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1.
《Polyhedron》1988,7(21):2209-2211
Reaction of Li+[(η5-C5H5)Re(NO)(PPh3)]− with Ph3GeCl and Ph2GeCl2 (THF, −75°C) gives germyl complexes (η5-C5H5)Re(NO)(PPh3)(GePh3) (84%) and (η5-C5H5) Re(NO)(PPh3)(GePh2Cl) (3, 82%), respectively. Reaction of 3 and (CH3)3SiOTf gives (η5-C5H5)Re(NO)(PPh3)(GePh2OTf) (4, 82%). Several properties show the triflate substituent in 4 to be extremely labile. First, reaction of 4 and pyridine to give [(η5- C5H5)Re(NO)(PPh3)(GePh2NC5H5)]+TfO− (5) is complete in < 5 min at −78°C; the pyridine in 5 rapidly exchanges with pyridine-d5 (CD2Cl2, −80°C). Second, the 13C NMR resonances of the diastereotopic germanium phenyl substituents in 4 coalesce upon warming (ΔG3268K (CD2Cl2) = 12.6±0.2 kcal mol−1). The most likely mechanisms for this dynamic behaviour entail initial triflate dissociation to give the germylene complex [(η5-C5H5)Re(NO)(PPh3)( GePh2)]+TfO−. 相似文献
2.
《Journal of organometallic chemistry》1988,354(3):C33-C36
Reaction of (η5-C5Me5)Re(NO)(PPh3)(CH3) and HBF4 · OEt2 in CH2Cl2 at −78°C gives the dichloromethane complex [η5-C5Me5Re(NO)(PPh3)(ClCH2Cl)]+ BF4−, which undergoes the title transformation at −35°C. The ReClCH2Cl carbon is attacked by halide nucleophiles (X−) to give XCH2Cl and the chloride complex (η5-C5Me5)Re(NO)(PPh3)(Cl), and exhibits a 13C NMR resonance that is coupled to phosphorus (d, 3J(CP) 5.0 Hz) and geminal hydrogens (t, 1J(CH) 186 Hz). 相似文献
3.
《Journal of organometallic chemistry》1991,402(3):C56-C58
Complete self-recognition of chirality is observed in the Michael addition of the enolate derived from R,S-[η5-C5H5Fe(CO)(PPh3-COCH3] to the acryloyl complex R,S-[(η5-C5H5Fe(CO)(PPh3)-COCHCH2)] to generate exclusively the single diastereoisomer of the glutaroyl complex RR,SS-[(η5-C5H5)Fe(CO)(PPh3)COCH2]2CH2. 相似文献
4.
Pandey KK 《The journal of physical chemistry. A》2011,115(30):8578-8585
Density functional theory calculations have been performed for the dimethylgallyl complexes of iron, ruthenium, and osmium [(η(5)-C(5)H(5))(L)(2)M(GaMe(2)] (M = Fe, Ru, Os; L = CO, PMe(3)) at the DFT/BP86/TZ2P/ZORA level of theory. The calculated geometry of the iron complex [(η(5)-C(5)H(5))(CO)(2)Fe(GaMe(2))] is in excellent agreement with structurally characterized complex [(η(5)-C(5)H(5))(CO)(2)Fe(Ga(t)Bu(2))]. The Pauling bond order of the optimized structures shows that the M-Ga bonds in these complexes are nearly M-Ga single bond. Upon going from M = Fe to M = Os, the calculated M-Ga bond distance increases, while on substitution of the CO ligand by PMe(3), the calculated M-Ga bond distances decrease. The π-bonding component of the total orbital contribution is significantly smaller than that of σ-bonding. Thus, in these complexes the GaX(2) ligand behaves predominantly as a σ-donor. The contributions of the electrostatic interaction terms ΔE(elstat) are significantly smaller in all gallyl complexes than the covalent bonding ΔE(orb) term. The absolute values of the ΔE(Pauli), ΔE(int), and ΔE(elstat) contributions to the M-Ga bonds increases in both sets of complexes via the order Fe < Ru < Os. The Ga-C(CO) and Ga-P bond distances are smaller than the sum of van der Waal radii and, thus, suggest the presence of weak intermolecular Ga-C(CO) and Ga-P interactions. 相似文献
5.
