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The title complex reacted readily with CS 2 and SCNPh to give the phosphinidene-cumulene adducts [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -P(CS 2 )C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] and [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -P(C(NPh)S)C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] respectively (Mes* = 2,4,6-C 6 H 2   Bu 3 ), as a result of the formal insertion of the C[double bond, length as m-dash]S bond of the heterocumulene into the metallocene Mo-P bond of the phosphinidene complex. The newly formed species bear a pyramidal P atom with a lone electron pair involved in fast inversion, and displayed strong nucleophilicity which enabled easy addition at the P site of carbon-based electrophiles and chalcogen atoms, while the uncoordinated S and N atoms were also competitive nucleophilic sites in these complexes. These air-sensitive materials readily added an O 2 molecule in the solid state, to give the corresponding derivatives [Mo 2 Cp{μ-κ 1  O :κ 1  S ,η 5 -OP(O)(C(X)S)C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] (X = S, NPh), and the CS 2 adduct reacted selectively with S 8 in solution to give the sulfide derivative [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -P(S)(CS 2 )C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )], which was stabilized through methylation, thus yielding the cationic complex [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -P(S)(C(SMe)S)C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] + . The CS 2 adduct could be methylated selectively at either the P or C[double bond, length as m-dash]S sites, depending on the reagent used, to give respectively the cationic complexes [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -PMe(CS 2 )C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] + or [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -P(C(SMe)S)C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] + . Further methylation could be accomplished through reaction with [Me 3 O]BF 4 o give the dipositive cation [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -PMe(C(SMe)S)C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] 2+ . In contrast, the SCNPh adduct was only methylated at the P site to yield the phosphanylthioformamidato complex [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -PMe(C(NPh)S)C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] + , but was readily protonated at the N site upon reaction with (NH 4 )PF 6 , to give the phosphanylthioformamide-like derivative [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -P(C(NHPh)S)C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] + . In the presence of Na(BAr' 4 ), this adduct was even able to displace chloride from the solvent (dichloromethane) to give the corresponding chloromethyl derivative [Mo 2 Cp{μ-κ 1  P :κ 1  S ,η 5 -P(CH 2 Cl)(C(NPh)S)C 5 H 4 }(CO) 2 (η 6 -HMes*)(PMe 3 )] + . The structures of the new complexes were analyzed using spectroscopic, diffractometric and, in some cases, density functional theory methods.

dalton transactions

Chemistry of CS2- and SCNPh-adducts of the pyramidal phosphinidene-bridged complex [Mo2Cp(μ–κ1:κ1,η5-PC5H4)(CO)2(η6-HMes*)(PMe3)]