title: Activation of Elemental Sulfur at a Two-Coordinate Platinum(0) Center.
abstract: 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(S2 )] (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 (S2 )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 (O2 ). 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.
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany.|Department of Chemistry, Indian Institute of Science Education and Research (IISER) Tirupati, Karakambadi Road, 517507, Tirupati, Andhra Pradesh, India.
authors.forename: Sudipta
authors.initials: S
authors.lastname: Roy
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany.
authors.forename: Christian J
authors.initials: CJ
authors.lastname: Schürmann
authors.affiliation: Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur, 741246, India.
authors.forename: Totan
authors.initials: T
authors.lastname: Mondal
authors.affiliation: Department of Chemical Sciences, Indian Institute of Science Education and Research (IISER) Kolkata, Mohanpur, 741246, India. koley@iiserkol.ac.in.
authors.forename: Debasis
authors.initials: D
authors.lastname: Koley
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany.
authors.forename: Regine
authors.initials: R
authors.lastname: Herbst-Irmer
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany. dstalke@chemie.uni-goettingen.de.
authors.forename: Dietmar
authors.initials: D
authors.lastname: Stalke
authors.affiliation: Institut für Anorganische Chemie, Georg-August-Universität, Tammannstrasse 4, 37077, Göttingen, Germany. hroesky@gwdg.de.
authors.forename: Herbert W
authors.initials: HW
authors.lastname: Roesky
keywords: carbenes; density functional calculations; monomeric PtS2; platinum; sulfur