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1.
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
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.
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
4.
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
5.
Erika A. Shaffer Alicia M. Beatty Hans-Jörg Schanz 《Journal of organometallic chemistry》2007,692(23):5221-5233
The reaction of (Ph3P)3RuCl2 with 1,1-diphenyl-2-propyn-1-ol was investigated in various solvents. The reaction in thf under reflux is reported to produce the (PPh3)2Cl2Ru(3-phenylindenylidene) complex (3) which has undergone rearrangement of the allenylidene C3-spine. We have improved the reliability of the reported synthesis by adding acetyl chloride which converts the formed water of the reaction and thus increases the acidity of the reaction solution. Without the additive, we observed the exclusive formation of an intermediate of the transformation and identified it as dinuclear (PPh3)2ClRu(μ-Cl)3(PPh3)2RuCCCPh2 complex (5). The reaction of (Ph3P)3−4RuCl2 with 1,1-diphenyl-2-propyn-1-ol in CH2Cl2 or C2H4Cl2 under reflux in the presence of excess conc. aqueous HCl afforded the new, neutral (PPh3)2Cl3RuC-CHCPh2 carbyne complex (7), an HCl adduct of previously elusive (PPh3)2Cl2RuCCCPh2 complex 6 in high yields. In contrast to the formation of complex 3, the reaction in a non-coordinating solvent did not afford the rearrangement of the allenylidene C3-spine. Complex 7 was converted into complex 3 in thf under reflux under loss of a molecule HCl. Complex 7 was converted with triethylamine under loss of HCl to complex 6. Pentacoordinate complex 6 was crystallized in the presence of O-donor ligands (EtOH, MeOH and H2O) to give hexacoordinate (PPh3)2Cl2(ROH)RuCCCPh2 (R = H, CH3, C2H5) complexes (9)-(11) with the O-donor coordinating in trans-position to the allenylidene moiety. The reaction of complex 7 with 2 equiv. of 4-(N,N-dimethylamino)pyridine (DMAP) gave hexacoordinate (PPh3)2Cl2(DMAP)RuCCCPh2complex (12) with one molecule DMAP also coordinating in trans-position to the allenylidene group. Methanol and acetic acid in the absence of strong bases afforded the Fischer-carbene complexes (PPh3)2Cl2RuC(OCH3)-CHCPh2 (14) and (PPh3)2Cl2RuC(OAc)-CHCPh2 (15) where the nucleophile added to the α-carbon atom. The structures of complexes 5, 7, 9-11, 14, and 15 were solved via X-ray crystallography. 相似文献
6.
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
7.
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
8.
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
9.
Esther Delgado Elisa Hernández Avelino Martín 《Journal of organometallic chemistry》2010,695(3):446-11252
The multifunctional ligands [(Z)-FcCCSC(H)C(H)XR] [X = O, R = Me (2a); X = O, R = Et (2b); X = S, R = Ph (3); X = S, R = C6F5 (5)] and [(Z,Z)-Fc(SR)CC(H)SC(H)C(H)SR] [R = Ph (4), C6F5 (6)] have been prepared through hydroalkoxylation and hydrothiolation processes of the alkyne groups in the compound FcCCSCCH 1. Reactions between compound 3 and the carbonyl metals Co2(CO)8, Os3(CO)10(NCMe)2 and Fe2(CO)9 have allowed the synthesis of the polynuclear compounds [(Z)-{Co2(CO)6}(μ-η2-FcCCSC(H)C(H)SPh)] 9, [(Z)-Os3(CO)9(μ-CO){μ3-η2-FcCCSC(H)C(H)(SPh)}] 10 and [(Z)-{Fe3(CO)9}[μ3,η3-(CCS)-FcCCSC(H)C(H)(SPh)] 11. All the compounds have been characterized by elemental analysis, 1H and 13C{1H} NMR spectroscopy, mass spectrometry and the crystal structure of compounds [(Z)-FcCCSC(H)C(H)OMe] 2a and [{Co2(CO)6}2(μ-η2:η2-FcCCSCCSiMe3)] 7 have been solved by X ray diffraction analysis. 相似文献
10.
11.
