The occurrence of interpenetration in metal–organic and inorganic networks has been investigated by a systematic analysis of the CSD and ICSD structural databases. For this purpose, a novel version of TOPOS (a program package for multipurpose crystallochemical analysis) has been employed, where the procedure of recognition of interpenetrating nets is based on the representation of a crystal structure as a finite reduced graph. In this paper we report a comprehensive list (301 Refcodes) of interpenetrating metal–organic 3D structures from CSD, that are analyzed on the basis of their topologies. Interesting trends and novel features have been observed and distinct classes of interpenetrating nets have been envisaged, depending on the relationships of the individual motifs.

Interpenetrating metal–organic and inorganic 3D networks: a computer-aided systematic investigation. Part I. Analysis of the Cambridge structural database

Metal-mediated reductive hydrodehalogenation of organic halides.

Rapid processes such as certain organic reactions or precipitations at high supersaturation require the rapid mixing provided by jet mixers. Micromixing in a confined impinging jets (CIJ) mixer was characterized employing the Damkohler number to correlate processing. A scaling theory for the characteristic micromixing time, proportional to momentum diffusion starting at the Kolmogorov microscale, is shown as sufficient to express the micromixing performance of the CIJ mixer. A recently characterized second-order competitive reaction set is used as a “chemical ruler” to assign an absolute value to the mixing time in the CIJ mixer. A wide range of characteristic time (320 to 5 ms) is evaluated with hydrochloric acid competing for sodium hydroxide neutralization or 2,2-dimethoxypropane acid catalyzed hydrolysis. This reaction set was sensitive enough to detect the onset of a turbulent-like flow at a Re of 90 and was able to demonstrate a decrease in undesired products up to the highest Re tested, 3,800 or a jet velocity of 19 m/s. It represents a significant advancement to the reaction sets and techniques used for previous mixing studies, which are reviewed. Experiments verify the characteristic mixing time in a CIJ mixer scales as the inverse of the jet velocity to the three halves power, and the “mesomixing volume” (the volume over which the majority of flow energy was dissipated) is best approximated as proportional to the internozzle separation cubed. For each of the different jet diameters, chamber diameters and outlet configurations tested, the selectivity of the reaction scaled linearly with the Damkohler number, as determined from the known reaction kinetics and the calculated Kolmogorov diffusion time. The first full characterization is provided of micromixing in impinging jets that allows the prediction of mixing performance, reaction selectivity, and scale-up criteria.

Chemical processing and micromixing in confined impinging jets

Structures and properties of Zn(II) coordination polymers

Purified LiAlH4 reacts with fluorinated alcs. HORF to give LiAl(ORF)4 (RF = -CH(CF3)2, 2a; -CMe(CF3)2, 2b; -C(CF3)3, 2c) in 77-90% yield. The crude Li aluminates LiAl(ORF)4 react metathetically with AgF to give the silver aluminates AgAl(ORF)4 (RF = -CH(CF3)2, 3a; -CMe(CF3)2, 3b; -C(CF3)3, 3c) in almost quant. yield. The solid-state structures of solvated 3a-c showed that the Ag cation is only weakly coordinated (CN(Ag) = 6-10; CN = coordination no.) by the solvent and/or weak cation-anion contacts Ag-X (X = O, F, Cl, C). The strength of the Ag-X contacts of 3a-c was analyzed by Brown's bond-valence method and then compared with other Ag salts of weakly coordinating anions (WCAs), for example [CB11H6Cl6]- and [M(OTeF5)n]- (M = B, Sb, n = 4, 6). Based on this quant. picture the Al{OC(CF3)3}4- anion is one of the most weakly coordinating anions known. Also, the AgAl(ORF)4 species are certainly the easiest WCAs to access preparatively (20 g in two days), addnl. at low cost. The Al-O bond length of Al(ORF)4- is shortest in the sterically congested Al{OC(CF3)3}4- anion-which is stable in H2O and aq. HNO3 (35%), and indicates a strong and highly polar Al-O bond that is resistant towards heterolytic alkoxide ion abstraction. This observation was supported by HF-DFT calcns. of OR-, Al(OR)3 and Al(OR)4- at the MPW1PW91 and B3LYP levels (R = CH3, CF3, C(CF3)3). The alkoxide ion affinity (AIA) is highest for R = CF3 (AIA = 384 +- 9 kJ mol-1) and R = C(CF3)3 (AIA = 390 +- 3 kJ mol-1), but lowest for R = CH3 (AIA = 363 +- 7 kJ mol-1). The gaseous Al(ORF)4- anions are stable against the action of the strong Lewis acid AlF3(g) by 88.5 +- 2.5 (RF = CF3) and 63 +- 12 kJ mol-1 (RF = C(CF3)3), while Al(OCH3)4- decomps. with -91 +- 2 kJ mol-1. Therefore, the presented fluorinated aluminates Al(ORF)4- appear to be ideal candidates when large and resistant WCAs are needed, for example, in cationic homogeneous catalysis, for highly electrophilic cations or for weak cationic Lewis acid/base complexes. [on SciFinder (R)]

