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

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(b7;6-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 D&#xed ; ez ; Joaqu&#xed ; n Garc&#xed ; a-Á ; lvarez ; Jos&#xe9 ; 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 PhB>2P(

bs.acs.org/images/entities/dbd_2.gif">S)CH₂P(

bs.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(

bs.acs.org/images/entities/dbd_2.gif">O)(OEt)₂ (2e), P(

bs.acs.org/images/entities/dbd_2.gif">O)(OPh)₂ (2f), P(

bs.acs.org/images/entities/dbd_2.gif">S)(OEt)₂ (2g), P(

bs.acs.org/images/entities/dbd_2.gif">S)(OPh)₂ (2h)) have been synthesized by oxidation of the phosphine unit in Ph₂PCH₂P(

bs.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(bc;-Cl)(b7;⁶-p-cymene)}₂] to afford the mononuclear derivatives [Ru{ba;³(C,N,S)-Ph₂P(

bs.acs.org/images/entities/dbd_2.gif">S)CHP(

bs.acs.org/images/entities/dbd_2.gif">NR)Ph₂}(b7;⁶-p-cymene)][Cl] (R = 2,4,6-C₆H₂Me₃ (3a), 4-C₆F₄CHO (3b), 4-C₆F₄CN (3c), 4-C₅F₄N (3d), P(

bs.acs.org/images/entities/dbd_2.gif">O)(OEt)₂ (3e), P(

bs.acs.org/images/entities/dbd_2.gif">O)(OPh)₂ (3f)), via tridentate ba;³(C,N,S) coordination of the anions to ruthenium. In contrast, complexes [Ru(ba;³(C,S,S)-Ph₂P(

bs.acs.org/images/entities/dbd_2.gif">S)CHP{

bs.acs.org/images/entities/dbd_2.gif">NP(

bs.acs.org/images/entities/dbd_2.gif">S)(OR)₂}Ph₂)(b7;⁶-p-cymene)][Cl] (R = Et (4g), Ph (4h)) are selectively formed in the reactions of [{RuCl(bc;-Cl)(b7;⁶-p-cymene)}₂] with the methanide anions derived from 2g−h. Deprotonation of 3a with NaH generates the carbenic derivative [Ru{ba;²(C,N)-Ph₂P(

bs.acs.org/images/entities/dbd_2.gif">S)CP(

bs.acs.org/images/entities/dbd_2.gif">N-2,4,6-C₆H₂Me₃)Ph₂}(b7;⁶-p-cymene)] (5), which readily reacts with an excess of 2,6-dimethylphenyl isocyanide to afford the octahedral complex [Ru{ba;²(C,N)-Ph₂P(S)C(C

bs.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 Ru

bs.acs.org/images/entities/dbd_2.gif">C bond of 5. The intermediate ketenimine complex [Ru{ba;³(C,C,N)-Ph₂P(

bs.acs.org/images/entities/dbd_2.gif">S)C(C

bs.acs.org/images/entities/dbd_2.gif">N-2,6-C₆H₃Me₂)P(

bs.acs.org/images/entities/dbd_2.gif">N-2,4,6-C₆H₂Me₃)Ph₂}(b7;⁶-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.