Zn(II) Complexes with Aliphatic Thiolates. (Et4N)[Zn(SAd)3] and (Et4N)2[{Zn(ScHex)2}2(μ-ScHex)2]

Abstract

New homoleptic aliphatic thiolato complexes with Zn(II), (Et4N)[Zn(SAd)3] (1) (HSAd = 1-adamantanethiol), and (Et4N)2[{Zn(ScHex)2}2(μ-ScHex)2] (2) (HScHex = 1-cyclohexanethiol), have a novel three-coordinate geometry for monomeric 1 and a tetrahedral geometry for dimeric 2, respectively. The complexes have been fully characterized by far-IR, Raman, and UV–vis absorption spectroscopy.

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

“…The Zn-S distance of 2.230(1) Å is almost the same as that of substituted hydrotris(1-pyrazolyl)borate complexes (average 2.21 Å ) with the same coordination mode [22,23]. Comparing with other zinc(II) complexes containing only simple ligands, the Zn-S distance of (8) is almost the same as the value of 2.262(4) Å for (Et 4 N)[Zn(SC 10 H 15 ) 3 ] [10].…”

“…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.…”

“…In general, the m(Zn-S) band is observed in the 300-350 cm )1 region. Complexes [10] also have m(Zn-S) bands in that region. Further, the band at 348 cm )1 was newly found after forming (8).…”

“…Assignments for (10) [[Cd(SC 10 H 15 )(tacn iPr )](ClO 4 )] and (11) [Cd 3 (SCH 2 CF 3 ) 6 (tacn iPr ) 2 ] were made based on those of (7)-(9) (see Figure S2, supporting information). In the spectrum of (11), two strong bands were observed in the 500-150 cm )1 region.…”

“…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.…”