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
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
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
The perfluoronitrosocycloalkanes, heptafluoronitrosocyclobutane and nonafluoronitrosocyclopentane, are convenient precursors to a family of new perfluorocycloalkyl(aryl) diazenes. With aniline and o-aminobenzamide, FNNH and FNNC(O)NH2 (x = 2,3) are formed. Additionally, heptafluoronitrosocyclobutane gives FNNF and FNNNH2 with 2,3,5,6-tetrafluoroaniline and o-phenylenediamine 相似文献
Thermolysis of (η5-cyclopentadienyl)(triphenylphosphine)cobaltacyclopentadiene complexes has been found to give (η5-cyclopentadienyl)(η4-cyclobutadiene)-cobalt complexes in reasonable yields. Similar treatment of benzyl-substituted cyclopentadienyl derivatives gave diene complexes, (η5-C5H5CH2R1CR2CR3CHR4)Co, which were formed by addition of the ortho hydrogen of the benzyl group to the cobaltacyclopentadiene ring. 相似文献
The structure of the compound trans-[PdCl {(Me)N-?-C6H4OMe} (PPh3)2] was solved, using a conventional combination of Patterson and Fourier functions, least-squares refinements and electron density difference maps, to a reliability index R of 0.069 for the 2923 observed reflections collected by four-circle diffractometer. The palladium arom is surrounded in a roughly planar fashion by two trans phosphorus atoms, a chlorine atom, and a σ-bonded carbon atom of the diazabutadienyl group. This group assumes a trans configuration, the NCCN fragment being virtually planar and nearly normal to the mean coordination plane. The Pdligand bond lengths are: PdC 1.98(1), PdCl 2.41(1),PDP(1) 2.33(1) and PdP(2) 2.35(1) Å. 相似文献
The metal carbonyl anions [Fe(η-C5H5(CO)2]? and [Re(CO)5] undergo regio- and site-specific [2 + 2]-cycloadditions with the ketenimines Ph2CCNR (R = Me, Ph) to give the (isolable) anionic complexes [Ln(O)}]? (LnM = Fe(η-C5H5)CO, Re(CO)4) which have been alkylated and acylated at the exocyclic oxygen atom of the carbonyl function. The result is stable neutral complexes having a metallaazetidine structure which is composed of an α-metallated enamine and an N,O carbene part. IR, 1H, and 13C NMR data are presented. 相似文献
When (t-Bu)2PCH2CHCH2CH2 is combined with [IrCl(C8H14)2]2 in toluene, the σ-bound cyclopropane complexes (P(t-Bu)2CH2H2) (1a, 1b) are formed. Complexes 1a,1b react readily with H2 to form IrClH2P(t-Bu)2CH2H2)2 (2). In polar solvents 1a,1b isomerize to the σ-vinyl chelated complex H)(P(t-Bu)2CH2H2) (3). The structure of this 5-coordinate, 16-electron IrIII complex was deduced from spectroscopic data, reaction chemistry, and from the crystal structure of its CO adduct (4). Compound 4 crystallizes in the monoclinic space group C2h5-P21/n (a 15.610(14), b 15.763(16), c 11.973(13) Å, and β 104.74(5)°) with 4 molecules per unit cell. The final agreement indices for 2326 reflections having Fo2 > 3σ(Fo2) are R(F) = 0.089 and Rw(F) = 0.095 (271 variables) while R(F2) is 0.148 for the 3423 unique data. Bond lengths in the 5-atom chelate ring are IrP 2.341(4), PC 1.857(26), CC 1.520(30), CC 1.341(25), and CIr 1.994(21) Å. The IrCl distance is 2.479(5) Å. 相似文献
Reactions between MX(PPh3)2(η-C5H5) (M = Ru, X = Cl; M = Os, X = Br) and 2-CH2CHC6H4PPh2 afford Ph2)(η-C5H5); the Os complex is obtained in two isomeric forms. The X-ray structure of the major isomer shows the CC double bond (OsC, 2.214, 2.195 Å; CC, 1.57 Å) is almost coplanar with the OsBr vector, with the terminal C cis to Br; the minor isomer is assumed to have the alternative, more sterically congested conformation, with the β-C cis to Br. The chlororuthenium complex reacts with NaOMe/MeOH to give the corresponding hydrido complex, which also exists as two isomers in solution; reaction of this complex with CS2 gives the expected dithio acid derivative Ph2)(η-C5H5), together with small amounts of a complex assumed to be Ph2](η-C5H5). The X-ray structure of the major product reveals an unusual η3-S2C mode of coordination of the dithio acid fragment (RuS, 2.418, 2.426(1) Å; RuC 2.175(4) Å). Crystals of OsBr(η2-CH2CHC6H4P)Ph2)( η-C5H5) are monoclinic, space group P21/n, with a 12.696(2), b 21.719(6), c 15.929(3) Å, β 79.77(2)°, Z = 8; 2867 data (I > 2.5σ(I)) were refined to R = 0.040, Rw = 0.044. Crystals of Ph2)(η-C5H5) are orthorhombic, space group Pbca, with a 8.921(2), b 15.982(9), c 32.216(5) Å, Z = 8; 1685 data (I > 2.5σ(I)) were refined to R = 0.027, Rw = 0.030. 相似文献
