Please use this identifier to cite or link to this item: http://hdl.handle.net/10397/8858
Title: Rhenium(VII) and -(V) imido and oxo complexes containing 1,4,7-triazacyclononane : synthesis, electrochemistry and crystal structures
Authors: Cheng, JYK
Cheung, KK
Chan, MCW
Wong, KY 
Che, CM
Keywords: Azamacrocycle complexes
Crystal structures
Electrochemisiry
Imido complexes
Rhenium complexes
Issue Date: 1998
Publisher: Elsevier
Source: Inorganica chimica acta, 1998, v. 272, no. 1-2, p. 176-187 How to cite?
Journal: Inorganica chimica acta 
Abstract: A new class of cationic rhenium(VII) imido and oxo complexes wilh the macrocyclic ligand 1,4,7-triazacyclononane (L) was prepared. Depending on the reaction conditions, [(L - H)Re(N tBu)2(OSiMe3)]+ (1) [(L-H) denotes deprotonation at N], [LRe(N tBu)2O] (2) and/or [LRe(N tBu)2(NH tBu)]2+ (4) can be obtained by the treatment of Re(N tBu)3(OSiMe3) with L. Reaction of 2·BPh4 with trifluoromethanesulfonic anhydride gives [(L - H)Re(N tBu)2(CF3SO3)]BPh4 (3-BPh4). Interaction of [Re(N tBu)2 (OSiMe3)(μ-O)]2 with L yields [LRe(N tBu)O2]+ (5). In contrast to the t-butylimido analogues, only [LRe(NAr)2O]Cl (6·Cl) is isolated from the reaction of Re(NAr)3Cl with excess L. Complexes 2, 5 and 6 are stable in 0.1 M CF3CO2H. Electrochemically, they undergo proton-coupled two electron reductions at pH 1 with Epc; (cathodic peak potential) of -0.30. -0.29 and -0.12 V versus SCE respectively. Constant potential electrolysis of 6 at -0.3 V affords a green solution which is rapidly oxidised in air to give [LRe(NAr)O2]+ (7). The reduction of 5-ClO4 by zinc in the presence of oxalic acid and CF3CO2H affords the rhenium(V) species [LRe(N tBu)(oxalate)]ClO4 (8·ClO4) and [LRe(N tBu)(CF3CO2)2]ClO4 (9·ClO4) respectively. The molecular structures of 2·ClO4,3·BPh4, 5·ClO4, 6·Cl·2H2O. and 8·ClO4 have been determined by X-ray crystal analysis. The Re-N(L) bonds which are trans to imido and oxo ligands are comparatively long (2.344-2.243 Å). The range of Re-N(imido) and Re-O(oxo) distances (1.67-1.78 Å and 1.71-1.76 Å respectively) can be rationalised by the oxo/imido ligand ratio in the Re(VII) complexes.
URI: http://hdl.handle.net/10397/8858
ISSN: 0020-1693
EISSN: 1873-3255
DOI: 10.1016/S0020-1693(97)05936-7
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