title: Long-range through-bond heteronuclear communication in platinum complexes.
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.
authors.affiliation: Department of Organic Chemistry, The Weizmann Institute of Science, 76100 Rehovot, Israel.
authors.forename: Olena V
authors.initials: OV
authors.lastname: Zenkina
authors.forename: Leonid E
authors.initials: LE
authors.lastname: Konstantinovski
authors.forename: Linda J W
authors.initials: LJ
authors.lastname: Shimon
authors.forename: Yael
authors.initials: Y
authors.lastname: Diskin-Posner
authors.forename: Mark A
authors.initials: MA
authors.lastname: Iron
authors.forename: Milko E
authors.initials: ME
authors.lastname: van der Boom