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INSERTION OF CARBON MONOXIDE INTO METAL CARBON BONDS: A CRYSTALLOGRAPHIC STUDY OF THREE BIS(PENTAMETHYL CYCLOPENTADIENYL) THORIUM ENOLATES AND CARBONYLS AND THE ZIRCONIUM AND HAFNIUM ANALOGUES OF TITANIUM BIS(CYCLOPENTADIENYL)PENTASULFUR: A CRYSTALLOGRAPHIC COMPARISON
Abstract
This thesis reports the single crystal X-ray diffraction study of three actinide compounds, bis(pentamethylCp) Th CO- neopentyl Cl, {bis(pentamethylCp) Th u-(COMe)2}2, and {bis(pentamethylCp) Th Th u-(COCO- neopentyl)Cl}2., and two isomorphous bisCp M penta-sulfur compounds, where M = Ti, and Hf. The first and the third complexes crystallize in the triclinic space group P1 - bar-Ci (No. 2), with 2 molecules per unit cell, the first having dimensions of a = 8.743(2)A, b = 9.849(3)A, c = 17.221(6)A, alpha = 89.83(3)(DEGREES), beta = 108.50(2)(DEGREES), and gamma = 105.04(2)(DEGREES). Least squares refinement of the first led to a value for the conventional R index (on F) of 0.067 for 4566 independent reflections having 2-theta(MoKalpha) less than 55 degrees and I greater than 3sigma(I). The second, fourth and fifth complexes crystallize in the monoclinic space group P21/n. The second has two molecules in a cell of dimensions a = 11.819(2)A, b = 13.661(3)A, c = 15.658(2)A, and beta = 107.08(1)(DEGREES). Least squares refinement gave an R index (on F) of 0.035 for 5968 independent reflections of the second compound having 2theta(MoKalpha) less than 63.7(DEGREES). The third complex has cell dimensions a = 10.625(3)A, b = 18.453(6)A, c = 19.391(4)A, alpha = 96.13(2)(DEGREES), beta = 116.15(2)(DEGREES), and gamma = 113.01(2)(DEGREES). Least squares refinement led to a value for the conventional R index (on F) of 0.053 for 9125 independent reflections having 2theta(MoKalpha) less than 58.7(DEGREES). The fourth and fifth compounds have four molecules in a cell of dimensions a = 8.984(3)A, b = 13.336(4)A, c = 11.421(2)A, and beta = 93.10(2)(DEGREES) for the fourth and a = 9.012(2)A, b = 13.391(2)A, c = 11.381(2)A, and beta = 93.25(1)(DEGREES) for the fifth. Least squares refinement gave an R index (on F) of 0.029 for 4465 independent reflections having 2theta(MoKalpha) less than 71.0(DEGREES) for the fourth compound and an R index of 0.038 for 3535 reflections having 2theta(MoKalpha) less than 63.7(DEGREES) for the fifth. The bis(Cp)M fragments of all are of the "bent sandwich" configuration, bis(Cp) M X2.
Subject Area
Chemistry
Recommended Citation
VOLLMER, SARA H, "INSERTION OF CARBON MONOXIDE INTO METAL CARBON BONDS: A CRYSTALLOGRAPHIC STUDY OF THREE BIS(PENTAMETHYL CYCLOPENTADIENYL) THORIUM ENOLATES AND CARBONYLS AND THE ZIRCONIUM AND HAFNIUM ANALOGUES OF TITANIUM BIS(CYCLOPENTADIENYL)PENTASULFUR: A CRYSTALLOGRAPHIC COMPARISON" (1982). ETD collection for University of Nebraska-Lincoln. AAI8228162.
https://digitalcommons.unl.edu/dissertations/AAI8228162