Versatility of Heterocyclic Thioamides in the Construction of a Trinuclear Cluster [Cu₃I₃(dppe)₃(SC₅H₄NH)] and Cu^I Linear Polymers {Cu₆(SC₅H₄NH)₆I₆}_n·2nCH₃CN and {Cu^I₆(SC₃H₆N₂)₆X₆}_n (X = Br, I)

Abstract

Reaction of copper(I) iodide with pyridine-2-thione (2-SC5H4NH) and 1,2-bis(diphenylphosphino)ethane (dppe) in a CH3CN-CHCl3 mixture yielded a triangular cluster, [Cu3I3(mu2-P,P-dppe)3 (eta1-SC5H4NH)], 1. Similar reaction with 2-SC5H4NH and a series of diphosphanes, Ph2P-X-Ph2P {X = -CH2- (dppm), -(CH2)3- (dppp), -(CH2)4- (dppb), -CH=CH- (dppen)}, gave a novel iodo-bridged hexanuclear Cu(I) linear polymer,{Cu6(mu3-SC5H4NH)4 (mu2-SC5H4NH)2 (I4)(mu-I)2-}n x 2nCH3CN, 2. Reactions of copper(I) iodide/copper(I) bromide with 1,3-imidazolidine-2-thione (SC3H6N2) in a CH3CN-CHCl3 mixture yielded hexanuclear Cu(I) linear chain polymers, [{Cu6(mu3-SC3H6N2)2 (mu2-SC3H6N2)4X2 (mu-X)4}n] (X = Br, 4; I, 5). In compound 1, two iodide atoms and one dppe form the dinuclear Cu(mu2-I)2 (mu2-dppe)Cu core, and two dppe ligands bridge this core with the third Cu(I) center coordinated to 2-SC5H4NH via the S atom. The chain polymer 2 has a centrosymmetric hexanuclear central core, Cu6S6I4 (mu-I)2--, formed by dimerization of six-membered trinuclear motifs, Cu3(mu2-SC3H6N2)3I3 via (mu3-S) bonding modes of the thione ligand, and has four terminal and two bridging iodine atoms in trans-orientations. Linear chains are separated by the nonbonded acetonitrile molecules. In 4 and 5, three copper(I) bromide or copper(I) iodide moieties and three SC3H6N2 ligands combined via bridging S donor atoms to form the six-membered trinuclear Cu3(mu2-SC3H6N2)3I3 cores which polymerized via S and X atoms in a side-on fashion to form linear chain polymers, [{Cu6(mu3-SC3H6N2)2 (mu2-SC3H6N2)4X2(mu-X)4}n]. The (mu3-S) modes of bonding of neutral heterocyclic thioamides are first examples, as are trinuclear cluster and linear polymers rare examples in copper chemistry.

Efficient Acid‐Catalyzed 18F/19F Fluoride Exchange of BODIPY Dyes

“…The construction of low‐dimensional coordination polymers has received intense attention for a long time because of their structural diversity and unusual properties 5,6. Among them, some one‐dimensional (1D) expanded chains with exotic topologies have been reported, such as ladders,7 ropes,8 and cluster‐based chains 9,10. They provide an intermediate step from 1D chains towards 2D networks, thus potentially helping the magnetic behavior at the border of 1D to 2D systems to be understood.…”

1, 9‐Dihydro‐purine‐6‐thione Derivatives of the d8–d10 Metal Ions (PdII, PtII, and CuI): Synthesis, Spectroscopy, and Structures

“…Likewise, copper(I) halides with pySH and pymSH have yielded mono‐ and dinuclear complexes, [Cu X (κ 1 ‐S‐pySH)(PPh 3 ) 2 ] ( X = Cl, Br),15,16 [Cu 2 Br 2 (κ 2 ‐μ‐S‐pySH) 2 (PPh 3 ) 2 ],16 [Cu X (κ 1 ‐S‐pymSH)(PPh 3 ) 2 ],17–20 and [Cu 2 (κ 2 ‐μ‐I) 2 (PPh 3 ) 2 (κ 2 ‐μ‐N, S‐pymSH)] 20. Recently, copper(I) iodide with pySH, in presence of bis(diphenylphosphanyl)alkanes, has also formed a trinuclear complex, [Cu 3 I 3 (κ 2 ‐P, P‐dppe) 3 (κ 1 ‐S‐pySH)] {dppe = 1, 2‐bis(diphenylphosphanyl)ethane} and a polynuclear complex, {Cu 6 (pySH) 6 } n · 2 n CH 3 CN 21…”

Cluster‐Based CuII–Azide Polymers: Synthesis, Structure, Magnetic Properties, and Effect of Polyamines on Crystal Structures

“…Like 2, the coexistence of up to five bridging modes for the azide is observed in 3. Although the complexes based on Cu 4 6 ] n ·2nCH 3 CN}, [51] those with Cu 4 + Cu 6 as a basic unit have not been reported.…”