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1.
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
2.
Norman H. Tennent Sophia R. Su Craig A. Poffenberger Andrew Wojcicki 《Journal of organometallic chemistry》1975,102(4):C46-C48
The reaction of Na[η5-C5H5Fe(CO)2] with large excess of SO2 in THF at ?78°C followed by warming to room temperature affords an iron—dithionite complex, (η5-C5H5)(CO)2FeS(O)2S(O)2Fe(CO)2(η5-C5H5). 相似文献
3.
Evidence for (η5-C5H5)Fe(Ph2PCH2CH2PPh2)(CHO) as an intermediate in the reduction of [(η5-C5H5)Fe(Ph2PCH2CH2PPh2)CO]PF6 to (η5-C5H5)Fe(CO)H(Ph2PCH2CH2PPh2) and for a metal-carbonyl hydride-formyl equilibrium is described. 相似文献
4.
Jay A. Labinger 《Journal of organometallic chemistry》1977,136(2):c31-c36
The course of the reaction of (η5-C5H5)Fe(CO)2(η1-C5H5) with phosphorus donor ligands depends strongly on the nature of the ligand; products derived from an Arbuzov-like rearrangement or from reduction have been found as well as the expected simple substitution product. The dynamic PMR behavior of (η5-C5H5)Fe(CO) (P(OPh)3) (η1-C5H5) has been examined. 相似文献
5.
Charles P. Casey William D. Jones Stephen G. Harsy 《Journal of organometallic chemistry》1981,206(3):C38-C42
The reaction of (η5-C5H5)W(CO)2(NO), 6W, with P(CH3)3 proceeds rapidly at 25°C to give (η5-C5H5)W(CO)(NO)[P(CH3)3], 7W. The rate of formation of 7W was found to be 4.48 × 10?2M?1 [6W] [P(CH3)3] at 25.0°c in THF. In neat P(CH3)3 at ?23°C, 6W is converted to (η1-C5H5)W(CO)2(NO)[P(CH3)3]2, 8W. In dilute solution, 8W decomposes to initially give a 2:1 mixture of 6W and 7W. The mixture is then converted to 7W. The reaction of (η5-C5H5)Mo(CO)(NO), 6Mo, with P(CH3)3 is 6.1 times faster than that of the tungsten analog. 相似文献
6.
Holger Braunschweig Rainer Dörfler Julian Mager Krzysztof Radacki Fabian Seeler 《Journal of organometallic chemistry》2009,694(7-8):1134-1137
The crystal structure of the molybdenum half sandwich alkali salt [Li(TMEDA)2][Mo(η5-C5H5)(CO)3] shows the occurrence of a separated ion pair in the solid state. Furthermore, the crystal structures of the long known organotin complexes [Mo(η5-C5H5)(SnMe3)(CO)3], [{Mo(η5-C5H5)(CO)3}2SnMe2] and [Mo(η5-C5H5)(SnMeCl2)(CO)3] have been recorded. The chlorination of [Mo(η5-C5H5)(SnMe3)(CO)3] with SnCl4 is presented as an improved synthetic access to [Mo(η5-C5H5)(SnMeCl2)(CO)3]. Finally, the reaction of Li[Mo(η5-C5H5)(CO)3] with tBu2(Cl)Sn–Sn(Cl)tBu2 leads to the novel molybdenum distannane complex [Mo(η5-C5H5){SntBu2-Sn(Cl)tBu2}(CO)3], which is fully characterized by NMR, elemental and X-ray analysis. 相似文献
7.
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
8.
