共查询到20条相似文献,搜索用时 31 毫秒
1.
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
2.
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
3.
The monocyclooctatetraene uranium complex [U(COT)(I) 2(THF) 2] (COT=η-C 8H 8; THF=tetrahydrofuran), isolated from the reaction of bis(cyclooctatetraene)uranium with iodine, is a precursor for the synthesis of the alkyl derivatives [U(COT)(CH 2Ph) 2i (HMPA) 2], [U(COT)(CH 2SiMe 3) 2(HMPA)] (HMPA=hexamethyl phosphorous triamide) and [U(COT)CH 2SiMe 3) 3] [Li(THF) 3] and of the mixed-ring compounds [U(COT)(η-C 5R 5)(I)] (R=H or Me). The last were used to prepare the amide and alkyl complexes [U(COT)(η-C 5H 5)(N{SiMe 3} 2)] and [U(COT)(η-C 5Me 5)(CH 2SiMe 3)]. 相似文献
4.
In situ reaction of Li[ closo-1-Ph-1,2-C 2B 10H 10] with 7-azabicyclo [4.1.0] heptane results in the formation of the disubstituted carborane, closo-1-Ph-2-(2′-aminocyclohexyl)-1,2-C 2B 10H 10 (1), in 63% yield. Decapitation of (1) with potassium hydroxide in refluxing ethanol produces the cage-opened nido-carborane, K[ nido-7-Ph-8-(2′-aminocyclohexyl)-7,8-C 2B 9H 10] − (2), in 80% yield. Deprotonation of the above monoanion with two equivalents of n-butyllithium followed by reaction with anhydrous MCl 4 · 2THF (M = Zr, Ti) provides d0-half-sandwich metallocarboranes, closo-1-M(Cl)-2-Ph-3-(2′- σ-(H) N-cyclohexyl)-2,3- η5-C 2B 9H 9 (3 M = Zr; 4 M = Ti) in 53% and 42% yields, respectively. The reaction of Li[ closo-1,2-C 2B 10H 11] with 7-azabicyclo [4.1.0] heptane in THF affords closo-1-(2′-aminocyclohexyl)-1,2-C 2B 10H 10 (5) in 59% yield. Immobilization of the carboranyl amino ligand (1) to an organic support, Merrifield’s peptide resin (1%), has been achieved by the reaction of the sodium salt of (5) with polystyryl chloride in THF to produce closo-1-(2′-aminocyclohexyl)-2-polystyryl-1,2-C 2B 10H 10 (6) in 87% yield. Further reaction of the dianion derived from (6) with anhydrous ZrCl 4 · 2THF led to the formation of the organic polystyryl supported d0-half-sandwich metallocarborane, closo-1-Zr(Cl)-2-(2′- σ-(H) N-cyclohexyl)-3-polystyryl-2,3-η 5-C 2B 9H 9 (7), in 38% yield. These new compounds have been characterized by elemental analyses, NMR, and IR spectra. Polymerizations of both ethylene and vinyl chloride with (3) and (7) have been performed in toluene using MMAO-7 (13% ISOPAR-E) as the co-catalyst. Molecular weights up to 32.8 × 10 3 ( Mw/ Mn = 1.8) and 9.5 × 10 3 ( Mw/ Mn = 2.1) were obtained for PE and PVC, respectively. 相似文献
5.
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
6.
The complexes [Fe{η-C 5H 4---( E)---CH=CH---4-C 6H 4CCX} 2] [X=SiMe 3 (1), H (2), Au(PCy 3) (3), Au(PPh 3) (4), Au(PMe 3) (5), RuCl(dppm) 2 (7), RuCl(dppe) 2 (8)] and [Fe{η-C 5H 4---( E)---CH=CH---4-C 6H 4CH=CRuCl(dppm) 2} 2](PF 6) 2 (6) have been prepared and the identities of 1 and 7 confirmed by single-crystal X-ray structural studies. Complexes 1–8 exhibit reversible oxidation waves in their cyclic voltammograms attributed to the Fe II/III couple of the ferrocenyl groups, 6–8 also showing reversible (7, 8) or non-reversible (6) processes attributed to Ru-centered oxidation. Cubic nonlinearities at 800 nm by the Z-scan method are low for 1–5; in contrast, complexes 6 and 7 exhibit large negative γreal and large γimag values. A factor of 4 difference in γ and two-photon absorption cross-section σ2 values for 6 and 7 suggest that they have potential as protically switchable NLO materials. 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.
