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91.
92.
Domenico Osella Mauro Ravera Carlo Floriani Euro Solari 《Journal of organometallic chemistry》1996,510(1-2):45-50
We describe the redox behaviour in non-aqueous solvents of some cyclopentadienyl(oxo)titanium derivatives. The derivative [Ti4{η5-C5H4(SiMe3)}4(μ-O)6] shows an electrochemically and chemically reversible le reduction process, followed by a multi-electron, chemically complicated reduction at a fairly cathodic potential. On the basis of the overall electrochemical features and the comparison with the redox behaviour of the quasi-planar compound [[Ti{η5-C5H4(SiMe3)}Cl(μ-O)]4] we propose an EECCEE mechanism for the first derivative, where the second electron-transfer induces a cascade of chemical reactions giving rise to irreversible cluster breakdown. The electrochemically induced fragmentation can be viewed as a retrosynthetic pathway. The heterometallic derivative [{Ti(η5-C5H4Me)2(μ2-MoO4)2}2] shows two consecutive reduction processes; the first is chemically reversible, and the second quasi-reversible. The molybdate bridges apparently increase the stability of the electrogenerated anions. However none of these poly-oxo clusters can be considered as good models of electron ‘sinks’. 相似文献
93.
Ab initio molecular orbital calculations using the STO3-21G basis set has been carried out for the cluster series Na
n
+
, Na
n
, and Na
n
–
(wheren=2–7). The basis set is shown to be reliable compared with more extensive basis sets at the Hartree-Fock level. Thirty-one optimized structures are reported and discussed, many of which (especially for the anions) have not been considered. The STO3-21G//STO3-21G calculations suggest that for most of the species the optimum geometries are planar. In particular, the optimized structures for the anionic species should provide a starting point for more sophisticated configuration interaction calculations. 相似文献
94.
Diphenylphosphine oxidatively adds to the ReRe bonds of Re2
X
4(-dppm)2 (X=Cl or Br; dppm=Ph2PCH2PPh2) and Re2Cl4(-dpam)2 (dpam=Ph2AsCH2AsPh2) to afford the dirhenium(III) complexes Re2(-X)(-PPh2)HX
3(-LL)2. The dppm complexes have also been prepared from the reactions of Re2(-O2CCH3)X
4(-dppm)2 with Ph2PH, and a similar strategy has been used to prepare Re2(-Cl)(-PPh2)HCl3(-dmpm)2 (dmpm=Me2PCH2PMe2) from Re2(-O2CCH3)Cl4(dmpm)2. Phenylphosphine likewise reacts with Re2
X
4(-dppm)2 to give Re2(-X)(-PHPh)HX
3(-dppm)2. An X-ray crystal structure determination on Re2(-Cl)(-PPh2)HCl3(-dppm)2 confirms its edge-shared bioctahedral structure. This complex crystallizes in the space group
(No. 148) witha=21.699(3) Å, =84.50(4)°,V=10084(5) Å3, andZ=6. The structure was refined toR=0.049 (R
w
0.069) for 5770 data withI>3.0(I). The Re-Re distance is 2.5918(7) Å. Oxidation of the bromide complex Re2(-Br)(-PPh2)HBr3(-dppm)2 with NOPF6 produces the unusual dirhenium(III, II) cation [Re2(-H)(-Br)[P(O)Ph2]Br2(NO)(-dppm)2]+ which has been structurally characterized as its perrhenate salt, [Re2(-H)(-Br)[P(O)Ph2]Br2(NO)(-dppm)2]ReO4 · 2CH2Cl2. This complex crystallizes in the space group
(No. 2) witha=14.187(7) Å,b=16.419(5) Å,c=16.729(5) Å, =98.76(2)°, =110.11(3)°, =104.66(3)°,V=3414(6) Å3,Z=2. The structure was refined toR=0.040 (R
w
=0.051) for 5736 data withI>3.0(I). The presence of a phosphorus-bound [P(O)Ph2]– ligand, a linear nitrosyl and a bridging hydrido ligand has been confirmed. The Re-Re distance is 2.6273(8) Å. 相似文献
95.
