title: Intermolecular (119)Sn,(31)P Through-Space Spin-Spin Coupling in a Solid Bivalent Tin Phosphido Complex.
abstract: A bivalent tin complex [Sn(NP)2] (NP = [(2-Me2NC6H4)P(C6H5)](-)) was prepared and characterized by X-ray diffraction and solution and solid-state nuclear magnetic resonance (NMR) spectroscopy. In agreement with the X-ray structures of two polymorphs of the molecule, (31)P and (119)Sn CP/MAS NMR spectra revealed one crystallographic phosphorus and tin site with through-bond (1)J((117/119)Sn,(31)P) and through-space (TS)J((117/119)Sn,(31)P) spin-spin couplings. Density functional theory (DFT) calculations of the NMR parameters confirm the experimental data. The observation of through-space (TS)J((117/119)Sn,(31)P) couplings was unexpected, as the distances of the phosphorus atoms of one molecule and the tin atom of the neighboring molecule (>4.6 Å) are outside the sum of the van der Waals radii of the atoms P and Sn (4.32 Å). The intermolecular Sn···P separations are clearly too large for bonding interactions, as supported by a natural bond orbital (NBO) analysis.
authors.affiliation: Institut für Anorganische Chemie, Universität Tübingen , Auf der Morgenstelle 18, 72076 Tübingen, Germany.|Theoretische Chemie, University of Munich (LMU Munich) , Butenandtstraße 7, 81377 Munich, Germany.
authors.forename: Janet
authors.initials: J
authors.lastname: Arras
authors.affiliation: Institut für Anorganische Chemie, Universität Tübingen , Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Klaus
authors.initials: K
authors.lastname: Eichele
authors.affiliation: Theoretische Chemie, University of Munich (LMU Munich) , Butenandtstraße 7, 81377 Munich, Germany.
authors.forename: Boris
authors.initials: B
authors.lastname: Maryasin
authors.affiliation: Institut für Anorganische Chemie, Universität Tübingen , Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Hartmut
authors.initials: H
authors.lastname: Schubert
authors.affiliation: Theoretische Chemie, University of Munich (LMU Munich) , Butenandtstraße 7, 81377 Munich, Germany.
authors.forename: Christian
authors.initials: C
authors.lastname: Ochsenfeld
authors.affiliation: Institut für Anorganische Chemie, Universität Tübingen , Auf der Morgenstelle 18, 72076 Tübingen, Germany.
authors.forename: Lars
authors.initials: L
authors.lastname: Wesemann