Structural diversity in the coordination of 1,4‐dihydro‐1,4‐diarsinine as a cyclic ditopic organoarsenic ligand to metal ions

Abstract

A number of different complexation structures of cis‐1,4‐dihydro‐1,4‐dimethyl‐2,3,5,6‐tetrakis(t‐butoxycarbonyl)‐1,4‐diarsinine (cis‐DHDAtBu) with gold(I) and iridium(III) were synthesized and characterized by 1H, 13C NMR spectra, X‐ray crystallography, and elemental analysis. Mono‐ and di‐nuclear gold(I) chloride complexes with cis‐DHDAtBu were obtained by simple addition of gold(I) chloride to cis‐DHDAtBu. A hetero‐trinuclear gold‐platinum‐gold complex (PtAu2Cl4(cis‐DHDAtBu)2) was obtained by complexation of a mononuclear platinum(II) complex (trans‐PtCl2(cis‐DHDAtBu)2), which was obtained by complexation of cis‐DHDAtBu with a half‐equimolar amount of PtCl2(PhCN)2, with a twice‐equimolar amount of gold(I) chloride. An iridium(III) complex with cis‐DHDAtBu (IrCl3(cis‐DHDAtBu)2) was prepared from hydrated iridium(III) chloride and cis‐DHDAtBu. The complex comprises a five‐membered chelate cis‐DHDAtBu and an usual monodentate cis‐DHDAtBu. The interior angles at around the arsenic and the As–C—C bond angles were significantly varied from 113.4° to 129.4° in the present crystal. These observations suggest that the flexibility of the bond angles at around the arsenic center is inherent property in the present organoarsenic compounds. © 2011 Wiley Periodicals, Inc. Heteroatom Chem 23:16–26, 2012; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20747

Molecular gold strings: aurophilicity, luminescence and structure–property correlations

“…4, gold strings with neutral chain links consist of neutral complexes, which form polymeric gold strings through unsupported aurophilic interactions. [157][158][159][160][161][162][163][164][165][166][167][168][169][170][171] As an example, Ecken et al studied the effect of anions on the solid state structure of (o-xylyl isocyanide)gold(I) (Cl (10a), Br (10b), I (10c), CN (10d)). 172 Their study revealed that the Au-Au distances decrease in the order I − > Br − > Cl − .…”

The Dawn of Functional Organoarsenic Chemistry

“…Dimerization of the E ‐form vinyl radical species produces cyclic diarsenic compounds, cis ‐DHDAs ( 32 ). Platinum, palladium, gold, and copper complexes with cis ‐DHDA ligands ( 33 – 37 ) were synthesized (Scheme ) . Notably, the two arsenic atoms are fixed at a short distance (ca.…”

“…Platinum,p alladium,g old, and copperc omplexes with cis-DHDA ligands (33)(34)(35)(36)(37)w ere synthesized (Scheme 18). [85][86][87][88][89][90][91][92] Notably,t he two arsenic atoms are fixed at as hort distance (ca. 3 ).…”