Ruthenium Complexes with Chiral Tetradentate Imino-Sulfoxide Ligands

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• 作者：Chui-Ying Lai ; Wing-Leung Mak ; Eddie Y. Y. Chan ; Yiu-Keung Sau ; Qian-Feng Zhang ; Samuel M. F. Lo ; Ian D. Williams ; and Wa-Hung Leung
• 刊名：Inorganic Chemistry
• 出版年：2003
• 出版时间：September 22, 2003
• 年：2003
• 卷：42
• 期：19
• 页码：5863 - 5870
• 全文大小：173K
• 年卷期：v.42,no.19(September 22, 2003)
• ISSN：1520-510X

文摘

Treatment of 2-(methylsulfinyl)benzaldehyde (1) with ethylenediamine or (1R,2R)-(-)-1,2-diaminocyclohexane affordedN,N'-bis[2-(methylsulfinyl)benzylidene]ethylenediamine (L¹) or (1R,2R)-N,N'-bis[2-(methylsulfinyl)benzylidene]-1,2-cyclohexanedia mine (L²), respectively. Lithiation of 2-bromobenzaldehyde diethylacetal with n-BuLi/TMEDA followedby reaction with (1R,2S,5R)-(-)-menthyl-(S)-p-toluenesulfinate afforded 2-(S)-(p-tolylsulfinyl)benzaldehyde diethylacetal (2). Deprotection of 2 with pyridinium tosylate followed by condensation with ethylenediamine, (1R,2R)-(-)-diaminocyclohexane, or (S,S)-(+)-diaminocyclohexane afforded N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]ethylenediamine (L³), (1R,2R)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((R,R)-L⁴), or (S,S)-N,N'-bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((S,S)-L⁴), respectively. Treatment of [Ru(PPh₃)₃Cl₂]with L afforded trans-[Ru(L)Cl₂] [L = L¹ (3), L² (4), L³ (5), (R,R)-L⁴ ((R,R)-6), (S,S)-L⁴ ((S,S)-6)]. The X-ray structuresof (S_S,R_S)-4, (R,R)-6, and (S,S)-6 have been determined. The average Ru-N, Ru-S, and Ru-Cl distances in(S_S,R_S)-4 are 2.063, 2.2301, and 2.4039 Å, respectively. The corresponding distances in (R,R)-6 are 2.071, 2.256,and 2.411 Å, and those in (S,S)-6, 2.058, 2.2275, and 2.3831 Å. Compound 3 exhibited a reversible Ru(III/II)couple at 0.56 V vs Cp₂Fe^+/0 in CH₂Cl₂. Treatment of 3 with AgNO₃ in water afforded the aqua compound trans-[Ru(L¹)Cl(H₂O)][PF₆] (7), which has been characterized by X-ray crystallography. The Ru-Cl, Ru-O, averageRu-N, and average Ru-S distances in 7 are 2.3733(6), 2.1469(16), 2.071, and 2.2442 Å, respectively. Treatmentof 3 with AgNO₃ followed by reaction with PPh₃ afforded [Ru(L¹)(PPh₃)₂][PF₆]₂ (8). Treatment of [Os(PPh₃)₃Cl₂] withL¹ resulted in deoxygenation of one sulfoxide group of L¹ and formation of [Os(L⁵)Cl₂(PPh₃)] (9) (L⁵ = N-[2-(methylsulfinyl)benzylidene]-N'-[2-(methylthio)benzylididene]ethylenediamine), which has been characterized by X-raycrystallography. The average Os-S(O), Os-N(trans to P), Os-N(trans to S), Os-P, and Os-Cl distances are2.1931, 2.085, 2.175, 2.3641, and 2.4266 Å, respectively.