The mechanism of chloride substitution in CF2CFCl with [Re(CO)5]− and [CpFe(CO)2]− anions is investigated experimentally and theoretically. The substitution reaction begins with the nucleophile addition to CF2CFCl producing the carbenoid anion [MCF2CFCl]− (A) (M = Re(CO)5, CpFe(CO)2). This is shown by trapping the intermediate A with electrophiles - proton donor (t-BuOH) to give MCF2CFClH or with CF2CFRe(CO)5 to give acylmetallate III, and by the formation of the substitution products CF2CFM from the anion A, generated by the deprotonation of MCF2CFClH with t-BuOK. 1,2-Shift of metal carbonyl group concerted with the α-elimination of chloride anion is proposed as the transformation pathway of carbenoid A into CF2CFM. A competing process of carbene insertion into Fe-CO bond is proposed to explain the formation of (XI). The feasibility of these two pathways is confirmed by DFT (B3LYP/SDD and 6-31G∗) calculations of the carbenes [MCF2CF:] and carbenoid anions [MCF2CFCl]−. Transition states (TS) for 1,2-shift (+3.2 kcal/mol) and for nucleophilic addition at CO ligand (+5.4 kcal/mol) are located for [(CO)5ReCF2CFCl]−, but only one TS corresponding to carbene insertion into Fe-CO bond (+2.1 kcal/mol) is located for [(CO)2CpFeCF2CFCl]−. The formation of other newly observed products, F(CO)CHFRe(CO)5 (V) and Cp(CO)2FeCCFeCp(CO)2 (VIII) is also discussed. 相似文献
12.
Vyacheslav V. Sushev Yuriy A. Min’ko Natalia V. Belina Yuriy A. Kurskiy Olga V. Kuznetsova Georgy K. Fukin Evgenii V. Baranov Vladimir K. Cherkasov Gleb A. Abakumov 《Journal of organometallic chemistry》2006,691(5):879-889
The reaction of diphosphinohydrazine PhNH-N(PPh2)2 (1) with cobalt(II) silylamide, Co[N(SiMe3)2]2, proceeds via formation of unstable phosphinohydrazide complex Co[NPh-N(PPh2)2]2 followed by rearrangement to a new chelating compound Co(NPh-PPh2N-PPh2)2 (2). Disproportionation of nickel(I) silylamide, (Ph3P)2Ni-N(SiMe3)2, in the presence of 1, yields Ni(0) and Ni(II) phosphinoamide complexes: Ni[(Ph2P)2N-NPhH]2 (3), Ni(NPh-PPh2N-PPh2)2 (4). X-ray analysis reveals tetrahedral environment of the cobalt atom in 2 and square-planar environment of the nickel atom in cis-4. In contrast to the crystalline patterns, the solutions of 2 in THF or toluene have EPR signal which is typical to square-planar low-spin d7 cobalt complex. The reactions of 2 with dioxygen, elemental sulfur and diphenyldiazomethane led to the spirocyclic insertion products Co(NPh-PPh2N-PPh2X)2 (X = O, S, NNCPh2) while the absorption of carbon monoxide is reversible. 相似文献
13.
Javier Martínez José M. Antelo Ma Teresa Pereira José M. Vila 《Journal of organometallic chemistry》2006,691(13):2891-2901
Treatment of the thiosemicarbazones 4-FC6H4C(Me)NN(H)C(S)NHR, (R = Me, a; Ph, b) and 2-ClC6H4C(Me)NN(H)C(S)NHR (R = Ph, c) with lithium tetrachloropalladate(II) in methanol or palladium(II) acetate in acetic acid gave the tetranuclear cyclometallated complex [Pd{4-FC6H3C(Me)NNC(S)NHR}]4 (1a, 1b) and [Pd{2-ClC6H3C(Me)NNC(S)NHPh}]4 (1c). Reaction of these tetramers with the diphosphines dppe, t-dppe, dppp or dppb in a 1:2 molar ratio gave the dinuclear cyclometallated complexes [(Pd{4-FC6H3C(Me)NNC(S)NHR})2(μ-Ph2P(CH2)nPPh2)], (n = 2, 2a, 2b; 3, 4a, 4b; 4, 5a, 5b), [(Pd{4-FC6H3C(Me)NNC(S)NHPh})2(μ-Ph2PCHCHPPh2)], (3a, 3b) and [(Pd{2-ClC6H3C(Me)NNC(S)NHR})2(μ-Ph2P(CH2)nPPh2)], (n = 2, 2c, 2d; 3, 4c, 4d; 4, 5c, 5d), [(Pd{2-ClC6H3C(Me)NNC(S)NHPh})2(μ-PPh2CHCHPPh2)], (3c, 3d). The X-ray crystal structure of the ligand b and the complexes 3c, 4a and 4d were determined. The structures of complexes 4a and 4d show that the different disposition of the chain cyclometallated of the thiosemicarbazones (in the same orientation or in the opposite one) is due to the different H bonds produced. 相似文献
14.
