Transition Metal Complexes of Neutral eta1-Carbon Ligands

doi:10.1007/978-3-642-04722-0

Topics in Organometallic Chemistry

2010

DOI: 10.1007/978-3-642-04722-0

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Transition Metal Complexes of Neutral eta1-Carbon Ligands

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Cited by 9 publications

References 77 publications

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NHC Core Phosphonium Ylide-based Palladium(II) Pincer Complexes: The Second Ylide Extremity Makes the Difference

et al. 2020

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The coordinating properties of NHC (A), phenolate (B) and phosphonium ylide (C) moieties have been investigated systematically through the preparation of a family of NHC, phosphonium ylide-based pincer ligands where the third donor extremity can be either a NHC, a phenolate or a phosphonium ylide. The overall donor character of such ligands [NHC(AaBbCc)] (a + b + c = 2) has been analyzed by comparison of the MOs (energy and shape), oxidation potentials (Ep ox), and IR nCO and nCN stretching frequencies of their isostructural pincer Pd(II) complexes [NHC(AaBbCc)PdL][OTf] (L = NCCH3, CO or CNtBu). The three categories of pincer complexes based on phosphonium ylides were easily obtained by acidic treatment of their highly stable ortho-metallated Pd(II) precursors prepared in a single step from readily available N-phosphonio-substituted imidazolium salts. Analysis of IR data indicated that NHC and phenolate ligands have a similar donor character but which remains lower than that of the phosphonium ylide. The impact on catalytic performance of the incorporation of a second strongly donating phosphonium ylide into the ligand architecture has been illustrated in the Pd-catalyzed allylation of aldehydes.

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NHC Core Phosphonium Ylide-based Palladium(II) Pincer Complexes: The Second Ylide Extremity Makes the Difference

et al. 2020

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Iron(II) Complexes of an Anionic Bis(ylide)diphenylborate Ligand

2020

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Double deprotonation of the salt [Ph2B(PMe3)2][OTf] (1) provides access to a bis(ylide)diphenylborate ligand that is readily transferred in situ to iron(II). Depending on the reaction stoichiometry, both the “ate” complex [Ph2B(Me2PCH2)2Fe(μ-Cl)2Li(THF)2] (2) and the homoleptic complex [Ph2B(Me2PCH2)2]2Fe(3) can be prepared from FeCl2(THF)1.5. Further reaction of 3 with FeCl2(THF)1.5 produces the chloride-bridged dimer [Ph2B(Me2PCH2)2Fe(μ-Cl)2Fe(CH2PMe2)2BPh2](4). Attempts to reduce or alkylate 4 provide 3 as the only isolable product, likely a consequence of the low steric hindrance of the bis(ylide)diphenylborate ligand. On the other hand, reaction of 4 with the strong field ligand CN t Bu provides the six-coordinate, diamagnetic complex [Ph2B(Me2PCH2)2Fe(CN t Bu)4][Cl](5). Electronic structure calculations for the bis(ylide)diphenylborate ligand and homoleptic complex 3 suggest that the C(ylide) atoms are strong σ-donors with little π-bonding character. These initial results suggest the potential for this bis(ylide)diphenylborate ligand in coordination chemistry.

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Phosphorus(V) Complexes with Acyclic Monoaminocarbene Ligands via Oxidative Addition

et al. 2013

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Transition Metal Complexes of Neutral eta1-Carbon Ligands

Cited by 9 publications

References 77 publications

NHC Core Phosphonium Ylide-based Palladium(II) Pincer Complexes: The Second Ylide Extremity Makes the Difference

NHC Core Phosphonium Ylide-based Palladium(II) Pincer Complexes: The Second Ylide Extremity Makes the Difference

Iron(II) Complexes of an Anionic Bis(ylide)diphenylborate Ligand

Phosphorus(V) Complexes with Acyclic Monoaminocarbene Ligands via Oxidative Addition

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