#### Date of Award

12-1998

#### Document Type

Thesis

#### Degree Name

Master of Science (MS)

#### Department

Chemistry

#### Abstract

Synthesis and single-crystal X-ray studies of the bis(fert-butylamido) cyclodiphosphazane cis-[(tBuNP)2(tBuNH)2], 1, and its lithium, magnesium, and tin(IV) salts are described. The pristine molecule has crystallographic C2 symmetry, both N-H groups being disposed in an endo fashion, and crystallizes in the monoclinic space group P2/c with unit cell dimensions (193 K) a = 9.600(4) A, b = 5.904(4) A, c = 18.97(1) A, /? = 101.09(3)°, and Z = 2. Treatment of 1 with "BuLi or (nBu)2Mg in refluxing THF yielded the heterocubic cA-[(tBuNP)2(*BuNLi • THF)2], 2, and the seco-heterocubic [(tBuNP)2(‘BuN)2]Mg»(THF)2, 3, respectively. The crystal data (233 K) for the dilithio compound are monoclinic space group P2/c, a = 10.691(1) A, b = 15.827(2) A, c = 19.424(4) A, /? = 105.617(7)°, and Z = 4, and those for the magnesium derivative (213 K) are monoclinic, space group P2x/n, a = 10.6272(4) A, b = 17.6643(7) A, c — 16.3625(6) A, p= 90.47(3)°, and Z = 4.

The interaction of 2 with SnCl2 in toluene/tetrahydrofuran mixture produced the carbenoid tin(II) compound [(tBuNP)2(tBuN)2Sn], 4 which has been used as a building block for tin chalcogenides. Treatment of 4 with SnCl4 has produced the heterocube [(tBuNP)2('BuN)2]SnCl2, 5 which crystallizes in the orthorhombic space group P2l2l2l with unit cell dimensions a = 9.901(2) A, b = 15.241(2) A, c = 16.26(2) A, and Z = 4. Furthermore, novel dinuclear polycyclic compounds of tin(IV) of the general formula [(tBuNP)2(tBuN)2SnE]2, E = O, S, Se were synthesized by treatment of 4 with the chalcogens 0 2, S8, and Sen.. Single-crystal X-ray studies revealed that all three products, [(tBuNP)2(tBuN)2SnO]2, 6, [(tBuNP)2(‘BuN)2SnS]2, 7, and [CBuNP)2CBuN)2SnSe]2,9, are dimers. These three complexes are isostructural, and crystallize in the monoclinic space group C.2/m. The unit cell dimensions (233 K) for 6, 7, and 9 are a = 24.0752(6) A,b = 11.6275(2) A, c = 9.8462(2) A, J3= 112.883(1)°, and Z = 2; a = 23.7096(1) A, b = 11.7950(1) A, c = 9.8365(1) A, /?= 109.216(1)°, andZ = 2; and a = 23.6374(1) A, b = 11.8163(1) A, c = 9.9063(1) A, /?= 108.541(1)°, Z = 2, respectively. A fourth dimer was prepared by treatment of 4 with 2 equivalents of sulfur to produce [(tBuNP)2(tBuN)2SnS2]2, 8 which crystallizes in the orthorhombic space group Pbca with unit cell dimensions a = 15.961(2) A, b = 10.790(2) A, c = 27.207(3) A, and Z = 4.

#### Recommended Citation

Schranz, Ingo, "Synthesis And Characterization Of Polycyclic Bis(tert-Butylamido)Cyclodiphosph(III)Azane Complexes Of Lithium, Magnesium, And Tin" (1998). *Theses and Dissertations*. 771.

https://commons.und.edu/theses/771