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Synthesis and Characterization of New Dicationic Dihydrogen Complexes of Ruthenium

Sivakumar, Vilvanathan and Nethaji, Munirathinam and Jagirdar, Balaji R and Mathew, Nisha (2007) Synthesis and Characterization of New Dicationic Dihydrogen Complexes of Ruthenium. In: Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 37 (9). pp. 677-684.

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Abstract

A series of new dicationic dihydrogen complexes of the type trans-$[Ru(\eta^2-H_2)(L)(dppm)_2][X]_2 (L=CH_3CN, CH_2=CHCN, C_6H_5CN, C_6H-5NC, CO; X 5 BF_4, OTf; dppm = Ph_2PCH_2PPh_2)$ have been prepared by protonating the precursor hydrides using either $HBF_4 . Et_2O or HOTf$. The variable temperature spinlattice relaxation times $(T_1, ms)$ and the H, D coupling constants of the $\eta^2-HD$ isotopomers indicate the intact nature of the H-H bond in these derivatives. The H-H distances of the dihydrogen complexes bearing trans-nitrile ligands are not significantly affected by the sterics and the electronics of the nitrile. On the other hand, the H-H distances of the dihydrogen complexes bearing either isonitrile or CO ligand are comparable to those possessing chelating diphosphine ligands of greater bite angle. Also, the thermal stabilities of these complexes are significantly less than those bearing diphosphines of greater bite angle. The trans- $[Ru(H)(CH_3CN)(dppm)_2][BF_4]$ complex has been characterized by X-ray crystallography.

Item Type: Journal Article
Publication: Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry
Publisher: Taylor & Francis
Additional Information: Copyright of this article belongs Taylor & Francis.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 29 May 2008
Last Modified: 19 Sep 2010 04:45
URI: http://eprints.iisc.ac.in/id/eprint/14094

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