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1.
Ruthenium carbonyl triphenylphosphine complexes Ru 2(CO) 6−n
(PPh 3)
n
{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} ( n=1, 2) were obtained by the reaction of complex Ru 2(CO) 6{μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} containing the ruthenacyclopentadiene moiety with PPh 3 in refluxing toluene. The complexes were characterized by IR and by 1H, 13C, and 31P NMR spectroscopy, and by X-ray analysis. The monophosphine derivative is identical to the complex formed by fragmentation
of the Ru 3(CO) 8(PPh 3){μ-C(CH=CHPh)C(Ph)C(CH=CHPh)C(Ph)} cluster and contains the PPh 3 ligand at the ruthenium atom of the ruthenacyclopentadiene moiety.
Translated from Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 1836–1843, September, 1998 相似文献
2.
In this work, a series of molecules with an extended π-conjugated bridge have been theoretically designed based on porphyrin, where -(CH=CH)n- (n = 1–4, 8, 12) chain is served as an extended π-conjugated bridge. It is found that all molecules exhibit large energy gaps in the range of 3.484–4.151 eV for porphyrin-(CH=CH)n-NH2, and 3.624–4.250 for porphyrin-(CH=CH)n-NO2. The maximum absorption wavelengths of all molecules show a red shift trend with increasing -(CH=CH)n- length, which leads to small transition energy. It is observed that long chain brings these molecules the large first hyperpolarizability, which are 1.04 × 105 au for porphyrin-(CH=CH)12-NH2, 1.26×105 au for porphyrin-(CH=CH)12-NO2. Moreover, compared with -(CH=CH)n-NH2 with the same chain length, -(CH=CH)n-NO2 chain can achieve larger nonlinear optical response. It is hoped that the research in this paper can provide a new strategy for the experimental design of nonlinear optical materials. 相似文献
3.
Monomeric complexes ML
n
X
m
, where M = Co 2
+, Ni 2
+, Zn 2
+, Cd 2
+, Cu 2
+, Pd 2
+, Sn 4
+; L = 1-allenylimidazole, 1-allenyl-2-methylimidazole, 1-allenylbenzimidazole; n = 2, 4; m = 1, 2, 4; X = Cl, OCOCH3, was prepared for the first time, and their structure was studied by NMR and IR spectroscopy. In the complexes, 1-allenylimidazoles act as monodentate ligands coordinating via the heteroring N3atom, and the CH2 = C = CH group is stabilized by coordination of the azolyl ring with the metal, which hinders elec- tron transfer from the heteroring to the allenyl fragment. The prospective use of the complexes of Zn(OCOCH3)2 with 1-allenyl imidazole derivatives as antidotes and antihypoxants was demonstrated. 相似文献
4.
Synthesis and Structure of Pentaalkylchlorohexastibane Sb 6R 5Cl [R = (Me 3Si) 2CH] The reaction of RSbCl 2 [R = (Me 3Si) 2CH] with Na‐K alloy in tetrahydrofuran gives besides the known rings Sb nR n (n = 3, 4), (Me 3Si) 2CH 2 and the pentaalkylchlorohexastibane Sb 6R 5Cl ( 1 ). 1 was characterized by spectroscopic methods (MS, 1H‐, 13C‐NMR, X‐ray diffraction). The structure of 1 consists of a folded four membered antimony ring in the all‐trans configuration with three alkyl groups and one Sb(R)—Sb(R)Cl fragment as substituents. 相似文献
5.
