The following p-substituted N,N-bis-trimethlsilyl anilines p-X? C6H4? N[Si(CH3)3]2 are prepared by silylation of free amines: X = H, CH3, C2H5, CH3O, CH3CO, F, Cl, Br, J, CN, C6HS, (CH3)3SiO, and [(CH3)3Si]2N, and the isotopic derivatives C6H5? 15N[Si(CH3)3]2 and C6D5N[Si(CH3)3]2. The vibrational spectra are reported and assigned. The molecular symmetry of p-[(CH3)3Si]2N? C6H4? N[Si(CH3)3]2 is determined. The influence of the mass of the substituents X on the positions of the νsSiNSi vibrational frequencies is discussed. 相似文献
Whereas (CH3)3Si? P(C2H5)2 does not react with LiP(C2H5)2 (I), there are reactions of SiH-containing silylphosphines with one P(C2H5)2 group as well as of SiH- and Simethylated silylphosphines with (I), yielding phosphorylated products and LiH according to equ. (1) (2). SiH-containing Silylphosphines, being Si? CH3-free and having more than one P(C2H5)2-group, such as HSi[P(C2H5)2]3, react with LiP(C2H5)2 by exchange of Li for H, acc. to equ.(3). With (CH3)3SiCl, LiSi[P(C2H5)2]3 yields (CH3)3Si? Si[P(C2H5)2]3 and with SiH3Br H3Si? Si[P(C2H5)2]3. There is a cleavage of the Si? P bond with Li-CH3 or n? LiC4H9. The reaction starts as shown in equ. (4), yielding (CH3)3SiH and (CH3)3Si? P(C2H5)2 as intermediate products and finally (CH3)4Si (equ. 5). 相似文献
Diphenyl-bis(P-trimethylphosphinimino)-phosphonium Chloride The reaction of Na⊕(CH3)3Si? N? P(C6H5)2? N? Si(CH3)3? III with (CH3)3PCI2 results in the elimination of NaCI and (CH3)3SiCI and the formation of (CH3)3P = N? P(C6H5)2? N = P(CH3)3 ⊕CI? VII . The mechanism of the reaction is discussed. (CH3)3P = N? P(C6H5)2 = N? Si(CH3)3 V can be obtained as an intermediate. This intermediate, when synthesized by an other independent route, is found to react with (CH3)3PCI2 to give the same product VII . 相似文献
SiH- and SiCl-containing Silylphosphines rearrange acc. to equ. (1), (2). Equations (1) and (2) are not reversible, because there are cleavages acc. to equ. (3). (4). Also HSiCl3 cleaves H3Si? P(C2H5)2 acc. to equ. (5). Si-methyl-free, SiH-containing Silylphosphines disproportionateal ready at room temperature within a few months acc. to equ. (6), (7). H2Si[P(C2H5)2]2 however, is stable under the same conditions. Si? CH3 containing silylphosphines such as CH3SiH2? P(C2H5)2, CH3Si[P(C2H5)2]3 and similar ones are stable compounds which can be destilled. To prepare pure HSi[P(C2H5)2]3, the side-reactions ace. to equ. (I) are avoided by reduction of the Sic1 groups with LiH. Reduction with LiAlH4 leads to a cleavage of the Si? P bond. 相似文献
Formation of Organosilicon Compounds. 66. (H2Si? CH2)2 and Si-substituted Derivatives (H2Si? CH2)2 1 is formed in the reaction of (Cl2Si? CH2)2 with LiAlH4. In 1 , the halogenation of the SiH bond is so much preferred compared to the ring cleavage reaction, that 1 reacts with Cl2 or Br2 to form successively all compounds form 1-monochlor-1,3-disilacyclobutane to (X2Si? CH2)2 (X = Cl, Br). The stability of the 1,3-disilacyclobutane skeleton towards HBr or Br2 increases as the electronegativity of the Si-substituents increases. Thus, (Cl2Si? CH2)2 is cleaved neither by HBr nor by Br2, whereas e. g. [H(C6H5)Si? CH2]2 reacts to [Br(C6H5)Si? CH2]2 with Br2, but yields meH(C6H5)Si? CH2? SiBr(C6H5)H (me = CH3) with HBr. In [me(C6H5)Si? CH2]2, the four-membered ring is cleaved by Br2 as well as by HBr. The 1H-, 29Si- and 13C-n.m.r. data are reported. 相似文献
