Silicagel support mediated nonphotolytic cleavage of the rhenium-rhenium bond of {NC5H4N = NC6H4(R)}(CO)(3)Re-0](2). Synthesis of the monomeric species Re-I{NC5H4N = NC6H4(R)}(CO)(3)Cl, crystal structure, spectroscopic and electron-transfer properties

Samanta, R. and Munshi, P. and Santra, B. K. and Lokanath, N. K. and Sridhar, M. A. and Shashidhara Prasad, J. and Lahiri, G. K. (1999) Silicagel support mediated nonphotolytic cleavage of the rhenium-rhenium bond of {NC5H4N = NC6H4(R)}(CO)(3)Re-0](2). Synthesis of the monomeric species Re-I{NC5H4N = NC6H4(R)}(CO)(3)Cl, crystal structure, spectroscopic and electron-transfer properties. Journal of Organometallic Chemistry, 579 (1-2). pp. 311-320.

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Abstract

The reaction of Re-2(CO)(10) with the 2-arylazopyridine ligand, L L=NC5H4-N=N-C6H4(R), R-H, o-Me/Cl, m-Me/Cl] in dry THF under a dinitrogen atmosphere afforded a metal-metal bonded product of the type (L)(CO)(3)Re-0-Re-0 (CO)(3)(L) 1. On a silica gel column and in the presence of chlorinated solvents (CHCl3 or CH2Cl2) the complex 1 transformed into a mononuclear complex of composition Re'(L)(CO)(3)Cl 2, where the cleavage of Re-Re bond of 1 and the oxidative addition of chlorine to the rhenium center have taken place consecutively. The molecular structure of the complex 2a (R=H) has been determined by single crystal X-ray diffraction. The crystal lattice consists of two crystallographically independent Re(L-1)(CO)(3)Cl molecules which are non-superimposable mirror images; d and 1 enantiomers, exist in a 1:1 ratio. The complexes 2 display irreversible Re-1--->Re-11 oxidation processes near 1.5 V versus SCE and two quasi-reversible azo (N=N) reductions in the ranges -0.28 to -0.48 V and -0.83 to -1.06 V versus SCE. The complexes of the type 1 exhibit only four successive azo reductions in the range 0 to -2 V versus SCE. Both the complexes (1 and 2) display d pi(Re) —> pi*L metal-to-ligand charge-transfer transitions near 500 nm and intraligand n-pi* and pi-pi* transitions near 300 and 300 nM, respectively. The complexes 2 are susceptible to a spontaneous chloride exchange reaction. (C) 1999 Elsevier Science S.A. All rights reserved.

Item Type:	Article
Subjects:	D Physical Science > Physics
Divisions:	Department of > Physics
Depositing User:	Users 23 not found.
Date Deposited:	17 Jun 2021 07:02
Last Modified:	07 Jul 2022 09:54
URI:	http://eprints.uni-mysore.ac.in/id/eprint/16801

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