Christina Dietz

Novel stannatranes of the type N(CH2CMe2O)3SnX (X = OR, SR, OC(O)R, SP(S)Ph2, halogen). Synthesis, molecular structures, and electrochemical properties.

The syntheses of the stannatrane derivatives of the type N(CH(2)CMe(2)O)(3)SnX (1, X = Ot-Bu; 2, X = Oi-Pr; 3, X = 2,6-Me(2)C(6)H(3)O; 4, X = p-t-BuC(6)H(4)O; 5, X = p-NO(2)C(6)H(4)O; 6, X = p-FC(6)H(4)O; 7, X = p-PPh(2)C(6)H(4)O; 8, X = p-MeC(6)H(4)S; 9, X = o-NH(2)C(6)H(4)O; 10, X = OCPh(2)CH(2)NMe(2); 11, X = Ph(2)P(S)S; 12, X = p-t-BuC(6)H(4)C(O)O; 13, X = Cl; 14, X = Br; 15, X = I; 16, X = p-N(CH(2)CMe(2)O)(3)SnOSiMe(2)C(6)H(4)SiMe(2)O) are reported. The compounds are characterized by X-ray diffraction analyses (3-8, 11-16), multinuclear NMR spectroscopy, (13)C CP MAS (14) and (119)Sn CP MAS NMR (13, 14) spectroscopy, mass spectrometry and osmometric molecular weight determination (13). Electrochemical measurements show that anodic oxidation of the stannatranes 4 and 8 occurs via electrochemically reversible electron transfer resulting in the corresponding cation radicals. The latter were detected by cyclic voltammetry (CV) and real-time electron paramagnetic resonance spectroscopy (EPR). DFT calculations were performed to compare the stannatranes 4, 8, and 13 with the corresponding cation radicals 4(+•), 8(+•), and 13(+•), respectively.

{4-t-Bu-2,6-[P(O)(O-i-Pr)2]2C6H2Sn}2: An Intramolecularly Coordinated Organotin(I) Compound with a Sn–Sn Single Bond, Its Disproportionation toward a Diorganostannylene and Elemental Tin, and Its Oxidation with PhI(OAc)2

Syntheses of the intramolecularly coordinated organotin(I) compound {4-t-Bu-2,6-[P(O)(O-i-Pr)(2)](2)C(6)H(2)Sn}(2) (2), which crystallized in two different pseudopolymorphs 2 and 2·C(7)H(8), of the diorganostannylene {4-t-Bu-2,6-[P(O)(O-i-Pr)(2)](2)C(6)H(2)}(2)Sn (3) and of the organotin(II) acetate 4-t-Bu-2,6-[P(O)(O-i-Pr)(2)](2)C(6)H(2)SnOAc (4) are reported. The compounds were characterized by multinuclear NMR, IR (3 and 4), UV-vis spectroscopy (2), electrospray ionization mass spectrometry (3 and 4), and single-crystal X-ray diffraction analyses. Density functional theory calculations on compound 2 revealed the stabilizing effect of the intramolecular P═O → Sn coordination.

Insights into the intramolecular donor stabilisation of organostannylene palladium and platinum complexes: syntheses, structures and DFT calculations.

The syntheses of the transition metal complexes cis-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)2MX2] (1, M = Pd, X = Cl; 2, M = Pd, X = Br; 3, M = Pd, X = I; 4, M = Pt, X = Cl), cis-[{2,6-(Me2NCH2)2C6H3SnCl}2MX2] (5, M = Pd, X = I; 6, M = Pt, X = Cl), trans-[{2,6-(Me2NCH2)2C6H3SnI}2PtI2] (7) and trans-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)PdI2]2 (8) are reported. Also reported is the serendipitous formation of the unprecedented complexes trans-[(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)2Pt(SnCl3)2] (10) and [(4-tBu-2,6-{P(O)(OiPr)2}2C6H2SnCl)3Pt(SnCl3)2] (11). The compounds were characterised by elemental analyses, (1)H, (13)C, (31)P, (119)Sn and (195)Pt NMR spectroscopy, single-crystal X-ray diffraction analysis, UV/Vis spectroscopy and, in the cases of compounds 1, 3 and 4, also by Mössbauer spectroscopy. All the compounds show the tin atoms in a distorted trigonal-bipyramidal environment. The Mössbauer spectra suggest the tin atoms to be present in the oxidation state III. The kinetic lability of the complexes was studied by redistribution reactions between compounds 1 and 3 as well as between 1 and cis-[{2,6-(Me2 NCH2)2C6H3SnCl}2PdCl2]. DFT calculations provided insights into both the bonding situation of the compounds and the energy difference between the cis and trans isomers. The latter is influenced by the donor strength of the pincer-type ligands.

