Polymorphism in P,P-[3]ferrocenophanes: insights from an NMR crystallographic approach

Wiegand, Thomas; Lüdeker, David; Brunklaus, Gunther; Bussmann, Kathrin; Kehr, Gerald; Erker, Gerhard; Eckert, Hellmut

doi:10.1039/c4dt01071j

Cited by 9 publications

(54 citation statements)

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“…NMR crystallography using 43 Ca NMR data characterized the first crystalline hybrid organic–inorganic phase with the arylboronate anions (PhB(OH) 3 ) coordinating to Ca 2+ in one-dimensional (1D) chains which interact through H-bonds to form two-dimensional (2D) layers . Finally, NMR crystallography was used for elucidation of the polymorphism in P,P-[3]ferrocenophanes induced by the reversible incorporation of dichloromethane in the crystal structures . These examples document the potential of this method for characterization of diamagnetic inorganic solids.…”

Section: Introductionmentioning

confidence: 91%

“…14 Finally, NMR crystallography was used for elucidation of the polymorphism in P,P- [3]ferrocenophanes induced by the reversible incorporation of dichloromethane in the crystal structures. 15 These examples document the potential of this method for characterization of diamagnetic inorganic solids. In the current manuscript we demonstrate the first application of NMR crystallography based on 51 V, 13 C, and 15 N NMR data for investigation of solid vanadium-containing coordination complexes, which can adopt several coordination geometries.…”

Section: ■ Introductionmentioning

confidence: 95%

“…15 These examples document the potential of this method for characterization of diamagnetic inorganic solids. In the current manuscript we demonstrate the first application of NMR crystallography based on 51 V, 13 C, and 15 N NMR data for investigation of solid vanadium-containing coordination complexes, which can adopt several coordination geometries.…”

Section: ■ Introductionmentioning

confidence: 95%

“…We have therefore explored the possibility to derive 3D structural information on the basis of multiple NMR parameters measured from the NMR-active nuclei in the sample, using an approach termed NMR crystallography. [1][2][3]8,64,65 For these systems, NMR observables, such as dipolar couplings and anisotropic tensorial properties of the 51 V nucleus and of the other atoms comprising the molecule (e.g., 15 N, 13 C, 1 H, 31 P, etc. ), provide exquisite information on the geometric and electronic structure, and can be used as constraints for deriving the 3D structure of the compound using quantum chemical methods.…”

Section: ■ Introductionmentioning

confidence: 99%

“…We and others have also demonstrated the utility of double resonance methods for the measurement of internuclear distances between 51 V and highnatural abundance spin-1/2 nuclei, such as 31 P, in inorganic vanadium-based solids. 69,70 In this work, we expand the application of NMR crystallography to the next level by combining the 51 V quadrupolar and CSA parameters with 51 V− 15 N internuclear distances as well as with 15 N CSA tensors and 13 C isotropic chemical shifts. These parameters are used as structural constraints for the DFT-based structural calculations.…”

Section: ■ Introductionmentioning

confidence: 99%

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NMR Crystallography for Structural Characterization of Oxovanadium(V) Complexes: Deriving Coordination Geometry and Detecting Weakly Coordinated Ligands at Atomic Resolution in the Solid State

Yehl

Hou

et al. 2015

Inorg. Chem.

