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  • Author: Mathias Noltemeyer x
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The title compound, C18H33B2N3S, isolated from the reaction of 3,5-bis(diisopropylamino)-1,2,4,3,5-dithiazadiborolidine with elemental sodium, crystallizes in space group P1̅ with cell constants a = 1034.3(6), b = 1230.4(8), c = 1728.5(12) pm, α = 97.50(6), β = 97.95(5), γ = 90.17(5)° and Z = 4. X-ray structure refinement converged at R = 0.087, wR = 0.085, w-1 = σ2(F0) + 0.004 Fo 2. The fourmcmbered ring B2NS is planar, the angle B—S—B being 70°.

Abstract

The title compound, isolated from the reaction of SS-diethyl-N,N'-bistrimethylsilylsulfodiimide and 3.5-dimethyl-1,2,4-trithiadiborolane, crystallizes in space group Pbca with cell constants a - 1218.7(6), b = 1295.8(6), c = 1455.7(9) pm, V = 2.2987 m-3, Z = 8, ϱ = 1.167 Mg m-3. The X-ray structure was refined to R = 0.053

Abstract

The reaction of lithiated 1,3-bis(fluorodimethyl)cyclotrisilazane with PF3 leads to the formation of a PF2-substituted six-membered Si-N ring (1). 1,5-Bis(difluorophosphanyl)-2,2,4,4,6,6,8,8-octamethyl-cyclotetrasilazane (2) is obtained in the reaction of the dilithium derivative of the cyclic tetrasilazane with trifluorophosphane in a molar ratio 1:2. The crystal structure of (F2P-N-SiMe2-NH-SiMe2)2 (2) has been determined.

2,4,6-Tri-tert-butylphenyltrifluorosilane (1) reacts with lithium amides to give the aminofluorosilanes (2 - 7); RSiF2NHR′ (R = 2,4,6-Me3CC6H2; R′ = H (2), CMe3 (3), SiMe2CMe3 (4)), (R-SiF2)2NH (5), RSiF(NHR′)2. R′ = CMe3 (6), C6H5 (7). The reaction of 5 with BuLi in THF leads to the formation of the monomeric lithium derivative 8, R-SiF2Li(THF)3-N -SiF2R. The polymeric lithium derivative 9 [R-SiF2-N-SiRF2Li(THF)2]n is obtained by recrystallisation of 8 in THF. In 8 and 9 lithium is only coordinated to fluorine and THF. Hydrolysis of 8 or 9 lead to the 1,3-disiloxane 10, (RSiF2)2O . 10 shows linearity at the oxygen and short Si-O bond lengths.

Bis(fluorodiisopropylsilyl)amine [(Me2HC)2SiF]2NH (1) reacts with the disodium salt of catechole or the disodium salt of resorcinol in a molar ratio 1:1 to give the seven-membered heteraphane [HN(Me2HC)2SiO]2C6H4 (2) resp. the 16-membered heteraphane [HN(Me2HC)2SiOC6H4OSi(CHMe2)2]2 (3). The chain-like compound [(Me2HC)2SiFNHSi(CHMe2)2O]2C6H4 (4) is obtained by the reaction of 1 with disodium resorcinolate.

A new method for the preparation of monoalkylamides of composition Cp′TiCl2NHR is reported. Me3SnNHR (R = tBu 1a, CHiPr2 1b) reacts with Cp′TiCl3 with elimination of Me3SnCl to yield Cp′TiCl2NHR (2) (2a: Cp′ = C5H5, R = tBu, 2b: Cp′ = Me3SiC5H4, R = tBu, 2c: Cp′ = (Me3Si)2C5H3, R = tBu, 2d: Cp′ = Me4C5H, R = tBu, 2e: Cp′ = Me5C5, R = tBu, 2f: Cp′ = C5H5, R = CHiPr2, 2g: Cp′ = Me3SiC5H4, R = CHiPr2, 2h: Cp′ = (Me3Si)2C5H3, R = CHiPr2, 2i: Cp′ = Me4C5H, R = CHiPr2, 2j: Cp′ = Me5C5, R = CHiPr2). Compounds 2a-2j are stable and eliminate HCl only in the presence of a strong base to form (C5H5TiClNtBu)2 (3a) or (Me3SiC5H4TiClNtBu)2 (3b) from 2a and 2b, respectively. In 3a the chlorine atoms are substituted by NHtBu groups in boiling THF by means of LiNHtBu to give (C5H5TiNHtBuNtBu)2 (4). The reactions of 2e and 2b with LiN(SiMe3)2·Et2O in the presence of pyridine yield Me5C5TiClNtBu · Py (5a) (Py = pyridine) and Me3SiC5H4TiClNtBu·Py (5b), respectively. Compounds 2e and 5a have been characterized by X-ray crystal structural analysis.

Abstract

The intramolecularly coordinating 2-(dimethylaminomethyl)phenyl-(X) and 4-terr-butyl-2,6-bis(dimethylaminomethyl)phenyl-(Y) ligands were employed in the preparation of the gallium and indium halides: X2InI (B), XInI2 (1), X2InBr (2), XInBr2 (3), XIn(Et)I (4), XGaI2 (6) and YInI2 (7). The first neutral indium hydride X2InH (5) was made in situ from LiInH4 and 2. Z2InCl (8) (Z = 2-pyridyl-bis(trimethylsilyl)methyl), and X3Ga (C) were also synthesized. The compounds are characterized by N. M. R. (1H, 13C, 29Si and for 6 71Ga) and mass spectrometry and elemental analyses or peak matching M. S.. N. M. R.-data are discussed as well as the X-ray structure analyses provided for B, 2, 4, 5, 7 and 8.

Abstract

Monomerie diiodides of 2,4,6-tri(tert-butyl)phenyl = (s-Mes), 2,4,6-triisopropylphenyl = (Trip)-and 2,4-di-tert-butyl-6-methylphenyl = (DBMP)-gallium and -indium were prepared by the reaction of the lithiated aryls with MI3 (M = Ga, In) in hexane/Et2O. s-MesInI2 (1), s-Mes2InI (2), s-MesGaI2 (3), s-Mes2GaI (4), Trip2InI (5) and (DBMP)2InI (6) were obtained and characterized by their mass and NMR spectra (1H, 13C), and/or by elemental analyses. An X-ray crystal structure analysis was carried out for 1.

Cp*TaF4 (1) (Cp* = η5-C5Me5) reacts with lithium salts of benzamidines or 1,3-diketones to form hexa-coordinated complexes of composition Cp*TaF3[(Me3SiN)2CPh] (2), Cp*TaF3[(Me3SiN)2C(p-CF3C6H4)] (3) and Cp*TaF3(O=CPhCH=CPhO) (4). The reactions proceed under elimination of LiF. The X-ray crystal structure of Cp*TaF3(O=CPhCH=CPhO) (4) has been determined shows tantalum to have a distorted octahedral environment, if the Cp* ligand is considered to occupy one coordination site.

Abstract S,S-Dimethylsulfoximinato-diphenyl-N-trimethylsilylphosphoranylidenamin (1) reacts in a molar ratio of 1:1 with TiCl4, CpTiCl3, (Cp = C5H5), VOCl3, and Cp*TaCl4 (Cp* = C5Me5) to yield the 1:1 adduct 1 · TiCl4 (2) and the substituted products Me2S(O) = NPPh2 = N-TiCpCl2 (3), Me2S(O) = NPPh2=N-VOCl2 (4) and Me2S(O) = NPPh2 = N-TaCp*Cl3 (5). The structures of 3, 4 and 5 show short metal-nitrogen bond lengths.