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Synthesis and Characterization of the First Examples of Dicationic Dihydrogen Complexes of Iron and Ruthenium with the PF3 Ligand

Nanishankar, HV and Nethaji, Munirathinam and Jagirdar, Balaji R (2004) Synthesis and Characterization of the First Examples of Dicationic Dihydrogen Complexes of Iron and Ruthenium with the PF3 Ligand. In: European Journal of Inorganic Chemistry, 2004 (15). pp. 3048-3056.

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Official URL: http://onlinelibrary.wiley.com/doi/10.1002/ejic.20...

Abstract

New dicationic dihydrogen complexes of the type trans- $[M(\eta ^2-H_2)(PF_3)(diphosphane)_2]^2+ [M = Ru, diphosphane = dppm (Ph_2PCH_2PPh_2); M = Fe, Ru, diphosphane = dppe (Ph_2PCH_2CH_2PPh_2)]$ have been prepared from the precursor hydrides trans- $[M(H)(PF_3)(diphosphane)_2]^+ $ upon reaction with HOTf. In the case of dppm, in addition to the trans-dihydrogen complex ci \varsigma-$[Ru(\eta^2-H_2)(PF_3)(dppm)_2]^2+ $was also obtained in the protonation reaction. The intact nature of the H-H bond in these derivatives has been established using the spin-lattice relaxation time measurements (short$ T_1$ values) and the large $J_H_,_D$ coupling constant of the H-D isotopomers. The H-H bond lengths and the stabilities of the dihydrogen complexes are discussed in terms of the \pi acidity of the $PF_3$ ligand and compared with other systems possessing trans CO and CNH ligands. The trans-$[Ru(\eta^2-H_2)(PF_3)(dppe)_2]^2+ $ complex was found to be remarkably stable with respect to the loss of bound H$_2$ for a period of about 16 h. The H-D isotopomer of this complex exhibits small temperature variations in the J$_H_,_D$ coupling constant. The X-ray crystal structure of trans-$[Ru(H)(PF_3)(dppm)_2][BF_4]$ has been determined

Item Type: Journal Article
Additional Information: Copyright for this article belongs to John Wiley and Sons.
Keywords: Dihydrogen complexes;H-H activation;Hydride ligands;Iron;Phosphane ligands;Ruthenium
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 03 Dec 2004
Last Modified: 17 Jan 2012 09:12
URI: http://eprints.iisc.ernet.in/id/eprint/2229

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