TY - JOUR
T1 - Ruthenium complexes with chiral tetradentate imino-sulfoxide ligands
AU - Lai, Chui Ying
AU - Mak, Wing Leung
AU - Chan, Eddie Y.Y.
AU - Sau, Yiu Keung
AU - Zhang, Qian Feng
AU - Lo, Samuel M.F.
AU - Williams, Ian D.
AU - Leung, Wa Hung
PY - 2003/9/22
Y1 - 2003/9/22
N2 - Treatment of 2-(methylsulfinyl)benzaldehyde (1) with ethylenediamine or (1R,2R)-(-)-1,2-diaminocyclohexane afforded N,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 followed by reaction with (1R,2S,5R)-(-)-menthyl-(S)-p-toluenesuifinate afforded 2-(S)-(p-tolylsulfinyl)benzaldehyde diethyl acetal (2). Deprotection of 2 with pyridinium tosylate followed by condensation with ethylenediamine, (1R,2R)-(-)-diaminocydohexane, or (S,S)-(+)-diaminocyclohexane afforded N,N′-bis[2-(S)-(p-tolylsulfinyl)benzylidene]ethylenediamine (L 3), (1R,2R)-N,N′ -bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((R,R)-L 4), or (S,S)-N,N′ -bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((S,S)-L 4), 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 structures of (S s,Rs)-4, (R,R)-6, and (S,S)-6 have been determined. The average Ru-N, Ru-S, and Ru-Cl distances in (Ss,Rs)-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, average Ru-N, and average Ru-S distances in 7 are 2.3733(6), 2.1469(16), 2.071, and 2.2442 Å, respectively. Treatment of 3 with AgNO3 followed by reaction with PPh3 afforded [Ru(L1)(PPh3) 2][PF6]2 (8). Treatment of [Os(PPh 3)3Cl2] with L1 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-ray crystallography. The average Os-S(O), Os-N(trans to P), Os-N(trans to S), Os-P, and Os-Cl distances are 2.1931, 2.085, 2.175, 2.3641, and 2.4266 Å, respectively.
AB - Treatment of 2-(methylsulfinyl)benzaldehyde (1) with ethylenediamine or (1R,2R)-(-)-1,2-diaminocyclohexane afforded N,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 followed by reaction with (1R,2S,5R)-(-)-menthyl-(S)-p-toluenesuifinate afforded 2-(S)-(p-tolylsulfinyl)benzaldehyde diethyl acetal (2). Deprotection of 2 with pyridinium tosylate followed by condensation with ethylenediamine, (1R,2R)-(-)-diaminocydohexane, or (S,S)-(+)-diaminocyclohexane afforded N,N′-bis[2-(S)-(p-tolylsulfinyl)benzylidene]ethylenediamine (L 3), (1R,2R)-N,N′ -bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((R,R)-L 4), or (S,S)-N,N′ -bis[2-(S)-(p-tolylsulfinyl)benzylidene]-1,2-cyclohexanediamine ((S,S)-L 4), 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 structures of (S s,Rs)-4, (R,R)-6, and (S,S)-6 have been determined. The average Ru-N, Ru-S, and Ru-Cl distances in (Ss,Rs)-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, average Ru-N, and average Ru-S distances in 7 are 2.3733(6), 2.1469(16), 2.071, and 2.2442 Å, respectively. Treatment of 3 with AgNO3 followed by reaction with PPh3 afforded [Ru(L1)(PPh3) 2][PF6]2 (8). Treatment of [Os(PPh 3)3Cl2] with L1 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-ray crystallography. The average Os-S(O), Os-N(trans to P), Os-N(trans to S), Os-P, and Os-Cl distances are 2.1931, 2.085, 2.175, 2.3641, and 2.4266 Å, respectively.
UR - https://www.webofscience.com/wos/woscc/full-record/WOS:000185431800014
UR - https://openalex.org/W1972097669
UR - https://www.scopus.com/pages/publications/0141814900
U2 - 10.1021/ic030075e
DO - 10.1021/ic030075e
M3 - Journal Article
SN - 0020-1669
VL - 42
SP - 5863
EP - 5870
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 19
ER -