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1.
The structure of a new ansa compound, (5-C5H4)CMe2(5-C9H6)TiCl2 (1), was studied by X-ray analysis:a = 15.00(1),b =15.500(5),c = 13.032(4) Å, = 92.66°(4),V = 3025.1(1) Å3, space groupP21/.,R = 0.038. The distorted tetrahedral coordination sphere of the Ti atom is formed by two Cl atoms and two -ligands. It was proposed that the angle () between theC-M direction and the line normal to M-Cp can be considered as one of the geometric parameters characteristic of the structure-properties correlation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 305–308, February, 1995.  相似文献   

2.
The electron distributions and bonding in Ru3(CO)9( 3- 2, 2, 2-C6H6) and Ru3(CO)9( 3- 2, 2, 2-C60) are examined via electronic structure calculations in order to compare the nature of ligation of benzene and buckminsterfullerene to the common Ru3(CO)9 inorganic cluster. A fragment orbital approach, which is aided by the relatively high symmetry that these molecules possess, reveals important features of the electronic structures of these two systems. Reported crystal structures show that both benzene and C60 are geometrically distorted when bound to the metal cluster fragment, and our ab initio calculations indicate that the energies of these distortions are similar. The experimental Ru–Cfullerene bond lengths are shorter than the corresponding Ru–Cbenzene distances and the Ru–Ru bond lengths are longer in the fullerene-bound cluster than for the benzene-ligated cluster. Also, the carbonyl stretching frequencies are slightly higher for Ru3(CO)9( 3- 2, 2, 2-C60) than for Ru3(CO)9( 3- 2, 2, 2-C6H6). As a whole, these observations suggest that electron density is being pulled away from the metal centers and CO ligands to form stronger Ru–Cfullerene than Ru–Cbenzene bonds. Fenske-Hall molecular orbital calculations show that an important interaction is donation of electron density in the metal–metal bonds to empty orbitals of C60 and C6H6. Bonds to the metal cluster that result from this interaction are the second highest occupied orbitals of both systems. A larger amount of density is donated to C60 than to C6H6, thus accounting for the longer metal–metal bonds in the fullerene-bound cluster. The principal metal–arene bonding modes are the same in both systems, but the more band-like electronic structure of the fullerene (i.e., the greater number density of donor and acceptor orbitals in a given energy region) as compared to C6H6 permits a greater degree of electron flow and stronger bonding between the Ru3(CO)9 and C60 fragments. Of significance to the reduction chemistry of M3(CO)9( 3- 2, 2, 2-C60) molecules, the HOMO is largely localized on the metal–carbonyl fragment and the LUMO is largely localized on the C60 portion of the molecule. The localized C60 character of the LUMO is consistent with the similarity of the first two reductions of this class of molecules to the first two reductions of free C60. The set of orbitals above the LUMO shows partial delocalization (in an antibonding sense) to the metal fragment, thus accounting for the relative ease of the third reduction of this class of molecules compared to the third reduction of free C60.  相似文献   

3.
《Polyhedron》1999,18(20):2583-2595
The reaction of the novel ferrocenyl Schiff base: [(η5-C5H5)Fe{(η5-C5H4)-CH=N-(C6H4-2-C6H5)}] (1) with Na2[PdCl4] and Na(CH3COO)·3H2O in a 1:1:1 molar ratio in methanol is reported. In this reaction two different di-μ-chloro-bridged cyclopalladated complexes: [Pd{[(η5-C5H3)-CH=N-(C6H4-2-C6H5)]Fe(η5-C5H5)}(μ-Cl)]2 (2a) and [Pd{[(C6H4-2-C6H4)-N=CH-(η5-C5H4)]Fe(η5-C5H5)}(μ-Cl)]2 (2b) can be formed depending on the experimental conditions. Compounds 2a and 2b, which differ in the nature of the metallated carbon atom (Csp2,ferrocene or Csp2,biphenyl, respectively), undergo cleavage of the ‘Pd(μ-Cl)2Pd’ bridges in the presence of thallium (I) acetylacetonate, deuterated pyridine or triphenylphosphine giving the monomeric derivatives: [Pd(CN)(acac)] (3a, 3b) and [Pd(CN)Cl(L)] {with L=py- d5(4a, 4b), PPh3(5a, 5b)}. The reactions of 2 with 1,2-bis(diphenylphosphino)ethane (dppe) reveal that the two isomers (2a and 2b) exhibit different reactivity versus dppe. These results have been interpreted on the basis of steric effects.  相似文献   

