Well-defined indium(iii) N-heterocyclic carbene complexes with triflate ligands: Structural models for the In(OTf)₃catalyst

Abstract

Reaction of 1,3-dimesitylimidazolium chloride [IMesH]Cl with InMe3 results in (IMes)InMe2Cl, which on treatment with one equivalent of TMS-OTf affords (IMes)InMe2(OTf), which can be converted to the bistriflate complex (IMes)In(Me)(OTf)2 on addition of HOTf.

1,4-Dialkyl-1,4-diazabutadienes: their reactions with aluminum and indium halides

“…Therefore it is assumed that the C-H imidazolium compounds may come from the 1,3-dialkyl-2-methaneiminealkyl imidazolium derivatives (11)(12)(13)(14), which in the presence of InCl 3 are transformed into the relatively stable carbene-InCl 3 . [35][36][37] The latter by reaction with labile protons affords the C-H derivatives, Scheme 11.…”

“…NMR (CDCl 3 , 25 1C; d ppm), 1 H: 7.89 (s, 2H, H2), 3.23 (m, 2H, H3), 3.67 (dd, 3 J 4. 35 Hz, 2H, H4a), 3.57 (dd, 3 J 7.70 Hz, 2H, H4b), 1.60 (qdd, 3 J 4.07 Hz, 2H, H5a), 1.77 (qdd, 3 J 4.22 Hz, 2H, H5b), 0.83 (t, 3 J 7.44 Hz, 6H, H6). 13 C:162.5 (C2), 73.6 (C3), 47.5 (C4), 2,2-Dichloro-1,3-bis[(S) 1-methylbenzyl]-1,3-diaza-2-aluminacyclopenta-3,5-diene tetrachloro aluminate (5).…”

Metal Triflimidates: Better than Metal Triflates as Catalysts in Organic Synthesis—The Effect of a Highly Delocalized Counteranion

“…[37] The h 2 -O,O mode seems to be the most frequent mode of coordination, with the anion adopting a cisoid conformation (the CF 3 groups lying on the same side of the S-N-S plane) which leads to a delocalized six-membered ring when coordinated to a metal center; the Tf 2 N À ion behaves more like a ligand. [39] By comparing data from metallic triflate and triflimidate salts, it appears that the bond lengths between the coordinating oxygen atom and the metal center are usually of the same order of magnitude [37][38][39][40][41][42] [38] Interestingly, when coordinated, the triflimidate anion has the capacity to undergo structural changes, compared to the free anion, depending on the environment. [37] It has been shown in the reactions of silicon-based Lewis acids that although the Bronsted acidity of HOTf is superior to that of HNTf 2 , R 3 SiNTf 2 is a superior Lewis acid than R 3 SiOTf because of the greater steric repulsion between the R 3 Si and NTf 2 groups.…”

Donor–Acceptor Complexes of Normal and Abnormal N‐Heterocyclic Carbenes with Group 13 (B, Al, Ga) Elements: A Combined DFT and Atoms‐in‐Molecules Study

“…Contrary to the potential applicability and experimental interest in this field of chemistry, there seems to be a paucity of theoretical reports. There are only a few reports that give theoretical insights into specific complexes 15,16. Frenking et al performed a theoretical analysis of the nature of bonding between diaminocarbenes and EF 3 and ECl 3 (E = B, Al, Ga, In) systems 16.…”