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Issue 8, 2010

Synthesis and structures of platinum diphenylacetylene and dithiolate complexes bearing diphosphinidenecyclobutene ligands (DPCB-Y)§

Author affiliations

Abstract

A series of platinum complexes of the type [Pt(D)(A)] having two kinds of π-conjugated ligand systems with donor and acceptor properties are prepared, using p-substituted diphenylacetylenes (tolan-X; X = OMe, H, CF3), 1,2-benzenedithiolato (bdt) and 1,3-dithia-2-thione-4,5-dithiolato (dmit) as π-donor ligands (D), and 1,2-diaryl-3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinidene]cyclobutenes (DPCB-Y; diaryl = 2C6H4-p-Y (Y = OMe, H, CF3), biphenyl-2,2′-diyl) as π-acceptor ligands (A). The electronic structures of the resulting complexes are examined in detail to investigate π-orbital interaction occurring in DPCB-Y complexes with a low-coordinate phosphorus ligand. The 31P NMR chemical shifts are highly sensitive to the Pt–P distances of the complexes, and linearly correlated with the bond lengths. The UV-vis absorption spectra of [Pt(tolan-X)(DPCB-Y)] display π–π* transitions in the visible region, which are shifted to longer wavelengths as the electron-donating ability of X and electron-withdrawing ability of Y increase, respectively. The complex [Pt(tolan-OMe)(DPCB-CF3)] with a donor–acceptor combination of substituents exhibits particularly low-energy absorption. The absorption is further red-shifted for [Pt(bdt)(DPCB-phen)] and [Pt(dmit)(DPCB-phen)] having dithiolates as strong π-donor ligands.

Graphical abstract: Synthesis and structures of platinum diphenylacetylene and dithiolate complexes bearing diphosphinidenecyclobutene ligands (DPCB-Y)

Supplementary files

Article information


Submitted
13 Feb 2010
Accepted
27 Apr 2010
First published
16 Jun 2010

New J. Chem., 2010,34, 1713-1722
Article type
Paper

Synthesis and structures of platinum diphenylacetylene and dithiolate complexes bearing diphosphinidenecyclobutene ligands (DPCB-Y)

Y. Nakajima, M. Nakatani, K. Hayashi, Y. Shiraishi, R. Takita, M. Okazaki and F. Ozawa, New J. Chem., 2010, 34, 1713 DOI: 10.1039/C0NJ00118J

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