共查询到20条相似文献,搜索用时 144 毫秒
1.
Guo-Liang Lu L. James Wright George R. Clark 《Journal of organometallic chemistry》2005,690(4):972-981
The thiocarbonyl analogue of Vaska’s compound is produced in high yield by first treating IrCl(CO)(PPh3)2 with CS2 and methyl triflate to give [Ir(κ2-C[S]SMe)Cl(CO)(PPh3)2]CF3SO3 (1), secondly, reacting 1 with NaBH4 to give IrHCl(C[S]SMe)(CO)(PPh3)2 (2), and finally heating 2 to induce elimination of both MeSH and CO to produce IrCl(CS)(PPh3)2 (3). When IrCl(CS)(PPh3)2 is treated with Hg(CHCHPh)2 the novel 2-iridathiophene, Ir[SC3H(Ph-3)(CHCHPh-5)]HCl(PPh3)2 (4) is produced. The X-ray crystal structure of the iodo-derivative of 4, Ir[SC3H(Ph-3)(CHCHPh-5)]HI(PPh3)2 (5) confirms the unusual 2-metallathiophene structure. Treatment of IrCl(CS)(PPh3)2 with Hg(CHCPh2)2 produces both a coordinatively unsaturated 1-iridaindene, Ir[C8H5(Ph-3)]Cl(PPh3)2 (6) and a chelated dithiocarboxylate complex, Ir(κ2-S2CCHCPh2)Cl(CHCPh2)(PPh3)2 (7). X-ray crystal structure determinations for 6 and 7 are reported. 相似文献
2.
Bimetallic alkylidene complexes of tungsten (R′O)2(ArN)WCH-SiR2-CHW(NAr)(OR′)2 (R = Me (1), Ph (2)) and (R′O)2(ArN)WCH-SiMe2SiMe2-CHW(NAr)(OR′)2 (3) (Ar = ; R′ = CMe2CF3) have been prepared by the reactions of divinyl silicon reagents R2Si(CHCH2)2 with known alkylidene compounds R′′-CHMo(NAr)(OR′)2. (R′′ = But, PhMe2C) Complexes 1-3 were structurally characterized. Ring opening metathesis polymerization (ROMP) of cyclooctene using compounds 1-3 as initiators led to the formation of high molecular weight polyoctenamers with predominant trans-units content in the case of 1 and 3 and predominant cis-units content in the case of 2. 相似文献
3.
The diiron complex [Fe2{μ-к1(O):η1(C):η3(C)-C(N(Me)(Xyl))C(H)C(Me)C(O)OMe}(μ-CO)(Cp)2] (2) has been obtained from the diiron bridging vinyliminium [Fe2{μ-η1:η3-C(Me)C(H)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (1; Xyl = 2,5-C6H3Me2) upon treatment with NaH in the presence of CH2CCMe2, followed by chromatography on alumina with MeOH as eluent. The reaction consists in the incorporation of a methylcarboxylate unit, assembled from CO and MeO−, into the bridging vinyliminium ligand. The resulting complex 2 exhibits a C4 fragment bridging the two iron centres through the carbonyl oxygen atom and the allylidene moiety.The X-ray molecular structure of 2 has been determined. 相似文献
4.
Beatriz Alonso Esther Delgado Elisa Hernández Rubén A. Toscano 《Journal of organometallic chemistry》2007,692(23):5117-5124
The compounds [Os3(CO)10{μ,η3-(SCH2CH2SCCHC(O)CHCH(C5H4)Fe (C5H5)}] (2), [Os3(CO)9{μ,η3-(SCH2CH2SCCHC(O)CHCH(C5H4)Fe(C5H5)}] (3) and [Os3(CO)8{μ3,η2-{CCHC(O)CHCH(C5H4)Fe(C5H5)}(SCH2CH2S)}] (4) have been obtained by rupture of S-C bonds in the ketene dithioacetal [C5H5FeC5H4CHCHC(O)CHC(SCH2CH2S)], in their reaction with the activated cluster [Os3(CO)10(NCMe)2]. The presence of an oxametallacycle in these derivatives has been confirmed by an X-ray diffraction analysis. The electrochemical study has indicated the ability of these compounds to modify the electrode surfaces. 相似文献
5.
