(η6-Arene)−Ruthenium(II) Complexes Containing Methanide and Methandiide Anions of Ph2P(S)CH2P(NR)Ph2: Unprecedented Insertion o

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• 作者：Victorio Cadierno ; Josefina Dí ; ez ; Joaquí ; n Garcí ; a-Á ; lvarez ; José ; Gimeno
• 刊名：Organometallics
• 出版年：2008
• 出版时间：April 28, 2008
• 年：2008
• 卷：27
• 期：8
• 页码：1809 - 1822
• 全文大小：306K
• 年卷期：v.27,no.8(April 28, 2008)
• ISSN：1520-6041

文摘

The novel (iminophosphoranyl)(thiophosphoranyl)methane ligands Ph₂P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">S)CH₂P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">NR)Ph₂ (R = 2,4,6-C₆H₂Me₃ (2a), 4-C₆F₄CHO (2b), 4-C₆F₄CN (2c), 4-C₅F₄N (2d), P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">O)(OEt)₂ (2e), P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">O)(OPh)₂ (2f), P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">S)(OEt)₂ (2g), P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">S)(OPh)₂ (2h)) have been synthesized by oxidation of the phosphine unit in Ph₂PCH₂P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">NR)Ph₂ with elemental sulfur. Treatment of 2a−f with LiⁿBu generates the corresponding methanide anions which react in situ with [{RuCl(μ-Cl)(η⁶-p-cymene)}₂] to afford the mononuclear derivatives [Ru{κ³(C,N,S)-Ph₂P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">S)CHP(rc="http://pubs.acs.org/images/entities/dbd_2.gif">NR)Ph₂}(η⁶-p-cymene)][Cl] (R = 2,4,6-C₆H₂Me₃ (3a), 4-C₆F₄CHO (3b), 4-C₆F₄CN (3c), 4-C₅F₄N (3d), P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">O)(OEt)₂ (3e), P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">O)(OPh)₂ (3f)), via tridentate κ³(C,N,S) coordination of the anions to ruthenium. In contrast, complexes [Ru(κ³(C,S,S)-Ph₂P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">S)CHP{rc="http://pubs.acs.org/images/entities/dbd_2.gif">NP(rc="http://pubs.acs.org/images/entities/dbd_2.gif">S)(OR)₂}Ph₂)(η⁶-p-cymene)][Cl] (R = Et (4g), Ph (4h)) are selectively formed in the reactions of [{RuCl(μ-Cl)(η⁶-p-cymene)}₂] with the methanide anions derived from 2g−h. Deprotonation of 3a with NaH generates the carbenic derivative [Ru{κ²(C,N)-Ph₂P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">S)CP(rc="http://pubs.acs.org/images/entities/dbd_2.gif">N-2,4,6-C₆H₂Me₃)Ph₂}(η⁶-p-cymene)] (5), which readily reacts with an excess of 2,6-dimethylphenyl isocyanide to afford the octahedral complex [Ru{κ²(C,N)-Ph₂P(S)C(Crc="http://pubs.acs.org/images/entities/dbd_2.gif">N-2,6-C₆H₃Me₂)P(N-2,4,6-C₆H₂Me₃)Ph₂}(CN-2,6-C₆H₃Me₂)₄] (7), via release of the arene ring and insertion of one isocyanide molecule into the Rurc="http://pubs.acs.org/images/entities/dbd_2.gif">C bond of 5. The intermediate ketenimine complex [Ru{κ³(C,C,N)-Ph₂P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">S)C(Crc="http://pubs.acs.org/images/entities/dbd_2.gif">N-2,6-C₆H₃Me₂)P(rc="http://pubs.acs.org/images/entities/dbd_2.gif">N-2,4,6-C₆H₂Me₃)Ph₂}(η⁶-p-cymene)] (6) could be isolated working under stoichiometric conditions. The structure of compounds 2f, 2h, 3f, 4g, and 7 has been determined by X-ray crystallography.