The synthesis of N→M intramolecularly coordinated
group
14 and 15 chalcogenites is reported. The N→Sn intramolecularly
coordinated organotin(IV) carbonate L(Ph)SnCO3 (1), where L is the N,C,N-chelating ligand 2,6-(Me2NCH2)2C6H3
–, reacts with SO2 and SeO2 to provide the organotin(IV)
sulfite L(Ph)SnSO3 (4) and selenite [L(Ph)SnSeO3]2 (5), respectively. Treatment of
[LSbO]2 (2) and [LBiO]2 (3) with SeO2 provided the organoantimony and bismuth
selenites LSbSeO3 (6) and [LBiSeO3]3 (7), respectively. Compounds 5–7 are rare examples of mixed element oxides
with well-defined stoichiometry MSeO3 (M = Sn, Sb, Bi).
Compounds 4–7 were characterized
by means of elemental analyses, 1H, 13C, 77Se, and 119Sn NMR spectroscopies, IR spectroscopy,
and single-crystal X-ray diffraction analysis.
Reaction of organoantimony and organobismuth oxides (LSbO)(2) and (LBiO)(2) (where L is [2,6-bis(dimethylamino)methyl]phenyl) with four equivalents of the organoboronic acids gave new heteroboroxines LM[(OBR)(2)O] 1a-2c (for M = Sb: R = Ph (1a), 4-CF(3)C(6)H(4) (1b), ferrocenyl (1c); for M = Bi: R = Ph (2a), 4-CF(3)C(6)H(4) (2b), and ferrocenyl (2c)). Analogously, reaction between organotin carbonate L(Ph)Sn(CO(3)) and two equivalents of organoboronic acids yielded compounds L(Ph)Sn[(OBR)(2)O] (where R = Ph (3a), 4-CF(3)C(6)H(4) (3b), and ferrocenyl (3c)). All compounds were characterized by elemental analysis and NMR spectroscopy. Their structure was described both in solution (NMR studies) and in the solid state (X-ray diffraction analyses 1a, 1c, 2b, 3b, and 3c). All compounds contain a central MB(2)O(3) core (M = Sb, Bi, Sn), and the bonding situation within these rings and their potential aromaticity was investigated by the help of computational methods.
The synthesis and structure of stiba-, stanna- and bismaheteroboroxines of a general formula L(E)M[(OBR)2O] supported by a N,C,N-chelating ligand L [where L = C6H3-2,6-(CH2NMe2)2, M, E = Sb, lone pair or Sn, Ph or Bi, lone pair] is reported. The target compounds are prepared by straightforward one-step reactions between oxides (LMO)2 (M = Sb or Bi) or organotin(iv) carbonate L(Ph)Sn(CO3) with four or two molar equivalents of corresponding organoboronic acid. All compounds were characterized with the help of elemental analysis, multinuclear NMR spectroscopy and on several occasions the molecular structure was determined using single-crystal X-ray diffraction analysis. The influence of both the substitution of the parent organoboronic acid and the central atom used on the feasibility of the condensation reaction was addressed. Furthermore, several heteroboroxines containing nitrogen donor functionality (i.e. NH2, NMe2, CN or 4-pyridyl) included in the boronic acid residue were synthesized and characterized with the aim to prepare boroxine-based covalent frameworks (through intermolecular N→B interactions) containing metal atoms in their structures. Although no such intermolecular bonding was detected in solution of these compounds, it was shown that the organotin(iv) heteroboroxine substituted by 4-pyridyl group forms an infinite polymeric chains via N→B interactions in the solid state. This polymer collapsed back to monomeric units upon dissolution.
The treatment of an intramolecularly coordinated organotin(IV) dichloride, [2,6-(Me2NCH2)2C6H3](Ph)SnCl2 (1), with Li2E (E = S, Se, Te) afforded thermally stable dimeric diarylstannanethione [{2,6-(Me2NCH2)2C6H3}(Ph)Sn(μ-S)]2 (2) and monomeric diarylstannaneselone and -tellurone [{2,6-(Me2NCH2)2C6H3}(Ph)SnE] (E = Se (3), Te (4)). Compounds 2–4 were characterized by means of elemental analyses and 1H, 13C, 77Se, 119Sn, and 125Te NMR spectroscopy. The molecular structures of 2 and 4 were determined by single-crystal X-ray diffraction analysis. Solution NMR studies revealed dependence of the structure of compounds 2 and 3 on the solvent (C6D6 or CDCl3). In addition, the synthesis of dimeric stannanetellurone [{2,6-(Me2NCH2)2C6H3}(Bu)Sn(μ-Te)]2 (5) showed an influence of the organic group R (R = Bu or Ph) on the structure of diorganotin(IV) tellurides 4 and 5.
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