T. Yu. Orlova Yu. S. Nekrasov P. V. Petrovskii M. G. Ezernitskaya Z. A. Starikova O. L. Lependina 《Russian Chemical Bulletin》2008,57(1):63-67
The metallation of the η5-C5H5(CO)2Fe-η1,η5-C5H4Mn(CO)3 complex with BunLi (THF, ?78 °C) followed by the treatment of the lithium derivative with Ph2PCl afforded the η5-Ph2PC5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3 complex. The reaction of the latter with η5-C5H5(CO)3WCl in the presence of Me3NO produced the trinuclear complex η5-C5H5Cl(CO)2W-η1,η5-(Ph2P)C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)3. The structure of the latter complex was established by IR, UV, and 1H and 31P NMR spectroscopy and X-ray diffraction. The reaction of MeSiCl3 with three equivalents of LiC5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3 gave the hexanuclear complex MeSi[C5H4(CO)2Fe-η1,η5-C5H4Mn(CO)2PPh3]3. 相似文献
6.
Wang Mei Miguel Daniel Riera Víctor Bois Claudette Jeannin Yves 《Transition Metal Chemistry》2001,26(4-5):566-569
A novel dimolybdenum complex [(3-C3H5)(CO)2Mo(-S2CPCy3)Mo(3-CH2CMeCH2)(CO)2], obtained by reacting the [(CO)2(3-C3H5)Mo(-S2CPCy3)Mo(CO)3]– anion with an excess of ClCH2CMe=CH2, has been characterized by i.r., 31P{1H}, 1H- and 13C-n.m.r. spectroscopy and by elemental analysis. The crystal structure of the complex, determined by X-ray diffraction, shows a definite preference for the central carbon of the S2CPCy3 bridge to bind to the Mo(2) atom coordinated by 3-2-methylallyl, rather than the Mo(1) atom attached to unsubstituted 3-allyl ligand. 相似文献
7.
Rainer Bartsch Christian Müller Axel Fischer Peter G. Jones 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Syntheses and structures of penta- and hexaphosphorus analogues of ferrocene have been described recently1. Unlike their simple ferrocene analogues, these complexes have further ligating potential towards other transition metal centres by virtue of the availability of the ring phosphorus lone-pair electrons that are not involved in the η5-coordination. We now describe the first examples of coordination compounds of the triphospha-ferrocene [Fe(η5-C5Me5) (η5-C2 tBu2P3]. In the ruthenium complex [Fe(η5-C5Me5)(η5-C2 tBu2P3) Ru3(CO)9] 2 two adjacent phosphorus atoms of the η5-C2 tBu2P3 ring are interlinked by a ruthenium carbonyl cluster in which all three ruthenium atoms interact with the phosphorus atoms. The tetrametallic nickel complex [Fe(η5-C5Me5)(η5-C2 tBu2P3)Ni(CO)2]2 3 represents the first example of intermolecular interlinkage of two phospha-ferrocene systems by two metal centres. 相似文献
8.
The reaction of [(η5-C5Me5)2Mo2(μ3-S)4(CuCl)2] 1 with Na2S in MeCN produced a trinuclear cluster [(η5-C5Me5)2Mo2(μ3-S)( μ3-S)3(CuCl)] 2. 2 crystallizes in the monoclinic system, space group P21/c with a=15.563(3), b=8.9547(18), c=17.846(4) (A), β=101.29(3)°, V=2438.9(9) (A)3, Z=4, Dc=1.878 g/cm3, T=193(2) K, C20H30ClCuMo2S4, Mr=689.60, F(000)=1376, μ(MoKα)=2.335 mm–1, S=1.050, R=0.0305 and wR=0.0688 for 4033 observed reflections with Ⅰ > 2σ(Ⅰ). In the structure of 2, one [(η5-C5Me5)2Mo2(μ-S)2S2] moiety and one CuCl unit are assembled into an incomplete cubane-like [Mo2S4Cu] core framework, in which the Cu center adopts a distorted tetrahedral geometry coordinated by oneμ3-S atom, twoμ-S atoms and one terminal chloride. The two Mo…Cu contacts are 2.7519(7) and 2.7689(8) (A), respectively. 相似文献
9.
《Journal of organometallic chemistry》1987,320(2):C19-C22
The complex [(η5-C5H5)Fe(CO)(PPh3)CH2CH3] is shown by 1H NMR spectroscopy and an X-ray crystal structure analysis to adopt a single conformation with the methyl group residing between the cyclopentadienyl and carbon monoxide ligands. 相似文献
10.
11.
