共查询到20条相似文献,搜索用时 16 毫秒
1.
Michael I. Bruce Marcus L. Cole Brian W. Skelton 《Journal of organometallic chemistry》2006,691(22):4601-4614
Complexes M(CCCSiMe3)(CO)2Tp′ (Tp′ = Tp [HB(pz)3], M = Mo 2, W 4; Tp′ = Tp∗ [HB(dmpz)3], M = Mo 3) are obtained from M(CCCSiMe3)(O2CCF3)(CO)2(tmeda) (1) and K[Tp′].Reactions of 2 or 4 with AuCl(PPh3)/K2CO3 in MeOH afforded M{CCCAu(PPh3)}(CO)2Tp′ (M = Mo 5, W 6) containing C3 chains linking the Group 6 metal and gold centres.In turn, the gold complexes react with Co3(μ3-CBr)(μ-dppm)(CO)7 to give the C4-bridged {Tp(OC)2M}CCCC{Co3(μ-dppm)(CO)7} (M = Mo 7, W 8), while Mo(CBr)(CO)2Tp∗ and Co3{μ3-C(CC)2Au(PPh3)}(μ-dppm)(CO)7 give {Tp∗(OC)2Mo}C(CC)2C{Co3(μ-dppm)(CO)7} (9) via a phosphine-gold(I) halide elimination reaction. The C3 complexes Tp′(OC)2MCCCRu(dppe)Cp∗ (Tp′ = Tp, M = Mo 10, W 11; Tp′ = Tp∗, M = Mo 12) were obtained from 2-4 and RuCl(dppe)Cp∗ via KF-induced metalla-desilylation reactions. Reactions between Mo(CBr)(CO)2Tp∗ and Ru{(CC)nAu(PPh3)}(dppe)Cp∗ (n = 2, 3) afforded {Tp∗(OC)2Mo}C(CC)n{Ru(dppe)Cp∗} (n = 2 13, 3 14), containing C5 and C7 chains, respectively. Single-crystal X-ray structure determinations of 1, 2, 7, 8, 9 and 12 are reported. 相似文献
2.
Heinrich Lang Petra Zoufalá Sami Klaib Amaya del Villar Gerd Rheinwald 《Journal of organometallic chemistry》2007,692(19):4168-4176
Heterobimetallic {cis-[Pt](μ-σ,π-CCPh)2}[Cu(NCMe)]BF4 (3a: [Pt] = (bipy)Pt, bipy = 2,2′-bipyridine; 3b: [Pt] = (bipy′)Pt, bipy′ = 4,4′-dimethyl-2,2′-bipyridine) is accessible by the reaction of cis-[Pt](CCPh)2 (1a: [Pt] = (bipy)Pt, 1b: [Pt] = (bipy′)Pt]) with [Cu(NCMe)4]BF4 (2). Substitution of NCMe by PPh3 (4) can be realized by the reaction of 3a with 4, whereby [{cis-[Pt](μ-σ,π-CCPh)2}Cu(PPh3)]BF4 (5) is formed. On prolonged stirring of 3 and 5, respectively, NCMe and PPh3 are eliminated and tetrametallic {[{cis-[Pt](η2-CCPh)2}Cu]2}(BF4)2 (6) is produced. Addition of an excess of NCMe to 6 gives heterobimetallic 3a.When instead of NCMe or PPh3 chelating molecules such as bipy (7) are reacted with 3a then the heterobimetallic π-tweezer molecule [{cis-[Pt](μ-σ,π-CCPh)2}Cu(bipy)]BF4 (8) is formed. Treatment of 8 with another equivalent of 7 produced [Cu(bipy2)]BF4 (9) along with [Pt](CCPh)2. However, when 3b is reacted with 1b in a 1:1 molar ratio then 10 and 11 of general composition [{[Pt](CCPh)2}2Cu]BF4 are formed. These species are isomers and only differ in the binding of the PhCC units to copper(I). A possible mechanism for the formation of 10 and 11 is presented.The solid state structures of 6, 10 and 11 are reported. In 11 the [{cis-[Pt](μ-σ,π-CCPh)2}2Cu]+ building block is set-up by two nearly orthogonal positioned bis(alkynyl) platinum units which are connected by a Cu(I) ion, whereby the four carbon-carbon triple bonds are unsymmetrical coordinated to Cu(I). In trimetallic 10 two cis-[Pt](CCPh)2 units are bridged by a copper(I) center, however, only one of the two PhCC ligands of individual cis-[Pt](CCPh)2 fragments is η2-coordinated to Cu(I) giving rise to the formation of a [(η2-CCPh)2Cu]+ moiety with a linear alkyne-copper-alkyne arrangement (alkyne = midpoint of the CC triple bond). In 6 two almost parallel oriented [Pt](CCPh)2 planes are linked by two copper(I) ions, whereby two individual PhCC units, one associated with each Pt building block, are symmetrically π-coordinated to Cu. 相似文献
3.
