共查询到20条相似文献,搜索用时 234 毫秒
1.
Richard D. Adams Mingwei Chen Eszter Trufan 《Journal of organometallic chemistry》2011,696(17):2894-2898
The first examples of bridging tin- and germanium-substituted metallocarboxylate ligands have been obtained from the reactions of Ph3SnOH and Ph3GeOH with Os3(CO)12 under basic conditions. Two products: Os3(CO)10(μ-η2-O=COSnPh3)(μ-OMe), 1 (18% yield) and Os3(CO)10(μ-OMe)(μ-OH), 2 (6.9% yield) were obtained from the reaction of Ph3SnOH with Os3(CO)12 in the presence of [Bu4N]OH in methanol solvent. The compound Os3(CO)10(μ-η2-O=COGePh3)(μ-OMe), 3 (7.3% yield) was prepared similarly by using Ph3GeOH in place of Ph3SnOH. Each of the products 1-3 were characterized structurally by single-crystal X-ray diffraction analysis. Compounds 1 and 3 each contain an μ-η2-O=COMPh3, M = Sn or Ge ligand bridging a pair of osmium atoms in a triosmium carbonyl cluster complex. 相似文献
2.
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
3.
Pek Ke Chan 《Journal of organometallic chemistry》2008,693(15):2641-2644
Reaction of the iridium tetracarbonylate [PPN][Ir(CO)4] (1a) with triphenylcyclopropenyl tetrafluoroborate [C3Ph3][BF4] afforded two dinuclear species Ir2(CO)4(μ,η1:η2-C3Ph3)(μ,η2:η3-C3Ph3) (2) and Ir2(CO)4(μ,η4:η4-C6Ph6) (3a) resulting from the ring opening and in the latter case, coupling of the resulting acyclic, propenyl ligands. The analogous reaction with [PPN][Rh(CO)4] (1b) afforded only the rhodium analogue for 3a. 相似文献
4.
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
5.
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
6.
Reaction of (Ph2P(o-C6H4)CHNCH2CH2)3N with 3 equiv. of Os3(CO)10(NCMe)2 at ambient temperature affords the triple cluster [Os3(CO)10Ph2P(o-C6H4)CHNCH2CH2]3N (1) through coordination of the phosphine and imine groups. Thermolysis of 1 in benzene leads to decarbonylation and C-H/C-N bond activation of the ligand to generate (μ-H)Os3(CO)8(μ3-Ph2P(o-C6H4)CHNCCH2) (2). The molecular structure of 2 has been determined by an X-ray diffraction study. 相似文献
7.
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
8.
Reaction of Os3(CO)10(NCMe)2 and 1,5-cyclooctadiene (C8H12) affords the diene complex Os3(CO)10(η4-C8H12) (1) with the two alkene moieties coordinated to an equatorial and an axial positions of one osmium atom. Thermolysis of 1 in refluxing n-hexane results in a vinylic C-H bond activation to form (μ-H)Os3(CO)9(μ,η4-C8H11) (2) in good isolated yield. The crystal structures of 1 and 2 have been established by an X-ray diffraction study. 相似文献
9.
Reaction of P2Ph4 with the diyne-diol complex [{Co2(CO)6}2(μ-η2:μ-η2-HOCH2CCCCCH2OH)] in toluene at 65 °C gives [{Co2(μ-P2Ph4)(CO)4}{Co2(CO)6}(μ-η2:μ-η2-HOCH2CCCCCH2OH)] (1). Thermolysis of 1 at 95 °C leads to [{Co2(CO)5}2(μ-P2Ph4)(μ-η2:μ-η2-HOCH2CCCCCH2OH)](2) and (μ2-PPh2)(μ2-CO)(CO)7] (3). The structures of 1-3 have been established by X-ray crystallography. In 1, a pseudoequatorial P2Ph4 ligand bridges the cobalt-cobalt bond of a Co2(CC)(CO)4 unit. By contrast, in isomeric 2, a pseudoaxial P2Ph4 ligand spans two Co2(CC)(CO)5 units, a new coordination mode for [{Co2(CO)5L}2(μ-η2:μ-η2-diyne)] complexes. Complex 3 arises from dehydration-cyclocarbonylation of the diyne-diol in 1 to give a 2(5H)-furanone, a process that has not been previously reported. Reaction of HOCH2CCCCCH2OH with [Co2(μ-PPh2)2(CO)6] at 80 °C in toluene gave [Co3(μ-PPh2)3(CO)6], [Co2(CO)6(μ-η2-HOCH2CCCCCH2OH)] and [Co2{μ-η4-PPh2C(CCCH2OH)C(CH2OH)CO}(μ-PPh2)(CO)4] (4). The regiochemistry of 4 was confirmed by X-ray crystallography. 相似文献
10.
