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 L 1 SnCl {1; L 1 = [2-(CH 2 NEt 2 )-4,6-(tBu) 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-iPr 2 ) 2 ]C 5 H 3 N} showed a rather different reactivity towards the ruthenium complex [(η 6cymene)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). Analo- [a]

Highly Active and Selective Ru‐PNH Catalyst in Aerobic Oxidation of Benzyl Amines

“…No over oxidations of tested benzyl amines were detected. The high catalytic activity of 3 maybe attributed to least negative charge on the central Ru atom (−0.34e) in comparison with others tested compounds. Since the efficient complex 3 contains donating ligand L 2 PPh 2 , where L 2 is amino‐phosphine with the PN H moiety, complex 3 has been efficiently anchored to silica gel via N H hydrogen bonding and heterogeneous catalyst 3 ‐ silica was prepared.…”

“…The compounds 1 , 3 and 5 were very active under these conditions, while complexes containing SnCl 3 ligand were less effective (Table ). Our previous study showed that the SnCl 3 group increased negative charge on the ruthenium atom (range of −0.78 to −1.02 e ) in comparison with Cl atom (the charge on the ruthenium −0.34 to −0.55 e ) . This indicates that negative charge on the Ru atom decrease the catalytic activity of the catalyst.…”

“…Starting ligand L 1 GeCl and Ru complexes [Ru(η 6 ‐cymene)(L 1 SnCl)Cl 2 ] ( 1 ), [Ru(η 6 ‐cymene)(L 1 SnCl)(SnCl 3 )Cl] ( 2 ), [Ru(η 6 ‐cymene)(L 2 PPh 2 )Cl 2 ] ( 3 ), [Ru(η 6 ‐cymene)(L 2 PPh 2 )(SnCl 3 )Cl] ( 4 ) were prepared according to the literature procedure . The germylene analogues were prepared by the reaction of L 1 GeCl with [(η 6 ‐cymene)RuCl] 2 (μ‐Cl) 2 to provide complex [Ru(η 6 ‐cymene)(L 1 GeCl)Cl 2 ] ( 5 ) (Scheme ).…”

“…Previously, we have reported preparation of the set [Ru(η 6 ‐cymene)(R)(X)Cl] (R=L 1 SnCl or L 2 PPh 2 , X=Cl or SnCl 3 , L 1 =[2‐(CH 2 NEt 2 )‐4,6‐( t Bu) 2 C 6 H 2 ] − , L 2 =2,6‐ i Pr 2 ‐C 6 H 3 ‐NH − ) complexes 1–4 (Figure ) that differed in type of either donor atom (Sn vs. P) or polar group (Cl vs. SnCl 3 ) . The DFT calculations clearly demonstrated that both factors strongly influenced the charge of the Ru atom …”

Synthesis and In Vitro (Anticancer) Evaluation of η6-Arene Ruthenium Complexes Bearing Stannyl Ligands

“…The reaction of half-sandwich ruthenium(II) arene complexes [(η 6 -C 6 H 6 )RuCl 2 (PR 3 )] (R = aryl or O-Aryl, O-alkyl) with SnCl 2 is also known to yield a Ru(II) complex exhibiting a strong covalent Ru-Sn bond via facile insertion of the SnCl 2 moiety into the Ru-Cl bond [35,36]. While the reaction of SnX 2 (X = halide) with other metals, such as palladium and platinum, has been extensively studied [37,38], the analogous reaction with ruthenium derivatives has received far less attention.…”