Issue 32, 2013

The structure and coordinative self-assembly of films based on a palladium compound of pyridyl-acetylene platinum and its application in Suzuki and Heck coupling reactions

Abstract

The platinum complex [Pt2(C[triple bond, length as m-dash]CPy)2(dppm)2] (Py = 4-pyridyl, dppm = bis(diphenylphosphino)methane) 1 has been prepared and characterized. Single crystal X-ray diffraction analysis reveals that the Pt2(C[triple bond, length as m-dash]CPy)2 fragment of 1 exhibits an approximately linear molecular geometry, in which the Pt–Pt bond may be considered as having been inserted within the delocalized π-electron system of the 1,4-bis(4′-pyridyl)buta-1,3-diyne. The ability of the two terminal pyridyl nitrogen atoms of 1 to coordinate to other metal centers has enabled the use of 1 as a linking ligand in the layer-by-layer (LbL) growth of heterometallic films. The self-assembly behavior of 1 with Pd(II), supported by chloride counter ions, on poly(ethylenimine) (PEI) functionalized solid surfaces has been investigated. The resulting multilayer films of general composition and form (PdCl2/1)n have been characterized using UV-vis absorption spectroscopy, atomic force microscopy (AFM) and X-ray photoelectron spectroscopy (XPS). On the basis of the UV-vis spectroscopic data, it was shown that the (PdCl2/1)n multilayer films could be grown in a regular fashion, with film thickness increasing linearly with increasing deposition of the metal–ligand bilayers. Consistent with this metal ion dependent LbL growth, AFM images of the multilayer films exhibited island-shaped nanostructures with a mean diameter of about 25 nm. The catalytic properties of the (PdCl2/1)n multilayers were investigated, and (PdCl2/1)n film-loaded slides were used as a catalyst reservoir capable of liberating catalytic amounts of a highly active Pd species, which was suitable for promoting C–C bond formations. The catalyst loading was as low as 2.76 × 10−6 mol% and gave high yields. The LbL catalyst and the technology presented in this work, show distinctive features that include extraordinarily low loading and high catalytic active characteristics.

Graphical abstract: The structure and coordinative self-assembly of films based on a palladium compound of pyridyl-acetylene platinum and its application in Suzuki and Heck coupling reactions

Supplementary files

Article information

Article type
Paper
Submitted
12 May 2013
Accepted
03 Jun 2013
First published
03 Jun 2013

J. Mater. Chem. A, 2013,1, 9164-9172

The structure and coordinative self-assembly of films based on a palladium compound of pyridyl-acetylene platinum and its application in Suzuki and Heck coupling reactions

X. Li, X. Zhao, S. Gao, S. Marqués-González, D. S. Yufit, J. A. K. Howard, P. J. Low, Y. Zhao, N. Gan and Z. Guo, J. Mater. Chem. A, 2013, 1, 9164 DOI: 10.1039/C3TA11868A

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