Pradeep Mathur Radhe Shyam Ji Amrendra K. Singh 《Journal of organometallic chemistry》2010,695(17):1986-141
Photolysis of a hexane solution containing ironpentacarbonyl, 1-ferrocenyl-4-phenyl-1,3-butadiyne at low temperature yields six new products: [Fe(CO)2{η2:η2-PhCCCC(Fc)C(CCPh)C(Fc)Fe(CO)3}-μ-CO] (1), [Fe2(CO)6{μ-η1:η1:η2:η2-PhCCCC(Fc)-C(O)-C(Fc)CCCPh}] (2), [Fe2(CO)6{μ-η1:η1:η2:η2-FcCC(CC Ph)-C(O)-C(Fc)CCCPh}] (3), [Fe2(CO)6{μ-η1:η1:η2:η2-FcCCCC(Fc)-C(O)-C(Fc)CCCPh}] (4), [Fe(CO)3{μ-η2: η2-[FcCC(CCPh)C(CCPh)C(Fc)}CO] (5) and [Fe(CO)3{μ-η2: η2-[FcCC(CCPh)C(CCPh)C(Fc)}CO] (6) formed by coupling of acetylenic moieties with CO insertion on metal carbonyl support. In presence of CO, formation of another new product 2,5-bis(ferrocenyl)-3,6-bis(tetracarbonylphenylmaleoyliron)quinone (7) was observed which on further reaction with ferrocenylacetyene gave the quinone, 2,5-bis(ferrocenyl)-3,6-bis(ethynylphenyl)quinone (8). Structures of 1-5 and 8 were established crystallographically. 相似文献
4.
Mi S. Lim 《Journal of organometallic chemistry》2006,691(19):4100-4108
The cationic aniline complex [Cp∗Rh(η6-2,6-(Me2CH)2C6H3NH2)](OTf)2 (1) was prepared from either [Cp∗Rh(η2-NO3)(η1-OTf)] or [Cp∗Rh(OH2)3](OTf)2 and 2,6-diisopropylaniline. Complex 1 underwent substitution with phosphines or phosphites, indicating the labile character of the η6-aniline ligand. Complex 1 mediated cycloaddition reactions of several alkynes in refluxing ethanol: the [2 + 2] dimerization for PhCCPh and the [2 + 2 + 1] trimerization for PhCCH and CH3C6H4CCH. The unexpected cyclobutadiene complex [Cp∗Rh(η4-C4(C(O)CH3)2H(SiMe3))] was obtained from complex 1 and Me3SiCCCCSiMe3 and structurally characterized by X-ray diffraction. 相似文献
5.
Michael I. Bruce Paul A. Humphrey Gary J. Perkins Allan H. White 《Journal of organometallic chemistry》2007,692(8):1748-1756
Proto-desilylation of 1-(Me3SiCC)-1′-{Cp∗(dppe)RuCC}Fc′ (1) afforded the corresponding ethynyl derivative 2, from which the green Co2(μ-dppm)n(CO)8−2n (n = 0, 1) adducts 3 and 4 were obtained. Replacement of the ethynyl proton in reactions between 2 and AuCl(PPh3), Hg(OAc)2 or FeCl(dppe)Cp∗ gave complexes 1-(RCC)-1′-{Cp∗(dppe)RuCC}Fc′ [R = Au(PPh3) 5, 1/2Hg 6, Fe(dppe)Cp∗8]; the latter gave bis-vinylidene 9 with MeI, characterised (as was 2) by a single crystal X-ray study. Oxidative coupling of 2 (CuCl/tmeda/acetone, air) gave diyne 10, while coupling of 5 with Co3(μ3-CBr)(μ-dppm)(CO)7 afforded 1-{Cp∗(dppe)RuCC}-1′-{(OC)7(μ-dppm)Co3(μ3-CCC)}Fc′ (11). Cyclic voltammetric measurements indicated that there was no significant electronic coupling between the end-groups through the ferrocene centre in any of these compounds. 相似文献
6.
