Issue 6, 2008

Acceptorless, intramolecular, alkyl dehydrogenation in the solid-state in a rhodium phosphine complex; reversible uptake of three equivalents of H2 per molecule

Abstract

Addition of H2 to the phosphine alkene ligated complex [Rh(dppe)(PCyp2Cyp′)][BArF4] 1 (Cyp = cyclo-C5H9; Cyp′ = cyclo-C5H7, ArF = 3,5-(CF3)2C6H3) in the solid state results in hydrogenation of the alkene and uptake of two further equivalents of H2 to afford the dihydridedihydrogen complex [Rh(dppe)(PCyp3)(H)22-H2)][BArF4] 2. Placing 2 under a vacuum or argon results in sequential loss of H2 and dehydrogenation of one of the cyclopentyl rings to reform 1. The hydrogenationdehydrogenation cycle has been repeated 5 times without apparent degradation and has been followed by solid-state 31P{1H} NMR spectroscopy. Intermediates on this process have been trapped using acetonitrile to give stable complexes that have been characterised in solution. We have previously shown that this hydrogenationdehydrogenation process also happens in the solution-state; and evidence is presented that shows that, apart from a subtle difference, the same overall transformation occurs in the solid-state.

Graphical abstract: Acceptorless, intramolecular, alkyl dehydrogenation in the solid-state in a rhodium phosphine complex; reversible uptake of three equivalents of H2 per molecule

Article information

Article type
Paper
Submitted
03 Dec 2007
Accepted
18 Dec 2007
First published
21 Jan 2008

New J. Chem., 2008,32, 966-969

Acceptorless, intramolecular, alkyl dehydrogenation in the solid-state in a rhodium phosphine complex; reversible uptake of three equivalents of H2 per molecule

T. M. Douglas and A. S. Weller, New J. Chem., 2008, 32, 966 DOI: 10.1039/B718615K

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