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1.
The compounds (π-C 5H 5)(CO) 2LM-X (L = CO, PR 3; M = Mo, W; X = BF 4, PF 6, AsF 6, SbF 6) react with H 2S, p-MeC 6H 4SH, Ph 2S and Ph 2SO(L′) to give ionic complexes [(π-C 5H 5)(CO) 2LML′] + X −. Also sulfur-bridged complexes, [(π-C 5H 5)(CO) 3W---SH---W(CO) 3(π-C 5H 5)] + AsF 6− and [(π-C 5H 5)(CO) 3M-μ-S 2C=NCH 2Ph-M(CO) 3(π-C 5H 5)], have been obtained. Reactions with SO 2 and CS 2 have been examined. 相似文献
2.
The preparation of novel 1-arsa-3,4-diphospholyl and 3-arsa-1,4-diphospholyl anions of the type (C 2tBu 2AsP 2) − is described. Spectroscopic and structural characterisation of mono-and bi-metallic complexes of these anions are also reported. 相似文献
3.
[1,8-C 10H 6(NR) 2]TiCl 2 (3; R=SiMe 3, Si iBuMe 2, Si iPr 3) complexes have been prepared from dilithio salts [1,8-C 10H 6(NR) 2]Li 2 (2) and TiCl 4 in diethyl ether in moderate yields (60–63%). These complexes showed significant catalytic activities for ethylene polymerization and for ethylene/1-hexene copolymerization in the presence of methylaluminoxane (MAO), methyl isobutyl aluminoxane (MMAO), Al iBu 3– or AlEt 3–Ph 3CB(C 6F 5) 4 as a cocatalyst. The catalytic activities performed in heptane (cocatalyst MMAO) were higher than those carried out in toluene (cocatalyst MAO): 709 kg-PE/mol-Ti·h could be attained for ethylene polymerization by using [1,8-C 10H 6(NSi iBuMe 2) 2]TiCl 2–MMAO catalyst system. 相似文献
4.
Reaction of Na[MCl 4] (M=Pd or Pd) with the azo-containing phosphines Ph 2P{1-(4-RC 6H 4N 2)-2-OR′-C 10H 5} {R=Me (I), NMe 2 (II); R′=C(O)Me} affords the complexes [MCl 2L 2] (1–4) in good yield. Complexes 1–4 have all been fully characterised by elemental analysis, 1H-, 13C{ 1H}-, and 31P{ 1H}-NMR spectroscopy and UV–visible spectroscopy. The use of 1 in the Heck reaction has been investigated and shown to effect up to 1000 turnovers. 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.
Synthesis and structural studies of the ruthenium(II) ‘sandwich’ complexes [Ru(η 5-P 3C 2tBu 2) 2], [Ru(η 5-P 3C 2C 2tBu 2)(η 5-P 2C 3tBu 3)], [Ru(η 5-C 5R 5)(η 5-P 3C 2tBu 2)] (R=H, Me) are described. The results of a single crystal X-ray structural study of [Ru(η 5-P 3C 2tBu 2) 2] are discussed. 相似文献
7.
The preparation and properties as well as some reactions of a series of arylcarbonylbis(triphenylphosphine)iridium(I) complexes [Ir(Ar)(CO)(PPh 3) 2] (Ar = C 6H 5, C 6F 5, 2-C 6H 4CH 3, 3-C 6H 4CH 3, 4-C 6H 4CH 3, 2-C 6H 4OCH 3, 2,6-C 6H 3-(OCH 3) 2, 4-C 6H 4N(CH 3) 2, 3-C 6H 4Cl, 4-C 6H 4Cl, 4-C 6H 4Cl, 3-C 6H 4CF 3, 4-C 6H 4CF 3) are described, and the most important IR data as well as the 31P NMR parameters of these, without exception trans-planar, compounds are given. Some of the complexes react with molecular oxygen to form well defined dioxygen adducts [Ir(Ar)(O2)(CO)(PPh3)2] (Ar = C6H5, 3-C6H4CH3, 4-C6H4CH3). Complexes with ortho-substituted aryl ligands are not oxygenated. This effect is referred to as a steric shielding of the metal center by the corresponding ortho-substituents. With SO2 the similar irreversible addition compound [Ir(4-C6H4CH3)-(SO2)(CO)(PPh3)2] is obtained. Sulfur dioxide insertion into the Ir---C bond cannot be observed. The first step of the reaction between [Ir(4-C6H4CH3)(CO)(PPh3)2] and hydrogen chloride involves an oxidative addition of HCl to give [Ir(H)(Cl)(4-C6-H4CH3)(CO)(PPh3)2]. Ir---C bond cleavage by reductive elimination of toluene from the primary adduct does not occur except at elevated temperature. 相似文献
8.
