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Title: Substitution of labile triflate in [(triphos)Re(CO)(2)(OTf)]: a new synthetic route to mononuclear and dinuclear Re(I) complexes
Authors: Bergamini, P.
Fabrizi De Biani, Fabrizia 
Marvelli, L.
Mascellani, N.
Peruzzini, M.
Rossi, Ranieri 
Zanello, Piero
Issue Date: 1999
Project: None 
New synthetic routes to the neutral complex [(triphos)Re(CO)2(OTf)] [triphos=MeC(CH2PPh2)3, OTf=CF3SO3-] (3) are reported. The triflate ligand in 3 is labile and can be easily replaced by different halides and pseudohalides (CN-, N3-, SCN-, SeCN-, OCN-) to give new mononuclear octahedral ReI complexes of formula [(triphos)Re(CO)2(X)] (X=Cl-, Br-, I-, CN-, N3-, SCN-, SeCN-, OCN-). In some cases, when a double proportion of 3 is treated with the appropriate pseudohalide, rare examples of binuclear ReI complexes featuring a single bridging pseudohalide ligand, [{(triphos)Re(CO)2}2(µ-X)]Y (X=CN-, N3-, SCN-, SeCN-; Y=OTf, BPh4-), have been obtained. All of the new ReI complexes have been characterized by conventional spectroscopic methods and by electrochemical and spectroelectrochemical techniques. Selected examples of regioselective electrophilic alkylations of both halide and pseudohalide ligands are also reported. Noticeably, selective methylation of [(triphos)Re(CO)2(η1-X-XCN)] (X=S, Se) affords the complexes [(triphos)Re(CO)2{η1-X-X(Me)(CN)}]OTf, which contain the unprecedented methylsulfocyanate and methylselenocyanate ligands.
ISSN: 1144-0546
DOI: 10.1039/a806683c
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