Reactions of (dimethylamido)halophosphorus(III) with aluminum(III) chloride and with some etherates of aluminum(III) chloride

Abstract

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,

New synthetic opportunities using Lewis acidic phosphines

“…Parry first recognised the interaction between haloaminophosphines upon reaction with aluminium chloride by virtue of the characteristic 1 J P-P (>200 Hz) coupling in the 31 P NMR spectra. [43][44][45] The compounds were appropriately assigned the phosphine-phosphenium complex formalism 13a, representing a coordination complex of a phosphine ligand on a phosphenium cation, as well as the phosphinophosphonium bonding model 13b. Lability and dynamic behaviour in solution renders these salts difficult to isolate, but corresponding reactions of dialkyl-and diaryl-halophosphines give similar 31 P NMR spectroscopic features.…”

Nitrogen ligands on a phosphinic Lewis acceptor including a 2,2′-dipyridyl chelate complex

“…3 The Lewis acidity of phosphines represents a more recent and developing area and demonstrates interesting bonding properties by virtue of the non-bonding electron pair at the acceptor site. Systems 1, 2 and 3, containing coordinatively unsaturated phosphinic centers form complexes with amines, [4][5][6][7] phosphines, 8 carbenes 9 and arenes, 10 and an example of a bis-ligand complex has been mentioned. 11 We have now developed the coordination chemistry of the phosphadiazonium cation 1 with nitrogen donors, and have isolated the first chelate complex.…”

A new approach to internal Lewis pairs featuring a phosphenium acid and a pyridine base

“…High (HRMS) resolution mass spectrometry was collected using a Finnigan MAT 8200 instrument. (10), 725 (13), 745(4), 764(1), 797 (8), 819 (5), 1037 (15), 1144 (14), 1221 (12), 1261 (9), 1345 (11), 1412 (7), 1437(2), 1448(3), 1487(6) cm -1 . FT-Raman (relative intensities) n = 117(1), 138(2), 168(3), 214 (6), 361 (8), 405 (7), 487 (13), 563 (10), 956 (5), 1210 (12), 1344 (15), 1436 (11), 1471 (9), 1609(4), 3059( 14) cm -1 .…”