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1.
Reaction of optically active ketone complexes (+)-( R)-[(η 5-C 5H 5)Re(NO)-(PPh 3)(η 1-O=C(R)(CH 3)] + BF 4− (R = CH 2CH 3, CH(CH 3) 2m C(CH 3) 3, C 6H 5) with K(s-C 4H 9) 3BH gives alkoxide complexes (+)-( RS)-(η 5-C 5H 5)Re(NO)(PPh 3)-(OCH(R)CH 3) (73–90%) in 80–98% de. The alkoxide ligand is then converted to Mosher esters (93–99%) of 79–98% de. 相似文献
2.
Thermal displacement of coordinated nitriles RCN (R = CH 3, C 2H 5 or n-C 3H 7) in [C 5H 5Fe(L 2)(NCR)]X complexes (L 2 = P(OCH 3) 3) 2, (P(OC 6H 5) 3) 2 or (C 6H 5) 2PC 2H 4P(C 6H 5) 2 (DPPE)) by E(CH 3) 2 affords high yields of [C 5H 5Fe(L 2)(E(CH 3) 2)]X compounds (E = S, Se and Te; X = BF 4 or PF 6). Spectroscopic data and ligand displacement reactions are presented and discussed together with related observations on [C 5H 5Fe(CO) 2(E(CH 3) 2)]BF 4 compounds. The molecular structure of [C 5H 5Fe(P(OCH 3) 3) 2(S(CH 3) 2)]PF 6 was determined by a single-crystal X-ray diffraction study: monoclinic, space group P2 1/ n- C52h (No. 14) with a = 8.4064(12), b = 11.183(2), c = 50.726(8) Å, β = 90.672(13)° and Z = 8 molecules per unit cell. The coordination sphere of the iron atom is pseudo-tetrahedral with an Fe---S bond distance of 2.238 Å. 相似文献
3.
The ruthenium(II) complex Ru(CO) 2(NH 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I has been prepared by the reaction of Ru(CO) 4(Si(C 6H 5)(CH 3) 2)I with benzylamine. Two-dimensional homonuclear 1H NMR experiments examine the scalar coupling of the enantiotopic amino and methylene protons of the benzylamine ligand. X-ray analysis of Ru(CO) 2(NH 2CH 2C 6H 5) 2(Si(C 6H 5)(CH 3) 2)I·1/3C 5H 12 (triclinic; P
; a = 14.266(4), b = 15.748(5), c = 20.082(6) Å; = 94.38(3), β = 96.30(2), γ = 101.52(2)°) indicates three crystallographically unique complexes form a clathrate with a pentane guest. 相似文献
4.
Treatment of 1,2- trans-C 5H 8(PCl 2) 2 with 1,2-C 2H 4(NHPr- i) 2 gave the C2-symmetric perhydro-1,6,2,5-diazaphosphocine C 5H 8{P(Cl)N(Pr- i)CH 2} 2- cyclo, which produced dissymmetric C 5H 8(PPh 2){P[N(Pr- i)CH 2] 2- cyclo} on further reaction with PhMgBr. Cleavage of the P---N bonds with gaseous HCl afforded C 5H 8(PPh 2)(PCl 2), which was converted to C 5H 8(PPh 2){P(OPh) 2} 2 by reaction with phenol. All chiral P, P derivatives were obtained as racemates as well as resolved (1 R,2 R)- and (1 S,2 S)-enantiomers. 相似文献
5.
Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C 5H 5)CH 2(2-C 4H 3NH) (2) with Ti(NMe 2) 4 affords bis(dimethylamido)titanium complex [(η 5-C 5H 4)CH 2(2-C 4H 3N)]Ti(NMe 2) 2 (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH 2(2-C 4H 3NH)} 2C 5H 4 (4), undergoes an analogous reaction with Ti(NMe 2) 4 to give [1,3-{CH 2(2-C 4H 3N)} 2(η 5-C 5H 3)]Ti(NMe 2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies. 相似文献
6.
