A Series of Cu₂I₂ Complexes of 10‐(Aryl)phenoxarsines: Synthesis and Structural Diversity

Abstract

Dinuclear complexes of the composition Cu2I2L2Py2 and Cu2I2L4 are obtained by the reaction of 10‐(aryl)phenoxarsine ligands (L) with copper iodide in pyridine or non‐coordinated solvent. Unexpectedly the 1D polymeric complex [Cu2I2L4]n is formed as the only product by the reaction of 10‐(p‐ethoxyphenyl)phenoxarsine with CuI in the molar ratio 1 : 2. All complexes and the initial phenoxarsine ligands are fully characterized by elemental analysis, NMR‐ and IR spectroscopy. X‐ray structure is determined for eight complexes and five ligands. In the 1D coordination polymer [Cu2I2L4]n copper atoms are in zigzag‐like chain arrangement demonstrating the first example of such Cu‐I−Cu‐I binding. The empirical Tolman cone angles for 10‐(aryl)phenoxarsine ligands in complexes are calculated to lie in the range of 125–152°. The dependence of the Tolman angle values on the position of aryl substituent at arsenic atom is demonstrated.

Platinum(II) Complexes with 10-(Aryl)phenoxarsines: Synthesis, Cis/Trans Isomerization, and Luminescence

“…Ligands 10-( p -chlorophenyl)­phenoxarsine ( L1 ), 10-( p -tolyl)­phenoxarsine ( L2 ), and 10-(phenyl)­phenoxarsine ( L3 ) were prepared by following the literature procedures. , Platinum­(II) dichloride complexes 1 – 3 containing 10-(aryl)­phenoxarsines were isolated as yellow solids from the reaction of ligands L1 – L3 with [Pt­(COD)­Cl 2 ] (where COD = 1,5-cyclooctadiene) in molar ratio of 2:1 in CH 2 Cl 2 . The subsequent treatment of complexes 1 – 3 by potassium iodide in chlorobenzene results in the corresponding platinum diiodide complexes 4 – 6 , which were isolated as orange solids in 72–79% yield (Scheme ).…”

“…Ligands 10-(p-chlorophenyl)phenoxarsine (L1), 10-(p-tolyl)phenoxarsine (L2), and 10-(phenyl)phenoxarsine (L3) were prepared by following the literature procedures. 34,35 Platinum(II) dichlor- All complexes are soluble in organic solvents such as dichloromethane (DCM, CH 2 Cl 2 ), chloroform, and chlorobenzene but sparingly soluble in dimethyl sulfoxide, dimethylformamide (DMF), benzene, and toluene, and they are stable under ambient conditions in the solid state as powders. The identity and purity of complexes 1−6 were ascertained by a combination of IR and NMR spectroscopies, mass spectrometry, and elemental analysis (see section 1 of the Supporting Information for details).…”

Definition of the Pnictogen Bond: A Perspective

“…Additionally, the attractive intramolecular interaction between arsenic and chlorine in crystalline 3,4,5,6-tetrachloro-1,2-diarsa-closo-hexaborane is a pnictogen bond, not a halogen bond [91]. The pnictogen-centered Pn•••A intermolecular interactions between interacting units in selected crystalline solids shown in Figure 1d-i [100]; (b) 3',3'',3'''-Phosphinetriyltripropionitrile [101]; (c) trifluoroamine [102]; (d) antimony triiodide molecular sulfur S8 [103]; (e) bis(tetrakis(4-methylphenyl)-antimony) hexabromo-iridium [104]; (f) tris(4-methylphenyl)-(2-(phenylsulfanyl)phenyl)-antimony tetrafluoroborate [42]; (g) diphenylphosphenium bromide [105]; (h) 4-(di-iodoarsino)anilinium 4methylbenzenesulfonate [106] [107] (j) 5-oxo-4,5-dihydrotetrazol-1-ide azane oxide [40]; (k) (2,2'-[sulfanediylbis(methylene)]di(phenyl))-iodo-bismuth(III) [108]; (l) 10-(4-fluorophenyl)-10H-phenoxarsinine [109]; (m) 2-diazonio-1-oxo-3a,4,5,6,7,7a-hexahydro-1H-4,7-methanoinden-3-olate [110]; (n); molecular nitrogen [111]; (o) naphthalene-2-diazonium-3-carboxylate [112]; and (p) azido-nitramino-carbonyl [50]. Selected bond lengths and bond angles are in Å and degrees, respectively.…”

Structural diversity in copper(I) iodide complexes with 6-thioxopiperidin-2-one, piperidine-2,6-dithione and isoindoline-1,3-dithione ligands

“…V: A search for structures with Cu-X zigzag chains that did not contain the Cu 2 ( 2 -X) 2 rhombus afforded 112 matches. Among these, 56 were for polymeric homometallic structures and three of these [refcodes: AFUDUA (Caradoc-Davies et al, 2002), CIQQOL (Musina et al, 2017), and FIWWAK (Cingolani et al, 2005)] contained one-dimensional Cu-I À zigzag chains. All three structures contain tetrahedral Cu I centers coordinated by the two 2 -I atoms and two neutral donor ligands (binding with sulfur and nitrogen for AFUNDA, arsenic for CIQQOL, and FIWWAK).…”