Zur Koordinationschemie des 1,3‐Dithiol‐2‐on‐4,5‐dithiolats (dmid) – ein Vergleich mit 1,3‐Dithiol‐2‐thion‐4,5‐dithiolat (dmit). Kristall‐ und Molekülstruktur des Tetrabutylammonium‐bis(1,3‐dithiol‐2‐on‐4,5‐dithiolato)nickelat(III), (n‐C4H9)4N[Ni(dmid)2]

Olk, Ruth‐Maria; Dietzsch, W.; Köhler, Klaus; Kirmse, R.; Reinhold, J.; Hoyer, Eberhard; Golič, L.; Olk, B.

doi:10.1002/zaac.19885670115

Cited by 34 publications

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“…Complex 4a was prepared and isolated similarly to (Bu 4 N) 2 {tto[Cu(mnt)] 2 } ( 2 ) with minor modifications. A solution of 455 mg (0.500 mmol) of (Bu 4 N) 2 [Zn(dmid) 2 ] in minimal (∼10 mL) CH 2 Cl 2 was added to a solution of 103 mg (0.250 mmol) of (Et 4 N) 2 tto in 25 mL of water, and the mixture was stirred for 5 min. After 85 mg (0.500 mmol) of CuCl 2 ·2H 2 O dissolved in 15 mL MeOH was added slowly to the organic layer, the biphasic solution was stirred for 40 min.…”

Section: Methodsmentioning

confidence: 99%

Extensively Conjugated Dianionic Tetrathiooxalate-Bridged Copper(II) Complexes for Synthetic Metals

et al. 1996

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Using a unique three-solvent biphasic method, we have prepared and characterized three new fully conjugated, chalcogen-rich, bridged copper(II) complexes for the preparation of molecular conductors and magnetic materials, having the general formula (Bu(4)N)(2){tto[Cu(L)](2)} (tto = C(2)S(4)(2)(-) = tetrathiooxalato; L = mnt = C(4)N(2)S(2)(2)(-) = 1,2-dicyanoethene-1,2-dithiolato for complex 2, dsit = C(3)Se(2)S(3)(2)(-) = 2-thioxo-1,3-dithiole-4,5-diselenolato for complex 3, dmid = C(3)OS(4)(2)(-) = 2-oxo-1,3-dithiole-4,5-dithiolato for complex 4a). The single-crystal X-ray structures of 2 and 3 have been determined: 2, (Bu(4)N)(2){tto[Cu(mnt)](2)}, monoclinic, space group C2/m, a = 19.549(4) Å, b = 13.519(3) Å, c = 10.162(2) Å, beta = 90.33(1) degrees, Z = 2; 3, (Bu(4)N)(2){tto[Cu(dsit)](2)}, monoclinic, space group P2(1)/c, a = 9.903(1) Å, b = 15.589(1) Å, c = 18.218(1) Å, beta = 90.40(1) degrees, Z = 2. Complex 2 displays perfect planarity, while 3 shows a slight tetrahedral distortion at the metal centers, resulting in a dihedral angle of 24.86(3) degrees. Cyclic voltammetry of (Bu(4)N)(2){tto[Cu(mnt)](2)} (2), (Bu(4)N)(2){tto[Cu(dsit)](2)} (3), and (Bu(4)N)(2){tto[Cu(dmid)](2)} (4a) shows each complex to exhibit two reversible redox processes which can be attributed to {tto[Cu(L)](2)}(2)(-) right arrow over left arrow tto[Cu(L)](2)}(-) and {tto[Cu(L)](2)}(1)(-) right arrow over left arrow {tto[Cu(L)](2)}(0) couples. The structural and electronic properties of 2, 3, and 4a will be compared to those of the recently communicated analogous complex (Bu(4)N)(2){tto[Cu(dmit)](2)} (1).

