Organotin(IV) Derivatives of Some O,C,O-Chelating Ligands

Abstract

The series of organotin(IV) complexes L 1-3 SnPh n Cl 3-n , where L 1-3 are O,C,O-chelating ligands (called the pincer ligands), 2,6-bis(alkoxymethyl)phenyl-, 2,6-, have been synthesized and characterized by 1 H, 13 C, and 119 Sn NMR spectroscopy, MS-ESI spectrometry, and elemental analysis. The structure of selected compounds L 1 SnPh 3 (1), L 1 SnPh 2 Cl (2), L 1 SnPhCl 2 (3), L 1 SnCl 3 (4), L 2 SnPhCl 2 (7), and L 3 SnPhCl 2 (11) was studied by X-ray crystallography and 119 Sn CP/ MAS NMR spectroscopy in the solid state. The determination of crystal structures reveals the similarity of all the shapes of coordination polyhedra. The deformations of the shapes of coordination polyhedra depend on the degree of donor-acceptor Sn-O interaction (from very weak (interatomic distance Sn-O 2.963(1) Å) to medium-strong (2.475(1) Å)), which increases with increasing Lewis acidity of the tin atom in the L 1-3 SnPh n Cl 3-n entities and decreases with increasing steric demands of substituents R (from Me to t-Bu). NMR spectroscopy indicates a similar structural arrangement of the studied compounds in solution.

Structural study of C,N‐chelated monoorganotin(IV) halides

“…22 and they are probably the products of a reaction of compounds with water molecule in an ion trap. This finding is supported by the fact that the spectra measured from single crystal of 1a are identical to those of analytically pure 1.…”

Close contacts involving germanium and tin in crystal structures: experimental evidence of tetrel bonds

“…1, left) seems to be determined by two intramolecular Sn···O TBs [48]. One interaction distance is slightly shorter than the other, with the two Nc values being 0.76 and 0.78.…”

17O NMR spectra of some organotin(IV) compounds containing O,C,O-chelating ligands

“…7,8 The 17 O NMR spectra were recorded on Bruker AMX360 and AVANCE500 spectrometers at 48.84 and 67.82 MHz respectively. The spectra were measured at 295 K. The instrumental settings were as follows: spectral width 40 kHz, 4K data points, pulse width 12 ms, acquisition time 54 ms, relaxation delay 100 ms, DE 100-150 µs, 20 000-200 000 scans, line broadening 250 Hz and CDCl 3 internal lock.…”

“…In organotin(IV) compounds measured, the 17 O chemical shifts are shifted considerably to higher frequencies (Table 1) as a consequence of the substitution of a phenyl group by a chlorine atom (increasing Lewis acidity of the tin center -compare the data for compounds 1c, 1d and 1e, Table 1). We tried to correlate the determined molecular structure parameters in the solid state using X-ray diffraction methods 7,8 for 1c, 1d, 1e-4e, especially the oxygen-tin bond lengths (290.8 and 296.6 pm for 1c, 256.7, 258.6, 289.1 and 299.3 pm (two independent molecules in the crystal unit cell) for 1d, 261.9 and 265.5 pm for 1e, 244.7 and 286.4 pm for 2e, 247.5 and 298.5 pm for 3e, and 277.5 and 288. coordination mode of Sn, C-C-O-C torsion angles (similar to carboxylic acids derivatives) 9a or molecular dynamics). 7,8 On the further representative set of compounds (diorganotin derivatives 1e-4e), the dependence of υ( 17 O) on the steric hindrance of the ligand used and the electronic properties of its alkoxy substituent might be shown ( in Fig.…”

“…The differences between both couples of compounds are probably caused by the above-mentioned phenomena (slightly different types of tin coordination polyhedra that change with the ligand used). 7,8 …”