Alvarez, Paula and Garcia, Felipe and Hehn, Joerg P. and Kraus, Florian and Lawson, Gavin T. and Korber, Nikolaus and Mosquera, Marta E. G. and McPartlin, Mary and Moncrieff, David and Pask, Christopher M. and Woods, Anthony D. and Wright, Dominic S. (2007) Reactions of Sn(NMe2)(2) with MPHCy: The effects of alkali metal phosphide coupling (Cy = cyclohexyl; M = Li, Na, K, Rb). CHEMISTRY-A EUROPEAN JOURNAL, 13 (4). pp. 1078-1089. ISSN 0947-6539, 1521-3765
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The reactions of the Sn-II base Sn(NMe2)(2) with CyPHM (Cy=cyclohexyl) produce a range of products, depending primarily on the alkali metal (M) involved. The 1:3 stoichiometric reaction of Sn(NMe2)(2) with CyPHNa in the presence of the Lewis base donor PMDETA (PMDETA=Me2NCH2- CH2)(2)NMe) gives [(Na(.)PMDETA)(2){Sn-(mu-PCY)}(3)] (3), containing the electron-deficient [(Sn(mu-PCy)(3)](2-) dianion. Natural bond order (NBO) and electron localisation function (ELF) calculations show that this species is described most appropriately by a two-electron, three-centre Sn-3 bonding model. Evidence that 3 results from phosphide coupling is provided by the 1:1 reaction of Sn(NMe2)(2) with CyPHNa in the presence of PMDETA, which gives 3 and trace amounts of (Na-PMDETA)(2)[{Sn(mu-PCy)}(2)( mu-PCyPCy)] (4) (containing one pCypCy(2-) dianion). Greater extents of phosphide coupling are observed as the size of the Group 1 metal is increased. Thus, the 1:3 reaction of Sn(NMe2)(2) with CyPHK in THF gives the co-crystalline product {(K(.)2THF)(2)[{Sn(mu-PCyPCy)}(2)( mu-PCy)]}(0.9){(K(.)2THF)(2)[{Sn-(mu-PCy)}(2)[{Sn-(mu-PCyPCy]}(0.1) (5) (containing [{Sn(mu-PCyPCy)}(2)(mu-pCy)](2-) and [{Sn(mu-PCy)}(2)(mu-PCyPCy)](2-) dianions), whereas the analogous reaction of Sn(NMe2)2 with RbPHCy gives [Rb(.)PMDETA{(CyP)(3)SnP(H)Cy}] (6) (containing a cyclic {(CYP)(3)Sn} unit).
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | ELECTRON LOCALIZATION FUNCTION; CORRELATED MOLECULAR CALCULATIONS; STABLE HOMOPOLYATOMIC ANIONS; SOLID-STATE STRUCTURE; GAUSSIAN-BASIS SETS; CRYSTAL-STRUCTURES; CHEMICAL-BOND; TOPOLOGICAL ANALYSIS; STRUCTURAL-CHARACTERIZATION; ZINTL COMPOUNDS; cage compounds; main group elements; phosphorus; structure elucidation; tin |
| Subjects: | 500 Science > 540 Chemistry & allied sciences |
| Divisions: | Chemistry and Pharmacy > Institut für Anorganische Chemie > Arbeitskreis Prof. Dr. Nikolaus Korber |
| Depositing User: | Dr. Gernot Deinzer |
| Date Deposited: | 11 Jan 2021 10:40 |
| Last Modified: | 11 Jan 2021 10:40 |
| URI: | https://pred.uni-regensburg.de/id/eprint/33362 |
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