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

作者：Roy Sudipta; Schuermann Christian J; Mondal Totan; Koley Debasis^*; Herbst Irmer Regine; Stalke Dietmar^*; Roesky Herbert W^*

来源：Chemistry - A European Journal, 2016, 22(36): 12629-12633.

DOI：10.1002/chem.201603030

• carbenes
• density functional calculations
• monomeric PtS2
• platinum
• sulfur

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.

• 出版日期2016-8-26