It has been shown that bis(cyclopentadienyl)(μ-cyclopentadiene)dinickel, (NiCP) 2(η-C 5H 6), and (η 5-cyclopentadienyl) (η 3-cyclopentenyl)nickel, CpNi(η 3-C 5H 7), are formed in the reaction of nickelocene with methyl-lithium and with 1-phenyl-2-methyl-propenyl-lithium. The compound (NiCp) 2(μ-C 5H 6) can be only formed as a result of the reduction of the cyclopentadienyl ring bonded to the nickel atom whereas the formation of CpNi(η 3-C 5H 7) can be explained by the further hydrogeneration of cyclopentadiene formed in the earlier reaction steps. (NiCp) 2(μ-C 5H 6) has been fully characterised spectrometrically and its X-ray structure determined. It crystallises in the orthorhombic system, space group Pnma, with four molecules per unit cell. 相似文献
9.
The acid–base chemistry of some ruthenium ethyne-1,2-diyl complexes, [{Ru(CO) 2(η-C 5H 4R)} 2(μ 2-CC)] (R=H, Me) has been investigated. Initial protonation of [{Ru(CO) 2{η-C 5H 4R}} 2(μ 2-CC)] gave the unexpected complex cation, crystallised as the BF 4 salt, [{Ru(CO) 2(η-C 5H 4R}} 3(μ 3-CC)][BF 4] (R=Me structurally characterised). This synthesis proved to be unreliable but subsequent, careful protonation experiments gave excellent yields of the protonated ethyne-1,2-diyl complexes, [{Ru(CO) 2{η-C 5H 4R)} 2(μ 2-η 1:η 2-CCH)](BF 4) (R=Me structurally characterised) which could be deprotonated in high yield to return the starting ethyne-1,2-diyl complexes. 相似文献
10.
Improved syntheses of [Fe(η-C 5H 5)(η-arene)][PF 6] salts are reported using a simple apparatus in an unmodified commercial microwave oven. The syntheses of [Fe(η-arene) 2][PF 6] 2 salts are also reported. 相似文献
11.
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
12.
The reaction of [ R-( R, R)]-(+) 589-[(η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}Fe(NCMe)]PF 6 with (±)-AsHMePh in boiling methanol yields crystalline [ R-[( R)-( R, R)]-(+) 589)-[(η5-C5H5){1,2-C6H4(PMePh)2}Fe(AsHMePH)PF 6, optically pure, in ca. 90% yield, in a typical second-order asymmetric transformation. This complex contains the first resolved secondary arsine. Deprotonation of the secondary arsine complex with KOBu t at −65°C gives the diastereomerically pure tertiary arsenido-iron complex [ R-[( R),( R, R)]]-[((η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}FeAsMePh] · thf, from which optically pure [ R-[( S),( R, R)]]-(+) 589-[(η 5-C 5H 5){1,2-C 6H 4(PMePh) 2}Fe(AsEtMePh)PF 6 is obtained by reaction with iodoethane. Cyanide displaces ( R)-(−) 589-ethylmethylphenylarsine from the iron complex, thereby effecting the asymmetric synthesis of a tertiary arsine, chiral at arsenic, from (±)-methylphenylarsine and an optically active transition metal auxiliary. 相似文献
13.
Liquid crystalline 4-XC 6H 4N=NC 6H 4X-4′ [X = C 4H 9 (1a), C 1OH 21 (1b), OC 4H 9 (1c), OC 8H 17(1d)] can be easily prepared in high yields from the corresponding anilines. In order to study the influence of metals on the thermal properties of these materials, we have obtained adducts [AuCl 3(4-C 4H 9OC 6H 4N=NC 6H 4OC 4H 9-4′)] (2) and [Ag(OC1O 3)L 2] [L = 4-XC 6H 4N=NC 6H 4X-4′; X = OC 4H, (3a), OC 8H 17 (3b)]. The silver adducts show themotropic behaviour. Mercuriation of dialkylazobenzenes 1a-b takes place with [Hg(OAc) 2] and LiCl to give [Hg(R)Cl] [R = C 6H 3(N=NC 6H 4X-4′)-2, X-5; X = C 4H 9 (bpap) (4a), C 10H 21 (dpap) (4b)] while dialkoxyazobenzenes 1c–d require [Hg (OOCCF 3) 2] to obtain [Hg(R)Cl] [R = C 6H 3(N---NC 6H 4X-4′)-2, X-5; X = OC 4H 9 (bxpap) (4c), OC 8H 17 (4d)]. 4a-c react with NaI to give [HgR 2] [R= bpap (5a), dpap (5b), bxpap (5c), oxpap (5d)l. Both chloroaryl-, 4a and 4c, and diaryl-mercurials, 5a and 5c, act readily as transmetailating agents towards [Me 4N] [AuCl 4] in the presence of [Me 4N]Cl to give [Au(η 2-R)Cl 2] [R = bpap (6a), bxpap (6b)]. After reaction of [AuCl 3(tht)] (tht = tetrahydrothiophene) with [Me 4N]Cl and 4b (1:2:1), [Me 4N][Au(dpap)Cl 3] (7) can be isolated. C---H activati bxpap (8b)]. None of the complexes 4–8 shows mesomorphic behaviour. 相似文献
14.
