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Issue 45, 2017
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Insertion of terminal alkyne into Pt–N bond of the square planar [PtI2(Me2phen)] complex

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Abstract

The reactivity of [PtX2(Me2phen)] complexes (X = Cl, Br, I; Me2phen = 2,9-dimethyl-1,10-phenanthroline) with terminal alkynes has been investigated. Although the dichlorido species [PtCl2(Me2phen)] exhibits negligible reactivity, the bromido and iodido derivatives lead in short time to the formation of five-coordinate Pt(II) complexes of the type [PtX2(Me2phen)(η2-CH[triple bond, length as m-dash]CR)] (X = Br, I; R = Ph, n-Bu), in equilibrium with the starting reagents. Similar to analogous complexes with simple acetylene, the five coordinate species can also undergo dissociation of an halido ligand and formation of the transient square-planar cationic species [PtX(Me2phen)(η2-CH[triple bond, length as m-dash]CR)]+. This latter can further evolve to give an unusual, sparingly soluble square planar product where the former terminal alkyne is converted into a :C[double bond, length as m-dash]C(H)(R) moiety with the α-carbon bridging the Pt(II) core with one of the two N-donors of coordinated Me2phen. The final product [PtX22-N,C-(Z)-[N with combining low line]1–N10–[C with combining low line][double bond, length as m-dash]C(H)(R)}] (N1–N10 = 2,9-dimethyl-1,10-phenanthroline; X = Br, I) contains a Pt–N–C–C–N–C six-membered chelate ring in a square planar Pt(II) coordination environment.

Graphical abstract: Insertion of terminal alkyne into Pt–N bond of the square planar [PtI2(Me2phen)] complex

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Publication details

The article was received on 27 Sep 2017, accepted on 18 Oct 2017 and first published on 19 Oct 2017


Article type: Paper
DOI: 10.1039/C7DT03644B
Citation: Dalton Trans., 2017,46, 15819-15826
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    Insertion of terminal alkyne into Pt–N bond of the square planar [PtI2(Me2phen)] complex

    M. Benedetti, F. De Castro, V. Lamacchia, C. Pacifico, G. Natile and F. P. Fanizzi, Dalton Trans., 2017, 46, 15819
    DOI: 10.1039/C7DT03644B

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