Degree Type

Thesis

Date of Award

2014

Degree Name

Master of Science

Department

Chemistry

First Advisor

Aaron D. Sadow

Abstract

An ambiphilic bis(oxazolinyl)borane proligand and zinc dialkyls react via alkyl group transfer or β-hydrogen abstraction. Both alkyl abstraction and β-hydrogen abstraction processes can be observed, and products vary with coordinating solvent or non-coordinating solvent. We interpret this by proposing that the latter process is favoured by formation of a bis(oxazolinyl)borane-zinc adduct that positions a β-hydrogen in the proximity of the Lewis acid center.

Rare earth benzyl complexes {MeC(C5Me4)(OxMe2)2}Ln(CH2Ph) (Ln = Sc, Lu, Y) are prepared in high yield by reactions between Ln(CH2Ph)3(THF)3 and the H{MeC(C5Me4)(OxMe2)2} ligand. These compounds are precursors for the first examples of terminal lutetium and yttrium imidoborate complexes. {MeC(C5Me4)(OxMe2)2}Lu=NHB(C6F5)3 and {MeC(C5Me4)(OxMe2)2}Y=NHB(C6F5)3 are synthesized by the reaction of NH3.B(C6F5)3 with {MeC(C5Me4)(OxMe2)2}Ln(CH2Ph)2 complexes (Ln = Lu, Y).

These compounds are also precursors for the first examples of terminal lutetium and yttrium imido complexes containing β-CH. Reactions between one equivalent of benzylic amines NH2CH2(Aryl) and {MeC(C5Me4)(OxMe2)2}Ln(CH2Ph)2 give imido complexes {MeC(C5Me4)(OxMe2)2}Lu=NCH2Ar and {MeC(C5Me4)(OxMe2)2}Y=NCH2Ar. β-CH agostic interactions are observed to stabilize these imido complexes. Bisamide complexes {MeC(C5Me4)(OxMe2)2}Ln(NHCH2Ar)2 are formed by the reaction of two equivalent of NH2CH2Ar amine and {MeC(C5Me4)(OxMe2)2}Ln(CH2Ph)2 complexes.

Copyright Owner

Jing Zhu

Language

en

File Format

application/pdf

File Size

75 pages

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