In contrast to ruthenocene [Ru(η5‐C5H5)2] and dimethylruthenocene [Ru(η5‐C5H4Me)2] ( 7 ), chemical oxidation of highly strained, ring‐tilted [2]ruthenocenophane [Ru(η5‐C5H4)2(CH2)2] ( 5 ) and slightly strained [3]ruthenocenophane [Ru(η5‐C5H4)2(CH2)3] ( 6 ) with cationic oxidants containing the non‐coordinating [B(C6F5)4]? anion was found to afford stable and isolable metal?metal bonded dicationic dimer salts [Ru(η5‐C5H4)2(CH2)2]2[B(C6F5)4]2 ( 8 ) and [Ru(η5‐C5H4)2(CH2)3]2[B(C6F5)4]2 ( 17 ), respectively. Cyclic voltammetry and DFT studies indicated that the oxidation potential, propensity for dimerization, and strength of the resulting Ru?Ru bond is strongly dependent on the degree of tilt present in 5 and 6 and thereby degree of exposure of the Ru center. Cleavage of the Ru?Ru bond in 8 was achieved through reaction with the radical source [(CH3)2NC(S)S?SC(S)N(CH3)2] (thiram), affording unusual dimer [(CH3)2NCS2Ru(η5‐C5H4)(η3‐C5H4)C2H4]2[B(C6F5)4]2 ( 9 ) through a haptotropic η5–η3 ring‐slippage followed by an apparent [2+2] cyclodimerization of the cyclopentadienyl ligand. Analogs of possible intermediates in the reaction pathway [C6H5ERu(η5‐C5H4)2C2H4][B(C6F5)4] [E=S ( 15 ) or Se ( 16 )] were synthesized through reaction of 8 with C6H5E?EC6H5 (E=S or Se). 相似文献
The new triphosphine CH3P[P(C6H5)2]2, m. p. 130–134º, has been prepared in high yield by the interaction of (C6H5)2PH and CH3P[N(CH3)2]2. This triphosphine is cleaved by CH3J and Br2. With sulfur it yields an adduct of the probable structure CH3P[P(S)(C6H5)2]2, m. p. 163,5–166º. 相似文献
The preparation of SiH-containing silylphosphines from SiH-containing chlorosilanes is successful by using an excess of chlorosilans. Chemical shift data and coupling constants of the compounds HxSi[P(C2H5)2]4?x and (CH3)xSi[P(C2H5)2]4?x are communicated and compared with those of HxSiX4?x and (CH3)xSiX4?x (X = halogen or H). 相似文献
CF3SO2N?SCl2 reagiert mit (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 oder (C5H10)S[NSi(CH3)3]2 unter Trimethylchlorsilanabspaltung zu den achtgliedrigen S4N4-Derivaten S4N4(NSO2CF3)2(CH3)4 3 , S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b . In den achtgliedrigen SN-Ringen haben die Schwefelatome die Koordinationszahl 3 und 4. Die Röntgenstrukturanalyse von 4a ergab eine Sessel-Konformation. 4a kristallisiert orthorhombisch in der Raumgruppe Pna21 mit a = 17,641(4), b = 6,406(2), c = 19,130(4) Å, dx = 1,815 g cm?3 und Z = 4. Die mittleren S? N-Abstände betragen an den vierfach koordinierten Schwefelatomen 1,597 Å und an den Schwefelatomen mit der Koordinationszahl 3 1,650 Å. CF3SO2N? SCl2 reagiert mit trimethylzinnhaltigen S? N-Verbindungen zum bekannten CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 und Dimethylzinndichlorid. Synthesis and X-Ray Structure Analysis of S4N4-Derivatives with Threefold and Fourfold Coordinated Sulfur Atoms CF3SO2N?SCl2 reacts with (CH3)2S[NSi(CH3)3]2, (C4H8)S[NSi(CH3)3]2 or (C5H10S[NSi(CH3)2]2 under elimination of (CH3)3SiCl to yield the eight-membered S4N4 derivatives S4N4?NSO2CF3)2(CH3)4, 3 , S4N4(NSO2CF3)2(C4H8)2 4a und S4N4(NSO2CF3)2(C5H1 0)2 4b . In the eight-membered SN-rings the sulfur atoms have the coordination number 3 and 4. The X-ray structure analysis of 4a revealed a chair conformation. 