Reaction of R---N=C=N---R (R= p-Me-C 6H 4) and R---P==C=P---R (R=2,4,6- tBu 3C 6H 2) with the di-iron aminocarbene complex [Fe 2(CO) 7{1μ-C(Ph)C(NEt 2)}] (1c) gave corresponding complexes [Fe 2(CO) 6{C(Ph)C(NEt 2)C(NC 6H 4Me)N (C 6H 4Me)}] (2) and [Fe 2(CO) 6{C(Ph)C(NEt 2)C(PC 6H 2tBu 3)P(C 6H 2tBu 3)}] (4), resulting from a coupling reaction with carbon-carbon bond formation. [Fe 2(CO) 5(CNC 6H 4Me){C(Ph)C(NEt 2)N(C 6H 4Me)}], complex 3, obtained in the reaction with R---N=C=N---R, resulted from C=N bond rupture insertion of a nitrene fragment into the Fe=C bond. Complexes 2–4 were characterized by X-ray diffraction. The different geornetries of complexes 2 and 4 are discussed. The formation of these complexes may be explained by cycloaddition on the Fe =C metal-carbene bond. 相似文献
9.
The dimethylphosphino substituted cyclopentadienyl precursor compounds [M(C 5Me 4CH 2PMe 2)], where M=Li + (1), Na + (2), or K + (3), and [Li(C 5H 4CR′ 2PMe 2)], where R′ 2=Me 2 (4), or (CH 2) 5 (5), [HC 5Me 4CH 2PMe 2H]X, where X −=Cl − (6) or PF 6− (7) and [HC 5Me 4CH 2PMe 2] (8), are described. They have been used to prepare new metallocene compounds, of which representative examples are [Fe(η-C 5R 4CR′ 2PMe 2) 2], where R=Me, R′=H (9); R=H and R′ 2=Me 2 (10), or (CH 2) 5 (11), [Fe(η-C 5H 4CMe 2PMe 3) 2]I 2 (12), [Fe{η-C 5Me 4CH 2P(O)Me 2} 2] (13), [Zr(η-C 5R 4CR′ 2PMe 2) 2Cl 2], where R=H, R′=Me (14), or R=Me, R′=H (15), [Hf(η-C 5H 4CMe 2PMe 2) 2]Cl 2] (16), [Zr(η-C 5H 4CMe 2PMe 2) 2Me 2] (17), {[Zr(η-C 5Me 4CH 2PMe 2) 2]Cl}{(C 6F 5) 3BClB(C 6F 5) 3} (18), [Zr{(η-C 5Me 4CH 2PMe 2) 2Cl 2}PtI 2] (19), [Mn(η-C 5Me 4CH 2PMe 2) 2] (20), [Mn{(η-C 5Me 4CH 2PMe 2B(C 6F 5) 3} 2] (21), [Pb(η-C 5H 4CMe 2PMe 2) 2] (23), [Sn(η-C 5H 4CMe 2PMe 2) 2] (24), [Pb{η-C 5H 4CMe 2PMe 2B(C 6F 5) 3} 2] (25), [Pb(η-C 5H 4CMe 2PMe 2) 2PtI 2] (26), [Rh(η-C 5Me 4CH 2PMe 2)(C 2H 4)] 29, [M(η,κ P-C 5Me 4CH 2PMe 2)I 2], where M=Rh (30), or Ir, (31). 相似文献
10.
