Versatile behavior of hydrido monometallic or heterobimetallic carbonyl anions toward dichlorophosphines and 1,1-dichlorodiphosphines

Article abstract of DOI:10.1021/om00103a033

The reactivity of 1,1-dichlorodiphosphine (i-Pr₂N)₂P-PCl₂ (5) toward [NEt₄][HW(CO)₅] (2) and [NEt₄][HFe(CO)₄] (1b) has been investigated. The first reaction leads to the neutral difunctionalized diphosphine complex (i-Pr₂N)P(Cl)-P(H)(N-i-Pr₂)W(CO)₅ (9), implying diisopropylamino group migration, while the second reaction affords [NEt₄][(i-Pr₂N)P(H)[Fe(CO)₄]-P(H)[Fe(CO) ₄]₂] (10) in which a phosphorus-nitrogen bond has been cleaved. The structures of 9 and 10 have been determined by X-ray diffraction. 9 is triclinic, space group P1, with a = 9.887 (4) ?, b = 10.349 (4) ?, c =14.309 (4) ?, α = 75.92 (3)°, β = 75.50 (3)°, γ = 64.72°, and Z = 2. The structure has been solved and refined to R and R_w values of 0.028 and 0.027, respectively, by using 3898 reflections. 10 is monoclinic, space group P2₁/n, with a = 10.018 (5) ?, b = 29.892 (13) ?, c = 12.337 (5) ?, β = 100.66 (4)°, and Z = 4. The structure has been refined to R and R_w values of 0.086 and 0.081, respectively, by using 2644 reflections. The reaction of dichlorophosphines RPCl₂ with [PPh₄][HFeW(CO)₉] (3) has also been examined: the [PPh₄][μ-RP-(Cl)[Fe(CO)₄][W(CO)₅]] complexes have been obtained (R = Ph, 14a; R = Me, 14b; R = 2,5-dimethyl-1,2,3-σ²-diazaphosphole, 14c). The formation of [PPh₄][PhP(H)[Fe(CO)₄][W(CO)₅]] (15a) from PhPCl₂W(CO)₅ and [PPh₄] [HFe(CO)₄] (1a), which requires 2 equiv of the iron anion, points out the specificity of the reaction of 3.