Degree Type
Dissertation
Date of Award
1990
Degree Name
Doctor of Philosophy
Department
Chemistry
First Advisor
John D. Corbett
Abstract
Fifteen centered zirconium chloride cluster phases with five different interstitial atoms (Z = H, Be, B, C, Fe) were successfully derivatized in solution by replacing the six terminal or intercluster bridging chlorine ligands of the starting (Zr[subscript]6Cl[subscript]12Z)Cl[subscript]6 type clusters with a variety of neutral (RNH[subscript]2, R[subscript]3P) or charged (Cl[superscript]-, Br[superscript]-) ligands. Acetonitrile was the only solvent used successfully for derivatization reactions;Reactions of solid KZr[subscript]6Cl[subscript]15C, Rb[subscript]5Zr[subscript]6Cl[subscript]18B, K[subscript]3Zr[subscript]6Cl[subscript]15Be, Na[subscript]4Zr[subscript]6Cl[subscript]16Be and KZr[subscript]6Cl[subscript]15Fe with X[superscript]- (X = Cl,Br) led to the isolation and X-ray crystallographic analyses of a series of eleven compounds containing ((Zr[subscript]6Cl[subscript]12Z)Cl[subscript]3X[subscript]3][superscript]4- clusters (Z = Be, B, C, for X = Cl; Z = Fe for X = Cl, Br), many with Et[subscript]4Y[superscript]+ (Y = N,P) or Ph[subscript]4P[superscript]+ cations. Oxidation of some of the normal 14-electron clusters centered by main group elements to the 13- and 12-electron clusters by the solvent was observed. While 13- and 14-electron clusters are known for solid state precursors, the 12-electron (Zr[subscript]6Cl[subscript]18Be)[superscript]4- cluster has been obtained exclusively by the non-aqueous solution route. The bond distances within the 13- and 12-electron clusters reflect the loss of one and two electrons from the metal-metal bonding HOMO (t[subscript] 2g[superscript]6) with an average increase in Zr-Zr bond lengths of 0.05A and 0.10A, respectively, relative to the distances in the solid state phases;Cyclovoltammograms of a (Zr[subscript]6Cl[subscript]18B)[superscript] n- solution in acetonitrile indicate the presence of not only 14-, 13-, and 12-electron clusters, which have already been isolated with different interstitial atoms, but also of a possible 15-electron cluster;Primary amines and Et[subscript]3P were used for the successful derivatization of K[subscript]3Zr[subscript]6Cl[subscript]15Be, Na[subscript]4Zr[subscript]6Cl[subscript]16Be and Li[subscript]6Zr[subscript]6Cl[subscript]18H in acetonitrile and subsequent isolation and X-ray crystallographic analysis of (Zr[subscript]6Cl[subscript]12Z)(RNH[subscript]2)[subscript]6·CH[subscript]3CN (Z = Be, R = Et, i-Pr; Z = H, R = Et) and (Zr[subscript]6Cl[subscript]12Be)(Et[subscript]3P)[subscript]6. The average bond lengths within these clusters show that the change from Cl[superscript]- exo ligands in the original phases to the neutral organic bases in the derivatives essentially does not affect the bond distances within the (Zr[subscript]6Cl[subscript]12Z) cluster core. ftn*This research was supported by the National Science Foundation - Solid State Chemistry - Grants DMR - 8318616 and - 8902954.
DOI
https://doi.org/10.31274/rtd-180813-12619
Publisher
Digital Repository @ Iowa State University, http://lib.dr.iastate.edu/
Copyright Owner
Friedhelm Rogel
Copyright Date
1990
Language
en
Proquest ID
AAI9100499
File Format
application/pdf
File Size
195 pages
Recommended Citation
Rogel, Friedhelm, "A novel solution chemistry of centered zirconium chloride clusters " (1990). Retrospective Theses and Dissertations. 9411.
https://lib.dr.iastate.edu/rtd/9411