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Issue 42, 2016
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The half-sandwich 18- and 16-electron arene ruthenium iminophosphonamide complexes

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Abstract

Novel half-sandwich 18ē and 16ē arene ruthenium iminophosphonamide complexes [(η6-C6Me6)RuCl{(R′N)2PR2}] (3a–c) and [(η6-C6Me6)Ru{(R′N)2PR2}]+(X) (4a–c) (a, R = Ph, R′ = p-Tol; b, R = Et, R′ = p-Tol; c, R = Ph, R′ = Me. X = BF4, PF6 or BArF4) were synthesized. The elongated Ru–Cl bond in the 18ē complexes is shown to dissociate even in apolar solvents to form the corresponding 16ē cations, which can be readily isolated as salts with non-coordinating anions. The coordinatively unsaturated 16ē complexes are stable species due to efficient π-electron donation from the nitrogen atoms of the zwitterionic NPN-ligand. The ruthenium iminophosphonamides are moderately active in the ROMP polymerization of norbornene; the 16ē complexes 4a,b yield high molecular weight polymers (Mn ∼ 300 × 103) with a narrow distribution Mw/Mn ∼ 1.6, while the 18ē complexes 3a,b give polymers of lower molecular weight (Mn < 50 × 103) with a wider polydispersity index Mw/Mn ∼ 2.5.

Graphical abstract: The half-sandwich 18- and 16-electron arene ruthenium iminophosphonamide complexes

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Publication details

The article was received on 11 Aug 2016, accepted on 16 Sep 2016 and first published on 16 Sep 2016


Article type: Paper
DOI: 10.1039/C6DT03202H
Citation: Dalton Trans., 2016,45, 17030-17041
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    The half-sandwich 18- and 16-electron arene ruthenium iminophosphonamide complexes

    T. A. Peganova, I. S. Sinopalnikova, A. S. Peregudov, I. V. Fedyanin, A. Demonceau, N. A. Ustynyuk and A. M. Kalsin, Dalton Trans., 2016, 45, 17030
    DOI: 10.1039/C6DT03202H

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