Polyoxometalate Derivatives with Multiple Organic Groups. 2. Synthesis and Structures of Tris(organotin) α, β-Keggin Tungstosilicates

Eight tris(organotin)-substituted Keggin tungstosilicate heteropolyanions have been synthesized and characterized by elemental analysis, infrared and Mössbauer spectroscopy, multinuclear NMR, and X-ray crystallography. The new anions contain α- or β-SiW9O3410- moieties and are of two structural types, [(RSn)3(SiW9O37)]7- (R, isomer:  Ph, α-, 1; n-Bu, α-, 2; Ph, β-, 3; n-Bu, β-, 4) and [(RSnOH)3(SiW9O34)2]14- (Ph, α-, 5; n-Bu, α-, 6; Ph, β-, 7; n-Bu, β-, 8). Crystals of Cs4H3[(PhSn)3(SiW9O37)]·8H2O (anion 3) are monoclinic, space group C2/c, with lattice constants a = 48.91(2) Å, b = 12.111(3) Å, c = 20.334(9) Å, β = 102.30°, and Z = 8. The anion has nominal C3v symmetry and has a structure with three corner-shared WO6 octahedra of the β-Keggin anion replaced by three PhSnO5 groups. Crystals of Cs9H5[(BuSnOH)3(SiW9O34)2]·36H2O (anion 6) are tetragonal, space group P4̄21m, with lattice constants a = b = 29.005(4) Å, c = 13.412(4) Å, and Z = 4. The anion has the anticipated D3h symmetry and contains three BuSnOH groups sandwiched between A,α-SiW9O3410- anions

Metal- and Ligand-Centered Monoelectronic Oxidation of μ-Nitrido[((tetraphenylporphyrinato)manganese)(phthalocyaninatoiron)], [(TPP)Mn−N−FePc]. X-ray Crystal Structure of the Fe(IV)-Containing Species [(THF)(TPP)Mn−N−FePc(H₂O)](I₅)·2THF

The reaction of μ-nitrido[((tetraphenylporphyrinato)manganese)(phthalocyaninatoiron)], [(TPP)Mn−N−FePc], with I2 in THF develops with the formation of two different species, i.e., [(THF)(TPP)Mn−N−FePc(H2O)](I5)·2THF (I) and [(TPP)MnIV−N−FeIIIPc](I3) (II). On the basis of single-crystal X-ray work and Mössbauer, EPR, Raman, and magnetic susceptibility data, I, found to be isostructural with the corresponding Fe−Fe complex, is shown to contain a low-spin triatomic MnIVNFeIV system (metal-centered oxidation). Data at hand for II (Mössbauer, EPR, Raman) show, instead, that oxidation takes place at one of the two macrocycles, very likely TPP (ligand-centered oxidation). The same cationic fragment present in I, and containing the MnIVNFeIV bond system, is also obtained when (TPP)Mn−N−FePc is allowed to react in THF with (phen)SbCl6 (molar ratio 1:1). There are indications that the use of (phen)SbCl6 in excess (2:1 molar ratio), in benzene, probably determines further oxidation with the formation of a species showing the combined presence of the MnIV−FeIV couple and of a π-cation radical

Preparation of Benzylstannanes by Zinc-Mediated Coupling of Benzyl Bromides with Organotin Derivatives. Physicochemical Characterization and Crystal Structures

Benzyltrialkyl- (1−13) and benzyltriphenylstannanes (16−22) have been easily prepared in a one-pot synthesis via coupling reaction of benzyl bromide derivatives (C6H5CH2Br and XYC6H3CH2Br, X = H, Y = o-, m-, p-CH3, o-, m-, p-F, o-, m-Cl, and p-Br; X = o-F, Y = p-Br) with R3SnCl compounds (R = Et, Pr, Bu, and Ph) in THF/H2O (NH4Cl) medium mediated by zinc powder. Such coupling also occurs with (Bu3Sn)2O. Dibenzyldibutylstannane (15) is prepared by reaction of benzyl bromide with Bu2SnCl2 or (Bu2SnCl)2O, and (2-naphthylmethyl)tributylstannane (14) by reaction of 2-(bromomethyl)naphthalene with Bu3SnCl. 13C- and 119Sn-NMR data are reported for all compounds, and Mössbauer data for benzyltributylstannanes 10 and 11 and benzyltriphenylstannanes 16−18 and 20−22. The crystal structures of Ph3SnBn, with Bn = o- (17) and m-ClC6H4CH2 (18) and o- (20) and m-FC6H4CH2 (21) have been determined

Preparation of Benzylstannanes by Zinc-Mediated Coupling of Benzyl Bromides with Organotin Derivatives. Physicochemical Characterization and Crystal Structures

Benzyltrialkyl- (1−13) and benzyltriphenylstannanes (16−22) have been easily prepared in a one-pot synthesis via coupling reaction of benzyl bromide derivatives (C6H5CH2Br and XYC6H3CH2Br, X = H, Y = o-, m-, p-CH3, o-, m-, p-F, o-, m-Cl, and p-Br; X = o-F, Y = p-Br) with R3SnCl compounds (R = Et, Pr, Bu, and Ph) in THF/H2O (NH4Cl) medium mediated by zinc powder. Such coupling also occurs with (Bu3Sn)2O. Dibenzyldibutylstannane (15) is prepared by reaction of benzyl bromide with Bu2SnCl2 or (Bu2SnCl)2O, and (2-naphthylmethyl)tributylstannane (14) by reaction of 2-(bromomethyl)naphthalene with Bu3SnCl. 13C- and 119Sn-NMR data are reported for all compounds, and Mössbauer data for benzyltributylstannanes 10 and 11 and benzyltriphenylstannanes 16−18 and 20−22. The crystal structures of Ph3SnBn, with Bn = o- (17) and m-ClC6H4CH2 (18) and o- (20) and m-FC6H4CH2 (21) have been determined