Michael I. Bruce Alexandre Burgun Brian W. Skelton 《Journal of organometallic chemistry》2010,695(4):619-3482
Reactions between 1,2-dichlorohexafluorocyclopentene and Ru(CCH)(dppe)Cp∗ or Ru(CCCCLi)(dppe)Cp∗ have given Ru(CC-c-C5F6Cl-2)(dppe)Cp∗ 4 and Ru(CCCC-c-C5F6Cl-2)(dppe)Cp∗ 7, respectively. Ready hydrolysis of 4 to the ketone Ru{CC[c-C5F4Cl(O)]}(dppe)Cp∗ 5 occurs, which can be converted to Ru{CC(c-C5F4Cl[C(CN)2])}(dppe)Cp∗ 6 by treatment with CH2(CN)2/basic alumina. Spectroscopic, electrochemical and XRD structural studies for 4-7 are reported: for 6, these suggest that the cyanated fluorocarbon ligand is a very powerful electron-withdrawing group. 相似文献
7.
Michael I. Bruce Martyn Jevric Wyona Patalinghug Brian W. Skelton Natasha N. Zaitseva 《Journal of organometallic chemistry》2008,693(17):2915-2920
Addition of [I(py)2]BF4 to Ru(CCH)(dppe)Cp∗ gave the iodovinylidene [Ru(CCHI)(dppe)Cp∗]BF41, which could be deprotonated to Ru(CCI)(dppe)Cp∗ 2. The attempted preparation of Ru(CCCCI)(dppe)Cp∗, followed by derivatisation with tcne, gave the dienynyl Ru{CCC[C(CN)2]CIC(CN)2}(dppe)Cp∗ 3. The Pd(0)/Cu(I)-catalysed reaction of 3 with Ru{CCCCAu(PPh3)}(dppe)Cp∗ afforded Ru{CCCC(CN)2CC(CN)2Au(PPh3)}(dppe)Cp∗ 4 by formal replacement of I+ by [Au(PPh3)]+. XRD structures of 1-4 are reported. 相似文献
8.
Michael I. Bruce Martin Jevric Mark E. Smith Natasha N. Zaitseva 《Journal of organometallic chemistry》2006,691(3):361-370
The syntheses of several diynylgold(I) phosphine complexes, including Au(CCCCH){P(tol)3} (1), Au(CCCCSiMe3)(PR3) (R = Ph 2-Ph, tol 2-tol), Au(CCCCFc)(PPh3) (3), {(tol)3P}Au(CC)nAu{P(tol)3} [n = 2 (4), 3 (6), 4 (7)], {(Ph3P)Au}CCCC{Au[P(tol)3]} (5), [ppn][Au{CCCCAu[P(tol)3]}2] (8), [Au2(μ-I)(μ-dppm)2][Au(CCCCSiMe3)2] (9), Hg{CCCCAu(PR3)}2 (R = Ph 10-Ph, tol 10-tol) and {(triphos)Cu}CCCC{Au[P(tol)3]} (11) are described. Of these, the X-ray molecular structures of 1, 2-tol, 3, 4 and 9 have been determined. 相似文献
9.
