Syntheses And Characterization Of Bis(amino)cyclodiphosphazane Complexes Of Group 4- And -15 Elements

In the first part of this work, the interaction of sodium tert-butoxide and sulfur with Group 4 metal bis(tert-butylamido)cyclodiphosph(III)azanes dichlorides, {[tBuNP)2tBuN)2]MCl2}, where M is Zr or Hf, is reported. The reaction of two equivalents of NaOtBu with {[tBuNP)2tBuN)2]MCl2}, M = Zr, Hf, resulted in the isolation of the first metal alkoxide complexes {[tBuNP)2tBuN)2]M(OtBu)2}, 35 (M =Zr) and 36 (M = Hf) of cyclodiphosphazanes. The oxidation of compounds 35 and 36 with elemental sulfur yielded {[tBuNP=S)2tBuN)2]M(OtBu)2}, 37 (M = Zr) and 38 (M = Hf), respectively. Similarly, the oxidation of {[tBuNP)2tBuN)2]MCl2}, M = Zr, Hf, with elemental sulfur led to the isolation of {[tBuNP=S)2tBuN)2]MCl2}, 39 (M = Zr) and 40 (M = Hf). The structures of compounds 37–40 were determined by X-ray crystallography and confirmed by multi-nuclear NMR spectroscopy and elemental analysis. In part two, the attack of two equivalents of the electrophiles Ph2PCl, PCl3, and CH3I on the dianionic bis(alkylamido)cyclodiphosph(III)azanes, {R = tert-butyl (48), cyclohexyl (54)} is described. The reaction of [(tBuNP)2(tBuNLi·thf)2 with Ph2PCl led to the isolation of two products: an asymmetric P, N product, 52A and a symmetric P, P substituted heterocycle, 52B. Treatment of cis-[(tBuNE)2(RNLi·thf)2], E = P, SiCH3 and R = tBu, Cy, with PCl3 yielded cis-{[E(μ-NtBu)]2(RNPCl2)2}, 55 (E = P, R = Cy) and 57 (E = SiCH3, R = tBu). While the reaction of MeI with compound 48 resulted in the isolation of the symmetrical product cis-{[(tBuNPMe)2(tBuNLi·thf)2]I2}, 58. Also, the lithiation of compound 59 with n-BuLi yielded 60. Compounds 52A, 52B, 54, 55, 57, and 60 were characterized by multi-nuclear NMR spectroscopy, X-ray crystallography, and elemental analysis. The last part of this work describes the syntheses and characterization of compounds derived from the reactions of {[(tBuNP)2(tBuN)2]ECl}, E = P, Sb, with various reagents. Treatment of {[(tBuNP)2(tBuN)2]PCl} with excess sulfur, AgSO3CF3, PhMgCl, and NaOtBu led to the isolation of the compounds [(tBuNP=S)3N], 66, [(tBuNP)2(tBuN)2]P]+SO3CF3-, 67, {[(tBuNP)2(tBuN)2]PPh}, 68, and {[(tBuNP)2(tBuN)2]POtBu}, 70, respectively. Meanwhile, oxidation of compound 68 with elemental sulfur resulted in {[(tBuNP)2(tBuN)2](P=S)Ph}, 69. Also, the reaction of {[(tBuNP)2(tBuN)2]SbCl} with PhMgCl and NaOtBu yiedeld {[(tBuNP)2(tBuN)2]SbPh}, 71 and {[(tBuNP)2(tBuN)2]SbOtBu}, 72, respectively. The structures of compounds 66, 67, 69, and 71 were determined by X-ray crystallography and confirmed by multi-nuclear NMR spectroscopy and elemental analysis