Synthesis, characterization, spectroscopy, electronic and redox properties of a new nickel dithiolene system

Basu, Partha; Nigam, Archana; Mogesa, Benjamin; Denti, Suzanne; Nemykin, Victor N.

doi:10.1016/j.ica.2010.04.004

Cited by 26 publications

(28 citation statements)

References 30 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…62–64 For instance, in [NEt 4 ][Ni(mnt) 2 ] complex, the C-S and the C-C distances are ~1.720(7) Å and ~1.375(10) Å, respectively. 30 The S1-C1-C2-S2 torsion angle of [ 1a ][BF 4 ] 2 is reduced to 13.05° from 36.87° that of the free ligand. Also in dithiolene complexes, the Ni-S distance is shorter due to the strong metal sulfur interactions.…”

Section: Resultsmentioning

confidence: 99%

“…58 It was found (Supporting Information Figure S4) that B3LYP exchange-correlation functional provides the best agreement between theory and experiment and thus, only data on these calculations are discussed below. 30 Wachter’s full-electron basis set was used for nickel, 59 while for all other atoms 6–311G(d) basis set 60 was employed. Geometries of Ni-containing cations, [ 1a ] 2+ and [ 2a ] 2+ , were fully optimized without any restrictions or substituent truncations.…”

Section: Methodsmentioning

confidence: 99%

See 1 more Smart Citation

Solution, Solid, and Gas Phase Studies on a Nickel Dithiolene System: Spectator Metal and Reactor Ligand

et al. 2015

Self Cite

View full text Add to dashboard Cite

The syntheses of cationic nickel complexes using N,N’-dimethyl piperazine 2,3-dithione (Me2Dt0) and N,N’-diisopropyl piperazine 2,3-dithione(iPr2Dt0) ligands are reported. These ligands were used in synthesizing bis- and tris-dithione nickel(II) complexes as tetrafluroborate or hexafluorophosphate salts i.e., [Ni(iPr2Dt0)2][BF4]2 ([1a][BF4]2), [Ni(iPr2Dt0)2][PF6]2 ([1a][PF6]2), [Ni(Me2Dt0)2][BF4]2 ([1b][BF4]2), [Ni(iPr2Dt0)3][BF4]2 ([2a][BF4]2) and [Ni(iPr2Dt0)3][PF6]2 ([2a][PF6]2), respectively. Complex [2a][PF6]2 was isolated from a methanolic solution of [1a][PF6]2. Compound [1a][BF4]2, crystallizes in a trigonal crystal system (space group, P31/c) and exhibits unique packing features, whereas [2a][BF4]2 crystallizes in a monoclinic (P21/n) space group. Cyclic volt-ammograms of [1a][BF4]2, and [1b][BF4]2 are indicative of four reduction processes associated with stepwise single-electron reduction of the ligands. Spectroelectrochemical experiments on [1a][BF4]2 exhibit an inter-valence charge transfer (IVCT) transition as a spectroscopic signature of the mixed-valence [Ni(iPr2Dt0)(iPr2Dt1−)]− species. Analysis of this IVCT band suggests this ligand based mixed valence complex, [Ni(iPr2Dt0)(iPr2Dt1−)]−, behaves more like a traditional class II/III metal based mixed-valence complex. The density functional theory (DFT) and time dependent DFT calculations provide a theoretical framework for understanding the electronic structures and the nature of excited states of the target compounds that are consistent with their spectroscopic and redox properties. Vibrational spectra of [1a]2+ and [2a]2+ were investigated as discrete species in the gas phase using infrared multiple photon dissociation (IRMPD) spectroscopy.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Solution, Solid, and Gas Phase Studies on a Nickel Dithiolene System: Spectator Metal and Reactor Ligand

et al. 2015

Self Cite

View full text Add to dashboard Cite

show abstract

“…The next step of the reactions is the hydrolysis and then the formation of neutral complexes using metal carbonyl or other reactive salts, e.g., NiCl 2 , PdCl 2 (PhCN) 2 . The following Scheme 4 gives an example of the preparation of a series of complexes from the corresponding 1,2-diketones [44,60,65,68,89,98,101,110,111]. Scheme 4.…”

