Mo(CO) 10 (μ 3 -Se) 2 ] and [Fe 2 Mo(CO) 10 (μ 3 -S) 2 ] with [LM(CO) 3 C⋮CPh] [where L = (η 5 -C 5 Me 5 ), (η 5 -C 5 H 5 ) and M = Mo or W], the structures of the new clusters obtained, and their electrochemical behavior.…”