The reductive electrochemistry of compounds of the type Cp Fe(CO) 2L (Cp = η-C 5H 5, η-C 5Me 5; L = SP(S)(OEt) 2, SP(S)(O iPr) 2) has been examined by polarography, cylic voltammetry and coulometry. The first one-electron reduction step leads to a bond rupture process with formation of a mercury compound, [Cp Fe(CO) 2] 2Hg, at a mercury electrode and the corresponding dimer species at a platinum electrode. The second reduction step corresponds to the reduction of the dimer [Cp Fe(CO) 2] 2, except in the polarographic reduction of pentamethylcyclopentadienyl compounds. 相似文献
11.
Toluene solutions of M 2(NMe 2) 6 (M = Mo, W) react with mesitylene selenol (Ar′SeH) to give M 2(SeAr′) 6 complexes. MO 2(OR) 6 (R = tBu, CH 2tBu) react with excess> 6 fold) Ar′SeH to give Mo 2 (SeAr′) 6, whilst W 2(OR) 6(py) 2 (R = iPr, CH 2tBu) react with excess (> 6 fold) Ar′SeH to give W 2(OR) 2(SeAr′) 4. Reaction of MO 2(OPr i) 6 with Ar′SeH produces Mo 2(OPr i) 2 (SeAr′) 4 which crystallizes in two different space groups. These areneselenato complexes are air-stable and insoluble in common organic solvents. X-ray crystallographic studies revealed that the Mo 2(SeAr′) 6 and W 2(SeAr′) 6 compounds are isostructural in the solid state and adopt ethane-like staggered configurations with the following important structural parameters, M---M (W---W/Mo---Mo) 2.3000(11)/2.2175(13) Å, M---Se 2.430 (av.)/2.440 (av.) Å, M---M---SE 97.0° (av.)°. In the solid state W 2(O iPr) 2(SeAr′) 4 adopts the anti-configuration with crystallographically imposed Ci symmetry and W---W 2.3077(7) Å, W---Se 2.435 (av.) Å, W---O 1.858(6) Å; W---W---SE 100.27(3)°, 93.8(3)° and W---W---O 108.41(17)°. Mo 2(OPr i) 2(SeAr′) 4 crystallizes in both P
and A2/ a space groups in which the molecules are isostructural with each other and the tungsten analogue. Important bond lengths and angles are Mo---Mo 2.180(24) Å, Mo---Se 2.432(av.) Å, Mo---O 1.872(9) Å, Mo---Mo---Se 99.39(9)°, 94.71(8)°, Mo---Mo---O 107.55(28)°. 相似文献
12.
Ir(H) 2(OR f)P 2 (P = P tBu 2Ph, R f = CH 2CF 3) reacts with ethylene at 25°C to give R fOH, ethane and Ir(P C)P(C 2H 4) (2) then Ir(P C)(C 2H 4) 2 (1) and Ir(P C)H(OR f)P (3) (P C = η 2-C 6H 4P tBu 2). It is shown that 2 and 1 are in equilibrium by P and C 2H 4 addition/dissociation. Compound 3 is a product “late” in the reaction sequence, and results from H---OR f oxidative addition to 2. Since 3 reacts with ethylene to give 2, 2 and 3 are in thermal equilibrium. Compound 3 reacts readily with H 2 to give IrH 5P 2 and R fOH. The reason why OR f and ethylene ligands seem to be mutually incompatible is discussed. 相似文献
13.
