"Through-space" nuclear spin-spin J(PP) coupling in tetraphosphine ferrocenyl derivatives: a (31)P NMR and X-ray structure correlation study for coordination complexes.
Herein, we report on (31)P(31)P solution-phase "through-space" nuclear spin-spin coupling constants (J(PP)) from a novel family of organometallic tetraphosphine nickel and palladium complexes. These J(PP) constants were accurately determined through NMR iterative simulation based on the second-order spectra obtained for the compounds. The corresponding solid-state X-ray structures of the complexes were determined, and the "through-space" P.P distances are reported. Due to the blocked conformation of the species in solution, a qualitative and semiquantitative experimental correlation is obtained, which links the geometric parameters and the intensity of the corresponding P.P coupling constant. The lone-pair overlap theory developed for (19)F(19)F and (15)N(19)F "through-space" couplings in organic compounds [J. Am. Chem. Soc. 1973, 95, 7747-7752; 2000, 122, 4108-4116] appears to be a reliable foundation on which to account for our results. Based on the reported observations, the lone-pair overlap model is extended to "through-space" (31)P(31)P coupling, and the model is broadened to encompass metal orbital contributions for coordination complexes. Some of the predictions and consequences of the proposed theory are discussed.
Hierso
Jean-Cyrille
JC
Contribution from the Laboratoire de Synthèse et d'Electrosynthèse Organométalliques, UMR-CNRS 5188, Université de Bourgogne, Facultés des Sciences Mirande, 9 Avenue Alain Savary, BP 47870 F-21078 Dijon Cedex, France. jean-cyrille.hierso@u-bourgogne.fr
Fihri
Aziz
A
Ivanov
Vladimir V
VV
Hanquet
Bernard
B
Pirio
Nadine
N
Donnadieu
Bruno
B
Rebière
Bertrand
B
Amardeil
Régine
R
Meunier
Philippe
P