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A novel asymmetric, edge-sharing bioctahedral complex with formamidinato ligands (
2-DAniF)Mo(-DAniF)2(-O,Cl)MoCl2, 1, (DAniF=N,N-di-p-anisylformamidinate) has been isolated as a byproduct from the preparation of the dimolybdenum(II,III) compound Mo2(DAniF)3Cl2. An X-ray crystallographic study shows that the structure consists of edge-sharing bioctahedra, with the shared edge defined by the vector joining the: -O and -Cl ligands. Compound 1 is best formulated as a mixed-valent MoIIIMoV compound, the Mo(V) ion being that with the two terminal Cl– ligands. The cyclic voltammogram of 1 shows a reversible reduction at –0.472 V and a reversible oxidation at 1.028 V vs. the Ag/AgCl reference electrode, while the absorption spectrum of 1 reveals an intense low energy absorption at 523 nm (
max=12 500) which is attributed to an intervalence charge transfer transition. Crystallographic data for 1 are as follows: a=13.387(1) Å, b=15.500(2) Å, c=21.855(2) Å, =98.786(2)°, V=4481.8(8) Å3, P21/c, R1 (wR2)=0.082 (0.177). 相似文献
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Reactions of W(CO)(6) with formamidines contrast with those of Mo(CO)(6) and Cr(CO)(6) in that the former do not yield quadruply bonded dimetal species. From the reaction of W(CO)(6) with HDAniF (HDAniF = N,N'-di-p-anisylformamidine), several new ditungsten carbonyl compounds (W(2)(mu-CO)(2)(mu-DAniF)(2)(eta(2)-DAniF)(2) (1), W(2)(mu-CO)(2)(mu-DAniF)(2)(eta(2)-DAniF)(eta(2)-CH(2)DAniF) (2), and W(2)(mu-CO)(mu-CNC(6)H(4)OCH(3))(mu-DAniF)(2)(eta(2)-DAniF)(2) (3)) have been isolated and fully characterized. In 2, CH(2)DAniF represents a DAniF ligand in which a methylene group has been added to one of the nitrogen atoms. This ligand binds to the tungsten atom using a nitrogen and a carbon atom. Compound 1 has a tungsten-tungsten bond distance of 2.476(1) A and a planar W(2)(mu-CO)(2) core structure which has C(2)(h)() symmetry with short and long W-C bond distances (1.99(1) and 2.28(1) A, respectively). DFT calculations on a model of 1 indicate that (a) the C(2)(h)() instead of D(2)(h)() symmetry of the ditungsten core may be attributed to W --> CO pi back-bonding interactions and (b) the bond between the tungsten atoms may be formulated as a double bond. The new tetragonal paddlewheel compound W(2)(DAniF)(4) (4) and the edge-sharing bioctahedron W(2)(mu-O)(mu-NC(6)H(3)Cl(2))(mu-D(Cl)PhF)(2)(eta(2)-D(Cl)PhF)(2) (5) (D(Cl)PhF = N,N'-di-(3,5-dichlorophenyl)formamidinate) have also been prepared. 相似文献
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G. Maerker E. T. Haeberer E. T. Donahue T. A. Foglia 《Journal of heterocyclic chemistry》1970,7(3):563-567
A series of aliphatic and aromatic carboxylic acids reacted with 2,3-dioctylaziridine to yield β-hydroxyalkyl amides in 69–89% yields and 2-substituted 4,5-di-n-octyl-δ2-oxazolines in amounts ranging from traces to 12% of the theoretical. No correlation could be found between carboxylic acid strength and either hydroxyamide or δ2-oxazoline yields. Solvents affected the product distribution. 相似文献
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A series of di- and trisilanes of general structure Ph3SiSiMe2R and (Ph3Si)2SiR′R″ were synthesized, and the 29Si and 13C chemical shifts and one-bond siliconsilicon coupling constants (1JSiSi) were measured. The coupling constants of the disilanes were found to be primarily dependent upon the inductive effect of the alkyl group, R, as measured by the Taft o★ constant. In both series of compounds, increasing alkyl substitution at silicon led to a decrease in 1JSiSi. 相似文献
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Shock Waves - Heterogeneous explosives contain a mixture of standard explosive material and reactive metal particles. The inclusion of metal particles alters the energy density and energy release... 相似文献