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1.
The reactions of [Fe2(η-C5H5)2(CO)2(L)(CNMe)] (L CO or CNME) with HgX2 (X Cl, Br or I) give [Fe(η-C5H5)(CO)2HgX] and [Fe(η-C5H5)(L)-(CNMe)X] as the sole products in ca. quantitative yields; this is consistent with the previously proposed mechanism for the reactions of electrophiles with polynuclear metal carbonyl derivatives. 相似文献
2.
《Journal of organometallic chemistry》1987,331(3):357-377
The oxidative cleavage of [Fe2(η-C5H5)2(CO)4-n(CNMe)n] (n=0−2) by 2AgX gives mononuclear products. It is shown to be a two-electron process in most solvents but a one-electron process in acetonitrile. The two-electron oxidations proceed by way of adducts such as [Fe2(η-C5H5)2(CO)(CNMe)(μ-CO){;μ-CN(Me)AgPPh3};]BF4 which are isolable when n = 2, detectable when n = 1 and postulatetd when n = 0. The one-electron process gives no adducts, and 1AgX cleaves all of the substrate to [Fe(η-C5H5)(CO)(L)(NCMe)]+ and [Fe(η-C5H5)(CO)(L)]. (L CO or CNME). The latter may combine or react with added CHBr3 to give [Fe(η-C5H5)(CO)(L)Br]. The structure of [Fe(η-C5H5)(CO)2-(CNMe)]BF4 has been determined by X-ray diffraction. 相似文献
3.
《Journal of organometallic chemistry》2002,649(1):21-24
The complexes [(η5-C5H5)Fe(CO)2(SCCR)] (R=tBu, SiMe3) have been obtained by reaction of [(η5-C5H5)Fe(CO)2I] and the corresponding LiSCCR. These are the first examples of mononuclear iron compounds containing alkynethiolate ligands. The crystal structure of [(η5-C5H5)Fe(CO)2(SCCSiMe3)] has been determined by X-ray diffraction. The role of [(η5-C5H5)Fe(CO)2(SCCSiMe3)] as a metalloligand in its reactions with metal carbonyls has been explored. 相似文献
4.
The versatile reagent [η5-C5H5)Fe(CO)2(THF)]BF4 has been isolated from the reaction of (η5-C5H5)Fe(CO)2I and AgBF4 in THF and shown to react in CH2Cl2 with olefins to yield [(η5-C5H5)Fe(CO)2(η2-olefin)]BF4 complexes. For most olefins the yields are high. The yield in these reactions can be increased by treating the CH2Cl2 solution of [(η5-C5H5)Fe(Co)2(THF)]BF4 and olefin with gaseous BF3 in order to complex the THF as the BF3-THF adduct. Most striking is the increase in yield for the cyclohexene complex from 17% to 92%. 相似文献
5.
《Journal of organometallic chemistry》1990,390(1):c10-c15
The reaction between InCl and [Mo2(CO)6(η-C5H5)2] affords [InCl&{;Mo(CO)3(η-C5H5)&};], 6a which has been characterised as a THF adduct [InCl(THF)&{;Mo(CO)3(η-C5H5)&};2], 10, by X-ray crystallography. An additional complex, [InCl2&{;Mo(CO)3(η-C5H5)&};2]−, 11, is also formed in this reaction. Similar products are reported for reactions involving [M2(CO)6(η-C5H5)2] (M = Cr, W). The reaction between InCl and [Fe2(CO)4(η-C5H5)2] affords [InCl{Fe(CO)2(η-C5H5)}2], 17, and [InCl2{Fe(CO)2(η-C5H5)}], whilst that between InI and [Fe2(CO)4(η-C5H5)2] affords [InI{Fe(CO)2(η-C5H5)}2], 19. 相似文献
6.
The new tris(ferrocenylamine) ditertiary phosphine 1,1′-{FcCH2N(CH2PPh2)CH2(η5-C5H4)}2Fe [Fc = (η5-C5H5)Fe(η5-C5H4)] has been prepared along with two coordination complexes. All compounds have been characterised by a combination of spectroscopic and analytical methods. The single crystal X-ray structure of the pentametallic Ru2Fe3 complex 5 has been determined. 相似文献
7.