Patrick J. West 《Journal of organometallic chemistry》2011,696(17):2886-2893
The complexes trans-[Os(CCC6H4-4-CCR)Cl(dppe)2] (R = SiPri31, H 2), trans,trans-[(dppe)2ClOs(CCC6H4-4-CC)RuX(dppe)2] (X = Cl 3, CCC6H4-4-CCSiPri34), trans-[Os(CCC6H4-4-CCC6H4-4-CCR)Cl(dppe)2] (R = SiPri35, H 6), and trans,trans-[(dppe)2ClOs(CCC6H4-4-CCC6H4-4-CC)RuCl(dppe)2] (7) have been synthesized, and the identities of 1, 2, and 6 confirmed by single-crystal X-ray diffraction studies. Cyclic voltammetry shows that the mononuclear complexes 1, 2, 5, and 6 are oxidized at potentials within a narrow range (0.45-0.49 V), in processes centered on the osmium ethynyl neighbourhood and for simplicity assigned as OsII/III, while the heterobinuclear complexes 3, 4, and 7 exhibit lower oxidation potentials for OsII/III and a second oxidation process assigned in a similar fashion to RuII/III; the difference in potential between the Os- and Ru-localized processes decreases as the π-bridge is lengthened. UV-vis-NIR spectroelectrochemical studies on 1 and 5 reveal the appearance on oxidation of a low-energy band ascribed to chloro to metal-ethynyl charge transfer. Osmium-centered oxidation at the heterobinuclear complexes 4 and 7 results in appearance of a low-energy band, which blue-shifts and increases in intensity on further oxidation to 42+ and 72+. 相似文献
10.
Reactions of Ru(CCPh)(PPh3)2Cp with (NC)2CCR1R2 (R1 = H, R2 = CCSiPri38; R1 = R2 = CCPh 9) have given η3-butadienyl complexes Ru{η3-C[C(CN)2]CPhCR1R2}(PPh3)Cp (11, 12), respectively, by formal [2 + 2]-cycloaddition of the alkynyl and alkene, followed by ring-opening of the resulting cyclobutenyl (not detected) and displacement of a PPh3 ligand. Deprotection (tbaf) of 11 and subsequent reactions with RuCl(dppe)Cp and AuCl(PPh3) afforded binuclear derivatives Ru{η3-C[C(CN)2]CPhCHCC[MLn]}(PPh3)Cp [MLn = Ru(dppe)Cp 19, Au(PPh3) 20]. Reactions between 8 and Ru(CCCCR)(PP)Cp [PP = (PPh3)2, R = Ph, SiMe3, SiPri3; PP = dppe, R = Ph] gave η1-dienynyl complexes Ru{CCC[C(CN)2]CRCH[CC(SiPri3)]}(PP)Cp (15-18), respectively, in reactions not involving phosphine ligand displacement. The phthalodinitrile C6H(CCSiMe3)(CN)2(NH2)(SiMe3) 10 was obtained serendipitously from (Me3SiCC)2CO and CH2(CN)2, as shown by an XRD structure determination. The XRD structures of precursor 7 and adducts 11, 12 and 17 are also reported. 相似文献
11.
Synthesis, structures and some reactions of Ru(CCCCFc)(PP)Cp (PP = dppm, dppe) and related compounds
Michael I. Bruce Frédéric de Montigny Martyn Jevric Brian W. Skelton Allan H. White 《Journal of organometallic chemistry》2004,689(18):2860-2871
The compounds Ru(CCCCFc)(PP)Cp [PP = dppe (1), dppm (2)], have been obtained from reactions between RuCl(PP)Cp and FcCCCCSiMe3 in the presence of KF (1) or HCCCCFc and K[PF6] (2), both with added dbu. The dppe complex reacts with Co2(CO)6(L2) [L2 = (CO)2, dppm] to give 3, 4 in which the Co2(CO)4(L2) group is attached to the outer CC triple bond. The PPh3 analogue of 3 (5) has also been characterised. In contrast, tetracyanoethene reacts to give two isomeric complexes 6 and 7, in which the cyano-olefin has added to either CC triple bond. The reaction of RuCl(dppe)Cp with HCCCCFc, carried out in a thf/NEt3 mixture in the presence of Na[BPh4], gave [Ru{CCC(NEt3)CHFc}(dppe)Cp]BPh4 (8), probably formed by addition of the amine to an (unobserved) intermediate butatrienylidene [Ru(CCCCHFc)(dppe)Cp]+. The reaction of I2 with 8 proceeds via an unusual migration of the alkynyl group to the Cp ring to give [RuI(dppe){η-C5H4CCC(NEt3)CHFc}]I3 (9). Single-crystal X-ray structural determinations of 1, 2 and 4-9 are reported. 相似文献
12.
