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61.
Mössbauer spectroscopy and magnetic moment measurements have been used to study the compound Fe(phen)2(NCBH3)2 in conjunction with other octahedral Fe(II) complexes. The result of both sets of measurements indicate that Fe(phen)2(NCBH3)2 is an intermediate spin (S = 1) complex at room temperature. Intermediate spin Fe(II) complexes are relatively unknown and very few, if any, are conclusively reported in the literature. 相似文献
62.
John Purcell 《The Journal of the Operational Research Society》1979,30(12):1037-1046
A model of industrial relations is developed distinguishing between rule making—the central purpose of collective bargaining—and the subsequent steps of rule implementation, rule maintenance and rule adaptation. A further step is identified as rule breaking or rule avoidance, indicating the incompleteness of the rule-making-application-maintenance process. The reasons for rule breaking are examined focusing on pressures exerted in the production system and the underlying philosophy of negotiation as a satisficing rather than optimising activity. The role that formal control systems can play in making the industrial relations system more effective is examined. A distinction is drawn on the one hand between strategic planning, management control and operational control and on the other hand between three levels of feedback from the control system to the industrial relations system. The object of controls is seen firstly to encourage rule maintenance, secondly to aid rule adaptation and thirdly to assist in the strategic planning and design of the industrial relations system. 相似文献
63.
This paper describes, for the first time, a simple and effective synthetic route for covalently bonding the chemiluminescence reagent, (4-[4-(dichloromethylsilanyl)-butyl]-4'-methyl-2,2'-bipyridyl)bis(2,2'-bipyridyl)ruthenium(II) onto silica particles. The subsequent preparation of chemically regeneratable detection cells and their preliminary analytical evaluation with both sequential injection analysis and flow injection analysis are also reported. Unoptimised analytical figures of merit were established for standard solutions of codeine and sodium oxalate with detection limits calculated from three times the standard deviation of the blank signal, of 1 x 10(-8) M and 3 x 10(-7) M respectively. The chemically immobilised reagent exhibited some intriguing solvent and kinetic effects, which are also briefly discussed. 相似文献
64.
Taylor RP Spehar B Wise JA Clifford CW Newell BR Hagerhall CM Purcell T Martin TP 《Nonlinear dynamics, psychology, and life sciences》2005,9(1):89-114
Fractals have experienced considerable success in quantifying the complex structure exhibited by many natural patterns and have captured the imagination of scientists and artists alike. With ever widening appeal, they have been referred to both as "fingerprints of nature" and "the new aesthetics." Our research has shown that the drip patterns of the American abstract painter Jackson Pollock are fractal. In this paper, we consider the implications of this discovery. We first present an overview of our research from the past five years to establish a context for our current investigations of human response to fractals. We discuss results showing that fractal images generated by mathematical, natural and human processes possess a shared aesthetic quality based on visual complexity. In particular, participants in visual perception tests display a preference for fractals with mid-range fractal dimensions. We also present recent preliminary work based on skin conductance measurements that indicate that these mid-range fractals also affect the observer's physiological condition and discuss future directions based on these results. 相似文献
65.
66.
The Variable Electronegativity Pariser–Parr–Pople method has been successfully applied to calculate the potential energy curve for the formation of a 1: 1 complex between quinone and hydroquinone. A consistent evaluation of core and electronic repulsion integrals is important to obtain a meaningful curve. A computationally simple procedure has been suggested for separating interactions due to electron exchange between the components from other intermolecular interactions. In agreement with experimental deductions the preferred configuration for the quinone-hydroquinone complex is found to be one in which the molecules are in parallel planes with their C—O bonds parallel. The equilibrium separation between the molecular planes is found to be 2.3 Å and the stabilization energy in this position is 1.2 eV. In this equilibrium position forces due to electron exchange constitute the major contributing factor to the stability of the complex. 相似文献
67.