4a crystallizes in the orthorhombic space group Pna21 with a = 17.641(4), b = 6.406(2), c = 19.130(4) Å, dx = 1.815 g cm?3, and Z = 4. The average S? N distance was found to be 1.597 Å at fourfold coordinated sulfur atoms and 1.650 Å at sulfur with coordination number 3. CF3SO2N=SCl2 reacts with trimethyl tin-containing S? N compounds to the known CF3SO2N[Sn(CH3)3]S(CH3)NSO2CF3 and dimethyl tin dichloride. 相似文献
Behaviour of Diethylamino-divinylphosphine The preparation of diethylamino-divinylphosphine 1 and its reaction with Sx, Br2, CH3J, HCl, HP(C6H5)2, and HSn(C4H9)3 are described. Whereas 1 and (C6H5)2P? CH?CH2 do'nt polymerize by a radical mechanism, (C2H5)2N? P(S)(CH?CH2)2 yields an unburnable polymerisation product. Copolymerisation of (C6H5)2P? CH?CH2 or 1 , respectively, and styrene results in a polymeric substance with a molecular weight of about 2600. 相似文献
Polymers [N(PN)4(C6H5)6N?P(C6H5)2(CH2)4P(C6H5)2]x and [N(PN)4(C6H5)6N?P–(C6H5)2C6H4C6H4P(C6H5)2]x have been formed by thermal copolymerization of trans-2,6-diazidohexaphenylcyclophosphonitrile [N3(PN)4(C6H5)6N3] with either 1,4-bis-(diphenylphosphino)butane [(C6H5)2P(CH2)4P(C6H5)2] or 4,4′-bis(diphenylphosphino)-biphenyl [(C6H5)2C6H4C6H4P(C6H5)2]. The maximum molecular weights obtained were about 10,000. A polymer endcapped with triphenyl phosphine was stable to 400°C. 相似文献
The complexes [2‐(1H‐imidazol‐4‐yl‐κN3)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)cobalt(II), [Co(C12H27O3SSi)2(C5H9N3)], and [2‐(1H‐imidazol‐4‐yl‐κN3)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)zinc(II), [Zn(C12H27O3SSi)2(C5H9N3)], are isomorphous. The central ZnII/CoII ions are surrounded by two S atoms from the tri‐tert‐butoxysilanethiolate ligand and by two N atoms from the chelating histamine ligand in a distorted tetrahedral geometry, with two intramolecular N—H...O hydrogen‐bonding interactions between the histamine NH2 groups and tert‐butoxy O atoms. Molecules of the complexes are joined into dimers via two intermolecular bifurcated N—H...(S,O) hydrogen bonds. The ZnII atom in [(1H‐imidazol‐4‐yl‐κN3)methanol]bis(tri‐tert‐butoxysilanethiolato‐κ2O,S)zinc(II), [Zn(C12H27O3SSi)2(C4H6N2O)], is five‐coordinated by two O and two S atoms from the O,S‐chelating silanethiolate ligand and by one N atom from (1H‐imidazol‐4‐yl)methanol; the hydroxy group forms an intramolecular hydrogen bond with sulfur. Molecules of this complex pack as zigzag chains linked by N—H...O hydrogen bonds. These structures provide reference details for cysteine‐ and histidine‐ligated metal centers in proteins. 相似文献
