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Dicationic Dihydrogen Complexes of Iron With Almost no Fe-h2-H2

Nanishankar, HV and Nethaji, Munirathinam and Jagirdar, Balaji R (2003) Dicationic Dihydrogen Complexes of Iron With Almost no Fe-h2-H2. In: Indian Journal Of Chemistry Section A-Inorganic Bio-Inorganic Physical Theoretical & Analytical Chem, 42 (9). pp. 2332-2338.

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Abstract

Transition metal hydride complexes of the type trans-[(dppe)(2)Fe(H)(RCN)][BF4] (dppe = Ph2PCH2CH2PPh2; R = CH3, CH3CH2, CH3CH2CH2, CH2=CH, C6H5, p-CH3C6H4CH2) have been prepared by substitution of the eta(2)-H-2 ligand in trans-[(dppe)(2)Fe(H)(eta(2)-H-2)][BF4] with the corresponding nitriles. Protonation of these hydride complexes using HBF4.Et2O gives the dicationic dihydrogen complexes trans-[(dppe)(2)Fe(eta(2)-H-2)(RCN)][BF4](2). The intact nature of the H-H bond in these derivatives has been established by the observation of substantial H-D coupling constants for the eta(2)-HD isotopomers and the short spin lattice relaxation times (T-1) for the eta(2)-HD ligand. The H-2 ligand in these complexes is not substantially elongated indicating reduced or almost no Fe-H-2 back-bonding. The bound H-2 ligand is quite labile, upon its loss, one of the BF4- counterions binds with the metal to afford trans-[(dppe)(2)Fe(BF4)(RCN)][BF4] derivative. Reactivity behaviour of the dihydrogen complexes toward Lewis bases such as acetonitrile, triethylamine, and piperidine has been studied. The X-ray structure of trans-[(dppe)(2)Fe(H)(CH3CH2CH2CN)][BF4] has been determined.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to National Institute Science Communication and Information Resources.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 18 May 2009 05:47
Last Modified: 18 May 2009 05:47
URI: http://eprints.iisc.ernet.in/id/eprint/17588

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