Experimental and theoretical evidence of unsupported Ag–Ag interactions in complexes with triazine-based ligands. Subtle effects of the symmetry of the triazine substituents

Carranza, M. Pilar; Manzano, Blanca R.; Jalón, Félix A.; Rodrı́guez, Ana; Santos, L.; Moreno, Miquel

doi:10.1039/c3nj00738c

Cited by 18 publications

(10 citation statements)

References 129 publications

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“…The compound is luminescent ( λ ex =355 nm, λ em =410, 460, and 485 nm) 81. Similar contacts have also been discussed for the dimers formed with other flat macrocycles, but there also the role of the anions is a point of concern 60…”

Section: Experimental and Computational Evidence For Argentophilicmentioning

confidence: 54%

“…Considering all these results, it has recently been pointed out that even in the absence of ligand bridging by conventional electron‐pair bonding ( 1 a–c ), the Ag + –Ag + interaction may not really be “unsupported” in any condensed phase: Many of the ubiquitous weak forces, such as hydrogen bonding, π–π stacking, ion–ion, ion–dipole, and dipole–dipole attraction, and last but not least, van der Waals interactions, established between the ligands can influence markedly the mode of aggregation and thus co‐determine the Ag + –Ag + distance between the mononuclear components 21. 60…”

Section: Experimental and Computational Evidence For Argentophilicmentioning

confidence: 99%

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Argentophilic Interactions

2014

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The decade 1990-2000 saw a growing interest in aurophilic interactions in gold chemistry. These interactions were found to influence significantly a variety of structural and other physical characteristics of gold(I) compounds. The attention paid to this unusual and counterintuitive type of intra- and intermolecular bonding between seemingly closed-shell metal centers has rapidly been extended to also include silver chemistry. Hundreds of experimental and computational studies have since been dedicated to the argentophilicity phenomenon. The results of this development are reviewed herein focusing on molecular systems where two or more silver(I) centers are in close contact leading to specific structural characteristics and a variety of novel physical properties. These include strongly modified ligand-to-metal charge-transfer processes observed in absorption and emission spectroscopy, but also colossal positive and negative thermal expansion on the one hand and unprecedented negative linear compressibility of crystal parameters on the other.

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Section: Experimental and Computational Evidence For Argentophilicmentioning

confidence: 54%

Section: Experimental and Computational Evidence For Argentophilicmentioning

confidence: 99%

Argentophilic Interactions

2014

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“…The Ag-O distance [Ag-O3 2.224(2) Å] is among the shortest known for silver triflate complexes; it is shorter than relatives such as {Ag[C6H5CH2OCH2Cpz3]}OTf (2.343 Å), (43) [Ag(4-MeO-2,6-pz*2-triazine)]OTf (2.292 Å), (44) and Ag[HC(pz 3tBu )3]}OTf (2.264 Å) (22a) and is between the distances found in {Ag2(μ2-4,13-dibenzyl-4,13-diaza-18-crown-6)}(OTf)2 [2.252(3) and 2.215(3) Å]. (45) The bond angles about silver in 1a give a τδ parameter (46) of 0.61 near the border of a distorted sawhorse coordination geometry (τδ = 0.63-0.45) and a distorted tetrahedral geometry (τδ = ∼0.9-0.63). 7O1-Ag1-N41 100.53(8) N11-Ag2-N32 136.66 9O3-Ag1-N21 138.16 7N21-Ag1-O3 85.92 7O1-Ag1-N51 85.39 9N21-Ag2-N32 138.86 9N2-Ag1-N11 80.90 6N2-Ag1-N41 135.99 9N2-Ag1-N21 77.27 6N2-Ag1-N51 141.51 9O3-Ag1-N2 127.21(6) N11-Ag1-N21 154.09 8O1-Ag1-N2 96.08(9) N11-Ag2-N21 82.83 9N11-Ag1-N21 80.61 6N41-Ag1-N51 80.63 9Complex 2a exists as a dimer with inversion symmetry as a result of two ligands that sandwich two closely spaced silver centers [Ag•••Ag separation 3.0588(4) Å; Figure 3].…”

