Article ID Journal Published Year Pages File Type
1324628 Journal of Organometallic Chemistry 2016 8 Pages PDF
Abstract

•New cyclometalated diplatinum(II) complexes are prepared.•The structures of diplatinum(IV) complexes bridged by two dppac ligand are determined.•The electronic structures of the complexes are theoretically studied.

The organoplatinum complexes cis-[PtAr2(SMe2)2] (Ar = p–MeC6H4 and p–MeOC6H4) and cis,cis-[Me2Pt(μ-SMe2)2PtMe2] react very easily - in acetone at room temperature - with 1 or 2 equiv 1,1′–bis(diphenylphosphino)acetylene (= dppac), to give the diplatinum(II) complexes [Pt2R4(μ–dppac)2], (1, R = Me; 2, R = p–MeC6H4; 3, R = p–MeOC6H4) in which two square-planar R2Pt units are held together by two bridging dppac ligands. All the complexes were characterized using multinuclear (1H, 31P and 195Pt) NMR spectroscopy and single crystal X-ray structure determination. Investigation of electronic structures and related DFT and TD-DFT calculations supported a mixed 1IL (intraligand charge transfer)/1MLCT (metal-to-ligand charge transfer) for R = Me and L'LCT (ligand-to-ligand charge transfer) for R = p–MeC6H4 and p–MeOC6H4.

Graphical abstractThe organoplatinum complexes cis-[PtAr2(SMe2)2] (Ar = p–MeC6H4 and p–MeOC6H4) and cis,cis-[Me2Pt(μ-SMe2)2PtMe2] react very easily with 1 or 2 equiv 1,1′–bis(diphenylphosphino)acetylene (= dppac), respectively, in acetone at room temperature to give the diplatinum(II) complexes [Pt2R4(μ–dppac)2], in which two R2Pt units held together by two bridging dppac ligands.Figure optionsDownload full-size imageDownload as PowerPoint slide

Related Topics
Physical Sciences and Engineering Chemistry Inorganic Chemistry
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