Sulfur K-edge extended X-ray absorption fine structure spectroscopy of homoleptic thiolato complexes with Zn(II) and Cd(II)

Synthesis and physicochemical characterization of zinc(II) and cadmium(II) complexes with simple ligands

“…The m(Cu-N) assignments of these copper(II) complexes (near 385 and 315 cm )1 ) are similar with those of (7)- (9). In the spectra of (7)- (9), a band at 315 cm )1 was not observed. This is probably because copper(II) complexes take an octahedral configuration and two tacn coordinate to one copper(II) which is different from (7)- (9).…”

“…The reaction of cadmium(II) with NaSC 6 H 11 did not give the corresponding complex, [Cd(SC 6 H 11 )(tacn iPr )], even when the reaction conditions (ratio, reaction time and others) were varied. The thiolato complexes (7) and (10) with NaSC 10 H 15 were obtained by initial reaction between the metal source and tacn iPr in order to prevent the formation of polymer and insoluble [M(l-SC 10 H 15 ) 2 ] n [9]. The corresponding cadmium(II) derivative of (9) has trinuclear structure such as (11).…”

“…spectra of tacn and its copper(II) complexes [[Cu (tacn) 2 ]X 2 , X = Cl or Br], in which tacn has no substitution groups, has been reported [28]. The m(Cu-N) assignments of these copper(II) complexes (near 385 and 315 cm )1 ) are similar with those of (7)- (9). In the spectra of (7)- (9), a band at 315 cm )1 was not observed.…”

“…The m(Zn-N) bands are slightly shifted from 461 and 427 cm )1 observed for the precursor complex (1) to 458 and 422 cm )1 for (3) (Figure 4). The m(Zn-S) bands are expected around 300 cm )1 [6,9,10]. The far-i.r.…”

“…We are interested in spectroscopic model complexes of zinc(II) and cadmium(II) ions with ''simple'' supporting ligands, which have an imidazole ring or do not contain any aromatic rings or multiple bonds [6][7][8][9][10]. We have demonstrated that the ''simple'' supporting ligands are useful to study spectroscopic assignments related to the metal and coordination atoms in the MX 2 S 2 complexes containing 1-methylimidazoline-2-thione (mitH) [MX 2 (mitH)] (M = Zn II or Cd II ; X = Cl, Br or I) [6], MX 2 N 2 complexes containing 1,4-dimethylhomopiperazine (hp¢) [MX 2 (hp¢)] (M = Zn II or Cd II ; X = Cl, Br or I) [7] and ( ) ) sparteine (sp) [MX 2 (sp)] (M = Zn II or Cd II ; X = Cl, Br or I) [8] and homoleptic thiolato complexes [(Et 4 N)[Zn(SC 10 H 15 ) 3 ] (HSC 10 H 15 = 1-adamantanethiol), (NEt 4 ) 2 [{Zn(SC 6 H 11 ) 2 } 2 (l-SC 6 H 11 ) 2 ] and (NEt 4 ) 2 [{Cd(SC 6 H 11 )} 4 (l-SC 6 H 11 ) 6 ] (HSC 6 H 11 = 1-cyclohexanethiol)] [9,10]. It is well known that zinc(II) takes a variety of coordination types such as N 2 S 2 , N 2 O 2 and others in the biological systems.…”