共查询到20条相似文献,搜索用时 640 毫秒
1.
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
2.
Kouki Matsubara Shoji Mima Takashi Oda Hideo Nagashima 《Journal of organometallic chemistry》2002,650(1-2):96-107
Novel isonitrile derivatives of a diruthenium carbonyl complex, (μ2,η3:η5-guaiazulene)Ru2(CO)5 (2), were synthesized by substitution of a CO ligand by an isonitrile, and were subjected to studies on thermal and photochemical haptotropic interconversion. Treatment of 2 (a 45:55 mixture of two haptotropic isomers, 2-A and 2-B) with RNC at room temperature resulted in coordination of RNC and alternation of the coordination mode of the guaiazulene ligand to form (μ2,η1:η5-guaiazulene)Ru2(CO)5(CNR), 5d–5f, [5d; R=tBu, 5e; 2,4,6-Me3C6H2, or 5f; 2,6-iPr2C6H3] in moderate to good yields. Thermal dissociation of a CO ligand from 5 at 60 °C resulted in quantitative formation of a desirable isonitrile analogue of 2, (μ2,η3:η5-guaiazulene)Ru2(CO)4(CNR), 4d–4f, [4d; R=tBu, 4e; 2,4,6-Me3C6H2, or 4f; 2,6-iPr2C6H3], as a 1:1 mixture of the two haptotropic isomers. A direct synthetic route from 2 to 4d–4f was alternatively discovered; treatment of 2 with one equivalent of RNC at 60 °C gave 4d–4f in moderate yields. All of the new compounds were characterized by spectroscopy, and structures of 5d (R=tBu) and 4d-A (R=tBu) were determined by crystallography. Thermal and photochemical interconversion between the two haptotropic isomers of 4d–4f revealed that the isomer ratios in the thermal equilibrium and in the photostatic state were in the range of 48:52–54:46. 相似文献
3.
Rainer Bartsch Peter B. Hitchcock John F. Nixon 《Journal of organometallic chemistry》1988,340(3):C37-C39
Syntheses of the novel sandwich compounds [Fe(η5-C5H5)(η5-C2R2P3)] and [Fe(η5-C5H5)(η5-C2R2P3)W(CO)5], (R = But), are described. The mode of attachment of the [W(CO)5] fragment in the latter compound has been determined by NMR and single crystal X-ray diffraction studies. 相似文献
4.
The complex [MoW(μ-CC6H4Me-4)(CO)2(η7-C7H7)(η5-C2B9H10Me)] reacts with diazomethane in Et2O containing EtOH to afford the dimetal compound [MoW(OEt)(μ-CH2){μ-C(C6H4Me-4)C(Me)O}(η7-C7H7)(η5-C2B9H10Me)]. The structure of this product was established by X-ray diffraction. The Mo---W bond [2.778(4) Å] is bridged by a CH2 group [μ-C---Mo 2.14(3), μ-C---W 2.02(3) Å] and by a C(C6H4Me-4)C(Me)O fragment [Mo---O 2.11(3), W---O 2.18(2), Mo---C(C6H4Me-4) 2.41(3), W---C(C6H4Me-4) 2.09(3), Mo---C(Me) 2.26(3) Å]. The molybdenum atom is η7-coordinated by the C7H7 ring and the tungsten atom is η5-coordinated by the open pentagonal face of the nido-icosahedral C2B9H10Me cage. The tungsten atom also carries a terminally bound OEt group [W---O 1.88(3) Å]. The 1H and 13C-{1H} NMR data for the dimetal compound are reported and discussed. 相似文献
5.
Erwan Le Grognec Rinaldo Poli Philippe Richard Rosa Llusar Santiago Uriel 《Journal of organometallic chemistry》2001,640(1-2):113-120
The reactions of the half-sandwich molybdenum(III) complexes CpMo(η4-C4H4R2)(CH3)2, where Cp=η5-C5H5 and R=H or CH3, with equimolar amounts of B(C6F5)3 have been investigated in toluene. EPR monitoring shows the formation of an addition product which does not readily react with Lewis bases such as ethylene, pyridine, or PMe3. The analysis of the EPR properties and the X-ray structure of a decomposition product obtained from dichloromethane, [CpMo(η4-C4H6)(μ-Cl)(μ-CH2)(O)MoCp][CH3B(C6F5)3], indicate that the borane attack has occurred at the methyl position. 相似文献
6.