Richard D. Adams Burjor Captain Jack L. Smith Jr. 《Journal of organometallic chemistry》2003,683(2):421-429
The reaction of Os3(CO)10(NCMe)2 (1) with an excess of acenaphthylene at room temperature provided the complex Os3(CO)10(μ-H)(μ-η2-C12H7) (2). Compound 2 contains a σ-π coordinated acenaphthyl ligand bridging an edge of the cluster. Compound 2 was converted to the complex Os3(CO)9(μ-H)2(μ3-η2-C12H6) (3) when heated to reflux in a cyclohexane solution. Compound 3 contains a triply bridging acenaphthyne ligand. Compound 3 reacts with acenaphthylene again at 160 °C to yield four new cluster complexes: Os4(CO)12(μ4-η2:η2-C12H6) (4); Os2(CO)6(μ-η4-C24H12) (5); Os3(CO)9(μ-H)(μ3-η4-C24H13) (6); and Os2(CO)5(μ-η4-C24H12)(η2-C12H8) (7). All compounds were characterized crystallographically. Compound 4 is a butterfly cluster of four osmium atoms bridged by a single acenaphthyne ligand. Compounds 5 and 7 are dinuclear osmium clusters containing metallacycles formed by the coupling of two equivalents of acenaphthyne. Compound 6 is a triosmium cluster formed by the coupling of an acenaphthyne ligand to an acenapthyl group that is coordinated to the cluster through a combination of σ and π-bonding. 相似文献
11.
Thermolysis of the mixed-metal cluster PhCCo2MoCp(CO)8 (1) with the diphosphine ligand 2,3-bis(diphenylphosphino)maleic anhydride (bma) in CH2Cl2 leads to the sequential formation of the phosphido-bridged cluster Co2MoCp(CO)5[μ2,η2,η1-C(Ph)CC(PPh2)C(O)OC(O)](μ-PPh2) (3) and the bis(phosphido)-bridged cluster Co2MoCp(CO)4[η3,η1,η1-C(Ph)CCC(O)OC(O)](μ-PPh2)2 (4). 3 and 4 have been isolated and characterized in solution by IR and NMR (1H, 13C, and 31P) spectroscopies, and the solid-state structures have been established by X-ray diffraction analyses. Both clusters contain 48e- and exhibit triangular Co2Mo cores. The structure of 3 reveals the presence of a phosphido moiety that bridges the Co-Co vector and a six-electron μ2,η2,η1-C(Ph)CC(PPh2)C(O)OC(O) ligand that caps one of the Co2Mo faces. The X-ray structure of 4 confirms that the five-electron η3,η1,η1- C(Ph)CCC(O)OC(O) ligand is σ-bound to the two cobalt centers in an η1 fashion and π-coordinated to the molybdenum center through a traditional η3-allylic interaction. The reaction between PhCCo2MoCp(CO)8 and the chiral diphosphine ligand 3,4-bis(diphenylphosphino)-5-methoxy-2(5H)-furanone (bmf) proceeds similarly, furnishing the phosphido-bridged cluster Co2MoCp(CO)5 [μ2,η2,η1-C(Ph)CC(PPh2)C(O)OCH(OMe)](μ-PPh2) (6), followed by conversion to Co2MoCp(CO)4[η3,η1,η1-C(Ph)CCC(O)OCH(OMe)](μ-PPh2)2 (7). The identities of clusters 6 and 7 have been ascertained by solution spectroscopic methods and X-ray crystallography. The overall molecular structure of cluster 6 is similar to that of cluster 3, except that the P-C(furanone ring) bond cleavage occurs with high regioselectivity and high diastereoselectivity. The cleavage of the remaining P-C(furanone ring) bond in cluster 6 gives rise to the bis(phosphido)-bridged cluster 7, whose structure is discussed relative to its bma-derived analogue 4. The diastereoselectivity that accompanies the formation of 6 and 7 is discussed relative to steric effects within the Co2Mo polyhedron. The cyclic voltammetric properties of cluster 3 have been examined, with three well-defined one-electron processes for the 0/+1, 0/−1, −1/−2 redox couples found. The composition of the HOMO and LUMO in 3 was established by extended Hückel MO calculations, with the data discussed relative to the parent tetrahedrane cluster 1. 相似文献
12.
