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101.
The generation of metal cyanide ions in the gas phase by laser ablation of M(CN)(2) (M = Co, Ni, Zn, Cd, Hg), Fe(III)[Fe(III)(CN)(6)] x xH(2)O, Ag(3)[M(CN)(6)] (M = Fe, Co), and Ag(2)[Fe(CN)(5)(NO)] has been investigated using Fourier transform ion cyclotron resonance mass spectrometry. Irradiation of Zn(CN)(2) and Cd(CN)(2) produced extensive series of anions, [Zn(n)(CN)(2n+1)](-) (1 < or = n < or = 27) and [Cd(n)(CN)(2n+1)](-) (n = 1, 2, 8-27, and possibly 29, 30). Cations Hg(CN)(+) and [Hg(2)(CN)(x)](+) (x = 1-3), and anions [Hg(CN)(x)](-) (x = 2, 3), are produced from Hg(CN)(2). Irradiation of Fe(III)[Fe(III)(CN)(6)] x xH(2)O gives the anions [Fe(CN)(2)](-), [Fe(CN)(3)](-), [Fe(2)(CN)(3)](-), [Fe(2)(CN)(4)](-), and [Fe(2)(CN)(5)](-). When Ag(3)[Fe(CN)(6)] is ablated, [AgFe(CN)(4)](-) and [Ag(2)Fe(CN)(5)](-) are observed together with homoleptic anions of Fe and Ag. The additional heterometallic complexes [AgFe(2)(CN)(6)](-), [AgFe(3)(CN)(8)](-), [Ag(2)Fe(2)(CN)(7)](-), and [Ag(3)Fe(CN)(6)](-) are observed on ablation of Ag(2)[Fe(CN)(5)(NO)]. Homoleptic anions [Co(n)(CN)(n+1)](-) (n = 1-3), [Co(n)(CN)(n+2)](-) (n = 1-3), [Co(2)(CN)(4)](-), and [Co(3)(CN)(5)](-) are formed when anhydrous Co(CN)(2) is the target. Ablation of Ag(3)[Co(CN)(6)] yields cations [Ag(n)(CN)(n-1)](+) (n = 1-4) and [Ag(n)Co(CN)(n)](+) (n = 1, 2) and anions [Ag(n)(CN)(n+1)](-) (n = 1-3), [Co(n)(CN)(n-1)](-) (n = 1, 2), [Ag(n)Co(CN)(n+2)](-) (n = 1, 2), and [Ag(n)Co(CN)(n+3)](-) (n = 0-2). The Ni(I) species [Ni(n)(CN)(n-1)](+) (n = 1-4) and [Ni(n)(CN)(n+1)](-) (n = 1-3) are produced when anhydrous Ni(CN)(2) is irradiated. In all cases, CN(-) and polyatomic carbon nitride ions C(x)N(y)(-) are formed concurrently. On the basis of density functional calculations, probable structures are proposed for most of the newly observed species. General structural features are low coordination numbers, regular trigonal coordination stereochemistry for d(10) metals but distorted trigonal stereochemistry for transition metals, the occurrence of M-CN-M and M(-CN-)(2)M bridges, addition of AgCN to terminal CN ligands, and the occurrence of high spin ground states for linear [M(n)(CN)(n+1)](-) complexes of Co and Ni.  相似文献   
102.
Two polymetallic iron(III) complexes 1 and 2 have been synthesised from the known corrosion inhibitor 3-(4-methylbenzoyl)-propionic acid HL1 and their crystal structures determined. Coordination geometries extracted from these structures have been used as the basis for molecular modelling onto idealised iron(III) oxide surfaces as an aid to understanding the efficacy of inhibitors of the 4-keto acid type. The proposed mode of action involves 1,3-bridging didentate coordination of the carboxylate function of L1 to two FeIII ions, hydrogen-bond formation between the 4-keto group of L1 and a bridging surface hydroxy group, as well as close packing of the aromatic end groups, which should generate a hydrophobic barrier on the surface. Adsorption isotherm experiments have been used to compare the strengths of binding of related carboxylic acids onto iron(III) oxide surfaces and indicate that the presence of the 4-keto function leads to the formation of significantly more stable surface complexes.  相似文献   
103.
104.
高聚合度Ⅱ-型聚磷酸铵的合成   总被引:3,自引:0,他引:3  
傅亚  陈君和  贾云  郭莉平 《合成化学》2005,13(6):610-613
用聚合反应-热处理两段工艺合成了高聚合度的聚磷酸铵(APP)阻燃材料,其结构经XRD,粒度及平均聚合度表征。优化反应条件为:磷酸氢二铵1mol,n(磷酸氢二铵):n(五氧化二磷):n(脲):1.0:1.0:0.3.干燥氨气氛下于290℃反应30min,再经250℃-280℃后处理100min-110min。APP的平均聚合度大于150,粒度小于50μm。  相似文献   
105.