Marcin Konkol 《Journal of organometallic chemistry》2006,691(12):2839-2845
The iridium dinitrogen complex [IrCl(N2)(PPh3)2] (1) was found to react with alkynylsilanes to form the vinylidene iridium(I) complexes trans- (R/R′ = Ph/Me, 2; Me/Me, 3; Bn/Me, 4; SiMe3/Me, 5; SiEt3/Et, 6; iPr/Me, 7) and with Me3SiCCC(O)R to yield the iridium η2-alkyne complexes trans-[IrCl{η2-Me3SiCCC(O)R}(PPh3)2] (R = OEt, 9; Me, 11). Complex 9 was found to isomerize upon heating or upon UV irradiation yielding the vinylidene complex trans-[IrCl{CC(SiMe3)CO2Et}(PPh3)2] (10). The reaction of 1 with Me3SiCCCCSiMe3 yielded the complex trans-[IrCl{CC(SiMe3)CCSiMe3}(PPh3)2] (8), whereas with MeO2CCCCO2Me the iridacyclopentadiene complex [Ir{C4(CO2Me)4}Cl(PPh3)2] (13) was formed. The complexes were characterized by means of 1H, 13C and 31P NMR spectroscopy as well as by IR spectroscopy and microanalysis. 相似文献
6.
Giovanni Natile Rino A. Michelin Silvia Mazzega Sbovata Roberta Seraglia 《Journal of organometallic chemistry》2005,690(8):2121-2127
The di-nitrile complexes trans-[PtCl2(NCR)2] (R = Me, Ph, CH2Ph) react with an excess of gaseous NH3 in CH2Cl2 at −10 °C to form, in high yield, the corresponding di-amidine complexes trans-[PtCl(NH3){HNC(NH2)R}2]Cl in which also one chlorine ligand has been displaced by NH3. The 1H NMR spectra in DMSO showed the formation of different species which were characterized through NOESY, TOCSY and 1H/13C heteronuclear correlations as trans-[Pt(NH3){HNC(NH2)R}2(DMSO)]Cl2 and trans-[PtCl{HNC(NH2)R}2(DMSO)]Cl. 相似文献
7.
Reaction of (Ph2P(o-C6H4)CHNCH2CH2)3N with 3 equiv. of Os3(CO)10(NCMe)2 at ambient temperature affords the triple cluster [Os3(CO)10Ph2P(o-C6H4)CHNCH2CH2]3N (1) through coordination of the phosphine and imine groups. Thermolysis of 1 in benzene leads to decarbonylation and C-H/C-N bond activation of the ligand to generate (μ-H)Os3(CO)8(μ3-Ph2P(o-C6H4)CHNCCH2) (2). The molecular structure of 2 has been determined by an X-ray diffraction study. 相似文献
8.
A Mo(0) complex containing a new tetraphosphine ligand [Mo(P4)(dppe)] (1; P4 = meso-o-C6H4(PPhCH2CH2PPh2)2, dppe = Ph2PCH2CH2PPh2) reacted with CO2 (1 atm) at 60 °C in benzene to give a Mo(0) carbonyl complex fac-[Mo(CO)(η3-P4O)(dppe)] (2), where the O abstraction from CO2 by one terminal P atom in P4 takes place to give the dangling P(O)Ph2 moiety together with the coordinated CO. On the other hand, reaction of 1 with TolNCS (Tol = m-MeC6H4) in benzene at 60 °C resulted in the incorporation of three TolNCS molecules to the Mo center, forming a Mo(0) isocyanide-isothiocyanate complex trans,mer-[Mo(TolNC)2(η2-TolNCS)(η3-P4S)] (4), where the S abstraction occurs from two TolNCS molecules by P4 and dppe to give the η3-P4S ligand and free dppeS, respectively, together with two coordinated TolNC molecules. The remaining site of the Mo center is occupied by the third TolNCS ligating at the CS bond in an η2-manner. The X-ray analysis has been undertaken to determine the detailed structures for 2 and 4. 相似文献
9.
