Visualizing the coordination-spheres of photoexcited transition metal complexes with ultrafast hard X-rays

2019 ◽  
Vol 21 (18) ◽  
pp. 9277-9284 ◽  
Author(s):  
D. Khakhulin ◽  
L. M. Lawson Daku ◽  
D. Leshchev ◽  
G. E. Newby ◽  
M. Jarenmark ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
X Rays ◽  
Molecular Assemblies ◽  
Rational Development ◽  
Modern Chemistry ◽  
Coordination Spheres

The concept of coordination sphere (CS) is central to the rational development of hierarchical molecular assemblies in modern chemistry.

scholarly journals X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

2017 ◽  
Vol 375 (2084) ◽  
pp. 20160028 ◽  
Author(s):  
Michael T. Huxley ◽  
Campbell J. Coghlan ◽  
Witold M. Bloch ◽  
Alexandre Burgun ◽  
Christian J. Doonan ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Metal Organic Frameworks ◽  
Void Space ◽  
X Ray ◽  
X Ray Crystallography ◽  
Metal Nitrates ◽  
Metal Organic

Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.

scholarly journals Reaktive π-Komplexe der elektronenreichen Übergangsmetalle, 11. Mitteilung/ Reactive π-Complexes of the Electron Rich Transition Metal Complexes, Part 11

1991 ◽  
Vol 46 (6) ◽  
pp. 729-737 ◽  
Author(s):  
Catherine Tolxdorff ◽  
Dongqi Hu ◽  
Bernhard Höferth ◽  
Hartmut Schaufele ◽  
Hans Pritzkow ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Room Temperature ◽  
Iron Complexes ◽  
Iron Complex

The highly reactive arene iron complex [(η4-toluene)(η6-toluene)iron] allows the formation of C4-units from alkynes below room temperature. By this route butadiene-, cyclobutadiene-, and ferracyclopentadiene(arene)iron complexes are accessible. Synthesis, structure and the properties of one example each are reported. Ferracyclopentadienes are potential intermediates for the catalytic cyclotrimerization of alkynes in the coordination sphere of arene iron complexes.

Hydride Exchange Processes in the Coordination Sphere of Transition Metal Complexes:  The OsH3(BH4)(PR3)2System

1996 ◽  
Vol 118 (35) ◽  
pp. 8388-8394 ◽  
Author(s):  
Isabelle Demachy ◽  
Miguel A. Esteruelas ◽  
Yves Jean ◽  
Agustí Lledós ◽  
Feliu Maseras ◽  
...  
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Exchange Processes

Ubergangsmetallkomplexe mit Schwefelliganden, CIX. Synthese und Reaktivität von meso-[Ru(L)('buS5')]-Komplexen mit L = NO+, CO, PR3 (R = Me, Ph, Cy), pyr, CN-, N2H4, NH2NHR (R = Me, Ph), NH2NMe2, NH3, NH2Ph, NHEt2 ('buS5' - H2 = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)di-ethylsulfid) / Transition Metal Complexes with Sulfur Ligands, CIX. Synthesis and Reactivity of meso-[Ru(L)('buS5')] Complexes with L = NO+, CO, PR3 (R = Me, Ph, Cy), pyr, CN-, N2H4, NH2NHR (R = Me, Ph), NH2NMe2, NH3, NH2Ph, NHEt2 ( 'buS5' - H2 = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsulfide)

1995 ◽  
Vol 50 (8) ◽  
pp. 1229-1244 ◽  
Author(s):  
Dieter Sellmann ◽  
Christine Rohm ◽  
Matthias Moll ◽  
Falk Knoch
Keyword(s):  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Mirror Plane ◽  
Fold Axis ◽  
Coordination Sites ◽  
Thiolate Ligand ◽  
Sterically Demanding ◽  
Coordination Spheres ◽  
Butyl Benzene

In a search of transition metal complexes with sulfur dominated coordination spheres and free coordination sites for the binding of small molecules, [Ru(L)('buS5')] complexes with the sterically demanding pentadentate thioether-thiolate ligand 'buS5'2- ( 'buS5'2- = 2,2'-Bis(2-mercapto-3,5-di-t-butylphenylthio)diethylsulfide(2-)) have been synthesized. Reaction of [RuCl3(NO)(PPh3)2] with 3,5-di(t-butyl)benzene-1,2-dithiolate, ′buS2'2-, yields the 16 electron complex [Ru(NO )('buS2')2]- which is isolated as the NBu4+-salt, 1. According to the NMR spectra, 1 contains a two-fold axis or a mirror plane. Alkylation of 1 with bis(β-bromethyl)sulfide under reflux leads stereoselectively to meso-[Ru(NO)('buS5')]Br, [2]Br. Reaction of [2]Br with LiBEt3H yields the barely soluble binuclear complex [Ru('buS5')]2, 3, with [Ru('buS5')Ru(NO)('buS2')('buS2'- C2H4SH)], 4, as a by-product. 4 ·THF, 4a, has been characterized by X-ray structure analysis. Reactions of 3 with σ-π- and σ-ligands yield mononuclear meso-[Ru(L)('buS5')] complexes which have been isolated and characterized with L = CO, PMe3, PPh3, PCy3, pyr, CN-, 5 - 10, NH2NHPh, NH2NHMe, NH2NMe2, NH2Ph und NHEt2, 13-17. Complexes 5 -10 are stable compounds. Complexes 13-17, however, are sensitive towards oxidation and/or substitution. Coordination of L = N2H4 and NH3 to 3 leads to insoluble [Ru(L)('buS5')]x complexes.

Structure of the Second Coordination Sphere of Transition Metal Complexes. IV. Solvent Effects

1973 ◽  
Vol 51 (24) ◽  
pp. 4137-4139 ◽  
Author(s):  
D. R. Eaton ◽  
K. L. Chua
Keyword(s):  
Dipole Moment ◽  
Carbon Tetrachloride ◽  
Transition Metal ◽  
Metal Complexes ◽  
Transition Metal Complexes ◽  
Coordination Sphere ◽  
Solvent Effects ◽  
Equilibrium Constants ◽  
Outer Sphere ◽  
Second Coordination Sphere

The participation of various solvents in the second coordination sphere of Co(II) pyrazolylborate has been investigated. Equilibrium constants relative to carbon tetrachloride as a second sphere ligand have been obtained. The ability of a solvent to participate in the second sphere depends predominantly on its dipole moment and it is concluded that Van der Waals forces are responsible for outer sphere binding.

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