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1.
Perfluoromethyl Element Ligands. XXX. Reactions of the Metal Hydridesπ-C5H5(CO)3MH (M = Cr, Mo, W) with Organoelement-Element Compounds of the Type R2 EER2 and RE′ ′E ′R (E = P, As; E′ = S, Se; R = CH3, CF3) Cleavage reactions of R2EER2 and RE′E′R, respectively, (E = P, As; E′ = S, Se; R = CH3, CF3) with complexes π-C5H5(CO)3MH (M = Cr, Mo, W) are used (a) to prepare known and novel complex subsituted phosphanes, arsanes, sulfanes, or selanes π-C5H5(CO)3MER2 (I) and π-C5H5(CO)3ME′R (II), respectively, (b) to study the reactivity trends as a function of E, E′, R, and M (see Inhaltsübersicht). The tendency observed for the formation of the binuclear complexes [π-C5H5(CO)2MER2]2 and [π-C5H5(CO)2ME′R]2, respectively, in following reactions of I and II increases in the series W ? Mo ≤ Cr and SeCF3 < As(CF3)2 < SCF3 ≈ P(CF3)2 < SeMe < AsMe2 ?; PMe2 ≈ SMe. 相似文献
2.
Perfluoromethyl Element Ligands. XXXII. Reactions of the Metal Hydrides π-C5H5(CO)3MH (M = Cr, Mo, W) with Diphosphanes [Ph2?nYnP]2 (Y = I, CN, SiMe3; n = 2, 1, 0) The reactions of π-C5H5(CO)3MH (M = Cr, Mo, W) ( 1a – c ) with the symmetric diphosphanes (Ph2P)2, [Ph(CN)P]2, [(CN)2P]2, and the cyclophosphane (PPh)5, respectively, occur under cleavage of the P? P bond. The reactivity decreases in the series The tendency to form binuclear complexes reflects the basicity of the metallated phosphanes π-C5H5(CO)3MPRR′ and increases in the order P(CN)2 < P(CN)Ph ? P(Ph)H < PPh2. Iodine containing diphosphanes [Ph(I)P? P(I)Ph and P2I4] undergo redox reactions with 1a – c , yielding π-C5H5(CO)3MI and unstable iodo-diphosphanes. No P? P bond cleavage occurs in the reaction of the silyl substituted diphosphanes [Ph(SiMe3)P]2 and [(Me3Si)2P]2 with 1a – c , but P? Si bond fission is the preferred reaction giving π-C5H5(CO)3MSiMe3. 相似文献
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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
5.
Alternative Ligands. XXVI. M(CO)4 L-Complexes (M ? Cr, Mo, W) of the Chelating Ligands Me2ESiMe2(CH2)2E′ Me2 (Me ? CH3; E ? P, As; E′ ? N, P, As) The reaction of M(CO)4NBD (NBD = norbornadiene; M ? Cr, Mo, W) with the ligands Me2ESiMe2(CH2)2E′ Me2 yields the chelate complexes (CO)4M[Me2ESiMe2]) for E,E′ ? P, As, but not for E and /or E′ ? N. The NSi group is not suited for coordination because of strong (p-d)π-interaction. In the case of the ligands with E ? P or As and E′ ? N chelate complexes can be detected in the reaction mixture, but isolable products are complexes with two ligands coordinated via the E donor group. The new compounds are characterized by analytical and spectroscopic (IR, NMR, MS) investigations. The spectroscopic data are also used to deduce the coordinating properties of the ligands. X-ray diffraction studies of the molybdenum complexes (CO)4Mo[Me2ESiMe2(CH2)2AsMe 2] (E ? P, As) in accord with the observed coordination effects show only small differences between SiE and CE donor functions. Attempts to use the ligands Me2ESiMe2(CH2)2AsMe2 (E ? P, As) for the preparation of Fe(CO)3L complexes result in the fission of the SiE bonds and the formation of the binuclear systems Fe2(CO)6(EMe2)2 (E ? P, As) together with the disilane derivative [Me2Si(CH2)2AsMe2]2. 相似文献
6.
