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The chloro(dimethylamido)phosphorus(III) ligands interact with AlC13 under appropriate conditions to give (CH3)2N-PC12.AICI3, ((CH3)2N)2PCl.AlC13, and [2((CH3)2N)2PCI].AlC13. Tris(dimethylamido)phosphorus(III) and AIC13 react under comparable conditions to give ((CH&N)3P*AlCI3. The tris ligand will also react with ((CH3)2N)2PCI*AlCI3 to give ((CH3)2N)3P.((CH3)2N)2PCl.AICl3 but it will not react with ((CH3)2N)jP-AlCI3 to give [2((CH3)2N)3P].AIC13. Trimethylamine will gradually replace some of the phosphorus ligand from the complex to give some (CH3)3N*AlC13. A solution of dichloro(dimethylamido)phosphorus(III) ligand in isopropyl ether was stable as was a solution of aluminum chloride in isopropyl ether. On the other hand, an isopropyl ether solution containing A1C13 and the dichloro(dimethylamido)phosphorus(III) ligand gave 1 mol of isopropyl chloride for each mole of PC13 and each mole of the dichloro(dimethy1amido)phosphorus ligand. The ether solution turned red as a result of the formation of an aluminum chloride-olefin complex. The splitting process to generate alkyl halide was not observed with diethyl ether. The chloride transferred came from the phosphorus ligand, not the AlC13. The ligand ((CH3)2N)zPCI will displace about 70% of the diisopropyl ether from the diisopropyl etherate of AIC13 and ((CH3)2N)3P will displace 1OC% of the ether. Models to interpret these facts are presented. Registry No. ((CH3)2N)2PCbAIC13, 60607-14-9; (CH3)zNP-C12.AIC13, 60594-92-5; [2((CH3)2N)2PCl].AlC13, 60594-85-6; ((CH3)2N)2PCl-((CH3)2N)3P-AlC13,60594-83-4; ((CH3)2N)3P*AlC13,

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M an ga nese and R hen i u m D i hydro b is ( pyrazo I y I ato ) borateco m pl exes