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1.
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
2.
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
3.
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
4.
Trimethyl- and triphenyl-tin(IV) hydroxide act on triphenyl(2-carboxyethyl)-phosphonium hydrochloride, which is made from 3-chloropropionic acid and triphenylphosphine, to release water in the presence of dimethylformamide (DMF) as a catalyst. The water is azeotropically distilled to drive the reaction forward and produce triphenylphosphonopropionbetainetrimethyl- and triphenyl-tin(IV) chlorides in high yield. The latter product also results from the displacement of chloride from triphenyltin(IV) chloride by the phosphobetaine, (C6H5)3P(CH2)2CO2, which is made by treating the phosphonium hydrochloride with bicarbonate, and the compounds [(C6H5)3P(CH2)2CO2Sn(C6H5)3]+X? where X = Cl, Br, I, N3, NCS, NO3, B(C6H5)4 and Co(CO)4 are made in the same way. The acetate salt results from metathesis from the chloride and lead(II) acetate. A double salt, [(C6H5)3P(CH2)2CO2SnR3]+ [R3SnX2]?, is formed for X = Cl, Br and N3 by adding additional (C6H5)3SnX to the already-formed simple salts. Double salts are also obtained from the reactions between the phosphobetaine and triphenyltin(IV) isocyanate and methyldiphenyltin(IV) chloride. The phosphonium chloride double salt could be converted to the thiophosphonium derivative by heating with elemental sulfur in ethanol. The products of these novel nucleophilic displacement reactions are high melting solids. Tin-119m Mössbauer data are consistent with five-coordinated, triorganotin(IV) formulations with the exception of the diphenyl(8-hydroxyquinolinato)tin(IV) chloride salt in which the tin atom is six-coordinated, and the diphenyltin system cis-oriented. The parameters otherwise do not change with the nature of the X group, which is the tetracarbonylcobaltate derivative is tetrahedral by infrared, establishing the ionicity of the products. The chloride exhibits a molar conductivity indicative of a electrolyte in DMF. A bridging acetate structure in the solid is consistent with the lowered ν(CO2) frequencies. The Mössbauer spectra of the double salts give simple doublets of lowered isomer shift (IS) and raised quadrupole splitting (QS) which may arise from a cross-linking ion pairing of the polymer chains in the solid, and the NMR spectra of the two methyltin derivatives shows only a single resonance line and tin satellites which is rationalized by a dynamic exchange process. The products are formulated as associated in carboxylate polymers with dangling triphenylphosphonium cations. 相似文献
5.
Reaction of the 16 electron monomer [Co(η5-C5H5)(S2C2{CN}2)] with various tertiary phosphines and phosphites (L) gives readily the 18 electron monomers [Co(η5-C5H5)(S2C2{CN}2)L] which for L = P(OR)3 have J(C55) ca. 6 Hz but J(C55) = 0 for L = PR3. 相似文献
6.
Excited iodine atoms I(2P) are formed by laser irradiation of C2F5I at 2950 Å. The mean radiative lifetime τ of these metastable atoms and their bimolecular rate constant k2 for deactivation in collissions with C2F5I were measured to be: τ = 108 ± 10 ms; k2 = (1.8 ± 0.1) × 10?17 cm3/molec s. 相似文献
7.
The reaction of C5H5Rh(CO)(PiPr3) (1] which is prepared from C5H5Rh(CO)2 and neat P1Pr3, with the nitriloxides 2-RC6H4CNO (R = H, Cl) leads to the formation of the metallaheterocycles C5H5(P1Pr3)
) (2, 3) in 90–95% yield. Compound 1 reacts with tosylazide to give the C,N-bound isocyanate complex C5 H5(PiPr3)Rh(η2-TosN=C=O) (6). Analogously, on treatment of C5Me5Co(CO)(PMe3) with phenylazide the phenylisocyanate derivative C5Me5(PMe3)Co(η2-PhN=C=O) (7) is formed. Protonation of 7 with CF3CO 2H affords the non-ionic carbamoylcobalt complex C5Me5(PMe3)Co[C(O)NHPh](O2CCF3) (8). The X-ray structural analysis of 2 reveals the presence of an almost planar
heterocycle in which the two Rh-C distances differ by 0.045 Å 相似文献
8.
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
9.
[Pd(C6F5)2(CNR)2] (R = Cy, But, p-MeC6H4 (p-Tol)) react with [PdCl2(NCPh)2] to give [Pd2(μ-Cl)2(C6F5)2(CNR)2]. In refluxing benzene insertion of isocyanide into the C6F5Pd bonds occurs only for R = p-Tol, to give a imidoyl bridged polynuclear complex cis-[Pd2 (μ-Cl)2[μ-C(C6F5) = N(Tol-p)]2n]. This complex reacts with (a) Tl(acac) to give [Pd2{μ-C(C6F5) = N(Tol-p)}2(acac)2]; (b) neutral monodentate ligands to afford dimeric complexes [Pd2{μ-C(C6F5) = N(Tol-p)}2Cl2L2] (L = NMe3, py, 4-Me-py, SC4H8), and (c) isocyanides to give insoluble complexes of the same composition which are thought to be polymeric, [(CNR)Cl{μ-C(C6F5) = (p-Tol)}]n (R = p-Tol, Me, But). Thermal decomposition of cis-[Pd2 (μ-Cl)2 [μ-C(C6F5) = N( p-Tol)]2n] gives the diazabutadiene species (p-Tol)NC(C6F5)C(C6F5)N(p-Tol) in high yield. 相似文献
10.
