ic034770y_si_001.cif (114.1 kB)
Construction of a Novel Copper(I) Chain Polymer of Hexanuclear Cu6(2-SC5H4NH)6I6 Cores with A New (μ3-S) Mode of Bonding of Pyridine-2-thione and of an Unusual Triangular Cu3I3(dppe)3(2-SC5H4NH) Cluster
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posted on 2003-12-01, 00:00 authored by Tarlok S. Lobana, Ritu Sharma, Elena Bermejo, Alfonso CastineirasThe reactions of copper(I) iodide with pyridine-2-thione
(2-SC5H4NH) in the presence of a series of diphosphane ligands,
Ph2PXPh2P {X = (CH2)m, m = 1(dppm), 2 (dppe), 3
(dppp), 4 (dppb); CHCH (dppen)}, yielded an iodo-bridged
hexanuclear CuI linear polymer, {Cu6(μ3-SC5H4NH)4(μ2-SC5H4NH)2(I4)(μ-I)2}n·2nCH3CN (1). A similar reaction with 1,2-bis(diphenylphosphino)ethane (dppe) and 2-SC5H4NH yielded a triangular
cluster, Cu3I3(dppe)3(2-SC5H4NH), 2. In the chain polymer 1, three
Cu(I) iodide and three 2-SC5H4NH ligands combined via bridging
S donor atoms to form a boat-shaped trinuclear Cu3S3I3 core, and
two such cores combined in an inverse manner via four S-donor
atoms (μ3-S) to form a centrosymmetric hexanuclear repeat unit,
Cu6S6I4(μ-I)2-, which finally formed the iodo-bridged infinite linear
chain polymer 1. Linear chains are separated by the nonbonded
acetonitrile molecules. Polymer 1 is the first such example of a
linear chain formed by the hexanuclear Cu6S6I6 core in copper
chemistry as well as in metal−heterocyclic thioamide chemistry.
In addition, it has the first μ3-S mode of neutral pyridine-2-thione
ever reported. In the moiety Cu3I3(dppe)3 of 2, two copper(I) centers
are bridged by the iodide ligands forming a Cu(μ-I)2Cu core, while
a third copper(I) center is terminally bonded to another iodide
ligand. Polymer 2 is also rare, and the first triangular cluster of
CuI with an heterocyclic thioamide.
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iodide ligands6 CoresPolymer 1nonbonded acetonitrile moleculesS modeSC 5 H 4 NHdppePolymer 2S donor atomsiodide ligandCu 6 S 6diphosphane ligandsCu 3copper chemistryμ 3heterocyclic thioamide6 coreCHCNhexanuclear Cu 6 S 6Linear chainschain polymer 1moiety Cu 3Unusual Triangular Cu 33 corecentrosymmetric hexanuclear
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