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1.
Chelate complexes of the type (CO)4M
iX2 (X = Me, Cl) have been prepared from Na[Mn(CO)5] and HMn (CO)5, respectively, by two-step reactions with the ligands Me2PCH2CH2SiX2R′ using alkali salt, amine or HCl elimination. (CO)4M
iCl2 is also obtained by cleavage of Mn2(CO)10 with Me2PCH2CH2SiCl3. IN the case of HMn (CO)5 the intermediates (CO)4Mn (H) L [L = Me2PSiMe3, Me2PCH2CH2SiMe2 (NMe2), Me2PCH2CH2SiCl2 (NMe2] can be isolated. The new compounds were identified by analytical and spectroscopic (IR, PMR, MS) methods. 相似文献
2.
G.A. Carriedo J.B.Parra Soto V. Riera X. Solans C. Miravitlles 《Journal of organometallic chemistry》1985,297(2):193-203
The phosphine Ph2PCH2CH2Cl reacts with fac-[XMn(CO)3(dppm)] (X = Cl or Br) in refluxing toluene to give the complexes cis,cis-[XMn(CO)2(dppm)(Ph2PCH2CH2Cl)] (I). Treatment of those species with Na amalgam in THF leads to the alkyl complex [Ph2n(CO)2(dppm)] (II), which does not react with CO under normal conditions but can be converted into cis,cis-[ClMn(CO)2(dppm)(PPh2Et)] by reacting with HCl (g) in ether. If the reduction of I with Na/Hg is carried out in the presence of CO the compound cis-[Ph2n(CO)2(dppm)] (III) is obtained. The latter has also been prepared directly from fac-[BrMn(CO)3(dppm)], Ph2PCH2CH2Cl, and Na/Hg in THF, and characterized by X-ray crystallography. The crystals are monoclinic, space group P21/n; refinement gave R = 0.053 for 2593 reflections with I ? 2.5σ(I). The reaction of the complex fac-[O3ClOMn(CO)3(dppm)] with Ph2PCH2CH2Cl in Cl2CH2 gives the salt fac-[Mn(CO)3(dppm)(Ph2PCH2CH2Cl)]ClO4 which isomerizes to mer-[Mn(CO)3(dppm)(Ph2PCH2CH2Cl)]ClO4 in boiling butanol. Both cationic carbonyl complexes give the acyl species III upon reduction with Na amalgam. 相似文献
3.
Hans-Peter Abicht Peter Lehniger Kurt Issleib 《Journal of organometallic chemistry》1983,250(1):609-616
The complexes of type R2)2 (M = Pd, Pt) are readily deprotonated by n-Buli under various conditions yielding μ-C-bis-dilithiated species. The resulting carbanions are attacked by the electrophiles Mel, Me3SiCl and Ph2PCl to form the corresponding disubstituted derivatives. The reaction with AuCl . PPh3 yields heterobimetallic complexes with two different MC σ-bonds. The compounds obtained are analytically and spectroscopically characterized. 相似文献
4.
The amine substituted phosphines (C6H5)2PN(H)CH2CH3 and (C6H5)2PN(H)CH2C6H5 react with C5H5Fe(CO)2CH(C6H5) (OCH3) photolytically to give moderate yields of the four-membered chelate ring complexes C5H5H (C6H5)] and C5H5H(C6H5)], respectively. Photolysis of C5H5Fe(CO)2CH(C6H5) (OCH3) in the presence of (S)-(?)-diphenyl(1-phenylethylamino)phosphine leads to the isolation of C5H5Fe(CO)[(C6H5)2PNC(CH3) (C6H5)]CH2C6H5 which is proposed to arise from a formally 1,3-hydrogen shift rearrangement of an intermediate four-membered chelate ring complex. 相似文献
5.