Leonid N. Bochkarev Alexander V. Nikitinskii Yulia E. Begantsova Vladislav I. Shcherbakov Natalia E. Stolyarova Irina K. Grigorieva Irina P. Malysheva Galina V. Basova Georgii K. Fukin Evgenii V. Baranov Yurii A. Kurskii Gleb A. Abakumov 《Journal of organometallic chemistry》2005,690(13):3212-3216
The novel germanium-containing alkylidene complexes of molybdenum R3Ge-CHMo(NAr)(OCMe2CF3)2 (Ar = 2,6-i-Pr2C6H3; R = Me, Ph) have been prepared by the reaction of organogermanium vinyl reagents R3 GeCHCH2 with known alkylidene compounds Alkyl-CHMo(NAr)(OCMe2CF3)2 (Alkyl = But, PhMe2C). The titled compounds were isolated as crystalline solids and characterized by elemental analysis, 1H NMR, 13C NMR spectroscopy and X-ray diffraction studies. The geometry of the Mo atoms in the compounds can be described as a distorted tetrahedron. 相似文献
10.
Selby A.R. Knox 《Journal of organometallic chemistry》2007,692(19):4119-4128
The diruthenium μ-allenyl complex [Ru2(CO)(NCMe)(μ-CO){μ-η1:η2-C(H)CC(Me)(Ph)}(Cp)2][BF4], 3b, reacts with halide anions to yield the neutral derivatives [Ru2(CO)2(X){μ-η1:η2-C(H)CC(Me)(Ph)}(Cp)2] [X = Cl, 4b; X = Br, 4c; X = I, 4d]. Complex 4b undergoes isomerization to the unprecedented bridging vinyl-chlorocarbene species [Ru2(CO)(μ-CO){μ-η1:η3- C(Cl)C(H)C(Me)(Ph)}(Cp)2], 10, upon filtration of a CH2Cl2 solution through an alumina column.Complex 3b reacts with an excess of NaBH4 to give five products: the allene complex [Ru2(CO)2{μ-η2:η2- CH2CC(Me)(Ph)}(Cp)2], 5; the hydride species trans-[Ru2(CO)2(μ-H){μ-η1:η2-CHCC(Me)(Ph)}(Cp)2], 6, and cis-[Ru2(CO)2(μ-H){μ-η1:η2-CHCC(Me)(Ph)}(Cp)2], 8; the vinyl-alkylidene [Ru2(CO)(μ-CO){μ-η1:η3- C(H)C(H)C(Me)(Ph)}(Cp)2], 9; and the cluster [Ru3(CO)3(μ-H)3(Cp)3], 7.Studies on the thermal stabilities of 5, 6, 8 and 9 have suggested a plausible mechanism for the formation of these complexes and for the synthesis of 10. 相似文献
11.
Treatment of RuHCl(CO)(PPh3)3 with (3E,5E,7E,9E,11E)-HCC-(CHCH)5- CCH produces [RuCl(CO)(PPh3)2]2[μ-(CHCH)7]. The later complex reacts with PMe3 to give [RuCl(CO)(PMe3)3]2[μ-(CHCH)7], the structure of which has been confirmed by X-ray diffraction. The through-space distance from one Ru to the other is 19.88 Å. 相似文献
12.
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14.
Nicholas A. Barnes Cheryl Fish James V. Morey Robin G. Pritchard John E. Warren 《Journal of fluorine chemistry》2010,131(11):1156-1164
The coordination chemistry of the fluorovinyl substituted phosphines PPh2(Z-CFCFH) and PPh2(E-CClCFH) with K2MX4 (M = Pd, Pt; X = Cl, Br, and I) salts has been investigated resulting in the first reported palladium(II) and platinum(II) complexes of phosphines containing partially fluorinated vinyl groups. The complexes have been characterised by a combination of multinuclear [1H, 13C{1H}, 19F, 31P{1H}] NMR spectroscopy, and IR/Raman spectroscopy. The single-crystal X-ray structures of trans-[PdX2{PPh2(CFCFH)}2], X = Cl (1), Br (2), I (3), trans-[PdCl2{PPh2(CClCFH)}2] (4), cis-[PtX2{PPh2(CFCFH)}2], X = Cl (5), Br (6), trans-[PtI2{PPh2(CFCFH)}2] (7), and both cis- and trans-[PtCl2{PPh2(CClCFH)}2] (8), have been determined. Results obtained from spectroscopic and crystallographic data suggest that replacement of a β-fluorine by hydrogen, whilst reducing the steric demand of the ligand, has little effect on the electronic character of the ligand. The presence of a proton in the vinyl group results in short proton-halide secondary interactions in the solid state (d(H?X) = 2.72(3) for 1, and 2.92(5) Å for 2) forming an infinite chain ribbon motif. 相似文献
15.
