共查询到20条相似文献,搜索用时 218 毫秒
1.
Md. Iqbal Hyder Md. Delwar H. Sikder Graeme Hogarth Shariff E. Kabir Christian J. Richard 《Journal of organometallic chemistry》2009,694(2):304-174
Reaction of [Ru3(CO)10(μ-dppm)] (1) with H2S at 66 °C affords high yields of the sulfur-capped dihydride [Ru3(CO)7(μ-H)2(μ-dppm)(μ3-S)] (2), formed by oxidative-addition of both hydrogen-sulfur bonds. Hydrogenation of [Ru3(CO)7(μ-dppm)(μ3-CO)(μ3-S)] (3) at 110 °C also gives 2 in similar yields, while hydrogenation of [Ru3(CO)7(μ-dppm)(μ3-CO)(μ3-Se)] (4) affords [Ru3(CO)7(μ-H)2(μ-dppm)(μ3-Se)] (5) in 85% yield. The molecular structures of 2 and 5 reveal that the diphosphine and one hydride simultaneously bridge the same ruthenium-ruthenium edge with the second hydride spanning one of the non-bridged edges. Both 2 and 5 are fluxional at room temperature being attributed to hydride migration between the non-bridged edges. Addition of HBF4 to 2 affords the cationic trihydride [Ru3(CO)7(μ-H)3(μ-dppm)(μ3-S)][BF4] (6) in which the hydrides are non-fluxional due to the blocking of the free ruthenium-ruthenium edge. 相似文献
2.
Thermal reaction of [Ru3(CO)12] with PH2Mes (Mes = mesityl) in refluxing toluene afforded mesitylphosphinidene-capped ruthenium carbonyl clusters, [Ru3(CO)9(μ-H)2(μ3-PMes)] (1), [Ru3(CO)8(PH2Mes)(μ-H)2(μ3-PMes)] (2), [Ru3(CO)9(μ3-PMes)2] (3), [Ru4(CO)10(μ-CO)(μ4-PMes)2] (4), and [Ru5(CO)10H2(μ4-PMes)(μ3-PMes)2] (5). All products were fully characterized and structurally confirmed by X-ray crystal structure analysis. Complexes 2-4 were also obtained in high yields by stepwise reaction starting from 1. Fluxional behavior of carbonyl groups was observed in case of 4. Complex 5 reveals a new type of skeletal structure, bicapped-octahedron having μ3- and μ4-phosphinidene ligands at the capping positions. Similar reaction of [Os3(CO)12] with PH2Mes yielded a phosphido-bridged osmium cluster [Os3(CO)10(μ-H)(μ-PHMes)] (6) and a phosphinidene-capped cluster [Os3(CO)9(μ-H)2(μ3-PMes)] (7). 相似文献
3.
