Synthesis, characterization and structure of a low coordinate desoxomolybdenum cluster stabilized by a dithione ligand

Perera, Eranda; Basu, Partha

doi:10.1039/b904113c

Cited by 13 publications

(17 citation statements)

References 32 publications

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“…thiolato and thione). The observed Mo-S distances are within the range of Mo–S (thiol) 24,25 and Mo–S (thione) 17,26 distances reported in the literature. 27,28 The C=S (thione) distances are 0.06Å shorter than C–S (thiol) bond lengths in MoO(SPh) 2 i Pr 2 Dt o .…”

Section: Resultssupporting

confidence: 82%

Large Ligand Folding Distortion in an Oxomolybdenum Donor–Acceptor Complex

et al. 2015

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Interligand charge transfer is examined in the novel metallo-dithiolene complex MoO(SPh)2(iPr2Dto) (where iPr2Dto is N,N′-isopropyl-piperazine-2,3-dithione). The title complex displays a remarkable 70° “envelope” type fold of the five member dithiolene ring, which is bent upward toward the terminal oxo ligand. A combination of electronic absorption and resonance Raman spectroscopies have been used to probe the basic electronic structure responsible for the large fold-angle distortion. The intense charge transfer transition observed at ~18,000 cm−1 is assigned as a thiolate → dithione ligand-to-ligand charge transfer (LL′CT) transition that also possesses Mo(IV) → dithione charge transfer character. Strong orbital mixing between occupied and virtual orbitals with Mo(x2−y2) orbital character derives from a strong pseudo Jahn-Teller effect, which drives the large fold angle distortion to yield a double well potential in the electronic ground state.

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Section: Resultssupporting

confidence: 82%

Large Ligand Folding Distortion in an Oxomolybdenum Donor–Acceptor Complex

et al. 2015

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“…The ligand, diisopropylpiperazine-2,3-dithione (i-Pr 2 Pipdt), was synthesized in air. [13] Solvents were purchased either from Aldrich Chemical Co or Acros Organics and were purified by distillation as follows: acetonitrile from CaH 2 , followed by Li 2 CO 3 -KMnO 4 and finally from P 2 O 5 ; CH 2 Cl 2 and CHCl 3 from CaH 2 ; diethyl ether and toluene from sodium benzophenone; methanol from sodium ethoxide. MoCl 5 , N,N- dimethyl ethylene diamine, N,N-diisopropyl ethylene diamine and Lawesson’s reagent were purchased from Aldrich and used without purification.…”

Section: Methodsmentioning

confidence: 99%

A Valence Bond Description of Dizwitterionic Dithiolene Character in an Oxomolybdenum–Bis(dithione) Complex

et al. 2011

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Metallo-dithiolene non-innocence is explored in an oxomolybdenum-bis(dithione) complex, [Mo4+O(i-Pr2Pipdt)2Cl][PF6] (where i-Pr2Pipdt is N,N’-piperazine-2,3-dithione), that possesses a piperazine ring as an integral part of the dithiolene ligand. The title complex displays unusual spectroscopic features for a formally reduced Mo(IV) dithiolene complex, namely a low energy metal-to-ligand charge transfer band with appreciable intensity and C-C and C-S stretching frequencies that are markedly different from those of oxomolydenum complexes coordinated to dianionic dithiolene ligands. The electronic structure of the ligand has been described in valence bond terms as a resonance hybrid of dithione and dizwitterionic dithiolene contributing structures.

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“…31–33 In contrast, a majority of the studies in exploring the redox noninnocence in metal-dithiolene systems have focused on the reduced state of the ligand. 1–3 It has been reported that oxidation removes electrons from the reduced ligands demonstrating the noninnocent nature of the ligands.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2015

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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.

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Synthesis, characterization and structure of a low coordinate desoxomolybdenum cluster stabilized by a dithione ligand

Cited by 13 publications

References 32 publications

Large Ligand Folding Distortion in an Oxomolybdenum Donor–Acceptor Complex

Large Ligand Folding Distortion in an Oxomolybdenum Donor–Acceptor Complex

A Valence Bond Description of Dizwitterionic Dithiolene Character in an Oxomolybdenum–Bis(dithione) Complex

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

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