The results of quantum chemical calculations of the electronic structure and geometry of octahedral clusters [Mo6S8(CN)6]6−, [Mo6Se8(CN)6]6−, [Re6S8(CN)6]4−, and Rh6(CO)16 by the ab initio SCF (RHF) and DFT (B3LYP) methods with various basis sets are presented. The electronic states of the clusters under study
in ideal spherically symmetric potential were classified in the orbital quantum number l (1s, 1p, 1d, 1f, 1g, 1h, 1i), l = 0–6. In real crystal field with Oh symmetry these states are split. The calculated new electronic states were matched to the irreducible representations of
the point symmetry group Oh. The polarizabilities of the compounds considered are 55–65 Å3. A new model for the electronic structure of octahedral clusters containing M6 groups was proposed. The model is based on the idea of free electrons moving in spherically symmetric potential field.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2617–2624, December, 2005. 相似文献
96.
Kinsel GR Knochenmuss R Setz P Land CM Goh SK Archibong EF Hardesty JH Marynick DS 《Journal of mass spectrometry : JMS》2002,37(11):1131-1140
The photoionization of (pro)(n)DHB (pro = proline, DHB = 2,5-dihydroxybenzoic acid, n = 0, 1, 2 or 4) clusters was studied both experimentally and computationally. Experimentally the (pro)(n)DHB clusters are generated in the gas phase by laser desorption and supersonic jet entrainment. The photoionization thresholds are then determined by the mass-selective measurement of both one- and two-color photoionization efficiency curves. These experiments demonstrate that the ionization energies (IEs) of the (pro)(n)DHB clusters are substantially reduced in comparison with the IE of free DHB. Computational studies of the (pro)(n)DHB clusters provide insights into the mechanism of IE reduction. For the (pro)DHB system the IE reduction results from spin delocalization in the ion state of the cluster. In contrast, for the (pro)(2)DHB and (pro)(4)DHB clusters the IE reduction results from an inductive delocalization of electron density from pro to DHB in the ground state of the cluster. This latter effect, which is a result of the specific hydrogen-bonding interactions occurring in the mixed clusters, leads to IE reductions of >1 eV. Finally, determination of the energetics of the (pro)(2)DHB radical cation demonstrate that the DHB-to-proline proton transfer reaction is a barrierless, exoergic process in the ion state and that energetic demands for cluster dissociation to protonated (pro)(2) plus a deprotonated DHB radical are substantially lower than those for cluster dissociation to (pro)(2) plus DHB(+*). Cumulatively, these studies provide new energetic and mechanistic insights into both primary and secondary MALDI ionization processes. 相似文献
97.
Noorjahan Begum Amarash C. Ghosh Shariff E. Kabir Md. Arzu Miah G.M. Golzar Hossain 《Polyhedron》2005,24(18):3074-3081
Four triosmium carbonyl clusters bearing terminal pyrazines, bridging hydroxy and methoxycarbonyl ligands of general formula [Os3(CO)9(μ-OH)(μ-OMeCO)L] (1, L = pyrazine; 2, L = 2-methylpyrazine; 3, L = 2,3-dimethylpyrazine; 4, L = 2,3,5-trimethylpyrazine) were synthesized by the reactions of [Os3(CO)12] with the corresponding pyrazine derivatives and water in the presence of a methanolic solution of Me3NO in moderate yields. Compounds [Os3(CO)9(μ-OH)(μ-OMeCO)L] react with a series of two electron donor ligands, L′ at ambient temperature to give [Os3(CO)9(μ-OH)(μ-OMeCO)L′] (5, L′ = PPh3; 6, L′ = P(OMe)3; 7, L′ = tBuNC; 8, L′ = C5H5N) in good yields by the displacement of the pyrazine ligands. This implies that the pyrazine ligands in 1–4 are relatively labile. Compounds 2, 3, 4, and 8 were characterized by single crystal X-ray diffraction analyses. All the four compounds possess two metal–metal bonds and a non-bonded separation of two osmium atoms defined by Os(1)Os(3), which are simultaneously bridged by OH and MeOCO ligands and a heterocyclic ligand is terminally coordinated to one of the two non-bonded osmium atoms. 相似文献
98.