《Journal of organometallic chemistry》1986,308(2):253-259
The CuI complex Cu(CH3CN)4+PF6− chemoselectively abstracts phosphine from Cp(CO)(PPh3FeCOCH3 and produces Cp(CO)2FeCH3 in good yield. No evidence for electrophilic CuI coordinating the acetyl ligand on Cp(CO)(L)FeCOCH3 (L = CO, PPh3), however, was obtained Reactions of CuI and Cp(CO)(PPh3)FeCH3, with and without the presence of CO, also were examined. With CO, this methyl complex first gives its acetyl derivative Cp(CO)(PPh3)FeCOCH3 (1 atm CO in CH2Cl2 solution, 5 min), and after excess CO is removed (it otherwise blocks further reaction), Cp(CO)2FeCH3 forms. 相似文献
12.
13.
《Journal of organometallic chemistry》1987,326(1):C13-C16
It is shown that (1,2,7-η3-2-Me-benzyl)(η5-C5H5)Mo(CO)2 exits in solution as one isomer which is fluxional, probably via (7-η1-2-Me-benzyl)((η5-C5H5)Mo(CO)2, with ΔG≠370 = 23.6 ± 1.0 kcal mol−1. In contrast, (1,2,7-η3-3-Me-benzyl)(η5-C5H5)Mo(CO)2 exits as two isomers at −20°C, which undergo interconversion at room temperature with ΔG≠ 15.7 kcal mol−1. This dynamic process is an allyl rotation. It is probable that there is also a low energy [1,5]-sigmatropic shift. 相似文献
14.
《Journal of organometallic chemistry》1990,381(1):C21-C25
The chiral aminoferrocenylphosphine [(η5-C5H4PPh2)(η5-C5H3(PPh2)CH(CH3)-N(CH3)CH2CH2N(CH3)2)Fe] (1) reacts with (H3C)2SAuCl to give neutral gold(I) complexes that are active catalysts for the enantioselective coupling of isocyanoacetate esters with aldehydes, forming dihydrooxazoles. The structure of the trimeric complex [(rac-1)2(AuCl)3] · Et2O has been determined by X-ray diffraction. 相似文献
15.
R. G. Gasanov M. V. Tsikalova E. V. Martynova Yu. N. Novikov 《Russian Chemical Bulletin》2008,57(2):309-315
Addition of the ·P(O)(OPri)2, Me·, Et·, ·But, and Cl3C· radicals to the (ν2-C60)Os(CO)-(PPh3)2(CNBut) complex (1) was studied by ESR spectroscopy. The spectral parameters of the spin-adducts of these radicals with complex 1 were determined. The predominant direction of the attack by the ·P(O)(OPri)2, ·But, and Cl3C· radicals are the cis-1 and cis-2 bonds of the fullerene molecule. The stability of the spin-adducts depends substantially on the nature of the added radical.
The addition rate constants of the ·P(O)(OPri)2, ·But, and Cl3C· radicals to complex 1 and the dimerization rate constants for these spin-adducts were determined.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 301–307, February, 2008. 相似文献
16.
《Comptes Rendus Chimie》2002,5(1):67-72
17.
《Journal of organometallic chemistry》1988,353(2):C23-C26
Mild, reductive carbonylation of (C5Me5)TaCl4 in the presence of trimethylphosphine gives (C5Me5)Ta(CO)4 in 47% yield. The intermediate (C5Me5)TaCl2- (CO)2(PMe3) has been isolated from the reaction of (C5Me5)TaCl2(PMe3)2 with carbon monoxide and its crystal structure determined (space group P212121). 相似文献
18.
《Journal of organometallic chemistry》1988,339(3):339-343
The 13C {1H} NMR spectra of a series of complexes [(η5-C5H4Me)Fe(CO)(L)I] (L t-BuNC, P(OMe)3, PMe3, PMe2Ph, PMePh3, PPh3 and P(C6H11)3) have been recorded and the five cyclopentadienyl resonances assigned to ring carbon atoms by means of CH correlated spectra. It has been observed that the C atoms ortho to the ring methyl group (C(2) and C(5)) as well as the quaternary C atom are always coupled to the ligand P atom. A correlation between the chemical shift difference Δ(C(2) – C(5)) and the Tolman cone angle, θ, has also been established. 相似文献
19.
《Tetrahedron letters》1988,29(49):6509-6512
The asymmetric synthesis of the α-pentyl succinate fragment of (-)-Actinonin is achieved using the chiral iron acetyl S-(+)-[(η5-C5H5)Fe(CO)(PPh3)COCH3] and subsequently converted to (-)-Actinonin in an overall yield of 41%. 相似文献