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Section: Methodsmentioning

confidence: 99%

Extensively Conjugated Dianionic Tetrathiooxalate-Bridged Copper(II) Complexes for Synthetic Metals

et al. 1996

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Chiral Metal-Dithiolene/Viologen Ion Pairs: Synthesis and Electrical Conductivity

et al. 2001

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Enantiomerically pure dithiolene complexes NBu4[Ni[(R,R)-diotte)2] and NBu4[Ni((S,S)-diotte]2] (diotte2- = a 1,3-dioxolane-tetrathiaethylene), were prepared from the corresponding enantiomers of a diotte2- precursor. The structure of the precursor was solved by single-crystal X-ray analysis; desulfurization afforded a novel tetrathiafulvalene derivative. Combination of the complex monoanion with the enantiomers of the viologen derivative bis(2-methyl-3-hydroxypropyl)-4,4'-dipyridinium (HiBV2+) afforded enantiomeric and diastereomeric ion-pair complexes of the type HiBV[Ni(diotte)2]2. For comparison, the analogous compounds A[Ni(diotte)2]2, (A2+ = methyl (MV2+), octyl (OV2-), stearyl (StV2+) viologen or two 2,2'-bipyridinium acceptors), HiBV-[Ni(diotte)L] [L = mnt2- (maleonitrile-1,2-dithiolate), dmit2- (2-thioxo-1,3-dithiol-4,5-dithiolate)], MV[Ni(dmit)2)]2, [Ni(diotte)2], and [Ni(diotte)(dmit)] were synthesized. An X-ray powder diffraction structural analysis of MV-[Ni(dmit)2)]2 revealed the presence of mixed stacks that contain the sequence anion-anion-cation. While no short contacts are observable within a stack, these are observed between the stacks for the dication-anion interaction by short S...H distances in the range of 2.77 to 2.86 A, and for the anion-anion interaction short S...S distances of 3.55 to 3.65 A. In agreement with the absence of intrastack interactions, no ion-pair charge-transfer band can be detected in this and the other complexes. ESR and UV/Vis data suggest that in [Ni(diotte)2]- electron delocalization is less pronounced than in the corresponding mnt2- and dmit2- complexes. The specific electrical conductivity (sigma) of pressed powder pellets ranges from 10(-2) to 10(-12) ohm(-1) cm(-1) and in all cases increases with increasing temperature (293 - 393 K) according to an Arrhenius law. Corresponding activation energies vary from 0.14 to 0.93 eV and increase linearly with log a for structurally similar ion pairs. Charge generation is postulated to occur by disproportionation of the monoanion as suggested by the almost linear increase of log(sigma) with decreasing disproportionation energy. The conductivity of diastereomers of ions with two unlike configurations like [(S,S)-HiBV]-[Ni[(R,R)-diotte]2]2 (1.1 x 10(-1) ohm(-1) cm(-1)) is one to two orders of magnitude higher as compared to the diastereomers with two like-configured ions.

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Tuning Lanthanide Reactivity Towards Small Molecules with Electron‐Rich Siloxide Ligands

et al. 2014

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The synthesis, structure, and reactivity of stable homoleptic heterometallic LnL 4 K 2 complexes of divalent lanthanide ions with electron-rich tris(tert-butoxy)siloxide ligands are reported. The [Ln(OSi(OtBu) 3 ) 4 K 2 ] complexes (Ln = Eu, Yb) are stable at room temperature, but they promote the reduction of azobenzene to yield the KPhNNPh radical anion as well as the reductive cleavage of CS 2 to yield CS 3 2À as the major product. The Eu III complex of the radical anion PhNNPh is structurally characterized. Moreover, [Yb(OSi(OtBu) 3 ) 4 K 2 ] can reduce CO 2 at room temperature. Release of the reduction products in D 2 O shows the quantitative formation of both oxalate and carbonate in a 1:2.2 ratio. The bulky siloxide ligands enforce the labile binding of the reduction products providing the opportunity to establish a closed synthetic cycle for the Yb II -mediated CO 2 reduction. These studies show that the presence of four electron-rich siloxide ligands renders their Eu II and Yb II complexes highly reactive.

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Cited by 34 publications

References 15 publications

Extensively Conjugated Dianionic Tetrathiooxalate-Bridged Copper(II) Complexes for Synthetic Metals

Extensively Conjugated Dianionic Tetrathiooxalate-Bridged Copper(II) Complexes for Synthetic Metals

Chiral Metal-Dithiolene/Viologen Ion Pairs: Synthesis and Electrical Conductivity

Tuning Lanthanide Reactivity Towards Small Molecules with Electron‐Rich Siloxide Ligands

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