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1.
Rubén A. Machado David Rivillo Lindora D’Ornelas Reinaldo Atencio Esperanza Galarza 《Journal of organometallic chemistry》2004,689(15):2486-2493
The reaction of the labile compound [Re2(CO)8(CH3CN)2] with trans-1,2-bis(2-pyridyl)ethene (C12H10N2) at room temperature in tetrahydrofuran affords the compounds [Re2(μ:η3-C12H10N2)(CO)8] (1) and the oxidative addition product [Re2(μ-H)(μ:η3-C12H9N2)(CO)7] (2). When the reaction is carried out at temperatures of refluxing tetrahydrofuran, besides compounds 1 and 2, the oxidative addition product [Re2(μ-H)(μ:η4-C12H9N2)(CO)6] (3), the insertion product [Re2(μ:η4-C12H10N2)(CO)8] (4) and [Re2(μ:η6-C24H18N4)(CO)6] (5) are obtained. Compound 5 contains the organic ligand rtct-tetrakis(2-pyridyl)cyclobutandiyl which is derived from a [2 + 2] cycloaddition of 1,2-bis(2-pyridyl)ethene mediated by its coordination to the bimetallic framework. The molecular structures of 1, 2, 4 and 5 were confirmed by X-ray crystallographic studies. 相似文献
2.
Padavattan Govindaswamy Georg Süss-Fink Ji?í Ludvík 《Journal of organometallic chemistry》2007,692(8):1661-1671
The mononuclear complexes [(η5-C5Me5)IrCl(L1)] (1), [(η5-C5Me5)RhCl(L1)] (2), [(η6-p-PriC6H4Me)RuCl(L1)] (3) and [(η6-C6Me6)RuCl(L1)] (4) have been synthesised from pyrazine-2-carboxylic acid (HL1) and the corresponding complexes [{(η5-C5Me5)IrCl2}2], [{(η5-C5Me5)RhCl2}2], [{(η6-p-PriC6H4Me)RuCl2}2], and [{(η6-C6Me6)RuCl2}2], respectively. The related dinuclear complexes [{(η5-C5Me5)IrCl}2(μ-L2)] (5), [{(η5-C5Me5)RhCl}2(μ-L2)] (6), [{(η6-p-PriC6H4Me)RuCl}2(μ-L2)] (7) and [{(η6-C6Me6)RuCl}2(μ-L2)] (8) have been obtained in a similar manner from pyrazine-2,5-dicarboxylic acid (H2L2). Compounds isomeric to the latter series, [{(η5-C5Me5)IrCl}2(μ-L3)] (9), [{(η5-C5Me5)RhCl}2(μ-L3)] (10), [{(p-PriC6H4Me)RuCl}2(μ-L3)] (11) and [{(η6-C6Me6)RuCl}2(μ-L3)] (12), have been prepared by using pyrazine-2,3-dicarboxylic acid (H2L3) instead of H2L2. The molecular structures of 2 and 3, determined by X-ray diffraction analysis, show the pyrazine-2-carboxylato moiety to act as an N,O-chelating ligand, while the structure analyses of 5-7, confirm that the pyrazine-2,5-dicarboxylato unit bridges two metal centres. The electrochemical behaviour of selected representatives has been studied by voltammetric techniques. 相似文献
3.
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
4.
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
5.
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
6.
You-Chen Hsiao 《Tetrahedron》2008,64(40):9507-9514
Several cobalt-containing P,N-ligands, alkyne-bridged dicobalt phosphines [(μ-PPh2CH2PPh2)Co2(CO)4(μ,η-Me2NCH2CCPR2)] (4a: R=tBu; 4b: R=Ph; 4c: R=Cy), were prepared from the reactions of corresponding alkynylphosphines Me2NCH2CCPR2 (2a: R=tBu; 2b: R=Ph; 2c: R=Cy) with a dppm-bridged dicobalt complex [Co2(CO)6(μ-P,P-PPh2CH2PPh2)] 3. A unique palladium complex ion pair [(μ-PPh2CH2PPh2)Co2(CO)4(μ,η-Me2NCH2CCP (tBu)2)Pd(η3-C3H5)]+[(η3-C3H5)PdCl2]−7a was obtained from the reaction of 4a with [(η3-C3H5)PdCl]2. Compounds 4a, 4b, and 4c are authentic cobalt-containing P,N-bidentate ligands and can be used for ligation of palladium from various sources such as Pd(OAc)2 or [(η3-C3H5)PdCl]2. Satisfactory efficiencies were observed for the amination reactions of aryl bromides with morpholine employing either a 4a-chelated palladium complex formed in situ or pre-formed 7a as the catalytic precursor. 相似文献
7.
