In:
European Journal of Inorganic Chemistry, Wiley, Vol. 26, No. 7 ( 2023-03)
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 Me 3 In and (NCN)InMe 2 [NCN=2,6‐bis(dimethylaminomethy)phenyl] with 3,4‐toluenedithiol (H 2 tdt) at room temperature afforded [MeIn(tdt)(py)] 2 ( 1 ) and (NCN)In(tdt) ( 2 ), respectively. A similar reaction of Me 3 In with 2‐aminobenzenethiol (H 2 abt) in toluene under reflux afforded [MeIn(abt)(py)] 2 ( 3 ). The reaction of (NCN)InCl 2 with one equivalent of Li 2 (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.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.202200542
Language:
English
Publisher:
Wiley
Publication Date:
2023
detail.hit.zdb_id:
1475009-0
detail.hit.zdb_id:
1409951-2
