Die fördernde Rolle von Phosphinoester‐Liganden bei der Synthese neutraler Carben‐, Vinyliden‐ und Allenyliden‐Ruthenium(II)‐Komplexe

Medientyp: E-Artikel
Titel: Die fördernde Rolle von Phosphinoester‐Liganden bei der Synthese neutraler Carben‐, Vinyliden‐ und Allenyliden‐Ruthenium(II)‐Komplexe
Beteiligte: Werner, Helmut; Stark, Arthur; Grönwald, Paul Steinert, Claus; Wolf, Justin
Erschienen: Wiley, 1995
Erschienen in: Chemische Berichte
Sprache: Englisch
DOI: 10.1002/cber.19951280108
ISSN: 0009-2940
Schlagwörter: Inorganic Chemistry
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Beschreibung: <jats:title>Abstract</jats:title><jats:p><jats:bold>Vinylidene Transition‐Metal Complexes, XXXV<jats:sup>[1]</jats:sup>. — The Supporting Role of Phosphino Ester Ligands for the Synthesis of Neutral Carbene, Vinylidene and Allenylidene Ruthenium(II) Complexes</jats:bold>The reaction of [RuCl<jats:sub>2</jats:sub>(PPh<jats:sub>3</jats:sub>)<jats:sub>3</jats:sub>] (<jats:bold>1</jats:bold>) with the phosphino esters <jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>P(CH<jats:sub>2</jats:sub>)<jats:sub><jats:italic>n</jats:italic></jats:sub>CO<jats:sub>2</jats:sub>R (<jats:bold>2–4</jats:bold>) leads to complete (<jats:italic>n</jats:italic> = 1; R  CH<jats:sub>3</jats:sub>, C<jats:sub>2</jats:sub>H<jats:sub>5</jats:sub>) or partial (<jats:italic>n</jats:italic> = 2; R CH<jats:sub>3</jats:sub>) displacement of the PPh<jats:sub>3</jats:sub> ligands and formation of the octahedral ruthenium(II) complexes [RuCl<jats:sub>2</jats:sub>{k<jats:sup>2</jats:sup>(<jats:italic>P,O</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>R}<jats:sub>2</jats:sub>] (<jats:bold>5, 6</jats:bold>) and [RuCl<jats:sub>2</jats:sub>(PPh<jats:sub>3</jats:sub>){k(<jats:italic>P</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}{k<jats:sup>2</jats:sup>(<jats:italic>P,O</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}] (<jats:bold>7</jats:bold>). Treatment of <jats:bold>5</jats:bold> with LiBr and LiI affords the dibromo‐ and diiodoruthenium derivatives <jats:bold>8</jats:bold> and <jats:bold>9.</jats:bold> While compound <jats:bold>5</jats:bold> reacts with CO and SO<jats:sub>2</jats:sub> by cleavage of one Ru—O bond to yield the 1:1 adducts [RuCl<jats:sub>2</jats:sub>(L){k(<jats:italic>P</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}{k<jats:sup>2</jats:sup>(<jats:italic>P,O</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}] (<jats:bold>10, 11</jats:bold>), the reaction of the dibromo derivative <jats:bold>8</jats:bold> with CO in solution gives the dicarbonyl complex [RuBr<jats:sub>2</jats:sub>(CO)<jats:sub>2</jats:sub>{k(<jats:italic>P</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}<jats:sub>2</jats:sub>](<jats:bold>13</jats:bold>). If CO is passed over <jats:bold>8</jats:bold> in the solid state, the corresponding monocarbonyl compound <jats:bold>14</jats:bold> is formed. The hydridoruthenium(II) complex <jats:bold>16</jats:bold>, which is obtained from equimolar amounts of [RuHCl(CO)(P<jats:italic>i</jats:italic>Pr<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>] (<jats:bold>15</jats:bold>) and <jats:bold>2</jats:bold>, reacts with HCCMe by insertion to give the vinyl derivative [RuCl{E—CHCHMe}(CO)(P<jats:italic>i</jats:italic>Pr<jats:sub>3</jats:sub>){k<jats:sub>2</jats:sub>(<jats:italic>P,O</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}] (<jats:bold>17</jats:bold>). Treatment of <jats:bold>5</jats:bold> with HC̊' (R'  H, Me, <jats:italic>t</jats:italic>Bu, Ph) and of <jats:bold>6, 8, 9</jats:bold> with HCCPh affords upon photochemical activation the octahedral vinylidene complexes [RuX<jats:sub>2</jats:sub>‐(CCHR){k(<jats:italic>P</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>R}{k<jats:sup>2</jats:sup>(<jats:italic>P,O</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>R}] (<jats:bold>18–21</jats:bold> and <jats:bold>23–25</jats:bold>) in good to excellent yield. At room temperature, these compounds (with the exception of <jats:bold>25</jats:bold>) are highly fluxional in solution. From <jats:sup>31</jats:sup>P‐NMR measurements, the free energies of activation Δ<jats:italic>G</jats:italic><jats:sup>‡</jats:sup> for the intramolecular rearrangement have been determined. Whereas the reaction of 5 with HCČH<jats:sub>2</jats:sub>CH<jats:sub>2</jats:sub>OH leads to the carbene complex <jats:bold>30</jats:bold> containing the cyclic oxycarbene :C(CH<jats:sub>2</jats:sub>)<jats:sub>3</jats:sub>O as ligand, the functionalized vinylidene derivatives <jats:bold>31</jats:bold> and <jats:bold>32</jats:bold> are formed on treatment of <jats:bold>5</jats:bold> with aryl‐substituted alkynols HC≡RR'OH (R  Ph, R'  Ph, <jats:italic>o</jats:italic>‐Tol). These react in toluene solution at 80°C by elimination of water to give the allenylidene complexes [RuCl<jats:sub>2</jats:sub>(CCCRR'){k(<jats:italic>P</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}{k<jats:sup>2</jats:sup>(<jats:italic>P,O</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}] (<jats:bold>33, 34</jats:bold>). The X‐ray structure analysis of <jats:bold>33</jats:bold> reveals a <jats:italic>trans</jats:italic> disposition of the chloro ligands, the phosphorus atoms as well as of one CO oxygen and the α‐C atom of the allenylidene unit. Compound <jats:bold>33</jats:bold> reacts with CO, CN<jats:italic>t</jats:italic>Bu and pyridine to give the 1:1 adducts [RuCl<jats:sub>2</jats:sub>(L)(CCCPh<jats:sub>2</jats:sub>){k(P)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}<jats:sub>2</jats:sub>] (<jats:bold>35–37</jats:bold>) and with HCl by attack on the central CC bond to yield the vinylcarbene complex [RuCl<jats:sub>2</jats:sub>(C(Cl)CHCRR'){k((<jats:italic>P</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>‐PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}{k<jats:sup>2</jats:sup>(<jats:italic>P,O</jats:italic>)‐<jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>CO<jats:sub>2</jats:sub>Me}] (<jats:bold>38</jats:bold>). The preparation of the phosphino ketone <jats:italic>i</jats:italic>Pr<jats:sub>2</jats:sub>PCH<jats:sub>2</jats:sub>C(O)CH<jats:sub>3</jats:sub> (<jats:bold>40</jats:bold>) and its ruthenium complexes <jats:bold>41</jats:bold> and <jats:bold>42</jats:bold> is briefly described.</jats:p>

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