Synthesis and Characterization of a Two‐Coordinate Manganese Complex and its Reaction with Molecular Hydrogen at Room Temperature

Samuel, Prinson P.; Mondal, Kartik Chandra; Roesky, Herbert W.; Hermann, Markus; Frenking, Gernot; Demeshko, Serhiy; Meyer, Franc; Stückl, A. Claudia; Christian, Jonathan H.; Dalal, Naresh S.; Ungur, Liviu; Chibotaru, Liviu F.; Pröpper, Kevin; Meents, A.; Dittrich, Birger

doi:10.1002/anie.201304642

Cited by 80 publications

(105 citation statements)

References 30 publications

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“…Recently, a cationic two-coordinate iron complex with the same ligand was synthesized, [6,7] but we focused on neutral complexes herein. The three (CAAC) 2 Mn/Cu/ Zn structures show linear coordination. [1,2,4] Structures with Mn, Ni, and Cu are toluene solvates, the Co structure is a THF hemisolvate, and for the Zn compound a desolvate was characterized.…”

Section: Methodsmentioning

confidence: 98%

“…The (CAAC) 2 Mn data set was reintegrated, which gave an improved R 1 (F) of 5.5 rather than 5.9 % for IAM refinement with SHELXL2013. To study a possible influence of anomalous dispersion, we additionally performed a series of experiments on (CAAC) 2 Ni at photon energies of 26, 19, 16, and 13 keV, which correspond to wavelengths of 0.4769, 0.6523, 0.7749, and 0.9537 , respectively, at the PX beamline of the PetraIII synchrotron (DESY, Hamburg). Due to the size of the Pilatus 6M detector, fulfilling the resolution requirements for a charge-density study became feasible with the shortest of these wavelengths.…”

Section: Methodsmentioning

confidence: 99%

“…As mentioned above, Table 1 lists the results from XD IAM and aspherical-atom refinements. CIF files for multiwavelength aspherical-atom refinements of (CAAC) 2 Ni with XD were deposited at the CCDC. CCDC-934645, -1018228, -1018229, -1018230, and -1018231 contain the supplementary crystallographic data for this paper.…”

Section: Crystallographic Refinements and Computational Detailsmentioning

confidence: 99%

“…Re-refinement with starting coordinates taken from the invariom step was performed to convergence by repeating the cycle of singlepoint computation, database generation, and refinement. ADPs of disordered toluene atoms were treated as a rigid body by invoking the KEEP RIGID command in XD in the (CAAC) 2 Mn/Ni/Cu solvate structures. As mentioned above, Table 1 lists the results from XD IAM and aspherical-atom refinements.…”

Section: Crystallographic Refinements and Computational Detailsmentioning

confidence: 99%

“…[a] Dr. 1 Depending on anomalous dispersion of the central atom at a particular wavelength, especially near the absorption edge, the element right of the correct one may be found by using the IAM. 2 Anomalous dispersion effects close to the absorption edge of the central element can complicate and even reverse the situation. This is studied in Section 3.1.…”

Section: Introductionmentioning

confidence: 98%

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Aspherical‐Atom Modeling of Coordination Compounds by Single‐Crystal X‐ray Diffraction Allows the Correct Metal Atom To Be Identified

et al. 2014

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Single-crystal X-ray diffraction (XRD) is often considered the gold standard in analytical chemistry, as it allows element identification as well as determination of atom connectivity and the solid-state structure of completely unknown samples. Element assignment is based on the number of electrons of an atom, so that a distinction of neighboring heavier elements in the periodic table by XRD is often difficult. A computationally efficient procedure for aspherical-atom least-squares refinement of conventional diffraction data of organometallic compounds is proposed. The iterative procedure is conceptually similar to Hirshfeld-atom refinement (Acta Crystallogr. Sect. A- 2008, 64, 383-393; IUCrJ. 2014, 1,61-79), but it relies on tabulated invariom scattering factors (Acta Crystallogr. Sect. B- 2013, 69, 91-104) and the Hansen/Coppens multipole model; disordered structures can be handled as well. Five linear-coordinate 3d metal complexes, for which the wrong element is found if standard independent-atom model scattering factors are relied upon, are studied, and it is shown that only aspherical-atom scattering factors allow a reliable assignment. The influence of anomalous dispersion in identifying the correct element is investigated and discussed.

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Section: Methodsmentioning

confidence: 98%

Section: Methodsmentioning

confidence: 99%

Section: Crystallographic Refinements and Computational Detailsmentioning

confidence: 99%

Section: Crystallographic Refinements and Computational Detailsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 98%

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Aspherical‐Atom Modeling of Coordination Compounds by Single‐Crystal X‐ray Diffraction Allows the Correct Metal Atom To Be Identified

et al. 2014

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Synthesis, Properties, and Reactivity of Linear Open‐Shell 3d‐Metal(I) Complexes

Werncke

Gómez

2022

Encyclopedia of Inorganic and Bioinorganic Chemistry

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Linear complexes with two‐coordinate, open‐shell 3d‐metal(I) ions are a young and rare class of compounds in coordination chemistry and are known so far for chromium to nickel. These complexes combine an uncommon coordination motif with an, for these metals, unusual oxidation state. The isolation of such compounds relies mostly on the use of sterically encumbering and/or electronically stabilizing ligands, such as bulky amides or N ‐heterocyclic carbenes, to support the highly unsaturated metal center. Given the labile nature of these linear complexes as well as their only recent history, the physical properties, as well as their reactivity concerning small molecules and various bonding types are only partially explored. Reports concerning their respective behavior indicate a high potential, for example remarkable single‐molecule magnetic properties or first use in catalysis. Herein, we wish to give a comprehensive overview about the current knowledge, and by this shed the scientific spotlight on this, in our eyes, underused yet highly intriguing class in coordination chemistry.

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Diborabutatrien: ein elektronenarmes Cumulen

et al. 2014

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Die Komplexierung von zwei ¾quivalenten eines cyclischen (Alkyl)(amino)carbens (CAAC) an Tetrabromdiboran führte unter nachfolgender Reduktion mit vier ¾qui-valenten Natriumnaphthalid zur Bildung des CAAC-stabilisierten Diboracumulens (CAAC) 2 B 2 . Gegenüber dem bereits bekannten Komplex, der eine von cyclischen Di(amino)carbenen stabilisierte B B-Bindung aufweist, führt das Vermçgen des CAAC-Liganden, p-Elektronendichte aufzunehmen (B 2 ! CAAC), zu signifikanten Unterschieden, wie etwa einer län-geren BÀB-und kürzeren BÀC-Bindungen. Die Analyse der Grenzorbitale lässt auf eine Verteilung der Valenzelektronen entlang der gesamten linearen C-B-B-C Einheit in (CAAC) 2 B 2 schließen, was durch natürliche Populationsanalyse und Cyclovoltammetrie weiter bestätigt wird.

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Synthesis and Characterization of a Two‐Coordinate Manganese Complex and its Reaction with Molecular Hydrogen at Room Temperature

Cited by 80 publications

References 30 publications

Aspherical‐Atom Modeling of Coordination Compounds by Single‐Crystal X‐ray Diffraction Allows the Correct Metal Atom To Be Identified

Aspherical‐Atom Modeling of Coordination Compounds by Single‐Crystal X‐ray Diffraction Allows the Correct Metal Atom To Be Identified

Synthesis, Properties, and Reactivity of Linear Open‐Shell 3d‐Metal(I) Complexes

Diborabutatrien: ein elektronenarmes Cumulen

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