Carbon–sulfur bond reductive coupling from a platinum(ii) thiolate complex. Issue 97 (5th October 2016)

• Record Type: Journal Article
• Authors: Niazi, Maryam; Shahsavari, Hamid R.; Haghighi, Mohsen Golbon; Halvagar, Mohammad Reza; Hatami, Samaneh; Notash, Behrouz
• Is Part Of: RSC advances. Volume 6:Issue 97(2016)
• Page Start: 95073
• Page End: 95084
• Publication Date: 2016-10-05
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/c6ra21756g
• Languages: English
• ISSNs: 2046-2069

Abstract

Abstract : Complex1 was reacted with different alkyl halides at room temperature. This reaction proceeded via formation of binuclear intermediate complex3 and through C–S bond reductive coupling to produce alkyl sulfides and corresponding halide complexes2 . Abstract : The room temperature addition of electrophilic alkyl halide reagents (RX = MeI, EtI and PhCH2 Br) to complex [Pt(ppy)( η 1 -S-Spy)(PPh3 )], 1a, in which ppyH = 2-phenylpyridine and pySH = pyridine-2-thiol, resulted in a rapid carbon–sulfur (C–S) bond reductive coupling to produce alkyl sulfides and corresponding halide complexes [Pt(ppy)(PPh3 )X], X = I (2a ) and Br (2b ). A mechanism for this C–S bond formation reaction was suggested based on 1 H and 31 P { 1 H} NMR spectroscopic analyses. In the suggested mechanism, the reaction proceeded through a binuclear intermediate complex [{Pt(ppy)(PPh3 )}2 ( μ 2 -Spy)]I, 3-I, which was separately synthesized by another counter anion (PF6 ) and it was fully characterized by multinuclear NMR spectroscopy and single X-ray crystallography. Also, density functional theory (DFT) calculations were used to theoretically assess the structures of intermediates and transition states in this bond formation reaction.