The synthesis and reactivity of {(η5-C5H4SiMe3)2Ti(CCSiMe3)2} MCl2 (M = Fe: 3a; M = Co: 3b; M = Ni: 3c) is described. The complexes 3 are accessible by the reaction of (η5-C5H4SiMe3) 2Ti(CSiMe3)2 (1) with equimolar amounts of MCl2 (2) (M = Fe, Co, Ni). 3a reacts with the organic chelat ligands 2,2′-dipyridyl (dipy) (4a) or 1,10-phenanthroline (phen) (4b) in THF at 25°C to afford in quantitative yields (η5-C5H4SiMe3)2Ti(CSiMe3)2 (1) and [Fe(dipy)2]Cl2 (5a) or [Fe(phen)2]Cl2 (5b). 1/n[CuIHal]n (6) or 1/n[AgIHal]n (7) (Hal = Cl, Br) react with {(η5 -C5H4SiMe3)2Ti(CCSiMe3)2}FeCl2 (3a), by replacement of the FeCl2 building block in 3a, to yield the compounds {(η5-C5H4SiMe3)2Ti(C CSiMe3)2}CuIHal (8) or {(η5-C5H4SiMe3)2Ti(CSiMe3)2}AgIHal (9) (Hal = Cl, Br), respectively. In 8 and 9 each of the two Me3SiCC-units is η2-coordinated to monomeric CuI Hal or AgIHal moieties. Compounds 8 and 9 can also be synthesized by the reaction of (η5-C5H4SiMe3)2 Ti(CSiMe3)2 (1) with 1/n[CuIHal]n (6) or 1/n [AgIHal]n (7) in excellent yields. All new compounds have been characterized by analytical and spectroscopic data (IR, 1H-NMR, MS). The magnetic moments of compounds 3 were measured. 相似文献
7.
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
8.
The interaction of [(η5-C5H4But)2YbCl · LiCl] with one equivalent of Li[(CH2) (CH2)PPh2] in tetrahydrofuran gave [Ph2PMe2][(η5-C5H4But)2Li] (1) and [(η5-C5H4But)2Yb(Cl)CH2P(Me)Ph2] (2) in 10% and 30% yields, respectively. 1 could also be prepared in 70% yield from the reaction of [Ph2PMe2][CF3SO3] with two equivalents of (C5H4But)Li. Both compounds have been fully characterized by analytical, spectroscopic and X-ray diffraction methods. The solid state structure of 1 reveals a sandwich structure for the [(η5-C5H4But)2Li]− anion. 相似文献
9.
Kathryn M. Carlson-Day Thomas E. Concolino Judith L. Eglin
Chun Lin
Tong RenEdward J. Valente
Jeffrey D. Zubkowski
《Polyhedron》1996,15(24):4469-4478The singlet-triplet separations for the edge-sharing bioctahedral (ESBO) complex W2(μ-H)(μ-Cl)(Cl4(μ-dppm)2 · (THF)3 (II) has been studied by 31P NMR spectroscopy. The structural characterization of [W2(μ-H)2(μ-O2CC6H5)2Cl2(P(C6H5)3)2] (I) by single-crystal X-ray crystallography has allowed the comparison of the energy of the HOMOLUMO separation determined using the Fenske-Hall method for a series of ESBO complexes with two hydride bridging atoms, two chloride bridging atoms and the mixed case with a chloride and hydride bridging atom. The complex representing the mixed case, [W2(μ-H)(μ-Cl)Cl4(μ-dppm)2 · (THF)3] (II), has been synthesized and the value of −2J determined from variable-temperature 31P NMR spectroscopy. 相似文献
10.
