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51.
Linda K. Bell Wolfgang A. Herrmann Gangolf W. Kriechbaum 《Journal of organometallic chemistry》1982,240(4):381-393
An unexpected novel coordination mode of diazoalkanes has been verified via addition of 2-diazopropane to the metal—metal triple bond of bis[dicarbonyl(η5-pentamethylcyclopentadienyl)molybdenum] (MoMo). The dinuclear 1:1 addition product isolated in nearly quantitative yield is structurally characterized by a bent, 4-electron type η1:η2-diazoalkane ligand, with the terminal nitrogen atom symmetrically bridging the metal-metal “single bond” (d(MoMo) 305.0(2) pm; d(Mo---N(1)) 212.0(12) and 212.6(10) pm, respectively) and the second nitrogen atom being bonded to one molybdenum atom only (d(Mo---N(2)) 213.4(13) pm). 相似文献
52.
Shavaleev NM Accorsi G Virgili D Bell ZR Lazarides T Calogero G Armaroli N Ward MD 《Inorganic chemistry》2005,44(1):61-72
Mononuclear complexes [Re(bpym)(CO)(3)Cl] and [Pt(bpym)(CC-C(6)H(4)CF(3))(2)] (bpym = 2,2'-bipyrimidine), in which one of the bipyrimidine sites is vacant, have been used as "complex ligands" to prepare heterodinuclear d-f complexes in which a lanthanide tris(1,3-diketonate) unit is attached to the secondary bipyrimidine site to evaluate the ability of d-block chromophores to act as antennae for causing sensitized near-infrared (NIR) luminescence from adjacent lanthanide(III) centers. The two sets of complexes so prepared are [Re(CO)(3)Cl(mu-bpym)Ln(fod)(3)] (abbreviated as Re-Ln; where Ln = Yb, Nd, Er) and [(F(3)C-C(6)H(4)-CC)(2)Pt(mu-bpym)Ln(hfac)(3)] (abbreviated as Pt-Ln; where Ln = Nd, Gd). Members of both series have been structurally characterized; the metal-metal separation across the bipyrimidine bridge is approximately 6.3 A in each case. In these complexes, the (3)MLCT (MLCT = metal to ligand charge-transfer) luminescences of the mononuclear [Re(bpym)(CO)(3)Cl] and [Pt(bpym)(CC-C(6)H(4)CF(3))(2)] complexes are quenched by energy transfer to those lanthanides (Ln = Yb, Nd, Er) that have low-lying f-f states capable of NIR luminescence; as a result, sensitized NIR luminescence is seen from the lanthanide center following excitation of the d-block unit. In the solid state, quenching of the luminescence from the d-block chromophore is complete, indicating efficient d --> f energy transfer, as a result of the short metal-metal separation across the bipyrimidine bridge. In a CH(2)Cl(2) solution, partial dissociation of the dinuclear complexes into the mononuclear units occurs, with the result that some (3)MLCT luminescence is observed from mononuclear [Re(bpym)(CO)(3)Cl] or [Pt(bpym)(CC-C(6)H(4)CF(3))(2)] present in the equilibrium mixture. Solution UV-vis and luminescence titrations, carried out by the addition of portions of Ln(fod)(3)(H(2)O)(2) or Ln(hfac)(3)(H(2)O)(2) to the d-block complex ligands, indicate that binding of the lanthanide tris(1,3-diketonate) unit at the secondary bipyrimidine site to give the d-f dinuclear complexes occurs with an association constant of ca. 10(5) M(-)(1). 相似文献
53.
Stephen Bell Xiaodong Zhu Gamil A. Guirgis James R. Durig 《Journal of Molecular Structure》2002,616(1-3):135-158
The infrared spectra (3500–50 cm−1) of the gas and solid and the Raman spectra (3500–50 cm−1) of the liquid and solid have been recorded for 2-hexyne, CH3–CC–CH2CH2CH3. Variable temperature studies of the infrared spectrum (3500–400 cm−1) of 2-hexyne dissolved in liquid krypton have also been recorded. Utilizing four anti/gauche conformer pairs, the anti(trans) conformer is found to be the lower energy form with an enthalpy difference of 74±8 cm−1 (0.88±0.10 kJ/mol) determined from krypton solutions over the temperature range −105 to −150 °C. At room temperature it is estimated that there is 42% of the anti conformer present. Equilibrium geometries and energies of the two conformers have been determined by ab initio (HF and MP2) and hybrid DFT (B3LYP) methods using a number of basis sets. Only the HF and DFT methods predict the anti conformer as the more stable form as found experimentally. A vibrational assignment is proposed based on the force constants, relative intensities, depolarization ratios from the ab initio and DFT calculations and on rotational band contours obtained using the calculated equilibrium geometries. From calculated energies it is shown that the CH3 group exhibits almost completely free rotation which is in agreement with the observation of sub-band structure for the degenerate methyl vibrations from which values of the Coriolis coupling constants, ζ, have been determined. The results are compared to similar properties of some corresponding molecules. 相似文献
54.
Azulene reacts with paraformaldehyde in the presence of florisil to give excellent yields of calix[4]azulene. 相似文献
55.
The reaction of CCl2F2 (CFC 12) with hydrogen has been studied on a Pt/-Al2O3 catalyst containing 0.5, 2 and 5 wt % of Pt at a temperature of 300°C and on 2% Pt at other temperatures. The product selectivity (distribution), and the extent of conversion, was shown to be highly dependent both on the metal coverage and on the temperature. 相似文献
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The completely relaxed ab initio structures of some forms of H2F2 and H3F3 reflect the cooperative nature of hydrogen bonding and can be used to estimate the order of magnitude of the variations in local geometry which are neglected when interactive potentials for HF in clusters or in the liquid state are evaluated with constrained geometries. 相似文献