Treatment of the μ-alkylidyne clusters [Fe2W(μ3-CC6H4Me-4)(μ-CO)- (CO)8(η-C5H5)] and [Co2W(μ3-CMe)(CO)8(η-C5H5)] with PPh2H affords a series of new μ-phosphido-μ-hydrido alkylidyne complexes which undergo protonation with HBF4·Et2O to give cationic derivatives. The X-ray structure of [Co2W(μ-H)(μ3-CMe)(μ-PPh2)(CO)6(η-C5H5)] has been determined. 相似文献
8.
《Journal of organometallic chemistry》1986,299(3):C51-C55
The coupling of [Ru(CO)2L(η4-cot)] (L = CO or PPh3, cot = cyclooctatetraene) with [Fe(CO)3(η5-cyclohexadienyl)]+ or [Fe{P(OMe)3}(NO)2(η3-allyl)]+ yields respectively the dimetallic species [Ru(CO)2L(η2,η3-C8H8{Fe(CO)3(η4-C6H7)}] (3) and the allyl-substituted derivative [Ru(CO)2L(η5-C8H8CH2C(Me)CH2)][PF6] (5) whose X-ray structure is reported; paramagnetic [Co(η-C5H5)2] and [Ru(CO)3(η5-cyclohexadienyl)]+ give diamagnetic [Ru(CO)3(η4-C6H7C5H6(o-C5H5)] (8) via CC bond formation and one-electron reduction. 相似文献
9.
The isocyanide complexes [Fe(η-C5H5)(CO)2CNR][PF6] and Cr(CO)5CNR (R = CH3, C6H11, C6H5) are conveniently prepared at ?50°C from carbonyl metallates, isothiocyanates, and phosgene. At room temperature Na[Fe(η-C5H5)(CO)2] reacts with isothiocyanates () to give the isocyanide bridged complexes [Fe2(η-C5H5)2(μ-CO)(μ-CNR)(CO)2]. 相似文献
10.
《Journal of organometallic chemistry》1987,326(2):229-246
Various di- and poly-nuclear transition metal complexes have been investigated as catalysts for the metal carbonyl substitution reaction. The complexes [{(η5-C5H4R)Fe(CO)2} 2] (R = H, Me, CO2Me, OMe, O(CH2)4OH) and [{(η5-C5H5)-Ru(CO)2} 2] are active catalysts for a range of substitution reactions including the probe reaction [Fe(CO)4(CNBut)] + ButNC → [Fe(CO)3(CNBut)2] + CO. [{(η5-C5Me5)Fe(CO)2}2] is catalytically active only on irradiation with visible light. For [{η5-C5H5)Fe(CO)2}2] and a range ofisocyanides RNC ( R = But, C6H5CH2, 2,6-Me2C6H3), catalyst modification by substitution with isocyanide is a major factor influencing the degree of the catalytic effects observed, e.g. [{(η5-C5H5)Fe(CO)(CNBut)}2] is approximately 35 times as active as [(η5-C5H5)2FE2(CO)3(CNBut)] for the [Fe(CO)4(CNBut)] → [Fe(CO)3(CNBut)2] conversion. Mechanistic studies on this system suggest that the catalytic substitution step probably involves a rapid intermolecular attack of isonitrile, possibly on a labile catalyst-substrate radical intermediate such as {[Fe(CO)4(CNR)][(η5-C5H5)Fe(CO)2]}; or on a reactive radical cation such as [Fe(CO)4(CNR)]+ generated via electron transfer between the substrate and the catalyst. Other transition metal complexes which also catalyze the substitution of CO by isocyanide in [Fe(CO)4(CNR)] (and [M(CO)6] (M = Cr, Mo, W), [Mn2(CO)10], [Re2(CO)10]) include [Ru3(CO)12], [H4Ru4(CO)12], [M4(CO)12] (M = Co, Ir) and [Co2(CO)8]. These reactions conform to the general mechanistic patterns established for [{(η5-C5H5)Fe(CO)2}2], suggesting a similar mechanism. A range of materials, notably PtO2, PdO and Pd/C, act as promoters for the homogeneous di- and poly-nuclear transition metal catalysts, and can even be used to induce activity in normally inactive dimer and cluster complexes e.g. [Os3(CO)12]. This promotion is attributed to at least three possible effects: the removal of catalyst inhibitors, a catalyzed substitution of the homogeneous catalyst partner, and a possible homogeneous-heterogeneous interaction which promotes the formation of catalytic intermediates. 相似文献
11.
