ChemInform Abstract: COORDINATION COMPLEXE

Abstract

Die offenkettigen Tetrathioäther (IV) wurden durch Reaktion von Na‐methylsulfid mit dem entsprechenden Chloralkohol (I) in absolutem Äthanol, Chlorierung des entstehenden Hydroxyalkylmethylsulfids (IIa) mit Thionylchlorid in wasserfreiem Chloroform und Umsetzung des Derivats (IIb) mit den Dithiolaten (III) in Äthanol dargestellt.

Macrocyclic selenoether complexes of nickel(II). Synthesis and properties of [NiX2([16]aneSe4)] ([16]aneSe4 = 1,5,9,13-tetraselenacyclohexadecane, X = Cl, Br or I) and [NiX2(MeSeCH2CH2SeMe)2] *

“…Reaction of NiX 2 (X = Cl, Br or I) with [16]aneSe 4 (1,5,9,13-tetraselenacyclohexadecane) under anhydrous conditions in n-butanol yielded trans-[NiX 2 ([16] [16]aneSe 4 complexes were obtained via nickel K-edge EXAFS (extended X-ray absorption fine structure), and the results compared with related complexes. A ligand field analysis of the UV/VIS spectra of [NiX 2 ([16]aneSe 4 )] and of the tetrathioether analogues [NiX 2 ([16]aneS 4 )] ( [16]aneS 4 = 1,5,9,13-tetrathiacyclohexadecane) showed that the ligand fields produced by 16-membered ring macrocycles [Dq(xy)] lie in the order N 4 > S 4 > Se 4 , with MeSeCH 2 CH 2 SeMe affording a stronger field that [16]aneSe 4 due to the smaller chelate ring size.…”

“…1,2 In contrast, macrocyclic thioethers are able to form stable complexes with most transition metals. 3 The synthesis 4 of macrocyclic selenoethers including [16]aneSe 4 opens up the possibility of similarly enhanced M᎐Se binding, and we have reported complexes with a variety of platinum metal centres, viz. [M( [16]aneSe 4 )] 2ϩ (M = Pd or Pt), 5 [PtX 2 ([16]aneSe 4 )] 2ϩ (X = Cl or Br), 6 [MX 2 ([16] ([16]aneSe 4 )] ϩ 10 both of which benefit from the kinetically inert metal centres.…”

“…3 The synthesis 4 of macrocyclic selenoethers including [16]aneSe 4 opens up the possibility of similarly enhanced M᎐Se binding, and we have reported complexes with a variety of platinum metal centres, viz. [M( [16]aneSe 4 )] 2ϩ (M = Pd or Pt), 5 [PtX 2 ([16]aneSe 4 )] 2ϩ (X = Cl or Br), 6 [MX 2 ([16] ([16]aneSe 4 )] ϩ 10 both of which benefit from the kinetically inert metal centres. Here we report the first examples of complexes of [16]aneSe 4 with the hard labile 3d ion nickel(), along with attempts to prepare acyclic diselenoether analogues.…”

“…[M( [16]aneSe 4 )] 2ϩ (M = Pd or Pt), 5 [PtX 2 ([16]aneSe 4 )] 2ϩ (X = Cl or Br), 6 [MX 2 ([16] ([16]aneSe 4 )] ϩ 10 both of which benefit from the kinetically inert metal centres. Here we report the first examples of complexes of [16]aneSe 4 with the hard labile 3d ion nickel(), along with attempts to prepare acyclic diselenoether analogues.…”

“…The reaction of anhydrous nickel() halides with [16]aneSe 4 in dry n-butanol gave pale green (X = Cl or Br) or brown (X = I) paramagnetic (µ ca. The UV/VIS spectrum of a high spin d 8 ion in O h symmetry is expected to show three bands in order of increasing energy, 3 A 2g → 3 T 2g , 3 A 2g → 3 T 1g (F) and 3 A 2g → 3 T 1g (P).…”