Hydrido(acylphenolato)cobaIt(III)-Verbindungen mit Trimethylphosphan-Liganden / Hydrido(acylphenolato)cobalt(III) Compounds Containing Trimethylphosphane Ligands

Author:

Klein Hans-Friedrich1,Haller Stefan1,Sun Hongjian1,Li Xiaoyan1,Jung Thomas1,Röhr Caroline2,Flörke Ulrich3,Haupt Hans-Jürgen3

Affiliation:

1. Institut für Anorganische Chemie der Technischen Hochschule Darmstadt, Petersenstraße 18, D-64287 Darmstadt

2. Institut für Anorganische Chemie der Universität Freiburg, Albertstraße 21, D-79104 Freiburg

3. Anorganische und Analytische Chemie der Universität/GH Paderborn, Warburger Straße 100, D-33095 Paderborn

Abstract

Abstract Salicylaldehyde derivatives and related β-hydroxo aldehydes CHO-CR=CR′-OH react with CoMe(PMe3)4 via oxidative substitution to form low-spin d6 complexes mer-CoH(CO-CR=CR-O)(PMe3)3. Reductive elimination of acyl and hydride functions from cis positions at the metal is less favourable than in carbonyl cobalt intermediates through a pronounced stabilization by neutral phosphane σ-donor and dianionic acylenolato chelate ligands. Reactions of the hydride complexes with iodomethane or with protic acids HX afford octahedral molecular complexes mer-CoX(CO-CR=CR′-O)(PMe3)3 (X =I, OAc) and mer-CoX(CO-CR=CR′-O)(PMe3)2 (X = OAc, O-CR′=CR-CHO) without opening of the acylenolato chelate ring.

Publisher

Walter de Gruyter GmbH

Subject

General Chemistry

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