Preparation and Properties of (CF3)2EMn(CO)5 (E ? P, As) The complexes (CF3)2EMn(CO)5 (E ? P, As) are formed by the reaction of E2(CF3)4 with HMn(CO)5. They can be converted quantitatively to the binuclear compounds [Mn(CO)4E(CF3)2]2 in a thermal (E ? P) or photochemical (E ? P, As) process. u. v. irradiation of a 1:1 mixture gives the mixed derivative Mn2(CO)8As(CF3)2P(CF3)2 together with the symmetrical systems. The Mn? E bond is less reactive with HBr and Me3SnBr than the M? E bond in derivatives of the type Me3ME(CF3)2 (M ? Si, Ge, Sn; Me ? CH3). The terminal (CF3)2E groups are found to be strong π-acceptor ligands. 相似文献
7.
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
8.
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
9.
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
10.
Ron S. Dickson Rhonda J. Nesbit Helen Pateras Jennifer M. Patrick Allan H. White 《Journal of organometallic chemistry》1984,265(2):c25-c28
Complexes of formula (η-C5H52Rh2{CF3C2CF3 · RNCO} have been prepared by three methods, from reactions between organic isocyanates and (η-C5H5)2Rh2(CO)(CF3C2CF3) or (η-C5H5)2Rh2(CO)2(CF3C2CF3); by treatment of (η-C5H5)2Rh2(CO)(CF3C2CF3) with organic azides; and by oxidation with Me3NO of the organic isocyanide in (η-C5H5)2Rh2(CO)(CNR)(CF3C2CF3). The crystal and molecular structure of the complex (η-C5H5)2Rh2{CF3C2CF3 · RNCO} with R = Ph has been determined from single crystal X-ray diffraction data. This reveals that the isocyanate has condensed with the hexafluorobut-2-yne to form an amide ligand of the form C(CF3)C(CF3)C(=O)N(R); this bridges the two rhodium atoms in a μ2η3-manner. 相似文献
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Coordination Chemistry of Functional Phosphorus Ylides. VII. Pentacarbonylmetal Complexes of Cyanomethylene Triphenylphosphorane, [Ph3P?CH(CN)] · M(CO)5 (M = Cr, Mo, W) The pentacarbonyl complexes [Ph3P?CH(CN)] · M(CO)5 ( 1a –c) are obtained by reaction of the irradiated metal hexacarbonyls M(CO)6 (M = Cr, Mo, W) with cyanomethylene triphenylphosphorane under exclusion of light. The IR and NMR spectra indicate N-coordination of the ligand, that means a nitrile complex. The chromium complex 1a crystallizes triclinic (space group P1 , Z = 2) with the lattice constant a = 1126.5(2), b = 1153.6(3), c = 951.4(3) pm; α = 103.47(3), β = 102.04(3), γ = 84.00(2)°. The linear array of the ligand atoms C7, C6, N forms an angle of 168.1(5)° with the metal-nitrogen bond. Significant bond distances are Cr? N = 206.2(6), N? C6 = 115.3(7), C6? C7 = 137.2(8) and P? C7 = 170.9(5) pm. 相似文献
13.
Ron S. Dickson Alan P. Oppenheim Geoff N. Pain 《Journal of organometallic chemistry》1982,224(4):377-386
Treatment of the μ(η1)-alkyne complex (η-C5H5)2Rh2(CO)2(CF3C2CF3) with trimethylamine-N-oxide results in mono-decarbonylation to give the μ(η2)- alkyne complex (η-C5H5)2Rh2(μ-CO)(CF3C2CF3). Coordinative addition of a variety of ligands L to the monocarbonyl complex has been achieved at room temperature, and stable adducts (η-C5H5)2Rh2(CO)L(CF3C2CF3) (L CO, CNBut, PPh3, PMePh2, P(OMe)3, AsPh3, PF3 and PF2(NEt2)) have been fully characterized by infrared and NMR spectroscopy. In each complex, there is a μ(η1)-attachment of the hexafluorobut-2-yne and a trans-arrangement of CO and L. The spectroscopic data establish that there is rapid scrambling of CO and L when L CNBut. An unstable adduct is formed when (η-C5H5)2Rh2(μ-CO)(CF3C2CF3) is dissolved in pyridine. 相似文献
14.
