Experimental and theoretical studies on the platinum-mediated selective C(sp)-Si bond cleavage of alkynylsilanes

Yasuhiro Okuda, Yuya Ishiguro, Seiji Mori, Kiyohiko Nakajima, Yasushi Nishihara

Research output: Contribution to journalArticle

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Abstract

A series of cis-alkynyl(silyl)platinum(II) complexes was prepared via the chemoselective C(sp)-Si bond cleavage of alkynylsilanes by a platinum(0) complex ligated with the P-N hemilabile bidentate ligand. The coordination of the triple bond to the platinum center triggers selective C(sp)-Si bond cleavage. Hammett plots of the 31P{1H} NMR spectroscopic properties (δ and J values) reflect an electronic effect on platinum(II) complexes; trans substituents of arylethynyl groups are influenced, but cis-positioned silyl groups are not affected, as evidenced by 29Si{1H} NMR. In comparison, Hammett plots show that C(sp)-Si bond cleavage rates are accelerated by electron-rich alkynylsilanes, which is opposite to the ordinary oxidative addition of aryl halides to transition metals often observed in catalytic cross-coupling reactions. A DFT calculation reveals that intermediates and transition states are stabilized by electron-rich alkynylsilanes and that the five-membered hemilabile P-N ligand is essential, in which a reactive electron-deficient 14-electron platinum(0) species is produced via the dissociation of nitrogen, giving rise to a monodentate phosphine coordination. Electron-rich alkynylsilanes allow decreased π back-donation from the platinum center to the ligand, accelerating the dissociation of the more labile nitrogen. Steric congestion between diisopropylphosphino and silyl groups thermodynamically disfavors C(sp)-Si bond cleavage.

Original languageEnglish
Pages (from-to)1878-1889
Number of pages12
JournalOrganometallics
Volume33
Issue number7
DOIs
Publication statusPublished - Apr 14 2014

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Platinum
cleavage
platinum
Electrons
phosphine
Ligands
electrons
ligands
Nitrogen
plots
Nuclear magnetic resonance
dissociation
nitrogen
nuclear magnetic resonance
congestion
cross coupling
Electron transitions
phosphines
Discrete Fourier transforms
halides

ASJC Scopus subject areas

  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

Experimental and theoretical studies on the platinum-mediated selective C(sp)-Si bond cleavage of alkynylsilanes. / Okuda, Yasuhiro; Ishiguro, Yuya; Mori, Seiji; Nakajima, Kiyohiko; Nishihara, Yasushi.

In: Organometallics, Vol. 33, No. 7, 14.04.2014, p. 1878-1889.

Research output: Contribution to journalArticle

Okuda, Yasuhiro ; Ishiguro, Yuya ; Mori, Seiji ; Nakajima, Kiyohiko ; Nishihara, Yasushi. / Experimental and theoretical studies on the platinum-mediated selective C(sp)-Si bond cleavage of alkynylsilanes. In: Organometallics. 2014 ; Vol. 33, No. 7. pp. 1878-1889.
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