Silicon- and Tin-Containing Open-Chain and Eight-Membered-Ring Compounds as Bicentric Lewis Acids toward Anions

Herein, we report the syntheses of silicon- and tin-containing open-chain and eight-membered-ring compounds Me2 Si(CH2 SnMe2 X)2 (2, X=Me; 3, X=Cl; 4, X=F), CH2 (SnMe2 CH2 I)2 (7), CH2 (SnMe2 CH2 Cl)2 (8), cyclo-Me2 Sn(CH2 SnMe2 CH2 )2 SiMe2 (6), cyclo-(Me2 SnCH2 )4 (9), cyclo-Me(2-n) Xn Sn(CH2 SiMe2 CH2 )2 SnXn Me(2-n) (5, n=0; 10, n=1, X=Cl; 11, n=1, X=F; 12, n=2, X=Cl), and the chloride and fluoride complexes NEt4 [cyclo- Me(Cl)Sn(CH2 SiMe2 CH2 )2 Sn(Cl)Me⋅F] (13), PPh4 [cyclo-Me(Cl)Sn(CH2 SiMe2 CH2 )2 Sn(Cl)Me⋅Cl] (14), NEt4 [cyclo-Me(F)Sn(CH2 SiMe2 CH2 )2 Sn(F)Me⋅F] (15), [NEt4 ]2 [cyclo-Cl2 Sn(CH2 SiMe2 CH2 )2 SnCl2 ⋅2 Cl] (16), M[Me2 Si(CH2 Sn(Cl)Me2 )2 ⋅Cl] (17 a, M=PPh4 ; 17 b, M=NEt4 ), NEt4 [Me2 Si(CH2 Sn(Cl)Me2 )2 ⋅F] (18), NEt4 [Me2 Si(CH2 Sn(F)Me2 )2 ⋅F] (19), and PPh4 [Me2 Si(CH2 Sn(Cl)Me2 )2 ⋅Br] (20). The compounds were characterised by electrospray mass-spectrometric, IR and (1) H, (13) C, (19) F, (29) Si, and (119) Sn NMR spectroscopic analysis, and, except for 15 and 18, single-crystal X-ray diffraction studies.

Crystal structure of catena-[dichlorido-μ2-4,4’-dithiodipyridine-κ2N:N’- zinc(II)], C10H8Cl2N2S2Zn

Abstract C10H8Cl2N2S2Zn, monoclinic, C2/c (no. 15), a = 12.317(2) Å, b = 9.868(2) Å, c = 10.947(2) Å, β = 92.37(2)°, V = 1329.3 Å3, Z = 4, Rgt(F) = 0.036, wRref(F2) = 0.132, T = 110 K.

[4-tBu-2,6-{P(O)(OiPr)2}2C6H2Sn(PPh3)Cr(CO)5]ClO4 – a salt containing a cationic triphenylphosphane-stabilized organostannylene transition metal complex

Abstract The isolation and molecular structure of bis(di-iso-propoxyphosphonyl)-4-tert-butyl]phenyl}tin triphenylphosphane perchlorate chromium pentacarbonyl, 2, is reported. It is the first example of an ionic compound containing an organostannylene transition metal complex cation stabilized by a phosphane donor. Slow reaction of compound 2 in acetonitrile gave trans-bis-triphenylphosphane chromium tetracarbonyl, trans-(Ph3P)2Cr(CO)4, in a new crystalline modification.

N-Aryl-substituted 5-aza-2,8-dioxasilabicyclo[3.3.01.5]octanes: syntheses, molecular structures, DFT calculations and cyclovoltammetric studies

Abstract The reaction of the silanes X2SiCl2 (X=H, Cl) with the dilithium salts of N-phenyldiethanolamine (1) and N-4-fluorophenyl-di-(2-dimethylpropan-2-ol)amine (2), respectively, gave the novel 5-aza-2,8-dioxasilabicyclo[3.3.01.5]octanes RN(CH2CR′2O)2SiX2 (3, R=Ph, R′=X=H; 4, R=Ph, R′=H, X=Cl; 5, R=4-FC6H4, R′=Me, X=H). These compounds were characterized by multinuclear NMR spectroscopy and single crystal X-ray diffraction analysis (1–4). The molecular structures of the dialkanolamines 1 and 2 are characterized by intra- and intermolecular O-H ··· O(H) hydrogen bridges giving rise to formation of eight-membered O4H4 rings (1) and polymeric chains (2). The 5-aza-2,8-dioxasilabicyclo[3.3.01.5]octanes show intramolecular N→Si interactions at distances of 2.961(2) (3) and 2.970(2) (4) Å, respectively. Also reported is the molecular structure of the hexachloridostannate salt [Ph(H)N(CH2CH2OH)2]2SnCl6 (6a) that was serendipitously obtained from the reaction of compound 3 with Ph3CSnCl5 under non-inert reaction conditions. Furthermore, DFT calculations on 3 and 4 as well as cyclovoltammetric studies were performed.