The Facile Preparation of Weakly Coordinating Anions: Structure and Characterisation of Silverpolyfluoroalkoxyaluminates AgAl(ORF)4, Calculation of the Alkoxide Ion Affinity

A structural and electrochemical study of some oxovanadium(IV) heterochelate complexes

Crystal structures have been determined for three
Ag(CB
 11
H
 6
X
 6
) compounds
(X = Cl, Br or I) crystallized from arene solvents. They
are all one-dimensional co-ordination polymers in the solid state with
hexahalogenocarborane anions acting as bridging ligands. The
co-ordination geometries of these three salts are, however, unique. The
type and number of donors to silver(I) varies from one to
another and is not particularly predictable.

Structural diversity in silver salts of hexahalogenocarborane anions, ag(cb11h6x6) (x= cl, br or i)

Catalytic and Stoichiometrically Directed Synthesis of Less Accessible Bromothiophenes and Bromobithiophenes. Trapping and Characterization of Catalytic Intermediates of trans-PdBr(C4H4-nBrn-1S-C)(PPh3)2 (n = 1−4), trans-PdBr(C8H4BrS2-C)(PPh3)2, and trans,trans-Pd2Br2(μ-C8H6-nBrn-2S2-C,C‘)(PPh3)4 (n = 2, 4)

SmI3 can be prepared by the reaction of SmI2 with O2 in dry condition. It crystallizes as an ionic complex, [SmI2(THF)5][SmI4(THF)2], from THF, rather than the simple coordination compound SmI3(THF)3.

Autoionization of SmI3 in Tetrahydrofuran. X-ray Crystal Structure of the Ionic Complex [SmI2(THF)5][SmI4(THF)2]

The new quadridentate, N3S-compound di-2-pyridyl ketone thiosemicarbazone (HL) has been characterized by spectroscopic techniques and single-crystal X-ray analysis. The thiosemicarbazone moiety adopts a configuration with N(1)cis to N(3). The chelating behaviour of the deprotonated compound (L) has been investigated in two dinuclear copper(II) complexes, [(CuLCl)2]·2dmf 1(dmf = dimethylformamide) and [{CuL(CN)}2]·2MeOH 2. The crystal structures of 1 and 2 were determined. The co-ordination geometry about the copper(II) in both compounds is distorted square pyramidal with one pyridine nitrogen atom, the sulfur, the imino nitrogen, and a chloro or cyano group in the basal plane; a pyridine nitrogen atom of an adjacent moiety occupies the apical position, serving as a bridge to form a centrosymmetric dimeric structure.

Synthesis and structural characterization of the new quadridentate N3S-compound di-2-pyridyl ketone thiosemicarbazone and its binuclear copper(II) complexes

Bo-Mu Wu

Papers

A structural and electrochemical study of some oxovanadium(IV) heterochelate complexes

Structural diversity in silver salts of hexahalogenocarborane anions, ag(cb11h6x6) (x= cl, br or i)

Autoionization of SmI3 in Tetrahydrofuran. X-ray Crystal Structure of the Ionic Complex [SmI2(THF)5][SmI4(THF)2]

Synthesis and structural characterization of the new quadridentate N3S-compound di-2-pyridyl ketone thiosemicarbazone and its binuclear copper(II) complexes