613265-08-0Relevant academic research and scientific papers
The kinetic instability of σ-bound aryloxide in coordinatively unsaturated or labile complexes of ruthenium
Snelgrove,Conrad,Yap,Fogg
, p. 268 - 278 (2008/10/08)
Reaction of RuCl2(PPh3)3 (1) or RuHCl(PPh3)3 (2) with KOAr (Ar=4-tBuC6H4) in non-alcohol solvents affords π-aryloxide derivatives Ru(η5-ArO)(o-C6H4PPh2) (PPh3) (3a) or RuH(η5-ArO)(PPh3) 2 (6a), respectively. The phenoxide analogues 3b and 6b are obtained on use of KOPh or TlOPh. Treatment of 1 with 1 equiv. KOAr in the presence of isopropanol liberates the phenol and acetone, affording clean 2 in quantitative yields. In 3:1 methanol-CH2Cl2, RuHCl(CO)(PPh3)3 (4) is also formed in small amounts. Reaction of 1 with 2 KOAr in 20% MeOH-CH2Cl2 affords a mixture of 6a and RuH2(CO)(PPh3)3 (5). In the corresponding reaction of 2 with 1 KOAr, σ-π isomerization of the σ-aryloxide ligand dominates, affording 6a·MeOH as the principal product. Treatment of 6a with ethereal HCl gives [RuH(η6-ArOH)(PPh3)2]Cl (7a); the corresponding reaction of 6b yields RuCl(η5-PhO)(PPh3)2 (8b). The crystal structures of 3a, 3b, 4, 5, 7a, and 8b are reported.
