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

Abstract

A set of neutral and ionic ruthenium arene trichlorostannyl complexes are reported herein. The tin(II) compounds L1SnCl {1; L1 = [2‐(CH2NEt2)‐4,6‐(tBu)2C6H2]–} and [L2SnCl][SnCl3] {2; L2 = 2,6‐[(CH3)C=N(C6H3‐2,6‐iPr2)2]C5H3N} showed a rather different reactivity towards the ruthenium complex [(η6‐cymene)RuCl]2(η‐Cl)2. As a consequence, the neutral complex [Ru(η6‐cymene)(L1SnCl)Cl2] (4) and the ionic compound [L2SnCl][Ru(η6‐cymene)(SnCl3)2Cl] (8) were isolated. The insertion reaction of 4 with SnCl2 provided the neutral trimetallic ruthenium complex [Ru(η6‐cymene)(L1SnCl)(SnCl3)Cl] (6). Analogous ruthenium complexes [Ru(η6‐cymene)(L3PPh2)Cl2] (5) and [Ru(η6‐cymene)(L3PPh2)(SnCl3)Cl] (7) containing the phosphane ligand L3PPh2 {3; L3 = [2,6‐iPr2‐(C6H3)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 complexes 4–7 was further evaluated by means of a distortion/interaction analysis.