AbstractReactions of non-gem-hexanedioxytetrachlorocyclotriphosphazene (1) with monofunctional nucleophilic reagents, 2-(2-hydroxyethyl)thiophene (2), benzyl alcohol (3) and 1,1,3,3-tetramethylguanidine (4) were investigated. The reactions, using an excess of NaH, in THF solutions, under refluxing conditions and with 1:2?mole ratios allow the synthesis of the following novel cyclotriphosphazene derivatives: 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-[2-(2-ethoxy)hiophene]-cyclotriphosphazatriene, N3P3Cl2[O(CH2)6O-(C6H8OS)2] (5); 2,4-(hexane-1,6-dioxy)-2,4,6,6-[2-(2-ethoxy) thiophene]-cyclotriphosphazatriene, N3P3[O(CH2)6O-(C6H8OS)4] (6); 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-(methoxybenzene)-cyclotriphosphazatriene, N3P3Cl2[O(CH2)6O-(C6H5CH2O)2] (7); 2,4-(hexane-1,6-dioxy)-2,4,6,6-(methoxybenzene)-cyclotriphosphazatriene, N3P3[O(CH2)6O-(C6H5CH2O)4] (8); and 2,4-dichloro-2,4-(hexane-1,6-dioxy)-6,6-(1,1,3,3-tetramethyguanidine)-cyclotriphosphazatriene, N3P3Cl2[O(CH2)6O-HN-CN2(CH3)4] (9). The structures of the synthesized compounds (5–9) have been characterized by elemental analysis, TLC-MS, 1H, 13C and 31P {+1H} and {?1H} NMR spectral data. 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
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
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
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
The new compound C10H6P(S)[NSi(CH3)3]2P(S) ( 3 ) which contains a P2N2 heterocycle has been prepared in low yield by partial thermal decomposition of 1-{[N,N′-bis(trimethylsilyl)acetamidinium]sulfido}-3-(trimethylsilylamino)-1 H,3 H,1 λ5,3 λ5-naphtho[1,8 a,8-cd][1,2,6]thiadiphosphinine-1,3-dithione [CH3C{NHSi(CH3)3}2]+[C10H6P(S)(NHSiMe3)SP(S)2]– ( 2 ). Reaction of 2 with potassium hydroxide in acetonitrile gives the completely desilylated product [CH3C(NH2)2]+[C10H6P(S)(NH2)SP(S)2]– ( 4 ). The structures of the new compounds 3 and 4 were elucidated by FTIR and NMR spectroscopy methods and by X-ray structure analyses. 相似文献
Dinuclear Silylene Bridged Cyclopentadienylrhodiumbis(ethene) Complexes, Photochemical Reaction with Benzene Derivatives, and Selective Inclusion of Methylcyclopentane into the Crystal Lattice of [Me2Si{3-But-C5H3Rh(C2H4)2}2] By reaction of [{(C2H4)2RhCl}2] with Na2[Me2Si(C5H4)2] or with Li2[Me2Si(3-But-C5H3)2] in THF the dinuclear silylene bridged complexes [Me2Si{C5H4Rh(C2H4)2}2] 1 and [Me2Si{3-But-C5H3Rh(C2H4)2}2] 2 , respectively, were synthesized. Due to the asymmetric substitution of the five-membered rings and their hindered rotation around the Si? C axes, 2 is formed as three isomers. The X-ray structure analysis of 2 obtained from hexane reveals the selective inclusion of methylcyclopentane, the content of which in the solvent is about 17%, into the crystal lattice. UV irradiation of 1 in hexane in the presence of benzene causes elimination of the ethene ligands yielding the μ-η3:η3 benzene complex [Me2Si(C5H4Rh2)2C6H6] which cannot be separated from unreacted 1 . However, separation is possible in case of the hexamethylbenzene compound 4 analogous with 3 . 相似文献
