Multinuclear ylide and pyrazolato complexes of group 11 metals /

Bibliographic Details
Main Author:	Raptis, Raphael George, 1957-
Other Authors:	Allen, Roland E. (degree committee member.), Cotton, F. Albert (degree committee member.), Darensbourg, Donald J. (degree committee member.)
Format:	Thesis Book
Language:	English
Published:	1988.
Subjects:	Gold > Metallurgy. Metal bonding. Major chemistry. Academic theses
Online Access:	ProQuest, Abstract Link to OAKTrust copy

Description
Abstract:	The study of dimeric Au^[III] complexes derived from the parent compound [Au(CH2)2PPh2]2 revealed four structural types novel to this system: 1) The characterization of a cofacial complex with an unprecedented trigonal-bipyramidal geometry, probes the fundamental differences between the chemistries of the isoelectronic Pt^[II] and Au^[III] metal centers; 2) A cationic "A-frame" complex with a bridging halide is a possible intermediate species for several observed reactions; 3) A dimer with cis geometry on both Au^[III] centers holds the two metal atoms at a distance which does not allow direct interaction; 4) Two mixed-valence, Au^[I]/Au^[III], complexes confirm an earlier report on these species and raise questions regarding the mechanism of their formation. The x-ray crystal structures of trans/trans-[Au(CH2)2PPh2]Br4, [(μ-Br)(Au(CH2)2PPh2)2Br2][IBr2], cis/cis-[Au(CH2)2PPh2]2Br4, trans-[Au(CH2)2PPh2]Br2, and trans-[Au(CH2)2PPh2]2Cl2 are presented. 3,5-Diphenylpyrazolato is a versatile mono- or bidentate ligand capable of acting as a σ-donor and π-acceptor. Although it shows a tendency to stabilize low oxidation states, a mixed-valence, Au^[I]2/Au^[III], metal core was also found in a planar metallocyclic species. Two-coordinate, planar metallocyclic complexes of Cu^[I], Ag^[I], and Au^[I] have been characterized, along with a topologically peculiar homologous Au[I]-hexamer. 3,5-Diphenylpyrazole forms a tetrameric aggregate. Heterobimetallic d8-d10 complexes have been prepared in a systematic fashion for all three group 11 metals..
Item Description:	Typescript (photocopy). Vita. "Major subject: Chemistry."
Physical Description:	xviii, 244 leaves : illustrations ; 29 cm
Bibliography:	Includes bibliographical references.