Treatment of (2-C 5H 4N)CH 2 3N (TPA) with one equivalent of MCl 2 in n-BuOH at elevated temperatures affords the six-coordinate complexes [(TPA)MCl 2] (M = Co (1), Fe (2)) and, in the case of CoCl 2, the five-coordinate chloride salt [(TPA)CoCl]Cl (3). Conversely, addition of an excess of CoCl 2 in the latter reaction leads to [(TPA)CoCl] 2[CoCl 4] (4) as the only isolable product. Interaction of one equivalent of (2-C 5H 4N)CH 2 2NH (DPA) and MCl 2 under similar reaction conditions to that described above affords the dimeric species [( fac-DPA)MCl(μ-Cl)] 2 (M = Co (5), Fe (6)), while the bis(ligand) halide salts [( fac-DPA) 2M]Cl 2 (M = Co (7), Fe (8)) are accessible on addition of two equivalents of DPA. In the presence of air, 6 undergoes oxidation to give [ ( fac-DPA)FeCl 2 2(μ-O)] (9). Single-crystal X-ray diffraction studies are reported for 1, 2 · MeCN, 3, , 7 · 3MeCN, 8 · 3MeCN and 9. 相似文献
14.
The synthesis and reactivity of {(η 5-C 5H 4SiMe 3) 2Ti(CCSiMe 3) 2} MCl 2 (M = Fe: 3a; M = Co: 3b; M = Ni: 3c) is described. The complexes 3 are accessible by the reaction of (η 5-C 5H 4SiMe 3) 2Ti(CSiMe 3) 2 (1) with equimolar amounts of MCl 2 (2) (M = Fe, Co, Ni). 3a reacts with the organic chelat ligands 2,2′-dipyridyl (dipy) (4a) or 1,10-phenanthroline (phen) (4b) in THF at 25°C to afford in quantitative yields (η 5-C 5H 4SiMe 3) 2Ti(CSiMe 3) 2 (1) and [Fe(dipy) 2]Cl 2 (5a) or [Fe(phen) 2]Cl 2 (5b). 1/ n[Cu IHal] n (6) or 1/ n[Ag IHal] n (7) (Hal = Cl, Br) react with {(η 5 -C 5H 4SiMe 3) 2Ti(CCSiMe 3) 2}FeCl 2 (3a), by replacement of the FeCl 2 building block in 3a, to yield the compounds {(η 5-C 5H 4SiMe 3) 2Ti(C CSiMe 3) 2}Cu IHal (8) or {(η 5-C 5H 4SiMe 3) 2Ti(CSiMe 3) 2}Ag IHal (9) (Hal = Cl, Br), respectively. In 8 and 9 each of the two Me 3SiCC-units is η 2-coordinated to monomeric Cu I Hal or Ag IHal moieties. Compounds 8 and 9 can also be synthesized by the reaction of (η 5-C 5H 4SiMe 3) 2 Ti(CSiMe 3) 2 (1) with 1/ n[Cu IHal] n (6) or 1/ n [Ag IHal] n (7) in excellent yields. All new compounds have been characterized by analytical and spectroscopic data (IR, 1H-NMR, MS). The magnetic moments of compounds 3 were measured. 相似文献
15.
