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Silicagel support mediated nonphotolytic cleavage of the rhenium–rhenium bond of [{NC5H4N=NC6H4(R)}(CO)3Re0]2.Synthesis of the monomeric species ReI{NC5H4N=NC6H4(R)}(CO)3Cl, crystal structure, spectroscopic and electron-transfer properties

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Title Silicagel support mediated nonphotolytic cleavage of the rhenium–rhenium bond of [{NC5H4N=NC6H4(R)}(CO)3Re0]2.Synthesis of the monomeric species ReI{NC5H4N=NC6H4(R)}(CO)3Cl, crystal structure, spectroscopic and electron-transfer properties
 
Creator SAMANTA, RAMAPATI
MUNSHI, PRADIP
SANTRA, BIDYUT KUMAR
LOKANATH, NK
SRIDHAR, MA
PRASAD, JS
LAHIRI, GOUTAM KUMAR
 
Subject rhenium
cleavage of rhenium
electron transfer
 
Description The reaction of Re2(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)3Re0–Re0 (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 ReI(L)(CO)3Cl 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(L1)(CO)3Cl molecules which are non-superimposable mirror images; d and l enantiomers, exist in a 1:1 ratio. The complexes 2 display irreversible ReI→ReII 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 dπ(Re)→π*L metal-to-ligand charge-transfer transitions near 500 nm and intraligand n–π* and π–π* transitions near 400 and 300 nm, respectively. The complexes 2 are susceptible to a spontaneous chloride exchange reaction.
 
Publisher Elsevier
 
Date 2009-03-23T09:44:54Z
2011-11-25T20:18:28Z
2011-12-26T13:08:07Z
2011-12-27T05:56:07Z
2009-03-23T09:44:54Z
2011-11-25T20:18:28Z
2011-12-26T13:08:07Z
2011-12-27T05:56:07Z
1999
 
Type Article
 
Identifier Journal of Organometallic Chemistry 579(1-2), 311-320
0022-328X
http://dx.doi.org/10.1016/S0022-328X(99)00016-9
http://hdl.handle.net/10054/1084
http://dspace.library.iitb.ac.in/xmlui/handle/10054/1084
 
Language en