Oxidation of the complexes -[M(CNR)2(dppe)2] (A) (M = Mo or W; R = Me, But or CH3C6H4-; dppe = Ph2PCH2CH2PPh2) with diiodine or silver (I) salts gives the paramagnetic cations -[M(CNR)2(dppe)2]+, (M = Mo, R = CH3C6H4-; M = W, R = But) and -[M(CNR)2(dppe)2]2+ (M = Mo, R = Me or CH3C6H4-; M = W, R = Me or But). Mixtures of products are generally produced when dichlorine or dibromine are the oxidising agents, however pure salts, the seven-coordinate complex cations [MX(CNC6H4CH3-)2(dppe)2]+ (B, X = Cl or Br) have been isolated. A simple molecular orbital scheme is proposed for complexes (A) and used to discuss their electronic spectra and their oxidation. 相似文献
11.
In the reaction of C5H5 Co(C3F7)(CO)I with the Schiff base NN′, derived from S-(-)-?-phenylethylamine and pyridine carbaldehyde-2, the salt [C5H5Co(C3F7)NN′]+ I? (Ia,b) is formed, which can be transformed to [C5H5 Co(C3F7)NN′]+ PF6? (IIa,b). The sodium salt Na+ [NN″]? of the Schiff base, derived from S-(-)-α-phenylethylamine and pyrrol carbaldehyde-2, in the reaction with C5H5 C0(C3F7)(CO)I yields the neutral complex C5H5 Co(C3F7)NN″ (IIIa,b). The diastereoisomeric pairs IIa,b and IIIa,b are separated by fractional crystallisation and chromatography respectively into the optically pure components which differ in their 1H NMR spectra. The IR, UV, CD, mass spectra and optical rotations of the new compounds IIa, IIb, IIIa and IIIb are compared. 相似文献
12.
Gordon K. Anderson Ronald J. Cross Ljubica Manojlovic-Muir Kenneth W. Muir Tihomir Solomun 《Journal of organometallic chemistry》1979,170(3):385-397
The known complex, -(η-C5H5)2Rh2(CO)2(CF3C2CF3) is formed in high yield from (η-C5H5)Rh(CO)2 and CF3FCCF3 at 100°. The less stable -isomer of the complex is obtained in low yield from the same reaction. The infrared, 1H, 19F and 13C NMR spectra of the two isomers are compared. The -isomer undergoes CO scrambling in solution at room temperature, and the variable temperature 13C NMR spectra are consistent with a pairwise bridge opening and closing mechanism. The mechanism is extended to account for the isomerization of to isomer, whihc has a half-life of 12 h at room temperature. The 13C spectrum indicates that the -isomer is static in solution at room temperature. The -isomer is reversibly protonated by protonic acids, and BF4? and PF6? salts of the protonated species can be isolated. The spectroscopic properties of these salts are consistent with protonation at one of the alkynyl-carbons, but it is not possible to distinguish between two alternative structures for the complex cation.Treatment of (η-C5H5)2Rh2(CO)2(CF3C2CF3) with (η-C5H5)Rh(CO)2 gives the trinuclear complex (η-C5H5)3Rh3(CO)(CF3C2CF3) in 80% yield. The analogoug but-2-yne complex is formed from (η-C5H5)3Rh3(CO)3 and MeCCMe. The infrared, 1H, 19F and 13C NMR spectra indicate that the hexafluorobut-2-yne complex exists in two different structural arrangements in solution. One has an edge bridging, and the other a face bridging carbonyl. The proportion of the isomers is affected by the solvent polarity. The spectra of the but-2-yne complex indicate it is fluxional at room temperature, and has a face bridging structure in solution regardless of the polarity of the solvent. Reversible protonation of the hexafluorobut-2-yne complex occurs in protonic acids, and the salt [(η-C5H5)3Rh3(CO)(CF3C2CF3)H]+[BF4]?,H2O can be isolated. The spectroscopic properties of this complex are consistent with a structure incorporating an edge-bridging carbonyl, and probably, an edge-bridging hydride ligand. 相似文献
13.
The reactions of [Co(η-C5H5)(CO)(PR3)] or [Co(η-C5GH5)(CO)2]/R3P mixtures (R = alkyl or aryl) with CS2 in refluxing CS2 or CS2/toluene gives rise to [Co(η-C5H5)(PR3)(CS)], [Co(η-C5H5)(PR3)(CS2)], [Co(η-C5H5)(PR3)(CS3)], and [Co3(η-C5H5)3 (CS)(S)] in reasonable yields. The corresponding reactions using PhNCS give [Co(η-C5H5)(PPh3)(PhNCS)] and a polymeric species which appears to be [Co4(η-C5H5)4 (PhNCS)]. Similar products are obtained with [Co(η-C5H5)(CO)(CNR)] or [Co(η0C5H5)(CO)2]/RNC mixtures. 相似文献
14.
