Armand Blaschette

Peroxo compounds: Part XVI. Electron diffraction investigation of the molecular structures of di-t-butyl peroxide Me3COOCMe3 and bis(trimethylsilyl) peroxide Me3SiOOSiMe3

Abstract The molecular geometries of Me 3 COOCMe 3 and Me 3 SiOOSiMe 3 , in the gas phase were determined by electron diffraction. For the skeleton of di- t -butyl peroxide the following geometric parameters ( r a -values) were obtained: r (O—O) = 1.480 A (assumed), . This dihedral angle is compared with the results of IR and Ram an spectroscopy, dipole moment measurements and photoelectron spectroscopy. The main geometric parameters for bis(trimethylsilyl) peroxide are . For both peroxides SCF-MO calculations in the CNDO/2 approximation do not reproduce the experimental results.

Infrarot-Spektren und Normalkoordinatenanalyse von Salzen mit den AnionenX3CSO 3 − (X=H, D, F, Cl)

ZusammenfassungDie IR-Spektren verschiedener Salze mit den Anionen CH3SO3−, CD3SO3−, CF3SO3− und CCl3SO3− sowie ein Raman-Skektrum des Ag[CF3SO3] werden mitgeteilt. Für die gen. Anionen sowie CH3PO32− und CD3PO32− wird mit einem für alle Ionen ähnlichen allgemeinen Valenzkraftfeld eine Normalkoordinatenanalyse durchgeführt. An den A1-Schwingungen von CF3SO3− und CCl3SO3− sind mehrere Koordinaten beteiligt; eine charakterisische CS-Valenzschwingung tritt in diesen Ionen nicht auf.AbstractThe infrared spectra of several salts with the anions CH3SO3− CD3SO3−, CF3SO3−, and CCl3SO3− and Raman data for Ag[CF3SO3] are reported. A normal coordinate analysis using a GVFF is performed for these anions as well as for CH3PO32− and CD3PO32−. The A1 modes of CF3SO3− and CCl3SO3− are mixed; consequently no characteristic CS stretching vibration occurs.

Polysulfonylamine: XLIII. Trimethylgermanium(IV)- und Trimethylblei(IV)-dimesylamid: Synthese und Festkörperstrukturen

Abstract The new compounds Me 3 GeN(SO 2 Me) 2 ( 3 ) and Me 3 PbN(SO 2 Me) 2 ( 4 ) were prepared from the corresponding chlorides Me 3 ECl and AgN(SO 2 Me) 2 in MeCN solution. The crystallographic data at −95°C are for 3 : triclinic, space group P 1 , a 771.7(2), b 1204.1(4), c 1388.4(5) pm, α 66.75(3), β 84.12(3), γ 74.15(2)°, V 1.1401 nm 3 , Z = 4; for 4 : monoclinic, space group P 2 1 / c , a 751.1(3), b 1065.5(4), c 1493.9(5) pm, β 100.99(3)°, V 1.1738 nm 3 , Z = 4. The crystal structure of 3 consists of two crystallographically independent, monomeric molecules with tetrahedral Ge atoms and trigonal- planar N atoms (average angle values: CGeC 112.7, CGeN 106.0, GeNS 121.1, SNS 117.3 °). The most striking features of the molecular structure are the extremely long GeN bond distances of 198.2(2) and 198.5(2) pm, which are equal to the uncorrected sum of the covalent single bond radii. In the crystal structure of 4 , Me 3 PbN(SO 2 Me) 2 units are linked by an intermolecular PbO interaction (265.3(6) pm) to form infinite parallel chains. The Pb atom has a distorted trigonal-bipyramidal arrangement (NPbO 169.3; average values: CPbC 119.2, CPbN 95.5, CPbO 84.8°), in which the N atom is trigonal-planar (SNS 119.2, mean PbNS 119.8°). The PbN distance is 248.4(6) pm, i.e. 30 pm longer than the sum of the covalent radii, suggesting a mainly ionic bond character. In both structures secondary intramolecular 1,4-interactions with Ge ⋯ O distances of 295.8 and Pb ⋯ O of 328 pm, respectively, are observed.

