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1.
Reaction between Os(CO)2(PPh3)3 and Me3SnH produces Os(SnMe3)H(CO)2(PPh3)2 (1). Multinuclear NMR studies of solutions of 1 reveal the presence of four geometrical isomers, the major one being that with mutually cis triphenylphosphine ligands and mutually trans CO ligands. Os(SnMe3)H(CO)2(PPh3)2 undergoes a redistribution reaction, at the trimethylstannyl ligand, when treated with Me2SnCl2 giving Os(SnMe2Cl)H(CO)2(PPh3)2 (2). Solutions of 2 again show the presence of four isomers but now the major isomer is that with mutually trans triphenylphosphine ligands and mutually cis CO ligands. The redistribution reaction of 1 with SnI4 produces Os(SnMeI2)H(CO)2(PPh3)2 (3) which exists in solution as only one isomer, that with mutually trans triphenylphosphine ligands and mutually trans CO ligands. Treatment of 3 with I2 cleaves the Os-H bond with retention of geometry giving Os(SnMeI2)I(CO)2(PPh3)2 (4). The crystal structure of 4 has been determined. No isomerization of the trans dicarbonyl complex 4 occurs when 4 is heated, instead there is a formal loss of “MeSnI” and formation of OsI2(CO)2(PPh3)2 (5). 相似文献
2.
Richard D. Adams Burjor Captain Wei Fu Mark D. Smith Lei Zhu 《Journal of Cluster Science》2006,17(1):87-95
Two new compounds Pd2Os3(CO)12
, 13 and Pd3Os3(CO)12
, 14 have been obtained from the reaction of
with Os3(CO)12 at room temperature. The products were formed by the addition of two and three
groups to the Os–Os bonds of Os3(CO)12. Compounds 13 and 14 interconvert between themselves by intermolecular exchange of the
groups in solution. Compounds 13 and 14 have been characterized by single crystal X-ray diffraction analyses.Dedicated to Professor Brian F. G. Johnson on the occasion of his retirement – 2005. 相似文献
3.
The product isolated from the reaction of (μ-H)2Os3(CO)9(PPh3) with ethylene is shown to be the ethylidene complex (μ-H)2Os3(CO)9(PPh3)(μ-CHCH3) (1) rather than the ethylene complex (μ-H)(H)Os3(CO)9(PPh3)(C2H4), as previously claimed. The characterization of 1 is based on a combination of 1H and 13C NMR results. The 1H NMR data (δ 6.84 (1 HD), 2.53 (3 HC), J(CD) = 7.4 Hz) establish the presence of the ethylidene moiety, whereas detailed analysis of the 1-D and 2-D 13C NMR spectra of 13CO-enriched 1 indicates the relative positions of the ethylidene, hydride, and phosphine ligands on the triosmium framework. 相似文献
4.
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
5.
The triosmium cluster 1,2-Os3(CO)10(MeCN)2 reacts rapidly with the diphosphine ligand 2,3-bis(diphenylphosphino)-N-p-tolylmaleimide (bmi) at room temperature to give bmi-bridged cluster 1,2-Os3(CO)10(bmi) (2b) as the major product, along with the chelating isomer 1,1-Os3(CO)10(bmi) (2c) and the hydride-bridged cluster HOs3(CO)9[μ-(PPh2)CC{PPh(C6H4)}C(O)N(tolyl-p)C(O)] (3) as minor by-products. All three cluster compounds have been isolated and fully characterized in solution by IR and NMR spectroscopies (1H and 31P), and X-ray crystallography in the case of 2c. Cluster 2b is unstable and readily isomerizes to 2c in quantitative yield on mild heating. The kinetics for the conversion of 2b → 2c have been measured over the temperature range of 318-348 K in toluene solution, and based on the observed activation parameters a nondissociative isomerization process that proceeds via a transient μ2-bridged phosphine moiety is presented. Near-UV photolysis of cluster 2c at room temperature affords HOs3(CO)9[μ-(PPh2)CC{PPh(C6H4)}C(O)N(tolyl-p)C(O)] (3) with a quantum yield of 0.017. The reactivity of clusters 2b, 2c, and 3 is discussed with respect to related diphosphine-substituted Os3(CO)10(P-P) clusters prepared by our groups. 相似文献
6.
A.V Safronova N.E Stolyarova I.K Grigorieva I.P Malysheva G.V Basova G.K Fukin Yu.A Kurskii S.Ya Khorshev G.A Abakumov 《Journal of organometallic chemistry》2004,689(7):1127-1130
The novel organosilicon, -germanium and -tin-containing carbene complexes of tungsten of the type Ph3E-CHWCl2(OBut)2 (E=Si, Ge, Sn) have been prepared by the reaction of heteroelement-containing carbene complexes of tungsten Ph3E-CW(OBut)3 (E=Si, Ge, Sn) with hydrogen chloride. The tin-containing carbene complex was identified in solution by 1H NMR spectroscopy. Silicon- and germanium-containing carbene complexes were isolated in high yields as crystalline solids and characterized by elemental analysis, IR, 1H NMR, 13C NMR and 29Si NMR spectroscopy and X-ray diffraction studies. The geometry of the W atoms in the compounds can be described as a distorted square pyramid. 相似文献
7.
