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  • Title: Long-range through-bond heteronuclear communication in platinum complexes.
    Author: Zenkina OV, Konstantinovski LE, Shimon LJ, Diskin-Posner Y, Iron MA, van der Boom ME.
    Journal: Inorg Chem; 2009 May 04; 48(9):4021-30. PubMed ID: 19338319.
    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 (19)F, (31)P, and (195)Pt nuclei communicate over large distances (0.9-1.3 nm) through bond rather than through space. Spin-spin couplings between (195)Pt and (19)F over seven bonds and between (31)P and (19)F over eight bonds are observed with (7)J(PtF) = 2.9 Hz and (8)J(PF) = 11.8 Hz. Remarkably, a very large spin coupling between (195)Pt and (19)F over six bonds ((6)J(PtF) = 40.1 Hz) is also observed in a structurally related pyridinium complex. Experimental and gNMR (version 5.0) simulated (19)F{(1)H}, (31)P{(1)H}, and (195)Pt{(1)H} spectra of the complexes reveal a three-spin AMY system (A = (31)P, M = (31)P, Y = (19)F) or a five-spin AMY(3) flanked by a four-spin AMXY or a six-spin AMXY(3) system (X = (195)Pt), respectively. Density functional theory calculations at the PBE0/SDD level of theory show a pi-conjugated metal-ligand network, which may contribute to the experimentally observed spin-spin interactions.
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