The complex (η5-C5H4CH3)Mn(NO)(PPh3)I has been prepared by the reaction of NaI with [(η5-C5H4CH3)Mn(NO)(CO)(PPh3)]+ and also by the reaction of [(η5-C5H4CH3)Mn(NO)(CO)2]+ with NaI followed by PPh3. This iodide compound reacts with NaCN to yield (η5-C5H4CH3)Mn(NO)(PPh3)CN which is ethylated by [(C2H5)3O]BF4 to yield [(η5-C5H4CH3)Mn(NO)(PPh3)(CNC2H5)]+. Both [(η5-C5H4CH3)Mn(NO)(CO)2]+ and [(η5-C5H4CH3)Mn(NO)(PPh3)(CO)]+ react with NaCN to yield [(η5-C5H4CH3)Mn(NO)(CN)2]?. This anion reacts with Ph3SnCl to yield cis-(η5-C5H4CH3)Mn(NO)(CN)2SnPh3 and with [(C2-H5)3O]BF4 to yield [(η5-C5H4CH3)Mn(NO)(CNC2H5)2]+. The reaction of (η5-C5-H4CH3)Mn(NO)(PPh3)I with AgBF4 in acetonitrile yields [(η5-C5H4CH3)Mn-(NO)(PPh3)(NCCH3)]+. The complex (η5-C5H4CH3)Mn(NO)(CO)I, produced in the reaction of [(η5-C5H4CH3)Mn(NO)(CO)2]+ with NaI, is not stable and decomposes to the dimeric complex (η5-C5H4CH3)2Mn2(NO)3I for which a reasonable structure is proposed. Similar dimers can be prepared from the other halide salts. The reaction of (η7-C7H7)Mo(CO)(PPh3)I with NaCN yields (η7-C7-H7)Mo(CO)(PPh3)CN which is ethylated by [(C2H5)3O]BF4 to yield [(η7-C7H7)-Mo(CO)(PPh3)(CNC2H5)]+. The interaction of this molybdenum halide complex with AgBF4 in acetonitrile and pyridine yields [(η7-C7H7)Mo(CO)(PPh3)-(NCCH3)]+ and [(η7-C7H7)Mo(CO)(PPh3)(NC5H5)]+, respectively. Both (η5-C5-H4CH3)Mn(NO)(PPh3)I and (η7-C7H7)Mo(CO)(PPh3)I are oxidized by NOPF6 to the respective 17-electron cations in acetonitrile at ?78°C but revert to the neutral halide complex at room temperature. This result is supported by electrochemical data. 相似文献
9.
Reaction of chlorodiphenylphosphine with (η5-C5H5)(η7-C7H6Li)Ti gave (η5-C5H5)[η7-C7H6P(C6H5)2]Ti in good yields. This novel phosphinetitanium (II) derivative displaced one carbonyl of metal carbonyl complexes [Ni(CO)4, Fe(CO)5 and Mo(CO)6] to afford heterobimetallic complexes containing low valent titanium, and behaved as a poor electron-donating phosphine. 相似文献
10.
T. Yu. Orlova Yu. S. Nekrasov P. V. Petrovskii M. G. Ezernitskaya 《Russian Chemical Bulletin》2004,53(9):1938-1941
The complex η5,η5-(CO)3Mn(C5H4-C5H4)(CO)2Fe-η1,η5-C5H4Mn(CO)3 was synthesized by the reaction of η5-Cp(CO)2Fe-η1,η5-C5H4Mn(CO)3 with BunLi (THF, ?78 °C) and then with anhydrous CuCl2. The complex μ-(C≡C)[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3]2 was prepared by the reaction of η5-IC5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 with Me3SnC≡CSnMe3 (2:1) in the presence of Pd(MeCN)2Cl2. 相似文献
11.
David L. Davies Andrew F. Dyke Andreas Endesfelder Selby A.R. Knox Pamela J. Naish A. Guy Orpen Dietrich Plaas Graham E. Taylor 《Journal of organometallic chemistry》1980,198(2):C43-C49
The ethyne-derived demetallocycle [Ru2(CO) (μ-CO){μ-C(O)C2H2}(η-C5H5)2 isomerises in boiling toluene to yield the μ-vinylidene complex [Ru2(CO)2(μ-CO)(μ-CCH2) (η-C5H5)2], which on protonation with dry HBF4 provides the μ-carbyne complex [Ru2(CO)2(μ-CO)(μ-CCH3)(η-C5H5)2][BF4]; the structure of each product has been determined by X-ray diffraction. The μ-carbyne cation is attacked by hydride to produce the μ-methylcarbene complex [Ru2(CO)2(μ-CO)(μ-CHCH3)(η-C5H5)2]. 相似文献
12.