Ten organotin derivatives of 2-mercaptobenzothiazole (Hmbt), 2-mercaptobenzoxazole (Hmbo) and 2-mercaptobenzimidazole (Hmbi) have been synthesised and thier structures characterised by spectroscopic methods. Triorganotin derivatives are all S-bonded to the ligand and four-coordinate at tin except Bu3Sn(mbo) which is five-coordinate trans-ONSnR3 polymer at 78K. The crystal structure of Cy3Sn(mbt) has been determined and confirms the tetrahedral geometry at tin. Bu2Sn(mbt)2 is weakly six-coordinate by N,S chelating ligands. Biocidal activity patterns are presented for Cy3Sn(mbt), Ph3Sn(mbt) and Ph3Sn(mbo). 相似文献
68.
Molecular-orbital calculations have been performed on sydnone, sydnone imine, ψ-oxatriazole, and isosydnone rings and their positive ionized forms by the Pariser–Parr–Pople–Brown–Heffernan method. The importance of elaborate open-shell calculations and the effect of introducing nonneighbor core resonance integrals in this order of approximation are investigated. The available experimental data on closely related compounds are qualitatively in agreement with the calculated values. The computed charges and bond orders demonstrate that certain structural features are common to all five-membered mesoionic ring systems and in agreement with recent experimental findings. 相似文献
69.
Thato N. Mtshali Walter Purcell Hendrik G. Visser Steven S. Basson 《Transition Metal Chemistry》2008,33(4):481-491
The kinetics of the reaction between [ReN(H2O)-(CN)4]2− with different κ2
N,O-donor ligands (quin− and 2,3-dipic−, respectively) have been studied in the pH 4–12 range in aqueous solution. Two consecutive reaction steps with the formation
of the [ReN(η1-quin)(CN)4]3− and [ReN(μ2-quin) (CN)3]2− complexes, respectively, were spectrophotometrically observed and kinetically investigated. The same reaction mechanism is
proposed for these two ligands. The first fast reaction (for quin−) is attributed to the aqua substitution of [ReN(H2O)(CN)4]2− with forward and reverse rate constants of 1.96(5) × 10−1 M−1 s−1 and 5.6(3) × 10−2 s−1, while a rate of 2.64(3) M−1 s−1 was observed for the reaction between the conjugate base [ReN(OH)(CN)4]3− and quin− at 40.2 °C. Due to small absorbance changes, it was difficult to obtain any good quality data for the fast reactions for
2,3-dipic−. The second, slower reaction is attributed to cyano substitution with rate constants (k
3
K
1) of 4.17(4) × 10−3 for quin− and 4.68(7) × 10−3 M−1 s−1 for 2,3-dipic−, at 80.02 °C, respectively. The acid dissociation constant for the aqua complex was spectrophotometrically determined as
11.58(3) and 11.54(2) and kinetically as 11.51(8) and 11.41(1), at 80.4 °C, respectively. Negative values of −83.5(2) and −144.1(2) J K−1 mol−1 as well as the of 71.4(3) and 47.3(3) kJ mol−1, for the slow quin− and 2,3-dipic− reactions, respectively, point to an ordered transition state where bond formation is responsible for the major driving force
of the reaction. The and for the fast forward reaction of quin− is indicative of expected associative activation in the transition state.
Electronic supplementary material The online version of this article (doi:) contains supplementary material, which is available to authorized users. 相似文献
70.
Three different [Ir(LL′)(cod)] complexes (LL′ = N-aryl-N-nitrosohydroxylaminato) (cupf), trifluoroacetylacetonato (tfaa), and (methyl 2-(methylamino)-1-cyclopentene-1-dithiocarboxylato-κN,κS) (macsm)) were synthesized, characterized, and their rates of oxidative addition with methyl iodide were determined. Formation of an isosbestic point during the oxidative addition of methyl iodide with the complexes containing tfaa and cupf as bidentate ligands indicated formation of only one product, while an increase in absorbance maximum observed for macsm confirms that the same reaction between the complex and methyl iodide occurs. Kinetic results for all complexes, except [Ir(tfaa)(cod)], showed simple second-order kinetics with a zero intercept (within experimental error). Rates of oxidative addition for bidentate ligands in acetonitrile showed an increase of an order of magnitude with a change in the type of bidentate ligands. Computational chemistry using density functional theory calculations showed that the oxidative addition reaction proceeds through a “linear” transition state with the methyl iodide unit tilted towards the LL′-bidentate ligand. 相似文献