The new ruthenium(II) complex [(C8H10)RuCl2]n (1) (C8H10 = 1,3,5-cyclooctatriene; n ⩾ 2) has been obtained from the reaction of RuCl3·xH2O with 1,3,5,7-cyclooctatetraene in refluxing ethanol. Reduction of [(C8H10)RuCl2]n and [(C7H8)RuCl2]2 (2) (C7H8 = 1,3,5-cyclooctatriene) by Na/Hg amalgam in the presence of isoprene (C5H8) gives the novel ruthenium(O) complexes [(η6-C8H10)Ru(η4-C5H8)] (3) and [(η6-C7H8)Ru(η4-C5H8)] (4). [(η6-C7H8Ru(η4-C5H8)] reacts with CO and HBF4 to give [(η6-C7H8)Ru(η3-C5H9)(CO)][BF4] (C5H9 = trans-1,2-dimethylallyl (5a); 1,1-dimethylallyl (5b)). 相似文献
The bis(silyl)triazene compound 2,6‐(Me3Si)2‐4‐Me‐1‐(N?N? NC4H8)C6H2 ( 4 ) was synthesized by double lithiation/silylation of 2,6‐Br2‐4‐Me‐1‐(N?N? NC4H8)C6H2 ( 1 ). Furthermore, 2,6‐bis[3,5‐(CF3)2‐C6H3]‐4‐Me‐C6H2‐1‐(N?N? NC4H8)C6H2 derivative 6 can be easily synthesized by a C,C‐bond formation reaction of 1 with the corresponding aryl‐Grignard reagent, i.e., 3,5‐bis[(trifluoromethyl)phenyl]magnesium bromide. Reactions of compound 4 with KI and 6 with I2 afforded in good yields novel phenyl derivatives, 2,6‐(Me3Si)2‐4‐MeC6H2? I and 2,6‐bis[3,5‐(CF3)2? C6H3]‐4‐MeC6H2? I ( 5 and 7 , resp.). On the other hand, the analogous m‐terphenyl 1,3‐diphenylbenzene compound 2,6‐bis[3,5‐(CF3)2? C6H3]C6H3? I ( 8 ) could be obtained in moderate yield from the reaction of (2,6‐dichlorophenyl)lithium and 2 equiv. of aryl‐Grignard reagent, followed by the reaction with I2. Different attempts to introduce the tBu (Me3C) or neophyl (PhC(Me)2CH2) substituents in the central ring were unsuccessful. All the compounds were fully characterized by elemental analysis, melting point, IR and NMR spectroscopy. The structure of compound 6 was corroborated by single‐crystal X‐ray diffraction measurements. 相似文献
The crystal and molecular structure of the complex Th[η5-(CH3)5C5]2[CH2-Si(CH3)3]2, which undergoes facile intramolecular cyclometalation to the thoracyclobutane Th[η5-(CH3)5C5]2(CH2)2Si(CH3)2, is reported. While the Th[η5-(CH3)5C5]2 ligation is unexceptional, the Th[CH2Si(CH3)3]2 fragment is highly unsymmetrical having Th-C (corresponding angle Th-C-Si) 2.51(1) Å (132.0(6)°) and 2.46(1) Å (148.0(7)°). This conformation, which appears to result from severe intramolecular non-bonded contacts, allows a methyl hydrogen atom of one CH2Si(CH3)3 ligand to approach within ca. 2.3 Å of the α-carbon atom of the other CH2Si(CH3)3 ligand. 相似文献
The optically active quaternary ammonium salt (S)-(?)-α-[(C6H5)CH(CH3)N(CH3)3I] reacts with AlR3 to afford optically active organoaluminum based inclusion compounds, liquid clathrates, of the formula (S)-(?)-α-[(C6H5)CH(CH3)N(CH3)3][Al2R6I] (R=CH3, C2H5). Specific rotation ([α]25D) for the Al(CH3)3 compound was determined to be ?13.19° while that for the Al(C2H5)3 analog was determined to be ?14.30°. There are 13.8 toluene molecules per anionic moiety for the trimethylaluminum based liquid clathrate while there are 15.0 toluene molecules per anion for the corresponding triethylaluminum inclusion compound. 相似文献
