Date of Award


Degree Type


Degree Name



Chemistry and Biochemistry

First Advisor

Stephan, Doug,


Chemistry, Inorganic.




A series of novel group 13 and 14 complexes incorporating imine and phosphinimine ligand systems were synthesized. The first metal-ligand system involved a 1,2-cyclopentadienyl diimine ligand H[(1,2-C5H3(C(Ph)NH) 2)] (25). This species reacted with aluminum and gallium reagents to yield complexes of the form [1,2-C5H 3(C(Ph)NH)2]MR2. Bidentate ligand systems incorporating a bis-phosphinimine ligand were constructed utilizing a methylene backbone [CH2(Ph 2P=NSiMe3)2] (38). Reaction of 38 with one equivalent of an alkyllithium, followed by reaction with Al, Ga or In alkyl chlorides led to novel group 13 complexes of the form [CH(PPh 2(NSiMe3))2]MR2 (M = Al, Ga, In). Reaction of 38 with two equivalents of an alkyllithium led to the isolation of the dilithiomethane derivative [Li2C(PPh2NSiMe 3)2]2 (40). This species represented the first dilithio-methane derivative to be characterized by X-ray crystallography. Continuing with phosphinimine ligands, a series of aluminum phosphinimide complexes of general formulae (R'3PNSiMe 3)AlRnCl3-n, were produced using an assortment of alkylchloride-aluminum reagents and various substituted phosphinimines. These systems gave unique reactivity with Lewis acids such as borane [B(C 6FS)3] and trityl borate [Ph3C][B(C6F 5)4], to produce a series of cationic species such as [( iPr3PNSiMe3)AlMe2][MeB(C6F 5)3] (65). An assortment of mono and bis-substituted group 14 phosphinimide complexes of the form [(tBU3PN)MMe 3] (M=Si 71, Ge 72, Sn 73) and [(tBU3PN)2MMe2] (M=Si 74, Ge 75, Sn 76) were synthesized. Both the Si and Sn mono and bis-phosphinimide complexes react with the borane [B(C6F5)3], to afford a series of unique dimeric cationic complexes. Compound 73 reacted with [B(C6F5)3] to give the cationic dimer species [(tBu3PN)SnMe2] 2[MeB(C6F5)3]2 (78 ), which was structurally characterized. A series of titanium thiolate phosphinimide complexes of the form [Cp( iPr3PN)Ti(SR)2] were produced. Reaction with AlMe3 resulted in C-H bond activation and the formation of Ti-thioiate carbide cluster complexes of the form [CpTi(mu2-SPh)(mu 2-NPiPr3)(mu4-C)(AlMe 2)2(mu-SPh)-AlMe] (86). Reactivity studies of the Ti-methyl carbide [CpTi(mu2-Me)(mu2-NP iPr3)(mu4C)(AlMe2)3] (88), with thiols or halide donors such as ClSnMe3 led to the formation of carbide clusters of the form [CpTi(mu2-R)(mu 2-NPiPr3)(mu4-C)(AlMe 2)2(mu-R)-AlMe] (R=StBu 87, R=Cl 91). The chemistry described herein is distinguished by the unique and novel reactivity incurred through the use of group 13 and 14 metals.Dept. of Chemistry and Biochemistry. Paper copy at Leddy Library: Theses & Major Papers - Basement, West Bldg. / Call Number: Thesis2001 .O54. Source: Dissertation Abstracts International, Volume: 62-10, Section: B, page: 4539. Adviser: Doug Stephan. Thesis (Ph.D.)--University of Windsor (Canada), 2001.