Syed J. Ahmed Shariff E. Kabir Antony J. Deeming Ebbe Nordlander 《Journal of organometallic chemistry》2006,691(3):309-322
Treatment of [Ru3(CO)10(μ-dppm)] (4) [dppm = bis(diphenylphosphido)methane] with tetramethylthiourea at 66 °C gave the previously reported dihydrido triruthenium cluster [Ru3(μ-H)2(μ3-S)(CO)7(μ-dppm)] (5) and the new compounds [Ru3(μ3-S)2(CO)7(μ-dppm)] (6), [Ru3(μ3-S)(CO)7(μ3-CO)(μ-dppm)] (7) and [Ru3(μ3-S){η1-C(NMe2)2}(CO)6(μ3-CO)(μ-dppm)] (8) in 6%, 10%, 32% and 9% yields, respectively. Treatment of 4 with thiourea at the same temperature gave 5 and 7 in 30% and 10% yields, respectively. Compound 7 reacts further with tetramethylthiourea at 66 °C to yield 6 (30%) and a new compound [Ru3(μ3-S)2{η1-C(NMe2)2}(CO)6(μ-dppm)] (9) (8%). Thermolysis of 8 in refluxing THF yields 7 in 55% yield. The reaction of 4 with selenium at 66 °C yields the new compounds [Ru3(μ3-Se)(CO)7(μ3-CO)(μ-dppm)] (10) and [Ru3(μ3-Se)(μ3-η3-PhPCH2PPh(C6H4)}(CO)6(μ-CO)] (11) and the known compounds [Ru3(μ-H)2(μ3-Se)(CO)7(μ-dppm)] (12) and [Ru4(μ3-Se)4(CO)10(μ-dppm)] (13) in 29%, 5%, 2% and 5% yields, respectively. Treatment of 10 with tetramethylthiourea at 66 °C gives the mixed sulfur-selenium compounds [Ru3(μ3-S)(μ3-Se)(CO)7(μ-dppm)] (14) and [Ru3(μ3-S)(μ3-Se){η1-C(NMe2)2}(CO)6(μ-dppm)] (15) in 38% and 10% yields, respectively. The single-crystal XRD structures of 6, 7, 8, 10, 14 and 15 are reported. 相似文献
4.
Michael I. Bruce Paul A. Humphrey Allan H. White 《Journal of organometallic chemistry》2004,689(15):2558-2561
The reaction between AuMe(PPh3) and Ru3(μ-H)3(μ3-CBr)(CO)9 (1) affords the novel heptanuclear cluster Au4Ru3(μ3-CMe)(Br)(CO)9(PPh3)3 (2), containing an Au/Ru3/Au trigonal pyramidal cluster face-capped by two Au(PPh3) groups and a CMe ligand, together with Au2Ru3(μ-H)(μ3-CMe)(CO)9(PPh3)2 (3), formed by isolobal replacement of two of the three μ-H atoms in 1 by Au(PPh3) groups. The latter co-crystallises with the analogous μ3-CH complex, as also shown spectroscopically. 相似文献
5.
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
6.
Yong Leng Kelvin Tan 《Journal of organometallic chemistry》2006,691(9):2048-2054
The heteronuclear cluster RuOs3(μ-H)2(CO)13 (4) reacts with refluxing toluene to form the clusters Ru2Os3(μ-H)2(CO)16 (5) RuOs3(CO)9(μ-CO)2(η6-C6H5Me) (6) and Ru2Os3(CO)12(μ-CO)(η6-C6H5Me) (7). Cluster 5 exists as a mixture of five isomers. The inter-relationship among the clusters has also been investigated. 相似文献
7.
Shamsuddin M. Azad Shariff E. Kabir Madhu S. Saha 《Journal of organometallic chemistry》2005,690(18):4206-4211
Treatment of the electronically unsaturated cluster [(μ-H)Os3(CO)8{Ph2PCH2P(Ph)C6H4}] (1) with primary phosphines PPhH2 and PCyH2 gives the phosphido bridged compounds [(μ-H)Os3(CO)8(μ-PPhH)(μ-dppm)] (2) and [(μ-H)Os3(CO)8(μ-PCyH)(μ-dppm)] (3), respectively, by P-H bond activation of the phosphines and demetallation of the phenyl ring of the diphosphine ligand. Thermolysis of 2 and 3 in refluxing octane at 128 °C results in the formation of the phosphinidene compounds [(μ-H)2Os3(CO)7(μ3-PPh)(μ-dppm)] (4) and [(μ-H)2Os3(CO)7(μ3-PCy)(μ-dppm)] (5), respectively, by further P-H bond cleavage of the phosphido groups. All the compounds have been characterized by infrared, 1H NMR, 31P{1H} NMR and mass spectroscopic data together with single-crystal X-ray diffraction studies for 4. Compound 4 consists of a triangular cluster of osmium atoms with a symmetrically capped phosphinidene ligand and a bridging dppm ligand. 相似文献
8.