Treatment of the thioether‐substituted secondary phosphanes R 2PH(C 6H 4‐2‐SR 1) [R 2=(Me 3Si) 2CH, R 1=Me ( 1 PH ), iPr ( 2 PH ), Ph ( 3 PH ); R 2= tBu, R 1=Me ( 4 PH ); R 2=Ph, R 1=Me ( 5 PH )] with nBuLi yields the corresponding lithium phosphanides, which were isolated as their THF ( 1 – 5 Pa ) and tmeda ( 1 – 5 Pb ) adducts. Solid‐state structures were obtained for the adducts [R 2P(C 6H 4‐2‐SR 1)]Li(L) n [R 2=(Me 3Si) 2CH, R 1= nPr, (L) n=tmeda ( 2 Pb ); R 2=(Me 3Si) 2CH, R 1=Ph, (L) n=tmeda ( 3 Pb ); R 2=Ph, R 1=Me, (L) n=(THF) 1.33 ( 5 Pa ); R 2=Ph, R 1=Me, (L) n=([12]crown‐4) 2 ( 5 Pc )]. Treatment of 1 PH with either PhCH 2Na or PhCH 2K yields the heavier alkali metal complexes [{(Me 3Si) 2CH}P(C 6H 4‐2‐SMe)]M(THF) n [M=Na ( 1 Pd ), K ( 1 Pe )]. With the exception of 2 Pa and 2 Pb , photolysis of these complexes with white light proceeds rapidly to give the thiolate species [R 2P(R 1)(C 6H 4‐2‐S)]M(L) n [M=Li, L=THF ( 1 Sa , 3 Sa – 5 Sa ); M=Li, L=tmeda ( 1 Sb , 3 Sb – 5 Sb ); M=Na, L=THF ( 1 Sd ); M=K, L=THF ( 1 Se )] as the sole products. The compounds 3 Sa and 4 Sa may be desolvated to give the cyclic oligomers [[{(Me 3Si) 2CH}P(Ph)(C 6H 4‐2‐S)]Li] 6 (( 3 S ) 6) and [[ tBuP(Me)(C 6H 4‐2‐S)]Li] 8 (( 4 S ) 8), respectively. A mechanistic study reveals that the phosphanide–thiolate rearrangement proceeds by intramolecular nucleophilic attack of the phosphanide center at the carbon atom of the substituent at sulfur. For 2 Pa / 2 Pb , competing intramolecular β‐deprotonation of the n‐propyl substituent results in the elimination of propene and the formation of the phosphanide–thiolate dianion [{(Me 3Si) 2CH}P(C 6H 4‐2‐S)] 2?. 相似文献
6.
Interesting varieties of heterobimetallic mixed-ligand complexes [Zr{M(OPr i)
n
} 2 (L)] (where M = Al, n = 4, L = OC 6H 4CH = NCH 2CH 2O (1); M = Nb, n = 6, L = OC 6H 4CH = NCH 2CH 2O (2); M = Al, n = 4, L = OC 10H 6CH = NCH 2CH 2O (3); M = Nb, n = 6, L = OC 10H 6CH = NCH 2CH 2O (4)), [Zr{Al(OPr i) 4} 2Cl(OAr)] (where Ar = C 6H 3Me 2-2,5 (5); Ar = C 6H 2Me-4-Bu 2-2,6 (6), [Zr{Al(OPr i) 4} 2(OAr) 2] (where Ar = C 6H 3Me 2-2,5 (7); Ar = C 6H 2Me-4-Bu 2-2,6 (8), [Zr{Al(OPr i) 4} 3(OAr)] (where Ar = C 6H 3Me 2-2,5 (9); Ar = C 6H 3Me 2-2,6 (10), [ZrAl(OPr i) 7-n
(ON=CMe 2)
n
] (where n = 4 (11); n = 7 (12), [ZrAl 2(OPr i) 10-n
(ON=CMe 2)
n
] (where n = 4 (13); n = 6 (14); n = 10 (15) and [Zr{Al(OPr i) 4} 2{ON=CMe(R)}
n
Cl 2–n] [where n = 1, R = Me (16); n = 2, R = Me (17); n = 1, R = Et (18); n = 2, R = Et (19)] have been prepared either by the salt elimination method or by alkoxide-ligand exchange. All of these heterobimetallic complexes
have been characterized by elemental analyses, molecular weight measurements, and spectroscopic (I.r., 1H-, and 27Al- n.m.r.) studies. 相似文献
7.
Europium and terbium mixed-ligand complexes with cinnamic acid of composition Ln(Cin) 3· nD · xH 2O, where Ln = Eu 3+or Tb 3+, Cin is a cinnamate ion (C 6H 5CH=CHCOO –), D = 1,10-phenantroline, 2,2"-dipyridyl, benzotriazole ( n= 2, x= 0), triphenylphosphine oxide ( n= 1, x= 2), or H 2O ( n= 0 or 1, x= 0), were synthesized. The compounds were characterized by elemental analysis, IR and luminescence spectroscopy. The Stark structure of the 5
D
0– 7
F
j( j= 0, 1, 2) electronic transitions in the low-temperature luminescence spectra of europium complexes was analyzed. IR study has revealed a bidentate coordination of the cinnamate ion in the compounds. 相似文献
8.