Katsutoshi Yasufuku Katsuyuki Aoki Hiroshi Yamazaki 《Journal of organometallic chemistry》1975,84(2):C28-C30
The mixed metal complex π-C5H5NiFe(CO)3Ph3PCCH, obtained from the reaction of π-C5H5Ni(PPh3)CCH with Fe2(CO)9, is shown by an X-ray diffraction study to contain the ethynyltriphenylphosphonium group as the bridging ligand. Based on this structure, new reactions of [Ph3PCCPh]Br with some organometallic compounds have been attempted from which π-C5H5NiFe(CO)3(Ph3PC2Ph) and CoFe(CO)6(Ph3PC2Ph) can be obtained. 相似文献
15.
Perfluoromethyl-Element-Ligands. XVIII. Preparation and Spectroscopic Investigation of M(CO)5L and M(CO)4L2 Complexes [L = MenP(CF3)3?n; n = 0–3; M = Cr, Mo, W] M(CO)5L and cis-M(CO)4L2 complexes, respectively [M = Cr, Mo, W; L = MenP(CF3)3?n; n = 0–3] are prepared reacting M(CO)5 · THF or M(CO)4norbor with L at room temperature. The cis-compounds isomerize above 50°C yielding the trans-complexes; the rate of isomerization increases with increasing number of CF3 groups. Thermal reaction of M(CO)6 (M = Cr, Mo, W) with P(CF3)3 yields M(CO)5P(CF3)3 and trans-M(CO)4[P(CF3)3]2. Introduction of three P(CF3)3 ligands by reaction with M(CO)3(cycloheptatriene) (M = Cr, Mo) proves unsuccessful; besides little M(CO)5P(CF3)3 trans-M(CO)4[P(CF3)3]2 is formed. The new compounds are characterized by analytical and spectroscopic (n.m.r., i.r., MS) methods. 相似文献
16.
Heterobimetallic Phosphanido-bridged Dinuclear Complexes - Syntheses of cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6-iPr3C6H2)}2M(CO)4] (R?Me, M?Cr, Mo; R?H, M?Mo) The zirconocene bisphosphanido complexes [(η-C5H4R)2Zr{PH(2,4,6-iPr3C6H2)}2] (R?Me, H) react with [(NBD)M(CO)4] (NBD?norbornadiene, M?Cr, Mo) to give only one diastereomer of the phosphanido-bridged heterobimetallic dinuclear complexes cis-rac-[(η-C5H4R)2Zr{μ-PH(2,4,6-iPr3C6H2)}2M(CO)4] [R?Me, M?Cr ( 1 ), Mo ( 2 ); R?H, M?Mo ( 3 )]. However, no reaction was observed between [(η-C5H5)2Zr{PH(2,4,6-tBu3 C6H2)}2] and [Pt(PPh3)4]. 1—3 were characterised spectroscopically. For 1—3 , the presence of the racemic isomer was shown by NMR spectroscopy. No reaction was observed at room temperature for 3 and CS2, (NO)BF4, Me3NO or PH(2,4,6-Me3C6H2)2. With Et2AlH or PhC?CH decomposition of 3 was observed. 相似文献
17.