Vincenzo G. Albano Fabio Marchetti Stefano Zacchini 《Journal of organometallic chemistry》2006,691(20):4234-4243
The diiron vinyliminium complexes [Fe2{μ-η1:η3-C(R′)C(H)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R=Me, R′ = SiMe3 (1a); R = Me, R′ = CH2OH (1b); R = CH2Ph, R′ = Tol (1c), Tol = 4-MeC6H4; R = CH2Ph, R′ = COOMe (1d); R = CH2Ph, R′ = SiMe3 (1e)) undergo regio- and stereo-selective addition by cyanide ion (from ), affording the corresponding bridging cyano-functionalized allylidene compounds [Fe2{μ-η1:η3-C(R′)C(H)C(CN)N(Me)(R)}(μ-CO)(CO)(Cp)2] (3a-e), in good yields. Similarly, the diiron vinyliminium complexes [Fe2{μ-η1:η3-C(R′)C(R′)CN(Me)(R)}(μ-CO)(CO)(Cp)2][SO3CF3] (R = R′ = Me (2a); R = Me, R′ = Ph (2b); R = CH2Ph, R′ = Me (2c); R = CH2Ph, R′ = COOMe (2d)) react with cyanide and yield [Fe2{μ-η1:η3-C(R′)C(R′)C(CN)N(Me)(R)}(μ-CO)(CO)(Cp)2] (9a-d). The reactions of the vinyliminium complex [Fe2{μ-η1:η3-C(Tol)CHCN(Me)(4-C6H4CF3)}(μ-CO)(CO)(Cp)2][SO3CF3] (4) with NaBH4 and afford the allylidene [Fe2{μ-C(Tol)C(H)C(H)N(Me)(C6H4CF3)}(μ-CO)(CO)(Cp)2] (5) and the cyanoallylidene [Fe2{μ-C(Tol)C(H)C(CN)N(Me)(C6H4CF3)}(μ-CO)(CO)(Cp)2] (6), respectively. Analogously, the diruthenium vinyliminium complex [Ru2{μ-η1:η3-C(SiMe3)CHCN(Me)(CH2Ph)}(μ-CO)(CO)(Cp)2][SO3CF3] (7) reacts with to give [Ru2{μ-η1:η3-C(SiMe3)CHC(CN)N(Me)(CH2Ph)}(μ-CO)(CO)(Cp)2] (8).Finally, cyanide addition to [Fe2{μ-η1:η3-C(COOMe)C(COOMe)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2][SO3CF3] (2e) (Xyl = 2,6-Me2C6H3), yields the cyano-functionalized bis-alkylidene complex [Fe2{μ-η1:η2-C(COOMe)C(COOMe)(CN)CN(Me)(Xyl)}(μ-CO)(CO)(Cp)2] (10). The molecular structures of 3a and 9a have been elucidated by X-ray diffraction. 相似文献
16.
Kotohiro Nomura Junji Yamada Wei Wang Jingyu Liu 《Journal of organometallic chemistry》2007,692(21):4675-4682
Ligand effects on the catalytic activity [and norbornene (NBE) incorporation] for both ethylene polymerization and ethylene/NBE copolymerization using half-titanocenes (titanium half-sandwich complexes) containing ketimide ligand of type Cp′TiCl2[NC(R1)R2] [Cp′ = Cp (1), C5Me5 (Cp∗, 2); R1,R2 = tBu,tBu (a), tBu,Ph (b), Ph,Ph (c)]-methylaluminoxane (MAO) catalyst systems have been investigated. CpTiCl2[NC(tBu)Ph] (1b) CpTiCl2(NCPh2) (1c), and Cp∗TiCl2(NCPh2) (2c) were prepared and identified; the structure of Cp∗TiCl2(NCPh2) (2c) was determined by X-ray crystallography. The catalytic activity for ethylene polymerization increased in the order: 1a > 1b > 1c, suggesting that an electronic nature of the ketimide ligand affects the activity. However, molecular weight distributions for resultant (co)polymers prepared by 1b,c and by 2c-MAO catalyst systems were bi- or multi-modal, suggesting that the ketimide substituent plays a key role in order for these (co)polymerizations to proceed with single catalytically-active species. CpTiCl2(NCtBu2) (1a) exhibited both remarkable catalytic activity and efficient NBE incorporation for ethylene/NBE copolymerization. 相似文献
17.