1-(Trimethylsilyl)-1-alkenes of general formula CH 3(CH 2) nCH?CHSi(CH 3) 3, where n = 3–15, have been prepared by a novel method, viz. by an effective cross-metathesis of vinyltrimethylsilane with 1-alkenes catalyzed by RuCl 2(PPh 3) 3. Excess of 1-alkene in the reaction mixture gave 1-(trimethylsilyl)-1-alkenes in good yields of up to 60% (in terms of vinylsilane). The products were identified by NMR spectroscopic ( 1H, 13C NMR) and GC MS methods. 相似文献
9.
{η 5 -C 5H 4[CH(CH 3)OC(O)CH = CH 2])Mn(CO)3, {η 5—C 5[CH-(CH 3)OC(O)C(CH 3)=CH 2]]Mn(CO) 3, and {η 5—C 5H 4[CH(CH 3)-OC(O)CH=C(CH 3)2])Mn(CO) 3 were synthesized (63, 57, and 51%, respectively) from {η 5—C 5H 4[CH(CH 3)OH])Mn(CO) 3, toluene-sulfonic acid, and the acrylic, methacrylic, and dimethylacrylic acids, and from (η 5-C 5H 4[CH(CH 3)OH]}Mn(CO) 3, pyridine, and the acrylic, methacrylic, and dimethylacrylic acyl chlorides [26, 48, and 25% (impure), respectively]. No product was obtained when NaH was used as the base in the latter method. The acrylate and methacrylate monomers were bulk homopolymerized at 65°C with AIBN (75% yield, Mn = 88,550 g/mol; 78% yield, Mn = 349,350 g/mol, respectively). The dimethylacrylate did not polymerize under these conditions. The polymers lost vinylcymantrene upon heating to 257 and 279°C, respectively. The polymers did not exhibit a clear Tg but were observed to soften at 85 and 160°C, respectively, and they could be pulled into fibers. 相似文献
10.
Leucine methyl and ethyl esters reacted with 3-bromobenzaldehyde and 4-chlorobenzaldehyde in anhydrous methanol in the presence of magnesium sulfate to afford the coresponding Schiff bases of the general formula (CH3)2CHCH2CH(COOR 1)N=CHR 2 [R 1 = CH3, C2H5, R 2= 3-BrC6H4, 4-ClC6H4]. Their reduction with sodium tetrahydridoborate yielded N-benzyl derivatives (CH3)2CHCH2CH(COOR 1)NHCH2R 2, which were converted into N-acyl- N-benzyl derivatives (CH3)2CHCH2CH(COOR 1)N(COR 3)CH2R 2[R 3= CH 3, C 6H 5]. 相似文献
11.
The polymerization of trimethylsilylacetylene was investigated by using W and Mo catalysts. Mixtures of WCl 6 with appropriate organometallic cocatalysts such as n-Bu 4Sn and Et 3SiH at 1:1 molar ratio provided poly(trimethylsilylacetylene) in high yields. On the other hand, MoCI 5 gave mainly methanol-soluble oligomers even in the presence of these cocatalysts. The polymer formed was a partly insoluble yellow powder, and the molecular weight of the soluble fraction was about 7000. The IR, 1H-NMR, and 13C-NMR spectra supported the polymer structure, (CH = CSiMe 3) n. Protodesilylation of poly(trimethylsilylacetylene) afforded a new polymer containing both acetylene and trimethylsilylacetylene units. 相似文献
12.
