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Issue 45, 2013
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Molecular rectangles from platinum(II) and bridging dicarbene, diisocyanide and 4,4′-bipyridine ligands

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Abstract

A series of benzobisimidazolium salts have been prepared and treated with [PtCl2(dppe)] or [PtCl2(dmpe)] in the presence of sodium acetate to yield dinuclear dicarbene-bridged complexes of the type [(P^P)(X)Pt(benzodicarbene)Pt(X)(P^P)](X)2 [5]Br2–[11]I2. The reaction of compounds [7]Br2 and [11]I2 with AgPF6 in acetonitrile led to the exchange of the metal-bound bromo or iodo ligands for acetonitrile and the formation of complexes [(dmpe)(MeCN)Pt(benzodicarbene)Pt(MeCN)(dmpe)](PF6)4 [12](PF6)4 and [13](PF6)4. The dinuclear complex [13](PF6)4 reacts with 4,4′-bipyridine (4,4′-bipy) to give the molecular rectangle [15](PF6)8 featuring two bridging dicarbene and two bridging 4,4′-bipy ligands. Complex [13](PF6)4 also reacts with β,β′-bis(triisopropylsiloxy)phenyl-1,4-diisocyanide 16 followed by hydrolysis of the Si–O bonds and intramolecular carbene formation to yield the molecular square [18](BF4)8 featuring bridging NR,NR- and NH,O-substituted dicarbene ligands. Reaction of the dinuclear complex [12](PF6)4 containing a sterically demanding N,N′,N′′,N′′′-substituted dicarbene ligand under otherwise identical reaction conditions did not lead to any molecular rectangles. The molecular square [19](BF4)8 was synthesized from β,β′-bis(triisopropylsiloxy)phenyl-1,4-diisocyanide 16 and [PtCl2(dmpe)] in the presence of AgBF4. It reacts to yield the molecular square [20](BF4)8 with four NH,O-substituted dicarbene ligands by Si–O bond cleavage and subsequent intramolecular cyclization.

Graphical abstract: Molecular rectangles from platinum(ii) and bridging dicarbene, diisocyanide and 4,4′-bipyridine ligands

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Publication details

The article was received on 05 Jul 2013, accepted on 16 Aug 2013, published on 16 Aug 2013 and first published online on 16 Aug 2013


Article type: Paper
DOI: 10.1039/C3DT51813B
Citation: Dalton Trans., 2013,42, 16128-16141
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    Molecular rectangles from platinum(II) and bridging dicarbene, diisocyanide and 4,4′-bipyridine ligands

    M. Schmidtendorf, T. Pape and F. E. Hahn, Dalton Trans., 2013, 42, 16128
    DOI: 10.1039/C3DT51813B

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