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The effect of halogen atom on the molecular quadratic nonlinearity of half sandwich complexes in the presence of an acceptor

Reddy, Ravikumar A and Ranjini, Sri A and Das, Puspendu K and Samuelson, Ashoka G (2007) The effect of halogen atom on the molecular quadratic nonlinearity of half sandwich complexes in the presence of an acceptor. In: Inorganica Chimica Acta, 360 (8). pp. 2778-2782.

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Official URL: http://dx.doi.org/10.1016/j.ica.2006.11.011

Abstract

Half sandwich complexes of the type [CpM(CO)(n)X] {X=Cl, Br, I; If, M=Fe, Ru; n=2 and if M=Mo; n=3} and [CpNiPPh3X] {X=Cl, Br, I} have been synthesized and their second order molecular nonlinearity (beta) measured at 1064 nm in CHCl3 by the hyper-Rayleigh scattering technique. Iron complexes consistently display larger beta values than ruthenium complexes while nickel complexes have marginally larger beta values than iron complexes. In the presence of an acceptor ligand such as CO or PPh3, the role of the halogen atom is that of a pi donor. The better overlap of Cl orbitals with Fe and Ni metal centres make Cl a better pi donor than Br or I in the respective complexes. Consequently, M-pi interaction is stronger in Fe/Ni-Cl complexes. The value of beta decreases as one goes down the halogen group. For the complexes of 4d metal ions where the metal-ligand distance is larger, the influence of pi orbital overlap appears to be less important, resulting in moderate changes in beta as a function of halogen substitution. (C) 2006 Elsevier B.V. All rights reserved.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Elsevier Science.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 10 Jun 2010 05:07
Last Modified: 19 Sep 2010 05:59
URI: http://eprints.iisc.ernet.in/id/eprint/26878

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