Methoxydimethylsilane and chlorodimethylsilane‐terminated telechelic polyoctenomer oligomers (POCT) have been prepared by acyclic diene metathesis (ADMET) chemistry using Grubbs' ruthenium Ru(Cl 2)(CHPh)(PCy 3) 2 [Ru] or Schrock's molybdenum Mo(CH CMe 2Ph)(N 2,6 C 6H 3 i Pr 2)(OCMe(CF 3) 2) 2 [Mo] catalysts. These macromolecules have been characterized by FTIR, 1H‐, 13C‐, and 29Si‐NMR spectroscopy. The molecular weight distributions of these polymers have been determined by GPC and vapor pressure osmometry (VPO). The number‐average molecular weight (Mn) values of the telechelomers are dictated by the initial ratio of the monomer to the chain limiter. The termini of these oligomers (Mn = 2000) can undergo a condensation reaction with hydroxy‐terminated poly(dimethylsiloxane) (PDMS) macromonomer (Mn = 3300) [HO Si(CH 3) 2 O { Si(CH 3) 2O } x Si(CH 3) 3], producing an ABA‐type block copolymer, as follows: (CH 3) 3SiO [ Si(CH 3) 2O ] x [ CHCH (CH 2) 6 ] y [ OSi(CH 3) 2 ] x OSi(CH 3) 3. The block copolymers were characterized by 1H‐ and 13C‐NMR spectroscopy, VPO, and GPC, as well as elemental analysis, and were determined by VPO to have a Mn of 8600. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 849–856, 1999 相似文献
13.
A new kind of surfactant, [CnH_(2n+1)OCH2CH(OH)CH2N(CH3)3]Cl (n=12, 14, 16) was synthesized. The solubility of benzyl alcohol in micellar solutions was determined by 1H NMR method. The results indicate that the length of alkyl chains of surfactant affects the solubility of ben-zyl alcohol in 2.5 × l0~(-2) mol/L micellar solutions. The solubility of benzyl alcohol per liter of micellar solution is 0.095 mole for n=12, 0.115 mole for n=14, 0.165 mole for n=16. The transfer free energy of benzyl alcohol from aqueous phase to micellar phase is -24.29 kJ/mol for n=12, -24.37 kJ/mol for n=14, -24.49 kJ/mol for n=16. 相似文献
14.
Summary The synthesis of three vinylbenzyl complexes (n 5-C 5H 5)-M(CO) n(CH 2C 6H 4CH=CH 2), [ 1), M=Mo, n=3; ( 2), M=W, n=3; ( 3), M=Fe, n=2] is reported. Complexes ( 1) and ( 2) have been copolymerized with monomers, such as styrene, methyl methacrylate, and N-vinyl-2-pyrrolidone, in benzene using azoisobutyronitrile as initiator. The rates of incorporation of ( 2) into copolymers with styrene and methyl methacrylate were the same as the rate of incorporation of the organic monomer. The homopolymerization of ( 2) was also carried out. Polymerizations occurred satisfactorily except for the copolymerization of ( 1) with styrene, where little incorporation of the organometallic monomer occurred. 相似文献
15.
A new class of bidentate, aza‐based phosphinic amide ligands of the type RN(H)P(?O)(2‐py) 2 (2‐py = 2‐pyridyl) was synthesized within minutes via a one‐pot process including Staudinger reaction of an organic azide (RN 3) with 2‐pyridylphosphines, followed by partial, unprecedented hydrolysis under loss of one aromatic substituent. The structure of the unusual‐hydrolysis product H 2C?CH(CH 2) 9N(H)P(?O)(2‐py) 2 ( 5a ) was characterized by IR, 1H‐ and 31P‐NMR, as well as by X‐ray crystal‐structure analysis ( Figure). The tetrahedral P‐atom was found to be surrounded by a trigonal‐pyramidal arrangement of the substituents. To gain insight into the formation of these novel phosphinic amides, a series of intermediate iminophosphoranes, H 2C?CH(CH 2) 9N?P(Ar) n(2‐py) 3 ? n ( n = 0–3), compounds 1a – 1f , were synthesized, and their hydrolyses were studied. All tested compounds followed the classical hydrolysis route of P?N cleavage under acidic conditions. Sequential hydrolysis to 5a – 5d only occurred under either basic conditions or in wet MeCN as solvent. Notably, H 2C?CH(CH 2) 9N?P(C 6H 5)(4‐MeO‐2‐py) 2 ( 1c ) was hydrolyzed at a much slower rate compared to its analogue 1b lacking the MeO group. On the contrary, the halogenated compounds H 2C?CH(CH 2) 9N?P(4‐X‐C 6H 4) 3 ( 1f,g ) (X = F, Cl) were hydrolyzed at a notably faster rate relative to the non‐halogenated congener 1e (X = H). 相似文献
16.
