The synthesis and reactivity of some hydrocarbyl complexes of iron and ruthenium

Gafoor, Mansoor Ahmed

The synthesis and reactivity of some hydrocarbyl complexes of iron and ruthenium

Master Thesis

1991

Publisher

University of Cape Town

Department

Department of Chemistry

Faculty

Faculty of Science

Abstract

We have reviewed the synthesis and properties of ethylene-bridged dinuclear transition metal complexes. The ethylene-bridged ruthenium complex [CpRu(CO)₂]₂[μ-(CH₂CH₂)] has been prepared. The characterization data (IR, ¹H and ¹³C NMR, and Mass spectral) and properties of this complex are discussed. The crystal structure of this complex has also been determined. The reactivity of this complex with donor ligands (CO, PMe₂Ph and PPh₃), protic acids (CF₃COOH and HCl), bromine, MeOH and with oxidants (Ph₃CPF₆ and AgBF₄) has been investigated. The new ruthenium complexes [{CpRu(CO)₂}₂{μ-(CnH₂n₋₁)}]PF₆ (n = 3 or 5), as well as their known iron analogues have been prepared. The crystal structures of [{CpM(CO)₂}₂{μ-(C₃H₅)}]PF₆ (M = Fe or Ru) have been determined. The fluxional behaviour of the complex [{CpRu(CO)₂}₂{μ-(C₃H₅)}]PF₆ has also been determined and discussed in comparison with the analogous iron complexes. A sequence of reactions of [CpM(CO)₂]₂[μ-(CH₂)₅] (M = Fe or Ru) with Ph₃CPF₆, CF₃COOH and NaI has been shown to give high yields of 1-pentene; the relevance of this reaction sequence is discussed. The synthesis and properties of the known ruthenium ethyl complex [CpRu(CO)₂(CH₂CH₃)] are compared with [CpRu(CO)₂]₂[μ-(CH₂CH₂)]. The synthesis, characterization and properties of the ruthenium haloalkyl complexes [CpRu(CO)₂{(CH₂)nX}] (n = 3, X= Cl, Br or I; n = 4 or 5, X= Br or I) are also described.

Keywords

Chemistry

Reference:

Collections

Masters

Full item page