László Párkányi Keith H. Pannell Carlos Hernandez 《Journal of organometallic chemistry》1983,252(2):127-132
Reaction of (η5-C5H5)(CO)2FeNa with ClSiMe2-SiPh3 yields (η5-C5H5)-Fe(CO)2SiMe2-SiPh3. The crystal structure of the compound has been determined by X-ray diffraction. The SiSi bond distance is 2.374(1) Å, which is longer by 0.018 Å than that in Me3Si-SiPh3. This difference is in agreement with spectroscopic data, and is presumably due to the σ-donor property of the silyl group. The SiFe bond length is 2.346(1) Å. 相似文献
13.
On the Reactivity of Disilylarsenido Iron Complexes towards Carbonyl Chlorides: The First Arsaalkenyl- and Diacylarsenido Complexes. X-Ray Structure Analysis of Z-[(η5-C5H5)(CO)2Fe? As?C(OSiMe3)(t-Bu)] The reaction of equimolar amounts of (η5-C5H5)(CO)2FeAs(SiMe3)2 ( 1a ) with the carbonyl chlorides RC(O)Cl (R = t-Bu, 2,4,6-Me3C6H2 and 2,4,6-t-Bu3C6H2) yields the arsaalkenyl complexes Z-[(η5-C5H5)(CO)2Fe? As?;C(OSiMe3)R ( 2–4 )]. The diacylarsenido complexes (η5-C5H5)(CO)2Fe? As[C(O)R]2 ( 5, 6 ) are generated by treatment of 1a with two equivalents of pivaloyl chloride or mesitoyl chloride, respectively. The As?C-double bond length of 2 (1.821(2) Å) was determined by single crystal x-ray analysis. 相似文献
14.
Georg Süss-Fink Ulf Thewalt Heinz-Peter Klein 《Journal of organometallic chemistry》1984,275(3):315-338
By reaction of (η-C5H5)W(CO)3SH with Os3(CO)11(NCCH3) the (η5-C5H5)W(CO)3S unit is introduced into the trinuclear osmium cluster through the sulfur atom. The primary reaction product (μ2-H)Os3(CO)10[μ2-SW(η5-C5H5)(CO)3] can be converted thermally into the pyramidal Os3SW cluster (η5-C5H5)(CO)11, whose structure was solved by a single crystal X-ray structure analysis. The molecule has a pyramidal Os3SW skeleton with, in a first approximation a planar Os3S basis. Only two of the three OsOs distances are in accordance with chemical bonds. 相似文献
15.
Michel O. Albers Neil J. Coville Eric Singleton 《Journal of organometallic chemistry》1982,232(3):261-266
The reaction between Fe(CO)5, and group V donor ligands L, (L PPh3, AsPh3, SbPh3, PMePh2, PMe2Ph, Asme2Ph, P(C6H11)3, P(n-Bu)3, P(i-Bu)3, P(OPh)3, P(OEt)3, P(OMe)3) in the presence of [(η5-C5Me5Fe(CO)2]2 (R H, Me) or [(η5-C5Me5)Fe(CO)2]2 as catalyst in refluxing toluene, rapidly gives the complexes Fe(CO)4L in yields > 85%. The reaction rate is essentially independent of the nature of L for [(η5-C5Me5)Fe(CO)2]2 as catalyst. For the other catalysts, the rate is influenced predominantly by the steric properties of L. These results are interpreted in terms of the interaction between the catalyst and the ligand L to give derivatives of the type (η5-C5H4R)2Fe2,(CO)3,(L). These derivatives were also found to catalyse the reaction between Fe(CO)5, and L. The complexes [(η-C5H4R)Fe(CO)2]2 (R H, Me) and [(η5-C5Me5)Fe(CO)2]2 also catalyse the reaction between Mn2(CO)10 and PPh3 to give Mn2(CO)8- PPh3)2 in > 80% yield. 相似文献
16.