On the basis of ab initio MP2/6–31 + + G(2d,2p) calculations, we examined the potential energy surfaces of the water·hydrocarbon complexes H 2O·CH 4, H 2O·C 2H 2 and H 2O·C 2H 2 to locate all the minimum energy structures and estimate the hydrogen bond energies and vibrational frequencies associated with the C(sp n)---H·O and the O---H·C(sp n) bonds ( n = 1−3). Our calculations show that H 2O·C 2H 2, H 2O·C 2H 4 and H 2O·CH 4 have two minimum energy structures (i.e., the C---H·O and O---H·C hydrogen bond forms), but H 2O·C 2H 4 has only one when the vibrational motion is taken into account, the O---H·C hydrogen bond form. We have also computed the barrier for the interconversion from one minimum to the other. The fully optimized geometries of H 2O·CH 4, H 2O·C 2H 4 and H 2O·C 2H 2 as well as the vibrational shifts of the C---H stretching frequencies in their C---H·O hydrogen-bonded forms are in good agreement with the available experimental data. The calculated hydrogen bond energies show that the C(sp n---H·O bond strengths decrease in the order C(sp)---H·O>C(sp 2)---H·O>C(sp 3)---O>C(sp 3---H·O, which is also consistent with the available experimental data. 相似文献
7.
Treatment of the diaminobenzene [C 6H 4{CH 2NMe 2} 2-1,3] (NCN-H, 1) with one or two equivalents of cis-PtCl 2(DMSO) 2 leads to exclusive formation of the doubly cycloplatinated species [C 6H 4{CH 2NMe 2} 2-1,5-{PtCl(DMSO)} 2-2,4] (3), which upon addition of triphenylphosphine yields the bisphosphine adduct [C 6H 4{CH 2NMe 2} 2-1,5-{PtCl(PPh 3)} 2-2,4] (4). The X-ray molecular structure of 4 revealed the presence of highly distorted square planar Pt(II) centers which is caused by close proximity of the two phosphine donor ligands. Complexes of type 3 can be regarded as suitable starting materials for the directional build-up of larger macromolecular structures. 相似文献
8.
The infrared spectra of solid samples of C 4H 7K and C 4D 7K have been investigated in the 4000 to 30 cm −1 range. A complete assignment of intramolecular fundamentals of C 4H 7− and C 4D 7− ions and of potassium-allyl vibrations is proposed and the intramolecular force constants are calculated. The C(CH 2) 32− anion has been identified spectroscopically. Structures of C 3H 5−, C 4H 7− and C(CH 3) 32− are discussed and compared with those optimised by the MINDO/3 method. 相似文献
9.
The reactions of the half-sandwich molybdenum(III) complexes CpMo(η 4-C 4H 4R 2)(CH 3) 2, where Cp=η 5-C 5H 5 and R=H or CH 3, with equimolar amounts of B(C 6F 5) 3 have been investigated in toluene. EPR monitoring shows the formation of an addition product which does not readily react with Lewis bases such as ethylene, pyridine, or PMe 3. The analysis of the EPR properties and the X-ray structure of a decomposition product obtained from dichloromethane, [CpMo(η 4-C 4H 6)(μ-Cl)(μ-CH 2)(O)MoCp][CH 3B(C 6F 5) 3], indicate that the borane attack has occurred at the methyl position. 相似文献
10.
Ab initio study of the reactions of n-heptyl radicals(1-C 7H 15, 2-C 7H 15, 3-C 7H 15, and 4-C 7H 15) with methanol was conducted over the temperature range of 300-1500 K. Transition states for the reaction channels producing C 7H 15OH, CH 3, C 7H 15OCH 3, H, C 7H 16, CH 2OH and CH 3O were identified and the geometries of all stationary points were calculated at BB1K/MG3S level of theory. The potential barrier heights of the corresponding transition states were predicted by the CBS-QB3//BB1K and G4//BB1K methods, indicating that the eight H-abstraction channels are more kinetically favorable than the channels where OH transfers from CH 3OH to C 7H 15 and where the C 7H 15OCH 3+H products are given. The rate constants of H-abstraction channels were calculated with TST and TST/Eck. Both the forward and reverse rate constants have positive temperature dependence and the tunneling effect is only important at the temperature lower than 700 K. For the reactions of H-atom abstraction from methyl in CH 3OH by n-heptyl, a reverse and the corresponding forward rate constant are roughly equal. For the reactions of H-atom abstraction from OH in CH 3OH by n-heptyl, a reverse rate constant is larger by several orders of magnitude than the corresponding forward one. 相似文献
11.
Modification of the liquid Ni(OR N) 2, R N = C 2H 4NMe 2, with stoichiometric or sub-stoichiometric amounts of carboxylic acids, HCOOH or CH 3COOH, results in formation of crystalline heteroleptic complexes Ni 6(OH) 2(OR N) 6(OCOR) 2, R = H (1), CH 3 (3) with the core structure closely analogous to that observed earlier for hexanuclear titanium (IV) alkoxide carboxylates and derived from hexagonal packing of the donor atoms. 相似文献
12.