The reactions of RNHSi(Me) 2Cl (1, R= t-Bu; 2, R=2,6-(Me 2CH) 2C 6H 3) with the carborane ligands, nido-1-Na(C 4H 8O)-2,3-(SiMe 3) 2-2,3-C 2B 4H 5 (3) and Li[ closo-1-R′-1,2-C 2B 10H 10] (4), produced two kinds of neutral ligand precursors, nido-5-[Si(Me) 2N(H)R]-2,3-(SiMe 3) 2-2,3-C 2B 4H 5, (5, R= t-Bu) and closo-1-R′-2-[Si(Me) 2N(H)R]-1,2-C 2B 10H 10 (6, R= t-Bu, R′=Ph; 7, R=2,6-(Me 2CH) 2C 6H 3, R′=H), in 85, 92, and 95% yields, respectively. Treatment of closo-2-[Si(Me) 2NH(2,6-(Me 2CH) 2C 6H 3)]-1,2-C 2B 10H 11 (7) with three equivalents of freshly cut sodium metal in the presence of naphthalene produced the corresponding cage-opened sodium salt of the “carbons apart” carborane trianion, [ nido-3-{Si(Me) 2N(2,6-(Me 2CH) 2C 6H 3)}-1,3-C 2B 10H 11] 3− (8) in almost quantitative yield. The reaction of the trianion, 8, with anhydrous MCl 4 (M=Ti and Zr) in 1:1 molar ratio in dry tetrahydrofuran (THF) at −78 °C, resulted in the formation of the corresponding half-sandwich neutral d 0-metallacarborane, closo-1-M[(Cl)(THF) n]-2-[1′-η 1σ-N(2,6-(Me 2CH) 2C 6H 3)(Me) 2Si]-2,4-η 6-C 2B 10H 11 (M=Ti (9), n=0; M=Zr (10), n=1) in 47 and 36% yields, respectively. All compounds were characterized by elemental analysis, 1H-, 11B-, and 13C-NMR spectra and IR spectra. The carborane ligand, 7, was also characterized by single crystal X-ray diffraction. Compound 7 crystallizes in the monoclinic space group P2 1/ c with a=8.2357(19) Å, b=28.686(7) Å, c=9.921(2) Å; β=93.482(4)°; V=2339.5(9) Å 3, and Z=4. The final refinements of 7 converged at R=0.0736; wR=0.1494; GOF=1.372 for observed reflections. 相似文献
16.
Thermodynamic properties of binary systems of C 60 with 1,2- and 1,3-dibromobenzenes have been studied by means of differential scanning calorimetry (DSC). Solid solvates with the compositions C 603(1,2-C 6H 4Br 2); C 602(1,3-C 6H 4Br 2) and C 600.6(1,3-C 6H 4Br 2) have been found. The solvates have been characterised by their enthalpies and temperatures of incongruent melting transition and in part by X-ray powder data. It has been shown that positional isomers 1,2- and 1,3- of the substituted benzenes formed two series of “typical” phase diagrams. Solubility behaviour of C 60 in positional isomers has been discussed. 相似文献
17.
Three families of heterobimetallic compounds were obtained by reaction of [Mo(CO) 3(CH 3CN) 2(Cl)(SnRCl 2)] (R = Ph, Me) with P(4-XC 6H 4) 3 (X = Cl, F, H, Me, MeO). The type of compound obtained dependent on the solvent and concentration of the starting compound. So, [Mo(CO) 2(CH 3COCH 3) 2(PPh 3)(Cl)(SnRCl 2)]· nCH 3COCH 3 (R = Ph, n = 0.5; R = Me, n = 1) (type I) and [Mo(CO) 3{P(4-XC 6H 4) 3}(μ-Cl)(SnRCl 2)] 2 (R = Ph, X = Cl, F, H, Me, MeO; R = Me, X = Cl, F) (type II) were isolated from acetone solution in ca 0.05 M and 0.1 M concentrations, respectively. However, [Mo(CO) 3(CH 3CN) {P(4-XC 6H 4) 3}(Cl)(SnRCl 2)] (R = Ph, X = H; R = Me, X = Cl, F, H) (type III) were obtained from dichloromethane solution independently of the concentration used. All new complexes showed a seven-coordinate environment at molybdenum, containing Mo---Cl and Mo---Sn bonds. Mössbauer spectra indicated a four-coordination at tin for type III complexes. 相似文献
18.
The interaction between Mo 2(O 2CCH 3) 4, Me 3SiI and I 2 in THF resulted in oxygen abstraction from the solvent and formation of [Mo 2(μ-O)(μ-I)(μ-O 2CCH 3) I 2(THF) 4] +[MoOI 4(THF)] − and I---(CH 2) 4---I. The molybdenum complex has been characterized by X-ray diffractometry. Crystal data: triclinic, space group P
, a = 13.827(3) Å; b = 15.803(7) Å; c = 9.950(3) Å; = 93.34(4)°; β = 102.40(2)°; γ = 90.09(2)°; V = 2120(2) Å 3; Z = 2; dcalc = 2.559 g cm −3; R = 0.0476 ( Rw = 0.0613) for 370 parameters and 3938 data with F02> 3σ( F02). The metal-metal distance in the cation is 2.527(2) Å and indicates a strong interaction. The magnetic behavior is consistent with the assignment of one unpaired electron to the Mo 27+ core of the cation and one to the d1 Mo(V) center of the anion. The interaction between Mo(CO) 6 and I 2 in THF also results in the formation of 1,4-diiodobutane. 相似文献
19.