Fluorination of triphenylarsine oxide by aqueous hydrogen fluoride (1–40%) in the absence of glass readily gives triphenylarsine difluoride. When the reaction with dilute (1%) aqueous hydrogen fluoride is carried out in borosilicate glass apparatus, the glass participates in the reaction resulting in the formation of the crystalline 2:1 adduct 2Ph3AsO·HBF4. Crystals of this compound are monoclinic, P21/c, a = 12.926(4), b = 17.819(6), c = 14.994(4) Å, β = 98.97(3)°, Z = 4. The structure contains cations [(Ph3AsO)2H]+ in which O?O is 2.44(2)Å, and anions BF4?.  相似文献   
106.
107.
A new cyanido-bridged Re(IV)-Mn(III) heterometallic 1D system, [Mn(III)(5-Me-saltmen)](2)[Re(IV)Cl(4)(CN)(2)]·3CH(3)CN (), was designed and structurally characterized. Interchain interactions stabilize a canted antiferromagnetic ordered state below 6.2 K that does not prevent slow relaxation of the magnetization reminiscent of the single-chain magnet properties of the individual chains.  相似文献   
108.
Phosphoryl transfer reactions are ubiquitous in biology and the understanding of the mechanisms whereby these reactions are catalyzed by protein and RNA enzymes is central to reveal design principles for new therapeutics. Two of the most powerful experimental probes of chemical mechanism involve the analysis of linear free energy relations (LFERs) and the measurement of kinetic isotope effects (KIEs). These experimental data report directly on differences in bonding between the ground state and the rate‐controlling transition state, which is the most critical point along the reaction free energy pathway. However, interpretation of LFER and KIE data in terms of transition‐state structure and bonding optimally requires the use of theoretical models. In this work, we apply density‐functional calculations to determine KIEs for a series of phosphoryl transfer reactions of direct relevance to the 2′‐O‐transphosphorylation that leads to cleavage of the phosphodiester backbone of RNA. We first examine a well‐studied series of phosphate and phosphorothioate mono‐, di‐ and triesters that are useful as mechanistic probes and for which KIEs have been measured. Close agreement is demonstrated between the calculated and measured KIEs, establishing the reliability of our quantum model calculations. Next, we examine a series of RNA transesterification model reactions with a wide range of leaving groups in order to provide a direct connection between observed Brønsted coefficients and KIEs with the structure and bonding in the transition state. These relations can be used for prediction or to aid in the interpretation of experimental data for similar non‐enzymatic and enzymatic reactions. Finally, we apply these relations to RNA phosphoryl transfer catalyzed by ribonuclease A, and demonstrate the reaction coordinate–KIE correlation is reasonably preserved. A prediction of the secondary deuterium KIE in this reaction is also provided. These results demonstrate the utility of building up knowledge of mechanism through the systematic study of model systems to provide insight into more complex biological systems such as phosphoryl transfer enzymes and ribozymes.  相似文献   
109.
A new in‐situ NMR strategy (termed CLASSIC NMR) for mapping the evolution of crystallization processes is reported, involving simultaneous measurement of both liquid‐state and solid‐state NMR spectra as a function of time. This combined strategy allows complementary information to be obtained on the evolution of both the solid and liquid phases during the crystallization process. In particular, as crystallization proceeds (monitored by solid‐state NMR), the solution state becomes more dilute, leading to changes in solution‐state speciation and the modes of molecular aggregation in solution, which are monitored by liquid‐state NMR. The CLASSIC NMR experiment is applied here to yield new insights into the crystallization of m‐aminobenzoic acid.  相似文献   
110.
The ligand 6,6"bis(4-methoxyphenyl)-4'-phenyl-2,2':6',2"terpyridine (2) has been prepared and characterized; deprotection using pyridinium chloride leads to the formation of 6,6"bis(4-hydroxyphenyl)-4'-phenyl-2,2':6',2"terpyridinium chloride ([H3]Cl). Treatment of the latter with 3-(2-(2-bromoethoxy)ethoxy)prop-1-ene under basic conditions yields ligand 4 containing pendant, alkene-terminated chains. Whereas direct complexation of 4 with ruthenium(II) proved problematical, the homoleptic complexes [Fe(2)(2)][PF(6)](2) and [Ru(2)(2)][PF(6)](2) were prepared in good to moderate yields. In the solid state, both complexes exhibit multiple face-to-face π-stacking of arene and pyridine rings which influences the coordination geometry about the metal ion. Consequential weakening of the ligand field results in [Fe(2)(2)][PF(6)](2) being high-spin. Variable temperature solution (1)H NMR spectroscopic studies confirm the iron(ii) centre remains high-spin between 200 and 295 K. The paramagnetically shifted (1)H NMR spectrum exhibits signals in the range δ 109.7 to -66.5 ppm and has been fully assigned. Paramagnetic relaxation enhancement (PRE) has been used to correlate the observed proton line-widths to the distances of the protons from the metal centre and these are in good agreement with the Fe···H separations observed in the solid state. The [Fe(2)(2)](2+) ion undergoes two dynamic processes (i) rotation of the pendant phenyl rings which is fast on the NMR timescale at 200 K, and (ii) twisting and sliding of the aromatic rings of the tpy and anisyl units which interconverts the two enantiomers of [Fe(2)(2)](2+) at 295 K.  相似文献   
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