Reduction of (C 5H 5) 2TiCl 2 with Zn in presence of benzyl cyanide gives the (μ-alkyl-ideneamido)titanocene complex [(C 5H 5) 2TiCl] 2[μ-{N=C(CH 2C 6H 5)---C(CH 2C 6H 5)=N}] with C---C bond formation between two benzyl cyanide molecules. X-ray structure investigation indicates a symmetrical structure. The C=N distances are smaller than usual, the Ti---N distances are very short, and the Ti---N---C angle differs only a little from 180°, which infers a heteroallene structure of the complex. 相似文献
13.
The compounds C 5H 5Co(η 2-CH 3CHS)PMe 3 (I) and C 5H 5Co(η 2-CH 3CHSe)PMe 3 (II) are prepared from C 5H 5Co(CO)PMe 3, CH 3CHBr 2 and NaSH or NaSeH, respectively. The synthesis of the corresponding rhodium complexes C 5H 5Rh(η 2-CH 3CHS)P(i-Pr) 3 (VI) and C 5H 5Rh(η 2-CH 3CHSe)P(i-Pr) 3 (VII) has been achieved through hydrogenation of C 5H 5Rh(η 2-EC=CH 2)P(i-Pr) 3 (E = S, Se), using RhCl(PPh 3) 3 as a catalyst. The crystal structure of VII has been determined. 相似文献
14.
Dissolution of Mo 2O 5((CH 3) 2NCH 2CH 2NHCH 2CH 2S) 2 in dimethylformamide results in the formation of a species without coordinated sulphur, as indicated by 95Mo NMR spectroscopy. Subsequent crystallization of this solution yielded the compound Mo 4O 12(C 12H 30N 4S 2) 2(C 3H 7ON) 2 which X-ray crystallography shows to consist of a novel Mo 4O 12 core, containing an eight-membered Mo 4O 4 ring with the two pairs of diagonal molybdenum atoms linked by disulphido-containing groups. 相似文献
15.
运用密度泛函(DFT)理论,采用Materials Studio 8.0,用GGA/BP方法研究了C_6H_2(OH)_3CH_3氧化成羟基苯甲酸的反应路径。结果表明,甲基上的氢原子被氧化成羟基以及羟基被氧化为醛基及醛基被氧化成羧基均为放热过程。分子C_6H_2(OH)_3CH_3中甲基氧化成羧基的主路径为三个氢原子氧化反应路径,其路径为C_6H_2(OH)_3CH_3+3O→C6H2(OH)3C(OH)3→C6H2(OH)3COOH+H2O,该路径受限于羟基直接被氧化成羧基过程,需克服130 k J/mol的反应势垒,反应速率常数对数ln(k)为-22.96 s-1;醛基、羟基优先被氧化成羧基的顺序为:-CHO-C(OH)3-HC(OH)2-H2C(OH);提高反应温度、氧气浓度均有利于羟基苯甲酸的生成,适当的催化剂有利于促进整个反应的进行。 相似文献
16.
Six new cluster derivatives [Rh 2Co 2(CO) 6(μ-CO) 4(μ 4,η 2-HCCR)] (R=FeCp 2 1, CH 2OH 2, (CH 3O)C 10H 6CH(CH 3)COOCH 2CCH 3) and [RhCo 3(CO) 6(μ-CO) 4(μ 4,η 2-HCCR)] (R=FeCp 2 4, CH 2OH 5, (CH 3O)C 10H 6CH(CH 3)COOCH 2CCH 6) were obtained by the reactions of [Rh 2Co 2(CO) 12] and [RhCo 3(CO) 12] with substituted 1-alkyne ligands HCCR [R=FeCp 2 7, CH 2OH 8, (CH 3O)C 10H 6CH(CH 3) COOCH 2CCH 9] in n-hexane at room temperature, respectively. Alkynes insert into the Co---Co bond of the tetranuclear clusters to give butterfly clusters. [Rh 2Co 2(CO) 6(μ-CO) 4(μ 4,η 2-HCCFeCp 2)] (1) was characterized by a single-crystal X-ray diffraction analysis. Reactions of 1, 2 with 7, 8 and ambient pressure of carbon monoxide at 25 °C gave two known cluster complexes [Co 2(CO) 6(μ 2, η 2-HCCR)] (R=FeCp 2 10, CH 2OH 11), respectively. All clusters were characterized by element analysis, IR and 1H-NMR spectroscopy. 相似文献
17.
