120262-36-4Relevant academic research and scientific papers
Versatile behavior of hydrido monometallic or heterobimetallic carbonyl anions toward dichlorophosphines and 1,1-dichlorodiphosphines
Westermann, Hermann,Nieger, Martin,Niecke, Edgar,Majoral, Jean-Pierre,Caminade, Anne-Marie,Mathieu, René,Irmer, Erhard
, p. 244 - 249 (1989)
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 Rw 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 Rw 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.
