Long-range through-bond heteronuclear communication in platinum complexes

Olena V. Zenkina, Leonid E. Konstantinovski, Linda J W Shimon, Yael Diskin-Posner, Mark A. Iron, Milko van der Boom

Research output: Contribution to journalArticle

2 Citations (Scopus)

Abstract

Four analogous platinum stilbene- and stilbazole-based complexes exhibit unusual long-range heteronuclear spin-spin coupling in solution. Single crystal analysis and NMR experiments show that the 19F, 31P, and 195Pt nuclei communicate over large distances (0.9-1.3 nm) through bond rather than through space. Spin-spin couplings between 195Pt and 19F over seven bonds and between 31P and 19F over eight bonds are observed with 7JPtF = 2.9 Hz and 8JPF = 11.8 Hz. Remarkably, a very large spin coupling between 195Pt and 19F over six bonds (6J PtF = 40.1 Hz) is also observed in a structurally related pyridinium complex. Experimental and gNMR (version 5.0) simulated 19F{ 1H}, 31P{1H}, and 195Pt{ 1H} spectra of the complexes reveal a three-spin AMY system (A = 31P, M = 31P, Y = 19F) or a five-spin AMY3 flanked by a four-spin AMXY or a six-spin AMXY3 system (X = 195Pt), respectively. Density functional theory calculations at the PBE0/SDD level of theory show a π-conjugated metal-ligand network, which may contribute to the experimentally observed spin-spin interactions.

Original languageEnglish
Pages (from-to)4021-4030
Number of pages10
JournalInorganic Chemistry
Volume48
Issue number9
DOIs
Publication statusPublished - May 4 2009

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Stilbenes
Platinum
Density functional theory
platinum
Metals
communication
Nuclear magnetic resonance
Single crystals
Ligands
Communication
Experiments
spin-spin coupling
stilbene
density functional theory
nuclear magnetic resonance
ligands
nuclei
single crystals
metals

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Physical and Theoretical Chemistry

Cite this

Zenkina, O. V., Konstantinovski, L. E., Shimon, L. J. W., Diskin-Posner, Y., Iron, M. A., & van der Boom, M. (2009). Long-range through-bond heteronuclear communication in platinum complexes. Inorganic Chemistry, 48(9), 4021-4030. https://doi.org/10.1021/ic801940h

Long-range through-bond heteronuclear communication in platinum complexes. / Zenkina, Olena V.; Konstantinovski, Leonid E.; Shimon, Linda J W; Diskin-Posner, Yael; Iron, Mark A.; van der Boom, Milko.

In: Inorganic Chemistry, Vol. 48, No. 9, 04.05.2009, p. 4021-4030.

Research output: Contribution to journalArticle

Zenkina, OV, Konstantinovski, LE, Shimon, LJW, Diskin-Posner, Y, Iron, MA & van der Boom, M 2009, 'Long-range through-bond heteronuclear communication in platinum complexes', Inorganic Chemistry, vol. 48, no. 9, pp. 4021-4030. https://doi.org/10.1021/ic801940h
Zenkina OV, Konstantinovski LE, Shimon LJW, Diskin-Posner Y, Iron MA, van der Boom M. Long-range through-bond heteronuclear communication in platinum complexes. Inorganic Chemistry. 2009 May 4;48(9):4021-4030. https://doi.org/10.1021/ic801940h
Zenkina, Olena V. ; Konstantinovski, Leonid E. ; Shimon, Linda J W ; Diskin-Posner, Yael ; Iron, Mark A. ; van der Boom, Milko. / Long-range through-bond heteronuclear communication in platinum complexes. In: Inorganic Chemistry. 2009 ; Vol. 48, No. 9. pp. 4021-4030.
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