Characterization and Electronic Structures of Metal Complexes Containing Benzene-1,2-dithiolate and Related Ligands

Baker-Hawkes, M. J.; Billig, E.; Gray, Harry B.

doi:10.1021/ja00973a021

Cited by 151 publications

(77 citation statements)

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“…One pair of reversible waves at 0.08 V vs. Ag/AgNO 3 was always present, as in (nBu 4 N) 2 [Ni(dcbdt) 2 ] (4), and it was ascribed to the couple Ni II /Ni III . This value should be compared with the corresponding one for the compound with the unsubstituted benzodithiolate ligand (bdt), Ni(bdt) 2 (Ϫ1.05 V), [12] showing that the two cyano groups stabilize the dianionic state. In fact, while the Ni(bdt) 2 Ϫ complex was obtained by oxidation of the dianion in air, obtaining Ϫ from the dianion required iodine as the oxidizing agent.…”

Section: Methodsmentioning

confidence: 99%

“…In 5 the Ni III complex presents a strong dimerization of the [Ni(dcbdt) 2 ] Ϫ units that are related by an inversion centre ( Figure 2) in Figure 4, the ligand where one sulfur atom is coordinat- [a] 2.3965(16) S(1)ϪC(1) 1.729 (6) 1.738(5) S(2)ϪC(2) 1.725 (6) 1.732(5) S(3)ϪC (9) 1.734(5) S(4)ϪC (10) 1.752(5) C(1)ϪC (6) 1.384 (7) 1.409(7) C(1)ϪC (2) 1.424 (8) 1.414(7) C(2)ϪC (3) 1.394 (7) 1.398(7) C(6)ϪC (5) 1.388 (7) 1.380(7) C(3)ϪC(4) 1.389 (7) 1.377(7) C(5)ϪC(4) 1.403 (8) 1.401(7) C(5)ϪC (7) 1.436 (8) 1.450(7) C(4)ϪC (8) 1.441 (8) 1.448(8) C (7)ϪN (1) 1.144 (7) 1.134(7) C(8)ϪN (2) 1.135 (6) 1.130(7) C(9)ϪC (14) 1.394(7) C(9)ϪC (10) 1.406(7) C(10)ϪC (11) 1.376 (6) C(14)ϪC (13) 1.385(7) C(11)ϪC (12) 1.374(7) C(13)ϪC (12) 1.411(7) C(13)ϪC (15) 1.447(8) C(12)ϪC (16) 1.444(7) C(15)ϪN (3) 1.125(7) C(16)ϪN(4) 1.131 (7) [a] Ϫx,Ϫy,Ϫz ϩ 1.…”

Section: Methodsmentioning

confidence: 99%

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Synthesis, Structure and Physical Properties of Tetrabutylammonium Salts of Nickel Complexes with the New Ligand dcbdt = 4,5-dicyanobenzene-1,2-dithiolate, [Ni(dcbdt)2]z− (z = 0.4, 1, 2)

Simão¹,

Alves²,

Belo³

et al. 2001

Eur. J. Inorg. Chem.

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The synthesis and characterization of the new aromatic ortho-dithiol, 4,5-dicyanobenzene-1,2-dithiol (3) is reported. This compound was used to prepare tetrabutylammonium salts of novel nickel complexes; the nickel(II) salt (nBu 4 N) 2 -[Ni(dcbdt) 2 ] (4), the nickel(III) salt (nBu 4 N) 2 [Ni(dcbdt) 2 ] 2 (5), and the partially oxidized Ni III/IV salt (nBu 4 N) 2 [Ni(dcbdt) 2 ] 5 (6). (dcbdt = 4,5-dicyanobenzene-1,2-dithiolate). The Ni II complex presents a square-planar coordination geometry and is diamagnetic, while in the paramagnetic Ni III complex

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Synthesis, Structure and Physical Properties of Tetrabutylammonium Salts of Nickel Complexes with the New Ligand dcbdt = 4,5-dicyanobenzene-1,2-dithiolate, [Ni(dcbdt)2]z− (z = 0.4, 1, 2)

Simão¹,

Alves²,

Belo³

et al. 2001

Eur. J. Inorg. Chem.

