Analysis of Canonical Molecular Orbitals to Identify Fermi Contact Coupling Pathways. 1. Through-Space Transmission by Overlap of P-31 Lone Pairs

Autor(es)

Contreras, Ruben H. ^{[1, 2]} ; Gotelli, Gustavo ^[3] ; Ducati, Lucas C. ^[4] ; Barbosa, Thais A. ^[4] ; Tormena, Claudio F. ^[4]

Afiliação do(s) autor(es)

^[1] Consejo Nacl Invest Cient & Tecn, RA-1033 Buenos Aires, DF - Argentina

^[2] Univ Buenos Aires, Dept Phys, FCEyN, Buenos Aires, DF - Argentina

^[3] Univ Buenos Aires, Dept Pharmaceut Technol, FFyB, Buenos Aires, DF - Argentina

^[4] Univ Estadual Campinas, Dept Organ Chem, Inst Chem, BR-13084971 Sao Paulo - Brazil

• Tipo de documento: Artigo Científico
• Fonte: Journal of Physical Chemistry A; v. 114, n. 2, p. 1044-1051, JAN 21 2010.
• Citações Web of Science: 25

Resumo

In this work, a new approach to studying Coupling pathways for the Fermi contact term of NMR spin-spin Coupling constants (SSCCs) is presented. It is based on the known form of propagating the Fermi hole through a canonical Molecular orbital (CMO). It requires having an adequate spatial description of the relevant canonical molecular orbitals, which are obtained by expanding CMOs in terms of natural bond orbitals (NBOs). For detecting the relevant contributions of CMOs to it given Fermi contact (FC) pathway, the description of the FC in terms of the triplet polarization propagator (PP) is used. To appreciate the potential of this approach, dubbed FCCP-CMO (Fermi contact coupling pathways-CMO), it is applied to analyze the through-space transmission of the FC term of J(PP) SSCCs by overlap of the P lone pairs. This method can be applied using well-known quantum chemistry software without any further modification, which makes it appealing for use as a complement to SSCC Measurements by NMR spectroscopy. (AU)

• Processo FAPESP: 08/06282-0 - Estudo do mecanismo de transmissão de constantes de acoplamento escalar envolvendo o átomo de flúor
• Beneficiário: Roberto Rittner Neto
• Linha de fomento: Auxílio à Pesquisa - Regular
• Processo FAPESP: 06/03980-2 - Interacoes de orbitais e seus efeitos nas constantes de acoplamento escalar em rmn: estudo experimental e teorico.
• Beneficiário: Claudio Francisco Tormena
• Linha de fomento: Auxílio à Pesquisa - Regular