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 : 003994 ( Main/Exploration ); précédent : 003993; suivant : 003995Chelate 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
Affiliations:
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James</name><affiliation wicri:level="1"><country xml:lang="fr">Canada</country><wicri:regionArea>Department of Chemistry, University of British Columbia, Vancouver, BC V6T 1ZI</wicri:regionArea><wicri:noRegion>BC V6T 1ZI</wicri:noRegion></affiliation></author></analytic><monogr></monogr><series><title level="j">Inorganica Chimica Acta</title><title level="j" type="abbrev">ICA</title><idno type="ISSN">0020-1693</idno><imprint><publisher>ELSEVIER</publisher><date type="published" when="1998">1998</date><biblScope unit="volume">273</biblScope><biblScope unit="issue">1–2</biblScope><biblScope unit="page" from="1">1</biblScope><biblScope unit="page" to="7">7</biblScope></imprint><idno type="ISSN">0020-1693</idno></series></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0020-1693</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>Aminophosphine complexes</term><term>Chelate ring complexes</term><term>Crystal structures</term><term>Ruthenium complexes</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><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></front></TEI><affiliations><list><country><li>Canada</li><li>Royaume-Uni</li></country><region><li>Écosse</li></region><settlement><li>Édimbourg</li></settlement><orgName><li>Université d'Édimbourg</li></orgName></list><tree><country name="Royaume-Uni"><region name="Écosse"><name sortKey="Guo, Zijian" sort="Guo, Zijian" uniqKey="Guo Z" first="Zijian" last="Guo">Zijian Guo</name></region><name sortKey="Habtemariam, Abraha" sort="Habtemariam, Abraha" uniqKey="Habtemariam A" first="Abraha" last="Habtemariam">Abraha Habtemariam</name><name sortKey="Sadler, Peter J" sort="Sadler, Peter J" uniqKey="Sadler P" first="Peter J." last="Sadler">Peter J. Sadler</name><name sortKey="Sadler, Peter J" sort="Sadler, Peter J" uniqKey="Sadler P" first="Peter J." last="Sadler">Peter J. Sadler</name></country><country name="Canada"><noRegion><name sortKey="James, Brian R" sort="James, Brian R" uniqKey="James B" first="Brian R." last="James">Brian R. James</name></noRegion></country></tree></affiliations></record>Pour manipuler ce document sous Unix (Dilib)
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