Transition Metal-substituted Acylphosphanes and Phosphaalkenes. 22. Insertions of Hexafluoroacetone into the PX-Bond of Metallophosphanes (η5-C5Me5)(CO)2M? PX2 (M = Fe, Ru; X = Me3Si, Cl). Structure Determination of (η5-C5Me5)(CO)2Fe? P(SiMe3)C(CF3)2(OSiMe3) Reaction of the metallophosphanes (η5-C5Me5)(CO)2M? P(SiMe3)2 ( 1a : M = Fe; 1b : M = Ru) with hexafluoroacetone (HFA) afforded the complexes (η5-C5Me5)(CO)2M? P(SiMe3)C(CF3)2(OSiMe3) ( 2a, b ). The attempted synthesis of a metallophosphaalkene from 2a by thermal elimination of hexamethyldisiloxane failed. The acid catalyzed hydrolysis of 2a afforded compound (η5-C5Me5) · (CO)2Fe? P(H)C(CF3)2(OSiMe3) ( 3 ). Hexafluoracetone and (η5-C5Me5)(CO)2Fe? PCl2 ( 4 ) under-went reaction to give the metallochlorophosphan (η5-C5Me5) · (CO)2Fe? P(Cl)? O? C(CF3)2Cl ( 5 ). Constitutions and configurations of the compounds ( 2–5 ) were established by elemental analyses and spectroscopic data (IR, 1H-, 13C, 19F-, 29Si-, 31P-NMR, MS). The molecular structure of 2a was determined by x-ray diffraction analysis. 相似文献
17.
Richard H. Hooker Antony J. Rest Ian Whitwell 《Journal of organometallic chemistry》1984,266(2):c27-c30
Infrared spectroscopic experiments using polyvinyl chloride film matrices at 12–200 K have shown for the first time that the photoinduced decarbonylation of Fe(η5-C5H5)(CO)2(COCH3) is thermally reversible, and that the photolysis of Fe(η5-C5H5)(CO)2(CH3) leads to the reversible formation of the new species Fe(η5-C5H5)(CO)(CH3). 相似文献
18.
The reactions of [Co(η-C5H5)(L)I2] with Na[S2CNR2] (R = alkyl or phenyl) give [Co(η-C5H5)(I)(S2CNR2)] (I) when L = CO and [Co(η-C5H5)(L)(S2CNR2)]I (II) when L is a tertiary phosphine, phosphite or stibine, or organo-isocyanide ligand. In similar reactions [Co(η-C5H5)(CO)(C3F7)I] gives [Co(η-C5H5)(C3F7)(S2CNMe2)] and [Mn(η-MeC5H4)(CO)2(NO)]PF6 forms [Mn(η-MeC5H4)(NO)(S2CNR2)]. The iodide ligands in I may be displaced by L, to give II, or by other ligands such as [CN]?, [NCS]?, H2O or pyridine whilst SnCl2 converts it to SnCl2I. The iodide counter-anion in II may be replaced by others to give [BPh4]?, [Co(CO)4]? or [NO3]? salts. However [CN]? acts differently and displaces (PhO)3P from [Co(η-C5H5){P(OPh)3}(S2CNMe)]I to give [Co(η-C5H5)(CN)(S2CNMe2)] which may be alkylated reversibly by MeI and irreversibly by MeSO3F to [Co(η-C5H5)(CNMe)(S2CNMe2)]+ salts. Conductivity measurements suggest that solutions of I in donor solvents are partially ionized with the formation of [Co(η-C5H5)(solvent)(S2CNR2)]+ I? species. The IR and 1H NMR spectra of the various complexes are reported. They are consistent with pseudo-octahedral “pianostool” molecular structures in which the bidentate dithiocarbamate ligands are coordinated to the metal atoms through both sulphur atoms. 相似文献
19.
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
20.
Ultraviolet irradiation of deaerated solutions of [Mo(η5-C5H5)2H2] results in elimination of H2 and generation of [Mo(η5-C5H5)2]. The transient molybdenocene can be trapped with substrates such as CO, C2H2, and PR3 to yield stable adducts, but in the absence of substrate, oligomerization to the previously described [Mo(η5-C5H5)2]x occurs. 相似文献