Distibines of the type R 2SbSbR′ 2 with R = CH 3, R′ = C 2H 5 (1), R = CH 3, R′= n-C 3H 7 (2), R = CH 3, R′= C 6H 5 (3), R = C 2H 5, R′= C 6H 5 (4), R = n-C 3H 7, R′ = C 6H 5 (5), and R = CH 3, R′ = 2,4,6-(CH 3) 2C 6H 2 (6) are formed in equilibria by exchange reactions of the respective distibines of the type R 4Sb 2 and R′ 4Sb 2. 相似文献
18.
A new tellurium-containing heterocyclic compound, 2,2,6,6-tetramethyl-1-oxa-4-tellura-2,6-disilacyclohexane (C 6H 16OSi 2Te) (1), has been prepared by treatment of 1,3-bis(chloromethyl)-1,1,3,3-tetramethyldisiloxane with sodium telluride. Mononuclear and dinuclear palladium complexes of this telluride have been prepared by the reaction of 1 with PdCl 2(PhCN) 2 and Na 2PdCl 4, respectively. The following new derivatives of 1 have also been produced: C 6H 16OSi 2TeI 2 (2), C 6H 16OSi 2TeBr 2, C 6H 16OSi 2TeCl 2, C 6H 16OSi 2Te(CH 3)I, and C 6H 16OSi 2Te(CH 2Ph)Br. IR, 1H and 13C NMR and mass spectral data of these new compounds are reported and discussed. 1H NMR studies revealed that in CDCl 3 solution both telluronium salts reductively eliminate alkyl halide. The crystal structure of compound 2 has been determined by X-ray diffraction. The compound crystallizes in the monoclinic space group, P2 1/ c, with four molecules in a unit cell of dimension a 12.960(3), b 8.846(2), c 13.754(4) Å, β 92.44(2)°, R = 0.049, and Rw = 0.067 for 3599 unique reflections with | F0| > 3σ( F0). The compound forms a six-membered ring of a slightly displaced boat type. The geometry about the Te atom is pseudo-octahedral, with two carbon atoms (Te-C = 2.156(7) and 2.137(6) Å) and two iodine atoms of the neighbouring molecules (weak intermolecular bonds, Te · I = 3.769 and 3.806 Å) in the equatorial positions and two iodine atoms (Te-I = 2.909(1) and 2.913(1) Å) in the axial positions. 相似文献
19.
The interaction of [(η 5-C 5H 4Bu t) 2YbCl · LiCl] with one equivalent of Li[(CH 2) (CH 2)PPh 2] in tetrahydrofuran gave [Ph 2PMe 2][(η 5-C 5H 4Bu t) 2Li] (1) and [(η 5-C 5H 4Bu t) 2Yb(Cl)CH 2P(Me)Ph 2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph 2PMe 2][CF 3SO 3] with two equivalents of (C 5H 4Bu t)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η 5-C 5H 4Bu t) 2Li] − anion. 相似文献
20.
LnCl 3 (Ln=Nd, Gd) reacts with C 5H 9C 5H 4Na (or K 2C 8H 8) in THF (C 5H 9C 5H 4 = cyclopentylcyclopentadienyl) in the ratio of 1 : to give (C 5H 9C 5H 4)LnCl 2(THF) n (orC 8H 8)LnCl 2(THF) n], which further reacts with K 2C 8H 8 (or C 5H 9C 5H 4Na) in THF to form the litle complexes. If Ln=Nd the complex (C 8H 8)Nd(C 5H 9C 5H 4)(THF) 2 (a) was obtained: when Ln=Gd the 1 : 1 complex [(C 8H 8)Gd(C %H 9)(THF)][(C 8H 8)Gd(C 5H 9H 4)(THF) 2] (b) was obtained in crystalline form. The crystal structure analysis shows that in (C8H8)Ln(C5H9C5H4)(THF)2 (Ln=Nd or Gd), the Cyclopentylcyclopentadieny (η5), cyclooctatetraenyl (η8) and two oxygen atoms from THF are coordinated to Nd3+ (or Gd3+) with coordination number 10. The centroid of the cyclopentadienyl ring (Cp′) in C5H9C5H4 group, cyclooctatetraenyl centroid (COTL) and two oxygens (THF) form a twisted tetrahedron around Nd3+ (or Gd3+). In (C8H8)Gd(C5H9C5H4)(THF), the cyclopentyl-cyclopentadienyl (η5), cyclooctatetraenyl (η8) and one oxygen atom are coordinated to Gd3+ with the coordination number of 9 and Cp′, COT and oxygen atom form a triangular plane around Gd3+, which is almost in the plane (dev. -0.0144 Å). 相似文献
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