4.
The bromide complex [(η-C5H5BMe)RhBr2]2 (1) was synthesized by the reaction of the cyclooctadiene derivative (η-C5H5BMe)Rh(1,5-C8H12) with Br2. The reaction of compound 1 with Tl[Tl(η-7,8-C2B9H11)] gave (boratabenzene)rhodacarborane (η-7,8-C2B9H11)Rh-(η-C5H5BMe) (2). The structure of compound 2 was determined by X-ray diffraction  相似文献   

5.
Thermolysis of [Ru3(CO)12] in cyclohexene for 24 h affords the complexes [Ru(CO)34-C6H8)] (1), [Ru3H2(CO)92121-C6H8)] (2), [Ru4(CO)124-C6H8)] (3) [Ru4(CO)94-C6H8)(η6-C6H6)] (4a and 4b, two isomers) and [Ru5(CO)1242-C6H8)(η4-C6H8)] (5), where 1, 3, 4a and 4b have been previously characterised as products of the thermolysis of [Ru3(CO)12] with cyclohexa-1,3-diene. The molecular structures of the new clusters 2 and 5 were determined by single-crystal X-ray crystallography, showing that two conformational polymorphs of 5 exist in the solid state, differing in the orientation of the cyclohexa-1,3-diene ligand on a ruthenium vertex.  相似文献   

6.
《Solid State Sciences》2001,3(7):783-788
The synthesis and structural characterization of the complex [Ru(η6-C6H6)(η6-C6H4(CH3)COOCH3)] [BF4]2 (2) and of its precursor [Ru(η6-C6H4(CH3)COOCH3)Cl2]2 (1) are reported. Compound (2) has been characterized in two polymorphic modifications (2a and 2b) and the molecular organization in the solid state has been investigated. The complex [Ru(η5-C5H5)(η6-C6H5OH)][PF6] (3) has also been investigated; it has been shown to possess a disorder similar to that observed in the high temperature phase of related systems such as [Ru(η5-C5H5)(η6-C6H6)][PF6].  相似文献   

7.
采用自洽场分子轨道UHF/6-31G**从头算法,研究了1,2-C4H6→2-C4H6异构化反应机理,优化了基态势能面上反应物、过渡态、中间体和产物的几何构型,并对各驻点能量进行了零点能校准.结果表明该反应经历一个1-甲基环丙烯生成产物比经两步氢迁移反应历程更易发生.  相似文献   

8.
Thermolysis of cyclooctaselenadiazole (2) yields only selenium-containing products. Compound 2 reacts with CpCo sources to give [(η5-C5H5)CO]22η32-C8H6Se), a fluxional compound whose structure has been determined by X-Ray crystallography.  相似文献   

9.
The reaction of [(η5-C9H7)Ru(η2-dppe)Cl] (1) with monodentate nitriles, (L) in the presence of NH4PF6 afforded the complexes [(η5-C9H7)Ru(η2-dppe)(L)]PF6, with L?=?CH3CN (2a), CH3CH=CHCN (2b), NCC6H4CN (2c), C6H5CH2CN (2d), respectively. However, reaction of 1 with NH4PF6 in methanol yielded an amine complex of the type [(η5-C9H7) Ru(η2-dppe)(NH3)]PF6 (3a). The complexes were fully characterized by spectroscopy and analytical data. The molecular structures of the complexes [(η5-C9H7)Ru(η2-dppe) (CH3CN)]PF6 (2a) and [(η5-C9H7)Ru(η2-dppe)(NH3)]PF6 (3a) have been determined by single crystal X-ray analyses.  相似文献   

10.
Compounds (η-C5R5)Fe[η-9-(Me2S)-7,8-C2B9H10] (R=H, Me) and (η-C4Me4)Co[η-9-(Me2S)-7,8-C2B9H10] were synthesized by the reactions of Na[9-(Me2S)-7,8-C2B9H10] with complexes [(η-C5H5)Fe(MeCN)3]PF6, [(η-C5Me5)Fe(MeCN)3]BF4, and [(η-C4Me4)Co(MeCN)3]PF6, respectively. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 177–179, January, 1999.  相似文献   

