24300-70-7Relevant articles and documents
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Crosby,J. et al.
, p. 2891 - 2900 (1970)
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Honeycomb sheet structures achieving high electrical conductivities in alkyl-substituted thiazolium bis(2-thioxo-1,3-dithiole-4,5-dithiolato) nickelate(III) complex salts
Tomiyama, Etsuko,Tomono, Kazuaki,Hashizume, Daisuke,Wada, Tatsuo,Miyamura, Kazuo
, p. 352 - 357 (2009)
A series of [Ni(dmit)2] (1) (dmit = 2-thioxo-1,3-dithiole-4,5- dithiolato) complex salts with 3,4-dimethylthiazolium (2), 2,3,4- trimethylthiazolium (3), and 3,4,5-trimethylthiazolium (4) cations (I, II, and III, respectively) were synthesized and characterized by single-crystal X-ray analysis and conductivity. The molecular structures of 1 were the same in all three complex salts. In the structure of I, the anions were arranged in hexagonal structures. Neighboring hexagons formed honeycomb sheet structures as the result of S-S interactions in the (001) plane. The sheets of the honeycomb structures were arranged along the c axis with translational symmetries that form columnar honeycomb channels along the [111] direction. In the structures of II and III, honeycomb sheet structures were formed as in I. But in contrast to I, the relative position of the stacked sheets in II and III was slightly dislocated, forming zig-zag channels instead. The IR spectra of I, II, and III show that the C=C stretching band is slightly red-shifted to 1337-1339 from 1350 cm-1 for [Ni(dmit)2]-, caused by the partial oxidation of the anion. The measured values of the electrical conductivities were 0.20, 0.094, and 0.16 S cm-1 for I, II, and III, respectively. These high conductivities may be ascribed to the partially oxidation of the anion. The S-S interactions regulate the honeycomb sheet structure of the crystal and should work as conduction pathways effectively.
Oxidative addition of the imidazolium cation to zerovalent Ni, Pd, and Pt: A combined density functional and experimental study
McGuinness,Cavell,Yates,Skelton,White
, p. 8317 - 8328 (2007/10/03)
Oxidative addition of different imidazolium cations to zerovalent group 10 metals, to afford heterocyclic carbene complexes, has been investigated by both density functional theory (DFT) and experimental studies. The theoretical analysis shows that addition of imidazoliums to Pt0 and Ni0 is more exothermic than to Pd0, and Ni0 is predicted to react with a much lower barrier than either Pt0 or Pd0 Strongly basic supporting ligands on the metal, as well as cis-chelating ligands, increase the exothermicity of the reaction and also lower the activation barrier. The addition of 2-H imidazoliums is easier and more exothermic than addition of 2-alkylimidazoliums, and a halo-imidazolium is expected to further lower the barrier to oxidative addition and increase the exothermicity. The DFT results show that all three of the metals should be able to oxidatively add imidazolium cations under appropriate conditions. Experimental studies confirmed that oxidative addition is possible, and a number of Pt- and Pd-carbene complexes were prepared via oxidative addition of imidazolium salts to M0 precursors. Most significantly, oxidative addition of 2-H azolium salts was found to readily occur, and the reaction of 1,3-dimethylimidazolium tetrafluoroborate with Pt(PPh3)2 and Pt(PCy3)2 affords [PtH(dmiy)(PPh3)2]BF4 (10) and [PtH(dmiy)(PCY3)2]BF4 (11), while reaction between 3,4-dimethylthiazolium tetrafluoroborate and Pt(PCy3)2 yields [PtH(dmty)(PCy3)2]BF4 (12) (dmiy = 1,3-dimethylimidazolin-2-ylidene, dmty = 3,4-dimethylthiazolin-2-ylidene). Addition of 2-iodo-1,3,4,5-tetramethylimidazolium tetrafluoroborate to Pt(PPh3)4 or Pd(dcype)(dba) yields [PtI(tmiy)(PPh3)2]BF4 (9) and [PdI(tmiy)(dcype)]BF4 (14), respectively (tmiy = 1,3,4,5-tetramethylimidazolin-2-ylidene, dcype = 1,3-bis(dicyclohexylphosphino)ethane)). X-ray crystal structures are reported for complexes 9 and 11 (cis and trans). These studies clearly show for the first time that oxidative addition of imidazolium and thiazolium cations is possible, and the results are discussed in terms of the ramifications for catalysis in imidazolium-based ionic liquids with both carbene-based and non-carbene-based complexes.