Some (η 5-cyclopentadienyl)(1,2-bis(diarylphosphino)ethane)(diorganosulfide)ruthenium complexes, [Ru(η 5-C 5H 5)(Ar 2PCH 2CH 2-PAr 2)(R 1R 2S)]BF 4 (Ar = Ph, p-Tol; R 1, R 2 = Ph, Et) were prepared. Variable temperature NMR spectra of these complexes showed the existence of two fluxional processes; inversion at the sulfur atom and δ-λ interconversion of the chelate ring. The former process was slower, and its barriers in these complexes were calculated as ca. 7 kcal mol −1. The spectral features of ethyl phenyl sulfide complexes suggested that substantiation of the new chiral center at sulfur induces a significant conformational rigidity at the chelate ring. 相似文献
15.
An S,S′-thioether—thioester chelating ligand [7,8- μ-SCH 2C(O)S-7,8-C 2B 9H 10] − (L 1), incorporating the unit [—(C) 2B 9H 10] − has been synthesized. Reactions have been conducted with RhCl(PPh 3) 3 and PdCl 2(PPh 3) 2 complexes in ethanol. With Rh, L 1 maintains its original cyclic nature and most probably chelation via thioether—thioester takes place. The carborane negative charge may stabilize this original thioether—thioester complex. The other two Rh positions are occupied by two PPh 3 ancillary ligands forming [Rh(L 1)(PPh 3) 2]. The reaction of L 1 with Pd induces ligand modifications and the cyclic nature of L 1 is lost. A transesterification process leading to a dianionic ligand L 2, [7-S-8-SCH 2C(O)OCH 2CH 3−7,8-C 2B 9H 10] 2− has taken place. In this way L 2 is capable of compensating the dipositive Pd charge. The other two Pd positions are occupied by two PPh 3. This reaction has been extended to methanol and isopropanol solvents. The crystal structure of [Pd(L 2)(PPh 3) 2] has been determined. 相似文献
16.
The chiral bis-imine (1 R,2 R)-C 6H 10-[ E---N=CH---C 6H 3---3,4-(OMe) 2] 2 1 (LH) reacts with [Pd(OAc) 2] (1:1 molar ratio; OAc=acetate) giving the orthometallated [Pd(OAc)( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)-C 6H 10--- N=CH---C 6H 3-3′,4′-(OMe) 2-κ-C,N,N)] 2 (abbreviated as [Pd(OAc)(L-κ-C,N,N)]), through C---H bond activation on only one of the aryl rings and N, N-coordination of the two iminic N atoms. 2 reacts with an excess of LiCl to give [Pd(Cl)(L-κ-C,N,N)] 3. The reaction of 3 with AgClO 4 and neutral or anionic ligands L′ (1:1:1 molar ratio) affords [Pd(L-κ-C,N,N)(L′)](ClO 4) (L′=PPh 3 4a, NCMe 5, pyridine 6, p-nitroaniline 7) or [Pd(I)(L-κ-C,N,N)] 8. Complex 4a reacts with wet CDCl 3 giving [Pd( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)---C 6H 10--- NH 2-κ-C,N,N)(PPh 3)](ClO 4) 4b as a result of the hydrolysis of the C=N bond not involved in the orthometallated ring. The molecular structure of 4b·CH 2Cl 2 has been determined by X-ray diffraction methods. Cleavage of the Pd---N bond trans to the C aryl atom can be accomplished by coordination of strongly chelating ligands, such as acetylacetonate (acac) or bis(diphenylphosphino)ethane (dppe), forming [Pd(acac- O, O′)(L-κ-C,N)] 9 and [Pd(L-κ-C,N)(dppe-P,P′)](ClO 4) 12, while classical N, N′-chelating ligands such as 1,10-phenantroline (phen) or 2,2′-bipyridyl (bipy) behave as monodentate N-donor ligands yielding [Pd(L-κ-C,N,N)(κ 1-N-phen)](ClO 4) 10 and [Pd(L-κ-C,N,N)(κ 1-N-bipy)](ClO 4) 11. Treatment of 1 with PtCl 2(DMSO) 2 (1:1 molar ratio) in refluxing 2-methoxyethanol gives Cl 2Pt[( NH 2) 2C 6H 10---N,N′] 13a and [Pt(Cl)( C6H 2---4,5-(OMe) 2---2-CH= N-(1 R,2 R)---C 6H 10--- NH 2-κ-C,N,N)] 13b, while [Pt(Cl)(L-κ-C,N,N)] 14 can be obtained by reaction of [Pt(μ-Cl)(η 3-2-Me---C 3H 4)] 2 with 1 in refluxing CHCl 3. Complexes 2 and 3 catalyzed the arylation of methyl acrylate giving good yields of the corresponding methyl cinnamates and TON up to 847 000. Complex 3 also catalyzes the hydroarylation of 2-norbornene, but with lower yields and without enantioselectivity. 相似文献
17.