Santiago Gómez-Ruiz Jesús Ceballos-Torres Mariano Fajardo Zorica D. Jurani? 《Journal of organometallic chemistry》2011,696(20):3206-3213
The reaction of 2,6-dimethoxypyridine-3-carboxylic acid (DMPH) with different precursors [Ti(η5-C5H5)2Cl2], [Ti(η5-C5H4Me)2Cl2], [Ti(η5-C5H4SiMe3)(η5-C5H5)Cl2], [Ti(η5-C5Me5)Cl3], SnMe3Cl and GatBu3 yielded the complexes [Ti(η5-C5H5)2(DMP-κO)2] (1), [Ti(η5-C5H4Me)2(DMP-κO)2] (2), [Ti(η5-C5H4SiMe3)(η5-C5H5)(DMP-κO)2] (3), [Ti(η5-C5Me5)(DMP-κ2O,O′)3] (4), [SnMe3(μ-DMP-κO:κO′)]∞ (5), and [GatBu2(μ-DMP-κO:κO′)]2 (6). 1-6 have been characterized by spectroscopic methods and the molecular structure of the complexes 1, 2, 3, 5 and 6 have been determined by X-ray diffraction studies. The cytotoxic activity of 1-6 was tested against the tumour cell lines human adenocarcinoma HeLa, human myelogenous leukaemia K562, human malignant melanoma Fem-x and human breast carcinoma MDA-MB-361. The results of this study show a higher cytotoxicity of the tin(IV) and gallium(III) derivatives in comparison to their titanium(IV) counterparts. Furthermore, the different titanium compounds showed differences in their cytotoxicities with a higher activity of complex 4 (mono-(cyclopentadienyl) derivative) compared to that of 1-3 (bis-(cyclopentadienyl) complexes). A qualitative UV-vis study of the interactions of these complexes with DNA has also been carried out. 相似文献
8.
Noorjahan Begum Mohammad Islam Dalia Rokhsana 《Journal of organometallic chemistry》2004,689(16):2633-2640
The valence saturated benzothiazolide triosmium cluster [Os3(CO)10(μ-η2-C7H4NS)(μ-H)] (1) reacts with tetramethylthiourea in refluxing toluene to give [Os3(CO)8(μ-η2-C7H4NS)(η2-SCNMe2NMeCH2)(μ-H)2] (5), which exists as a mixture of two isomers in solution, whereas the electron-deficient cluster [Os3(CO)9(μ3-η2-C7H4NS)(μ-H)] (2) reacts with tetramethylthiourea in refluxing cyclohexane to give two new compounds [Os3(CO)8(μ-η2-C7H4NS)(η2-SCNMe2NMeCH2)(μ-H)2] (6) and [Os3(CO)9(μ-η2-C7H4NS)(η1-SC(NMe2)2)(μ-H)] (7). In contrast, the reaction of [Os3(CO)9(μ3-η2-C7H3(2-CH3)NS)(μ-H)](3) with tetramethylthiourea in refluxing cyclohexane at 81 °C, gives only [Os3(CO)9(μ-η2-C7H3(2-CH3)NS)(η1-SC(NMe2)2)(μ-H)] (8) in 15% yield. Compound 7 converts into 6 in refluxing toluene whereas a similar thermolysis of 8 results non-specific decomposition. All the compounds have been characterized by elemental analysis, IR, 1H NMR and mass spectroscopic data together with single crystal X-ray diffraction analysis for 5 and 7. Both compounds 5 and 6 contain a cyclometallated tetramethylthiourea ligand which is chelating at the rear osmium atom and are structurally very similar. In 5, the benzothiazolide ligand is coordinated to Os3 triangle via the nitrogen lone pair and C(2) carbon atom of the heterocyclic ring whereas in 6 the ligand is coordinated to the Os3 triangle via the nitrogen lone pair and the C(7) carbon atom of carbocyclic ring. In 7 and 8, the tetramethylthiourea ligand is coordinated at an equatorial site of the osmium atom which is also bound to the nitrogen atom of the benzothiazolide ligand. 相似文献
9.
