A New Type of Phosphaferrocene–Pyrrole–Phosphaferrocene P-N-P Pincer Ligand

Tian, Rongqiang; Ng, Yongxiang; Ganguly, Rakesh; Mathey, François

doi:10.1021/om300061d

Cited by 22 publications

(18 citation statements)

References 23 publications

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“…The formation of 2 from bis (dimethylaminomethyl)pyrrole occurs in higher yield than that for 1 presumably due to the increased nucleophilicity of the secondary alkyl phosphine. 31 P NMR spectra of 2 display a single peak at −7.67 consistent with trivalent phosphorus. 33 Similar to compound 1 , no J HP coupling is observed between the methylene protons of the pincer “arms” and the phosphorus nuclei by 1 H NMR spectroscopy (see Supporting Information).…”

Section: Resultsmentioning

confidence: 98%

Synthesis, Characterization, and Catalytic Activity of Nickel(II) Alkyl Complexes Supported by Pyrrole–Diphosphine Ligands

et al. 2013

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The organometallic Ni(II) chemistry of the pyrrole-based pincer ligands, (P 2 R Pyr) − (P 2 R Pyr = 2,5-(R 2 PCH 2 ) 2 C 4 H 2 N, R = Ph or Cy) is reported. Reactions of Grignard reagents with [NiCl(P 2 R Pyr)] afford a variety of alkyl and aryl complexes (methyl, ethyl, benzyl, phenyl, and allyl) that all display square planar geometries about nickel. The hydride complex, [NiH(P 2 Cy Pyr)], can also prepared either through treatment of [NiCl(P 2 Cy Pyr)] with LiHBEt 3 , or by reaction of H(P 2 R Pyr) with [Ni(COD) 2 ] (COD = 1,4-cyclooctadiene). Reactions of the methyl and hydride complexes with CO and CO 2 , respectively, evince clean migratory insertion chemistry of the Ni-C and Ni-H bonds. Both the alkyl and chloride complexes are active catalysts for the Kumada coupling of aryl chlorides and aryl or alkyl Grignard reagents at room temperature. The solid-state structures of several of the complexes are reported.

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Section: Resultsmentioning

confidence: 98%

Synthesis, Characterization, and Catalytic Activity of Nickel(II) Alkyl Complexes Supported by Pyrrole–Diphosphine Ligands

et al. 2013

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“…The closely related PyrPhos (PNP)H, which forms six‐membered chelates upon coordination to a metal ion (shown for Rh I ), has so far only appeared in a single publication. This may be due to its greater stereochemical complexity: Its isolation was reported in the form of an equimolar rac/meso ‐mixture limiting its usefulness as a general structural motif . However, it was shown that the larger six‐membered chelate rings are readily integrated into a pincer structure, provided the central pyrrole motif is twisted significantly to allow for meridional complexation .…”

Section: N‐heterocyclic Pnp Pincers: An Overviewmentioning

confidence: 99%

“…This may be due to its greater stereochemical complexity: Its isolation was reported in the form of an equimolar rac/meso ‐mixture limiting its usefulness as a general structural motif . However, it was shown that the larger six‐membered chelate rings are readily integrated into a pincer structure, provided the central pyrrole motif is twisted significantly to allow for meridional complexation . This inclusion of six‐membered chelate rings into pincers was further established by the preparation of CbzC ( R PNP)H in 2013 – formally by introducing two methylene units into the rigid Cbz ( R PNP)H platform .…”

Section: N‐heterocyclic Pnp Pincers: An Overviewmentioning

confidence: 99%

Phosphines and N‐Heterocycles Joining Forces: an Emerging Structural Motif in PNP‐Pincer Chemistry

2020

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Aminodiphosphines and their monoanionic amido derivatives are among the most widely used tridentate ligands. A good share of these ligands, in particular the ones that are based on a rigid N‐heterocyclic core, is predisposed to coordinate in a meridional fashion. Negatively charged derivatives of these meridionally coordinating N‐heterocyclic ligands satisfy all the criteria for PNP pincer scaffolds. Herein, these ligands and their coordination chemistry is reviewed from the perspective of coordination chemistry. For our discussion, ligands containing a protonated N‐heterocycle (e.g. pyrrole‐ or carbazole‐based PNP scaffolds) are to be distinguished from their counterparts that do not contain such an NH‐functionality (e.g. pyridine‐ or triazine‐based PNP scaffolds). Different synthetic methodologies for the preparation of PNP pincer complexes are presented and shown to often depend on the presence or absence of the aforementioned NH‐proton. The different reactivity patterns of the resulting complexes are sub‐divided into two categories, namely into metal‐centered reactions and reactions that result in a chemical transformation at the metal and the ligand. The latter represent ligand‐cooperative transformations, which often play a key role in catalysis, and are showcased by discussing selected applications in catalysis. It will become evident in this review that this relatively young research field is still emerging and far from reaching maturity. Finally, a brief overview on ligand/metal combinations that have not been explored to date is provided, to stimulate future research on PNP pincers featuring a central N‐heterocycle.

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“…最近他们又报道了利用化合物 66 合成新型 P-N-P 型 Rh 的钳形配合物 70 (Eq. 2), 并考察了其在烯烃氢甲酰化反应中的应用 [43] . C＝P 键(-10.3 eV)能级的巨大差异 [44] , 而无法有效的协同为一个 P,N-双齿配体与金属进行配位.…”

Section: Scheme 19unclassified

Recent Advances of [1,5]-Sigmatropic Shift of Phospholes

王丽丽¹,

田荣强²,

段征³

et al. 2013

Chin. J. Org. Chem.

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Phosphole plays an important role in the modern organophosphorus chemistry. Due to its structure specialities, the exocyclic P-R σ bond shows significant interaction with the π* orbital of the dienic system and this overlap favors the [1,5]-sigmatropic shift of the substitutent (R) of P from phosphorus to carbon. This provides an efficient method to prepare various functionalized phospholes. This review is concerning the recent application of [1,5]-sigmatropic shift of phospholes in the organophosphorus and material chemistry.

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A New Type of Phosphaferrocene–Pyrrole–Phosphaferrocene P-N-P Pincer Ligand

Cited by 22 publications

References 23 publications

Synthesis, Characterization, and Catalytic Activity of Nickel(II) Alkyl Complexes Supported by Pyrrole–Diphosphine Ligands

Synthesis, Characterization, and Catalytic Activity of Nickel(II) Alkyl Complexes Supported by Pyrrole–Diphosphine Ligands

Phosphines and N‐Heterocycles Joining Forces: an Emerging Structural Motif in PNP‐Pincer Chemistry

Recent Advances of [1,5]-Sigmatropic Shift of Phospholes

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