Mark J. Alder Wendy I. Cross Kevin R. Flower R. G. Pritchard 《Journal of organometallic chemistry》1999,590(2):7813-128
Reaction of Na[MCl4] (M=Pd or Pd) with the azo-containing phosphines Ph2P{1-(4-RC6H4N2)-2-OR′-C10H5} {R=Me (I), NMe2 (II); R′=C(O)Me} affords the complexes [MCl2L2] (1–4) in good yield. Complexes 1–4 have all been fully characterised by elemental analysis, 1H-, 13C{1H}-, and 31P{1H}-NMR spectroscopy and UV–visible spectroscopy. The use of 1 in the Heck reaction has been investigated and shown to effect up to 1000 turnovers. 相似文献
11.
Won Seok Seo Youn Jaung Cho Sung Cheol Yoon Joon T. Park Younbong Park 《Journal of organometallic chemistry》2001,640(1-2):79-84
Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C5H5)CH2(2-C4H3NH) (2) with Ti(NMe2)4 affords bis(dimethylamido)titanium complex [(η5-C5H4)CH2(2-C4H3N)]Ti(NMe2)2 (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH2(2-C4H3NH)}2C5H4 (4), undergoes an analogous reaction with Ti(NMe2)4 to give [1,3-{CH2(2-C4H3N)}2(η5-C5H3)]Ti(NMe2) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies. 相似文献
12.
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
13.
Alberto R. Dias Adelino Galvo M. Helena Garcia Maria J. Villa de Brito 《Journal of organometallic chemistry》2001,620(1-2):276-281
An unexpected trimanganese(I) tetrathiolate-bridged complex, [Mn3(CO)9(μ-SC6H5)4]−, with an incomplete cubane structure, was obtained by thermal reaction of [Mn2(CO)10] with [Mo(η5-C5H5)2(SC6H5)2]. The structure, established by single-crystal X-ray diffraction studies, shows the cation, [Mo(η5-C5H5)2(H)CO]+, directed towards the vacant site of the cubane structure. Possible routes by which the anion and the cation could be formed are discussed. 相似文献
14.
Maria Augusta Antunes ngela Domingos Isabel Cordeiro dos Santos Nomia Marques Josef Takats 《Polyhedron》2005,24(18):3038-3045
Reaction of [U(TpMe2)2(NR2)] (R = Ph, SiMe3) with protic substrates such as 2,4,6-trimethylphenol (HOC6H2-2,4,6-Me3), 3,5-dimethylpyrazole (Hdmpz), 2-mercaptopyridine (HSC5H4N) and phenylacetylene (HCCPh) afforded the corresponding [U(TpMe2)2(OAr)] (Ar = C6H2-2,4,6-Me3) (1), [U(TpMe2)2(dmpz)] (2), [U(TpMe2)2(η2-SC5H4N)] (3), and [U(TpMe2)2(CCPh)] (4) compounds. Reaction of [U(TpMe2)2(NR2)] with Me3SnCl or Me3SiBr gave [U(TpMe2)2Cl] (5) and [U(TpMe2)2Br] (6), respectively, in high yield. The amido precursors failed to react with cyclopentadiene, but metathesis of [U(TpMe2)2I] with NaCp yielded [U(κ3-TpMe2)(κ2-TpMe2)(η5-Cp)] (7). Thermolysis of 7 resulted in oxidation of the metal centre and redistribution of the ligands, giving [UCp3(dmpz)] (8), pyrazabole (9) and [U(TpMe2)(dmpz)3] (10). The complexes have been fully characterized by spectroscopic methods and the structures of 1, 2, and 5 were confirmed by X-ray crystallographic studies. In the solid state the complexes exhibit distorted pentagonal bipyramidal geometries. 相似文献
15.
A high yield synthesis of the carbonyl dithiocarbamato derivative Fe(CO)2(η2-S2CNMe2)2 and Fe(η2-S2CNMe2)2 by photolysis with visible light of solutions containing Fe2(CO)9 or Fe3(CO)12 and [(η5-C5H5)(CO)3W(η1-SCSNMe2)] is reported. 相似文献
16.
