Hypercoordinated diorganoantimony(III) compounds of types [2‐(Me 2 NCH 2 )C 6 H 4 ] 2 SbL and [PhCH 2 N(CH 2 C 6 H 4 ) 2 ]SbL (L = Cl, ONO 2 , OSO 2 CF 3 ). Synthesis, structure and catalytic behaviour in the Henry reaction

The compounds [2‐(Me 2 NCH 2 )C 6 H 4 ] 2 SbL (L = ONO 2 ( 2 ), OSO 2 CF 3 ( 3 )) and [PhCH 2 N(CH 2 C 6 H 4 ) 2 ]SbL (L = ONO 2 ( 5 ), OSO 2 CF 3 ( 6 )) were prepared by reacting [2‐(Me 2 NCH 2 )C 6 H 4 ] 2 SbCl ( 1 ) and [PhCH 2 N(CH 2 C 6 H 4 ) 2 ]SbCl ( 4 ), respectively, with the appropriate silver(I) salt in a 1:1 molar ratio. The new species 2 – 6 were structurally characterized in solution using multinuclear NMR and in the solid state using infrared spectroscopy. The solid‐state structures for compounds 2 , 4 and 6, as well as for the hydrolysis ionic product [{2‐(Me 2 N + HCH 2 )C 6 H 4 }{2‐(Me 2 NCH 2 )C 6 H 4 }SbOH][CF 3 SO 3 ] − ( 3h ) were determined using single‐crystal X‐ray diffraction. Medium to strong intramolecular N→ Sb interactions were observed in all these four compounds, thus resulting in hypercoordinated organoantimony(III) species 14‐Sb‐6 in 2 and 10‐Sb‐4 in the cation of 3h and in 4 and 6 . Compounds 1 – 6 and the starting amines PhCH 2 NMe 2 and PhCH 2 N(CH 2 C 6 H 4 Br‐2) 2 were investigated as catalysts in the Henry (nitroaldol) addition of nitromethane to benzaldehyde. The activity of compounds 1 – 6 resulted as an effect of the cooperation of the positively charged antimony with the negatively charged nitrogen.