María G. Hernández-Cruz Micaela Hernández-Sandoval María J. Rosales-Hoz Verónica Salazar Francisco J. Zuno-Cruz 《Journal of organometallic chemistry》2011,696(10):2177-4078
The reaction between [Ru3(CO)10(NCMe)2] and [AuClPPh3] gave compound [Ru3(CO)10(μ-Cl)(μ-AuPPh3)] (1) in quantitative yield under very mild conditions. The reaction of 1 with 4-mercaptopyridine (4-pyS) using ultrasonic reaction conditions gave the heteronuclear compound [Ru3(CO)10(μ-AuPPh3)(μ-SC5H4N)] (2) in moderate yield. There was no spectroscopic evidence that indicates the formation of the hydride isolobal analog in this reaction. The homonuclear cluster [Ru3(CO)8(μ-H)(μ-SC5H4N)(μ-dppe)] (3) was prepared by a selective reaction employing the ruthenium-diphosphine derivative [Ru3(CO)10(μ-dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) with 4-pyS in THF solution. The isolobal analog to compound 3, compound [Ru3(CO)8(μ-AuPPh3)(μ-SC5H4N)(μ-dppe)] (4) was synthesized by the reaction between compound 2 and dppe in refluxing dichloromethane. Compounds 1-4 were characterized in solution by spectroscopic methods and the molecular structure of compounds 2 and 3 in the solid state was obtained by single crystal X-ray diffraction studies. 相似文献
9.
Chunxiang Li 《Journal of organometallic chemistry》2008,693(7):1292-1300
The reaction of [Os3(CO)10(μ-H)(μ-OH)], 1, or [Os3(CO)10(NCCH3)2], 2, with bifunctional ligands carrying -OH, -SH and -COOH groups affords, as the major product, clusters of the general formula [Os3(CO)10(μ-H)(μ-E?E′H)] (E, E′ = O, S or COO). In some cases, a minor product with general formula [Os3(CO)10(μ-H)(μ,μ-E?E′)Os3(CO)10(μ-H)] was also obtained. With Ru3(CO)12, 3b, only the first type of products is obtained. The structures of eight of the compounds have also been determined by single crystal X-ray crystallography. 相似文献
10.
Arun K. Raha Iqbal Hossain Brian K. Nicholson Luca Salassa 《Journal of organometallic chemistry》2011,696(10):2153-2160
The ruthenium-tin complex, [Ru2(CO)4(SnPh3)2(μ-pyS)2] (1), the main product of the oxidative-addition of pySSnPh3 to Ru3(CO)12 in refluxing benzene, is [Ru(CO)2(pyS)(SnPh3)] synthon. It reacts with PPh3 to give [Ru(CO)2(SnPh3)(PPh3)(κ2-pyS)] (2) and further with Ru3(CO)12 or [Os3(CO)10(NCMe)2] to afford the butterfly clusters [MRu3(CO)12(SnPh3)(μ3-pyS)] (3, M=Ru; 4, M=Os). Direct addition of pySSnPh3 to [Os3(CO)10(NCMe)2] at 70 °C gives [Os3(CO)9(SnPh3)(μ3-pyS)] (5) as the only bimetallic compound, while with unsaturated [Os3(CO)8{μ3-PPh2CH2P(Ph)C6H4}(μ-H)] the previously reported [Os3(CO)8(μ-pyS)(μ-H)(μ-dppm)] (6) and the new bimetallic cluster [Os3(CO)7(SnPh3){μ-Ph2PCH2P(Ph)C6H4}(μ-pyS)[(μ-H)] (7) are formed at 110 °C. Compounds 1, 2, 4, 5 and 7 have been characterized by X-ray diffraction studies. 相似文献
11.
