|
|||||
|
|
Synthesis and reactivity of ruthenium complexes with 1,1′-dithiolate ligands |
|
| Authors: | Fang-Hui Wu Taike Duan Qian-Feng Zhang Wa-Hung Leung |
| Institution: | a Institute of Molecular Engineering and Applied Chemistry, Anhui University of Technology, 59 Hudong Road, Ma’anshan, Anhui 243002, PR China b Material Chemistry Laboratory, Nanjing University of Science and Technology, Nanjing 210094, PR China c Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong, PR China |
| Abstract: | Reactions of Ru(PPh3)3Cl2] with ROCS2K in THF at room temperature and at reflux gave the kinetic products trans-Ru(PPh3)2(S2COR)2] (R = nPr 1, iPr 2) and the thermodynamic products cis-Ru(PPh3)2(S2COR)2] (R = nPr 3, iPr 4), respectively. Treatment of RuHCl(CO)(PPh3)3] with ROCS2K in THF afforded RuH(CO)-(S2COR)(PPh3)2] (R = nPr 5, iPr 6) as the sole isolable products. Reaction of RuCl2(PPh3)3] with tetramethylthiuram disulfide Me2NCS2]2 gave a Ru(III) dithiocarbamate complex, Ru(PPh3)2(S2CNMe2)Cl2] (7). This reaction involved oxidation of ruthenium(II) to ruthenium(III) by the disulfide group in Me2NCS2]2. Treatment of 7 with 1 equiv. of M(MeCN)4]ClO4] (M = Cu, Ag) gave the stable cationic ruthenium(III)-alkyl complexes Ru{C(NMe2)QC(NMe2)S}(S2CNMe2)(PPh3)2]ClO4] (Q = O 8, S 9) with ruthenium-carbon bonds. The crystal structures of complexes 1, 2, 4·CH2Cl2, 6, 7·2CH2Cl2, 8, and 9·2CH2Cl2 have been determined by single-crystal X-ray diffraction. The ruthenium atom in each of the above complexes adopts a pseudo-octahedral geometry in an electron-rich sulfur coordination environment. The 1,1′-dithiolate ligands bind to ruthenium with bite S-Ru-S angles in the range of 70.14(4)-71.62(4)°. In 4·CH2Cl2, the P-Ru-P angle for the mutually cis PPh3 ligands is 103.13(3)°, the P-Ru-P angles for other complexes with mutually trans PPh3 ligands are in the range of 169.41(4)-180.00(6)°. The alkylcarbamate C(NMe2)QC(NMe2)S]− (Q = O, S) ligands in 8 and 9 are planar and bind to the ruthenium centers via the sulfur and carbon atoms from the C S and NC double bonds, respectively. The Ru-C bond lengths are 1.975(5) and 2.018(3) Å for 8 and 9·2CH2Cl2, respectively, which are typical for ruthenium(III)-alkyl complexes. Spectroscopic properties along with electrochemistry of all complexes are also reported in the paper. |
| Keywords: | Ruthenium Sulfur 1 1&prime -Dithiolate Phosphine Synthesis Crystal structure |
| 本文献已被 ScienceDirect 等数据库收录！ | |