Synthesis and Structure of Ruthenium Complexes \(\rm[{Ph_{3}PR]_2^+[RuCl_6]^{2-}}\) (R = C2H5, CH=CHCH3, CH2CH=CHCH3, CH2OCH3), and \(\rm[{Ph_{3}PCH_2CH=CHCH_2{PPh_3}]_2^{2+}[Ru_2Cl_{10}O]^{4-}}\)· 4H2O

Abstract

Complexes \(\rm[{Ph_{3}PR]_2^+[RuCl_6]^{2-}}\), where R = C₂H₅ (I), CH=CHCH₃ (II), CH₂CH=CHCH₃ (III), and CH₂OCH₃ (IV), have been prepared by the reaction between ruthenium(III) chloride hydrate and triphenylorganylphosphonium chlorides in dimethylsulfoxide in the presence of hydrochloric acid. A hydrochloric acid solution of ruthenium(III) chloride hydrate when mixed with an aqueous solution of 2-butylene-1,4- bis(triphenylphosphonium dichloride) followed by recrystallization from dimethylsulfoxide results in complex \(\rm[{Ph_{3}PCH_2CH=CHCH_2{PPh_3}]_2^{2+}[Ru_2Cl_{10}O]^{4-}}\)· 4H₂O (V). According to X-ray diffraction data, phosphorus atoms in mono- and binuclear cations have slightly distorted tetrahedral coordination (CPC 105.54(13)°−113.00(8)°, P−C 1.758(9)−1.839(7) Å). In slightly distorted octahedral anions [RuCl₆]²⁻ of complexes I–IV, the Ru−Cl bond lengths vary in the range 2.3222(6)−2.340(2) Å; the cis-ClRuCl and trans-ClRuCl angles are 89.133(18)°–90.867(18)° and 179.53(13)°–180°, respectively. In the binuclear [(RuCl₅)₂O]⁴⁻ anion of complex V, RuCl₅ fragments are bonded by a bridging oxygen atom. The Ru–Cl bond lengths fall in the range 2.3375(8)−2.3957(8) Å; the Ru–O bond length is 1.7832(2) Å. The cis-ClRuCl, trans-ClRuCl, cis-ORuCl, and trans-ORuCl angles are 86.67(3)°−91.28(3)°, 174.60(3)°−174.83(3)°, 91.49(2)°−93.65(2)°, and 178.39(2)°, respectively. In crystals I–V, interionic hydrogen bonds Cl···H_cation (2.63−2.95 Å), Cl··· \({\rm{H}_{{H_2}O}}\) (2.35−2.79 Å), and H_cation···\({\rm{O}_{{H_2}O}}\) (1.72−1.93 Å) (for V) are found.