Ronald L. Bennett Michael I. Bruce F.Gordon A. Stone 《Journal of organometallic chemistry》1975,94(1):65-74
The interaction of azobenzene and MnR(CO)5 (R Me, Et, CH2Ph, CH2-C6Me5, COCF3, COCH2C6F5, COCH2OPh, Ph or C6F5) affords MPh)-(CO)4, together with a binuclear complex Mn2(CO)6(C12H10N2) in some cases. The metallation reaction is shown to proceed most readily with Mn-(CH2Ph)(CO)5; with this reagent, the metallated complexes MMe2)-(CO)3[PMe2(CH2Ph)] (two isomers) and MsMe2(CO)4 have been obtained on treatment with EMe2(CH2Ph) (E P and As, respectively). 相似文献
6.
D. Lalage S. Brown Joseph A. Connor Henry A. Skinner 《Journal of organometallic chemistry》1974,81(3):403-409
From measurements of the heats of iodination of CH3Mn(CO)5 and CH3Re(CO)5 at elevated temperatures using the ‘drop’ microcalorimeter method, values were determined for the standard enthalpies of formation at 25° of the crystalline compounds: ΔHof[CH3Mn(CO)5, c] = ?189.0 ± 2 kcal mol?1 (?790.8 ± 8 kJ mol?1), ΔHof[Ch3Re(CO)5,c] = ?198.0 ± kcal mol?1 (?828.4 ± 8 kJ mo?1). In conjunction with available enthalpies of sublimation, and with literature values for the dissociation energies of MnMn and ReRe bonds in Mn2(CO)10 and Re2(CO)10, values are derived for the dissociation energies: D(CH3Mn(CO)5) = 27.9 ± 2.3 or 30.9 ± 2.3 kcal mol?1 and D(CH3Re(CO)5) = 53.2 ± 2.5 kcal mol?1. In general, irrespective of the value accepted for D(MM) in M2(CO)10, the present results require that, D(CH3Mn) = D(MnMn) + 18.5 kcal mol?1 and D(CH3Re) = D(ReRe) + 30.8 kcal mol?1. 相似文献
7.
The addition of trimethylphosphane to five-membered metallacyclic vinylketone complexes of the type ArR) (I) (Ar = η5-aromatic ring system: C5H5, C5H4Me, C5Me5; R = Me, Et, n-Bu; M = Mo, W) in pentane solution results in the formation of the ylidic metallacyclopropane complexes ArH(COR)] (II). In these 1:1 adducts the three-membered ring is stabilized by an electron-donating phosphonium and an electron-attracting acyl substituent. The negative charge in the ylidic complexes II is localized on the central metal providing it with Lewis base properties. An extraordinary high electron density can be observed on the metal of the derivative C5H5H-(COMe)] (III) which is formed by a 1:2 addition of C5H5W(CO)(C2H2)-(COMe) and PMe3. The metallacyclopropane complexes II and III are characterized by IR, 1H NMR, 13C NMR, 31P NMR and mass spectroscopy. For C5H5H(COMe)], the results of an X-ray structure determination are presented. 相似文献
8.
F.Y. Petillon F. Le Floch-Perennou J.E. Guerchais D.W.A. Sharp Lj. Monojlovic-Muir K.W. Muir 《Journal of organometallic chemistry》1980,202(1):23-37
The electron deficient acetylene, hexafluorobut-2-yne, reacts with molybdenum and tungsten methanethiolate derivatives (prepared in situ) to give vinyl and three-, five-, or six-membered heterocyclic derivatives: [Cp(OC)- Me], [Cp(OC)2Me], [CpW(CO)3C(CF3C(CF3)SMe], [CpW{η3-(O)}-(CO)2]. These reactions contrast with those of trifluoropropyne where no organometallic species are obtained. On heating or irradiation with CF3CCCF3 [CpMH(CO)3] gives known bridged species and in the presence of dimethyl disulphide the vinyl derivative [CpM(CO)3C(CF3)C(CF3)H]and an isomer of undetermined structure. 相似文献
9.
《Polyhedron》2001,20(9-10):1089-1095
10.
11.