Heinrich Lang Amaya del Villar Thomas Stein Petra Zoufalá Tobias Rüffer Gerd Rheinwald 《Journal of organometallic chemistry》2007,692(23):5203-5210
Complexes of type {cis-[Pt](μ-σ,π-CCPh)2}AgX (3a, [Pt] = (bipy′)Pt, X = FBF3; 3b, [Pt] = (bipy′)Pt, X = FPF5; 3c, [Pt] = (bipy)Pt, X = OClO3; 3d, [Pt] = (bipy′)Pt, X = BPh4; bipy′ = 4,4′-dimethyl-2,2′-bipyridine; bipy = 2,2′-bipyridine) are accessible by combining cis-[Pt](CCPh)2 (1a, [Pt] = (bipy′)Pt; 1b, [Pt] = (bipy)Pt) with equimolar amounts of [AgX] (2a, X = BF4; 2b, X = PF6; 2c, X = ClO4; 2d, X = BPh4). In 3a-3d the platinum(II) and silver(I) ions are connected by σ- and π-bonded phenyl acetylide ligands. When the molar ratio of 1 and 2 is changed to 2:1 then trimetallic [{cis-[Pt](μ-CCPh)2}2Ag]X (8a, [Pt] = (bipy)Pt, X = BF4; 8b, [Pt] = (bipy′)Pt, X = PF6; 8c, [Pt] = (bipy)Pt, X = BF4) is produced. The solid state structure of 8a was determined by single X-ray crystal structure analysis. In 8a the silver(I) ion is embedded between two parallel oriented cis-[Pt](CCPh)2 units. Within this structural arrangement the phenyl acetylides of individual [Pt](CCPh)2 entities possess a μ-bridging position between Pt(II) and Ag(I). In addition, a very weak dative Pt → Ag interaction is found (Pt-Ag 2.8965(3) Å). The respective silver carbon distances Ag-Cα (2.548(7), 2.447(7) Å) and Ag-Cβ (3.042(7), 2.799(8) Å)(PtCαCβPh) confirm this structural motif.Complexes 8a-8c isomerize in solution to form trimetallic [{cis-[Pt](μ-σ,π-CCPh)2}2Ag]X (9a, [Pt] = (bipy)Pt, X = BF4; 9b, [Pt] = (bipy′)Pt, X = PF6; 9c, [Pt] = (bipy)Pt, X = ClO4). In the latter molecules the organometallic cation [{cis-[Pt](μ-σ,π- CCPh)2}2Ag]+ is set-up by two nearly orthogonal positioned [Pt](CCPh)2 entities which are hold in close proximity by the group-11 metal ion. Within this assembly all four PhCC units are η2-coordinated to silver(I). A possible mechanism for the formation of 9 is presented. 相似文献
13.
The reaction of [Ti](CCR)2 {[Ti] = (η5-C5H4SiMe3)2Ti; 1a, R = Fc, Fc = (η5-C5H4)Fe(η5-C5H5); 1b, R = Ph} with MX {2a, MX = [Cu(NCCH3)4]BF4; M = Ag; 2b, X = ClO4; 2c, X = NO3} in a 2:1 molar ratio produces the trinuclear heterobimetallic (Ti2M) or heptanuclear heterotrimetallic (Ti2MFe4) complexes [{[Ti](μ-σ,π-CCR)2}2M]X (R = Fc: 3a, M = Cu, X = BF4; 3b, M = Ag, X = ClO4. R = Ph: 3c, M = Cu, X = BF4; 3d, M = Ag, X = ClO4: 3e, M = Ag, X = NO3) in high yield. Complexes 3c-3e are also accessible, when {[Ti](μ-σ,π-CCPh)2}MX (M = Cu: 4a, X = FBF3; M = Ag: 4b, X = OClO3; 4c, X = ONO2) is reacted with one equivalent of 1b. Transferring this reaction scheme to [Ti](CCSiMe3)2 (1c) only the formation of the heterobimetallic tweezer complex {[Ti](μ-σ,π-CCSiMe3)2}MX {4d, MX = [Cu(NCCH3)]BF4; 4e, MX = AgOClO3} is observed which is attributed to the bulkiness of the acetylide-bound Me3Si group. The solid-state structure of 3e is reported. In 3e, two [Ti](CCPh)2 tweezer moieties are chelate-bound by their carbon-carbon triple bonds to a silver(I) ion, resulting in a pseudo-tetrahedral environment at the group-11 metal. is acting as counter-ion to cationic [{[Ti](CCPh)2}2Ag]+.Additionally, the result of cyclic voltammetric studies on [{[Ti](μ-σ,π-CCPh)2}2Cu]BF4 (3c) is reported. 相似文献
14.