11.
The reactions of [Ru3(CO)10(μ-dppm)] 4 with quinolines afforded [Ru3 (μ-CO)(CO)732-P(C6H5)CH2P(C6H5)2)}{μ-η2-C9H5(R)N}] (8, R = 4-Me; 9, R = H) as the major products along with small amounts of known compound [Ru3(CO)933-P(C6H5)CH2P(C6H5)(C6H4)}] 5. The molecular structure of 8 has been determined by single crystal X-ray studies. The reaction of 5 with 4-methylquinoline in refluxing cyclohexane afforded 8 and two known dinuclear compounds, [Ru2(CO)6{μ-CH2P(C6H5)(C6H4)P(C6H5}] 10 and [Ru2(CO)6 {μ-(C6H4)P(C6H5)(CH2)P(C6H5}] 11, in 40, 12, and 10% yields, respectively. The compounds 10 and 11 are also formed from the thermolysis of 4 in addition to the major compound 5. The solid state structure of the previously reported [Ru3(CO)10(η-H){μ-η2-C9H6N}] 2a is also reported for comparison.  相似文献   

12.
(η^5-C5H5)(η^5-C5H4R)TiCl2类化合物的新合成方法   总被引:1,自引:0,他引:1  
本文报道了取代环戊二烯基负离子与[(η~5-C_5H_5)TiCl_2]_2O反应生成(η~5-C_5H_5)(η~5-C_5H_4R)·TiCl_2的新方法。研究了取代环戊二烯基负离子的空间位阻和(η~5-C_5H_5)TiCl_3,[(η~5-C_5H_5)TiCl_2]_2O的结构以及反应温度对产物产率的影响。合成了七个新的(η~5-C_5H_5)(η~5-C_5H_4R)TiCl_2类型的化合物及七个相应的二氟化合物。  相似文献   

13.
陈寿山  姚文庆 《化学学报》1990,48(3):262-265
本文报道了取代环戊二烯基负离子与[(η^5-C5H5)TiCl2]2O反应生成(η^5-C5H5)(η^5-C5H4R).TiCl2的新方法. 研究了取代环戊二烯基负离子的空间位阻和(η^5-C5H5)TiCl3, [(η^5-C5H5)TiCl2]2O的结构以及反应温度对产物产率的影响. 合成了七个新的(η^5-C5H5)(η^5C5H4R)TiCl2类型的化合物及七个相应的二氟化合物。  相似文献   

14.
Single addition of the nucleophiles X (X = H, CN, OH) to the less sterically hindered ring in [(η6-C6Me6)Ru(η6-C16H16)][BF4]2 (1) proceeds smoothly to produce, as the sole product, [(exo5-C6Me6X)Ru(η6-C16H16)][BF4]. Use of Na[BD4] in place of Na[BH4] gives the expected shift in ν(C-Hexo) in the infrared spectrum.  相似文献   

15.
Tetranuclear organobismuth complex Bi4(O)2(O2CC6H2F3-3,4,5)8 · 26-65Me with four bismuth atoms joined via the bridging carboxylate ligands and oxygen atoms was studied using X-ray diffraction analysis. The coordination sphere of either of the two terminal bismuth atoms contains the chelate carboxylate ligand and the toluene molecule. For the bridging tricoordinated oxygen atoms, the Bi–O distances are 2.083(2), 2.119(2), and 2.276(2) Å. The average distance between the bismuth atom and the center of toluene molecule is equal to 3.131 Å.  相似文献   

16.
The dimeric complex [{(η6-p-cymene)Ru(μ-Cl)Cl}2] (1) reacts with S,N-donor Schiff base ligands, para-substituted S-(thiophen-2-ylmethylene)phenylamines in methanol to give mononuclear amine complexes of the type [(η6-p-cymene)RuCl2(NH2–C6H4p-X)] {X?=?H (2a); X?=?CH3 (2b); X?=?OCH3 (2c); X?=?Cl (2d); Br (2e) X?=?NO2 (2f), respectively} by hydrolysis of the imine group of the ligand after coordination to the metal. The complexes were characterized by analysis and IR and NMR spectroscopy. The molecular structure of [(η6-C10H14)RuCl2(H2N–C6H4p-Cl)] (2d) was established by a single-crystal X-ray diffraction study.  相似文献   

