Article ID Journal Published Year Pages File Type
1322734 Journal of Organometallic Chemistry 2009 8 Pages PDF
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 CS 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.

Graphical abstractReaction of [RuCl2(PPh3)3] with tetramethylthiuram disulfide [Me2NCS2]2 gave a Ru(III) dithiocarbamate complex [Ru(PPh3)2(S2CNMe2)Cl2]. This reaction involved oxidation of ruthenium(II) to ruthenium(III) by the disulfide group in [Me2NCS2]2. Treatment of [Ru(PPh3)2(S2CNMe2)Cl2] with 1 equiv. of [M(MeCN)4][ClO4] (M = Cu, Ag) afforded the stable cationic ruthenium(III)-alkyls [Ru{C(NMe2)QC(NMe2)S}(S2CNMe2)(PPh3)2][ClO4] (Q = O, S) with ruthenium–carbon bonds.Figure optionsDownload full-size imageDownload as PowerPoint slide

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Physical Sciences and Engineering Chemistry Inorganic Chemistry
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