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“…7 The gold-dithiolene complexes-though much less studied than the Ni dithiolenes-are known in a range of oxidation states. [8][9][10][11][12][13][14][15][16][17][18][19] As shown in the present paper, the oddelectron compound bis-͑benzene-1,2-dithiolato͒-gold ͓Au͑bdt͒ 2 ͔ belongs to the group of planar molecules, which in the solid state form electrically ͑semi͒conducting molecular stacks with a half-filled electronic band. A more wellknown member of this group is K-TCNQ ͑tetracyanoquinodimethane͒.…”

Section: Introductionmentioning

confidence: 99%

Structural, electrical, magnetic, and optical properties of bis-benzene-1,2-dithiolato-Au(IV) crystals

et al. 1996

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“…These NIR absorption bands have been ascribed to the charge transfer of t*(ligand)-dt*(metal). 16 It is stressed that no measurable absorption due to free ligand is present at the chelate absorption bands (800 -1200 nm). The conditions for the NIR color formation and the spectral data for the mnt and tcbt systems are also listed in Table 1.…”

Section: Resultsmentioning

confidence: 99%

Aromatic 1,2-Dithiols and 1,2-Diamines as Chromogenic Reagents for Nickel, Palladium and Platinum in Near-Infrared Spectrophotometry

et al. 1994

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The near-infrared (NIR) color forming reagents are described for Ni, Pd, and Pt ions, ~r-electron conjugated 1,2-dithiols and 1,2-diamines. The dithiol ligands forms the yellow 1: 2 chelates with these metal ions and subsequent oxidation with 12 or 103 -ion yields the corresponding NIR active species. The spectroscopic data are: Ni-tcbt, 2=878 nm (E=1.49X104 M-1 cm-1); Pd-tcbt, 2=1125 nm (~=2.00X104); Pt-tcbt, 2=880 nm (E=1.92X104), where tcbt means 3,4,5,6-tetrachlorobenzene-l,2-dithiol.In contrast with the dithiolato chelates, the complexation and oxidation processes for metal-diamine systems are concurrently accomplished under slightly acidic (for Pt ion) or slightly alkaline (for Pd ion) conditions, respectively. Very large E values are obtained: Pd-Br2dab, 2=828 nm (4.54X l04); Pt-Br2dab, 2=738 nm (e=1.29X105), where Br2dab denotes 3,5-dibromo-l,2-diaminobenzene.A new idea for designing unique NIR color formation systems is reported; the complexation reactions must be linked with reduction-oxidation processes. The satisfactory selectivity of the Br2dab system for Pt in the presence of iron, copper, and zinc ions is demonstrated for Pt determination in possible clinical practices. KeywordsNear-infrared, spectrophotometry, nickel, palladium, platinum, aromatic dithiol, aromatic diamineThe far-visible to near-infrared (NIR) spectral region (longer than 700 nm) does not seem to be so important in analytical chemistry. This wavelength region seems to have been left transparent, since it lies between vibrational and electronic transitions in molecular spectroscopy. The most outstanding applications are the determinations of water, sugars and other compounds having hydroxyl groups using their vibrational overtone absorption.12 Limited use of this wavelength region has also resulted mainly from the low sensitivity of photomultiplier tubes. But the NIR region is now becoming increasingly important in a wide range of technology such as optical data storage, photography, and photochemotherapy, in close connection with a rapid development of economical photosemiconductor devices.3 Many NIR absorbing dyes for such purposes were comprehensively reviewed More recently a new development of analytical NIR measurements has begun with sensitive fluorimetry.6'' Advantages of the NIR fluorescence labels or tags over the more conventional ones include the great sensitivity combined with freedom from the matrix emission and scattered light problems.8 Nonetheless, study of a new class of NIR spectrophotometric reagents for metal ions seems to be stagnated in spite of the unique selectivity and lower background absorption. Although only limited information is available for the underlying chemistry of NIR absorbing complexes, a new strategy for the inorganic spectrophotometry needs to be established in this spectral region.In this report are described it-electron conjugated (aromatic) 1,2-dithiols and diamines as ligands for d8 metal ions which give the strongly NIR absorbing chelates. The ligands employed in this work and related c...

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Characterization and Electronic Structures of Metal Complexes Containing Benzene-1,2-dithiolate and Related Ligands

Cited by 151 publications

References 0 publications

Synthesis, Structure and Physical Properties of Tetrabutylammonium Salts of Nickel Complexes with the New Ligand dcbdt = 4,5-dicyanobenzene-1,2-dithiolate, [Ni(dcbdt)2]z− (z = 0.4, 1, 2)

Synthesis, Structure and Physical Properties of Tetrabutylammonium Salts of Nickel Complexes with the New Ligand dcbdt = 4,5-dicyanobenzene-1,2-dithiolate, [Ni(dcbdt)2]z− (z = 0.4, 1, 2)

Structural, electrical, magnetic, and optical properties of bis-benzene-1,2-dithiolato-Au(IV) crystals

Aromatic 1,2-Dithiols and 1,2-Diamines as Chromogenic Reagents for Nickel, Palladium and Platinum in Near-Infrared Spectrophotometry

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