A reinvestigation of the reaction between C2(CO2Me)2 and RuH(PPh3)2(η-C5H5) and some related complexes is reported. Initial cis addition is followed by conversion into the trans isomer. In the case of the bis-(PPh3) complex, isomerisation is followed by chelation of the ester CO group with concomitant displacement of one PPh3ligand. The resulting chelate complex reacts with CO or CNBut to give the (Z)-RuC(CO2Me)CH(CO2Me) complexes; the (E)-isomer of the carbonyl complex is obtained by addition of C2(CO2Me)2to RuH(CO)(PPh3)(η-C5H5). The 1Hand 13C NMR spectra are not a reliable guide to assignment of the stereochemistry of the vinyl group. Other products isolated from the initial reaction are the bis-insertion product CH(CO2Me)} -(PPh3)(η-C5H5) and the 1/2 PPh3/C2(CO2Me)2 adduct. The molecular structures of Ru{(Z)-C(CO2Me)CH(CO2Me)}(CO)(PPh3(η-C5H5) · 0.5EtOH, Ru{(E)-C(C2Me)CH(CO2Me)}(dppe)(η-C5H5) and CH(CO2Me)}(PPh3)(η-C5H5) have been determined. The cis isomer is monoclinic, space group P21,with a 9.328(8), b 17.385(10), c 10.356(7) Å, β 101.78(3)° and Z = 2; 2107 data with I ≥ 2.5σ(I) were refined to R = 0.076 Rw = 0.085. The trans isomer is triclinic, space group P, with a 10.404(7) b 11.221(6), c 13.230(9) Å, α 92.67(5), β 110.56(5), γ 106.21(5)° and Z = 2; 2520 data with I ≥ 2.5σ(I) were refined to R = 0.055 Rw = 0.068. The butadienyl complex is monoclinic, space group P21/a, with a 19.655(8), b 8.674(4), c 21.060(5) Å, β 116.22(3)° and Z = 4; 2724 data with I ≥ 2.5σ(I) were refined to R = 0.042, Rw = 0.047. 相似文献
Mechanistic and synthetic highlights of out studies during the past twenty years on azides derived from fluorocarbon systems {alkenes ( CF3CFCFN3), aza-alkenes and -cycloalkenes [(CF3)N3], arenes ( C6F5N3), and heteroarenes( 4-N3.C5F4N)} will be discussed with emphasis on recent results bearing on the synthesis of novel seven-membered -heterocycles. 相似文献
The η-hexamethylbenzenehydridoruthenium(II) complexes RuHCl(η-C6Me6)L (L = PPh3 (11), AsPh3 (12), P(C6H4-p-F)3 (14), P(C6H4-p-Me)3 (15), P(C6H4-p-OMe)3 (16), P-t-BuPh2 (17), P-i-PrPh2 (18), P-i-Pr3 (19), PCy3 (20) and P-t-BuMe2 (21)) have been made by heating [RuCl2(η-C6Me6)]2, the ligand and sodium carbonate in propan-2-ol. The triarylphosphine complexes 11, 14 and 15 react with methyllithium to give aryl ortho-metallated hydridoruthenium(II) complexes such as Ph2)(η-C6Me6) (22) and 19 similarly gives the isopropyl cyclometallated complex -i-Pr2(η-C6Me6) (29) as a mixture of diastereomers. Reaction of 17 with methyllithium gives initially the t-butyl cyclometallated complex Ph2)(η-C6Me6) (25) which isomerizes by a first order process (k.2 h?1 in C6D6 or THF-d8 at 50°C) to the aryl ortho-metallated complex -t-BuPh)(η-C6Me6) (26). The similarly generated isopropyl cyclometallated complex Ph2)(η-C6Me6) (27) has not been isolated in a pure state owing to rapid isomerization to -i-PrPh)(η-C6Me6) (28); both 27 and 28 exist as a pair of diastereomers. The formation of the cyclometallated complexes and the isomerizations are thought to involve intermediate 16-electron ruthenium(O) complexes Ru(η-C6Me6)L. 相似文献
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
The cyclometallation of p-RC6H4CHNCH2C6H2, (R = H, Cl, NO2) by PdX2 (X = Cl, AcO) has been studied.In every case the cyclometallation occurs with formation of a five-membered ring containing the methine group. The structure of these compounds [CH2C6H5)]2, derived from 1H NMR spectra, are different from those reported previously. Reaction of these compounds with PEt3 gives the compounds [PdX(p-RC6H3CHNCH2C6H5)(PEt3)2] but with an excess of PPh3 only the complexes [CH2C6H5)(PPh3)] are formed. 相似文献
Treatment of [{Ir(COD)(μ-Cl)}2] with excess of the electron-rich olefin [Ar]2 (abbreviated as (LAr)2, Ar = C6H4Me-p or C6H4OMe-p) affords the ortho-metallated tricycle [)3], which for Ar = C6H4Me-p (Ia) with HCL yields [)2(LAr)]Cl (IV); X-ray data show that in IV there is an unexpectedly close Ir?C(o-aryl) contact (2;52(1) Å) involving the “free” LAr which compares with an IrC(o-aryl) distance of 2.09(3) Å in Ia or 2.07(3) Å in the ortho-metallated LAr ligand of complex IV. 相似文献
Sulfinyl fluoride and N-(F-isoprophyl)iminosulfur difluoride form the compounds, O(CH3) and i-C3F7N(CH3 with symdimethylethylenediamine (1). In contrast, CF3C(O)NSF2 and (Rf)2SF2 (Rf = CF3, i-C3F7 form only acyclic compounds, CF3C(O)N(CH3)CH2CH2N(CH3)C(O)CF3 and RfSN(CH3)CH2CH2N(CH3)SRf with (1). With PF3, PF5 and OPF3, cyclic compounds F, F3, and -(O)F result. When the latter two compounds are reacted further with LiNC(CF3)2, N(CH3)CH2CH2N(CH3)PF2NC(CF3)2 and (O)NC(CF3)2) form. 相似文献