Michael I. Bruce Martyn Jevric Brian W. Skelton 《Journal of organometallic chemistry》2007,692(8):1757-1765
Reactions between 1,1′-(Me3SiCC)2Rc′ [Rc′ = ruthenocen-1,1′-diyl, Ru(η-C5H4-)2] and RuCl(PP)Cp′ in the presence of KF gave 1,1′-{Cp(PP)RuCC}2Rc′ [Cp′ = Cp, PP = PPh31, P(m-tol)32, dppe 3, dppf 4; Cp′ = Cp∗, PP = dppe 5]. Compounds 1 and 2 react with tcne to give two diastereomers a/b of the allylic (vinylcarbene) complexes 6 and 7, while methylation of 5 gave the bis-vinylidene [1,1′-{Cp∗(dppe)RuCCMe}2Rc′](BPh4)2 (8). The X-ray structures of 4, 6b and 8 have been determined. Cyclic voltammograms indicate that there is some electronic communication between the ruthenium end-groups through the Rc′ centre. 相似文献
15.
Séverine Roué 《Journal of organometallic chemistry》2005,690(3):594-604
The synthesis of the new complexes Cp*(dppe)FeCC2,5-C4H2SR (Cp* = 1,2,3,4,5-pentamethylcyclopentadienyl; dppe = 1,2-bis(diphenylphosphino)ethane; 2a, R = CCH; 2b, R = CCSi(CH3)3; 2c, R = CCSi(CH(CH3)2)3; 3a, R = CC2,5-C4H2SCCH; 3c, R = CC2,5-C4H2SCCSi(CH(CH3)2)3) is described. The 13C NMR and FTIR spectroscopic data indicate that the π-back donation from the metal to the carbon rich ligand increases with the size of the organic π-electron systems. The new complexes were also analyzed by CV and the chemical oxidation of 2a and 3c was carried out using 1 equiv of [Cp2Fe][PF6]. The corresponding complexes 2a[PF6] and 3c[PF6] are thermally stable, but 2a[PF6] was too reactive to be isolated as a pure compound. The spectroscopic data revealed that the coordination of large organic π-electron systems to the iron nucleus produces only a weak increase of the carbon character of the SOMO for these new organoiron(III) derivatives. 相似文献
16.
17.
