title: Changes in Tricarbastannatrane Transannular N-Sn Bonding upon Complexation Reveal Lewis Base Donicities.
abstract: Hypercoordinated complexes involving tricarbastannatrane cation [N(CH2CH2CH2)3Sn]+with various Lewis bases are investigated in the gas and solution phases using a combination of infrared multiple photon dissociation (IRMPD) spectroscopy, NMR spectroscopy, and density functional theory calculations. Coordination is found to occur at the apical position leading to a pentacoordinated Sn center. Strongly electron donating Lewis bases disrupt the N···Sn transannular interaction and induce higher degrees of geometric distortion at the metal center than weakly donating Lewis bases, an effect that manifests as anharmonic shifts in the vibrational spectra. Once characterized in the gas phase, [N(CH2CH2CH2)3Sn(Lewis base)]+structures were embedded in a dichloroethane polarizable continuum model to investigate solution phase properties. Calculated119Sn NMR chemical shifts were found to be in good agreement with those measured experimentally, thus suggesting that the bonding properties of [N(CH2CH2CH2)3Sn]+are essentially the same in the gas and solution phases.
authors.affiliation: Department of Chemistry, University of Waterloo , Waterloo, OntarioN2L 3G1, Canada.
authors.forename: Petar
authors.initials: P
authors.lastname: Simidzija
authors.affiliation: Department of Chemistry, University of Waterloo , Waterloo, OntarioN2L 3G1, Canada.
authors.forename: Michael J
authors.initials: MJ
authors.lastname: Lecours
authors.affiliation: Department of Chemistry, University of Waterloo , Waterloo, OntarioN2L 3G1, Canada.
authors.forename: Rick A
authors.initials: RA
authors.lastname: Marta
authors.affiliation: Laboratoire Chimie Physique-CLIO, Bâtiment 201, Porte 2, Campus Universitaire d'Orsay , Orsay, 91405, France.
authors.forename: Vincent
authors.initials: V
authors.lastname: Steinmetz
authors.affiliation: Department of Chemistry, University of Waterloo , Waterloo, OntarioN2L 3G1, Canada.
authors.forename: Terrance B
authors.initials: TB
authors.lastname: McMahon
authors.affiliation: Department of Chemistry, University of Waterloo , Waterloo, OntarioN2L 3G1, Canada.
authors.forename: Eric
authors.initials: E
authors.lastname: Fillion
authors.affiliation: Department of Chemistry, University of Waterloo , Waterloo, OntarioN2L 3G1, Canada.
authors.forename: W Scott
authors.initials: WS
authors.lastname: Hopkins