Date of Award


Degree Type


Degree Name

Doctor of Philosophy


This thesis describes the synthesis of methyl(aryl)platinum(II), -gold(III) and -titanium(IV) complexes and their reactions with electrophiles and with unsaturated reagents. Methyl or phenyl for halogen exchange reactions of dimethyl- and diphenyltitanium complexes are also discussed.;The electrophilic reagents HCl and HgCl(,2) selectively cleave the methyl-platinum bond in the complexes cis- PtMeAr(PMePh(,2))(,2) (Ar = Ph, 4-MeOC(,6)H(,4)), whereas in the complexes cis- AuMe(,2)PhL (L = PMe(,3), PPh(,3)) the phenyl-gold bond is preferentially cleaved. It is argued that the difference in reactivity of the gold and platinum complexes indicates the operation of different mechanisms of electrophilic cleavage.;SO(,2) inserts selectively into the metal-methyl bond of cis- PtMeAr(PMePh(,2))(,2) (Ar = Ph, 4-MeOC(,6)H(,4)) and cis- AuMe(,2)PhL (L = PMe(,3), PPh(,3)), giving the S-sulfinate complexes cis- Pt(SO(,2)Me)Ar(PMePh(,2))(,2) and AuMe(SO(,2)Me)PhL . It is argued that SO(,2) does not behave as a classic electrophile, and the mechanism may involve coordination of SO(,2) to the metal prior to insertion.;Reaction of hexafluorobut-2-yne with cis- PtMeAr(PMePh(,2))(,2) (Ar = Ph, 4-MeOC(,6)H(,4)) gives cis- PtMe C(CF(,3))=C(CF(,3))Ar (PMePh(,2))(,2) .;The synthesis and reactions with electrophiles of a series of methyl(aryl)titanium(IV) complexes TiMeAr((eta)('5)-C(,5)H(,5))(,2) are described. The electrophiles HCl, HOAc, HgCl(,2) and HgClMe show little selectivity for cleavage of a titanium-aryl vs. a titanium-methyl bond, except in the case where Ar = 4-MeOC(,6)H(,4). Methyl or phenyl for halogen exchange reactions between TiR(,2)((eta)('5)-C(,5)H(,5))(,2) (R = Me, Ph) and TiX(,2)((eta)('5)-C(,5)H(,5))(,2) (X = F, Cl, Br, I) are described. In general, TiMe(,2)((eta)('5)-C(,5)H(,5))(,2) and TiPh(,2)((eta)('5)-C(,5)H(,5))(,2) react at similar rates. Possible mechanisms for the reactions of the organotitanium complexes are discussed.



To view the content in your browser, please download Adobe Reader or, alternately,
you may Download the file to your hard drive.

NOTE: The latest versions of Adobe Reader do not support viewing PDF files within Firefox on Mac OS and if you are using a modern (Intel) Mac, there is no official plugin for viewing PDF files within the browser window.