Synthesis, Structure, and Reactivity of Novel Ruthenium(II) Phenolate Complexes
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- 作者：Teruyuki Kondo ; Fumiaki Tsunawaki ; Yasuyuki Ura ; Kazuo Sadaoka ; Tomomichi Iwasa ; Kenji Wada ; and Take-aki Mitsudo
- 刊名：Organometallics
- 出版年：2005
- 出版时间：February 28, 2005
- 年：2005
- 卷：24
- 期：5
- 页码：905 - 910
- 全文大小：216K
- 年卷期：v.24,no.5(February 28, 2005)
- ISSN：1520-6041
文摘
Reaction of Ru(
6-cot)(dmfm)2 (1) [cot = 1,3,5-cyclooctatriene, dmfm = dimethyl fumarate]with phenol was investigated. At 110 
C, a novel ruthenium(II) phenolate complex, Ru(5-C6H5O)(5-C8H11) (2), was obtained by the reaction of 1 with phenol in an isolated yield of52% (74% by NMR). When the reaction was carried out at 130 C, further dehydrogenativering-closure in an 5-cyclooctadienyl ligand occurred to give Ru(5-C6H5O)(5-C8H9) (3) inan isolated yield of 61% (76% by NMR). For both complexes, the 5-oxocyclohexadienylbonding mode of a phenoxo ligand was clearly shown by X-ray crystallography and DFTcalculation. Complex 2 was smoothly transformed into complex 3 in the presence of dmfmat 130 C for 3 h. Selective O-methylation of an 5-oxocyclohexadienyl ligand in complex 3proceeded with methyl p-toluenesulfonate to give a novel cationic ruthenium(II) complex,[Ru(6-C6H5OMe)(5-C8H9)]+OTs- (4), in an isolated yield of 74%.
6-cot)(dmfm)2 (1) [cot = 1,3,5-cyclooctatriene, dmfm = dimethyl fumarate]with phenol was investigated. At 110 C, a novel ruthenium(II) phenolate complex, Ru(5-C6H5O)(5-C8H11) (2), was obtained by the reaction of 1 with phenol in an isolated yield of52% (74% by NMR). When the reaction was carried out at 130 C, further dehydrogenativering-closure in an 5-cyclooctadienyl ligand occurred to give Ru(5-C6H5O)(5-C8H9) (3) inan isolated yield of 61% (76% by NMR). For both complexes, the 5-oxocyclohexadienylbonding mode of a phenoxo ligand was clearly shown by X-ray crystallography and DFTcalculation. Complex 2 was smoothly transformed into complex 3 in the presence of dmfmat 130 C for 3 h. Selective O-methylation of an 5-oxocyclohexadienyl ligand in complex 3proceeded with methyl p-toluenesulfonate to give a novel cationic ruthenium(II) complex,[Ru(6-C6H5OMe)(5-C8H9)]+OTs- (4), in an isolated yield of 74%.