Alejandro J. Arce Farrah Cañavera Ysaura De Sanctis Julian Ascanio Rubén Machado Teresa González 《Journal of organometallic chemistry》2009,694(12):1834-1839
The reaction between 1-pyrenecarboxaldehyde (C16H9CHO) and the labile triosmium cluster [Os3(CO)10(CH3CN)2] gives rise to the formation of two new compounds by competitive oxidative addition between the aldehydic group and an arene C-H bond, to afford the acyl complex [Os3(CO)10(μ-H)(μ-COC16H9)] (1) and the compound [Os3(CO)10(μ-H) (C16H8CHO)] (2), respectively. Thermolysis of [Os3(CO)10(μ-H)(μ-C16H9CO)] (1) in n-octane affords two new complexes in good yields, [Os3(CO)9(μ-H)2(μ-COC16H8)] (3) and the pyryne complex [Os3(CO)9(μ-H)2(μ3-η1:η1:η2-C16H8)] (4).In contrast, when 1-pyrenecarboxaldehyde reacts with [Ru3(CO)12] only one product is obtained, [Ru3(CO)9(μ-H)2(μ3-η1:η1:η2-C16H8)] (5), a nonacarbonyl cluster bearing a pyrene ligand. All compounds were characterized by analytical and spectroscopic data, and crystal structures for 1, 2, 4 and 5 were obtained. 相似文献
12.
Michael I. Bruce Paul A. Humphrey Brian W. Skelton 《Journal of organometallic chemistry》2005,690(3):784-791
Bis(dimethylphosphino)naphthalene, 1,8-(PMe2)2C10H6 (dmpn), reacts readily with Ru3(CO)12 or Ru3(μ-dppm)(CO)10 with replacement of one of the PMe2 groups by H to give Ru3(CO)12 − n{PMe2(nap)}n (n = 1 2, 2 3) or Ru3(μ-dppm)(CO)9{PMe2(nap)} 4; the complex Ru3(CO)10(dmpn) 1 is obtained only in small amount. Thermolysis of 2 or 4 gives Ru3(μ-H)2{μ3-PMe2(C10H5)}(μ-dppm)n (CO)8-2n (n = 0 5, 1 6, respectively) containing μ3-naphthalyne groups. 相似文献
13.
Renato Rosseto 《Journal of organometallic chemistry》2004,689(1):111-121
The synthesis and characterisation of μ3-η2-alkynyl triruthenium clusters, [Ru3(μ3-η2-R1-4-C6H4CCR2)(μ-dppm)(μ-CO)(CO)7] (1, saturated), [Ru3(μ3-η2-R1-4-C6H4CCR2)(μ-dppm)(CO)7] (2, unsaturated) and [Ru3(μ3-η2-R1-4-C6H4CCR2)(μ-dppm)(PPh3)(CO)7] (3, saturated) containing symmetrical and asymmetrical alkynes in which R1 and R2 are electron donor or electron withdrawing groups in the para position of the aromatic ring(s) or R2 is ferrocenyl, are reported. Clusters 1 were obtained from the reactions of [PPN][Ru3(μ-Cl)(CO)10] with R1-4-C6H4CCR2 and dppm. Clusters 1 were successfully decarbonylated to give unsturated clusters 2, with the exception of the FcCCC6H4-4-NO2 containing cluster, which is stable. Novel adducts 3 were obtained in high yields by addition of PPh3 to unsaturated clusters 2. Clusters 1-3 were characterised by analytical and spectroscopic data, and structures were proposed on the basis of systematic 31P NMR studies and correlations with X-ray structural data of related compounds available in the literature. Saturated compounds 1 contain a CO and a dppm ligands bridging the same edge, which is also parallel to the μ3-η2-alkyne, as opposed to the structure previously proposed for the PhCCPh and other derivatives, and established by X-ray crystallography for the PhCCCCPh cluster derivative, in which the dppm ligand bridges a different edge. Unsaturated compounds 2 exhibit the same structure established for the PhCCPh derivative in the solid state, with the alkyne bonded in the μ3-η2-mode perpendicular to the Ru2 edge supported by the dppm ligand. Because the dppm phosphorus chemical shifts were sensitive to the alkyne electronic asymmetry, it was possible to show that clusters containing electronically asymmetrical alkynes exist in two inseparable isomeric forms, which differ with respect to the alkyne orientation. Similarly to their osmium analogues, saturated compounds 3 exist as inseparable mixtures of isomers that differ with respect to the position of the bridging CO and dppm ligands, and in the cases of asymmetrical alkyne derivatives, also with respect to the orientation of the alkyne. This work has established, therefore, that μ-CO and dppm ligand positions respective to the μ3-η2-alkyne in saturated clusters 1 and 3 are sensitive both to the nature of the coordinated alkyne and to the presence of a PPh3 in place of a CO ligand on the metal frame. 相似文献
14.
