WF6 reacts with phosphines R3P forming 1:1 compounds. With R=P(CH3)3 the coordination around the tungsten atom is capped trigonal prismatic, with R=P(CH3)2C6H5 the coordination is capped octahedral, as established by single‐crystal structure determinations: [(CH3)3P? WF6]: a=752.5(21), b=945.7(24), c=629.8(18) pm. β=110.36(13)°, space group Cm, Z=2; [(CH3)2(C6H5)P? WF6]: a=762.2(2), b=1123.5(2), c=2647.5(6) pm, space group Pbca, Z=8. [(CF3CH2)2N? WF5] reacts smoothly with P(C6H5)3 forming known P(C6H5)3(F)2 and [(CF3CH2)2N? WF4? P(C6H5)3], a stable, green, molecular species, identified among other methods with an crystal structure determination: a=914.9(1), b=956.0(1), c=1449.8(2) pm, α=7.642(4), β=81.648(3), γ=81.519°, space group P$\bar 1$ , Z=2. 相似文献
The capability of resorcinarenes to bind anions within the alkyl feet at the lower rim has been exploited as the starting point for developing a new cavitand able to engulf contact ion pairs of primary ammonium salts in chlorinated solvents with association constants (Kass) in the range of 103–104 M ?1. Methylene bridges were introduced into the upper rim to freeze the resorcinarene in the cone conformation with the four Hdown protons converging in the lower pocket, thereby maximizing the CH–anion interactions responsible for the anion binding. Four additional phosphate moieties were introduced into the lower rim in close proximity to the anionic site to provide hydrogen‐bonding‐acceptor P?O groups and promote cation complexation at the bottom of the cavitand. The binding ability of the synthesized ligands was analyzed by 1H NMR spectroscopy and, when possible, by isothermal titration calorimetry (ITC); the data were in agreement when complementary techniques were used. 相似文献
The ability of bridging thiophenolate groups (RS?) to transmit magnetic exchange interactions between paramagnetic NiII ions is examined. Specific attention is paid to complexes with large Ni? SR? Ni angles. For this purpose, dinuclear [Ni2L1(μ‐OAc)?I2][I5] ( 2 ) and trinuclear [Ni3L2(OAc)2][BPh4]2 ( 3 ), where H2L1 and H2L2 represent 24‐membered macrocyclic amino‐thiophenol ligands, are prepared and fully characterized by IR‐ and UV/Vis spectroscopy, X‐ray crystallography, static magnetization M measurements and high‐field electron spin resonance (HF‐ESR). The dinuclear complex 2 has a central N3Ni2(μ‐S)2(μ‐OAc)Ni2N3 core with a mean Ni? S? Ni angle of 92°. The macrocycle L2 supports a trinuclear complex 3 , with distorted octahedral N2O2S2 and N2O3S coordination environments for one central and two terminal NiII ions, respectively. The Ni? S? Ni angles are at 132.8° and 133.5°. We find that the variation of the bond angles has a very strong impact on the magnetic properties of the Ni complexes. In the case of the Ni2‐complex, temperature T and magnetic field B dependencies of M reveal a ferromagnetic coupling J=?29 cm?1 between two NiII ions (H=JS1S2). HF‐ESR measurements yield a negative axial magnetic anisotropy (D<0) which implies a bistable (easy axis) magnetic ground state. In contrast, for the Ni3‐complex we find an appreciable antiferromagnetic coupling J′=97 cm?1 between the NiII ions and a positive axial magnetic anisotropy (D>0) which implies an easy plane situation.相似文献
It is shown that the end group parameter, which describes the influence of the end group on retention, can be determined in RP chromatography from two chromatograms of a nonfunctional and a monofunctional sample, if a sufficient number of peaks with the same number of repeat units in each sample can be reasonably resolved and identified. The same procedure can also be applied for pairs of di‐ and monofunctional polymers. End group parameters have been determined in three different mobile phases: acetonitrile–water, acetone–water and methanol–water of different compositions. The temperature dependence of the interaction parameter of the repeat unit and the end group parameter has been found to be different, which allows a fine‐tuning of retention. 相似文献
Modeling of the solvent is important when using quantum chemical methods for the assignment of mechanisms from experimental studies of the exchange of water between metal aquo ions and the bulk solvent. In the present study, we have investigated if and how the mechanisms for water exchange in the UO2(OH2)52+–H2O system is affected by the choice of chemical models for the second coordination sphere and physical models for describing the cavity in conductor-like polarizable continuum (CPCM) models. In the first case, we have compared models with one and five waters in the second coordination sphere. For both models, we have compared cavities in which each atom is assigned one spherical cavity and one in which the water molecules are described by a single spherical cavity (the United Atom model). There are significant differences in the relative energy of dissociative and associative intermediates; however, they are not large enough to affect the conclusion that the water exchange proceeds through an associative/interchange mechanism. 相似文献
In a glass house : Silica‐encapsulated self‐assembled monolayers (SAMs) on tunable gold/silver nanoshells were used as labels for surface‐enhanced Raman scattering (SERS). This concept combines the spectroscopic advantages arising from maximum surface coverage and uniform molecular orientation of the Raman reporter molecules within the complete monolayer together with the high chemical and mechanical stability of the glass shell.
N2 is one of the major gaseous nitrogen compounds released by soils due to N-transformation processes. Since it is also the major constituent of the earth's atmosphere (78.08% vol.), the determination of soil N2 release is still one of the main methodological challenges with respect to a complete evaluation of the gaseous N-loss of soils. Commonly used approaches are based either on a C2H2 inhibition technique, an artificial atmosphere or a 15N-tracer technique, and are designed either as closed systems (non-steady state) or gas flow systems (steady state). The intention of this work has been to upgrade the current gas flow technique using an artificial atmosphere for a 15N-aided determination of the soil N2 release simultaneously with N2O. A 15N-aided artificial atmosphere gas flow approach has been developed, which allows a simultaneous online determination of N2 as well as N2O fluxes from an open soil system (steady state). Fluxes of both gases can be determined continuously over long incubation periods and with high sampling frequency. The N2 selective molecular sieve K?strolith SX6 was tested successfully for the first time for dinitrogen collection. The presented paper mainly focuses on N2 flux determination. For validation purposes soil aggregates of a Haplic Phaeozem were incubated under aerobic (21 and 6 vol.% O2) and anaerobic conditions. Significant amounts of N2 were released only during anaerobic incubation (0.4 and 640.2 pmol N2 h(-1) g(-1) dry soil). However, some N2 formation also occurred during aerobic incubation. It was also found that, during ongoing denitrification, introduced [NO3]- will be more strongly delivered to microorganisms than the original soil [NO3]-. 相似文献