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
13.
Alexander Hildebrandt 《Journal of organometallic chemistry》2011,696(20):3231-3237
The synthesis and properties of heterobimetallic Ti-M complexes of type {[[Ti](μ-η1:η2-CCSiMe3)][M(μ-η1:η2-CCSiMe3)(CO)4]} (M = Mo: 5, [Ti] = (η5-C5H5)2Ti; 6, [Ti] = (η5-C5H4SiMe3)2Ti; M = W: 7, [Ti] = (η5-C5H5)2Ti; 8, [Ti] = (η5-C5H4SiMe3)2Ti) and {[Ti](μ-η1:η2-CCSiMe3)2}MO2 (M = Mo: 13, [Ti] = (η5-C5H5)2Ti; 14, [Ti] = (η5-C5H4SiMe3)2Ti). M = W: 15, [Ti] = (η5-C5H5)2Ti; 16, [Ti] = (η5-C5H4SiMe3)2Ti) are reported. Compounds 5-8 were accessible by treatment of [Ti](CCSiMe3)2 (1, [Ti] = (η5-C5H5)2Ti; 2, [Ti] = (η5-C5H4SiMe3)2Ti) with [M(CO)5(thf)] (3, M = Mo; 4, M = W) or [M(CO)4(nbd)] (9, M = Mo; 10, M = W; nbd = bicyclo[2.2.1]hepta-2,5-diene), while 13-16 could be obtained either by the subsequent reaction of 1 and 2 with [M(CO)3(MeCN)3] (11, M = Mo; 12, M = W) and oxygen, or directly by oxidation of 5-8 with air. A mechanism for the formation of 5-8 is postulated based on the in-situ generation of [Ti](CCSiMe3)((η2-CCSiMe3)M(CO)5), {[Ti](μ-η1:η2-CCSiMe3)2}-M(CO)4, and [Ti](μ-η1:η2-CCSiMe3)((μ-CCSiMe3)M(CO)4) as a result of the chelating effect exerted by the bis(alkynyl) titanocene fragment and the steric constraints imposed by the M(CO)4 entity.The molecular structure of 5 in the solid state were determined by single crystal X-ray diffraction analysis. In doubly alkynyl-bridged 5 the alkynides are bridging the metals Ti and Mo as a σ-donor to one metal and as a π-donor to the other with the [Ti](CCSiMe3)2Mo core being planar. 相似文献
14.
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
15.
Beatriz Alonso Esther Delgado Elisa Hernández Rubén A. Toscano 《Journal of organometallic chemistry》2007,692(23):5117-5124
The compounds [Os3(CO)10{μ,η3-(SCH2CH2SCCHC(O)CHCH(C5H4)Fe (C5H5)}] (2), [Os3(CO)9{μ,η3-(SCH2CH2SCCHC(O)CHCH(C5H4)Fe(C5H5)}] (3) and [Os3(CO)8{μ3,η2-{CCHC(O)CHCH(C5H4)Fe(C5H5)}(SCH2CH2S)}] (4) have been obtained by rupture of S-C bonds in the ketene dithioacetal [C5H5FeC5H4CHCHC(O)CHC(SCH2CH2S)], in their reaction with the activated cluster [Os3(CO)10(NCMe)2]. The presence of an oxametallacycle in these derivatives has been confirmed by an X-ray diffraction analysis. The electrochemical study has indicated the ability of these compounds to modify the electrode surfaces. 相似文献
16.