Stefan Buck 《Journal of organometallic chemistry》2006,691(12):2774-2784
The dinuclear ruthenium complexes [Ru2(μ-sac)2(CO)6] (1), [Ru2(μ-sac)2(CH3CN)2(CO)4] (3), [Ru2(μ-sac)2(CO)5(PPh3)] (4) and [Ru2(μ-sac)2(CO)4(PPh3)2] (5) as well as the tetranuclear ruthenium complex [Ru2(μ-sac)2(CO)5]2 (2) (sac = saccharinate, C7H4NO3S−) were synthesized starting from Ru3(CO)12 and saccharin. X-ray crystal structure analysis of 1, 3A × p-xylene, 4 × CH2Cl2 and 5 × 3CH2Cl2 showed that the core is bridged through the amidate moieties of the two saccharinate ligands, with a head-tail arrangement in complexes 1, 3A and 5, and a head-head arrangement in 4. For complex 3, an equilibrium mixture of the head-head regioisomer 3A and a second species 3b exists in solution. Complexes 1 and 2 are suitable catalysts for the cyclopropanation of nucleophilic alkenes (styrene, cyclohexene and 2-methyl-2-butene) with methyl diazoacetate. 相似文献
15.
Leonard Joachim Pereira 《Journal of organometallic chemistry》2005,690(4):1033-1043
TMNO-activated reaction of the heteronuclear cluster Os3Ru(μ-H)2(CO)13 (1) with diphenylphosphine afforded the novel phosphido-bridged clusters Os3Ru(μ-PPh2)(μ-H)3(CO)11 (2), Os3Ru(μ-PPh2)2(μ-H)2(CO)10 (3), Os3Ru(μ-PPh2)2(μ-H)4(CO)9 (4), and Os3Ru(μ-PPh2)(μ-H)3(CO)11(PPh2H) (5). The formation of 2-5 proceeded via P-H bond cleavage in the adduct Os3Ru(μ-H)2(CO)12(PPh2H) (6). Reaction of 2 with PPh3 afforded the adduct Os3Ru(μ-PPh2)(μ-H)3(CO)11(PPh3) (7) and the substituted derivative Os3Ru(μ-PPh2)(μ-H)3(CO)10(PPh3) (8). 相似文献
16.
Yong Leng Kelvin Tan 《Journal of organometallic chemistry》2007,692(4):768-773
The heteronuclear cluster RuOs3(μ-H)2(CO)13 (1) reacts with indene under thermal activation to afford the novel clusters RuOs3(μ-H)(CO)9(μ-CO)2(η5-C9H7) (3), RuOs3(μ-H)(CO)9(μ3,η5:η2:η2-C9H7) (4) and Ru2Os3(μ-H)(CO)11(μ3,η5:η2:η2-C9H7) (5), the latter two possessing indenyl ligands in the μ3,η5:η2:η2 bonding mode. Cluster 5 exists as a mixture of two isomers. The inter-relationship among the clusters has also been investigated. 相似文献
17.
