2015
DOI: 10.1107/s2053229615001436
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New isostructural transition metal complexes with a non-innocent dithiolate ligand

Abstract: Three new complexes with 3,6-dichlorobenzene-1,2-dithiol (bdtCl2), namely methyltriphenylphosphonium bis(3,6-dichlorobenzene-1,2-dithiolato-κ(2)S,S')cobaltate(1-), (C19H18P)[Co(C6H2Cl2S2)2], (I), bis(methyltriphenylphosphonium) bis(3,6-dichlorobenzene-1,2-dithiolato-κ(2)S,S')cuprate(2-) dimethyl sulfoxide disolvate, (C19H18P)2[Cu(C6H2Cl2S2)2]·2C2H6OS, (II), and methyltriphenylphosphonium bis(3,6-dichlorobenzene-1,2-dithiolato-κ(2)S,S')cuprate(1-), (C19H18P)[Cu(C6H2Cl2S2)2], (III), have been synthesized and cha… Show more

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Cited by 3 publications
(3 citation statements)
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“…In addition, this EPR signal is very similar to those observed for Ni­(III) complexes with dithiolate ligands both at room and low temperatures as illustrated by lines 2 in Figure a . The recent results of the X-ray diffraction analysis of (MePh 3 P)­[M­(bdt) 2 ] (M = Cu, Ni, Co, bdt = benzene-1,2-dithiolate) showed that the M–S bond lengths are shorter than the reported values for M­(II) complexes, providing further evidence that the formal oxidation state of the metal in previously mentioned dithiolate structures is +3 . However, the dithiolate ligands are severely noninnocent, and the distribution of the electron density between the central atom and the ligand is more complex making it difficult to determine the physical/formal oxidation state of the central atom.…”
Section: Resultssupporting
confidence: 81%
See 1 more Smart Citation
“…In addition, this EPR signal is very similar to those observed for Ni­(III) complexes with dithiolate ligands both at room and low temperatures as illustrated by lines 2 in Figure a . The recent results of the X-ray diffraction analysis of (MePh 3 P)­[M­(bdt) 2 ] (M = Cu, Ni, Co, bdt = benzene-1,2-dithiolate) showed that the M–S bond lengths are shorter than the reported values for M­(II) complexes, providing further evidence that the formal oxidation state of the metal in previously mentioned dithiolate structures is +3 . However, the dithiolate ligands are severely noninnocent, and the distribution of the electron density between the central atom and the ligand is more complex making it difficult to determine the physical/formal oxidation state of the central atom.…”
Section: Resultssupporting
confidence: 81%
“…38 The recent results of the X-ray diffraction analysis of (MePh 3 P)[M(bdt) 2 ] (M = Cu, Ni, Co, bdt = benzene-1,2-dithiolate) showed that the M−S bond lengths are shorter than the reported values for M(II) complexes, providing further evidence that the formal oxidation state of the metal in previously mentioned dithiolate structures is +3. 39 However, the dithiolate ligands are severely noninnocent, and the distribution of the electron density between the central atom and the ligand is more complex making it difficult to determine the physical/formal oxidation state of the central atom. Other recently reported formally Ni(III) systems exhibit EPR spectra that are neither typical Ni(III) nor organic radical in character.…”
Section: ■ Introductionmentioning
confidence: 99%
“…The S-Cu-S bond angles (3), S4-Cu1-S3 = 92.26 (3), S2-Cu1-S1 = 92.14 (4) and S3-Cu1-S1 = 88.45 (3) ] slightly deviate from 90 , and the Cu-S bond lengths vary from 2.1722 (9) to 2.1776 (9) Å . These geometrical parameters agree well with those observed in a similar compound containing the same anion but with the methyltriphenylphosphonium cation (Herich et al, 2015).…”
Section: Structure Descriptionsupporting
confidence: 87%