om5002759_si_001.cif (139.59 kB)
Reactivity Studies on an Intramolecularly Coordinated Organotin(IV) Carbonate
dataset
posted on 2014-06-23, 00:00 authored by Barbora Mairychová, Petr Štěpnička, Aleš Ru̇žička, Libor Dostál, Roman JamborThe
reactivity of the intramolecularly coordinated organotin(IV)
carbonate L(Ph)Sn(CO3) (1), where L stands
for an N,C,N-chelating ligand, 2,6-(Me2NCH2)2C6H3, was studied. The treatment of 1 with ferrocene-based carboxylic acids RCOOH afforded the
organotin(IV) dicarboxylates LPhSn(O2CR)2, where
R is ferrocenyl (2), 2-ferrocenylethyl (3), and [(1E)-2-ferrocenyl]ethenyl (4). Surprisingly, compounds 2–4 are
sensitive to moisture and easily hydrolyze with condensation into
the corresponding hexameric organotin oxo clusters (PhSnO)6(O2CR)6 (R = ferrocenyl (5), 2-ferrocenylethyl
(6), and [(1E)-2-ferrocenyl]ethenyl
(7)) possessing a Sn6O6 drumlike
core. On the other hand, treatment of 1 with non-carboxylic
acids such as HOTf, H3BO3, H3PO3, and t-BuPO3H2 afforded
the triflate salt of a cationic organotin(IV) hydroxide {[LPh(H2O)Sn(μ-OH)]2}(OTf)2 (8), stannaboroxine LPhSnB2O3(OH)2 (9), and organotin(IV) phosphite [L(Ph)Sn(HPO3)]2 (10) and phosphonate {[L(Ph)Sn]2(μ-OH2)(μ-t-BuPO3)2} (11), respectively. Compounds 2–11 were characterized by elemental analysis
and multinuclear NMR spectroscopy, and the molecular structures of
compounds 6 and 9–11 were determined by single-crystal X-ray diffraction analysis. In
addition, compounds 2–7 bearing redox-active
ferrocenyl groups were studied by cyclic voltammetry.
