Complexes of Bulky β‐Diketiminate Ligands

Alkyl backbone variations in common β-diketiminate ligands and applications to N-heterocyclic silylene chemistry

“…Installing two ethyl groups into the backbone unit, i.e. , forming EtAr nacnacH proligands, can be achieved by simply modifying a common acid-catalysed condensation reaction 22,32 according to Scheme 1. This requires stoichiometric para -toluenesulfonic acid hydrate ( p TsOH·H 2 O), an arene solvent such as toluene and heating under reflux with the use of a Dean–Stark trap to remove water from the condensation reaction system.…”

“…A common method for the synthesis of nacnac ligands is a simple condensation reaction between a β-diketone and two equivalents of anilines or primary amines, 1,21–24 although for some examples, the activation of the diketone via a Meerwein salt has been employed. 1 For the construction of bulky backbone variants like t BuDip nacnacH, t BuMes nacnacH 21 and PhDip nacnacH, 25 however, two ArN-containing halves have to be synthesised followed by linking these in a C–C bond formation reaction to build the backbone unit in a multistep approach.…”

Expanding the Utility of β-Diketiminate Ligands in Heavy Group VI Chemistry of Molybdenum and Tungsten

“…C 6 D 6 was dried over sodium/benzophenone followed by vacuum transfer and three freeze–pump–thaw cycles. H­[BDI], Li­[BDI], KC 8 , , MoOCl 3 (THF) 2 , and WOCl 3 (THF) 2 were synthesized according to the literature; LiOMes, LiNHTol, and LiNTol 2 were obtained by deprotonating the corresponding phenol or aniline in pentane using 1.2 equiv of n -BuLi and filtering off the white products. DMAP and OPEt 3 were used as commercially received, without any additional purification or drying steps.…”

Bimetallic Reactivity Enabled by Ligand Flexibility in (β-Dialdiminato)iron Complexes

“…Our group is interested in the reactivity of (β-diiminato)­iron complexes , and their application to iron-catalyzed synthetic transformations. , Prior work by the Holland group showed that the ostensibly remote iminyl substituent within the β-diketiminate backbone can have substantial effects on reaction outcome. , For example, the iron­(II) chloride compound exists as a three-coordinate monomer in the tert -butyl-substituted system (Scheme a, tBu L = 3,5-bis­(2,6-diisopropylphenylimino)-2,2,6,6-tetramethylheptyl) but presents as a four-coordinate dimer or lithium chloride adduct when the backbone substituent is a methyl group (Scheme a, Me L = 2,4-bis­(2,6-diisopropylphenylimino)­pentyl). We were curious to explore the corresponding β-dialdiminate system (Scheme a, H L = 1,3-bis­(2,6-diisopropylphenylimino)­propyl) and its impact on the coordination environment and reactivity.…”