Stéphanie M. Cornet Andrés E. Goeta Judith A.K. Howard Mark D. Roden Amber L. Thompson 《Journal of organometallic chemistry》2005,690(16):3630-3637
Oxidative addition reactions of Cl2CPR (R = 2,4,6-tris(trifluoromethyl)phenyl (Ar) or 2,6-bis(trifluoromethyl)phenyl (Ar′) with Pt(PPh3)4 yield the cis and trans (at platinum) complexes [PtCl(ClCPAr)(PPh3)2] and [PtCl(ClCPAr′)(PPh3)2]. All starting materials and intermediates have been characterised by NMR spectroscopy. The crystal and molecular structures of the trans-platinum complexes have been determined by single-crystal X-ray diffraction at low temperature. 相似文献
18.
Yulia G. Budnikova Oleg G. Sinyashin Tatyana P. Gryaznova Mikhail P. Egorov 《Journal of organometallic chemistry》2007,692(19):4067-4072
Convenient synthetic route to prepare the germylene complexes of tungsten pentacarbonyls, W(CO)5GeCl2 and W(CO)5GeW(CO)5, electrochemically is developed. Combined quantum-chemical/IR spectroscopic approach is used for identification of the synthesized compounds. Good agreement between theoretical and experimental spectra can be regarded as one of the proofs of their supposed structures. 相似文献
19.
Katsuhiko Takeuchi 《Journal of organometallic chemistry》2011,696(6):1156-12481
The reaction of 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne 1 with secondary or primary amines produced amino-substituted disilenes R(R2′N)SiSiHR 2a-d (R = SiiPr[CH(SiMe3)2]2, R2′NEt2N (2a), (CH2CH2)2N (2b), tBu(H)N (2c), and Ph2N (2d)). Spectroscopic and X-ray crystallographic analyses of 2 showed that 2a-c have a nearly coplanar arrangement of the SiSi double bond and the amino group, giving π-conjugation between the SiSi double bond and the lone pair on the nitrogen atom, whereas 2d has a nearly perpendicular arrangement precluding such conjugation. Theoretical calculations indicate that π-conjugation between the π-orbital of the SiSi double bond and the lone pair on the nitrogen atom is markedly influenced by the torsional angle between the SiSi double-bond plane and the amino-group plane. 相似文献
20.
Adriano Boni Tiziana Funaioli Guido Pampaloni Stefano Zacchini 《Journal of organometallic chemistry》2011,696(22):3551-3556
The dimetallacyclopentenone complexes [Fe2Cp2(CO)(μ−CO){μ−η1:η3−CαHCβ(R)C(O)}] (R = CH2OH, 1a; R = CMe2OH, 1b; R = Ph, 1c) were prepared by photolytic reaction of [Fe2Cp2(CO)4] with alkyne according to the literature procedure. The X-ray and the electrochemical characterization of 1c are presented. The μ-allenyl compound [Fe2Cp2(CO)2(μ−CO){μ−η1:η2α,β−CαHCβCMe2][BF4] ([2][BF4]), obtained by reaction of 1b with HBF4, underwent monoelectron reduction to give a radical species which was detected by EPR at room temperature. The EPR signal has been assigned to [Fe2Cp2(CO)2(μ−CO){μ−η1:η2α,β-CαHCβCMe2}], [2]•. The molecular structures of [2]+ and [2]• were optimized by DFT calculations. The unpaired electron in [2]• is localized mainly at the metal centers and, coherently, [2]• does not undergo carbon-carbon dimerization, by contrast with what previously observed for the μ-vinyl radical complex [Fe2Cp2(CO)2(μ−CO){μ−η1:η2-CHCH(Ph)}]•, [3]•. Electron spin density distributions similar to the one of [2]• were found for the μ-allenyl radical complexes [Fe2Cp2(CO)2(μ-CO){μ-η1:η2α,β-CαHCβC(R1)(R2)}]• (R1 = R2 = H, [4]•; R1 = H, R2 = Ph, [5]•; R1 = R2 = Ph, [6]•). 相似文献