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First hyperpolarizability of Ru-half-sandwich complexes: The effect of halogen atom substitution on the ancillary ligand

De, Soumi and Mitra, Raja and Samuelson, AG and Das, Puspendu K (2015) First hyperpolarizability of Ru-half-sandwich complexes: The effect of halogen atom substitution on the ancillary ligand. In: JOURNAL OF ORGANOMETALLIC CHEMISTRY, 785 . pp. 72-76.

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Official URL: http://dx.doi.org/10.1016/j.jorganchem.2015.01.013

Abstract

The first hyperpolarizability (beta) of a series of half-sandwich Ru complexes with a mercaptobenzothiazole ligand bearing a halogen atom substitution in the para-position has been investigated by hyper-Rayleigh scattering and quantum chemical calculations. The heterocyclic ligand with a bromine atom in the para position makes it a very good donor and charge flows to the Ru center enhancing the beta value of the complex by a factor of 2 compared to the complex with the ligand without the halogen substitution. The resonance (+R) and the inductive (-I) effects exerted by the halogen atom in the para position push electrons in opposing directions in the complex. For the Br and Cl atoms the resonance effect dominates which enables the ligand to donate electrons to the metal center thereby increasing the hyperpolarizability whereas for the fluorine atom, the inductive effect is dominant which reduces the charge flow to the metal and the hyperpolarizability drops even below that of the unsubstituted ligand. This unprecedented halogen atom effect on beta of metal complexes is reported. (C) 2015 Elsevier By. All rights reserved.

Item Type: Journal Article
Additional Information: Copy right for this article belongs to the ELSEVIER SCIENCE SA, PO BOX 564, 1001 LAUSANNE, SWITZERLAND
Keywords: Halogen atom effect; First hyperpolarizability; Resonance effect; Inductive effect; Half-sandwich complex
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Depositing User: Id for Latest eprints
Date Deposited: 22 May 2015 07:10
Last Modified: 22 May 2015 07:10
URI: http://eprints.iisc.ac.in/id/eprint/51547

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