Rational Syntheses and Serendipity: Complexes [LSnPtCl2(SMe2)]2, [{LSnPtCl(SMe2)}2SnCl2], [(LSn)3(PtCl2)(PtClSnCl){LSn(Cl)OH}], and [O(SnCl)2(SnL)2] with L=MeN(CH2CMe2O)2

Syntheses and molecular structures of the dimeric tin-platinum complex [LSnPtCl2 (SMe2 )]2 (2), the tin-platinum clusters [{LSnPtCl(SMe2 )}2 SnCl2 )] (3) and [(LSn)3 (PtCl2 )(PtClSnCl)(LSnOHCl)] (6) (L=MeN(CH2 CMe2 O- )2 ), and of the unprecedented tin(II) aminoalkoxide-tin oxide chloride complex [O(SnCl)2 ⋅(SnL)2 ] (5) are reported. The compounds were characterized by NMR spectroscopy (1 H, 13 C, 119 Sn, 195 Pt), 119 Sn Mössbauer spectroscopy (1-3, 6), electrospray ionization mass spectrometry, elemental analyses, and single-crystal X-ray diffraction analyses (2⋅CH2 Cl2 , 3⋅2 C4 H8 O, 5, 6⋅3CH2 Cl2 ). The tin(II) aminoalkoxide [MeN(CH2 CMe2 O)2 Sn]2 (1) behaves like a neutral ligand, inserts into a Pt-Cl bond, or is involved in rearrangement reactions with the different behavior occurring even within one compound (3, 6). DFT calculations show that the tin-platinum compounds behave like electronic chameleons.

Arylphosphonic acid esters as bridging ligands in coordination polymers of bismuth

Abstract The reaction of the arylphosphonic acid esters 4,4′-[(i-PrO)2P(O)]C6H4C6H4[P(O)(Oi-Pr)2] (L1), 1,3,5-[(i-PrO)2P(O)]3C6H3 (L2), and 5-t-Bu-1,3-[(i-PrO)2P(O)]2C6H3 (L3), respectively, with bismuth halides BiX3 (X=Cl, Br, I) gave seven novel bismuth coordination polymers that have been characterized by single-crystal X-ray diffraction analysis. The solid-state structures of [(BiCl3)(L1)] (1), [(BiBr3)(L1)]·0.25CH3CN (2·0.25CH3CN), [(BiI3)2(L1)]·0.25CH3CN (3·0.25CH3CN), [(BiCl3)(L2)] (4), [(BiCl3)2(L2)] (5), [(BiBr3)2 (L2)]·CH3CN (6·CH3CN), and [(BiCl3)(L3)] (7) are presented. Thermal analysis of [(BiCl3)2(L2)] (5) is indicative of a conversion of the complexes into a bismuth phosphonate by complete i-PrX elimination, whereas for [(BiBr3)2(L2)] (6), elimination of i-PrBr and BiBr3 is assumed. Compounds 1–3 form one-dimensional coordination polymers, whereas two-dimensional networks are observed for compounds 4–7.

(Hexafluorosilicato-ƙ-2F,F')bis(1,10-phenanthroline-ƙ2N,N')zinc(II) methanol monosolvate

The title compound, [Zn(SiF6)(C12H8N2)2]·CH3OH, contains a neutral heteroleptic tris-chelate Zn(II) complex, viz. [Zn(SiF6)(phen)2] (phen is 1,10-phenanthroline), exhibiting approximate molecular C2 point-group symmetry. The Zn(II) cation adopts a severely distorted octahedral coordination. As far as can be ascertained, the title complex represents the first structurally characterized example of a Zn(II) complex bearing a bidentate-bound hexafluorosilicate ligand. A density functional theory study of the isolated [Zn(SiF6)(phen)2] complex was undertaken to reveal the influence of crystal packing on the molecular structure of the complex. In the crystal structure, the methanol solvent molecule forms a hydrogen bond to one F atom of the hexafluorosilicate ligand. The hydrogen-bonded assemblies so formed are tightly packed in the crystal, as indicated by a high packing coefficient (74.1%).