The clusters [Ru4(μ-CO)(CO)10(μ4-η1:η2:η1:η2-C5H6)2] (1), [Ru4(CO)8(μ4-η4:η1:η1:η1:η3-C10H12)(μ3-η3:η2:η1-C5H6)] (2) and [Ru4(CO)10(μ4-η4:η1:η1:η3:η1-C15H16)] (3) have been prepared from the reaction of [H4Ru4(CO)12] with 1-penten-3-yne. This reaction is observed to proceed with dimerization and trimerization through the triple bonds. The products were characterized spectroscopically by 1H- and 13C-NMR. X-ray crystal structures of compounds 1 and 2 are also described. 相似文献
10.
Paul R. Raithby Jack Lewis Catherine A. Morewood M. Carmen Ramirez de Arellano Gregory P. Shields 《Journal of Cluster Science》2006,17(1):13-26
Thermolysis of [Ru3(CO)12] in cyclohexene for 24 h affords the complexes [Ru(CO)3(η4-C6H8)] (1), [Ru3H2(CO)9(μ2-η1:η2:η1-C6H8)] (2), [Ru4(CO)12(μ4-C6H8)] (3) [Ru4(CO)9(μ4-C6H8)(η6-C6H6)] (4a and 4b, two isomers) and [Ru5(CO)12(μ4-η2-C6H8)(η4-C6H8)] (5), where 1, 3, 4a and 4b have been previously characterised as products of the thermolysis of [Ru3(CO)12] with cyclohexa-1,3-diene. The molecular structures of the new clusters 2 and 5 were determined by single-crystal X-ray crystallography, showing that two conformational polymorphs of 5 exist in the solid state, differing in the orientation of the cyclohexa-1,3-diene ligand on a ruthenium vertex. 相似文献
11.
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
12.
Shariff E. Kabir Faruque Ahmed Mohammad R. Hassan Sergey V. Lindeman Tasneem A. Siddiquee 《Journal of organometallic chemistry》2007,692(20):4337-4345
Reactions of the labile compound [Re2(CO)8(MeCN)2] with thiazole and 4-methylthiazole in refluxing benzene afforded the new compounds [Re2(CO)7{μ-2,3-η2-C3H(R)NS}{η1-NC3H2(4-R)S}(μ-H)] (1, R = H; 2, R = CH3), [Re2(CO)6{μ-2,3-η2-C3H(R)NS}{η1-NC3H2(4-R)S}2(μ-H)] (3, R = H; 4, R = CH3) and fac-[Re(CO)3(Cl){η1-NC3H2(4-R)S}2] (5, R = H; 6, R = CH3). Compounds 1 and 2 contain two rhenium atoms, one bridging thiazolide ligand, coordinated through the C(2) and N atoms and a η1-thiazole ligand coordinated through the nitrogen atom to the same Re as the thiazolide nitrogen. Compounds 3 and 4 contain a Re2(CO)6 group with one bridging thiazolide ligand coordinated through the C(2) and N atoms and two N-coordinated η1-thiazole ligands, each coordinated to one Re atom. A hydride ligand, formed by oxidative-addition of C(2)-H bond of the ligand, bridges Re-Re bond opposite the thiazolide ligand in compounds 1-4. Compound 5 contains a single rhenium atom with three carbonyl ligands, two N-coordinated η1-thiazole ligands and a terminal Cl ligand. Treatment of both 1 and 2 with 5 equiv. of thiazole and 4-methylthiazole in the presence of Me3NO in refluxing benzene afforded 3 and 4, respectively. Further activation of the coordinated η1-thiazole ligands in 1-4 is, however, unsuccessful and results only nonspecific decomposition. The single-crystal XRD structures of 1-5 are reported. 相似文献
13.