Polysulfonylamine. XXXIX: Charakterisierung des Kations [Me2Sn(H2O)4]2+ im kristallinen Zustand : Bildung und Röntgenstrukturanalyse von tetraaquadimethylzinn(IV)-bis(1,1,3,3-tetraoxo-1,3,2-benzodithiazolid)

Abstract Crystals of the title compound [Me2Sn(H2O)4]2+(Z−)2, where Z− is the anion of benzene-1,2-disulfonic imide, were fortuitously obtained by reacting Me2SnCl2 with AgZ (1/2) in acetonitrile and crystallizing the primary product from an acetonitrile solution that was not kept completely dry. The crystallographic data at −95°C are: monoclinic, space group P2/c, a 764.4(2), b 1382.0(3), c 2282.8(4) pm, β 96.96(2)°, U 2.3937 nm3, Z = 4. Two independent cations lie with their tin atoms on a twofold crystallographic axis and display trans-octahedral geometry (SnC 208.7–208.9, SnO 220.7–226.0 pm, CSNC 178.9/180.0, (OSnO)trans 178.8–179.7, (OSnO)cis 88.9–92.1, CSNO 89.5–90.9°). The bicyclic frameworks of the two independent anions are essentially planar. The ionic crystal packing is further stabilized by a three-dimensional hydrogen bond network (O ⋯ O 263.9–273.6 pm), in which all H atoms of the water ligands act as donors and all O atoms of the anions as acceptors.

Thermochemical analysis of solvate complexes of silver dimesylaminide

Abstract Two new solvate complexes of silver dimesylaminide with water and acetonitrile were analyzed using several thermoanalytic and calorimetric methods (thermogravimetry, differential scanning calorimetry, thermooptical analysis, solution calorimetry). The hydrate AgN (SO 2 CH 3 ) 2 · 1 4 H 2 O loses its crystal water above 120°C. The dehydratation is overlapped by a phase transition which occurs at 174°C. The acetonitrile complex AgN(SO 2 CH 3 ) 2 ·2 CH 3 CN decomposes between −15 and 95°C. The existence of the hydrate complex is remarkable, because silver salts usually do not form hydrates. For this salt, the coordination of the water molecules to silver ions has been proved by X-ray structure determination.

Polysulfonylamine: XLVII. Darstellung und Kristallstrukturanalyse der ionischen Verbindung catena-Poly[(μ-4,4′-bipyridin)trimethylzinn]-dimesylamid-Acetonitril (1/1)

Abstract Me3SnN(SO2Me)2 · 4,4′-bpy is obtained as an amorphous powder by treating a suspension of Me3SnN(SO2Me)2 in Et2O with one equivalent of 4,4′-bipyridine. It crystallizes from MeCN as a labile (1/1)-solvate. The crystallographic data of the latter at −95°C are: monoclinic, space group P21/n, a 930.9(2), b 1105.9(4), c 2227.4(7) pm, β 92.27(2)°, U 2.2910 nm3, Z = 4. The crystal packing consists of linear-polymeric [Me3Sn(μ-4,4′-bpy)-]nn+ cations in which the monomers are related by a glide plane, discrete (MeSO2)2N− anions, and non-coordinating MeCN molecules. The angle between the C5N planes of the bipyridine is 32°. The tin atom has a trigonal-bipyramidal environment with two apical nitrogen atoms: SnN 241.1/242.0, SnC 211.9–213.0 pm; NSNN 176.8, CSNC 115.9123.9, NSNC 87.0–94.0°.

Polysulfonylamine. LIII: Triphenylphosphinoxid-Komplexe von Organozinn(IV)-dimesylamiden : Darstellung und Festkörperstrukturen ionischer Komplexe des Typs [R3Sn(OPPh3)2]+[(MeSO2)2N]- und des Molekülkomplexes [Me2Sn{OS(:O, Me)NSO2Me}2(OPPh3)2]

