Degree Type

Dissertation

Date of Award

1988

Degree Name

Doctor of Philosophy

Department

Chemistry

First Advisor

Robert A. Jacobson

Abstract

The crystal and molecular structures of three rose bengal derivatives and four selected organometallic compounds have been determined by X-ray single crystal method. A brief description of the structural results for each compound is given below;C[subscript]20H[subscript]4CL[subscript]4I[subscript]4O[subscript]5· 11[over]2C[subscript]4H[subscript]8O[subscript]2 (1) crystallizes in the triclinic space group P1 with a = 12.669(6), b = 12.989(2), c = 10.693(4) A and [alpha] = 92.60(4), [beta] = 111.04(5), [gamma] = 102.32(5)°. The lactoid form is clearly revealed. The length of the lactonic bond is found to be 1.469(7) A;C[subscript]34H[subscript]16CL[subscript]4I[subscript]4O[subscript]5 (2) crystallizes in the triclinic space group P1 with a = 13.637(5), b = 15.284(6), c = 9.021(3) A, [alpha] = 102.38(3), [beta] = 96.59, [gamma] = 108.11(4)°. Careful analyses of electron density and difference electron density maps point to 2 being a dibenzyl ester;C[subscript]32H[subscript]34CL[subscript]4I[subscript]4N[subscript]2O[subscript]5 (3) crystallizes in the triclinic space group P1 with a = 18.293(8) b = 18.907(6), c = 13.534(3) A, [alpha] = 95.76(3), [beta] = 90.99(3), [gamma] = 61.32(3)°. Unlike the case of 2, the quinoidic end of the molecule has some phenoxide character; (CLC[subscript]6H[subscript]12NHgCL) HgCL[subscript]3 (4) crystallizes in the monoclinic space group Pc with a = 10.532(6), b = 9.866(2), c = 14.093(7) A, [beta] = 99.23(6)°. An interesting feature of the molecular structure is that of the hitherto unobserved discrete HgCL[subscript]3[superscript]- anion which shows a distorted trigonal geometry;RhCL (P(C[subscript]6H[subscript]6)[subscript]3) [subscript]2C[subscript]9H[subscript]12 (5) crystallizes in the orthorhombic space group Pbca with a = 23.629(6), b = 23.91(3), c = 13.173(8) A. The coordination around the rhodium atom is essentially square planar. The central [pi] bond of the cumulene ligand is lengthened (1.36 A) relative to the distance in the free ligand (1.27 A). The cumulene ligand shows an interesting "flapping" disorder; (Ag ([eta][superscript]5-C[subscript]5H[subscript]5)[subscript]2Fe[subscript]2(CO)[subscript]3CS[subscript]3) BF[subscript]4 (6) crystallizes in the triclinic space group P1 with a = 13.771(4), b = 15.047(7), c = 12,544(4) A, [alpha] = 109.55(3), [beta] = 93.77(3), [gamma] = 90.76(3)°. The coordination around the silver atom is essentially trigonal;SiO[subscript]4NC[subscript]8H[subscript]17 (7) crystallizes in the monoclinic space group P2[subscript]1/n with a = 10.956(4), b = 11.187(2), c = 17.638(8) A, [beta] = 95.84(4)°. The coordination around the silicon atom is nearly trigonal bipyramidal. The length of the N→Si bond distance is 2.152 A. ftn*DOE Report IS-T-1340. This work was performed under contract No. W-7405-Eng-82 with the U.S. Department of Energy.

DOI

https://doi.org/10.31274/rtd-180813-12722

Publisher

Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/

Copyright Owner

Musiri N. Janakiraman

Language

en

Proquest ID

AAI8825405

File Format

application/pdf

File Size

169 pages

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