Areneruthenium(ii) complexes containing bulky phosphines with various functionalities as ligandsDedicated with great sympathy to Professor Peter M. Maitlis on the occasion of his 70th birthday
| Autor: | Gerhard Henig, Michael Schulz, Bettina Windmüller, Helmut Werner |
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| Rok vydání: | 2003 |
| Předmět: | |
| Zdroj: | Dalton Transactions. :441-448 |
| ISSN: | 1477-9234 1477-9226 |
| DOI: | 10.1039/b208891f |
| Popis: | The dimeric starting materials [Ru(η6-arene)Cl2]2 (arene = mes, C6Me6) react with the functionalized phosphines Pri2PCH2X (X = CH2OMe, CO2Me) to give the mononuclear compounds [Ru(η6-arene)(κP-Pri2PCH2X)Cl2] 3–6 which upon treatment with AgPF6 afford the chelate complexes [Ru(η6-arene)(κ2P,O-Pri2PCH2CH2OMe)Cl]PF67, 8 and [Ru(η6-arene){κ2P,O-Pri2PCH2C(O)OMe}Cl]PF69, 10, respectively. Complexes 7 and 8 react with CO and CNBut to yield the chiral-at-metal compounds [Ru(η6-arene)(κP-Pri2PCH2CH2OMe)(L)Cl]PF611–14. Treatment of 8 (arene = C6Me6) with Na2CO3 in the presence of water produces the carbonatoruthenium(II) derivative [Ru(η6-C6Me6)(κ2O,O-O2CO)(κP-Pri2PCH2CH2OMe)] 17. The reaction of 9 (arene = mes) with KOBut leads to the formation of the uncharged phosphinoester enolate complex [Ru(η6-mes)(κ2P,O-Pri2PCHC(O)OMe)Cl] 18 which in benzene at room temperature smoothly rearranges to the phosphinomethanide isomer [Ru(η6-mes)(κ2P,C-Pri2PCHCO2Me)Cl] 19. The corresponding phosphinoacetate complexes [Ru(η6-arene){κ2P,O-Pri2PCH2C(O)O}Cl] 21, 22 were obtained as the major products from 5 or 6 and NaH/Al2O3 in THF. Compound 18 reacts with water by ester hydrolysis to form 21 and with phenylisocyanate and diphenylketene to afford 24 and 25 by insertion of the heterocumulene into the enolate C–H bond. The molecular structures of 19 and 25 were determined crystallographically. |
| Databáze: | OpenAIRE |
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