Synthesis, Structure, and Electrochemistry of [(η⁵-C₅H₅)₂Mo₂WFe₂(O)₂(S)₂(CO)₉(CCPh)₂]

Abstract

Thermolysis of a toluene solution containing [Fe 2 W(CO) 10 (µ 3 -S) 2 ] (1) and [(η 5 -C 5 H 5 )Mo(CO) 3 (CCPh)] (2) in the presence of air at 70 °C yields the mixed-metal cluster [(η 5 -C 5 H 5 ) 2 Mo 2 WFe 2 (O) 2 (S) 2 (CO) 9 (CCPh) 2 ] (3). The structure of 3 has been established crystallographically. It consists of a triangular Fe 2 W unit, each face of which is capped by a sulfido ligand. Each Fe atom bears three carbonyl groups, while the W atom is attached to two different Mo-containing moieties. It is π-bonded to the CtC bond of a (η 5 -C 5 H 5 )Mo(CO) 3 (CtCPh) unit, and it is also bonded to a second Mo atom, and this bond is bridged by an oxo group and a µ 2 ,η 2 -CCPh group. Also attached to this Mo atom is a terminal oxo group. Compound 3 has been investigated electrochemically.

Insertion of CS2 into a metal acetylide bond and conversion of the bonding mode of S2CCCPh from η2 to η3

“…5). Absence of bands in the carbonyl region, and a band at 975 cm (1 (6) or 973 cm (1 (7) assignable to a MoÄ/O group are the notable features in their IR spectra [28,29]. Presence of (h 5 -C 5 H 5 ), (h 5 -C 5 Me 5 ) and phenyl groups were confirmed by 1 H-NMR spectra.…”

“…Various modes of coupling reactions were observed and these were found to be dependent on the nature of chalcogen bridges as well as the reaction conditions used [23 Á/27]. Under oxidising conditions we were able to isolate some novel oxo*/containing mixed */metal clusters with chalcogen and acetylide bridges [28,29]. Here we report another facet to the reactions of metal acetylide complexes, namely the photolytic reaction of molybdenum acetylide complexes with CS 2 under aerobic and anaerobic reaction conditions.…”

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

“…In 3 there are two types of W centers, W 1 / W 2 and W 3 . Since the chemically equivalent W 1 and W 2 are different from the third one, W 3 , therefore it can logically be ascribed that the responses I and III are due to the simultaneous oxidation and reduction of the W 1 and W 2 centers and responses II and IV correspond to the oxidation and reduction of the third W 3 center [24].…”

Chalcogen–acetylide interaction and unusual reactivity of coordinated acetylide with water: synthesis and characterisation of [(η5-C5R5)Fe3(CO)6(μ3-E)(μ3-ECCH2RI)] (R=H, Me; RI=Ph, Fc; E=S, Se) and [(η5-C5R5)MoFe2(CO)6(μ3-S)(μ-SCCH2Ph)] (R=H, Me)

“…Bonding of acetylides to the cluster framework has been shown to be quite sensitive to the nature of chalcogen present, as well as reaction conditions used. Thus, by careful selection of the conditions, different types of acetylide couplings are observed and under certain aerobic conditions, some oxo-and acetylide-containing clusters can be prepared [10,11]. In all such clusters, the chalcogen atom serves as stabilising caps over certain faces of the cluster framework, but does not itself interact directly with the acetylide groups.…”