TY - JOUR
T1 - Long-range through-bond heteronuclear communication in platinum complexes
AU - Zenkina, Olena V.
AU - Konstantinovski, Leonid E.
AU - Shimon, Linda J.W.
AU - Diskin-Posner, Yael
AU - Iron, Mark A.
AU - Van Der Boom, Milko E.
PY - 2009/5/4
Y1 - 2009/5/4
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=66149091607&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=66149091607&partnerID=8YFLogxK
U2 - 10.1021/ic801940h
DO - 10.1021/ic801940h
M3 - Article
C2 - 19338319
AN - SCOPUS:66149091607
VL - 48
SP - 4021
EP - 4030
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 9
ER -