Role of the Trichlorostannyl Ligand in Tin–Ruthenium Arene Complexes: Experimental and Computational Studies

A set of neutral and ionic ruthenium arene trichlorostannyl complexes are reported herein. The tin(II) compounds L 1 SnCl { 1 ; L 1 = [2‐(CH 2 NEt 2 )‐4,6‐( t Bu) 2 C 6 H 2 ] – } and [L 2 SnCl][SnCl 3 ] { 2 ; L 2 = 2,6‐[(CH 3 )C=N(C 6 H 3 ‐2,6‐ i Pr 2 ) 2 ]C 5 H 3 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)Cl 2 ] ( 4 ) and the ionic compound [L 2 SnCl][Ru(η 6 ‐cymene)(SnCl 3 ) 2 Cl] ( 8 ) were isolated. The insertion reaction of 4 with SnCl 2 provided the neutral trimetallic ruthenium complex [Ru(η 6 ‐cymene)(L 1 SnCl)(SnCl 3 )Cl] ( 6 ). Analogous ruthenium complexes [Ru(η 6 ‐cymene)(L 3 PPh 2 )Cl 2 ] ( 5 ) and [Ru(η 6 ‐cymene)(L 3 PPh 2 )(SnCl 3 )Cl] ( 7 ) containing the phosphane ligand L 3 PPh 2 { 3 ; L 3 = [2,6‐ i Pr 2 ‐(C 6 H 3 )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 [SnCl 3 ] – moiety on the Ru–E interaction (E = Sn, P). The influence of the trichlorostannyl ligand on the Ru–E interaction in the complexes 4 – 7 was further evaluated by means of a distortion/interaction analysis.