共查询到20条相似文献,搜索用时 15 毫秒
1.
Corry Decker 《Journal of organometallic chemistry》2004,689(9):1691-1701
The reactions of [Fe3(CO)12] or [Ru3(CO)12] with RNC (R=Ph, C6H4OMe-p or CH2SO2C6H4Me-p) have been investigated using electrospray mass spectrometry. Species arising from substitution of up to six ligands were detected for [Fe3(CO)12], but the higher-substituted compounds were too unstable to be isolated. The crystal structure of [Fe3(CO)10(CNPh)2] was determined at 150 and 298 K to show that both isonitrile ligands were trans to each other on the same Fe atom. For [Ru3(CO)12] substitution of up to three COs was found, together with the formation of higher-nuclearity clusters. [Ru4(CO)11(CNPh)3] was structurally characterised and has a spiked-triangular Ru4 core with two of the CNPh ligands coordinated in an unusual μ3-η2 mode. 相似文献
2.
Javier A. Cabeza Faizel Mulla Víctor Riera 《Journal of organometallic chemistry》1994,470(1-2):173-177
The cationic diphenylphosphido-bridged compound [Ru2(μ-PPh2)(μ-OH)2(η6-p-cymene)2][PF6) (2) has been prepared by reaction of the tri-μ-hydroxo complex [Ru2(μ-OH)3(η-p-cymene)2][PF6] (1) with diphenylphosphine. Complex 2 eliminates water on reaction with protic acids, incorporating the conjugate base of the added acid as a bridging ligand. Formic acid, acetic acid, phenol, and aniline react with 2 to give the monosubstituted compounds [Ru2(μ-PPh2)(μ-OH)(μ-L)(η6-p-cymene)2]PF6] (L = HCO2, MeCO2, OPh, or NHPH), whereas methanol, thiophenol, 1,2-benzenedithiol, hydrochloric acid and isopropanol afford the disubstituted derivatives [Ru2(μ-PPh2)(μ-L)2(η6-p-cymene)2]PF6] (L = OMe, SPh,
S2C6H4, Cl, or H). 相似文献
3.
K. O. Kallinen M. Ahlgr n T. T. Pakkanen T. A. Pakkanen 《Journal of organometallic chemistry》1996,510(1-2):37-43
The reaction between Ru3(CO)12 and a cyclic olefin (cis-cyclooctene or trans-cyclododecene) at 100 °C for several hours gives the title compounds (μ-H)2RU3(CO)9(μ3-η2-C8H12) (1), and (μ-H)RU3(CO)9(μ3-η3-C12H19) (2), both of which have been characterized by X-ray diffraction studies, IR and NMR spectral measurements and elemental analysis. The prolonged reaction between Ru3(CO)12 and cis-cyclooctene gives compound HRu3(CO)9(C8H11) (3). Compound 3 has been characterized with IR and NMR spectral analyses. In 1 the cyclooctene ring is linked via a μ3-η2-alkyne type of bonding to the face of the Ru3 cluster. It is formally σ-bonded to two of the three Ru atoms and π-bonded to the third Ru. The two hydrides in 1 are bridging Ru---Ru bonds. In 2 the cyclododecene ring is bonded to the Ru3 face via the μ3-η3-CCHC linkage. There are two formal σ-bonds from the allyl part to the hydrido-bridged Ru atoms and the η3-allyl linkage to the third Ru atom. 相似文献
4.
