Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)
Identifieur interne : 004009 ( Main/Merge ); précédent : 004008; suivant : 004010Chelate ring-opening ruthenium complexes: X-ray crystal structure and solution studies of cis , trans -bis(2-dimethyl-aminoethyl)-diphenyl-phosphino(dichloro)ruthenium(II)
Auteurs : Zijian Guo [Royaume-Uni] ; Abraha Habtemariam [Royaume-Uni] ; Peter J. Sadler [Royaume-Uni] ; Brian R. James [Canada]Source :
- Inorganica Chimica Acta [ 0020-1693 ] ; 1998.
English descriptors
Abstract
Abstract: The Ru(II) complex cis,trans-[Ru(Me2NCH2CH2PPh2-P,N)2Cl2] (1) has been characterized in the solid state and in solution. X-ray crystallography showed that complex 1 is monoclinic, space group C2/c; a = 36.0421, b = 11.4866, c = 31.0540 Å; β = 104.556°. The structure refined to R = 0.0925 and Rw = 0.223. There are two independent molecules in the unit cell, with normal Ru-P bonds (2.24–2.26 Å), but the Ru-N bonds (2.37–2.42 Å) are 0.2 Å longer than typical values for Ru-N trans to phosphorus. The Cl-Ru-Cl bond angles of 1 are 171.78 and 173.14°. Complex 1 is stable in methylene chloride solution and cyclic voltammetry showed that it undergoes a fully reversible one-electron oxidation at 0.326 V. In methanol, however, 1 (both in air or under N2) undergoes a two-stage ionization/solvolysis with first order constants at 293 K: 5.40 ± 0.02 × 10−4 s−1 for the first step, and 3.29 ± 0.03 × 10−5 s−1 for the second step accompanied by a colour change from red to green. 1H and 31P{1H} NMR spectroscopic studies suggest that the solvolysis is accompanied by P,N-chelate ring-opening. These processes are inhibited by the presence of excess of lithium chloride.
Url:
DOI: 10.1016/S0020-1693(97)05911-2
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<front><div type="abstract" xml:lang="en">Abstract: The Ru(II) complex cis,trans-[Ru(Me2NCH2CH2PPh2-P,N)2Cl2] (1) has been characterized in the solid state and in solution. X-ray crystallography showed that complex 1 is monoclinic, space group C2/c; a = 36.0421, b = 11.4866, c = 31.0540 Å; β = 104.556°. The structure refined to R = 0.0925 and Rw = 0.223. There are two independent molecules in the unit cell, with normal Ru-P bonds (2.24–2.26 Å), but the Ru-N bonds (2.37–2.42 Å) are 0.2 Å longer than typical values for Ru-N trans to phosphorus. The Cl-Ru-Cl bond angles of 1 are 171.78 and 173.14°. Complex 1 is stable in methylene chloride solution and cyclic voltammetry showed that it undergoes a fully reversible one-electron oxidation at 0.326 V. In methanol, however, 1 (both in air or under N2) undergoes a two-stage ionization/solvolysis with first order constants at 293 K: 5.40 ± 0.02 × 10−4 s−1 for the first step, and 3.29 ± 0.03 × 10−5 s−1 for the second step accompanied by a colour change from red to green. 1H and 31P{1H} NMR spectroscopic studies suggest that the solvolysis is accompanied by P,N-chelate ring-opening. These processes are inhibited by the presence of excess of lithium chloride.</div>
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