Synthesis,Structure and Reactivity of Organoindium 1,2-Benzenedithiolates and 2-Amidobenzenethiolates |
| |
| Authors: | Prof. Dr. Glen G. Briand Tanner George Gregory A. MacNeil Prof. Dr. Jason D. Masuda Prof. Dr. Brian J. MacLean Michael W. R. Mosher Dr. Gregory M. Sandala Padmapriya Srinivasan Alexander H. Stockli Rachel L. Vanderkloet Prof. Dr. Charles J. Walsby |
| |
| Affiliation: | 1. Department of Chemistry and Biochemistry, Mount Allison University, Sackville, New Brunswick, E4L 1G8 Canada;2. Department of Chemistry, Saint Mary's University, Halifax, Nova Scotia, BH3 C3C Canada;3. Department of Chemistry, Simon Fraser University, 8888 University Dr., Burnaby, British Columbia, V5A1S6 Canada;4. Department of Chemistry, St. Francis Xavier University, P.O. Box 5000, Antigonish, Nova Scotia, B2G 2W5 Canada |
| |
| Abstract: | Organoindium compounds of redox active 1,2-benzenedithiolate and 2-amidobenzenethiolate ligands were synthesized and tested for reactivity against mild oxidants. The reaction of Me3In and (NCN)InMe2 [NCN=2,6-bis(dimethylaminomethy)phenyl] with 3,4-toluenedithiol (H2tdt) at room temperature afforded [MeIn(tdt)(py)]2 ( 1 ) and (NCN)In(tdt) ( 2 ), respectively. A similar reaction of Me3In with 2-aminobenzenethiol (H2abt) in toluene under reflux afforded [MeIn(abt)(py)]2 ( 3 ). The reaction of (NCN)InCl2 with one equivalent of Li2(abt) or two equivalents of Li(Habt) afforded the compounds [(NCN)In(abt)]⋅LiCl(thf)2 ( 4 ⋅LiCl(thf)2) and (NCN)In(Habt)2 ( 5 ), respectively. The X-ray crystal structures of 1 and 3 are similar and show dimeric structures via μ-S-(tdt) and μ-N-(abt) ligands, respectively. Compounds 2 and 4 possess similar monomeric structures and tridentate NCN pincer ligands. DFT computational studies have been used to rationalize the observed solid-state structures and discern the potential reactivity of compounds 1 – 4 against oxidants. The reaction of 1 and 2 with excess iodine resulted in loss of the 3,4-toluenedithiolate ligand and the formation of the oligomeric disulfide [tdt]n, while 3 and 4 showed no reactivity under similar conditions. This contrasts the reactivity of previously reported organoindium o-amidophenolate complexes which undergo oxidative addition of iodine to afford ligand-centered radical species. |
| |
| Keywords: | 1,2-benzenedithiolates 2-amidobenzenethiolates indium redox-active ligands X-Ray diffraction |
|
|
