Date of Award

January 2015

Document Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

First Advisor

Mathew E. Otang

Abstract

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.

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