Substitution of labile triflate in [(triphos)Re(CO)2(OTf)]:: a new synthetic route to mononuclear and dinuclear ReI complexes

被引:21
作者
Bergamini, P
De Biani, FF
Marvelli, L
Mascellani, N
Peruzzini, M
Rossi, R
Zanello, P
机构
[1] CNR, Ist Studio Stereochim & Energet Composti Coordina, I-50132 Florence, Italy
[2] Univ Ferrara, Dipartmento Chim, I-44100 Ferrara, Italy
[3] Univ Siena, Dipartimento Chim, I-53100 Siena, Italy
关键词
D O I
10.1039/a806683c
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
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-, N-3(-), SCN-, SeCN-, OCN-) to give new mononuclear octahedral Re-I complexes of formula [(triphos)Re(CO)(2)(X)] (X = Cl-, Br-, I-, CN-, N-3(-), SCN-, SeCN-, OCN-). In some cases, when a double proportion of 3 is treated with the appropriate pseudohalide, rare examples of binuclear Re-I complexes featuring a single bridging pseudohalide ligand, [{(triphos)Re(CO)(2)}(2)(mu-X)]Y (X = CN-, N-3(-), SCN-, SeCN-; Y = OTf, BPh4-), have been obtained. All of the new Re-I 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 C(triphos)Re(CO)(2)(eta(1)-X-XCN)] (X = S, Se) affords the complexes [(triphos)Re(CO)(2){eta(1)-X-X(Me)(CN)}OTf, which contain the unprecedented methylsulfocyanate and methylselenocyanate ligands.
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页码:207 / 217
页数:11
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