Abstract By treating the corresponding organotin dimesylamides with the appropriate amounts of triphenylphosphine oxide in dichloromethane or acetonitrile, the following novel complexes were obtained: [R 3 Sn(OPPh 3 ) 2 ] + [(MeSO 2 ) 2 N] − , where R = Me ( 3a ) or Ph ( 4 ); [Me 3 Sn(OPPh 3 ) 2 ] + [(MeSO 2 ) 2 N] − · Ph 3 PO ( 3b ); [Me 2 Sn{N(SO 2 Me) 2 } 2 (OPPh 3 ) 2 ] ( 6 ). The crystallographic data (at −95°C) are for 3a : triclinic, space group P 1 , a = 797.3(2), b = 1666.6(4), c = 1709.7(5) pm, α = 66.22(2), β = 86.50(2), γ = 89.63(2)°, V = 2.0747 nm 3 Z = 2; for 3b : triclinic, space group P 1 , a = 798.8(2), b = 1731.7(3), c = 2061.6(4) pm, α = 99.14(2), β = 93.28(2), γ = 92.44(2)°, V = 2.8609 nm 3 , Z = 2; for 6 : monoclinic, space group P 2 1 / c , a = 1245.2(3), b = 1591.8(3), c = 1161.7(2) pm, β = 99.42(2)°, V = 2. 2716 nm 3 , Z = 2. As indicated above, 3a , 3b and 4 display ionic crystal structures. In 3b , a non-coordinating third Ph 3 PO molecule resides in a lattice cavity. The structure of 4 shows disorder of the anions and could not be satisfactorily refined. The tin atom in the [Me 3 Sn(OPPh 3 ) 2 ] + cation has a trigonal-bipyramidal geometry with axial Ph 3 PO ligands. Important bond lengths (pm) and angles (°) are for 3a ( 3b ): SnC 210.9–212.1 (210.8–211.5), SnO 223.2 and 226.1 (221.9 and 228.4), OP 150.4 and 151.2 (149.4 and 150.4 for coordinating, 148.3 for non-coordinating Ph 3 PO); OSNO 177.3 (175.9), CSNC 118.6–122.0 (119.3–121.4), CSNO 86.6–92.5 (88.6–92.0), SNOP 150.4 and 159.8 (156.5 and 166.1). In the centrosymmetric unchanged molecule 6 , where the dimesylamide groups act as monodentate O-ligands, the tin atom features an all- trans octahedral geometry with SnC 209.3, SnO(P) 221.1, SnO(S) 227.4, OP 150.6 pm; cis - angles 86.7–93.3, SNOP 165.4, SNOS 137.2°.

POLYSULFONYLAMINE: TEIL XXXII.1 SYNTHESE UND FESTKÖRPERSTRUKTUREN VON N-PHOSPHOR(III)- UND N-PHOSPHOR(V)-DERIVATEN DBS DIMESYLAMINS: MOLEKÜLE MIT SEHR LANGENPHOSPHOR-STICKSTOFF-BINDUNGEN UND INTRAMOLEKULAREN 1,4-WECHSELWIRKUNGEN DES TYPS P … O

Abstract We report the first examples of phosphorus-containing derivatives of a disulphonylamine in which the phosphorus atom is bound directly to the amine nitrogen. Ph2P[sbnd]N(SO2Me)2 (1), 2-dimesylamino-1,3,2-benzodioxaphosphole (2a) and P[N(SO2Me)2]3 (3) are obtained by elimination of Me3SiCl from the corresponding phosphorus chlorides and stoichiometric amounts of Me3SiN(SO2Me)2. 2a is also formed by silver salt metathesis between the 2-chlorophosphole and AgN(SO2Me)2. Cleavage of R2P(S[sbnd]P(S)R2 with ClN(SO2Me)2 affords R2P(S)[sbnd]N(SO2Me)2 with R = Me (4a) and Et (4b), the co-product being R2P(S)Cl. 2a reacts with oxygen to form 2-dimesylamino-2-oxo-1,3,2-benzodioxaphosphole (2b). 1 crystallizes in the monoclinic space group P21/n with a = 1461.8(5), b = 732.2 (3), c = 1511.0(4) pm, β = 97.59(3)°, V = 1.6030 nm,3 Z = 4. The crystallographic data for 2a are: Triclinic, space group P1, a = 561.5(2), b = 886.8(2), c = 1272.9(4) pm, α = 73.99(3), β = 83.56(3), γ = 81.54(3)°, V = 0.6009 nm,3 Z = 2. ...