Reaction of C5H4(SiMe3)2 with Mo(CO)6 yielded [(η5-C5H3(SiMe3)2)Mo(CO)3]2, which on addition of iodine gave [(η5-C5H3(SiMe3)2Mo(CO)3I]. Carbonyl displacement by a range of ligands: [L = P(OMe)3, P(OPri)3,P(O-o-tol)3, PMe3, PMe2Ph, PMePh2, PPh3, P(m-tol)3] gave the new complexes [(η5-C5H3(SiMe3)2 MO(CO)2(L)I]. For all the trans isomer was the dominant, if not exclusive, isomer formed in the reaction. An NOE spectral analysis of [(η5-C5H3(SiMe3)2)Mo(CO)2(L)I] L = PMe2Ph, P(OMe)3] revealed that the L group resided on the sterically uncongested side of the cyclopentadienyl ligand and that the ligand did not access the congested side of the molecule. Quantification of this phenomenon [L = P(OMe)3] was achieved by means of the vertex angle of overlap methodology. This methodology revealed a steric preference with the trans isomer (less congestion of CO than I with an SiMe3 group) being the more stable isomer for L = P(OMe)3. 相似文献
17.
Reaction of optically active ketone complexes (+)-(R)-[(η5-C5H5)Re(NO)-(PPh3)(η1-O=C(R)(CH3)]+ BF4− (R = CH2CH3, CH(CH3)2m C(CH3)3, C6H5) with K(s-C4H9)3BH gives alkoxide complexes (+)-(RS)-(η5-C5H5)Re(NO)(PPh3)-(OCH(R)CH3) (73–90%) in 80–98% de. The alkoxide ligand is then converted to Mosher esters (93–99%) of 79–98% de. 相似文献
18.
[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
19.
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
20.
María P. García M. Victoria Jimnez Teresa Luengo Luis A. Oro 《Journal of organometallic chemistry》1996,510(1-2):189-195
The reaction of the anionic mononuclear rhodium complex [Rh(C6F5)3Cl(Hpz)]t- (Hpz = pyrazole, C3H4N2) with methoxo or acetylacetonate complexes of Rh or Ir led to the heterodinuclear anionic compounds [(C6F5)3Rh(μ-Cl)(μ-pz)M(L2)] [M = Rh, L2 = cyclo-octa-1,5-diene, COD (1), tetrafluorobenzobarrelene, TFB (2) or (CO)2 (4); M = Ir, L2 = COD (3)]. The complex [Rh(C6F5)3(Hbim)]− (5) has been prepared by treating [Rh(C6F5)3(acac)]− with H2bim (acac = acetylacetonate; H2bim = 2,2′-biimidazole). Complex 5 also reacts with Rh or Ir methoxo, or with Pd acetylacetonate, complexes affording the heterodinuclear complexes [(C6F5)3Rh(μ-bim)M(L2)]− [M = Rh, L2 = COD (6) or TFB (7); M = Ir, L2 = COD (8); M = Pd, L2 = η3-C3H5 (9)]. With [Rh(acac)(CO)2], complex 5 yields the tetranuclear complex [{(C6F5)3Rh(μ-bim)Rh(CO)2}2]2−. Homodinuclear RhIII derivatives [{Rh(C6F5)3}2(μ-L)2]·- [L2 = OH, pz (11); OH, StBu (12); OH, SPh (13); bim (14)] have been obtained by substitution of one or both hydroxo groups of the dianion [{Rh(C6F5)3(μ-OH)}2]2− by the corresponding ligands. The reaction of [Rh(C6F5)3(Et2O)x] with [PdX2(COD)] produces neutral heterodinuclear compounds [(C6F5)3Rh(μ-X)2Pd(COD)] [X = Cl (15); Br (16)]. The anionic complexes 1–14 have been isolated as the benzyltriphenylphosphonium (PBzPh3+) salts. 相似文献