TY - JOUR
T1 - Stable Divalent Triarylstannates R3SnLi Derived from 2-[(Dimethylamino)methyl]phenyllithium and SnCl2 or R2Sn
AU - Jastrzebski, Johann T B H
AU - Van Klaveren, Mayra
AU - Van Koten, Gerard
PY - 2015/6/8
Y1 - 2015/6/8
N2 - The triarylstannate lithium compound [{κ1-C-(2-Me2NCH2C6H4)2}{κ2-C, N-(2-Me2NCH2C6H4)}SnLi(THF)2] (3a) was obtained in 63% yield from the reaction of 2-Me2NCH2C6H4Li (1) with SnCl2 in THF. Quantitative formation of 3a was also observed on reacting 1 with [κ2-C, N-(2-Me2NCH2C6H4)2Sn] (2). Removal of one THF molecule occurred when 3a was kept in vacuo; this process afforded [{κ1-C-(2-Me2NCH2C6H4)}{κ2-C, N-(2-Me2NCH2C6H4)2}SnLi(THF)2] (3b). Also, THF-free (2-Me2NCH2C6H4)3SnLi (3c) is likewise accessible. In the solid state (X-ray) both 3a and 3b are monomeric; notable structural features are the Sn-Li distances (2.860(6) and 2.72(2) Å, respectively) and the distortion of the tetrahedral geometry at Sn in the direction of a trigonal pyramidal one. In 3a, one of the 2-Me2NCH2C6H4 anions is C-bonded to Sn, while N-coordination occurs to Li; in 3b, two of the three 2-Me2NCH2C6H4 anions are κ2-C,N bonded. 1H, 13C, 119Sn, and 7Li NMR spectroscopic studies of the species 3 in toluene showed that both 3a and 3b are monomeric in solution; at temperatures below 253 K, via both the 119Sn and 7Li NMR spectra (toluene-d8), the 119Sn-7Li coupling (289 Hz) is nicely resolved. The exchange of aryl groupings (vide infra) as well as between coordinated and free-NMe2 substituents remains fast on the NMR time scale at 183 K. 2D 1H-1H EXSY spectroscopy confirmed that the 2-Me2NCH2C6H4 groups present in stannate 3b and bisaryltin(II) 2 undergo chemical exchange. The 2D 7Li-7Li EXSY spectrum points to the occurrence of chemical exchange of the lithium atoms of stannate 3b and aryllithium 1 (Chemical Equation).
AB - The triarylstannate lithium compound [{κ1-C-(2-Me2NCH2C6H4)2}{κ2-C, N-(2-Me2NCH2C6H4)}SnLi(THF)2] (3a) was obtained in 63% yield from the reaction of 2-Me2NCH2C6H4Li (1) with SnCl2 in THF. Quantitative formation of 3a was also observed on reacting 1 with [κ2-C, N-(2-Me2NCH2C6H4)2Sn] (2). Removal of one THF molecule occurred when 3a was kept in vacuo; this process afforded [{κ1-C-(2-Me2NCH2C6H4)}{κ2-C, N-(2-Me2NCH2C6H4)2}SnLi(THF)2] (3b). Also, THF-free (2-Me2NCH2C6H4)3SnLi (3c) is likewise accessible. In the solid state (X-ray) both 3a and 3b are monomeric; notable structural features are the Sn-Li distances (2.860(6) and 2.72(2) Å, respectively) and the distortion of the tetrahedral geometry at Sn in the direction of a trigonal pyramidal one. In 3a, one of the 2-Me2NCH2C6H4 anions is C-bonded to Sn, while N-coordination occurs to Li; in 3b, two of the three 2-Me2NCH2C6H4 anions are κ2-C,N bonded. 1H, 13C, 119Sn, and 7Li NMR spectroscopic studies of the species 3 in toluene showed that both 3a and 3b are monomeric in solution; at temperatures below 253 K, via both the 119Sn and 7Li NMR spectra (toluene-d8), the 119Sn-7Li coupling (289 Hz) is nicely resolved. The exchange of aryl groupings (vide infra) as well as between coordinated and free-NMe2 substituents remains fast on the NMR time scale at 183 K. 2D 1H-1H EXSY spectroscopy confirmed that the 2-Me2NCH2C6H4 groups present in stannate 3b and bisaryltin(II) 2 undergo chemical exchange. The 2D 7Li-7Li EXSY spectrum points to the occurrence of chemical exchange of the lithium atoms of stannate 3b and aryllithium 1 (Chemical Equation).
UR - http://www.scopus.com/inward/record.url?scp=84931275365&partnerID=8YFLogxK
U2 - 10.1021/om5012215
DO - 10.1021/om5012215
M3 - Article
SN - 0276-7333
VL - 34
SP - 2600
EP - 2607
JO - Organometallics
JF - Organometallics
IS - 11
ER -