Classification of P,N-binucleating ligands for hetero- and homobimetallic complexes

Maggini, Simona

doi:10.1016/j.ccr.2009.01.030

Cited by 95 publications

(35 citation statements)

References 151 publications

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“…[10] The archetypical P,N ligand 2-pyridyldiphenylphosphane (B) has found widespread application in coordination chemistry and catalysis [10c, 11] in spite of its structurally limited N-donor site. [12] Iminophosphanes (i.e., phosphaamidines C), in contrast, offer an easily tunable imine fragment which allows facile steering of the steric and electronic properties of the ligand, but they are difficult to access.…”

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confidence: 99%

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

et al. 2014

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Readily accessible nitrilium triflates are convenient imine building blocks for the expedient synthesis of a novel class of 1,3-P,N ligands as demonstrated for the reaction with primary phosphanes. This procedure allows variation of all substituents. X-ray crystal structures are reported for nitrilium ions, phosphaamidines, and three phosphaamidinate complexes. The lithium phosphaamidinate is N coordinated and its reaction with [AuCl(tht)] (tht = tetrahydrothiophene) gives a unique P-bridged gold trimer, while a P,N-bidentate complex results from [{RhCl(cod)}2]. The nitrilium ion methodology allows extension of the 1,3-P,N motive to bis(imino)phosphanes, which are the neutral phosphorus analogues of the valuable β-diketiminate ligand.

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confidence: 99%

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

et al. 2014

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“…In particular, ligand 1 having an amidic nitrogen led to a Pd-dinuclear species with the concomitant transfer of the methyl group from the metal centre to the phosphorus atom, while ligand 2 gave the expected mononuclear derivative. This different behavior might be related to the different nature of the nitrogen atom deriving from 2-aminopyridine: in ligand 1 this nitrogen atom is sp 2 hybridized enforcing a planar, more strained, conformation of the N-P-N heterocycle, while in ligand 2 this nitrogen atom is sp 3 hybridized and thus the related heterocycle should result more flexible and, as a consequence, more stable than in ligand 1.…”

Section: Discussionmentioning

confidence: 99%

“…Indeed, the π-acceptor character of phosphorus atom can stabilize a metal center in a low oxidation state, while the nitrogen σ-donor ability makes the metal more susceptible to oxidative addition reactions, features that can play a crucial role in stabilizing intermediate oxidation states and/or geometries during a catalytic cycle [1]. In addition, the possibility of varying the electronic and steric properties of this kind of ligands allows to obtain potentially multidentate ligands that are able to bind or bridge one or more metal ions affording homo-or hetero-, bi-or polymetallic complexes [1,2].…”

Section: Introductionmentioning

confidence: 99%

New Chiral P-N Ligands for the Regio- and Stereoselective Pd-Catalyzed Dimerization of Styrene

et al. 2011

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Abstract:Two new chiral, enantiomerically pure, hybrid P-N ligands, namely (2R,5S)-2-phenyl-3-(2-pyridyl)-1,3-diaza-2-phosphanicyclo[3,3,0]octan-4-one (1) and (2R,5S)-2-phenyl-3-(2-pyridyl)-1,3-diaza-2-phosphanicyclo[3,3,0]octane (2), have been synthesized starting from L-proline. The two ligands differ in the presence or not of a carbonyl group in the diazaphosphane ring. Their coordination chemistry towards Pd(II) was studied by reacting them with [Pd(CH 3 )Cl(cod)]. A different behaviour was observed: ligand 2 shows the expected bidentate chelating behaviour leading to the mononuclear Pd-complex, while ligand 1 acts as a terdentate ligand giving a dinuclear species. The corresponding cationic derivatives were obtained from the palladium neutral complexes, both as mono-and dinuclear derivatives, and tested as precatalysts for styrene dimerization, yielding E-1,3-diphenyl-1-butene regio-and stereoselectively as the sole product. A detailed analysis of the catalytic behaviour is reported.

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“…Many of these complexes have been designed and prepared for other purposes such as structural studies, luminescent property studies and host-guest chemistry etc. [82]. Here, we only discuss some typical examples of transition metal homobimetallic complexes in organic catalytic Scheme 25 Preparation of substituted benzene from 1,4-diiron-1,3-diene.…”

Section: Homobimetallic Catalysis For Organic Synthesismentioning

confidence: 99%

Recent developments in homobimetallic reagents and catalysts for organic synthesis

Shimeng

et al. 2011

Chin. Sci. Bull.

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Organometallics are a family of useful organic chemicals because they play important roles in organic synthesis as reagents and as catalysts. They can be classified according to the number of metals they contain. Bimetallic compounds are important organometallics and they are either homobimetallic or heterobimetallic depending on whether the two metals are the same or different. In this paper, we focus on homobimetallic compounds. Homobimetallic compounds are generally used as dianions to react with electrophiles in organic synthesis. Recently, homobimetallics have also been used as catalysts in organic reactions such as in asymmetric reactions. homobimetallics, reagent, catalyst, synthesis, application Citation:Wu W, Gu D L, Wang S M, et al. Recent developments in homobimetallic reagents and catalysts for organic synthesis.

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Classification of P,N-binucleating ligands for hetero- and homobimetallic complexes

Cited by 95 publications

References 151 publications

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

Facile Synthesis of Phosphaamidines and Phosphaamidinates using Nitrilium Ions as an Imine Synthon

New Chiral P-N Ligands for the Regio- and Stereoselective Pd-Catalyzed Dimerization of Styrene

Recent developments in homobimetallic reagents and catalysts for organic synthesis

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