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Dario M. Bassani Jean-Marie Lehn Katharina Fromm Dieter Fenske 《Angewandte Chemie (International ed. in English)》1998,37(17):2364-2367
The introduction of different metal ions in specific positions is achieved in the synthesis of [2×2] grid-type heterometallic complexes (see schematic representation; the black bars symbolize the ditopic ligands, and the circles the different metals ions). This novel method for the construction of inorganic architectures opens the way to a number of developments. 相似文献
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Geometry and Spin Change at the Heart of a Cobalt(II) Complex: A Special Case of Solvatomorphism 下载免费PDF全文
Mihaela Cibian Prof. Dr. Garry S. Hanan 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9474-9481
Structural analysis and spectroscopic methods revealed a special case of solvatomorphism: hydrogen‐bonding‐induced geometry and spin change within a same N,O‐(bis)chelate of cobalt(II). Solid‐state structures are presented for both the tetrahedral and the solvated square‐planar forms of the complex. Magnetic‐moment measurements and ESR spectroscopy confirmed the high‐spin state of the tetrahedral form (μeff=4.7 μB) and the low‐spin state of the square‐planar solvatomorph. Specific hydrogen‐bonding interactions between the solvent molecules and the complex chelate ring (O1 ??? H?CHCl2 (d=2.26 Å, D=3.24 Å, θ=173°); O2 ??? H?CHCl2 (d=2.22 Å, D=3.19 Å, θ=165°)) play a pivotal role in biasing the system toward the low‐spin ground state. 相似文献
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Divergent Coordination Chemistry: Parallel Synthesis of [2×2] Iron(II) Grid‐Complex Tauto‐Conformers 下载免费PDF全文
Dr. Bernhard Schäfer Dr. Jean‐François Greisch Dr. Isabelle Faus Dr. Tilmann Bodenstein Dr. Ivan Šalitroš Dr. Olaf Fuhr Priv.‐Doz. Dr. Karin Fink Prof. Dr. Volker Schünemann Prof. Dr. Manfred M. Kappes Prof. Dr. Mario Ruben 《Angewandte Chemie (International ed. in English)》2016,55(36):10881-10885
The coordination of iron(II) ions by a homoditopic ligand L with two tridentate chelates leads to the tautomerism‐driven emergence of complexity, with isomeric tetramers and trimers as the coordination products. The structures of the two dominant [FeII4 L 4]8+ complexes were determined by X‐ray diffraction, and the distinctness of the products was confirmed by ion‐mobility mass spectrometry. Moreover, these two isomers display contrasting magnetic properties (FeII spin crossover vs. a blocked FeII high‐spin state). These results demonstrate how the coordination of a metal ion to a ligand that can undergo tautomerization can increase, at a higher hierarchical level, complexity, here expressed by the formation of isomeric molecular assemblies with distinct physical properties. Such results are of importance for improving our understanding of the emergence of complexity in chemistry and biology. 相似文献
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Coordination of Alkaline Earth Metal Ions in the Inverted Cucurbit[7]uril Supramolecular Assemblies Formed in the Presence of [ZnCl4]2− and [CdCl4]2− 下载免费PDF全文
Qing Li Yun‐Qian Zhang Qian‐Jiang Zhu Sai‐Feng Xue Zhu Tao Prof. Dr. Xin Xiao 《化学:亚洲杂志》2015,10(5):1159-1164
A convenient method to isolate inverted cucurbit[7]uril (iQ[7]) from a mixture of water‐soluble Q[n]s was established by eluting the soluble mixture of Q[n]s on a Dowex (H+ form) column so that iQ[7] could be selected as a ligand for coordination and supramolecular assembly with alkaline earth cations (AE2+) in aqueous HCl solutions in the presence of [ZnCl4]2? and [CdCl4]2? anions as structure‐directing agents. Single‐crystal X‐ray diffraction analysis revealed that both iQ[7]–AE2+–[ZnCl4]2?–HCl and iQ[7]–AE2+–[CdCl4]2?–HCl interaction systems yielded supramolecular assemblies, in which the [ZnCl4]2? and [CdCl4]2? anions presented a honeycomb effect, and this resulted in the formation of linear iQ[7]/AE2+ coordination polymers through outer‐surface interactions of Q[n]s. 相似文献
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A Two‐Coordinate Cobalt(II) Imido Complex with NHC Ligation: Synthesis,Structure, and Reactivity 下载免费PDF全文
Jingzhen Du Linbo Wang Prof. Dr. Meihua Xie Prof. Dr. Liang Deng 《Angewandte Chemie (International ed. in English)》2015,54(43):12640-12644
The synthesis, structural characterization, and reactivity of the first two‐coordinate cobalt complex featuring a metal–element multiple bond [(IPr)Co(NDmp)] ( 4 ; IPr=1,3‐bis(2′,6′‐diisopropylphenyl)imidazole‐2‐ylidene; Dmp=2,6‐dimesitylphenyl) is reported. Complex 4 was prepared from the reaction of [(IPr)Co(η2‐vtms)2] (vtms=vinyltrimethylsilane) with DmpN3. An X‐ray diffraction study revealed its linear C? Co? N core and a short Co? N distance (1.691(6) Å). Spectroscopic characterization and calculation studies indicated the high‐spin nature of 4 and the multiple‐bond character of the Co? N bond. Complex 4 effected group‐transfer reactions to CO and ethylene to form isocyanide and imine, respectively. It also facilitated E? H (E=C, Si) σ‐bond activation of terminal alkyne and hydrosilanes to produce the corresponding cobalt(II) alkynyl and cobalt(II) hydride complexes as 1,2‐addition products. 相似文献