Javier A. Cabeza Angela Llamazares Víctor RieraPierrette Briard Lahcne Ouahab 《Journal of organometallic chemistry》1994,480(1-2):205-212
The compound [RU3(μ3,η2- -ampy)(μ3η1:η2-PhC=CHPh)(CO)6(PPh3)2] (1) (ampy = 2-amino-6-methylpyridinate) has been prepared by reaction of [RU3(η-H)(μ3,η2- ampy) (μ,η1:η2-PhC=CHPh)(CO)7(PPh3)] with triphenylphosphine at room temperature. However, the reaction of [RU3(μ-H)(μ3, η2 -ampy)(CO)7(PPh3)2] with diphenylacetylene requires a higher temperature (110°C) and does not give complex 1 but the phenyl derivative [RU3(μ3,η2-ampy)(μ,η 1:η2 -PhC=CHPh)(μ,-PPh2)(Ph)(CO)5(PPh3)] (2). The thermolysis of complex 1 (110°C) also gives complex 2 quantitatively. Both 1 and 2 have been characterized by0 X-ray diffraction methods. Complex 1 is a catalyst precursor for the homogeneous hydrogenation of diphenylacetylene to a mixture of cis- and trans -stilbene under mild conditions (80°C, 1 atm. of H2), although progressive deactivation of the catalytic species is observed. The dihydride [RU3(μ-H)2(μ 3,η2-ampy)(μ,η1:η2- PhC=CHPh)(CO)5(PPh3)2] (3), which has been characterized spectroscopically, is an intermediate in the catalytic hydrogenation reaction. 相似文献
5.
6.
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
7.
John S. Field Raymond J. Haines Eric Minshall Diana N. Smit 《Journal of organometallic chemistry》1986,310(3)
Treatment of closo-[Ru4(μ4-PPh)2(μ2-CO)(CO)10] with acetylene under ambient conditions leads to the insertion of the acetylene into the skeletal framework of the cluster and the formation of [Ru4(μ4-PPh){μ4-η3-P(Ph)CHCH}(μ2-CO)(CO)10], the structure of which has been determined X-ray crystallographically. 相似文献
8.
Padmamalini Srinivasan 《Journal of organometallic chemistry》2006,691(3):371-379
The reactions of the heterometallic cluster Cp*IrOs3(μ-H)2(CO)10 with phosphines, isonitriles and pyridine under TMNO activation afforded the substitution products Cp*IrOs3(μ-H)2(CO)10−nLn (n = 1, 2; L = PPh3, P(OMe)3, tBuNC, CyNC or py) in good yields. For the monosubstituted derivatives, the substitution site was exclusively at an osmium atom in an axial position for L = phosphine or phosphite. Spectroscopic evidence suggested the presence of isomers in solution for the PPh3 derivative. In contrast, for L = isonitrile, the ligand occupied an equatorial site. In the disubstituted derivatives, the group 15 ligands were coordinated to two different osmium atoms, one each at an axial and an equatorial site. The isomerism and fluxional behaviour of some of these clusters have also been examined. 相似文献
9.
[Co(η2-CO3)(NH3)4](NO3)·0.5H2O and [(NH3)3Co(μ-OH)2(μ-CO3)Co(NH3)3][NO3]2·H2O were prepared by prolonged aerial oxidation of a solution of Co(NO3)2·6H2O and ammonium carbonate in aqueous ammonia. The formation of these side products highlights the richness of the chemistry of these systems and the possibility of by products if methods are not strictly adhered to. The X-ray crystal structures of [Co(η2-CO3)(NH3)4][NO3]·0.5H2O and [(NH3)3Co(μ-OH)2(μ-CO3)Co(NH3)3][NO3]2·H2O reveal a monomeric octahedral cobalt center with η2-bound CO32− in the former, while the latter consists of a dimeric array where the two cobalt centers are bridged by two OH− and one μ2-CO32− groups with three terminal NH3 ligands for each Co center. In both complexes extensive hydrogen bonding interactions are evident. 相似文献
10.