Isomeric mixtures of compounds Me nM(CH?CHMe) 4?n (M=Si, Pb; n=0?3) have been prepared and studied, as well as pure Me 3M(CMe?CH 2) and mixtures containing propenyl isopropenyl residues bonded to silicon and lead. 1H, 13C, 29Si and 207Pb NMR data are presented; as previously observed for the corresponding tin compounds, the 29Si and 207Pb shifts for the Me 3MC 3H 5 isomers can be used to calculate the shifts expected for the other isomers; while for lead the agreement is good, calculated and observed values for silicon diverge with decreasing n due, at least in part, to steric factors. 相似文献
17.
In the cross-metathesis reaction of tri(methyl, ethoxy)vinylsilanes with propene and/or 1-butene catalyzed by RuCl 2(PPh 3) 3 activated in benzene at 115–130 °C, a series of l-alkenylsilanes of general formula CH 3(CH 2) mCH = CHSiMe 3−n(OEt) n, where m=0, 1, and n=0–3 (1-silyl-1-alkenes), as well as of formula CH 2=C(Me)SiMe 3−n(OEt) n, where n=1, 2 (2-silyl-1-alkenes), were obtained. Additional products determined were allysilanes of general formula CH 2=CHCH 2SiMe 3−n(OEt) n and CH 3CH= CHCH 2SiMe 3−n(OEt) n, where n=1–3. © 1997 John Wiley & Sons, Ltd. 相似文献
18.
Previously unknown 1,1-diethylnylsilacycloalkanes (CH 2) 4nSi(C& = CH) 2 ( n = 3, 4) were prepared by the reaction of HC& = CMgBr with 1,1-dichlorosilacycloalkanes (CH 2) 4nSiCl 2 ( n = 3, 4). The reaction of (CH 2) 4Si(C& = CMgBr) 2 with (CH2)4SiCl2 in THF under conditions of high dilution gives cyclo(tetramethylene)- silethynes [(CH2)4SiC& = C]4 with an admixture of cyclodi(tetramethylene)silethyne [(CH2)4SiC& = C]2. The re- action of Me2Si(C& = CSiMe2C& = CMgBr)2 with (CH2)4SiCl2 was used to prepare 1,1,4,4,7,7-hexamethyl-10,10- tetramethylene-1,4,4,10-tetrasilacyclododeca-2,5,8,11-tetrayne. 相似文献
19.
Living cationic polymerization of 2‐adamantyl vinyl ether (2‐vinyloxytricyclo[3.3.1.1] 3,7decane; 2‐AdVE) was achieved with the CH 3CH(OiBu)OCOCH 3/ethylaluminum sesquichloride/ethyl acetate [CH 3CH(OiBu)OCOCH 3/Et 1.5AlCl 1.5/CH 3COOEt] initiating system in toluene at 0 °C. The number‐average molecular weights ( Mn's) of the obtained poly(2‐AdVE)s increased in direct proportion to monomer conversion and produced the polymers with narrow molecular weight distributions (MWDs) ( Mw/ Mn = ~1.1). When a second monomer feed was added to the almost polymerized reaction mixture, the added monomer was completely consumed and the Mn's of the polymers showed a direct increase against conversion of the added monomer. Block and statistical copolymerization of 2‐AdVE with n‐butyl vinyl ether (CH 2?CH? O? CH 2 CH 2CH 2CH 3; NBVE) were possible via living process based on the same initiating system to give the corresponding copolymers with narrow MWDs. Grass transition temperature ( Tg) and thermal decomposition temperature ( Td) of the poly(2‐AdVE) (e.g., Mn = 22,000, Mw/ Mn = 1.17) were 178 and 323 °C, respectively. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1629–1637, 2008 相似文献
20.
The NMR spectrum of acrolein and acroyl fluoride (CH 2?CH? COX with X?H and F) oriented in a nematic phase has been measured and information about conformational equilibrium s- cis ? s- trans has been obtained. The barrier to internal rotation of the COX group has been studied with various hypotheses. Good agreement between experimental and calculated spectra has been obtained using the potential equation V(?) = Σ nVn(1 – cos n?)/2, with V1 = ?200 cal mol ?1, V2 = 1500 cal mol ?1 and V3 = 400 cal mol ?1 for the fluorine compound, and V1 = 1200 cal mol ?1, V2 = 3000 cal mol ?1 and V3 = 2000 cal mol ?1 for acrolein; this last compound is found to be mostly in the s- trans conformation. 相似文献
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