The reaction of N(CH2CH2Cl)3 (I) with KAs(C6H5)2·dioxane () in THF yields, as Sacconi et al. reported earlier, 80% of N[CH2CH2As(C6H5)2]3 (II). II is now obtained in a still higher quantity from the reaction of [HN(CH2CH2Cl)3]Cl (III) with NaAs(C6H5)2 in liquid ammonia. Treatment of II with gaseous HI in dry CH2Cl2 results in the formation of [HN(CH2CH2AsI2)3]I (IV), which is isolated by recrystallisation from THF as [HN(CH2CH2AsI2)3]I · THF () (IVa). IVa reacts with H2O/NH3 or H2S/N(C2H5)3 to give the novel cryptands [N(CH2CH2)3]8-(As4O4)6 (V) or [N(CH2CH2)3]8(As4S4)6 (VI), which also can be denoted as spherands. The reaction of V with dry gaseous HCl in benzene leads to [HN(CH2-CH2AsCl2)3]Cl (VII). All the new compounds are characterized, as far as possible, by their IR, FIR, Raman, 1H NMR and mass spectra. To determine the structure of V a single X-ray crystal study was carried out. Moreover II, which is already well-known but not completely characterized, is included in this discussion only for spectroscopic comparison. 相似文献
Crystal Structure of Tetraphenylphosphonium Monothiocyanatohydro-closo-Decaborate, [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN The X-ray structure determination of [P(C6H5)4]2[2-(SCN)B10H9] · CH3CN (monoclinic, space group P21/n, a = 10.6040(10), b = 13.8880(9), c = 33.888(3) Å, β = 94.095(8)°, Z = 4) reveals the S coordination of the SCN substituent with a B? S distance of 1.913(6) Å and a B? S? C angle of 105.3(3)°. The SCN group is nearly linear (178.2(7)°). 相似文献
Preparation of New Alkylaminofluorosilanes Aminofluorosilanes of the composition RSiF2NR′R″ (R = H, CH3, C2H3, C6H5; R′ = Si(CH3)3; R″ = C(CH3)3; R′ = R″ = i-C3H7), as well as C6H5SiF2N[C(CH3)2CH2]2CH2 are obtained by the reaction of fluorosilanes with the lithium salts of the corresponding amines in a molar ratio 1:1. The further reaction of these compounds with the lithium salts of alkylamines and anilin leads to the formation of the diaminofluorosilanes RSiFNR′R″NHR? (R? = C(CH3)3, i-C3H7, C6H5). The 1H, 19F, 29Si n.m.r. and mass spectra of the above mentioned compounds are reported. 相似文献
On Chalcogenolates. 179. Copper(I) Thioxanthates and Thioxanthatocuprates(I) Copper(I) thioxanthates Cu[S2C? SR], where R = C2H5, nC4H9, and CH2? C6H5, have been prepared by two procedures and studied by means of diverse methods. They are soluble in ethanolic and acetonic solutions containing the corresponding [S2C? SR]? ions in excess to yield thioxanthatocuprates(I) [Cun(S2C? SR)n+1]?. The compounds [(C6H5)4P][Cun(S2C? SC2H5)n+1] with n = 1, 4, 6 have been isolated. The existence of [(C6H5)4P][Cu4(S2C? SC4H9)5] and [(C6H5)4P][Cu6(S2C? SCH2? C6H5)7] has been ascertained. 相似文献
Nitriles react with PF5 and also with AsF5, SbF5 forming 1:1-adducts. Using C2Cl3F3 as a solvent is of advantage for this reaction. PF5·CH3CN and [N(C2H5)4]SH give [N(C2H5)4][P2S2F8] with a sulfur double bridge and hexafluorophosphate in acetonitrile [1]. In case of AsF5·CH3CN a salt with the anion [AsF5NHCSCH3]? has been isolated [2]. Following products have been confirmed in a reaction mixture of PF5·CH3CN and SH? in acetonitrile by NMR (31P and 19F): [PF6]?, [F5PSPF5]2?, , F4PSH, F3PS, HPS2F2, [PS2F2]?, [F5PNC(SH)CH3]?, [F5PNHCSCH3]?, [F5PSH]?. With a ratio PF5·CH3CN: SH? = 2:1 the S-bridge-complexes are prefered whereas in case of a ratio 1:1 the non-bridged P-complexes are the main products. 相似文献
