Dynamics of H-atom exchange in stable cis-dihydrogen/hydride complexes of ruthenium( II) bearing phosphine and N-N bidentate ligands

Bera, Barun and Patil, Yogesh P and Nethaji, Munirathinam and Jagirdar, Balaji R (2014) Dynamics of H-atom exchange in stable cis-dihydrogen/hydride complexes of ruthenium( II) bearing phosphine and N-N bidentate ligands. In: DALTON TRANSACTIONS, 43 (12). pp. 4726-4733.

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Abstract

Synthesis and characterization of cis, trans-RuH(eta(2)-H-2)(PPh3)(2)(N-N)]OTf] (N-N = 2,2'-bipyridyl (bpy) 1a, 2,2'-bipyrimidine (bpm) 2a; OTf = trifluoromethane sulfonate (CF3SO3)) complexes are reported. The cis-H-2/hydride ligands are involved in H-atom site exchange between the two moieties. This dynamics was investigated by variable temperature NMR spectral studies based on which the mechanism of the exchange process was deduced. The Delta G(#) for the exchange of H-atoms between the eta(2)-H-2 and hydride ligands was determined to be around 8 and 13 kJ mol(-1), respectively, for 1a and 2a. The H-H distances (d(HH), A) in complexes 1a and 2a have been calculated from the T-1(minimum) and (1)J(H, D) and are found to be 1.07 A (slow) and 0.95 A for 1a and 1.04 A (slow) and 0.94 A for 2a, respectively. The molecular structure of 1a was determined by X-ray crystallography.

Item Type:	Journal Article
Publication:	DALTON TRANSACTIONS
Publisher:	ROYAL SOC CHEMISTRY
Additional Information:	Copyright for this article belongs to the ROYAL SOC CHEMISTRY, ENGLAND
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	12 May 2014 05:36
Last Modified:	12 May 2014 05:36
URI:	http://eprints.iisc.ac.in/id/eprint/48925

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