Bis[tris(trimethylsilyl)cyclopentadienyl]europium, Eu{C5H2[Si(CH3)3]3}2 (1) , has been synthesized by a modified transmetallation route between Tl{C5H2[Si(CH3)3]3} and europium powder in toluene. 1 crystallizes in the monoclinic space group C2/c (No. 15) with a = 20.293(5) Å, b = 20.221(5) Å, c = 9.654(2) Å, β = 106.412(5)°, V = 3800.1(15) Å3, Z = 4. The unit cell contains monomeric molecules that adopt a bent metallocene conformation with two partially staggered Cp? ligands. Magnetic susceptibility measurements in the temperature range 2–300 K display ideal Curie paramagnetic behaviour of the 4f7 system with Curie constant C = 9.6 × 10?5 m3 K mol?1 corresponding to temperature independent μeff = 7.8. 相似文献
Characterization of Distortional Isomers of the Anions Pentacyano-oxo-molybdate(IV) and of Tetracyano-aqua-oxo-molybdate(IV) in the Solid State. Crystal Structures of [(C6H5)4P]3[MoO(CN)5] · 7 H2O (green), [(C6H5)4As]2[MoO(OH2)(CN)4] · 4 H2O (blue), and [(C6H5)4P]2[MoO(OH2) (CN)4] · 4 H2O (green) Preparation of a series of salts containing the new pentacyano-oxo-molybdate(IV) anion is described: Cs2H[MoO(CN)5] (blue), [(CH3)4N]2H[MoO(CN)5] · 2 H2O (blue) and [Cr(en)3] [MoO(CN)5] · 4 H2O (green). The green [(C6H5)4P]3[MoO(CN)5] · 7 H2O crystallizes triclinic in the space group P1 . The molybdenum(IV) center is in an pseudo-octahedral environment of a terminal oxo-group (d(Mo?O); 1.705(4) Å), a CN? group in the trans-position (d(Mo? C): 2.373(6) Å), and four equatorial CN? groups (averaged d(Mo? C): 2.178 (Å). The blue and green salts exhibit v(Mo?O) stretching frequencies at 948 cm?1 and 920 cm?1, respectively. Blue and green salts containing the [MoO(OH2)(CN)4]2? anion and [(C6H5)4P]+ or [(C6H5)4As]+ cations have been prepared and characterized by single crystal crystallography. [(C6H5)4P]2[MoO(OH2)(CN)4] · 4 H2O (green) and [(C6H5)4As]2[MoO(OH2)(CN)4] · 4 H2O (blue) crystallize monoclinic in the space group C—P21/n. They are considered to be distortional isomers of the complex anion: the green species has a Mo?O bond distance of 1.72(2) Å whereas for the blue species d(Mo?O) = 1.60(2) Å is found; the corresponding v(Mo?O) frequencies are at 920 cm?1 and 980 cm?1. 相似文献
Reaction of the Cage-like Silicic Acid Derivative [(CH3)2HSi]8Si8O20 with Unsaturated Organic Compounds By 29Si, 1H, and 13C NMR investigations were shown that the eight HSi?groups of the double four-ring silicic acid derivative [(CH3)2HSi]8Si8O20 react with the following unsaturated compounds: vinylcyclohexene, allyl glycidyl ether, methyl methacrylate, octadecene-1, and styrene. The resulting oily products are soluble in organic solvents. The compounds were characterized by the chemical shifts of the 29Si, 1H, and 13C NMR signals. Their formulae are [C6H9(CH2)2Si(CH3)2]8Si8O20, [CH3OOCCH(CH3)CH2Si(CH3)2]8Si8O20, [CH3(CH2)17Si(CH3)2]8Si8O20 and [C6H5(CH2)2Si(CH3)2]8Si8O20, and [C6H5CH(CH3)Si(CH3)2]8 Si8O20, respectively. Mainly the addition reactions do not follow the Markovnikov rule. 相似文献