Richard D. Adams Fang Fang Mark D. Smith Qiang Zhang 《Journal of organometallic chemistry》2011,696(17):2904-2909
A reinvestigation of the reaction of Ir(CO)Cl(PPh3)2, 1 with HSnPh3 has revealed that the oxidative-addition product Ir(CO)Cl(PPh3)2(H)(SnPh3), 2 has the H and SnPh3 ligands in cis-related coordination sites. Compound 2 reacts with a second equivalent of HSnPh3 by a Cl for H ligand exchange to yield the new compound H2Ir(CO)(SnPh3)(PPh3)2, 3. Compound 3 contains two cis- related hydride ligands. Under an atmosphere of CO, 1 reacts with HSnPh3 to replace the Cl ligand with SnPh3 and one of the PPh3 ligands with a CO ligand and also adds a second equivalent of CO to yield the 5-coordinate complex Ir(CO)3(SnPh3)(PPh3), 4. Compound 4 reacts with HSnPh3 by loss of CO and oxidative addition of the Sn-H bond to yield the 6-coordinate complex HIr(CO)2(SnPh3)2(PPh3), 5 that contains two trans-positioned SnPh3 ligands. 相似文献
8.
Reaction of 1,3,5-trimethyl-1,3,5-triazacyclohexane [(MeNCH2)3] with Os3(CO)12 in refluxing toluene results in C-H and C-N bond activation of the (MeNCH2)3 ligand to afford three amidino cluster complexes (μ-H)Os3(CO)10[μ,η2-CH(NMe)2] (1), (μ-H)Os3(CO)9[μ3,η2-CH(NMe)2] (2), and Os2(CO)6[μ,η2-CH(NMe)2]2 (3). The controlled experiments show that thermolysis of 1 yields 2, and heating 2 in the presence of (MeNCH2)3 ligand produces 3. The molecular structures of 1 and 3 have been determined by an X-ray diffraction study. 相似文献
9.
Fujico Iwasaki Martin J. Mays Paul R. Raithby Philip L. Taylor Peter J. Wheatley 《Journal of organometallic chemistry》1981,213(1):185-206
Twelve new trinuclear complexes containing terminal PH2Ph, edge-bridging PHPh and/or capping PPh ligands have been isolated from the reaction of M3(CO)12 (M = Ru or Os) with PH2Ph in refluxing solvents. HRu3(CO)10(PHPh) (IIIa) crystallises in the monoclinic space group P21/c with a = 8.761(3), b = 11.402(4), c = 22.041(7) Å,β = 98.89(2)°, and Z = 4. The structure was solved by a combination of direct methods and Fourier difference techniques, and refined by blocked-cascade least squares to R = 0.027 for 3676 unique observed intensities. The X-ray analysis shows that one edge of the Ru3 triangle is bridged by a hydride and the PHPh ligand, and that the phosphorus-bound hydrogen atom lies over the metal triangle and the phenyl group away from it. This provides an explanation for the ready formation of the capped species H2Ru3(CO)9(PPh) (Va) on pyrolysis of the edge-bridged complex as opposed to the previously reported conversion of HOs3(CO)10(NHPh) to an orthometallated derivative under similar conditions. An X-ray analysis of H2Ru3(CO)9-(PPh) (Va) confirms the capped geometry. the complex crystallises in the monoclinic space group P21/n with a = 9.323(4), b = 15.110(6), c = 45.267(15) Å,β = 91.84(3)°, and Z = 12. the structure was solved and refined using the same techniques as described previously. The final residual R is 0.061 for 4839 reflections. Some reactions of Va show that the phosphorous cap is difficult to displace and stabilises the molecule with respect to decomposition to non-cluster species. 相似文献
10.
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
11.
Michael I Bruce Paul A Humphrey Brian W Skelton 《Journal of organometallic chemistry》2004,689(14):2415-2420
Reactions of Os3(CO)12 with 1,8-bis(diphenylphosphino)naphthalene (dppn) are described. Crystallographically characterised complexes isolated from a reaction carried out in refluxing toluene are Os3(μ-H)2{μ-PPh2(nap)PPh(C6H4)}2(CO)6 (1), Os3(μ-H){μ3-PPh2(nap)PPh(C6H4)}(CO)8 (2) and Os2(μ-PPh2){μ-PPh2(nap)}(CO)5 (3) (nap=1,8-C10H6), while at r.t. in the presence of ONMe3, only Os3(CO)11{PPh2(1-C10H7)} (4) was isolated. While 1 and 2 contain ligands formed by metallation of a Ph group of dppn, as found also in complexes obtained from dppn and Ru3(CO)12, ligands in 3 and 4 are formed by cleavage of a P-nap bond, not found in the Ru series. 相似文献
12.
