Synthesis, Spectral, Cyclic Voltammetric Studies, and Single Crystal X‐Ray Structure Determination of the Planar NiS₂P₂, NiS₂PN, and NiS₂PC Chromophores

Abstract

dedtc ϭ diethyldithiocarbamate, 4-MP ϭ tri(4-methylphenyl)phosphine, PPh 3 ϭ triphenylphophine) are reported. IR spectra of complexes 1-4 show the characteristic thioureide (C-N) bands at higher wave numbers compared to that of the parent dithiocarbamate complex [Ni(dedtc) 2 ]. The d-d transitions are observed in the region 452Ϫ482 nm. Synthese, Spektroskopie, Cyclovoltammetrie und Einkristall-Strukturanalysen von planaren NiS 2 P 2 -, NiS 2 PN-und NiS 2 PC-Chromophoren Inhaltsübersicht. Es wird über die Synthese, die spektroskopische und cyclovoltammetrische Charakterisierung von [Ni(dedtc)-(4-MP) 2 ](ClO 4 ) (1), [Ni(dedtc)(4-MP)(NCS)] (2), [Ni(dedtc)(PPh 3 )-(NCS)] (3) und [Ni(dedtc)(PPh 3 )(CN)] (4) (dedtc ϭ diethyldithiocarbamat, 4-MP ϭ Tri(4-methylphenyl)phosphin, PPh 3 ϭ Triphenylphosphin) berichtet. Die IR-Spektren der Komplexe 1-4 zeigen die charakteristische Thioharnstoff-(CN)-Bande bei größeren Wellenzahlen verglichen mit dem homoleptischen Dithiocarbamat-Komplex [Ni(dedtc) 2 ]. Die d-d-Übergänge werden im Bereich von ‡ Present address: 187The CV studies clearly show the presence of reduced electron density on the nickel ions in mixed ligand complexes 1-4 compared to the parent dithiocarbamate. Single crystal X-ray structure studies show all the complexes to containplanar NiS 2 P 2 , NiS 2 PN, and NiS 2 PC chromophores in keeping with the observed diamagnetism. In all the complexes the Ni-S distances are asymmetric. The thioureide C-N distance of the complexes 1-4 are less thanthe C-N distance observed in the parent [Ni(dedtc) 2 ]. 452-482 nm beobachtet. Die CV-Untersuchungen zeigen eine deutlich reduzierte Elektronendichte der Nickelionen in den Gemischtligand-Komplexen 1-4 im Vergleich zu [Ni(dedtc) 2 ]. Nach den Einkristallstrukturanalysen enthalten alle Komplexe planare NiS 2 P 2 -, NiS 2 PN-und NiS 2 PC-Chromophore, entsprechend ihrem Diamagnetismus. In allen Komplexen sind die NiϪS-Bindungen asymmetrisch. Die ThioharnstoffϪCN-Abstände sind in 1-4 kürzer als im Ausgangskomplex [Ni(dedtc) 2 ]. 1 H and 31 P nmr chemical shifts are listed to ± 0.01 ppm accuracy and the 13 C nmr chemical shifts to ± 0.1 ppm accuracy

Morphological Studies, Photocatalytic Activity, and Electrochemistry of Platinum Disulfide Nanoparticles from Bis(morpholinyl-4-carbodithioato)-platinum(II)

“…The ν­(C–N) stretching vibration that appeared as a single band at 1457 cm –1 in the ligand shifted to 1498 cm –1 in the complex. This band is an intermediated between ν­(C–N) and ν­(CN) and indicates a shift in electron density toward the metal center as a result of the coordination of the morpholinyl dithiocarbamate ligand to the Pt­(II) ion …”

“…This band is an intermediated between ν(C–N) and ν(C=N) and indicates a shift in electron density toward the metal center as a result of the coordination of the morpholinyl dithiocarbamate ligand to the Pt(II) ion. 23 …”

“…This band is an intermediated between ν(C−N) and ν(CN) and indicates a shift in electron density toward the metal center as a result of the coordination of the morpholinyl dithiocarbamate ligand to the Pt(II) ion. 23 In the absorption spectra of the ligand, the bands at 263 and 287 nm are assigned to the intra-ligand transition due to the S CS and NCS thioureide moiety of the dithiocarbamate ligand. In the Pt(II) complex, the absorption bands observed at 257 and 353 nm are assigned to intra-ligand charge transfer transitions of the ligand, while the band at 419 nm is ascribed to the superposition of charge transfer transitions and d−d transition of the Pt(II) ion (Figure S2).…”

trans Influence and Steric Effect on the Distortions in Planar NiS4, NiS2PN, and NiS2P2 Chromophores

“…13 C chemical shifts of thioureide carbon atoms are correlated to π bonding in the NCS 2 – fragment 9. Generally higher ν(C–N) values correlate with lower N 13 CS 2 for d‐block elements.…”