[en] Five complexes with the generic formula [ReBr(CO)3([small kappa]2-S,S[prime or minute]-S2C[middle dot]NHC)] were obtained by reacting [ReBr(CO)5] with a set of representative imidazol(in)ium-2-dithiocarboxylate zwitterions. These ligands are the adducts of N-heterocyclic carbenes (NHCs) and carbon disulfide. The monometallic Re(i) compounds were further coupled with Na[Re(CO)5] to afford bimetallic Re(0) species. Depending on the experimental conditions, either octacarbonyl dimers [Re2(CO)8([small mu ]2-[small kappa]1-S,[small kappa]1-S[prime or minute]-S2C[middle dot]NHC)] or hexacarbonyl clusters [Re2(CO)6([small kappa]2-S,S[prime or minute]-[small kappa]3-S,C,S[prime or minute]-S2C[middle dot]NHC)] were isolated. All the products were fully characterized using various analytical techniques. Single crystal XRD analysis helped establish with certainty the various binding modes exhibited by the NHC[middle dot]CS2 ligands. With bite angles ranging from ca. 104 to 130[degree], these zwitterions displayed a remarkable flexibility, which also permitted significant twists of the thiometallated rings to preserve a staggered arrangement of the carbonyl groups in the bimetallic systems. Monitoring the chemical shift of the CS2- moiety by 13C NMR spectroscopy was most useful to detect its change of hapticity upon decarbonylation of the octacarbonyl compounds into hexacarbonyl derivatives. IR spectroscopy was another very convenient tool to identify the type of complex formed in a reaction, based on the pattern of its carbonyl vibration bands. Advanced mass spectrometry techniques showed that all the compounds underwent partial or total decarbonylation in the gas phase with no concomitant fragmentation of the bimetallic assemblies into monometallic ions.
Disciplines :
Chemistry
Author, co-author :
Beltran Alvarez, Tomás Francisco ; Université de Liège > Département de chimie (sciences) > Chimie organométallique et catalyse homogène
Zaragoza, Guillermo
Delaude, Lionel ; Université de Liège > Département de chimie (sciences) > Chimie organométallique et catalyse homogène
Language :
English
Title :
Synthesis, characterization, and gas-phase fragmentation of rhenium-carbonyl complexes bearing imidazol(in)ium-2-dithiocarboxylate ligands
Publication date :
2016
Journal title :
Dalton Transactions
ISSN :
1477-9226
eISSN :
1477-9234
Publisher :
Royal Society of Chemistry (RSC), Cambridge, United Kingdom
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