title: "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.
abstract: 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.
authors.affiliation: 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
authors.forename: Jean-Cyrille
authors.initials: JC
authors.lastname: Hierso
authors.forename: Aziz
authors.initials: A
authors.lastname: Fihri
authors.forename: Vladimir V
authors.initials: VV
authors.lastname: Ivanov
authors.forename: Bernard
authors.initials: B
authors.lastname: Hanquet
authors.forename: Nadine
authors.initials: N
authors.lastname: Pirio
authors.forename: Bruno
authors.initials: B
authors.lastname: Donnadieu
authors.forename: Bertrand
authors.initials: B
authors.lastname: Rebière
authors.forename: Régine
authors.initials: R
authors.lastname: Amardeil
authors.forename: Philippe
authors.initials: P
authors.lastname: Meunier