Kom-Bei Shiu Shih-Wei Jean Yu Wang Gene-Hsiang Lee 《Journal of organometallic chemistry》2002,650(1-2):268-273
The reactions of the diruthenium carbonyl complexes [Ru2(μ-dppm)2(CO)4(μ,η2-O2CMe)]X (X=BF4− (1a) or PF6− (1b)) with neutral or anionic bidentate ligands (L,L) afford a series of the diruthenium bridging carbonyl complexes [Ru2(μ-dppm)2(μ-CO)2(η2-(L,L))2]Xn ((L,L)=acetate (O2CMe), 2,2′-bipyridine (bpy), acetylacetonate (acac), 8-quinolinolate (quin); n=0, 1, 2). Apparently with coordination of the bidentate ligands, the bound acetate ligand of [Ru2(μ-dppm)2(CO)4(μ,η2-O2CMe)]+ either migrates within the same complex or into a different one, or is simply replaced. The reaction of [Ru2(μ-dppm)2(CO)4(μ,η2-O2CMe)]+ (1) with 2,2′-bipyridine produces [Ru2(μ-dppm)2(μ-CO)2(η2-O2CMe)2] (2), [Ru2(μ-dppm)2(μ-CO)2(η2-O2CMe)(η2-bpy)]+ (3), and [Ru2(μ-dppm)2(μ-CO)2(η2-bpy)2]2+ (4). Alternatively compound 2 can be prepared from the reaction of 1a with MeCO2H–Et3N, while compound 4 can be obtained from the reaction of 3 with bpy. The reaction of 1b with acetylacetone–Et3N produces [Ru2(μ-dppm)2(μ-CO)2(η2-O2CMe)(η2-acac)] (5) and [Ru2(μ-dppm)2(μ-CO)2(η2-acac)2] (6). Compound 2 can also react with acetylacetone–Et3N to produce 6. Surprisingly [Ru2(μ-dppm)2(μ-CO)2(η2-quin)2] (7) was obtained stereospecifically as the only one product from the reaction of 1b with 8-quinolinol–Et3N. The structure of 7 has been established by X-ray crystallography and found to adopt a cis geometry. Further, the stereospecific reaction is probably caused by the second-sphere π–π face-to-face stacking interactions between the phenyl rings of dppm and the electron-deficient six-membered ring moiety of the bound quinolinate (i.e. the N-included six-membered ring) in 7. The presence of such interactions is indeed supported by an observed charge-transfer band in a UV–vis spectrum. 相似文献
11.
R.A. Al-Mandhary Muna Jack Lewis Paul R. Raithby 《Journal of organometallic chemistry》1997,530(1-2):247-250
The ionic coupling of [Os4H2(CO)12]2− with [Ru(η6-C6H6)(MeCN)3]2+ affords the neutral mixed metal cluster Os4Ru(μH)2(CO)12(η6-C6H6) 1. The reaction of 1 with trimethylphosphite leads to the initial formation of the addition product Os4Ru(μH)2(CO)12(η6-C6H6)P(OMe)3 2, but this complex rearranges in solution to give Os4Ru(μ-H)3(CO)12(μ3-η6-C6H5)P(OMe)3 3. An X-ray structure of 3 shows that the metal core of the cluster is a ruthenium-spiked Os4 tetrahedron, with one hydrogen atom from the arene having transferred to the Os4 core, and one arene carbon bridging an Os-Os edge, while the ring as a whole remains η6-bound to the Ru atom. 相似文献
12.
Garth Cripps Sylvie Chardon-Noblat Alain Deronzier 《Journal of organometallic chemistry》2004,689(2):484-488
The selective in situ synthesis of trans and cis(CH3CN)-[Ru(bpy)(CO)2 (CH3CN)2]2+ isomers from the same [Ru(CO)2 (CH3CN)3]22+ dimer precursor but using either an electrochemical-chemical or chemical-electrochemical process is described. 相似文献
13.