Reaction of [PdCl2(PBut2Ph)]2 with silver acetate gives the internally metalated complex [PButPh]2(μ-Cl)2. This reacts with TlC5H5 and LiC5Me5 with chloride-bridge cleavage to yield C5R5PPButPh (R = H, Me). The complex [PBut2]2(μ-Cl)2,prepared from [PdCl2(PBut3)]2 and CH3COOAg, is analogously converted into C5R5But2. The chloride complex C5H5Pd(PBut5Ph)CI does not eliminate HCl to form C5H5PButPh. 相似文献
12.
The compounds and Ba3.6Al0.4Fe2S6[S0.6(S2)0.4], designated I and II, were prepared by reacting BaS, Fe, and S powders and Al foils in graphite containers sealed in evacuated quartz ampoules at approximately 1100°C. The crystal structure of I was determined using 1682 independent, nonzero X-ray reflections, while 3589 were used for II. They are triclinic, : BaS6 trigonal prisms share edges to form distorted hexagonal rings which form one-dimensional chains leaving two free lateral edges. The chains link in a stairstep manner with the rings offset along the [301] direction. These stairsteps join in a complicated manner to form a three-dimensional network. Fe ions are in two sites forming isolated FeS4 tetrahedra and isolated Fe2S6 dimers by edge-sharing tetrahedra. The Al substitution occurs in the trigonal prisms which have free edges with Al replacing Ba. Room-temperature Mössbauer isomer shifts are 0.20 mm/sec. for I and 0.30 mm/sec for II. These data indicate that upon Al substitution charge compensation occurs by reducing Fe3+. Valence calculations indicate that Fe in edge-sharing tetrahedra are reduced while the Fe in the isolated tetrahedron remains unchanged. The effective charge distribution in the Al substituted compound is approximately Fe3+, Fe2.5+ with electron delocalization across the shared edge. Room temperature electrical resistivity is 105 ohm/cm. The compositions of the crystals are best represented by the formulas and [Ba3AlFe2S7]0.4·[Ba4Fe2S7]0.2·[Ba4Fe2S6(S2)]0.4. The replacement of a sulfide by a disulfide ion is thought to be strongly dependent on the sulfur activity during the preparation. 相似文献
13.
C5H5FeC5H4CH2NMe2 reacts with sodium chloropalladate(II) in the presence of sodium acetate to give the internally metallated binuclear species [Me2}2] (X = Cl). The corresponding iodide was prepared as were mononuclear species [Me2}] and [Me2}L] L = PMe2Ph, AsMe2Ph, P(OMe)3 or PPh3. 1H NMR data are given. 相似文献
14.
Treatment of Ir2Cl2(C8H14)4 with the phosphines t-Bu3?nP(CH2CMe3)n (n = 3,2,1) in hot toluene followed by crystallization of the products from C7H8/ EtOH mixtures gave the cyclometallated hydrides (C8H14)2Ir-μ-Cl2(CH2CMe3)2][P(CH2 (I) [t-BuP(CH2CMe3)2]2H2Ir-μ-Cl2But(CH2CMe3)][t-BuP(CH2CMe3)2] (II), and [(t-Bu2rCl]2 (III). The dihydrides IrH2Cl[t-BuP(CH2CMe3)2]2 (IIa) and IrH2Cl(t-Bu2PCH2CMe3)2 (IIIa) were also isolated; these species were, however, more conveniently obtained by bubbling hydrogen through the solution of Ir2Cl2 (C8H14)4 and the respective phosphine in toluene. i-Pr3 reacted with the olefiniridium(I) precursor in C7H8/EtOH to yield the carbonyl complexes (i-Pr3P)2H2Ir-μ-Cl2Ir(CO)(PPri3)2 (IV) and IrCl(CO)(PPi3)2 (IVa), no cyclometallated product being detected. The stereochemistries of the complexes were deduced from IR, 1H, 31P, and 13C NMR data. The crystal structures of IIIa and IVa were also determined. 相似文献
15.