The reaction of Ln(NO 3) 3·6H 2O (Ln=La, Ce, Pr or Nd) with a sixfold excess of Ph 3PO in acetone formed [Ln(Ph 3PO) 4(NO 3) 3]·Me 2CO. The crystal structure of the La complex shows a nine-coordinate metal centre with four phosphine oxides, two bidentate and one monodentate nitrate groups, and PXRD studies show the same structure is present in the other three complexes. In CH 2Cl 2 or Me 2CO solutions, 31P NMR studies show that the complexes are essentially completely decomposed into [Ln(Ph 3PO) 3(NO 3) 3] and Ph 3PO. Similar reactions in ethanol gave [Ln(Ph 3PO) 3(NO 3) 3] only. In contrast for Ln=Sm, Eu or Gd, only the [Ln(Ph 3PO) 3(NO 3) 3] are formed from either acetone or ethanol solutions. For the later lanthanides Ln=Tb–Lu, acetone solutions of Ln(NO 3) 3·6H 2O and Ph 3PO gave [Ln(Ph 3PO) 3(NO 3) 3] only, even with a large excess of Ph 3PO, but from cold ethanol [Ln(Ph 3PO) 4(NO 3) 2]NO 3 (Ln=Tb, Ho–Lu) were obtained. The structure of [Lu(Ph 3PO) 4(NO 3) 2]NO 3 shows an eight-coordinate metal centre with four phosphine oxides and two bidentate nitrate groups. In solution in CH 2Cl 2 or Me 2CO the tetrakis-complexes show varying amounts of decomposition into mixtures of [Ln(Ph 3PO) 3(NO 3) 3], [Ln(Ph 3PO) 4(NO 3) 2]NO 3 and Ph 3PO as judged by 31P{ 1H} NMR spectroscopy. The [Ln(Ph 3PO) 3(NO 3) 3] also partially decompose in solution for Ln=Dy–Lu, forming some tetrakis(phosphine oxide) species. 相似文献
20.
Effects of substituents on cyclopentadienyl group for homopolymerization of ethylene, 1-hexene, and for ethylene/1-hexene copolymerization using a series of nonbridged (cyclopentadienyl)(ketimide)titanium complexes of the type, Cp′TiCl 2(N=C tBu 2) [Cp′ = Cp (1), tBuC 5H 4 (2), C 5Me 5 (Cp *, 3), and indenyl (4)] have been explored in the presence of methylaluminoxane (MAO) cocatalyst. Complexes 1–3 showed the similar catalytic activities for ethylene polymerization although the activity by 4 was somewhat low, whereas the activity for 1-hexene polymerization increased in the order 1 > 4 2 > 3. These complexes showed significant activities for ethylene/1-hexene copolymerization affording high molecular weight poly(ethylene- co-1-hexene)s with unimodal molecular weight distributions, and the activity increased in the order: 4 > 1 2, 3. The rErH values in the polymerization by 1–3 at 40 °C were 0.35–0.52 which clearly indicate that the 1-hexene incorporation in the copolymerization did not proceed in a random manner. The rE values by 1–3 were 6.0–6.4 and the values were independent upon the cyclopentadienyl fragment employed; the rE values by 4 at 40 °C were 10.2–10.9 which were close to those by ansa-metallocene complex catalysts. These values were influenced by the polymerization temperature, and the 1-hexene incorporation by 1–4 became inefficient at higher temperature, although the observed activities especially by 1, 4 were highly remarkable. 相似文献
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