Abstract
The synthesis, structure, and reactivity of organoyttrium phosphides toward phenyl isocyanate (PhNCO) and phenyl isothiocyanate (PhNCS) are described. Reaction of (TpMe2)CpYCH2Ph(THF) (TpMe2 = tris(3,5-dimethylpyrazolyl)borate; Cp = C5H5) with 1 equiv of HPPh2 in THF at ambient temperature gives an organoyttrium phosphide (TpMe2)CpYPPh2(THF) (1). Treatment of 1 with 1 equiv of PhNCO in THF at ambient temperature results in monoinsertion of PhNCO into the Y–P σ-bond to yield complex (TpMe2)CpY[OC(PPh2)NPh](THF) (2), whereas reaction of 1 with 2 equiv of PhNCO affords the PhNCO diinsertion product (TpMe2)CpY[OC(PPh2)N(Ph)C(O)NPh] (4). However, reaction of 1 with PhNCS under the same conditions is independent of the stoichiometric ratio and gives only the monoinsertion product (TpMe2)CpY[SC(PPh2)NPh] (3). Moreover, 1 can effectively catalyze the cyclotrimerization of PhNCO under mild conditions, but does not catalyze the cyclotrimerization of PhNCS. In addition, the reaction of Cp2LnPPh2(THF) with PhNCS affo...
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