Polysulfonylamine: XXXVIII. Darstellung und Festkörperstruktur von Bis(trimethylzinn)-dimesylamid-hydroxid [Me3Sn{μ-(MeSO2)2N}Me3Sn(μ-OH)]n☆

The title compound 1 is obtained from equimolar amounts of Me3SnN(SO2Me)2 (2) and Me3SnOH in ethanol or by partial hydrolysis of 2 in CH2Cl2 solution and in presence of a nitrogen base, e.g. pyridine. 1 crystallizes in the triclinic space group P1 with (at −95°C) a = 825.4(3), b = 856.2(3), c = 1341.6(5) pm, α = 81.97(3), β = 74.72(3), λ = 79.75(3)°, U = 0.8958 nm3, Z = 2. The structure consists of infinite chains, in which Me3Sn groups are bridged by alternating O(H) and (α-O, ω-O)-bonded dimesylamide groups. Antiparallel chains are interconnected by OH⋯N hydrogen bonds to form a “ladder” structure. There are two independent tin atoms. The SnO(H) distances are 211.8(2) and 212.6(2) pm, the SnO(S) distances 268.2(2) and 253.3(2) pm, the O(H)SnO(S) angles 174.5(1) and 173.8(1)°, and the SnO(H)Sn angle is 136.9(1)°. In the trigonal-bipyramidal (C3O2) environment of the tin atoms, the CSNC angles are slightly smaller than 120°, the O(H)SnC angles significantly greater than 90°, and the O(S)Sn C angles correspondingly smaller than 90°. Thus, the chain structure might reasonably be viewed as consisting of [(Me3Sn)2OH]+ ions alternating with [(MeSO2)2N]− ions.

Polysulfonylamine LXII. Dimesylamid als nichtkoordinierendes gegenion für organozinn-komplexkationen: Synthese und strukturen von [R3Sn(L)(L′)]+[(MeSO2)2N]− (L = L′ = HMPA, Ph3AsO, imidazol, 4-dimethylaminopyridin; L = H2O und L′ = Pyridin-N-oxide)☆

Abstract The ability of dimesylamide to act as a non-coordinating counter-ion for complex organotin cations in the solid state is corroborated by new examples. Treating R 3 SnN(SO 2 Me) 2 (R = Me, Ph) with two equivalents of L = hexamethylphosphorotriamide (HMPA), Ph 3 AsO, imidazole (Him) or 4-dimethylaminopyridine affords the complete series of eight ionic complexes [R 3 Sn(L) 2 ] + [(MeSO 2 ) 2 N] − . With one equivalent of pyridine- N -oxide (pyO), the triorganotin dimesylamides form the presumably uncharged complexes [R 3 Sn{(MeSO 2 ) 2 N}(pyO)] ( 5a , R = Me; 5b , R = Ph). Unlike 5b , the methyl compound 5a reacts spontaneously with water vapour or with one equivalent of water in MeCN solution to form the ionic complex [Me 3 Sn(H 2 O)(pyO)] + [(MeSO 2 ) 2 N] − ( 6 ). By X-ray crystallography at low temperature, the solid-state structures of the following compounds were determined (all triclinic, space group P 1 ): [Ph 3 Sn(hmpa) 2 ][(MeSO 2 ) 2 N] ( 1b ), [Me 3 Sn(Ph 3 AsO) 2 ][(MeSO 2 ) 2 N] ( 2a ), [Ph 3 Sn(Him) 2 ][(MeSO 2 ) 2 N] ( 3b ), and 6 . The four structures consist of dimesylamide anions and organotin cations in which the tin atoms display trigonal bipyramidal coordinations with the ligands L in the axial position (imidazole N 3 bonded, all other ligands O bonded). In 3b and 6 , the cations and anions are connected into infinite chains or rings consisting of double ionic pairs, respectively, by hydrogen bonds originating from the imidazole N 1 H groups or the water protons. The most important bond distances (pm) and angles (deg) are as follows: for 1b , SnO 220.6 and 221.3, OSnO 174.4, SnOP 152.1 and 162.6; for 2a , SnO 220.4 and 224.0, OSnO 177.2, SnOAs 141.7 and 152.0; for 3b , SnN 231.2 and 235.5, NSnN 170.2; for 6 , SnOH 2 227.4, SnOpy 225.7, OSnO 171.1, SnON 119.4.