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
18.
采用自制的新型双苯并环己酮芳亚胺镍催化剂双苯并环己酮-2,6-二甲基苯亚胺镍(Ⅱ)(Ni{C 10H 8(O)C[2,6-C 6H 3(CH 3) 2N]CH 3} 2, C1)和双苯并环己酮-2,6-二氯苯亚胺镍(Ⅱ)(Ni{C 10H 8(O)C[2,6-C 6H 3Cl 2N]CH 3} 2, C2)与三五氟苯硼[B(C 6F 5) 3]结合, 在一定的反应条件下可高效催化降冰片烯(NB)与甲基丙烯酸正丁酯( n-BMA)的乙烯基加成共聚合. 提出了催化聚合时存在的可能失活机理; 研究了不同单体投料比对催化活性、 产率及产物性能的影响. 根据Kelen-Tüdõs方法分别估算出2种单体在不同催化体系下的竞聚率, 即当催化体系为C1/B(C 6F 5) 3时, 竞聚率 rn-BMA=0.02, rNB=16.28, rNB· rn-BMA=0.32; 当催化体系为C2/B(C 6F 5) 3时, rn-BMA=0.01, rNB=64.83, rNB· rn-BMA=0.65. 结果表明, 2种单体在2种体系催化下均为无规共聚合. 相似文献
19.
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
20.
The syntheses of the 1,3,5-trimethyl- and tri- tert-butyl-1,3,5-triazacyclohexane-supported imido complexes [M(NR)(R′ 3tach)Cl 2] (M = Ti or Zr (NMR only); R = Bu t or 2,6-C 6H 3Pr i2; R′ = Me or Bu t) are reported, along with that of the thermally robust dibenzyl derivative [Ti(NBu t)(Me 3tach)(CH 2Ph) 2]. The tert-butylimido ligand in [Ti(NBu t)(Me 3tach)Cl 2] undergoes exchange with ArNH 2 (Ar = 4-C 6H 4Me or 2,6-C 6H 4Me or 2,6-C 6H 3Pr i2) to form the corresponding arylimides [Ti(NAr)(Me 3tach)Cl 2]. The Me 3tach ring in [Ti(NR)(Me 3tach)Cl 2] undergoes slow exchange with Bu t3tach or Me 3tacn (1,4,7-trimethyl-1,4,7-triazacyclononane) to give the ring-exchanged products [Ti(NR)(Bu t3tach)Cl 2] and [Ti(NR)(Me 3tacn)Cl 2], respectively. The complexes [Ti(NR)(Me 3tach)X 2] (R = Bu t or 2,6-C 6H 3Pr i2; X = Cl or CH 2Ph) exhibit room-temperature dynamic NMR behaviour via an unusual trigonal twist of the facially coordinated Me 3tach ligand, and the activation parameters for these processes have been measured and are discussed. The X-ray structures of [Ti(NR)(Bu t3tach)Cl 2] (R = Bu t or 2,6-C 6H 3Pr i2) and [Ti(NBu t)(Me 3tach)(X) 2] [X= Cl or CH 2Ph) are reported. Me 3tach and Bu t3tach = 1,3,5-trimethyl- and tri- tert-butyl-1,3,5-triazacyclohexane, respectively. 相似文献
|