Hans‐Christian Bttcher Marion Graf Kurt Merzweiler Christoph Wagner 《无机化学与普通化学杂志》2000,626(6):1335-1340
Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐ray Crystal Structures of [Ru2(CO)3L(μ‐η1 : η2‐C≡CPh)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (L = CO, PnBu3) [Ru2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 1 ) reacts with several phosphines (L) in refluxing toluene under substitution of one carbonyl ligand and yields the compounds [Ru2(CO)3L(μ‐H)(μ‐PtBu2)(μ‐dppm)] (L = PnBu3, 2 a ; L = PCy2H, 2 b ; L = dppm‐P, 2 c ; dppm = Ph2PCH2PPh2). The reactivity of 1 as well as the activated complexes 2 a – c towards phenylethyne was studied. Thus 1 , 2 a and 2 b , respectively, react with PhC≡CH in refluxing toluene with elimination of dihydrogen to the acetylide‐bridged complexes [Ru2(CO)4(μ‐η1 : η2‐C≡CPh)(μ‐PtBu2)(μ‐dppm)] ( 3 ) and [Ru2(CO)3L(μ‐η1 : η2‐C≡CPh)(μ‐PtBu2)(μ‐dppm)] ( 4 a and 4 b ). The molecular structures of 3 and 4 a were determined by crystal structure analyses. 相似文献
14.
LI Xiu-juan ZENG Zheng-zhi 《高等学校化学研究》2006,22(1):6-10
IntroductionSince K pf[1]discovered that dicyclopenta die-nyltitanium dichloride possesses antitumour action in1979,a large number of cyclopentadienyltitanium com-plexes with different substituents have been synthe-sized[2,3].The experimental data reveal … 相似文献
15.
Ruaq2+(OTs)2 complexes in aqueous solution to unsaturated cyclic ketones. These aromatized on heating to π-arene Ru complexes. Thus, with cyclohexonone the main product was Ru(η6-phenol)22+, 4, along with some Ru(η6-phenol)(η6-OTs)+, 6. Similarly gave cyclopentenone in the presence of various arenes Ru(η5-hydroxycyclopentadienyl)(η6-arene)+. Duruquinone complexed to Ruaq2+ as a monoprotanated hydroquinolate in Ru(η6-2,3,5,6-tetramethyl-1,4-hydroquinone)(η6-OTs), 14. Ru(η5-cyclopentadienyl)(η6-OTs), 8, and 14 were characterized by single crystal x-ray structure analyses, data see Table 1. Whereas both ligands in 8 are planar, the 1,4-hydroquinone ligand in 14 shows distinct bending of the COH groups. 相似文献
16.
Richard D. Adams Burjor Captain Eszter Trufan 《Journal of organometallic chemistry》2008,693(24):3593-3602
The compounds Ru3(CO)9(SnPh3)2(NCMe)(μ-H)2 (1), Ru3(CO)10(SnPh3)2(μ-H)2 (2), Ru(CO)4(SnPh3)2 (3) and Ru(CO)4(SnPh3)(H) (4) were obtained from the reaction of Ru3(CO)10(NCMe)2 with HSnPh3 in hexane solvent. Compounds 1, 3 and the new compound Ru3(CO)7(SnPh3)3(NCMe)2(μ-H)3 (5) were obtained from reaction of Ru3(CO)10(NCMe)2 with HSnPh3 in a CH2Cl2 and MeCN solvent mixture. Compound 2 and the new compound Ru3(CO)9(SnPh3)3(μ-H)3 (6) were obtained from reactions of 1 and 5 with CO, respectively. Compounds 2 and 6 eliminated benzene when heated to yield Ru3(CO)10(μ-SnPh2)2 (7) and Ru3(CO)9(μ-SnPh2)3 (8) which contain bridging SnPh2 ligands. Compound 7 was found to react with to yield the adduct, (9) in 59% yield by the addition of groups to two of the Ru-Sn bonds to the bridging SnPh2 ligands. Fenske-Hall molecular orbital calculations were performed to provide an understanding of the metal-metal bonding in the clusters of 7 and 9. Compounds 1, 2, 5, 6, 7 and 9 were characterized structurally by single crystal X-ray diffraction analysis. 相似文献
17.
