1,1′‐Bis(pyrazol‐4‐yl)ferrocenes: Potential Clip Ligands and Their Supramolecular Structures

Veronelli, Mattia; Dechert, Sebastian; Schober, Anne; Demeshko, Serhiy; Meyer, Franc

doi:10.1002/ejic.201600644

Cited by 13 publications

(5 citation statements)

References 52 publications

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“…Ferrocene, comprising an Fe II ion coordinated by two cyclopentadienyl (Cp) rings, is a versatile metalloligand precursor because of its reactivity and chemical stability. − Introducing donor substituents to the Cp ring is a rational approach to obtaining functional metalloligands. − For example, 1,1′-disubstituted ferrocenes such as 1,1′-ferrocenedicarboxylic acid and 1,1′-bis(diphenylphosphino)ferrocene are representative metalloligands that have yielded many discrete mixed-metal complexes and one-dimensional (1D) coordination polymers. − We previously reported 1,1′-disubstituted ferrocenes bearing two thiopyridine moieties, 1,1′-di(4-pyridylthio)ferrocene and 1,1′-di(2-pyridylthio)ferrocene (Figure a,b), which act as bridging ligands to produce redox-active 1D coordination polymers . However, 1,2-disubstituted ferrocenes have rarely been employed as bridging ligands, although many studies have investigated their use as chiral ligands for asymmetric synthesis. − We expected 1,2-disubstituted ferrocenes to produce more topologically diverse complexes than 1,1′-disubstituted ferrocenes due to their lower symmetry and additional chelating ability.…”

Section: Introductionsupporting

confidence: 77%

Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

Horikoshi

Tominaga

Mochida

2018

Crystal Growth & Design

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Various metalloligands and inorganic−organic hybrid bridging ligands have been incorporated in polynuclear complexes and bimetallic coordination polymers. Ferrocene, exhibiting redox activity and facile chemical modification, is a versatile metalloligand component. However, most metal complexes with ferrocene-containing ligands form discrete low-dimensional chelate complexes or coordination polymers. Thus, we designed and synthesized ferrocene-based multidentate ligands, 1,2-di(4-pyridylthio)ferrocene (L1) and 1,2-di(2-pyridylthio)ferrocene (L2). Here we report the synthesis and structures of molecular square complexes and coordination polymers containing L1, which reacted with M(hfac) 2 (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) and AgCF 3 SO 3 to yield molecular square complexes [M(hfac) 2 (L1)] 2 •2C 6 H 5 CH 3 [M = Ni (1) and Co (2)] and [Ag(CF 3 SO 3 )(L1)(H 2 O) 0.5 ] 2 •2CH 2 Cl 2 •H 2 O (3). The molecular square units comprise two metal ions bridged by two ligands. Isomorphic complexes 1 and 2 accommodate two toluene molecules above and below the molecular square. L1 reacted with Cu(hfac) 2 and CuI to yield zigzag, {[Cu(hfac) 2 (L1)]} n •0.25n(CH 2 Cl 2 ) (4), and ribbon-shaped, {[Cu 4 I 4 (L1) 2 ]} n (5), coordination polymers. In 4, L1 behaves as a bidentate N,N-ligand bridging the Cu II ions, while in 5 it acts as a tridentate S,N,N-ligand linking the stepped-cubane Cu 4 I 4 units. L1 reacted with AgX to form two-dimensional coordination polymers {[Ag(ClO 4 )(L1)]} n (6) and {[Ag(L1)]PF 6 } n (7), in which it acted as a tetradentate S,S,N,N-ligand. These complexes have topologies based on multidentate coordination of 1,2-substituted L1.

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Section: Introductionsupporting

confidence: 77%

Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

Horikoshi

Tominaga

Mochida

2018

Crystal Growth & Design

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“…All Ag–C NHC bond lengths (2.073 – 2.104 Å for [Ag 6 (L 1 ) 2 ] 4+ ; 2.062 – 2.087 Å for [Ag 6 (L 2 ) 2 ] 4+ ) and all Ag–N pz bond lengths (2.102/2.105 Å for [Ag 6 (L 1 ) 2 ] 4+ ; 2.095/2.103 Å for [Ag 6 (L 2 ) 2 ] 4+ ) are in the typical range of previously reported silver(I) NHC and pyrazolato complexes, respectively , , . However, the different arrangement of the ligand strands with respect to the central {Ag 6 } array, which appears to be a result of the different lengths of the ligand side arms, gives rise to distinct variations in Ag I ··· Ag I distances within the {Ag 6 } decks.…”

Section: Resultssupporting

confidence: 62%

“…The 1 H NMR spectrum of [H 5 L 1 ](PF 6 ) 4 in dry [D 3 ]MeCN at 298 K and 500 MHz shows rather broad resonances for all protons of the imidazolium groups close to the pyrazole (H 2a/b , H 4a/b and H 6a/b ) and two closely spaced signals for the CH 2 groups attached to the 3‐ and 5‐positions of the pyrazole (H 10a /H 10b ; Figure ). These features are attributed to slow NH prototropy on the NMR time scale, which is well known for pyrazoles and pyrazole‐based ligands and was already described for some related ligand scaffolds in the literature . The H 10a/b protons are closest to the pyrazole unit and are most affected by the tautomerism.…”

