Role of the Trichlorostannyl Ligand in Tin–Ruthenium Arene Complexes: Experimental and Computational Studies. Issue 9 (8th March 2017) - Novák, Miroslav
Abstract : A set of neutral and ionic ruthenium arene trichlorostannyl complexes are reported herein. The tin(II) compounds L 1 SnCl {1 ; L 1 = [2‐(CH2 NEt2 )‐4, 6‐( t Bu)2 C6 H2 ] – } and [L 2 SnCl][SnCl3 ] {2 ; L 2 = 2, 6‐[(CH3 )C=N(C6 H3 ‐2, 6‐ i Pr2 )2 ]C5 H3 N} showed a rather different reactivity towards the ruthenium complex [(η 6 ‐cymene)RuCl]2 (η‐Cl)2 . As a consequence, the neutral complex [Ru(η 6 ‐cymene)(L 1 SnCl)Cl2 ] (4 ) and the ionic compound [L 2 SnCl][Ru(η 6 ‐cymene)(SnCl3 )2 Cl] (8 ) were isolated. The insertion reaction of4 with SnCl2 provided the neutral trimetallic ruthenium complex [Ru(η 6 ‐cymene)(L 1 SnCl)(SnCl3 )Cl] (6 ). Analogous ruthenium complexes [Ru(η 6 ‐cymene)(L 3 PPh2 )Cl2 ] (5 ) and [Ru(η 6 ‐cymene)(L 3 PPh2 )(SnCl3 )Cl] (7 ) containing the phosphane ligand L 3 PPh2 {3 ; L 3 = [2, 6‐ i Pr2 ‐(C6 H3 )NH] – } were also prepared to evaluate the donor–acceptor strength of the tin(II)‐ and phosphorus‐containing ligands. The structural characterization and DFT calculations of the above‐mentioned complexes suggest a strong influence of the [SnCl3 ] – moiety on the Ru–E interaction (E = Sn, P). The influence of the trichlorostannyl ligand on the Ru–E interaction in the complexes4 –7 was further evaluated by means of a distortion/interaction analysis. Abstract : Sn II –Ru arene trichlorostannyl complexes have been prepared. Depending on the properties of the Sn II donor ligands, either neutral or ionic trimetallic arene Ru complexes were isolated. Structurally related phosphanes were also prepared and the E–Ru donor–acceptor interactions (E = Sn, P) studied by DFT. Moreover, the influence of the trichlorostannyl ligand on the Ru–E interaction was evaluated.