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Guanidinates: a new class of ligands for dimetal units with multiple metal-metal bonds

This dissertation concerns the discovery of the ability of the guanidinate ligand
hpp (hpp = anion of 1,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine) to stabilize high
oxidation states of dimetal units (particularly dimolybdenum species) and attempts to
control solubility and redox potential through modification of the ligand. Two general
strategies were used for the ligand modifications: alteration of the ring size, and addition
of alkyl substituents.
All of the dimetal complexes using these ligands show a significant shift in redox
potential compared to other commonly used classes of ligands (i.e. carboxylates and
formamidinates) allowing access to the Mo2
4+, Mo2
5+ and Mo2
6+ oxidation states. The
solubility of the complexes increases with increasing ring size, or with increasing length
of the alkyl substituent. The physical and chemical properties of the ligands and their
dimolybdenum complexes are described in detail.

Identiferoai:union.ndltd.org:tamu.edu/oai:repository.tamu.edu:1969.1/ETD-TAMU-1002
Date15 May 2009
CreatorsWilkinson, Chad C.
ContributorsCotton, F. A., Fackler, J. P
Source SetsTexas A and M University
Languageen_US
Detected LanguageEnglish
TypeBook, Thesis, Electronic Dissertation, text
Formatelectronic, application/pdf, born digital

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