769131-49-9Relevant academic research and scientific papers
Through-space nuclear spin-spin JPP coupling in tetraphosphine ferrocenyl derivatives: A 31P NMR and x-ray structure correlation study for coordination complexes
Hierso, Jean-Cyrille,Fihrin, Aziz,Ivanov, Vladimir V.,Hanquet, Bernard,Pirio, Nadine,Donnadieu, Bruno,Rebiere, Bertrand,Amardeil, Regine,Meunier, Philippe
, p. 11077 - 11087 (2004)
Herein, we report on 31P31P solution-phase through-space nuclear spin-spin coupling constants (JPP) from a novel family of organometallic tetraphosphine nickel and palladium complexes. These JPP 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 19F19F and 15N 19F 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 31P31P 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.
