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Homoleptic Molybdenum Cluster Sulfides Functionalized with Noninnocent Diimine Ligands: Synthesis, Structure, and Redox Behavior
Author(s) -
Gushchin Artem L.,
Laricheva Yuliya A.,
Abramov Pavel A.,
Virovets Alexander V.,
Vicent Cristian,
Sokolov Maxim N.,
Llusar Rosa
Publication year - 2014
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201402343
Subject(s) - chemistry , homoleptic , diimine , thiourea , redox , molybdenum , ligand (biochemistry) , cyclic voltammetry , crystallography , chalcogen , cluster (spacecraft) , metal , medicinal chemistry , inorganic chemistry , electrochemistry , catalysis , organic chemistry , electrode , biochemistry , programming language , receptor , computer science
Thiourea (tu) has been coordinated to the Mo 3 S 4 4+ cluster unit to afford the new cluster compound [Mo 3 S 4 (tu) 8 (H 2 O)]Cl 4 · 4H 2 O ( 1 ). The high substitutional lability of the thiourea ligands can be exploited to achieve smooth ligand substitution in the Mo 3 S 4 cluster. The reactions of 1 with 1,10‐phenanthroline (phen) and 2,2′‐bipyridine (bpy) have resulted in new trisubstituted diimino complexes [Mo 3 S 4 Cl 3 L 3 ] + [L = phen ( 2 ), bpy ( 3 )]. The crystal structure of [Mo 3 S 4 Cl 3 (phen) 3 ]Cl · 4H 2 O was determined by X‐ray analysis. A solid‐state cyclic voltammetry study of 2 shows a ligand‐centered reversible two‐electron reduction. DFT calculations for [Mo 3 S 4 Cl 3 (phen) 3 ] + and the 2e‐reduced species [Mo 3 S 4 Cl 3 (phen) 3 ] – support our interpretation of the reduction process. Compound 3 undergoes a reversible two‐electron reduction, which is more metal‐centered on the basis of DFT calculations.