Zhong-Xia Wang Cheng-Sheng Jia Zhong-Yuan Zhou Xiang-Ge Zhou 《Journal of organometallic chemistry》1999,580(2):205
Reaction of the Et3NH+ salts of the [(μ-RS)(μ-CO)Fe2(CO)6]− anions (R=But, Ph or PhCH2) with (μ-S2)Fe2(CO)6 gives reactive intermediates [(μ-RS)(μ-S){Fe2(CO)6}2(μ4-S)]−. Reactions of the latter with alkyl halides, acid chlorides and Cp(CO)2FeI have been studied. X-Ray structure of (μ-ButS)(μ-PhCH2S)[Fe2(CO)6]2(μ4-S) was determined. 相似文献
18.
Shin-Guang Shyu Pei-Jung Lin Teng-Yuan Dong Yuh-Shang Wen 《Journal of organometallic chemistry》1993,460(2):229-236
Structures of non metal-metal bonded phosphido-bridged heterobimetallic complexes, including CpFe(CO)2(μ-PPh2)W(CO)5 (1-W) and metal-metal bonded CpFe(CO)(μ-CO)(μ-PPh2)W(CO)4 (2), were determined by a single crystal X-ray diffraction study. In 1-W, the long distance between Fe and W indicates no metal-metal bond to exist. In 2, a Fe---W bond with bond length 2.851 Å and a semibridging carbonyl with W---C---O angle 153° were observed. Mössbauer spectra of 1-W and 2 were taken at 77 K. Isomer shifts of 1-W and 2 were − 0.0203 mm s−1 and 0. 1917 mm s−1 respectively. 相似文献
19.
Giuliana Gervasio Domenica Marabello Enrico Sappa Andrea Secco 《Journal of Cluster Science》2007,18(1):67-85
Ru3(CO)12 has been reacted with the compounds hex-1-en-3-yne [EtC≡CCH=CH2], 2-methyl-hex-1-en-3-yne [EtC≡CC(=CH2)CH3] and with 3(ethoxy-silyl)propyl isocyanate [(EtO)3Si(CH2)3NCO] and the compound tb [(EtO)3Si(CH2)3NHC(=O)OCH2C≡CCH2OC(=O)NH(CH2)3Si(OEt)3] in hydrocarbon solution. Some reactions in CH3OH/KOH solution (followed by acidification) have also been performed.
The main products of the reactions with ene-ynes are the clusters Ru3(CO)6(μ-CO)2L2 (L = C6H8, C7H10) and their demolition products, the “ferrole” Ru2(CO)6L2 complexes. One of the isomers of Ru3(CO)6(μ-CO)2L2, and Ru2(CO)6L2 (L = C7H10) have been reacted with vinyl-triethoxysilane [(EtO)3SiCH=CH2]: these reactions did not afford complexes containing new carbon–carbon bonds or triethoxy-silyl groups. Only polymerization
of vinyl-triethoxysilane occurred.
The reactions of Ru3(CO)12 with triethoxysilyl-propyl-isocyanate and tb (in the presence of Me3NO) lead to the same products, that is the isomeric complexes (μ-H)Ru3(CO)9[C=N(H)(CH2)3Si(OEt)3] with a “perpendicular” ligand (complex 3, as proposed on the basis of spectroscopic results) and (μ-H)Ru3(CO)9[HC=N(CH2)3Si(OEt)3] with a “parallel” ligand (complex 4, as confirmed by a X-ray analysis). The reaction pathways leading to these products are discussed. Complex 4 has been reacted with tetraethyl orthosilicate and the resulting material has been characterized. These reactions are part
of a study on the synthesis of inorganic-organometallic materials through sol–gel techniques.
This paper is dedicated to Prof. Gunther Schmid in the occasion of his 70th birthday. 相似文献
20.
Reaction of the square antiprismatic cluster [ppn][Ru8(μ8-P)(μ-CO)2(CO)20] [ppn = bis(triphenylphosphoranylidene)ammonium] with triphenylphosphine proceeds by loss of one cluster core vertex, phosphine P-C cleavage, and CO insertion into the putative Ru-phenyl bond to afford [ppn][Ru7(μ7-P)(μ-η2-OCPh)(μ-PPh2)(μ-CO)(CO)17] in low yield, the first heptaruthenium μ7-phosphido-ligated cluster. 相似文献