Ekkehard Lindner Faouzi Bouachir Wolfgang Hiller 《Journal of organometallic chemistry》1981,210(3):C37-C40
The heterocycle [(h5-C5H5)NiSP(CH3)2]2 is obtained by treatment of (h5-C5H5)2Ni with (CH3)2HPS in toluene and crystallizes monoclinic in the space group P21/c with Z = 2. The highly reactive three-membered ring (h5-C5H5)(CH3)2 which is a dissociation product of [(h5-C5H5)NiSP(CH3)2]2, can be trapped with bis(methoxycarbonyl)acetylene to give the PS containing nickelacyclopentadiene (h5-C5H5)R (R CO2CH3). 相似文献
16.
Henri Brunner Gundelinde Kerkien Joachim Wachter 《Journal of organometallic chemistry》1982,224(3):295-300
η5-C5H5(CO)2FeNa reacts with the benzimide chlorides C6H5(Cl)CNR (R CH(CH3)2, C6H5) in boiling THF to give the η1-iminoacyl complexes η5-C5H5 (CO)2Fe[η1-C(C6H5)NR]. Alternatively, the new Fe complexes [η5-C5H5(CO)FeCH3PF6 (IV) and [η5-C5H5(CO)2FeC(C6H5)N(CH3)C(C6H5)NCH3]PF6 (V) are formed under the same conditions, if R CH3. Hudrolysis of the CN single bond of the ligand in V, not stabilized by a chelate effects as in IV, results in the formation of [η5-C5H5(CO)2FeC(C6H5)NHCH3]PF6 (VII). Reaction of η5-C5H5(CO)2 with N-benyzylbenzimido chloride yields η5-C5H5(CO)2FeCH2C6H5 as the only isolated product. 相似文献
17.
18.
The magnetic interaction in the structural units [Fe2O7]8?, built of two corner-sharing FeO4 tetrahedra, in Na8Fe2O7 () has been studied by magnetic susceptibility measurements (4.2–500 K). An exchange integral of ?37 K is obtained by comparison of the experimental values and the calculated ones using a Heisenberg-Dirac-Van Vleck-type Hamiltonian ? = . The hypothesis of magnetically isolated [Fe2O7]8? groups is corroborated by Mössbauer spectroscopy between 1.5 and 77 K. The susceptibility measurements of the solid solutions Na8Fe2?xMxO7 (M = Al, Ga; 0 ≤ x ≤ 0.2 for Al; 0 ≤ x ≤ 2 for Ga) leads to the same conclusion of the existence of isolated Fe3+Fe3+ pairs in Na8Fe2O7. The type of substitution of Fe by Al or Ga is determined; homonuclear Fe3+Fe3+ and M3+M3+ pairs and heteronuclear Fe3+M3+ pairs are formed. 相似文献
19.
Raymond G. Teller James F. Brazdil Robert K. Grasselli Robert Thomas Lester Corliss Julius Hastings 《Journal of solid state chemistry》1984,52(3):313-319
The structure of Bi1.8Ce0.2(MoO4)3 has been refined with powder neutron diffraction data by the Rietveld method. The structure can be derived by severely distorting the scheelite structure (AMO4) and is perhaps better written , where Ø = cation vacancy. Of the two bismuth atom sites, cerium preferentially occupies the more symmetric of the two (Bi(2) in the structure) with some cerium found in the scheelite subcell vacancies also. This site preference is understood by examining the symmetries of the two Bi sites. Crystal data: monoclinic, space group , β = 115.19. 相似文献
20.
Edward W. Abel Gary D. King Keith G. Orrell Graham M. Pring Vladimir Sik T.Stanley Cameron 《Polyhedron》1983,2(11):1117-1124
Variable temperature 1H NMR spectroscopy has been used in the study of 1,3-intramolecular shifts of the M(CO)5 moiety in complexes of the general formula [M(CO)5L], (M = Cr or w), L = H2, H2 and H2. For the 1,3,5-trithian complexes precise energy barriers for the process have been obtained by detailed computer simulation of the static and dynamic spectra. Our results suggest that the magnitude of ΔG≠ (298.15 K) for the 1,3-shift is largely dependent upon the skeletal flexibility of the ligand system. In this context we have investigated the X-ray crystal structure of the highly substituted trithian complex [W(CO)5{β-H(Me)}]. 相似文献