一种中性有机金属氟配合物可以是一种优良的配体。

A neutral organometallic fluoro complex can be a good ligand.

作者信息

Coue Laurent, Cuesta Luciano, Morales Dolores, Halfen Jason A, Pérez Julio, Riera Lucía, Riera Víctor, Miguel Daniel, Connelly Neil G, Boonyuen Supakorn

机构信息

Departamento de Química Orgánica e Inorgánica-IUQOEM, Facultad de Química, Universidad de Oviedo-CSIC, 33071 Oviedo, Spain.

出版信息

Chemistry. 2004 Apr 19;10(8):1906-12. doi: 10.1002/chem.200305706.

DOI:10.1002/chem.200305706

PMID:15079829

Abstract

The reaction of the complex [Mo(OTf)(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1) (OTf = trifluoromethylsulfonate; phen = 1,10-phenanthroline) with tetrabutylammonium fluoride trihydrate afforded the fluoride complex [MoF(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (2). The IR spectrum and the oxidation potential of 2 reflect the fact that its metal center is more electron-rich than that of the chloro analogue [MoCl(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)]. Compound 2 reacted with 1 affording the homobinuclear complex [Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)(mu-F)][OTf] (3), with a fluoride bridge. Compound 2 also reacts with the species generated in situ by triflate abstraction from [M(OTf)(CO)(3)('N-N')] (M = Mn, Re; 'N-N' = 2,2'-bipyridine (bipy), phen) using NaBAr'(4) (Ar' = 3,5-bis(trifluoromethyl)phenyl), affording the heterobinuclear complexes [Mo(eta(3)-C(3)H(4)-Me-2)(CO)(2)(phen)[M(CO)(3)('N--N')]][BAr'(4)] (M = Mn, 'N-N' = bipy (4); M = Re, 'N-N' = phen (5)). All new compounds have been characterized by spectroscopic methods (IR and NMR) and, in the case of 1, 2, 3, and 4, also by means of X-ray diffraction analysis.

摘要

配合物[Mo(OTf)(η(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (1)（OTf = 三氟甲磺酸盐；phen = 1,10-菲咯啉）与三水合四丁基氟化铵反应得到氟化物配合物[MoF(η(3)-C(3)H(4)-Me-2)(CO)(2)(phen)] (2)。2的红外光谱和氧化电位反映出其金属中心比氯代类似物[MoCl(η(3)-C(3)H(4)-Me-2)(CO)(2)(phen)]的金属中心电子密度更高这一事实。化合物2与1反应生成具有氟桥的同双核配合物[Mo(η(3)-C(3)H(4)-Me-2)(CO)(2)(phen)(μ-F)][OTf] (3)。化合物2还与使用NaBAr'(4)（Ar' = 3,5-双（三氟甲基）苯基）从[M(OTf)(CO)(3)('N-N')]（M = Mn，Re；'N-N' = 2,2'-联吡啶（bipy），phen）原位脱去三氟甲磺酸盐生成的物种反应，得到异双核配合物[Mo(η(3)-C(3)H(4)-Me-2)(CO)(2)(phen)[M(CO)(3)('N--N')]][BAr'(4)]（M = Mn，'N-N' = bipy (4)；M = Re，'N-N' = phen (5)）。所有新化合物均通过光谱方法（红外和核磁共振）进行了表征，对于1、2、3和4，还通过X射线衍射分析进行了表征。