Title

Nickel(0) catalyzed carbon-hydrogen bond activation: A mechanistic study of the formation of a nickel(I)-nickel(I) complex.

Date of Award

2006

Degree Type

Thesis

Degree Name

M.Sc.

Department

Chemistry and Biochemistry

Keywords

Chemistry, Inorganic.

Rights

CC BY-NC-ND 4.0

Abstract

The first part of this thesis deals with a mechanistic investigation into the conversion of the known benzyne complex, Ni(eta2-C 6H2F2)(PEt3)2, to the novel dinuclear Ni(I)-Ni(I) complex, (PEt3)4Ni2(eta 2-C6H2-4,5-F2)2. The coupling of two molecules of Ni(eta2-C6H2F 2)(PEt3)2 does not result in the formation of (PEt3)4Ni2(eta2-C6 H2-4,5-F2)2. There is a rearrangement in the disposition of the hydrogen atoms from para disposed in Ni(eta 2-C6H2F2)(PEt3)2 to ortho disposed in (PEt3)4Ni2(eta 2-C6H2-4,5-F2)2, which was found to be the result of C-H bond activation catalyzed by Ni(0). Proposed mechanisms involving the isolated reaction intermediates Ni2(mu-eta 2:eta2-C6H2F2)(PEt 3)2 and (PEt3)2(PMe3) 2Ni2(eta2-C6H2-3,4-F 2)2 are given and supported by 19F NMR spectroscopy and deuterium labelling studies. The second part of this thesis deals with the formation and characterization of an organized transition metal cluster. A novel tripodal ligand design was developed that involves both amido and phosphine donor groups. An organized copper(I) cluster, [P(CH2NC6H3-3,5-(CF 3)3)3]2Cu9(mu-2,4,6-Me 3C6H2)3 was synthesized by reacting the ligand, [P(CH2NC6H3-3,5-(CF3) 3)3], with mesitylcopper. The cluster contains eight copper(I) centres arranged in a zig-zag motif around a central copper(I) atom and is soluble in pentane. Source: Masters Abstracts International, Volume: 45-01, page: 0323. Thesis (M.Sc.)--University of Windsor (Canada), 2006.