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41.
Olivier Kahn 《Angewandte Chemie (International ed. in English)》1985,24(10):834-850
When two paramagnetic transition metal ions are present in the same molecular entity, the magnetic properties can be totally different from the sum of the magnetic properties of each ion surrounded by its nearest neighbors. These new properties depend on the nature and the magnitude of the interaction between the metal ions through the bridging ligands. If both ions have an unpaired electron (e.g. Cu2+ ions), then the molecular state of lowest energy is either a spin singlet or a spin triplet. In the former case, the interaction is said to be antiferromagnetic, in the latter case ferromagnetic. The nature and the order of magnitude of the interaction can be engineered by judiciously choosing the interacting metal ions and the bridging and terminal ligands, and, thus, by the symmetry and the delocalization of the orbitals centered on the metal ions and occupied by the unpaired electrons (magnetic orbitals). The first success in this “molecular engineering” of bimetallic compounds was in the synthesis of a Cu2+VO2+ heterobimetallic complex in which the interaction is purely ferro-magnetic. The same strategy could be utilized for designing molecular ferromagnets, one of the major challenges in the area of molecular materials. Another striking result is the possibility of tuning the magnitude of the interaction through a given bridging network by modifying the nature of the terminal ligands, which, in some way, play the role of “adjusting screws”. By careful selection of the bridging and terminal ligands, a very large antiferro-magnetic interaction can be achieved, even if the metal ions are far away from each other. Some sulfur-containing bridges are especially suitable in this respect. 相似文献
42.
In a copper(II) dimer, two situations, I and II, may lead to a J = 0 singlet—triplet energy gap. In situation I, the metal ions do not interact and all the contributions to J vanish. In situation II, the metal ions interact, but the positive and negative contributions cancel. The aim of this letter is to specify the differences between these situations, to analyse how they can be distinguished from a physical point of view, particularly from EPR spectroscope, and to propose some typical geometries corresponding to both situations. 相似文献
43.
The gas-phase decomposition of diallylvinylphosphine 1 into C5H5P 12 is studied by DFT/6-311+G(d,p) calculations with the B3LYP functional, followed by single-point energy-only calculations at the CCSD(T)/6-311+G(d,p) level. According to these calculations, the first step involves a retro-ene elimination that yields 3-phosphahexatrienes 2Z and 2E. Both compounds equilibrate through the formation of 1,2- and 3,4-dihydrophosphetes 3 and 4, and it is shown that the formation of 2Z is favored by the exothermic formation of the 3,4-dihydrophosphinine 5 through a 6pi-electrocyclization. Though 5 can easily isomerize into 2,3- (6) and 1,2-diyhydrophosphinines (7) by successive 1,5-hydrogen shifts, the formation of 12 from 5, 6, or 7 through an elimination of H2 is found to be a high energy process. It is also shown that the elimination of H2 from lambda5-phosphinine 8 following a C2v pathway is a symmetry-forbidden process. Finally, 1,4-dihydrophosphinine 9, which can be formed through a 1,4-hydrogen shift from lambda5-phosphinine 8, is found to be a convenient precursor of 12 through a 1,4-elimination of H2. The formation of 9 from 5 involves the intermediary formation of 3-phosphabicyclo[3.1.0]hex-2-ene 10. The mechanism eventually proposed for the formation of 12 from 2Z is given in Scheme 16 at the CCSD(T) level. 相似文献
44.
The synthesis of alkylarylphosphines is easily carried out by hydrophosphination of unactivated alkenes under mild thermal activation; gram scale amounts of products can be prepared by this simple methodology. 相似文献
45.
Magnani A Marchettini N Ristori S Rossi C Rossi F Rustici M Spalla O Tiezzi E 《Journal of the American Chemical Society》2004,126(37):11406-11407
The present work deals with the spatially extended oscillatory Belousov Zhabotinsky reaction-diffusion system carried out in an anisotropic environment of phosphatidylcholines/water binary system, which presents layered aqueous domains separated by lipid bilayers. We report the occurrence of stable Turing patterns, spiral waves, and other exotic structures in phospholipids bilayers that are generally used as a models for cell plasma membranes. 相似文献
46.
47.
Phosphines react with butterfly tetranuelear nitrido-iron clusters, [Fe4N(CO)12]− and [Fe4N(CO)11(NO)], to give mono- and di-substituted complexes. X-Ray analyses of the title compounds showed that the phosphine ligands are bound to the wing-tip atoms. 相似文献
48.
