Activation of Elemental Sulfur at a Two-Coordinate Platinum(0) Center

Roy Sudipta; Schuermann Christian J.; Mondal Totan; Koley Debasis; Herbst-Irmer Regine; Stalke Dietmar; Roesky Herbert W.

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Activation of Elemental Sulfur at a Two-Coordinate Platinum(0) Center

机译：在两个坐标的Platinum（0）中心活化元素硫

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Platinum dichalcogenides have been known to exhibit two-dimensional layered structures. Herein, we describe the syntheses, isolation, and characterization of air-stable crystalline cyclic alkyl(amino) carbene (cAAC)-supported monomeric platinum disulfide three-membered ring complex [(cAAC)(2)Pt(S-2)] (2). The highly reactive platinum(0) [(cAAC)(2)Pt] complex (1) with two-coordinate platinum activates elemental sulfur to give 2. The brown crystals of bis-carbene platinum(II) monosulfate [(cAAC)(2)Pt(SO4)(x)(S-2)(1-x)] (4) have been isolated when the reaction was performed in air. The dioxygen analogue of 2 was formed upon exposing the THF solution of 1 to aerial oxygen (O-2). The binding of oxygen at the Pt-0 center was found to be reversible. Additionally, DFT study has been performed to elucidate the electronic structure and bonding scenario of 2, 3, and 4. Quantum chemical calculations showed donor-acceptor-type interaction for the Pt-S bonds in 2 and Pt-O bonds in 3 and 4.

机译：已知二硫化二铂铂具有二维分层结构。在这里，我们描述了空气稳定的结晶环状烷基（氨基）卡宾（cAAC）负载的单体二硫化铂三元环配合物[（cAAC）（2）Pt（S-2）]的合成，分离和表征（ 2）。高活性的铂（0）[（cAAC）（2）Pt]配合物（1）与二配位的铂活化，生成元素硫，得到2。双卡宾单硫酸铂（II）棕色晶体[（cAAC）（2）在空气中进行反应时，已分离出（Pt（SO4）（x）（S-2）（1-x）]（4）。将1的THF溶液暴露于空气中的氧气（O-2）后，形成2的双氧类似物。发现氧在Pt-0中心的结合是可逆的。此外，已经进行了DFT研究，以阐明2、3和4的电子结构和键合情况。量子化学计算显示2和3和4中Pt-S键和Pt-O键的供体-受体类型相互作用。

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《Chemistry: A European journal》 |2016年第36期|共5页
作者
Roy Sudipta; Schuermann Christian J.; Mondal Totan; Koley Debasis; Herbst-Irmer Regine; Stalke Dietmar; Roesky Herbert W.;
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正文语种 eng
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carbenes; density functional calculations; monomeric PtS2; platinum; sulfur;

机译：卡宾;密度泛函计算;单体PtS2;铂;硫;

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2. Activation of Elemental Sulfur at a Two-Coordinate Platinum(0) Center [J] . Roy Sudipta, Schuermann Christian J., Mondal Totan, Chemistry: A European journal . 2016,第36期

机译：在两个坐标的Platinum（0）中心活化元素硫
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Activation of Elemental Sulfur at a Two-Coordinate Platinum(0) Center

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