
Inorganic Chemistry p. 1634 - 1636 (1964)
Update date:2022-07-30
Topics:
Lindahl, Charles B.
Jolly, William L.
Diphosphorus tetrachloride displaces carbon monoxide from nickel carbonyl at 0°. With large excesses of P2Cl4, the P2Cl4 reacts as a monofunctional base to form Ni(CO)2(P2Cl4)2 and probably Ni(CO)(P2Cl4)3 and Ni(P2Cl4)4. With large excesses of nickel carbonyl, the P2Cl4 reacts as a difunctional base to form (CO)3NiP2Cl4Ni(CO)3. With intermediate ratios of P2Cl4 to Ni(CO)4, polymeric compounds containing both mono- and difunctional P2Cl4 groups are formed. In reactions with nickel carbonyl, P2Cl4 is a stronger base than PCl3. Diphosphorus tetrachloride decomposes in the presence of boron tribromide at 0° to form a phosphorus trihalide and a phosphorus subhalide, (PX)x. Halogen exchange occurs as completely as possible; with a sufficient excess of BBr3, the adduct PBr3 · BBr3 forms.
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