Froelich O Desos P Bonin M Quirion JC Husson HP Zhu J 《The Journal of organic chemistry》1996,61(19):6700-6705
The asymmetric synthesis of a series of 2-(1-aminoalkyl) piperidines using (-)-2-cyano-6-phenyloxazolopiperidine 1 is described. LiAlH(4) reduction of 1 followed by hydrogenolysis led to the diamine 3. The same strategy applied to C-2-methylated compound 7 afforded [(2S)-2-methylpiperidin-2-yl]methanamine (9). Addition of lithium derivatives to the cyano group of 1 resulted in the formation of an intermediate imino bicyclic system (11a-c) which could be diastereoselectively reduced to substituted diamino alcohols 13a-c. The addition of an excess of PhLi to 1 in the presence of LiBr furnished disubstituted amine 19, the precursor of diphenyl[(2S)-piperidin-2-yl]methanamine (22). 相似文献
49.
We have prepared four complexes of the type [Re(guanine)(2)(X)(CO)(3)] (guanine = 9-methylguanine or 7-methylguanine, X = H(2)O or Br) in order to understand the factors determining the orientation of coordinated purine ligands around the [Re(CO)(3)](+) core. The 9-methylguanine ligand (9-MeG) was chosen as the simplest N(9) derivatized guanine, and 7-methylguanine (7-MeG) was chosen because metal binding to N(9) does not impose steric hindrance. Two types of structures have been elucidated by X-ray crystallography, an HH (head-to-head) and HT (head-to-tail) conformer for each of the guanines. All complexes crystallize in monoclinic space groups: [Re(9-MeG)(2)(H(2)O)(CO)(3)]ClO(4) (2) in P2(1)/n with a = 12.3307(10) A, b = 16.2620(14) A, c = 13.7171(11) A, and beta = 105.525(9) degrees, V = 2650.2(4) A(3), with the two bases in HT orientation and its conformer [Re(9-MeG)(2)(H(2)O)(CO)(3)]Br (3) in P2(1)/n with a = 15.626(13) A, b = 9.5269(5) A, c = 15.4078(13) A, and beta = 76.951(1) degrees, V = 2234.5(3) A(3), and the two bases in an HH orientation. Similarly, [Re(7-MeG)(2)(H(2)O)(CO)(3)]ClO(4) (4) crystallizes in P2(1)/c with a = 13.0708(9) A, b = 15.4082(7) A, c = 14.316(9) A, and beta = 117.236(7) degrees, V = 2563.5(3) A(3), and exhibits an HT orientation and [ReBr(7-MeG)(2)(CO)(3)] (5) in P2/c with a = 17.5117(9) A, b = 9.8842(7) A, c = 15.3539(1) A, and beta = 100.824(7) degrees, V = 2610.3(3) A(3), and shows an HH orientation. When crystals of any of these complex pairs are dissolved in D(2)O, the (1)H NMR spectrum shows a single peak for the H(8) resonance of the respective coordinated purine indicating a rapid equilibrium between HH and HT conformations in solution. DFT calculations simulating the rotation of one ligand around its Re-N bond showed energetic barriers of less than 8.7 kcal/mol. We find no hypochromic effect in the Raman spectrum of 3, which showed base stacking in the solid state. Neither steric interactions nor hydrogen bonding are important in determining the orientation of the ligands in the coordination sphere. 相似文献
50.
Oxidation of some 2-(N,N-dimethylaminomethyl)ferrocenylalkylcarbinols by MnO2 is totally diastereoselective: only one diastereomer is oxidized. A study was performed to highlight the influential factors of this phenomenon. Several ferrocenyl alcohols have been studied. First, two diastereomers of the ferrocenyl amino alcohol bearing a deuterium as an R group have been synthesized and oxidized. The good reactivity of both diastereomers displayed the importance of the size of the alkyl group, which needs to be bulkier than a deuterium. The synthesis and the oxidation of endo- and exo-α-hydroxy [4](1,2)ferrocenophane enabled the elimination of the hypothesis involving the spatial position of the hydroxy group, while the two diastereomers were oxidized. The replacement of the dimethylamino group by a methoxy or a methyl, the oxidation of these compounds, and the study of the preferential conformation of each diastereomer showed clearly the influence of an intramolecular hydrogen bond. So,the diastereoselectivity was shown to depend on the steric bulk of the alkyl group and on the presence of a strong intramolecular hydrogen bond between the hydroxy group and the nitrogen. 相似文献