Keith P Carruthers 《Journal of organometallic chemistry》2004,689(4):848-859
Protonation of the cycloheptatriene complex [W(CO)3(η6-C7H8)] with H[BF4] · Et2O in CH2Cl2 affords the cycloheptadienyl system [W(CO)3(η5-C7H9)][BF4] (1). Complex 1 reacts with NaI to yield [WI(CO)3(η5-C7H9)], which is a precursor to [W(CO)2(NCMe)3(η3-C7H9)][BF4], albeit in very low yield. The dicarbonyl derivatives [W(CO)2L2(η5-C7H9)]+ (L2=2PPh3, 4, or dppm, 5) were obtained, respectively, by H[BF4] · Et2O protonation of [W(CO)2(PPh3)(η6-C7H8)] in the presence of PPh3 and reaction of 1 with dppm. The X-ray crystal structure of 4 (as a 1/2 CH2Cl2 solvate) reveals that the two PPh3 ligands are mutually trans and are located beneath the central dienyl carbon and the centre of the edge bridge. The first examples of cyclooctadienyl tungsten complexes [WBr(CO)2(NCMe)2(1-3-η:5,6-C8H11)] (6) and [WBr(CO)2(NCMe)2(1-3-η:4,5-C8H11)] (7) were synthesised by reaction of [W(CO)3(NCR)3] (R=Me or Prn) with 3-Br-1,5-cod/6-Br-1,4-cod or 5-Br-1,3-cod/3-Br-1,4-cod (cod=cyclooctadiene), respectively. Complexes 6 and 7 are precursors to the pentahapto-bonded cyclooctadienyl tungsten species [W(CO)2(dppm)(1-3:5,6-η-C8H11)][BF4] and [W(CO)2(dppe)(1-5-η-C8H11)][BF4] · CH2Cl2. 相似文献
14.
Sanjay K Singh 《Journal of organometallic chemistry》2004,689(12):2073-2079
The synthesis and characterization of binuclear ruthenium complexes [{(η6-C6H6)Ru}2(μ-bsh)2] (1), [{(η6-C10H14)Ru}2(μ-bsh)2] (2), [{(η6-C6Me6)Ru}2(μ-bsh)2] (3), and rhodium complex [{(η5-C5Me5)RhCl}2(μ-bsh)] (4) (bsh=N,N′-bis(salicylidine)-hydrazine dianion) are reported. The complexes have been fully characterized by analytical and spectral techniques and unusual coordination mode of the ligand H2bsh has been confirmed by single crystal X-ray analysis of the complex 2. Structural data revealed extensive inter- and intra-molecular C-H?O and C-H?π interactions and involvement of methyl and isopropyl hydrogen from the p-cymene in hydrogen bonding. 相似文献
15.
Chih-Yu Wu Wen-Shu Hwang Huang-Shiuh Chen 《Journal of organometallic chemistry》2004,689(13):2192-2200
The reaction of N-(5-methyl-2-thienylmethylidene)-2-thiolethylamine (1) with Fe2(CO)9 in refluxing acetonitrile yielded di-(μ3-thia)nonacarbonyltriiron (2), μ-[N-(5-methyl-2-thienylmethyl)-η1:η1(N);η1:η1(S)-2-thiolatoethylamido]hexacarbonyldiiron (3), and N-(5-methyl-2-thienylmethylidene)amine (4). If the reaction was carried out at 45 °C, di-μ-[N-(5-methyl-2-thienylmethylidene)-η1(N);η1(S)-2-thiolethylamino]-μ-carbonyl-tetracarbonyldiiron (5) and trace amount of 4 were obtained. Stirring 5 in refluxing acetonitrile led to the thermal decomposition of 5, and ligand 1 was recovered quantitatively. However, in the presence of excess amount of Fe2(CO)9 in refluxing acetonitrile, complex 5 was converted into 2-4. On the other hand, the reaction of N-(6-methyl-2-pyridylmethylidene)-2-thiolethylamine (6) with Fe2(CO)9 in refluxing acetonitrile produced 2, μ-[N-(6-methyl-2-pyridylmethyl)-η1 (Npy);η1:η1(N); η1:η1(S)-2-thiolatoethylamido]pentacarbonyldiiron (7), and μ-[N-(6-methyl-2-pyridylmethylidene)-η2(C,N);η1:η1(S)-2- thiolethylamino]hexacarbonyldiiron (8). Reactions of both complex 7 and 8 with NOBF4 gave μ-[(6-methyl-2-pyridylmethyl)-η1(Npy);η1:η1(N);η1:η1(S)-2-thiolatoethylamido](acetonitrile)tricarbonylnitrosyldiiron (9). These reaction products were well characterized spectrally. The molecular structures of complexes 3, 7-9 have been determined by means of X-ray diffraction. Intramolecular 1,5-hydrogen shift from the thiol to the methine carbon was observed in complexes 3, 7, and 9. 相似文献
16.