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NMR crystallography is an emerging method for atomic-resolution structural analysis of ubiquitous vanadium(V) sites in inorganic and bioinorganic complexes as well as vanadium-containing proteins. NMR crystallography allows for characterization of vanadium(V) containing solids, based on the simultaneous measurement of (51)V-(15)N internuclear distances and anisotropic spin interactions, described by (13)C, (15)N, and (51)V chemical shift anisotropy and (51)V electric field gradient tensors. We show that the experimental (51)V, (13)C, and (15)N NMR parameters are essential for inferring correct coordination numbers and deriving correct geometries in density functional theory (DFT) calculations, particularly in the absence of single-crystal X-ray structures. We first validate this approach on a structurally known vanadium(V) complex, ((15)N-salicylideneglycinate)-(benzhydroxamate)oxovanadium(V), VO(15)NGlySalbz. We then apply this approach to derive the three-dimensional structure of (methoxo)((15)N-salicylidene-glycinato)oxovanadium(V) with solvated methanol, [VO((15)NGlySal)(OCH3)]·(CH3OH). This is a representative complex with potentially variable coordination geometry depending on the solvation level of the solid. The solid material containing molecules of CH3OH, formally expressed as [VO((15)NGlySal)(OCH3)]·(CH3OH), is found to have one molecule of CH3OH weakly coordinated to the vanadium. The material is therefore best described as [VO((15)NGlySal)(OCH3)(CH3OH)] as deduced by the combination of multinuclear solid-state NMR experiments and DFT calculations. The approach reported here can be used for structural analysis of systems that are not amenable to single-crystal X-ray diffraction characterization and which can contain weakly associated solvents.

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Section: Introductionmentioning

confidence: 91%

Section: ■ Introductionmentioning

confidence: 95%

Section: ■ Introductionmentioning

confidence: 95%

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 3 more Smart Citations

NMR Crystallography for Structural Characterization of Oxovanadium(V) Complexes: Deriving Coordination Geometry and Detecting Weakly Coordinated Ligands at Atomic Resolution in the Solid State

Yehl

Hou

et al. 2015

Inorg. Chem.

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Opportunities and Challenges in Applying Solid‐State NMR Spectroscopy in Organic Mechanochemistry

et al. 2023

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In recent years it was shown that mechanochemical strategies can be beneficial in directed conversions of organic compounds. Finding new reactions proved difficult, and due to the lack of mechanistic understanding of mechanochemical reaction events, respective efforts have mostly remained empirical. Spectroscopic techniques are crucial in shedding light on these questions. In this overview, the opportunities and challenges of solid‐state nuclear magnetic resonance (NMR) spectroscopy in the field of organic mechanochemistry are discussed. After a brief discussion of the basics of high‐resolution solid‐state NMR under magic‐angle spinning (MAS) conditions, seven opportunities for solid‐state NMR in the field of organic mechanochemistry are presented, ranging from ex‐situ approaches to structurally elucidate reaction products obtained by milling to the potential and limitations of in‐situ solid‐state NMR approaches. Particular strengths of solid‐state NMR, for instance in differentiating polymorphs, in NMR‐crystallographic structure‐determination protocols, or in detecting weak noncovalent interactions in molecular‐recognition events employing proton‐detected solid‐state NMR experiments at fast MAS frequencies, are discussed.This article is protected by copyright. All rights reserved

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A cyclo‐P₆ Ligand Complex for the Formation of Planar 2D Layers