Molybdenum(II) Halide Clusters with six Alcoholate Ligands: (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6CH3OH and (C18H36N2O6Na)2[Mo6Cl8(OC6H5)6] . The reaction of Na2[Mo6Cl8(OCH3)6] and 2,2,2-crypt yields (C18H36N2O6Na)2[Mo6Cl8(OCH3)6] · 6 CH3OH ( 1 ), which is converted to (C18H36N2O6Na)2[Mo6Cl8(OC6H5)6] ( 2 ) by metathesis with phenol. According to single crystal structure determinations ( 1 : P3 1c, a=14.613(3) Å, c=21.036(8) Å; 2 : P3 1c, a=15.624(1) Å, c=19.671(2) Å) the compounds contain anionic clusters [Mo6Cl8i(ORa)6]2? ( 1 : d(Mo—Mo) 2.608(1) Å to 2.611(1) Å, d(Mo—Cl) 2.489(1) Å to 2.503(1) Å, d(Mo—O) 2.046(4) Å; 2 : d(Mo—Mo) 2.602(3) Å to 2.608(3) Å, d(Mo—Cl) 2.471(5) Å to 2.4992(5) Å, d(Mo—O) 2.091(14) Å). Electronic interactions of the halide cluster and the phenolate ligands in [Mo6Cl8(OC6H5)6]2? is investigated by means of UV/VIS spectroscopy and EHMO calculations. 相似文献
The reaction between BiI3 and two equivalents of dmpu (dmpu = N,N′-dimethylpropylene urea) in thf (tetrahydrofuran) or toluene affords dark red crystals of the complex [Bi(dmpu)6][Bi3I12] which was characterised by X-ray crystallography and consists of octahedral [Bi(dmpu)6]3+ cations and [Bi3I12]3? anions both with 3 symmetry. An analogous reaction between SbI3 and dmpu afforded orange crystals of what is probably a hydrolysis product, [C5NH6]2[H(dmpu)2][Sb2I9], which was also characterised by X-ray crystallography and contains a face-shared bioctahedral [Sb2I9]3? anion with two pyridinium cations and a hydrogen bonded [H(dmpu)2]+ cation. [CH2?C(C6H4-4-NO2)CH2NMe3]I and one equivalent of SbI3 afforded the orange crystalline complex [CH2?C(C6H4-4-NO2)CH2NMe3]3[Sb2I9] an X-ray crystallographic study of which revealed a face-shared bioctahedral [Sb2I9]3? anion similar to that present in [C5NH6]2[H(dmpu)2][Sb2I9]. Four equivalents of BiI3 and [CH2?C(C6H4-4-NO2)CH2NMe3]I afforded the complex [CH2?C(C6H4-4-NO2)CH2NMe3]3[Bi3I12], the [Bi3I12]3? anion being essentially identical to that encountered in [Bi(dmpu)6][Bi3I12]. [CH3(CH2)2COS(CH2)2NMe3]I and four equivalents of SbI3 yielded orange crystals of the complex [CH3(CH2)2COS(CH2)2NMe3]4[Sb8I28] which was also characterised by X-ray crystallography and shown to contain a new structural type of [E8X28]4? anion (E = As, Sb, Bi; X = halide). 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
Synthesis and NMR Spectra of λ5-Diphosphets. Structure of 2,4-Diphenyl-1,1,3,3-tetrakis (diethylamino)-1λ5, 3λ5-diphosphete Preparation, properties, and n.m.r. spectra of C2H5PF2[N(C2H5)2]2, CH2?PF[N(C2H5)2]2, and the diphosphetes {RC?P[N(C2H5)2]2}2 (R) ? H ( 5a ), CH3 [( 5b )] are described. The λ5-diphosphete {HC?P(NR2)2}2 (R ? CH3) reacts with BF3 · O(C2H5)2 to give which is transformed into by n-C4H9Li. The crystal and molecular structure of 2,4-diphenyl-1,3,3-tetrakis(diethylamino)-1λ5,3λ5-diphosphete 2 are reported and discussed. 相似文献
Bis-(trimethylsilyl)acetamide (BSA) reacts with borazines [RNBX]3, R=H,X=F; R=CH3,X=F; R=C6H5,X=F and R=C6H5,X=Cl to the corresponding borazines,X=OSi(CH3)3. The1H-NMR signal of the Si(CH)3-groups of [C6H5NBOSi(CH3)3]3 is at abnormally high field. With [CH3NBCl]3,BSA forms borazines which contain both Si(CH3)3O- and O?C(CH3)=NSiR3 groups bonded to the boron atoms. With LiN[Si(CH3)3]2, [CH3NBCl]3 forms silylaminoboranes.1H-NMR, mass spectrometric and analytical data are reported. 相似文献
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