Michael I. Bruce Benjamin G. Ellis Allan H. White 《Journal of organometallic chemistry》2005,690(3):792-801
Whereas {Ru(dppm)Cp*}2(μ-CCCC) (2) is the only product formed by deprotonation of [{Ru(dppm)Cp*}2{μ(CCHCHC)}]+ with dbu, a mixture of 2 with Ru{CCCHCH(PPh2)2[RuCp*]}(dppm)Cp* (3) and {Cp*Ru(PPh2CHCCH-)}2 (4) is obtained with KOBut. A similar reaction with [{Ru(dppm)Cp*}2{μ(CCMeCMeC)}]+ (5) gave Ru{CCCMeCH(PPh2)2[RuCp*]}(dppm)Cp* (6). X-ray structures of 4, 5 and 6 confirm the presence of the 1-ruthena-2,4-diphosphabicyclo[1.1.1]pentane moiety, which is likely formed by an intramolecular attack of the deprotonated dppm ligand on C(1) of the vinylidene ligand. Protonation of {Ru(dppe)Cp*}2(μ-CCCC) (8-Ru) regenerates its precursor [{Ru(dppe)Cp*}2{μ(CCHCHC)}]2+ (7-Ru). Ready oxidation of the bis(vinylidene) complex affords the cationic carbonyl [Ru(CO)(dppe)Cp*]PF6 (9) (X-ray structure). 相似文献
15.
Treatment of [Fc-1-R1-1′-R2] (R1 = H, R2 = CH(O); R1 = H, R2 = CMe(O); R1 = R2 = CMe(O)) with LiCCCH2OLi (prepared in situ from HCCCH2OH and n-BuLi) affords the ferrocenyl-substituted but-2-yne-1,4-diol compounds of general formula [Fc-1-R1-1′-{CR(OH)CCCH2OH}] (R1 = R = H (1a); R1 = H, R = Me (1b); R1 = CMe(O), R = Me (1c)) in low to high yields, respectively (where Fc = Fe(η5-C5H4)2). In the case of the reactions of [Fc-1-R1-1′-R2] (R1 = H, R2 = CH(O); R1 = R2 = CMe(O)), the by-products [Fc-1-R1-1′-{CR(OH)(CH2)3CH3}] (R1 = R = H (2a); R1 = CMe(O), R = Me (2c)) along with minor quantities of [Fc-1,1′-{CMe(OH)(CH2)3CH3}2] (3) are also isolated; a hydrazide derivative of dehydrated 2c, [1-(CMeCHCH2CH2CH3)-1′-(CMeNNH-2,4-(NO2)2C6H3)] (2c′), has been crystallographically characterised. Interaction of 1 with Co2(CO)8 smoothly generates the alkyne-bridged complexes [Fc-1-R1-1′-{Co2(CO)6-μ-η2-CR(OH)CCCH2OH}] (R1 = R = H (4a); R1 = H, R = Me(4b); R1 = CMe(O), R = Me (4c)) in good yield. Reaction of 4a with PhSH, in the presence of catalytic quantities of HBF4 · OEt2, gives the mono- [Fc-1-H-1′-{Co2(CO)6-μ-η2-CH(SPh)CCCH2OH}] (5) and bis-substituted [Fc-1-H-1′-{Co2(CO)6-μ-η2-CH(SPh)CCCH2SPh}] (6) straight chain species, while with HS(CH2)nSH (n = 2,3) the eight- and nine-membered dithiomacrocylic complexes [Fc-1-H-1′-{cyclo-Co2(CO)6-μ-η2-CH(S(CH2)n-)CCCH2S-}] [n = 2 (7a), n = 3 (7b)] are afforded. By contrast, during attempted macrocyclic formation using 4b and HSCH2CH2OCH2CH2SH dehydration occurs to give [Fc-1-H-1′-{Co2(CO)6-μ-η2-C(CH2)CCCH2OH}] (8). Single crystal X-ray diffraction studies have been reported on 2c′, 4b, 4c, 7b and 8. 相似文献
16.
Rüdiger Mews Tobias Borrmann Enno Lork Jan Petersen Wolf-Dieter Stohrer Paul G. Watson 《Journal of fluorine chemistry》2004,125(11):1649-1655
One of the most interesting compounds in sulfur nitrogen fluorine chemistry is NSF2NS(O)F2 (3) (reported by Glemser and Höfer 30 years ago): in the NS backbone a triple and a double bond are connected by a single bond. Electrophiles (metal cations, fluoro Lewis acids, “CH3+”) attack this multifunctional system exclusively at the thiazyl nitrogen of the triple bond. [M(NSF2NS(O)F2)4][AsF6]2 (M = Ni (4b), Cu (4c)), [Re(CO)5(NSF2NS(O)F2)][AsF6]− (5), F5A·NSF2NS(O)F2 (A = As (6), Sb (7)), F3B·NSF2NS(O)F2 (8) and [H3CNSF2NS(O)F2]+[AsF6]− (9) were isolated. The X-ray structures of 4c, 6, 8 and 9 are reported, bonding in these complexes is compared with the recently reported related NSAr2NS(X)Ar2 (X = O, NH) species. 相似文献
17.
