Issue 26, 2016

Cobalt-bis(imino)pyridine complexes as catalysts for hydroalumination–isomerisation of internal olefins

Abstract

The insertion of α- and internal octenes (hydroalumination) and chain walking isomerisation at di-n-octylaluminium hydride [Al(Oct)2H], catalysed by bis(imino)pyridine–Co complexes has been investigated by NMR spectroscopy. The Co-based catalysts promote efficient hydroalumination of 1-octene. Internal olefins are partially hydroaluminated, with isomerisation to the primary alkyls, but the catalyst responsible appears to deactivate rapidly. The reaction between the Co precatalysts and [Al(Oct)2H] generates a Co-hydride species, likely to be a hydride bridged dinuclear Co and Al complex. This species is reactive towards α-olefins but inert towards internal olefins. In contrast to hydroalumination, the catalysts promote efficient hydroboration, where insertion and isomerisation of internal octenes goes to completion. The differences between the systems may be partially ascribed to formation of an active mononuclear Co catalyst in the borane system versus a less active Co/Al dinuclear complex in hydroalumination.

Graphical abstract: Cobalt-bis(imino)pyridine complexes as catalysts for hydroalumination–isomerisation of internal olefins

Supplementary files

Article information

Article type
Paper
Submitted
22 Mar 2016
Accepted
09 Jun 2016
First published
09 Jun 2016

Dalton Trans., 2016,45, 10842-10849

Cobalt-bis(imino)pyridine complexes as catalysts for hydroalumination–isomerisation of internal olefins

N. M. Weliange, D. S. McGuinness, M. G. Gardiner and J. Patel, Dalton Trans., 2016, 45, 10842 DOI: 10.1039/C6DT01113F

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