Trimethylstannyl (diphenylphosphino)acetate (1), which is readily accessible from potassium (diphenylphosphino)acetate and trimethylstannyl chloride, may serve as the source of (diphenylphosphino)acetate anion in the preparation of coordination compounds. Thus, the reactions between [M(cod)Cl2] (M = Pd and Pt; cod = η2:η2-cycloocta-1,5-diene) and two equivalents of 1 give [M(Ph2PCH2CO2-κ2O,P)2] (2 and 3), while the reaction of [{Pd(μ-Cl)Cl(PFur3)}2] (4; Fur = 2-furyl) with one equivalent of 1 yields [SP-4-3]-[PdCl(Ph2PCH2CO2-κ2O,P)(PFur3)] (5). The reactions of 1 with the dimers [{Rh(η5-C5Me5)Cl(μ-Cl)}2] and [{Ru(η6-1,4-MeC6H4(CHMe2))Cl(μ-Cl)}2] (at 1-to-metal ratio 1:1) produce O,P-chelated complexes as well, albeit as stable adducts with the liberated Me3SnCl: [RhCl(η5-C5Me5)(Ph2PCH2CO2-κ2O,P)] · Me3SnCl (6) and[RuCl(η6-1,4-MeC6H4(CHMe2))(Ph2PCH2CO2-κ2O,P)] · Me3SnCl (8). The related complexes with P-monodentate (diphenylphosphino)acetic acid, [RhCl2(η5-C5Me5)(Ph2PCH2CO2H-κ,P)] (7) and [RuCl2(η6-1,4-MeC6H4(CHMe2))(Ph2PCH2CO2H-κP)] (9), were obtained by bridge splitting in the dimers with the phosphinocarboxylic ligand. All new compounds were characterized by spectral methods and combustion analyses, and the structures of 2 · 3CH2Cl2, 3, 4, 5, 6 and 8 were determined by X-ray crystallography. 相似文献
17.
Bin Li 《Journal of organometallic chemistry》2008,693(4):667-674
The N-N bond cleavage of diazoalkane Ar2CN2 following a orthometalation of the aryl occurred in the thermal reactions with (Me2C)(Me2Si)[(η5-C5H3)Mo(CO)3]2 (1), which led to (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)2(O){μ-η1:η2-NC(RC6H3)(RC6H4)}] [R = H (2), p-Me (3)]. Two products (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(μ-η1:η2-CS)] (4) and (Me2C)(Me2Si)[(η5-C5H3)2Mo2(CO)4(μ-η2:η2-CS3)] (5) were isolated in the reaction of complex 1 with CS2 with the disproportionation of carbon disulfide. The molecular structures of 2-5 have been determined by X-ray diffraction analysis. The proposed mechanism was discussed. 相似文献
18.
