Reactions of tris(amino)phosphines with arylsulfonyl azides: Product dependency on tris(amino)phosphine structure

The Staudinger reaction of N(CH2CH2NR)(3)P [R = Me (1), Pr-i (2)] with 1 equiv of N3SO2C6H4Me-4 gave the ionic phosphazides [N(CH2CH2NR)(3)PN3][SO2C6H4Me-4] [R = Me (3), R = Pr-i (5a)], and the same reaction of 2 with N3SO2C6H2Me3-2,4,6 gave the corresponding aryl sulfinite 5b. On the other hand, the reaction of 1 with 0.5 equiv of N3SO2Ar (Ar = C6H4W-4) furnished the novel ionic phosphazide {[N(CH2CH2NMe)(3)P](2)(mu-N-3)}[SO2Ar] (6). Data that shed light on the mechanistic pathway leading to 3 were obtained by low temperature P-31 NMR spectroscopy. 1 A crystal and molecular structure analysis of the phosphazide sulfonate [N(CH2CH2NMe)(3)PN3][SO3C6H4Me-4] (4), obtained by atmospheric oxidation of 3, indicated an ionic structure, the cationic part of which is stabilized by a transannular P-N bond. A crystal and molecular structure analysis of 6 also indicated an ionic structure in which the cation features two untransannulated N(CH2CH2NMe)(3)P cages bridged by an azido group in an eta(1):mu:eta(1) fashion. The reaction of P(NMe2)(3) with N3SO2Ar (Ar = C6H4Me-4) in a 1:0.5 molar ratio furnished {[(Me2N)(3)P](2)(mu-N-3)}[SO2Ar] (11) in quantitative yield. On the other hand, the same reaction involving a 1:1 molar ratio of P(NMe2)3 and N3SO2Ar produced a mixture of 11, [(Me2N)(3)PN3][SO2Ar] (12), and the iminophosphorane (Me2N)(3)P=NSO2Ar (10). In contrast, the bicyclic tris(amino)phosphines MeC(CH2NMe)(3)P (7) and O=P(CH2NMe)(3)P (8) reacted with N3SO2Ar (Ar = C6H4Me-4) to give the iminophosphorane MeC(CH2NMe)(3)P=NSO2Ar (14) (structured by X-ray means) and O=P(CH2NMe)(3)P=NSO2Ar (16) via the intermediate phosphazides MeC(CH2NMe)(3)PN3SO2Ar (13) and O= P(CH2NMe)(3)PN3SO2Ar (15), respectively. The variety of products obtained from the reactions of arylsulfonyl azides with proazaphosphatranes (11 and 2), acyclic P(NMe2)(3), bicyclic tris(amino)phosphines 7 and 8 are rationalized in terms of steric and basicity variations among the phosphorus reagents.