17.
IntroductionSince K pf[1]discovered that dicyclopenta die-nyltitanium dichloride possesses antitumour action in1979,a large number of cyclopentadienyltitanium com-plexes with different substituents have been synthe-sized[2,3].The experimental data reveal …  相似文献   

18.
Treatment of the electronically unsaturated 4-methylquinoline triosmium cluster $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu_3\hbox{-}\upeta^{2}\hbox{-}\hbox{C}_{9}\hbox{H}_{5} \hbox{(4-Me)N})(\upmu\hbox{-H})]$ (1) with tetramethylthiourea in refluxing cyclohexane at 81°C gave $[\hbox{Os}_{3}\hbox{(CO)}_{8}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5} \hbox{(4-Me)N})(\upeta^2\hbox{-SC}(\hbox{NMe}_2\hbox{NCH}_2\hbox{Me})(\upmu \hbox{-H})_2]$ (2) and $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5}\hbox{(4-Me)N})(\upeta^1\hbox{-SC}(\hbox{NMe}_2)_2)(\upmu\hbox{-H})]$ (3). In contrast, a similar reaction of the corresponding quinoline compound $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu_{3}\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N})(\upmu\hbox{-H})]$ (4) with tetramethylthiourea afforded $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu\hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N})(\upeta^{1}\hbox{-SC(NMe}_{2})_{2})(\upmu\hbox{-H)}]$ (5) as the only product. Compound 2 contains a cyclometallated tetramethylthiourea ligand which is chelating at the rear osmium atom and a quinolyl ligand coordinated to the Os3 triangle via the nitrogen lone pair and the C(8) atom of the carbocyclic ring. In 3 and 5, the tetramethylthiourea ligand is coordinated at an equatorial site of the osmium atom, which is also bound to the carbon atom of the quinolyl ligand. Compounds 3 and 5 react with PPh3 at room temperature to give the previously reported phosphine substituted products $[\hbox{Os}_{3}\hbox{(CO)}_{9}(\upmu \hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{5}\hbox{(4-Me)N)(PPh}_{3})(\upmu\hbox{-H)}]$ (6) and $[\hbox{Os}_{3}\hbox{(CO}_{9}(\upmu \hbox{-}\upeta^{2}\hbox{-C}_{9}\hbox{H}_{6}\hbox{N)(PPh}_{3})(\upmu\hbox{-H)}]$ (7) by the displacement of the tetramethylthiourea ligand.  相似文献   

19.
It is shown that (1,2,7-η3-2-Me-benzyl)(η5-C5H5)Mo(CO)2 exits in solution as one isomer which is fluxional, probably via (7-η1-2-Me-benzyl)((η5-C5H5)Mo(CO)2, with ΔG370 = 23.6 ± 1.0 kcal mol−1. In contrast, (1,2,7-η3-3-Me-benzyl)(η5-C5H5)Mo(CO)2 exits as two isomers at −20°C, which undergo interconversion at room temperature with ΔG 15.7 kcal mol−1. This dynamic process is an allyl rotation. It is probable that there is also a low energy [1,5]-sigmatropic shift.  相似文献   

20.
Rhodacarboranes closo-3,3-(Ph3P)2-3-H-3,1,2-RhC2B9H11 and closo-(2,3-C7H7CH2)-3,1,2-RhC2B9H11 are catalysts for the alcoholysis of hydridesilanes. Closo-3,3-(2,3-C7H7CH2)-3,1,2-RhC2B9H11 displays greater activity than closo-3,3-(Ph3P)2-3-H-3,1,2-RhC2B9H11 though both rhodacarboranes catalyze the alcoholysis of hydridesilanes more efficiently than (Ph3P)3RhCl.A. N. Nesmeyanov Institute of Organometallic Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 7, pp. 1657–1660, July, 1992.  相似文献   

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