A new family of quaternary carbon and nitrogen containing Rare Earth (RE: Sc, Y, Ho, Er, Tm and Lu) borides: REB15.5CN, has been synthesized and structurally characterized by powder X-ray diffraction data. They are all isotypic with Sc1−xB15.5CN whose structure was solved based on single-crystal X-ray data and HRTEM investigations. The structure refinement converged at a R(F2) value of 0.044 for 364 reflections. The new structure type of Sc1−xB15.5CN is composed of a three-dimensional network based on interconnected slabs of boron (B12)ico icosahedra and (B6)oct octahedra. A linear [CBC] chain and nitrogen tightly bridges icosahedra. Sc partially occupies voids in the sheets of boron octahedra. It crystallizes with the trigonal space group P3m1, with Z=2. Lattice parameters (nm) are as follows: for RE: Sc, a,b=0.5568(4), c=1.0756(2); Y, a,b=0.55919(6), c=1.0873(2); Ho, a,b=0.55883(7), c=1.0878(6); Er, a,b=0.55889(5), c=1.0880(6); Tm, a,b=0.5580(1), c=1.0850(6); Lu, a,b=0.55771(9), c=1.0839(4). Magnetic characterization of ErB17C1.3N0.6 has been performed. 相似文献
99.
Mirka Bergamo Tiziana Beringhelli Giuseppe D'Alfonso Luca Garavaglia Pierluigi Mercandelli Massimo Moret Angelo Sironi 《Journal of Cluster Science》2001,12(1):223-242
Three and tetranuclear ring clusters have been obtained by treatment of [Re2(CO)8(THF)2] with carbonyl-rhenates containing two terminal hydrides. The reaction with [ReH2(CO)4]- provided a selective route to the previously known [Re3(-H)2(CO)12]- triangular cluster anion 1. The reaction with [Re2H2(-H)(CO)8]- gave the novel [Re4(-H)3(CO)16]- anion 2, containing a rare example of a puckered-square metal cluster. Protonation of 1 is known to afford the neutral [Re3(-H)3(CO)12] species 3. Analogously the reaction of 2 with a strong acid afforded the previously known square metal clusters [Re4(-H)4(CO)16] 4. The reaction could not be reversed by treatment with bases. Photolysis of 4 gave the unsaturated complex [Re2(-H)2(CO)8] 5: this is the reverse of the dimerization reaction, that in THF at room temperature produces 4 from 5. Thermal treatment (reflux in cyclohexane for 24 h) left 4 almost unchanged. A single crystal X-ray analysis of [NEt4]2 showed a s/e/s/s (e=eclipsed, s=staggered) conformation of the Re(CO)4 units, leading to a puckered geometry of the ring, at variance with the square-planar geometry of 4 (all eclipsed). Two of the three hydrides of 2 have been located as bridging the Re–Re edges from inside the metal ring, as previously observed in 4. Density functional computations indicated a puckered conformation as the most stable for both 2 and 4, with very low activation energies for ring inversion (6.6 and 2.2 kcal·mol-1, respectively), but ruled out solid state fluxionality for 4, whose observed planar geometry must be attributed to packing stabilization. 相似文献
100.
Summary A comparison of three binary mobile phases in LC separation of C60 and C70 fullerences on chemically bonded 2,4-dinitroanilinopropyl (DNAP) stationary phase was carried out, n-Hexane-benzene has been found to be the best mobile phase for efficient separation of the all-carbon molecules permitting high loads in preparative LC. 相似文献