Mien Wei Lum 《Journal of organometallic chemistry》2003,687(1):203-208
Reaction of the cluster Os3(μ-H)(μ-OH)(CO)10 (1) with 1-naphthol afforded the isomeric clusters 2a and 3a with the formulae Os3(μ-H)2(μ3-1-OC10H6)(CO)9. A similar reaction with 2-naphthol, however, gave Os3(μ-H)(μ-2-OC10H7)(CO)10, 4b, and the analogue of 2a. These clusters have been structurally characterised to confirm the mode of anchoring of the naphthols. 相似文献
18.
Tobias Mayer 《Journal of organometallic chemistry》2011,696(21):3415-3420
A convenient synthesis and the characterization of six new electronically and coordinatively unsaturated complexes of the formula [Ru2(CO)4(μ-H)(μ-PtBu2)(μ-L2)] (2b-g) (RuRu) is described exhibiting a close relation to the known [Ru2(CO)4(μ-H)(μ-PtBu2)(μ-dppm)] (2a). The complexes 2b-g were obtained in a kind of one-pot synthesis starting from [Ru3(CO)12] and PtBu2H in the first step followed by the reaction with the bidentate bridging ligand in the second step. The method was developed for the following bridging ligands (μ-L2): dmpm (2b, dmpm = Me2PCH2PMe2), dcypm (2c, dcypm = Cy2PCH2PCy2), dppen (2d, dppen = Ph2PC(=CH2)PPh2), dpppha (2e, dpppha = Ph2PN(Ph)PPh2), dpppra (2f, dpppra = Ph2PN(Pr)PPh2), and dppbza (2g, dppbza = Ph2PN(CH2Ph)PPh2). The molecular structures of all new complexes 2b−g were determined by X-ray diffraction. 相似文献
19.
Padmamalini Srinivasan 《Journal of organometallic chemistry》2006,691(5):941-951
The mixed metal cluster Cp*IrOs3(μ-H)2(CO)10 (1) reacted readily with a number of group 16 substrates under chemical activation with TMNO. It reacted with C6H5SH to afford the novel cluster Cp*IrOs3(μ-H)3(CO)9(μ-SPh) (2). It also reacted readily with Ph3PSe to afford five new clusters, viz., Cp*IrOs3(μ-H)2(CO)9(μ3-Se) (3) Os3(μ-H)2(CO)7(μ3-Se)(PPh3)2 (4), Cp*IrOs3(μ-H)2(CO)9(PPh3) (5), Cp*IrOs3(μ-H)2(μ3-Se)(CO)8(PPh3) (6) and Cp*IrOs3(μ-H)2(μ3-Se)2(CO)7(PPh3) (7). The reaction pathway for this reaction has been studied carefully and suggests that Ph3PSe functioned primarily as a selenium atom transfer agent to give initially the even more reactive 3. The reaction of 1 with di-p-tolyl ditelluride yielded three new clusters, 8-10, which were non-interconverting stereoisomers with the formulation Cp*IrOs3(μ-H)2(μ-Te-p-C6H4CH3)2(CO)8. 相似文献
20.
Two isomers of Ru5(C)(CO)14(O2CC6H5)(μ-H): Ru5(C)(CO)14(η2-O2CC6H5)(μ-H), 2 and Ru5(C)(CO)14(μ-O2CC6H5)(μ-H), 3 were obtained from the reaction of Ru5(C)(CO)15 with benzoic acid (PhCO2H). Both compounds were characterized structurally by X-ray diffraction analysis. Compound 2 contains an opened pentaruthenium cluster with a chelating benzoate ligand on the ruthenium atom that was opened. Compound 3 contains an opened pentaruthenium cluster with a benzoate ligand on that bridges a pair of ruthenium atoms which are not mutually bonded. Compound 2 can be converted partially to 3 and 3 partially back to 2 and they form a 1.54/1.0 ratio (3/2) at equilibrium in solution at 95 °C. 相似文献