Gian Angelo Vaglio 《Journal of organometallic chemistry》1979,169(1):83-85
The negative-ion mass spectra at 70 eV of the compounds Os3(CO)12X2 and Os3(CO)10X2 (X =Br, I) are reported. Negative molecular ions are absent and only Os3-containing fragments due to the loss of carbonyl groups are observed. [M CO]? is the base peak in the spectrum of Os3(CO)10I2 and has a very high abundance in that of Os3(CO)10Br2, whereas it is very weak in the spectra of Os3(CO)12X2, where [M 3 CO]? is the base peak. This change in the ionic intensities is related to the closed and open structure of the Os3 unit in Os3(CO)10X2 and Os3(CO)12X2 respectively. 相似文献
13.
Timothy I. Odiaka 《Journal of organometallic chemistry》1985,284(1):95-99
Triosmium clusters of the type [Os3(CO)10(μ-H)(NHCOR)] (1; R = H, Me, Ph, Et or Pr) are formed in high yields form the reaction of [Os3(CO)10(NCMe)2] (2) with amides. The nature of the products formed from thermolysis of 1 depend on the group, R. 相似文献
14.
Leonard Joachim Pereira 《Journal of organometallic chemistry》2006,691(11):2448-2456
Tertiary group 15 ligand monosubstituted derivatives of the heteronuclear cluster RuOs3(μ-H)2(CO)13 have been prepared and their solid state and solution structures examined. A number of isomeric structural types have been identified in solution, and these appear to be correlated to disorder in the solid state. Hydride fluxionality and restricted rotation about the metal-phosphorus bond have also been observed. 相似文献
15.
R. Psaro R. Ugo G.M. Zanderighi B. Besson A.K. Smith J.M. Basset 《Journal of organometallic chemistry》1981,213(1):215-247
16.
Jouni Pursiainen Tapani A. Pakkanen Juhani Jääskeläinen 《Journal of organometallic chemistry》1985,290(1):85-98
A new ruthenium-rhodium mixed-metal cluster HRuRh3(CO)12 and its derivatives HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2 have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh3(CO)12: monoclinic, space group P21/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh3(CO)10(PPh3)2·C6H14: triclinic, space group P, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo3(CO)10(PPh3)2·CH2Cl2: triclinic, space group P, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)4? and (Ru(CO)3Cl2)2 tetrahydrofuran followed by acid treatment yields HRuRh3(CO)12 in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh3(CO)10(PPh3)2, which is closely related to HRuCo3(CO)10(PPh3)2 and HFeCo3(CO)10(PPh3)2. The phosphines are axially coordinated. 相似文献
17.
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
18.
Yongqiang Ma Jinshan Li Zhenai Xuan Runchang Liu 《Journal of organometallic chemistry》2001,620(1-2):235-242
A series of novel arylantimony(V) triphenylgermanylpropionates with the formula (Ph3GeCHR1CHR2CO2)nSbAr(5−n) (R1=H, Ph; R2=H, CH3; n=1, 2) were synthesized and characterized by elemental analysis, IR, 1H-NMR, 13C-NMR and mass spectroscopy. The crystal structures of Ph3GeCH(Ph)CH2CO2SbPh4 and [Ph3GeCH2CH(CH3)CO2]2Sb(4-ClC6H4)3 were determined by X-ray diffraction. The in vitro antitumor activities of some selected compounds against five cancer cells are reported. 相似文献
19.
许多化学工作者对单齿膦配体(PPh3,PBun3,PEt2Ph,P(OEt)3,P(OC6H5)3)与母体簇合物FeCo2(CO)9(μ3-S)的取代反应进行过详细研究[1-3],但对双齿膦配体与母体簇合物的取代反应研究报导较少.Aime[4]合成了含双齿膦配体的簇合物FeCo2(CO)7(μ3-S)(Ph2PCH2PPh2),并用13CNMR和IR光谱方法对其结构进行了表征.到目前为止,含双齿膦配体的该类簇合物的晶体与分子结构还未见报导.RosannaRossetti[2]通过研究母体簇合物与… 相似文献
20.
Reaction between Os[B(OEt)2]Cl(CO)(PPh3)2 and 1,2-ethanediol in the presence of Me3SiCl (1 equivalent) leads to the tethered boryl complex, Cl(CO)(PPh3)2 (1), in which one ethoxy substituent on the boryl ligand is exchanged with one hydroxy group of the 1,2-ethanediol leaving the other OH group available to coordinate to osmium, so giving a six coordinate complex. This formulation is confirmed by crystal structure determination. The same reactants, but with 2 equivalents of Me3SiCl, lead to the yellow, coordinatively unsaturated complex, OsCl(CO)(PPh3)2 (2). Complex (2) adds CO to give OsCl(CO)2 (PPh3)2 (3). Crystal structure determinations of 2 and 3 reveal a very marked difference in the Os-B distances found in the five coordinate complex 2 (2.043(4) Å) and the six coordinate complex 3 (2.179(7) Å). In a reaction similar to that used for forming 2 but with 1,3-propanediol replacing 1,2-ethanediol, the product is OsCl(CO)(PPh3)2 (4). The crystal structure for 4 is also reported. 相似文献