Section: Resultsmentioning

confidence: 57%

Linear Pyrazole‐bridged Tetra(N‐heterocyclic carbene) Ligands and Their Hexanuclear Silver(I) Complexes

Resch

Dechert

Meyer

2019

Zeitschrift anorg allge chemie

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New hybrid ligands are reported that combine two types of popular donor groups within a single linear scaffold, viz., a central pyrazolate bridge and two appended bis(N-heterocyclic carbene) units; the ligand strands thus provide two potentially tridentate {NCC} compartments. The pyrazole/tetraimidazolium proligands, [H 5 L 1 ](PF 6 ) 4 and [H 5 L 2 ](PF 6 ) 4 , were synthesized via multi-step protocols, and the NH prototropy of [H 5 L 1 ](PF 6 ) 4 was examined by variable temperature (VT) NMR spectroscopy, giving solvent dependent activation parameters (ΔH ‡ = 27.6 kJ·mol -1 , ΔS ‡ = -125 J·mol -1 ·K -1 in [D 3 ]MeCN; 605ΔH ‡ = 40.4 kJ·mol -1 , ΔS ‡ = -86.9 J·mol -1 ·K -1 in [D 6 ]DMSO) that are in the range typical for pyrazoles. Reaction of the proligands with Ag 2 O gave hexametallic complexes [Ag 6 (L 1 ) 2 ](PF 6 ) 4 and [Ag 6 (L 2 ) 2 ](PF 6 ) 4 that involve all six potential donor atoms of the ligands, viz. the four C NHC and two N pz donors, in metal coordination. X-ray crystallography revealed a chair-like central {Ag 6 } deck in both complexes but different arrangements of the ligand strands, which goes along with significantly different Ag I ···Ag I distances that indicate more pronounced argentophilic interactions in case of [Ag 6 (L 1 ) 2 ] 4+ .

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“…APPENDIX A References to experimental data used in this work Sorted alphabetically by CSD refcodes: ACUCIN (Nikonova et al, 2018), ADOWUO (Hermann et al, 2017), AHUKIZ (Weber et al, 2015), AMEPOS (Janicki & Starynowicz, 2010), ARAQUH (Hemgesberg et al, 2016), BECFAT (Veronelli et al, 2017), CAMVES (Dittrich et al, 2002), DAYCEO (Uppal et al, 2017), DNEDAM01 (Gruhne et al, 2021), DUBWAB (Nugrahani et al, 2019), DUCMAQ (Grabowsky et al, 2009), EDAWIP (Evans & Gilardi, 2001), EGUFIY (Malassis et al, 2019), GLYALB08 (Capelli et al, 2014), IYAQOP02 (Marshall et al, 2016), KOVPIX (Thanzeel et al, 2019), LETHIE (Chen et al, 2018), LOKPOT (Ballmann et al, 2019), LOSLEL (Johnas et al, 2009), MANMUJ08 (Jorgensen et al, 2014), MOSCOP (Clegg, 2019), MOVPIZ (Lapointe et al, 2019), MUHBOI (Butschke et al, 2015), OXACDH46 (Kamin ´ski et al, 2014), PCYPOL04 (Mohanraj et al, 2018), PPHCHN11…”

Section: Discussionmentioning

confidence: 99%

Fragmentation and transferability in Hirshfeld atom refinement

Chodkiewicz¹,

Pawlędzio²,

Woińska³

et al. 2022

IUCrJ

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Hirshfeld atom refinement (HAR) is one of the most effective methods for obtaining accurate structural parameters for hydrogen atoms from X-ray diffraction data. Unfortunately, it is also relatively computationally expensive, especially for larger molecules due to wavefunction calculations. Here, a fragmentation approach has been tested as a remedy for this problem. It gives an order of magnitude improvement in computation time for larger organic systems and is a few times faster for metal–organic systems at the cost of only minor differences in the calculated structural parameters when compared with the original HAR calculations. Fragmentation was also applied to polymeric and disordered systems where it provides a natural solution to problems that arise when HAR is applied. The concept of fragmentation is closely related to the transferable aspherical atom model (TAAM) and allows insight into possible ways to improve TAAM. Hybrid approaches combining fragmentation with the transfer of atomic densities between chemically similar atoms have been tested. An efficient handling of intermolecular interactions was also introduced for calculations involving fragmentation. When applied in fragHAR (a fragmentation approach for polypeptides) as a replacement for the original approach, it allowed for more efficient calculations. All of the calculations were performed with a locally modified version of Olex2 combined with a development version of discamb2tsc and ORCA. Care was taken to efficiently use the power of multicore processors by simple implementation of load-balancing, which was found to be very important for lowering computational time.

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1,1′‐Bis(pyrazol‐4‐yl)ferrocenes: Potential Clip Ligands and Their Supramolecular Structures

Cited by 13 publications

References 52 publications

Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

Mixed-Metal Coordination Polymers and Molecular Squares Based on a Ferrocene-Containing Multidentate Ligand 1,2-Di(4-pyridylthio)ferrocene

Linear Pyrazole‐bridged Tetra(N‐heterocyclic carbene) Ligands and Their Hexanuclear Silver(I) Complexes

Fragmentation and transferability in Hirshfeld atom refinement

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