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Homoleptic Two‐Coordinate Silylamido Complexes of Chromium(I), Manganese(I), and Cobalt(I) 下载免费PDF全文
Dr. C. Gunnar Werncke Dr. Elizaveta Suturina Philip C. Bunting Dr. Laure Vendier Prof. Jeffrey R. Long Prof. Dr. Mihail Atanasov Prof. Dr. Frank Neese Dr. Sylviane Sabo‐Etienne Dr. Sébastien Bontemps 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(5):1668-1674
Anionic two‐coordinate complexes of first‐row transition‐metal(I) centres are rare molecules that are expected to reveal new magnetic properties and reactivity. Recently, we demonstrated that a N(SiMe3)2? ligand set, which is unable to prevent dimerisation or extraneous ligand coordination at the +2 oxidation state of iron, was nonetheless able to stabilise anionic two‐coordinate FeI complexes even in the presence of a Lewis base. We now report analogous CrI and CoI complexes with exclusively this amido ligand and the isolation of a [MnI{N(SiMe3)2}2]22? dimer that features a Mn?Mn bond. Additionally, by increasing the steric hindrance of the ligand set, the two‐coordinate complex [MnI{N(Dipp)(SiMe3)}2]? was isolated (Dipp=2,6‐iPr2‐C6H3). Characterisation of these compounds by using X‐ray crystallography, NMR spectroscopy, and magnetic susceptibility measurements is provided along with ligand‐field analysis based on CASSCF/NEVPT2 ab initio calculations. 相似文献
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Natarajan R Savitha G Dominiak P Wozniak K Moorthy JN 《Angewandte Chemie (International ed. in English)》2005,44(14):2115-2119
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The mer‐octahedral complexes(2‐carbonyl)(4‐Me)(6‐tBu)phenolato[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 1 ) or ‐(1‐carbonyl)(2‐oxo)(1,2‐diphenylethene)[C,O]hydridotris(trimethylphosphine)cobalt(III) ( 2 ) via formal insertion of propynoic acid ethyl ester into Co‐H functions afford pentacoordinate vinylcobalt(III) 3 and 4 , respectively, that are diamagnetic and attain a square pyramidal structure as exemplified by an X‐ray diffraction analysis of 3 . 相似文献
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Peter Nockemann Dr. Michael Pellens Kristof Van Hecke Dr. Luc Van Meervelt Prof. Dr. Johan Wouters Prof. Dr. Ben Thijs Dr. Evert Vanecht Tatjana N. Parac‐Vogt Prof. Dr. Hasan Mehdi Stijn Schaltin Jan Fransaer Prof. Dr. Stefan Zahn Barbara Kirchner Prof. Dr. Koen Binnemans Prof. Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(6):1849-1858
A series of nitrile‐functionalized ionic liquids were found to exhibit temperature‐dependent miscibility (thermomorphism) with the lower alcohols. Their coordinating abilities toward cobalt(II) ions were investigated through the dissolution process of cobalt(II) bis(trifluoromethylsulfonyl)imide and were found to depend on the donor abilities of the nitrile group. The crystal structures of the cobalt(II) solvates [Co(C1C1CNPyr)2(Tf2N)4] and [Co(C1C2CNPyr)6][Tf2N]8, which were isolated from ionic‐liquid solutions, gave an insight into the coordination chemistry of functionalized ionic liquids. Smooth layers of cobalt metal could be obtained by electrodeposition of the cobalt‐containing ionic liquids. 相似文献
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Reactivity of the Donor‐Stabilized Silylenes [iPrNC(Ph)NiPr]2Si and [iPrNC(NiPr2)NiPr]2Si: Activation of CO2 and CS2 下载免费PDF全文
Felix M. Mück Johannes A. Baus Marco Nutz Dr. Christian Burschka Dr. Jordi Poater Prof. Dr. F. Matthias Bickelhaupt Prof. Dr. Reinhold Tacke 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(46):16665-16672
Activation of CO2 by the bis(amidinato)silylene 1 and the analogous bis(guanidinato)silylene 2 leads to the structurally analogous six‐coordinate silicon(IV ) complexes 4 (previous work) and 8 , respectively, the first silicon compounds with a chelating carbonato ligand. Likewise, CS2 activation by silylene 1 affords the analogous six‐coordinate silicon(IV ) complex 10 , the first silicon compound with a chelating trithiocarbonato ligand. CS2 activation by silylene 2 , however, yields the five‐coordinate silicon(IV ) complex 13 with a carbon‐bound CS22? ligand, which also represents an unprecedented coordination mode in silicon coordination chemistry. Treatment of the dinuclear silicon(IV ) complexes 5 and 6 with CO2 also affords the six‐coordinate carbonatosilicon(IV ) complexes 4 and 8 , respectively. 相似文献