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• 37299-50-6 [Rh[FeP(C6H5)2(CO)2(η-C5H5)]2][B(C6H5)4] 

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Reactions of metal carbonyl derivatives. 23. Donor behavior of [FeP(C6H5)2(CO)2(η-C 5H4R)] (R = H, CH3) toward various rhodium and iridium complexes and the role of the solvent in the type of product formed.

The metal-containing phosphine [P(C6H5)2MLn] (MLn = Fe(CO)2(η-C5H4R) (R = H or CH3)) reacts with various compounds of rhodium in alcohol, including [RhCl3·3H2O] and [{Rh(C8H12)Cl}2], to produce in each case, when present in slight excess, a cationic species of stoichiometry [Rh{FeP(C6H5)2(CO)2(η-C 5H4R)}2]+, having a nonclosed structure in which the iron and rhodium atoms are bridged by a carbonyl as well as by a phosphino group. The iridium analogue is formed in the corresponding reaction involving [Ir(C8H12)(solvent)x]+ but not [{Ir(C8H12)Cl}2]. Coordinating solvents such as tetrahydrofuran, acetone, diglyme, methanol, and acetonitrile react reversibly with these cationic species to afford products containing terminal carbonyls only. Controlled addition of P(OCH3)3, P(C6H5)3, halide ions, or pseudohalide ions to [Rh{FeP(C6H5)2-(CO)2(η-C 5H4R)}2]+ leads to the formation of simple adducts of the parent compound, in which the bridged structure is retained, while treatment of [M′{FeP(C6H5)2(CO) 2(η-C5H4R)}2]+ (M′ = Rh, Ir) with carbon monoxide in dichloromethane or chloroform gives rise to a compound characterized as [M′(CO)3{P(C6H5)2ML n}2]+. Whereas the carbonylation of [Rh{FeP(C6H5)2(CO)2(η-C 5H4R)}2]+ is reversible, that involving the iridium species is irreversible. Hydrogen also reacts with [M′{FeP(C6H5)2(CO) 2(η-C5H4R)}2]+ although high pressures are required for the rhodium reaction. Treatment of [{Rh(CO)2Cl}2] or [{Rh(C8H12)Cl}2] with [P(C6H5)2MLn] in benzene affords neutral [Rh(CO){P(C6H5)2MLn}2Cl] which can be converted to [Rh{FeP(C6H5)2(CO)2(η-C 5H4R)}2]+ by treatment with silver ions. The iridium compound [Ir-(CO){P(C6H5)2MLn}2Cl] is obtained similarly from [{Ir(C8H12)Cl}2]. Reaction of [RhL′2(solvent)x]+ or [Rh(C8H12)L′2]+ (L′ = P(OC6H5)3, P(CH3)2C6H5; 2L′ = C8H12 or (C6H5)2PC2H4P(C 6H5)2) with an equimolar amount of [P(C6H5)2MLn] in alcohol gives a dinuclear product, [RhL′2{FeP(C6H5)2(CO) 2(η-C5H5)}]+, which, similar to the trinuclear species, contains both a bridging carbonyl and a bridging phosphino group. The donor properties of [SR′MLn] (R′ = C2H5, t-C4H9, C6H5) toward various rhodium derivatives are also described.