Phosphido- and Arsenido-bridged Dinuclear Complexes. Synthesis and Molecular Structure of (η5-C5H4R)2Zr{μ-P(SiMe3)2}2M(CO)4 (R = Me, M = Cr; R = H, M = Mo) and Synthesis of (η5-C5H5)2Zr{μ-As(SiMe3)2}2Cr(CO)4 The reaction of (η5-C5H4R)2Zr{E(SiMe3)2}2 with M(CO)4(NBD) (NBD = norbornadiene) yields the dinuclear phosphido- or arsenido-bridged complexes (η5-C5H4R)2Zr{μ-E(SiMe3)2}2M(CO)4 (R = Me, E = P, M = Cr ( 1 ); R = H, E = P, M = Mo ( 2 ); R = H, E = As, M = Cr ( 3 )). No formation of dinuclear complexes was observed in the reaction of (η5-C5H4Me)2Zr{P(SiMe3)2}2 with Ni(PEt3)4, Ni(CO)2(PPh3)2 or with NiCl2(PPh3)2 in the presence of Mg. Complexes 1 – 3 were characterised spectroscopically (i. r., n. m. r., m. s.), and X-ray structure investigations were carried out on 1 and 2 . The central four-membered ZrP2M ring is slightly puckered (dihedral angle between planes ZrP2/CrP2 14.7°, ZrP2/MoP2 14.2°). The Zr? P bond lengths are equivalent ( 1 : Zr? P1 2.654(4), Zr? P2 2.657(4) Å; 2 : Zr? P1 2.6711(9), Zr? P2 2.6585(7) Å), as are the M? P bond lengths (M = Cr ( 1 ): Cr? P1 2.513(4), Cr? P2 2.502(4) Å; M = Mo ( 2 ): Mo? P1 2.6263(7), Mo? P2 2.6311(10) Å). The long Zr ··· M distances of 3.414 Å (M = Cr ( 1 )) and 3.461 Å (M = Mo ( 2 )) indicate the absence of a metal-metal bond. 相似文献
18.
Reaction of MoCo(CO)5(PPh3)2(η5-C5H5) (1a) with trimethylsilylacetylene in tetrahydrofuran at 58° C yielded two acetylene bridged heterobimetallic compounds, MoCo(CO)4(PPh3){μ-HC?CSiMe3}(η5-C5H5) (4) and MoCo (CO)5{μ-HC?CSiMe3}(η5-C5H5)(5). (4) was characterized by mass, infrared, 1H, 13C and 31P NMR spectra. The X-ray crystal structure of (4) was determined:triclinic, P-1, a=8.821(1) Å, b=11.315(3) Å, c=17.029(2) Å, α=70.73(1)°, β=78 .72(1)°, γ=86.10(2)°,V =1573.4(6) Å3, Z=2, R = 3.92%,Rw = 6.06% for 4285 (F > 4σ (F)) observed reflections. The core of this molecule is a quasi-tetrahedron containing Mo, Co and two carbons of acetylene. The triphenylphosphine ligand is attached to cobalt rather than molybdenum center. 相似文献
19.
There is activation of olefinic C? H bonds when (η-C5H5)2Rh2(CO)(CF3C2CF3) is treated with vinyl acetate or allyl cyanide. These reactions are initiated by exposure to sunlight. In the vinyl acetate reaction, each of the three vinylic C? H bonds can be broken, but there is strong preference for cleavage at the substituted carbon. The products formed in these reactions are bisalkenyl complexes of the type (η-C5H5)2Rh2{μ-C(CF3)C(CF3)H}(μ-CR?CR′R″), and all isomers have been thoroughly characterized by NMR analysis. Similar reactions with allylamine and other amines (NH2R, NHMe2) occur in the dark and proceed by N? H bond cleavage. Near-quantitative amounts of the products, (η-C5H5)Rh2{C(CF3)C(CF3)H}(C(O)NRR′) are isolated. Spectroscopic data indicate a bridging carboxamide ligand attached to the Rh? Rh bond from oxygen and nitrogen donor sites. It is proposed that coordination of O or N to rhodium has a strong influence on all of the reactions studied. 相似文献
20.
Complex Chemistry of Reactive Organic Compounds. XLV. Organometallic Methanediazo Complexes: Protonation and Cycloaddition The reactions of the methanediazo tungsten complex (η5-C5H5)W(CO)2(N2CH3) ( 1 ) with protic acids are strongly governed by solvent effects: while trifluoromethylsulfonic acid induces clean protonation with formation of the ionic derivative [(η5-C5H5)W(CO)2(HN2CH3)]+CF3SO3? ( 3 ) when diethylether is used as a solvent, compound 4 is formed in the presence of acetonitril which latter solvent has good coordination capabilities itself. Compound 4 originates from a novel type of cycloaddition reaction in which the protonated species of composition [(η5-C5H5)W(CO)(CH3CN)(HN2-CH3)]+CF3SO3? is involved. Complete elimination of the nitrogeneous ligand ensemble with concomitant formation of the halogen complex (η5-C5H5)W(CO)2Br3 ( 5 ) occurs upon treatment of 1 with hydrogen bromide. 相似文献