Sascha Dietrich 《Journal of organometallic chemistry》2011,696(13):2491-2498
The synthesis and properties of heterobimetallic Ti-Cd complexes of type {[Ti](μ-η1:η2-CCR)2}CdX2 ([Ti] = Ti(η5-C5H4SiMe3)2; R = SiMe3: 3a, X = Cl; 3b, X = Br; 3c, X = I; R = Fc: 3d, X = Br; Fc = Fe(η5-C5H4)(η5-C5H5) is reported. These compounds were accessible by treatment of [Ti](CCR)2 (1a, R = SiMe3; 1b, R = Fc) with the cadmium salts CdX2 (2a, X = Cl; 2b, X = Br; 2c, X = I) in a 1:1 M ratio in diethyl ether. Dissolving, for example, 3b in tetrahydrofuran afforded coordination polymer [Cd(μ-Br)2(thf)2]n (4) along with the tweezer molecule 1a. Treatment of 3b with two equiv of LiCCFc (5) gave {[Ti](μ-η1:η2-CCSiMe3)2}Cd(CCFc)2 (6) which eliminated at ambient temperature the all-carbon buta-1,3-diyne FcCC-CCFc (7) producing 1a and elemental Cd. The same reaction behavior was observed, when 2b was reacted with 5. The thus obtained bis(alkynyl) cadmium complex Cd(CCFc)2 (8) is redox-active at low temperature producing 7 and Cd(0). When mercury halides HgX2 (9a, X = Cl; 9b, X = Br) are used, then the titanocene dihalides [Ti]X2 (10a, X = Cl; 10b, X = Br) together with Me3SiCC-CCSiMe3 (11) and Hg(0) were formed. Nevertheless, mercury acetylides were available by treatment of Hg(OAc)2 (12) with HCCFc (13) in a 1:2 M ratio. Thus obtained Hg(CCFc)2 (14) gave with [CuBr] (15) coordination polymer [{Hg(η2-CCFc)2}(Cu2(μ-Br)2]n (16), while with [AgPF6] oxidation of the ferrocenyl moieties took place affording dicationic [Hg(CCFc)2]2+ (18).The structures of 3b and 4 in the solid state are reported. Compound 3b shows the typical characteristics for heterobimetallic organometallic π-tweezer complexes with cadmium in a tetrahedral environment, while 4 corresponds to a one-dimensional coordination polymer in which the Cd(II) ions are linked in a edge-sharing fashion by bromide bridges in the pseudo-equatorial plane. The appropriate tetrahydrofuran molecules are completing the pseudo-octahedral coordination sphere at cadmium.The cyclic voltammogram of 14 is reported showing a single reversible redox event at E0 = 0.108 V with ΔEp = 76 mV indicating that there is no communication between the Fc termini along the mercury acetylide unit. 相似文献
18.
Michael I. Bruce Paul A. Humphrey Brian W. Skelton 《Journal of organometallic chemistry》2007,692(12):2564-2574
The synthesis of Fc(CC)3Ru(dppe)Cp (2) from Fc(CC)3SiMe3 and RuCl(dppe)Cp is described, together with its reactions with tcne to give the tetracyano-dienyl FcCCCC{C[C(CN)2]}2Ru(dppe)Cp (3) and -cyclobutenyl FcCCCC{CCC(CN)2C(CN)2}Ru(dppe)Cp (4), with Co2(μ-dppm)n(CO)8−2n (n = 0, 1) to give FcC2{Co2(CO)6}C2{Co2(CO)6}CCRu(dppe)Cp (5) and FcCCCCC2{Co2(μ-dppm)(CO)4}Ru(dppe)Cp (6), respectively, and with Os3(CO)10(NCMe)2 to give Os3{μ3-C2CCCC[Ru(dppe)Cp]}(CO)10 (7). On standing in solution, the latter isomerises to the cyclo-metallated derivative Os3(μ-H){μ3-C[Ru(dppe)Cp]CCC[(η-C5H3)FeCp]}(CO)8 (8). X-ray structural determinations of 1, 2, 6 and 7 are reported. 相似文献
19.
Michael I. Bruce Martyn Jevric Allan H. White 《Journal of organometallic chemistry》2011,696(2):461-467
In contrast to the simple diynyl complexes formed in reactions between HCCCCFc and MCl(dppe)Cp∗; (M = Fe, Ru), an analogous reaction with RuCl(PPh3)2Cp∗; in the presence of KPF6 and dbu resulted in dimerisation of the diyne at the Ru centre to afford a mixture of [Ru{η1,η2-C(CCFc)C(L)CHCCCHFc}(PPh3)Cp∗]PF6 (L = dbu 1, PPh32). Similar reactions with RuCl(PR3)2L gave [Ru{η1,η2-C(CCFc)C(dbu)CHCCCHFc}(PR3)L]PF6 (L = Cp, R = Ph 3, m-tol 4; L = η5-C9H7, R = Ph 5). The reaction between 3 and I2, followed by crystallization of the paramagnetic product from MeOH, afforded the dicationic [Ru{C(CCFc)C(dbu)CHC(OMe)C(OMe)CHFc}(PPh3)Cp](I3)26. The molecular structures of 2·2CH2Cl2 and 6.S (S = 2CH2Cl2, C6H6) were determined by single-crystal XRD studies. 相似文献