Section: Methodsmentioning

confidence: 99%

“…More information concerning the ligands of Table 1 can be found in [6][7][8][9][10][11][12][13][14][15][16]20,21,24,[26][27][28]30,31,34,36,[48][49][50]53,[61][62][63][64]72,77,79,88,89,92,94,[100][101][102][103][104]. More information concerning the ligands of Table 2 can be found in the corresponding references for L1 [34], L2 [34,98], L3 [33,95,102], L4 [56,…”

Section: Introductionmentioning

confidence: 99%

Neutral Metal 1,2-Dithiolenes: Preparations, Properties and Possible Applications of Unsymmetrical in Comparison to the Symmetrical

2012

View full text Add to dashboard Cite

This paper is an overview concerning the preparations and properties as well as possible applications of neutral (one component) metal 1,2-dithiolenes (and selenium analogues). The structural, chemical, electrochemical, optical and electrical behavior of these complexes depend strongly on the nature of ligand and/or the metal. The results of unsymmetrical in comparison to those of symmetrical complexes related to the properties of materials in the solid state are primarily discussed. The optical absorption spectra exhibit strong bands in the near IR spectral region ca. 700 to ca. 1950 nm. X-ray crystal structure solutions show that the complexes usually have square-planar geometry with S-S and/or M-S contacts. Some of them behave as semiconductors or conductors (metals) and are stable in air. The cyclic voltammograms at negative potentials are different from the corresponding potentials of tetrathiafulvalenes (TTFs). As a consequence, the LUMO bands occur at much lower levels than those of TTFs. Consequently, electrical measurements under conditions of field effect transistors exhibit n-type or ambipolar behavior. Illumination of materials with high power lasers exhibits non-linear optical behavior. These properties enable metal 1,2-dithiolene complexes to be classified as promising candidates for optical and electronic applications, (e.g., saturable absorbers, ambipolar inverters). OPEN ACCESSCrystals 2012, 2 763

show abstract

“…An established method of preparing an arene dithiolene is the reductive dealkylation of 1,2‐C 6 H 4 (SR) 2 , or alternatively through directed lithiation of thiphenols followed by electrophilic addition . Substitution on benzene rings provides an entry to different functionalized dithiolene derivatives . 1,2‐Alkene dithiolenes are generally prepared as salts or as latent precursors that can be deprotected before ligation to a metal ion.…”

Section: Introductionmentioning

confidence: 99%

Dithiolopyranthione Synthesis, Spectroscopy, and an Unusual Reactivity with DDQ

Pimkov

Nigam

Venna

et al. 2013

J. Heterocyclic Chem.

Self Cite

View full text Add to dashboard Cite

The bicyclic pyran thiolone tetrahydro-3αH-[1,3]dithiolo[4,5-β]pyran-2-thione (3a) engages in a highly unusual fragmentation in the presence of DDQ. The pyran thiolone, 3a, was synthesized by chlorination of 3,4-dihydro-2H-pyran (1), followed by condensing with CS2 and NaSH. Reaction of 3a with DDQ generates the isomerized pyran thiolone tetrahydro-3αH-[1,3]dithiolo[4,5-β]pyran-2-thione (3b) and 4-benzyl-5-(3-hydroxypropyl)-1,3-dithiole-2-thione (4) via a deep-seated rearrangement. The identity of 3b was confirmed by single crystal X-ray analysis: P21/c, a=5.807(9) Å, b = 12.99(2) Å, c = 11.445(15), β=113.23(6)°. Mechanistic experiments and computational insight is used to explain the likely sequence of events in the highly unusual formation of 4. Collectively, these results establish fundamental reactivity patterns for further research in this area.

show abstract

Synthesis, characterization, spectroscopy, electronic and redox properties of a new nickel dithiolene system

Cited by 26 publications

References 30 publications

Solution, Solid, and Gas Phase Studies on a Nickel Dithiolene System: Spectator Metal and Reactor Ligand

Solution, Solid, and Gas Phase Studies on a Nickel Dithiolene System: Spectator Metal and Reactor Ligand

Neutral Metal 1,2-Dithiolenes: Preparations, Properties and Possible Applications of Unsymmetrical in Comparison to the Symmetrical

Dithiolopyranthione Synthesis, Spectroscopy, and an Unusual Reactivity with DDQ

Contact Info

Product

Resources

About