TY - JOUR
T1 - Triorganotin cations stabilized by intramolecular SnN coordination; synthesis and characterization of {C,N,N′-2,6-bis[(dimethylamino)methyl]phenyl}diorganotin bromides {A figure is presented}
AU - van Koten, Gerard
AU - Jastrzebski, Johann T B H
AU - Noltes, Jan G.
AU - Spek, Anthony L.
AU - Schoone, Jean C.
PY - 1978/3/28
Y1 - 1978/3/28
N2 - The synthesis of {2,6-bis[(dimethylamino)methyl]phenyl}diorganotin bromides, 2,6-(Me2NCH2)2C6H3SnRR′+ Br- is described. The compounds in which R = R′ = Me or Et and R = Me, R′ = Ph are extremely soluble in water and other polar solvents and insoluble or slightly soluble (R = R′ = Et) in apolar solvents. The diphenyl compounds shows the opposite solubility behaviour. The dimethyl compound is completely dissociated in water in to a triorganotin of 84.8 ohm-1 cm-1 (1/1 electrolyte). NMR spectroscopy reveals that the triorganotin cation has a TBP structure in which the N atoms occupy axial sites. Dynamic NMR spectra of the methylphenyl compound show that above -90°C ratedetermining SnN dissociation occurs and that above 5°C second process, involving rate-determining rotation of the substituted aryl group around the (N2)CSn bond begins. An X-ray investigation of single crystals of the dimethyl compound, which is unstable towards X-rays, establishes the ionic structure of the triorganotin halide in the solid (shortest SnBr 4.99 Å) as well as the molecular geometry of the triorganotin cation. Crystals are monoclinic, space group P21/n with Z = 4 in a unit cell of dimensions: a = 11.13(1), b = 16.73(2), c =10.10(1) Å, and β 114.2(1)°.
AB - The synthesis of {2,6-bis[(dimethylamino)methyl]phenyl}diorganotin bromides, 2,6-(Me2NCH2)2C6H3SnRR′+ Br- is described. The compounds in which R = R′ = Me or Et and R = Me, R′ = Ph are extremely soluble in water and other polar solvents and insoluble or slightly soluble (R = R′ = Et) in apolar solvents. The diphenyl compounds shows the opposite solubility behaviour. The dimethyl compound is completely dissociated in water in to a triorganotin of 84.8 ohm-1 cm-1 (1/1 electrolyte). NMR spectroscopy reveals that the triorganotin cation has a TBP structure in which the N atoms occupy axial sites. Dynamic NMR spectra of the methylphenyl compound show that above -90°C ratedetermining SnN dissociation occurs and that above 5°C second process, involving rate-determining rotation of the substituted aryl group around the (N2)CSn bond begins. An X-ray investigation of single crystals of the dimethyl compound, which is unstable towards X-rays, establishes the ionic structure of the triorganotin halide in the solid (shortest SnBr 4.99 Å) as well as the molecular geometry of the triorganotin cation. Crystals are monoclinic, space group P21/n with Z = 4 in a unit cell of dimensions: a = 11.13(1), b = 16.73(2), c =10.10(1) Å, and β 114.2(1)°.
UR - http://www.scopus.com/inward/record.url?scp=0001145328&partnerID=8YFLogxK
U2 - 10.1016/S0022-328X(00)90980-X
DO - 10.1016/S0022-328X(00)90980-X
M3 - Article
AN - SCOPUS:0001145328
SN - 0022-328X
VL - 148
SP - 233
EP - 245
JO - Journal of Organometallic Chemistry
JF - Journal of Organometallic Chemistry
IS - 3
ER -