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.
Bergamini, P., FABRIZI DE BIANI, F., Marvelli, L., Mascellani, N., Peruzzini, M., Rossi, R., et al. (1999). Substitution of labile triflate in [(triphos)Re(CO)(2)(OTf)]: a new synthetic route to mononuclear and dinuclear Re(I) complexes. NEW JOURNAL OF CHEMISTRY, 23(2), 207-217 [10.1039/a806683c].
Substitution of labile triflate in [(triphos)Re(CO)(2)(OTf)]: a new synthetic route to mononuclear and dinuclear Re(I) complexes
FABRIZI DE BIANI, FABRIZIA;ZANELLO, PIERO
1999-01-01
Abstract
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.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
https://hdl.handle.net/11365/22891
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