Neil D. Feasey Nigel J. Forrow Graeme Hogarth Selby A.R. Knox Kirsty A. Macpherson Michael J. Morris A. Guy Orpen 《Journal of organometallic chemistry》1984,267(3):c41-c44
UV irradiation of [Ru2(CO)4(η-C5H5)2] yields the tri- and tetra-ruthenium complexes [Ru2(CO)4(η-C5H5){η-C5H4Ru(CO)2(η-C5H5)}] and [Ru4(CO)6(μ3-C5H4)2(η-C5H5)2]. The μ3-C5H4 ligand in the latter has been characterised through an X-ray diffraction study on [Ru4(CO)5{P(OMe)3}(μ3-C5H4)2(η-C5H5)2]. 相似文献
12.
Jaisheila Rajput John R. Moss Christopher Imrie 《Journal of organometallic chemistry》2006,691(22):4573-4588
The preparation of a series of complexes of the types [RhCl(CO)2(L)], [RhCl(cod)(L)] and [Rh(cod)(L)2]ClO4, where L is a ligand incorporating a ferrocenyl group and a pyridine ring is described. Complexes were characterized using NMR, IR and electronic spectroscopy. The electrochemical behaviour of the complexes was examined using cyclic voltammetry. The X-ray structures of three of the complexes, [RhCl(CO)2{NC5H4CNC6H4(η5-C5H4)Fe(η5-C5H5)}], [RhCl(cod)(3-Fcpy)] and [RhCl(cod){3-Fc(C6H4)py}], were determined. 相似文献
13.
《Journal of organometallic chemistry》1986,312(2):c21-c23
Nucleophilic addition to a carbonyl ligand has been shown to compete with attack at the metal or dienyl ring in the reactions of [Fe(CO)3(1–5-η-dienyl)]+ cations with iodide ion. Thus, the novel acyl iodide complex [Fe(CO)2(COI)(1–5-η-C6H7)] is found to be a major product from the reaction of [Fe(CO)3(1–5-η-C6H7)]+ with I− in nitromethane or acetone solvents. The other major initial product is the ring adduct [Fe(CO)3(1–4-η-IC6H7)]. Exposure of the acyl iodide species to light causes its rapid decomposition. Analogous behaviour towards I− is shown by the related [Fe(CO)3(1–5-η-C7H9)]+ and [Fe(CO)3(1–5-η-2-MeOC6H6)]+ cations. 相似文献
14.
Bis-(η4-1,5-cyclooctadiene)nickel(0) reacted with η5-C5H5Fe(CO)2Cl, η3-C5H5Fe(CO)3Cl, Mn(CO)5Cl and {Mn[P(OMe)3](CO)4}2 to form metal metal bonded coupling products. Partial reduction of Mn(CO)5Cl gave [MnCl(CO)3(THF)]2 shown to have a chlorine-bridged C2h structure by X-ray diffraction analysis. Ligand transfer also accompanied the reduction of Fe[P(OMe)3]2(CO)2Br2 and Fe(CO)4Cl2 to Fe[P(OMe)3]2(CO)3 and Fe(CO)5, respectively. Only partial reduction was observed for Ti(acac)2Cl2 and (η5-C5H5)2TiCl2 which gave [Ti(acac)2Cl]2 and (η5-C5H5)2Ti(py)Cl, respectively. 相似文献
15.
[MoCl(CO)3(η5-C5H5)] on photolysis with allyl or crotyl halides C5H4RX gives MoIV complexes [MoX2(CO)(η3-C3H4R)(η5-C5H5)] (R = H, X = Cl, Br, I; R = Me, X = Cl, Br). [WCl(CO)3(η5-C5H5)] under similar conditions gives trihalides [WX3(CO)2(η5-C5H5)] (X = Cl, Br) on reaction with C3H5Cl and C3H5Br while [WCl(CO)3(η5-C5H4SiMe3)] and [CrI(CO)3(η5-C5H5)] react with allyl chloride to give [WCl3(CO)2(η5-C5H4SiMe3)] and [CrCl2(η5-C5H5)] respectively. 相似文献
16.
《Journal of organometallic chemistry》1990,381(2):C47-C51
[Fe(η-C5Me5)(CO)2(OH2)]+ BF4- (2a) reacts with alkenes and alkynes to give the new complexes [Fe(η-C5Me5)(CO)2(alkene)]+ BF4- and [Fe(η-C5Me5)(CO)2(alkyne)]+ BF4-. The crystal structure of the ruthenium analogue [Ru(η-C5Me5)(CO)2(OH2)]+ CF3SO3- (2b) is described. 相似文献
17.
