Syntheses and structures of heterobicyclic bis(tert-butylamido)cyclodiphosph(III)azane compounds having phosphorus(III) and arsenic(III) centers

Syntheses and single-crystal X-ray diffraction studies of heterobicyclic cyclodiphosphazanes having central phosphorus(III) and arsenic(III) atoms are described. Interaction of PCl3 or AsCl3 with cis-[(tBuNP)2(tBuNLixTHF)2] produced the isomorphous ([(tBuNP)2(tBuN)2]ECl); E = P(1), As(4), respectively. These Cs-symmetric molecules crystallize with two molecules in the monoclinic space group P2(1)/m. Unit cell dimensions of 1 are (293 K) a = 9.777(1) A, b = 11.745(1) A, c = 9.986(2) A, and beta = 97.44(1) degrees; those of 4 are (213 K) a = 9.688(3) A, b = 11.873(3) A, c = 9.975(3) A, and beta = 97.80(3) degrees. When ([(tBuNP)2(tBuN)2]PCl) was treated with NaN3 or LiN(SiMe3)2, ([(tBuNP)2(tBuN)2]PN3)(2) and ([(tBuNP)2(tBuN)2]PN(SiMe3)2)(3), respectively, were obtained. Compound 2 crystallizes in the monoclinic space group P2(1)/m and has until-cell dimensions (213 K) of a = 9496(7) A, b = 12455(7) A, c = 10043(6) A, and beta = 9723(4) degrees, Z = 2.