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
17.
Arun K. Raha Md. Manzurul Karim Noorjahan Begum Edward Rosenberg 《Journal of organometallic chemistry》2008,693(24):3613-3621
Treatment of unsaturated [Os3(CO)8{μ3-Ph2PCH2P(Ph)C6H4}(μ-H)] (2) with tBuNC at room temperature gives [Os3(CO)8(CNBut)){μ3-Ph2PCH2P(Ph)C6H4}(μ-H)] (3) which on thermolysis in refluxing toluene furnishes [Os3(CO)7(CNBut){μ3-Ph2PCHP(Ph)C6H4}(μ-H)2] (4). Reaction of the labile complex [Os3(CO)9(μ-dppm)(NCMe)] (5) with tBuNC at room temperature affords the substitution product [Os3(CO)9(μ-dppm)(CNBut)] (6). Thermolysis of 6 in refluxing toluene gives 4. On the other hand, the reaction of unsaturated [Os3(CO)9{μ3-η2-C7H3(2-Me)NS}(μ-H)] (7) with tBuNC yields the addition product [Os3(CO)9(CNBut){μ-η2-C7H3(2-Me)NS}(μ-H)] (8) which on decarbonylation in refluxing toluene gives unsaturated [Os3(CO)8(CNBut){μ3-η2-C7H3(2-Me)NS}(μ-H)] (9). Compound 9 reacts with PPh3 at room temperature to give the adduct [Os3(CO)8(PPh3)(CNBut){μ-η2-C7H3(2-Me)NS(μ-H)] (10). Compound 8 exists as two isomers in solution whereas 10 occurs in four isomeric forms. The molecular structures of 3, 6, 8, and 10 have been determined by X-ray diffraction studies. 相似文献
18.
Mohammad A. Rahman Shishir Ghosh Graeme Hogarth Ebbe Nordlander 《Journal of organometallic chemistry》2011,696(2):607-612
Addition of tri(2-furyl)phosphine, PFu3, to [Os3(CO)10(μ-H)2] at room temperature gives [HOs3(CO)10(PFu3)(μ-H)] (1), while in refluxing toluene the same reactants afford [Os3(CO)9{μ3-PFu2(C4H2O)}(μ-H)] (2) resulting from orthometallatation of a furyl ring. Reaction of PFu3 with [Os3(CO)10−n(NCMe)n] (n = 0, 1, 2) affords the substituted clusters [Os3(CO)12−n(PFu3)n] (n = 1-3) (3-5), the phosphine ligands occupying equatorial position in all cases. Heating [Os3(CO)11(PFu3)] (3) in refluxing octane gives [Os3(CO)9(μ3-PFu)(μ3-η2-C4H2O)] (6) which results from both carbon-hydrogen and carbon-phosphorus bond activation and contains both μ3-η2-furyne and furylphosphinidene ligands. All new clusters have been characterized by spectroscopic methods together with single crystal X-ray diffraction for 2, 3 and 6. 相似文献
19.
Victor Wee Lin Ng 《Journal of organometallic chemistry》2004,689(20):3210-3217
The facile reaction of [CpCr(CO)3]2 (Cp = η5-C5H5) (1) with one mole equivalent of 2,2′-dithiodipyridine ((C5H4NS)2(SPy)2) at ambient temperature led to the isolation of dark brown crystalline solids of CpCr(CO)2(η2-SPy) (2) in ca. 72% yield. 2 undergoes quantitative conversion to CpCrCl2(η1-SPyH) (3) with HCl. The reaction 1 with one mole equivalent of 2-mercaptopyrimidine (C4H3N2SHHSPym) at ambient temperature led to the isolation of reddish-brown crystalline solids of CpCr(CO)2(η2-SPym) (4) and green solids of CpCr(CO)3H (5) in yields of ca. 42% and 46%, respectively. Reaction of 4 with HCl and subsequent workup in acetonitrile resulted in the cleavage of the thiolate ligand, giving the 15-electron chromium(III) species CpCrCl2(CH3CN) (6) and free 2-mercaptopyrimidine. The complexes 2-4 have been determined by single X-ray diffraction analysis. 相似文献
20.
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