Heindl

Peresypkina

Lüdeker

et al. 2016

Chemistry A European J

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The all-phosphorus analogueo fb enzene, stabilized as middle deck in triple-decker complexes, is ap romising building block for the formation of graphene-like sheet structures. The reaction of [(CpMo) 2 (m,h 6 :h 6 -P 6 )] (1) with CuX (X = Br,I )l eads to self-assembly into unprecedented 2D networks of [{(CpMo) 2 P 6 }(CuBr) 4 ] n (2)a nd [{(CpMo) 2 P 6 }(CuI) 2 ] n (3). X-ray structural analyses show au nique deformation of the previously planar cyclo-P 6 ligand.T his includes bending of one Pa tom in an envelope conformation as well as ab isallylic distortion. Despite this, 2 and 3 form planar layers. Both polymers were furthermore analyzed by 31 P{ 1 H} magic angle spinning (MAS) NMR spectroscopy,r evealing signals corresponding to six non-equivalent phosphorus sites. Ap eak assignment is achieved by 2D correlation spectra as well as by DFT chemical shift computations.Ta iloreds yntheses of the inorganic analogues of organicm olecules, is af ascinating area of fundamental research. Following the so-called isolobal principle, [1] substitution of methine moieties by phosphorus atoms appearsq uite promising. In fact, 2016 marks the 50th anniversary of the first successful synthesis of ap hosphabenzenei nw hich one CH unit is replacedb y aPatom, [2] which set the stage for the ultimate goal, namely the preparation of carbon-free hexaphosphabenzene.S ince then,m any theoreticals tudies with respect to its aromaticity were reportedt hat outlined the instability of af ree cyclo-P 6 unit. [3] Nevertheless, its detection in an inert stabilizing matrix at low temperature might be feasible such that the challenge remains. As ynthetic approach demonstrated by the Scherer groupisthe stabilizationofthe P 6 ring by coordination to transition metals, thus affording at riple-decker complex [(Cp*Mo) 2 (m,h 6 :h 6 -P 6 )] (Cp* = h 5 -C 5 Me 5 )b earing ap lanar P 6 middle deck for the first time (Figure 1). [4] Triple-deckerc omplexesc ontaining the cyclo-P 6 unit could also be obtainedf or vanadium, [5] tungsten, [5] or niobium. [6] Quite recently,t he sandwich complex[ (CpMo) 2 (m,h 6 :h 6 -P 6 )] (1)w ith the parent Cp ligandsw as synthesized and characterized. [7] In the case of the Mo and Wc omplexes, the cyclo-P 6 ring has ap erfect D 6h symmetry, whereas Va nd Nb derivatives exhibit as light bisallylic distortion. [6a] It should be noted that the middled eck in [(Cp*Ti) 2 (m,h 3 :h 3 -P 6 )] has ac hair conformation (Figure 1). [8] In contrastt ob enzene, the presence of lone pairs at the phosphorus atoms converts these triple-decker complexes into excellent buildingb locks for supramolecular chemistry.P articularly intriguingis the possibility of graphene-like honeycomb networks resulting from reaction with Lewis acidic metal salts, an unmet challenge to date.We have appliedL ewis acidic coinage metal salts forl inkage of unsubstituted P n complexes [9] and also for [(Cp R Mo) 2 (m,h 6 :h 6 -P 6 )] (Cp R = Cp*, Cp Bn = h 5 -C 5 (CH 2 C 6 H 5 ) 5 ). [10] For example, the coordination of the bare cationsC u...

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Polymorphism in P,P-[3]ferrocenophanes: insights from an NMR crystallographic approach

Cited by 9 publications

References 67 publications

NMR Crystallography for Structural Characterization of Oxovanadium(V) Complexes: Deriving Coordination Geometry and Detecting Weakly Coordinated Ligands at Atomic Resolution in the Solid State

NMR Crystallography for Structural Characterization of Oxovanadium(V) Complexes: Deriving Coordination Geometry and Detecting Weakly Coordinated Ligands at Atomic Resolution in the Solid State

Opportunities and Challenges in Applying Solid‐State NMR Spectroscopy in Organic Mechanochemistry

A cyclo‐P₆ Ligand Complex for the Formation of Planar 2D Layers

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Polymorphism in P,P-[3]ferrocenophanes: insights from an NMR crystallographic approach

Cited by 9 publications

References 67 publications

NMR Crystallography for Structural Characterization of Oxovanadium(V) Complexes: Deriving Coordination Geometry and Detecting Weakly Coordinated Ligands at Atomic Resolution in the Solid State

NMR Crystallography for Structural Characterization of Oxovanadium(V) Complexes: Deriving Coordination Geometry and Detecting Weakly Coordinated Ligands at Atomic Resolution in the Solid State

Opportunities and Challenges in Applying Solid‐State NMR Spectroscopy in Organic Mechanochemistry

A cyclo‐P6 Ligand Complex for the Formation of Planar 2D Layers

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A cyclo‐P₆ Ligand Complex for the Formation of Planar 2D Layers