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Title:Reactions of Organonitrogen Compounds With Unsaturated and Lightly-Stabilized Osmium Carbonyl Clusters
Author(s):Samkoff, Deborah Elizabeth
Department / Program:Chemistry
Discipline:Chemistry
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Chemistry, Inorganic
Abstract:The improved reactivities of the unsaturated cluster hydride H(,2)Os(,3)(CO)(,10) (I) and the "lightly-stabilized" derivative Os(,3)(CO)(,10)(NCCH(,3))(,2) (II) over that of the parent compound Os(,3)(CO)(,12) have been exploited in the preparation of several compounds which would otherwise not be isolable, due to thermal instability at the temperatures required to labilize Os(,3)(CO)(,12).
Part One of this thesis examines the reactions of (I) with the arenediazonium salts ArN(,2)('+)BF(,4)('-) (Ar = p-C(,6)H(,4)CH(,3), Ph, p-C(,6)H(,4)F) to insert the N(,2) group into a metal-hydrogen bond. The initial products of these reactions are formulated as HOs(,3)(CO)(,10)(N(,2)Ar) on the basis of routine spectral data. Monohapto bridging modes for the arylazo ligands in these compounds have been deduced from ('15)N NMR studies, and the structure of HOs(,3)(CO)(,10)((eta)('1)-N=N-p-C(,6)H(,4)CH(,3)) has been confirmed by a single-crystal x-ray diffraction study performed by M. R. Churchill and H. J. Wasserman. These monohapto bridged clusters are reversibly interconvertible with a series of dihapto bridged isomers whose bridging modes have also been deduced from ('15)N NMR studies. The structure of HOs(,3)(CO)(,10)((eta)('2)-N=N-Ph) has been confirmed by a single-crystal x-ray diffraction study, also by Churchill and Wasserman.
Part Two of this thesis deals with the reaction of (II) with a series of aromatic nitrogen heterocycles, to produce compounds in which the heterocycles have been "oxidatively" added across one edge of the osmium triangle. Isomers are formed, where possible, with modest regioselectivity, and, once formed, do not interconvert. The structures of all addition products have been deduced from their ('1)H NMR spectra, and the structure of one imidazole derivative has been confirmed by a single-crystal x-ray diffraction study performed by C. Bueno and M. R. Churchill.
Part Three of this thesis describes the use of (II) in a rational synthesis of the previously known compound HOs(,3)(CO)(,10)(NHNCPh(,2)). The solution structure of this latter compound has been deduced from its ('13)C {('1)H} NMR spectrum, and the hydrolytic stability of the bridging ligand has been examined.
Issue Date:1981
Type:Text
Description:137 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1981.
URI:http://hdl.handle.net/2142/70170
Other Identifier(s):(UMI)AAI8203575
Date Available in IDEALS:2014-12-15
Date Deposited:1981


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