Heinrich Lang Katrin Döring Uwe Siegert Tobias Rüffer 《Journal of organometallic chemistry》2009,694(1):27-35
Rigid-rod structured homobimetallic palladium complexes of type [{trans-(Me(O)CS-4-C6H4-C6H4)(Ph3P)2Pd}2(μ-N∩N)](OTf)2 (8a, μ-N∩N = 4,4′-bipyridine, bpy; 8b, μ-N∩N = C5H4N-CHN-NCH-C5H4N; 8c, μ-N∩N = C5H4N-CHCH-C6H4-CHCH-C5H4N; 8d, μ-N∩N = C5H4N-CHN-C6H4-NCH-C5H4N) were synthesized by the reaction of trans-[(Me(O)CS-4-C6H4-C6H4)(Ph3P)2Pd](OTf) (6) with 0.5 equivalents of N∩N (7a, N∩N = bpy; 7b, N∩N = C5H4N-CHN-NCH-C5H4N; 7c, N∩N = C5H4N-CHCH-C6H4-CHCH-C5H4N; 7d, N∩N = C5H4N-CHN-C6H4-NCH-C5H4N) in high yield. Complex 6 was accessible by the subsequent reaction of I-4-C6H4-C6H4-4′-SC(O)Me (2) with [(PPh3)4Pd] (3) to produce trans-[(I)(Me(O)CS-4-C6H4-C6H4)(Ph3P)2Pd] (4) which further reacted with AgOTf (5) to give 6.The structures of 4 and 8c in the solid state are reported. Most characteristic for these systems is the square-planer coordination geometry of palladium with trans-positioned PPh3 groups. This automatically positions the iodo ligand and the Me(O)CS-4-C6H4-C6H4 unit (complex 4) or the nitrogen donor atoms of the C5H4N-CHCH-C6H4-CHCH-C5H4N connectivity and the thio-acetyl group Me(O)CS-C6H4-C6H4 (complex 8c) trans to each other. In 8c a Pd-Pd separation of 20.156 Å is typical.The electrochemical redox behavior of 2, 4 and 8 is discussed. 相似文献
18.
Hao Li 《Journal of organometallic chemistry》2011,696(10):2129-2134
Self-assembly of a novel class of bis-imine-cyclometalated macrocycles [(Cp∗Ir)2(Ph-NC-Ph-CN-Ph)]2(4,4′-bipyridine)2·(OTf)4 (3a) and [(Cp∗Ir)2(Me-NC-Ph-CN-Me)]2(4,4′-bipyridine)2·(OTf)4 (3b) was directed by double-site C-H activations of aromatic bis-imine substrates. Two synthetic routes were established, using either (i) binuclear cyclometalated complexes (Cp∗Ir)2L1Cl2 (1a) and (Cp∗Ir)2L2Cl2 (1b) or (ii)4,4′-bipyridine(bpy)-bridged complex (Cp∗IrCl2)2(bpy) (2) as starting materials. All the products were characterized by IR, 1H NMR and EA. Isomers were found in macrocyclic complexes, which were thermodynamically stable from reversible transformation in days. Highly robust structure of the cyclometalated macrocycles was indicated by the existence of stable isomer pairs. One isomer of 3b was determined by single-crystal X-ray diffraction. It was a rare case for half-sandwich metallosupramolecular macrocycles that weak interactions between macrocycles and OTf ions were fully captured in detail, and were demonstrated to be essential for the maintenance of tunnel structures of macrocycles in crystal packing. 相似文献
19.
Fang Liu 《Journal of organometallic chemistry》2010,695(6):809-3960
A series of heterobinuclear ferrocene-ruthenium complexes Fc(CHCH)nRuCl(CO)(PMe3)3 (n = 1, 3; n = 2, 12), Fc(CHCH)RuCl(CO)(Py)(PPh3)2 (4), and trimetallic Fc(CHCH)RuCl(CO)(PPh3)2(Py-E-(CHCH)Fc) (6) have been prepared. The length of the molecular rods is extended by successive insertion of CHCH spacers in the bridging ligands or the ancillary ligands. The respective products have been fully characterized and the structures of 3 and 12 have been established by X-ray crystallography. Electrochemical studies have revealed that ethenyl heterobimetallic complexes display two successive one-electron processes, and that intermetallic electronic communication between the two endgroups is attenuated with the increase of the length of the conjugated bridge. The electrochemical behavior of the trimetallic complex reveals strong electronic communication between ruthenium and ferrocene transmitted through the ethenyl bridge, however, it also reveals a very weak interaction between ruthenium and ferrocene transmitted through the (E)-CHCH-Py bridge. 相似文献