38420-68-7Relevant academic research and scientific papers
Pseudohalide HCN aggregate ions: [N3(HCN)3]?, [OCN(HCN)3]?, [SCN(HCN)2]?and [P(CN·HCN)2]?
Harloff, J?rg,Schulz, Axel,Stoer, Philip,Villinger, Alexander
, p. 13345 - 13351 (2020)
In the presence of μ-nitridobis(triphenylphosphonium) cation, [PPN]+, it was possible to stabilize and isolate [PPN]+-salts bearing the highly labile hydrogen cyanide aggregate anions of pseudohalides X (X = N3, OCN and SC
Heavy Neutral and Anionic Pnictogen Thiocyanates
Arlt, S?ren,Harloff, J?rg,Schulz, Axel,Stoffers, Alrik,Villinger, Alexander
, p. 5305 - 5313 (2019)
When [PPN]SCN (1; PPN = [Ph3P-N-PPh3]) is treated with Me3Si-SCN in methanol, [PPN][H(NCS)2] (2), a hydrogen diisothiocyanate salt bearing the [H(NCS)2]- anion, was generated, isolated, and fully characterized. Pure heavy E(NCS)3 [E = Sb (3), Bi (4)] species were obtained from the reaction of EF3 and an excess of Me3Si-SCN, while the tetrahydrofuran (THF) solvates E(NCS)3·THF were isolated when the product was recrystallized from THF. When 2 equiv of 1 was combined with Me3Si-SCN and SbF3, [PPN]2[Sb(NCS)5] (5) could be isolated. When 1 was added to BiF3, [PPN]2[Bi(NCS)3(SCN)2·THF] (6·THF), containing three SCN- ions coordinating via the N atom and two coordinating via the S atom, was isolated after recrystallization from THF. The structures of 1, 2, 3·THF, 4·THF, 5, and 6·THF were determined. 3·THF displayed a typical [3 + 3] coordination mode with a trigonal-pyramidal environment in the first coordination sphere of the Sb3+ ion, and the dianion of 5, [Sb(NCS)5]2-, featured a classical square-pyramidal molecular geometry around the Sb3+ ion with one additional Menshutkin-type interaction to one aryl ring of the [PPN]+ cation. 4·THF exhibited a distorted pentagonal-bipyramidal structure within a two-dimensional network, while in 6·THF, an octahedrally surrounded Bi3+ ion was observed.
Substitution Reactions toward 2-Nitrobenzyl Pseudohalides. The Crystal Structure of 2-Nitrobenzyl Tellurocyanate
Grung, Knut Eric,Roemming, Christian,Songstad, Jon
, p. 518 - 526 (2007/10/02)
The reactions between 2-nitrobenzyl pseudohalides, 2-NO2-PhCH2XCN, and pseudohalide ions, NCX- (X = S, Se or Te) have been studied kinetically in acetonitrile at 25.0 deg C.The reactions proceed through nucleophilic attack at the methylene carbon atom, forming exclusively the exchange products.The average nucleophilicity order, NCTe- >> NCSe- > NCS-, and the average leaving group order, NCTe- >/= NCSe- >/= NCS-, lead to a carbon basicity order NCTe- > NCSe- >/= NCS-, which is confirmed with equilibrium studies.A crystal structure determination of 2-nitrobenzyl tellurocyanate at ca. 135 deg C has revealed that the TeCN group is syn-clinal (gauche) to the C(CH2)-C(Ar) bond with a torsion angle of -48.5(5) deg.The TeCC plane forms an angle of 103.4(5) deg with the phenyl ring plane.In this conformation the steric influence of the 2-NO2 group in substitution reactions at the methylene carbon atom will be negligible except for bulky nucleophiles.The tellurium atom forms two fairly strong intermolecular bonds to nitrogen atoms from neighbouring tellurocyanate groups, viz. 2.889(6) Angstroem trans to the cyano group and 3.382(6) Angstroem trans to the methylene group.In the crystalline state the compound may be considered both as a tellurium(II) complex and as an organic pseudohalide.No intermolecular tellurium-oxygen contacts could be observed.
SYNTHESIS AND VIBRATIONAL SPECTROSCOPIC STUDY OF COMPOUNDS CONTAINING THE I(SCN)2-, I2(SCN)-, AND I(SCN)2- IONS
Bowmaker, Graham A.,Rogers, David A.
, p. 1146 - 1151 (2007/10/02)
The salt (N(PPh3)2)(I(SCN)2) has been prepared by addition of thiocyanogen to (N(PPh3)2)I.Bands due to the ν(CN) and ν(IS) vibrations of the I(SCN)2- ion have been assigned in the i.r. and Raman spectra of this compound, and the results indicate a structure in which the S atoms of the SCN groups are bound to the iodine atom to give a linear or almost linear S-I-S arrangement.The stretching and interaction force constants for the S-I-S group are similar to those for the trihalide ions IX2- (X = Cl, Br, or I).The salt (N(PPh3)2)(I2(SCN)) could not be obtained as a pure compound, but has been obtained as a mixture with the I3- and I(SCN)2- salts in several synthetic experiments.Bands due to the I2(SCN)- ion could be identified in the low-frequency vibrational spectra of these mixtures, and these indicate that this ion has an unsymmetrical structure with an I-I-S arrangement.The salt (N(PPh3)2)(I(SeCN)2) has been prepared by addition of selenocyanogen to (N(PPh3)2)I.The vibrational spectra of this compound do not allow definite conclusions to be drawn about the structure of the I(SeCN)2-ion.