Preparation of R4?nPb[Mn(CO)4P(C6H5)3]n Compounds (R?CH3, C6H5; n = 1, 2) As the first examples of organolead manganese carbonyls substituted in the manganese carbonyl ligand compounds of the type R4?nPb[Mn(CO)4P(C6H5)3]n (R?CH3, C6H5; n = 1, 2) have been prepared by the alkali salt method from R4?nPbCln and NaMn(CO)4P(C6H5)3. (C6H5)2Sn[Mn(CO)4P(C6H5)3]2 has been gained by the same method and also by thermal ligand exchange. According the IR data the ligand P(C6H5)3 is trans to the tetrahedrally surrounded lead. In solution to compounds are monomeric. 相似文献
The stabilization of the labile, zwitterionic “half‐parent” phosphasilene 4 L′Si?PH (L′=CH[(C?CH2)CMe(NAr)2]; Ar=2,6‐iPr2C6H3) could now be accomplished by coordination with two different donor ligands (4‐dimethylaminopyridine (DMAP) and 1,3,4,5‐tetramethylimidazol‐2‐ylidene), affording the adducts 8 and 9 , respectively. The DMAP‐stabilized zwitterionic “half‐parent” phosphasilene 8 is capable of transferring the elusive parent phosphinidene moiety (:PH) to an unsaturated organic substrate, in analogy to the “free” phosphasilene 4 . Furthermore, compounds 4 and 8 show an unusual reactivity of the Si?P moiety towards small molecules. They are capable of adding dimethylzinc and of activating the S?H bonds in H2S and the N?H bonds in ammonia and several organoamines. Interestingly, the DMAP donor ligand of 8 has the propensity to act as a leaving group at the phosphasilene during the reaction. Accordingly, treatment of 8 with H2S affords, under liberation of DMAP, the unprecedented thiosilanoic phosphane LSi?S(PH2) 16 (L=HC(CMe[2,6‐iPr2C6H3N])2). Compounds 4 and 8 react with ammonia both affording L′Si(NH2)PH2 17 , respectively. In addition, the reaction of 8 with isoproylamine, p‐toluidine, and pentafluorophenylhydrazine lead to the corresponding phosphanylsilanes L′Si(PH2)NHR (R=iPr 18 a ; R=C6H5?CH3 18 b , R=NH(C6F5) 18 c ), respectively. 相似文献
The silylated cyclopentadiene derivative, (MeO)3Si(CH2)3C5H5, synthesised from commerically-available (MeO)3Si(CH2)3Cl, has been used to prepare the complexes [η5-(MeO)3Si(CH2)3C5H4]Rh(CO)2, [η5-(MeO)3Si(CH2)3C5H4]Rh(COD) (COD = cyclo-octa-1,5-diene), and [η5-(MeO)3Si(CH2)3C5H4]2TiCl2. The complex [η5-(MeO)3Si(CH2)3C5H4]TiCl3, prepared by reaction of NaC5H4(CH2)3Si(OMe)3 with TiCl4 (1/1 molar ratio) and also by reaction of [η5-(MeO)3Si(CH2)3C5H4]Ti(OEt)3 with CH3COCl, proved to be very unstable. Attempts to synthesise the complex [η5-(MeO)3Si(CH2)3C5H4](η5-C5H5)TiCl2, either by reaction of [η5-(MeO)3Si(CH2)3C5H4]TiCl3 with NaC5H4 or reaction of (η5-C5H5)TiCl3 with NaC5H4(CH2)3Si(OMe)3, gave none of the expected product and only (η5-C5H5)2TiCl2 could be isolated from these reactions. The cyclo-octadiene rhodium complex supported on silica has been shown to be an efficient cyclotrimerization catalyst, and the silica-supported titanium complex (SIL-(CH2)3C5H4)2TiCl2 is, after reduction with butyllithium, an efficient and selective catalyst for the hydrogenation of alk-1-enes. 相似文献
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