Formation of Difluorosulfane Complexes of the Third Row Transition Metals by Sulfur-to-Metal Fluorine Migration in Trifluorosulfane Metal Complexes: The Anomaly of Trifluorosulfane Iridium Tricarbonyl
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- 作者：Xiaozhen Gao ; Nan Li ; R. Bruce King
- 刊名：Inorganic Chemistry
- 出版年：2014
- 出版时间：December 1, 2014
- 年：2014
- 卷：53
- 期：23
- 页码：12635-12642
- 全文大小：442K
- ISSN：1520-510X
文摘
The stability of the experimentally known complex (Et<sub>3sub>P)<sub>2sub>Ir(CO)(Cl)(F)(SF<sub>3sub>) of the third row transition metal iridium suggests that SF<sub>3sub> complexes of the third row transition metals might be viable species in contrast to the SF<sub>3sub> complexes of the first row transition metals previously studied by theoretical methods. However, the metal complexes [M](SF<sub>3sub>) ([M] = Ta(CO)<sub>5sub>, Re(CO)<sub>4sub>, CpW(CO)<sub>2sub>, CpOs(CO), and CpPt) containing three-electron donor tetrahedral SF<sub>3sub> ligands are thermodynamically disfavored relative to the isomeric [M](SF<sub>2sub>)(F) derivatives with predicted energy differences ranging from 鈭?9 to 鈭?4 kcal/mol. The one exception is an Ir(SF<sub>3sub>)(CO)<sub>3sub> isomer containing a one-electron donor pseudo-square-pyramidal SF<sub>3sub> ligand having essentially the same energy as the lowest energy Ir(SF<sub>2sub>)(F)(CO)<sub>3sub> isomer. This, as well as the stability of the known (Et<sub>3sub>P)<sub>2sub>Ir(CO)(Cl)(F)(SF<sub>3sub>), suggests that metal complexes containing one-electron donor pseudo-square-pyramidal SF<sub>3sub> ligands might be viable synthetic objectives in contrast to those containing three-electron donor tetrahedral SF<sub>3sub> ligands. The [M](SF<sub>2sub>)(F) derivatives formed by sulfur-to-metal fluorine migration from isomeric [M](SF<sub>3sub>) complexes are predicted to be viable toward SF<sub>2sub> dissociation to give the corresponding [M](F) derivatives. This suggests the possibility of synthesizing metal complexes of the difluorosulfane (SF<sub>2sub>) ligand via the corresponding metal trifluorosulfane complexes with the SF<sub>3sub><sup>+sup> cation as the ultimate source of the SF<sub>2sub> ligand. Such a synthetic approach bypasses the need for the very unstable SF<sub>2sub> as a synthetic reagent.