Halogen-bonded tris(2,4-bis(trichloromethyl)-1,3,5-triazapentadienato)-M(iii) [M = Mn, Fe, Co] complexes and their catalytic activity in the peroxidative oxidation of 1-phenylethanol to acetophenoneElectronic supplementary information (ESI) available: Tables listing bond distances and angles, hydrogen and halogen bond geometry of compounds 1-3. CCDC 989102, 988933 and 986029. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4nj00797b

One-pot template condensation of CCl 3 C&z.tbd;N with ammonia on a metal source [MnCl 2 ·4H 2 O, FeCl 3 ·6H 2 O or Co(CH 3 COO) 2 ·4H 2 O] in DMSO led to the formation of tris{2,4-bis(trichloromethyl)-1,3,5-triazapentadienato}-M( iii ) complexes, [M{NH&z.dbd;C(CCl 3 )NC(CCl 3 )&z.dbd;NH} 3 ]· n (CH 3 ) 2 SO [M = Mn, n = 1 ( 1 ); M = Fe, n = 2 ( 2 ); M = Co, n = 2 ( 3 )], which were characterized using elemental analysis, and IR, ESI-MS and single-crystal X-ray analysis. The role of inter- and intramolecular non-covalent halogen and hydrogen bonds in the synthesis of 1-3 is discussed. It is shown that the crystal ionic radii of the metal ions [68.5 (Co) < 69 (Fe) < 72 (Mn), pm] are related to the corresponding Cl Cl distances [3.178 ( 3 ) > 3.155 ( 2 ) > 3.133 ( 1 ) Å]. Compounds 1-3 and the related di(triazapentadienato)-Cu( ii ) complex [Cu{NH&z.dbd;C(CCl 3 )NC(CCl 3 )&z.dbd;NH} 2 ]·2(CH 3 ) 2 SO ( 4 ) act as catalyst precursors for the additive-free microwave (MW) assisted homogeneous oxidation of 1-phenylethanol with tert -butylhydroperoxide (TBHP), leading to the formation of acetophenone with yields up to 99% and TONs up to 5.0 × 10 3 after 1 h of low power (10 W) MW irradiation. Non-covalent halogen interactions play a relevant role in the synthesis of (1,3,5-triazapentadienato)-M( iii ) complexes (M = Mn, Fe and Co), which are effective catalysts for the oxidation of 1-phenylethanol to acetophenone.