Hisako Hashimoto Kazuyoshi Kurashima Hiroshi Ogino 《Journal of organometallic chemistry》2004,689(9):1481-1495
A phosphido-bridged unsymmetrical diiron complex (η5-C5Me5)Fe2(CO)4(μ-CO)(μ-PPh2) (1) was synthesized by a new convenient method; photo-dissociation of a CO ligand from (η5-C5Me5)Fe2(CO)6(μ-PPh2) (2) that was prepared by the reaction of Li[Fe(CO)4PPh2] with (η5-C5Me5)Fe(CO)2I. The reactivity of 1 toward various alkynes was studied. The reaction of 1 with tBuCCH gave a 1:1 mixture of two isomeric complexes (η5-C5Me5)Fe2(CO)3(μ-PPh2)[μ-CHC(tBu)C(O)] (3) containing a ketoalkenyl ligand. The reactions of 1 with other terminal alkynes RCCH (R=H, CO2Me, Ph) afforded complexes incorporating one or two molecules of alkynes and a carbonyl group. The principal products were dinuclear complexes bridged by a new phosphinoketoalkenyl ligand, (η5-C5Me5)Fe2(CO)3(μ-CO)[μ-CR1CR2C(O)PPh2] (4a: R1=H, R2=H; 4b: R1=CO2Me, R2=H; 4c: R1=H, R2=Ph). In the cases of alkynes RCCH (R=H, CO2Me), dinuclear complexes having a new ligand composed of two molecules of alkynes, a carbonyl group, and a phosphido group; i.e. (η5-C5Me5)Fe2(CO)3[μ-CRCHCHCRC(O)PPh2] (5a: R=H; 5b: R=CO2Me), were also obtained. In all cases, mononuclear complexes, (η5-C5Me5)Fe(CO)[CR1CR2C(O)PPh2] (6a: R1=H, R2=H; 6b: R1=H, R2=CO2Me; 6c: R1=H, R2=Ph) were isolated in low yields. The structures of 1, 4c, 5b, and 6a were confirmed by X-ray crystallography. The detailed structures of the products and plausible reaction mechanisms are discussed. 相似文献
19.
Bin-Qiu Liu Peng-Fei Yan Ju-Wen Zhang Peng Chen Guang-Ming Li 《Journal of organometallic chemistry》2010,695(22):2441-2446
A series of m-ferrocenylbenzoate [m-ferrocenylbenzoate = m-NaOOCH4C6Fc, Fc = (η5-C5H5)Fe(η5-C5H4)] lanthanide coordination polymers, namely [Ln(μ2-OOCH4C6Fc)(η2-OOCH4C6Fc)(μ2-η2-OOCH4C6Fc)(CH3OH)2]n [Ln = La (1), Pr (2), Nd (3), Sm (4) and Gd (5)], have been synthesized by reactions of m-ferrocenylbenzoate with Ln(NO3)3·nH2O. X-ray crystallographic analyses reveal that 1, 2 and 5 are essentially isostructural with unique one-dimensional linear chain structure. Three types of coordination modes for m-ferrocenylbenzoate are observed in the unit structure which consists of the eight-membered metallacycle Ln2(COO)2 and the rhomboid Ln2O2. Electrochemical studies indicate that 1-5 exhibit a reversible redox wave of FeII/FeIII and the half-wave potentials of 1-5 are slightly more positive than that of m-ferrocenylbenzoic acid. Magnetic investigations show that an antiferromagnetic interaction between Gd(III) ions exists in 5. 相似文献
20.
Shishir Ghosh Daniel T. Haworth Tasneem A. Siddiquee Graeme Hogarth 《Journal of organometallic chemistry》2009,694(18):2941-202
Reaction of tri(2-furyl)phosphine (PFu3) with [Re2(CO)10−n(NCMe)n] (n = 1, 2) at 40 °C gave the substituted complexes [Re2(CO)10−n(PFu3)n] (1 and 2), the phosphines occupying axial position in all cases. Heating [Re2(CO)10] and PFu3 in refluxing xylene also gives 1 and 2 together with four phosphido-bridged complexes; [Re2(CO)8−n(PFu3)n(μ-PFu2)(μ-H)] (n = 0, 1, 2) (3-5) and [Re2(CO)6(PFu3)2(μ-PFu2)(μ-Cl)] (6) resulting from phosphorus-carbon bond cleavage. A series of separate thermolysis experiments has allowed a detailed reaction pathway to be unambiguously established. A similar reaction between [Re2(CO)10] and PFu3 in refluxing chlorobenzene furnishes four complexes which include 1, 2, 6 and the new binuclear complex [Re2(CO)6(η1-C4H3O)2(μ-PFu2)2] (7). All new complexes have been characterized by a combination of spectroscopic data and single crystal X-ray diffraction studies. 相似文献