Section: Solid Statementioning

confidence: 85%

“…All of these values are within the ranges for either a distorted tetrahedral (τδ = ∼0.90-0.63) or a distorted sawhorse (τδ = ∼0.63-0.45) geometry. (46) The unbound "confused" pyrazolyls in each complex involve disparate noncovalent interactions that help to differentiate the supramolecular structures. The SO groups of the tosyl unit in each solvate of 1b (rather than of the triflate) are hydrogen-bonded to the methine hydrogen atoms of the neighboring cations to help to organize the three-dimensional extended structure ( Figures S2 and S3).…”

Section: Solid Statementioning

confidence: 99%

Reaction Chemistry of Silver(I) Trifluoromethanesulfonate Complexes of Nitrogen-Confused C-Scorpionates

et al. 2018

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Two new C-scorpionate ligands with a bis(3,5-dimethylpyrazol-1-yl)methyl group bound to the 3 position of either an N-tosyl (L*) or an N-H pyrazole (L*) ring have been prepared. The silver(I) complexes of these new ligands and the two previously reported analogous ligands with unsubstituted bis(pyrazol-1-yl)methyl groups (L and L) in both 1:1 and 2:1 ligand/metal ratios were investigated to explore the effects of ligand sterics on their physical and chemical properties. The structurally characterized derivatives of the type [Ag(L)](OTf) are four-coordinate, where the confused pyrazolyl is not bound to the metal. On the other hand, three 1:1 complexes [Ag(L)](OTf) had all pyrazolyls bound, while the μ-κ,κ-L derivative had an unbound confused pyrazolyl. The molecularity of the latter four ranged from polymeric to dimeric to monomeric in the solid with increasing steric bulk of the ligand. The utility of these complexes in stoichiometric ligand-transfer reactions and in styrene aziridination was demonstrated. Thus, tricarbonylmanganese(I) complexes were prepared as kinetically inert models for comparative solution diffusion NMR studies. Also, [Fe(L)](OTf) was prepared for similar reasons and to compare the effects of anion on spin-crossover properties.

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“…Similar dinuclear systems with Ag and pyrazole‐based ligands were also described in which the ligands bridge two metal centers . Other dinuclear systems with different ligand systems were also described . In more detail, in the dinuclear complex [Ag(L pzH )] 2 (NO 3 ) 2 ( 1 , Figure ) the N atoms of two different pyrazole rings are bound on two different metal centers, and the additional coordination of a monodentate NO 3 – anion implies that silver exhibits a distorted T geometry (Table ).…”

Section: Resultsmentioning

confidence: 91%

Silver(I) Bis(pyrazolyl)methane Complexes and Their Implementation as Precursors for Metallic Silver Deposition

et al. 2015

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The following Ag I bis(pyrazolyl)methane complexes with BF 4 -/NO 3 as counteranions were synthesized and characterized:[Ag(L pzH )] 2 (NO 3 ) 2 (1), [Ag(L pzMe )] 2 (NO 3 ) 2 (2), [Ag(L pzH )] n (BF 4 ) n (3), and [Ag(L pzMe )] n (BF 4 ) n (4) [L pzH = bis(pyrazolyl)methane; L pzMe = bis(3,5-dimethylpyrazolyl)methane]. These complexes were prepared to identify optimum precursors for the thermolytic deposition of metallic silver. The crystal structures of 1 and 2 show that the complexes are dinuclear and that the NO 3 anions interact with the metals. In contrast, 3 is polymeric and the BF 4 does not interact with the metal. When crystallizing 1-4 in non-anhydrous solvents, the presence of adventitious water further reacts with 3 and 4 (but not with 1 and 2) to yield dinuclear complexes [Ag(L pzH )(H 2 O) 2 ] 2 (BF 4 ) 2[a]

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Experimental and theoretical evidence of unsupported Ag–Ag interactions in complexes with triazine-based ligands. Subtle effects of the symmetry of the triazine substituents

Cited by 18 publications

References 129 publications

Argentophilic Interactions

Argentophilic Interactions

Reaction Chemistry of Silver(I) Trifluoromethanesulfonate Complexes of Nitrogen-Confused C-Scorpionates

Silver(I) Bis(pyrazolyl)methane Complexes and Their Implementation as Precursors for Metallic Silver Deposition

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