Synthesis and Characterization of the First Doubly‐bridged N,N‐dimethylthiocarbamoyl Metal Complex: Crystal Structure of [Mo(Cl)(CO)₂(PPh₃)]₂(η¹:η²:μ‐SCNMe₂)₂

Abstract

] (1) in dichloromethane at room temperature. Complex 2 is a dimer with each thiocarbamoyl unit coordinating through sulfur and carbon to one metal center and bridging both metals through sulfur. Complex 2 is characterized by X-ray diffraction analysis.

Synthesis and Characterization of Dimethylthiocarbamoyl-Modified Thiacalix[n]arenes for Selective Pd(II)-Ion Extraction

“…The FT-IR spectra of the complexes were significantly different from those of 1 and 2 , indicating complex formation between 1 and 2 with the Pd(II) ions. After coordination of Pd(II) ions, the peak corresponding to CS in 1 shifted from 1540 to 1552 cm –1 , and a new peak appeared at 1583 cm –1 , which is assigned to CN that forms because of resonance stabilization. , For the 2 –Pd complex, the peak corresponding to CS in 2 shifted from 1533 to 1549 cm –1 , and a new peak appeared at 1584 cm –1 , which is also proposed to correspond to CN formation through resonance stabilization. , The C–N stretching peaks of extractants 1 and 2 shifted from 1106 and 1108 cm –1 , respectively, to 1118 and 1114 cm –1 , respectively, after coordination of Pd(II) ions. Thermal analyses (i.e., TGA and DTA) of 1 -Pd(II) were performed, and a characteristic TGA weight loss curve is shown in the Supporting Information (Figure S2).…”

“…After coordination of Pd(II) ions, the peak corresponding to CS 33 in 1 shifted from 1540 to 1552 cm −1 , and a new peak appeared at 1583 cm −1 , which is assigned to CN that forms because of resonance stabilization. 11,34 For the 2−Pd complex, the peak corresponding to CS in 2 shifted from 1533 to 1549 cm −1 , and a new peak appeared at 1584 cm −1 , which is also proposed to correspond to CN formation through resonance stabilization. 11,34 The C−N stretching peaks of extractants 1 and 2 shifted from 1106 and 1108 cm −1 , respectively, to 1118 and 1114 cm −1 , respectively, after coordination of Pd(II) ions.…”

“…11,34 For the 2−Pd complex, the peak corresponding to CS in 2 shifted from 1533 to 1549 cm −1 , and a new peak appeared at 1584 cm −1 , which is also proposed to correspond to CN formation through resonance stabilization. 11,34 The C−N stretching peaks of extractants 1 and 2 shifted from 1106 and 1108 cm −1 , respectively, to 1118 and 1114 cm −1 , respectively, after coordination of Pd(II) ions. Thermal analyses (i.e., TGA and DTA) of 1-Pd(II) were performed, and a characteristic TGA weight loss curve is shown in the Supporting Information (Figure S2).…”

“…Based on literature reports, compounds 3 and 4 extract Pd(II) ions through coordination to the bridging sulfur as well as two flanking phenolate oxygen atoms. In contrast, compounds 1 and 2 likely complex Pd(II) ions through the thiocarbamoyl groups. ,,, The proposed major Pd(II) ion–extraction mechanism of compound 1 and 2 is shown in the Supporting Information (Figure S6).…”

Comparative Study on Palladium(II) Extraction Using Thioamide-Modified Acyclic and Cyclic Extractants

“…FT-IR spectra of 1 and the 1 -Pd complex are shown in Figure . In the 1 -Pd complex, broad v (CS) peaks appeared between 1510 and 1485 cm –1 , − and a peak at 1598 cm –1 corresponds to a formation of v (CN), due to a partial double bond character in the C–S and SC–N bonds after Pd­(II) extraction. , The 1 H NMR spectrum of 1 after Pd­(II) extraction is shown in Figure S3. After the complexation of Pd­(II) and extractant 1 , the methyl peaks of the −N­(CH 3 ) 2 groups in extractant 1 shifted from 3.43 ppm (cf.…”