《Journal of organometallic chemistry》1987,328(3):375-385
The reaction between [η5-C5H5)Fe(CO)2I] (I) and 1 equivalent of L (group 15 donor ligand) in the presence of catalysts (e.g. Pd/CaCO3, PdO, [η5-C5H5)Fe(CO)2]2 (II)) yields [η5-C5H5)Fe(CO)(L)I] (phosphines, diphosphines, phosphite), [η5-C5H5)Fe(CO)2L]I (phosphines) and [η5-C5H5)Fe(CO)(LL)]I (diphosphines). [η5-C5H5)Fe(CO)2L]I can be converted into [η5-C5H5)Fe(CO)(L)I] in the presence of II. The reaction between [η5-C5H5)Fe(CO)(PMePh2)I] or [η5-C5H5)Fe(CO)2(PMePh2)]I and PMePh2 is also catalysed by II and yields in both instances [η5-C5H5)Fe(CO)(PMePh2)2]I. In the series of catalysed reactions the displacement sequence was found to be PMePh2 > I− > CO. 相似文献
18.
Heterometallic Cluster Complexes of the Types Re2(μ-PR2)(CO)8(HgY) and ReMo(μ-PR2)(η5-C5H5)(CO)6(HgY) (R = Ph, Cy; Y = Cl, W(η5-C5H5)(CO)3) Dinuclear complexes Re2(μ-H)(μ-PR2)(CO)8 and ReMo(μ-H)(μ-PR2)(η5-C5H5)(CO)6 (R = phenyl, cyclohexyl) were deprotonated and reacted as anions with HgCl2 to compounds of the both types Re2(μ-PR2)(CO)8HgCl) and ReMo(μ-PR2)(η5-C5H5)(CO)6(HgCl). The heterometallic three-membered cluster complexes correspond to an isolobal exchange of a proton against a cationic HgCl+ group. For one of the products ReMo(μ-PCy2)(η5-C5H5)(CO)6(HgCl) has been shown its conversion with NaW(η5-C5H5)(CO)3 to ReMo(μ-PCy2)(η5-C5H5)(HgW(η5-C5H5)(CO)3) under substitution of the chloro ligand, par example. The newly prepared compounds were characterized by means of IR, UV/VIS and 31P NMR data. A complete determination of the molecular structure by single crystal analyses was done in the case of Re2(μ-PCy2)(CO)8(HgCl) and of ReMo(μ-PCy2)(η5-C5H5)(CO)6(HgCl) which both are dimer because of the presence of an asymmetric dichloro bridge, and of ReMo(μ-PCy2)(η5-C5H5)(CO)6(HgW(η5-C5H5)(CO)3). The structural study illustrates through comparison the influence of various metal types on an interaction between centric and edge-bridged frontier orbitals in three-membered metal rings. 相似文献
19.
Transition Metal Substituted Acylphosphanes and Phosphaalkenes. 17. Synthesis and Structure of the μ-Isophosphaalkyne Complexes [(η5-C5H5)2(CO)2Fe2(μ-CO)(μ-C?PC6H2R3)] (R = Me, iPr, tBu) . Condensation of (η5-C5H5)2(CO)2Fe2(μ-CO)(μ-CSMe)}+SO3CF3? ( 6 ) with 2,4,6-R3C6H2PH(SiMe3) ( 7 ) ( a : R = Me, b : R = iPr, c : R = tBu) affords the complexes (η5-C5H5)2(CO)2Fe2(μ-CO)(η-C?PC6H2R3-2,4,6) ( 9 a–c ) with edge-bridging isophosphaalkyne ligands as confirmed by the x-ray structure analysis of 9 a . 相似文献
20.
《Polyhedron》1988,7(6):443-448
The salts [Re(CR)CO)2(η5-C9H7)][BF4] [R = C6H4Me-4 or C6H3Me-2,6; η5- C9H7 = indenyl] have been prepared and used to synthesize the dimetal compounds [FeRe(μ-CR)(μ-NO)(CO)4(η5-C9H7)]. The iron-rhenium species containing a bridging p- tolylmethylidyne ligands react with [Fe2(CO)9] or with [Ru(CO)4(η-C2H4)], respectively, to yield the trimetal compounds ([FeMRe(μ3-CC6H4Me-4)(μ-CO)(μ-NO)(CO)6(η 5-C9H7)] (M = Fe or Ru). 相似文献