Isomerisation reactions of 1-phenyl 1-butanone X+? () and five other C10H12O+? ions are demonstrated to proceed via a single intennediate (); the H2O elimination occurs from the tetralol structure (). 相似文献
15.
Reaction of Me5C5Li and Ni(CO)4 gave [(n5-Me5C5)Ni(CO)]2 () in 40 % yield. Reaction of with iodine followed by addition of a tertiary phosphine or reaction of (PPh3)2NiX2 with Me5C5Li or Me5C5SnBu3 gave (n5-Me5C5)Ni(L)X () (L = tertiary phosphine, X = halogen). Treatment of with RLi (R = Me, PhCC) afforded (n5-Me5C5)Ni(L)R (). The spectroscopic properties and the reactivities of n5-pentamethylcyclopentadienylnickel complexes indicate that the n5-Me5C5 ligand is more electron-donating and a sterically more bulky than the n5-C5H5 ligand. 相似文献
16.
R. Schwesinger K. Piontek W. Littke O. Schweikert H. Prinzbach C. Krüger Y.-H. Tsay 《Tetrahedron letters》1982,23(24):2427-2430
According to X-ray crystal structure analyses “cis-benzenetrisimine” () and “cis-benzenetrioxide” () act as tridentate ligands in their 2:1- and 4:1-complexes (Co(C6H9N3)2(NO3)3) and (Ba(C6H6O3)4(ClO4)2), resp. The latter is the rare example of an organic complex with the (approximate) T-symmetry. 相似文献
17.
Grant D.W. Anderson Malcolm L.H. Green Ino C. Vei 《Journal of organometallic chemistry》2004,689(24):4407-4419
Reactions between [Fe(η-C5H5)(MeCO)(CO)(L)], L = PPh3 (1), PMe3 (2), PPhMe2 (3), PCy3 (4), CO (5), and B(C6F5)3 give new complexes [Fe(η-C5H5){MeCOB(C6F5)3}(CO)(L)] L = PPh3 (7), PMe3 (8), PPhMe2 (9), PCy3 (10), CO (11), where B(C6F5)3 coordinates selectively to the O-acyl groups. Hydrolysis of 7 gives [Fe(η-C5H5){HOB(C6F5)3}(CO)(PPh3)] (6). The X-ray structures of 6, 8 and 11 have been determined. Calculations, using density functional theory, demonstrate that the charge transfer to the acyl group on Lewis acid coordination is more significant in the σ than the π system. Both effects lead to a lengthening of the acyl C-O bond thus π populations cannot be inferred from the distance changes. 相似文献
18.
Antimony(III)pentafluoroorthotellurate has been synthesized from SbF3 and B(OTeF5)3. Contrary to a previous report it is a low melting, sublimable solid (mp = 28°, bp (0.1 torr) = 68°, 19F - NMR: AB4 spinsystem δ (A) = ?42.7, δ (B) = ?38.1, J (AB) = 186 Hz). It reacts with F2, Cl2 and Br2 to give SbF2(OTeF5)3, SbCl4+Sb(OTeF5)6? and SbBr4+ Sb(OTeF5)6? respectively. Interaction of Xe(OTeF5)2 and Sb(OTeF5)3 yields Sb(OTeF5)5, which is unstable at room temperature. Salts containing the new anion Sb(OTeF5)6? have been synthesized either from Sb(OTeF5)5 and a corresponding pentafluoroorthotellurate e.g. Sb(OTeF5)5 + NMe4+ OTeF5? = NMe4+ Sb(OTeF5)6?, or from SbCl4 Sb(OTeF5)6? and an appropriate chloride SbCl4+ Sb(OTeF5)6? + NOCl = SbCl5 + NO+ Sb(OTeF5)6?, or oxidatively, using a mixture of Xe(OTeF5)2 and Sb(OTeF5)5, e.g. C6F6 + Xe(OTeF5)2 + Sb(OTeF5)5 = C6F6+ Sb(OTeF5)6? + Xe. 相似文献
19.
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
20.
Absolute rate constants are reported for reactions of C2O(3Σ?) under pseudo-first-order decay conditions. C2O is generated by laser photodissociation of C3O2 at 266 nm, and detected by dye-laser induced fluorescence on the 3Πi-3Σ? transition. Rate constants of (433 ± 12), (3.30 ± 0.12) and (1.12 ± 0.05) × 10?13 cm3 molecule?1 s?1 are reported for reactions with NO, O2 and isobutene. The NO value is approximate due to an apparent dark reaction between NO and C3O2. Upper limits of 1 × 10?14 cm3 molecule?1 s?1 are reported for reactions with H2, CO2, C3H2 and C2H4. The C2O + C3O2 reaction does not follow pseudo-first-order decay kinetics. Two explanations are proposed to explain this observation. Results are compared with previous relative rate measurements and are discussed in terms of their relevance to combustion chemistry. 相似文献