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Regioselective reactivity, molecular cleft selectivity, and conformational properties have been examined in the skeletally stabilized triphosphazanes C 6 H 4 N 2 [P(NEt 2 ) 2 ] 2 PNEt 2 (4), C 6 H 4 N 2 -[P(S)(NEt 2 ) 2 ] 2 PCl (5), and C 6 H 4 N 2 [P(S)(NEt 2 ) 2 ] 2 P(S)NEt 2 (9) and in a series of new derivatives. 3 is oxidized/coordinated regioselectively by O 3 , Se, PhN 3 , and BH 3 to C 6 H 4 N 2 [P(O)(NEt 2 ) 2 ] 2 PNEt 2 and C 6 H 4 N 4 [P(O)(NEt 2 ) 2 ] 2 P(O)NEtz

Synthese et reactivite de PhN(PCl 2 ) 2 Mo(CO) 4 , PhN[P(NHPh) 2 ] 2 Mo(CO) 4 , [(PhNH)PNPh] 3 Mo(CO) 4 et [(PhNH)P 2 (NPh) 2 ] 2 NPhMo(CO) 4 . Structure cristalline du 2eme

The 1,3,2,4-diazadiphosphetidine-based dimer ((PhNH)PNPh)/sub 2/ (1) or trimer ((PhNH)PNPh)/sub 3/ (2) forms from (Et/sub 2/N)/sub 3/P-PhNH/sub 2/ transamination or PhN(P(NHPh)/sub 2/)/sub 2/ thermolysis reactions. 2 is an intermediate in the formation of 1 from PhN(P(NHPh)/sub 2/)/sub 2/. An x-ray single-crystal diffraction analysis of the solvate 2-C/sub 2/-H/sub 5/OH has been carried out. 2-C/sub 2/H/sub 5/OH is monoclinic, space group C2/c, with a = 23.156 (9) /angstrom/, b = 14.533 (5) /angstrom/, c = 22.243 (8) /angstrom/, ..beta.. = 110.63 (3)/degrees/, Z = 8, d/sub calcd/ = 1.24 g/cm/sup 3/, and d/sub obsd/ = 1.15 g/cm/sup 3/ (24/degrees/C, Mo K..cap alpha..). 2 c C/sub 2/H/sub 5/OH refined to R = 0.069 and R/sub w/ = 0.083 for 1850 independent reflections. 2 contains PhNH- and -N(PH)P(NHPh)/sub 2/ substituents at phosphorus atoms of the 1,3,2,4-diazadiphosphetidine ring. 2 has approximately C/sub s/ molecular symmetry. Complete characterization data for 1 are given. The /sup 31/P NMR spectrum of 1, in contrast to that of 2, is temperature dependent. Below -40/degrees/C, 1 in toluene assumes an unsymmetrical conformation of approximately C/sub s/ symmetry in which the PhNH groups are rotated opposite to each other, with respect to the lone-pair electrons of the P/sub 2/N/sub 2/ ringmore » phosphorus atoms. The dimer (1)-trimer (2) interconversion is discussed and related to more general phosphazane oligomerization. 37 references, 6 figures, 3 tables.« less