1,3,2-Diazaphosphinines:  New, Versatile Precursors of 1,2-Azaphosphinines and Polyfunctional Phosphinines

Avarvari, Narcis; Floch, and Pascal Le; Mathey, François

doi:10.1021/ja962736v

Cited by 100 publications

(70 citation statements)

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“…Fully unsaturated 1,3,2-diazaphosphinines are readily prepared in fair yields of 40-45% in a one-pot reaction from Cp 2 TiMe 2 (Scheme 16 ) [84,85] . The starting material is first reacted with pivalonitrile or benzonitrile to give 1,3,2-diazatitanacyclohexadienes which are then quenched by subsequent addition of phosphorus trichloride followed by triethylamine.…”

Section: Synthesesmentioning

confidence: 99%

“…1,2-Dihydrol,3,2-diazaphosphinines react via a unique [5 + 2] cycloaddition to dimethyl acetylenedicarboxylate to furnish bicyclic iminophosphoranes which may subsequently undergo further rearrangement to yield isomeric ylides [87,95] . The significance of 1,3,2-diazaphosphinines lies in their use to react with alkynes under formation of phosphinines [84,85] . The transformation is like the 1,3,2-diazaphosphole/ 1,2-azaphosphole transformation [70] 31 P NMR but is usually directly subjected to a second [4 + 2]-cycloaddition/cycloreversion sequence with the same or a different alkyne which furnishes finally the desired phosphinine.…”

Section: Chemical Reactivitymentioning

confidence: 99%

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Recent Developments in the Chemistry of N-Heterocyclic Phosphines

Gudat

2009

Topics in Heterocyclic Chemistry

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This chapter gives a survey on five-and six-membered phosphorusnitrogen heterocyclic compounds whose rings combine a phosphazene (>N-P = N-) or phosphazane (>N-P(X)-N<) unit with an unsaturated C 2 or C 3 building block. Representatives contain structurally diverse species like aromatic 1,3,2-diazaphosphinines and (benzo)-1,3,2-diazaphospholes, cationic counterparts of subvalent main-group carbene analogues like 1,3,2-diazaphospholenium ions and phosphenium-diketiminates, and neutral heterocycles like 1,3,2-diazaphospholenes featuring unusual structures and reactivities. The exploration of these species developed rapidly in the last two decades in the wake of cutting edge research on multiple bonding and low coordination in the chemistry of heavier main-group elements, and the discovery of stable carbenes. This review summarizes the elaboration of synthetic approaches for different types of N -heterocyclic phosphine derivatives, discusses their characterization by physical and computational methods which furnished a thorough understanding of structure and bonding, and finally highlights accomplishments in the exploration of the chemical properties at the border of classical organic heterocyclic chemistry and molecular inorganic chemistry.

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Section: Synthesesmentioning

confidence: 99%

Section: Chemical Reactivitymentioning

confidence: 99%

Recent Developments in the Chemistry of N-Heterocyclic Phosphines

Gudat

2009

Topics in Heterocyclic Chemistry

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“…[24,25] This precursor proved to be a very efficient source of tetrafunctionalised phosphinines through successive [4 ϩ 2] cycloaddition/cycloreversion processes with functionalised alkynes. We first focused our work on the synthesis of diphenyl(3-R-5,6-diphenylphosphinin-2-yl)phosphane sulfide derivatives.…”

Section: Resultsmentioning

confidence: 99%

“…Elemental analyses were performed by the ''Service d'analyse du CNRS'', at Gif sur Yvette, France. Diazaphosphinine 1, [24] diphenyl(1-propynyl)phosphane sulfide [50] and [RuCl 2 (η 6 -C 10 H 14 )] 2 [51] were prepared according to reported procedures.…”

Section: Methodsmentioning

confidence: 99%

A New Mixed P,S‐Bidentate Ligand Featuring a λ⁴‐Phosphinine Anion and a Phosphanyl Sulfide Group − Synthesis, X‐ray Crystal Structures and Catalytic Properties of Its Chloro(cymene)ruthenium and Allylpalladium Complexes

et al. 2004

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Keywords: Density functional calculations / Homogeneous catalysis / P ligands / Ruthenium / Palladium / S ligands 1,3,2-Diazaphosphinine (1) reacts successively with diphenylacetylene and diphenyl(1-propynyl)phosphane sulfide to afford the P,S-bidentate phosphinine 3. Reaction of nBuLi with 3 followed by complexation with [RuCl 2 (C 10 H 14 )] 2 gave two diastereoisomers 5a,b. Variable-temperature NMR spectroscopy and ONIOM DFT calculations were carried out to rationalize their formation. Complexes 5a,b were used as catalysts in hydrogen-transfer hydrogenation (TON up to

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“…To circumvent this limitation, we developed a simple strategy relying on the reactivity of 1,3,2-diazaphosphinines. [11] As shown below, these heterocycles react with one equivalent of alkyne to give 1,2-azaphosphinines, which can subsequently be transformed into phosphinines at higher temperatures when a second equivalent of alkyne is reacted (Scheme 1). These thermally promoted transformations involve two successive [4ϩ2] cycloaddition/cycloreversion sequences with the concomitant release of two molecules of nitrile.…”

Section: Resultsmentioning

confidence: 99%

Syntheses of Phosphinine-Based Tripodal Ligands

Rhörig

Mézailles

Maigrot

et al. 2000

Eur. J. Inorg. Chem.

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The syntheses of several tripodal phosphinine‐based ligands are presented. 1,3,2‐Diazaphosphinine (1) undergoes Diels−Alder reactions with tris‐(propynyl)phenylsilane to yield tris‐(1,2‐azaphosphinine)phenylsilane 6. This intermediate serves as precursor for the preparation of two tripodal ligand. First, tris(phosphinine)phenylsilane (7) is obtained from the reaction with trimethylsilylacetylene. Under more drastic conditions, compound 6 reacts with 4‐octyne to yield the tripodal ligand 8 containing six n‐propyl groups. Reaction of 8 with [W(CO)5(THF)] affords the corresponding W(CO)3 complex 9 whose structure was confirmed by an X‐ray crystallographic study. The synthesis of two extended tripodal ligands 12 and 13 containing three phosphinine units each connected to the same CH linker by dimethylsilyl groups was also studied. As a prerequisite, the precursor tris(propynyldimethylsilyl)methane (10) was synthesized by reaction of three equivalents of propynyllithium with tris(bromodimethylsilyl)methane. Reaction of excess 1 with 10 yielded the corresponding tris(dimethylsilyl‐1,2‐azaphosphinine)methane (11) as an intermediate. The formation of ligands 12 and 13 was achieved by reacting 11 with trimethylsilylacetylene or 4‐octyne, respectively, in excess. The reaction of ligand 13 with [W(CO)5(THF)] in toluene yielded the corresponding W(CO)3 complex 14 which was structurally characterized.

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1,3,2-Diazaphosphinines: New, Versatile Precursors of 1,2-Azaphosphinines and Polyfunctional Phosphinines

Cited by 100 publications

References 10 publications

Recent Developments in the Chemistry of N-Heterocyclic Phosphines

Recent Developments in the Chemistry of N-Heterocyclic Phosphines

A New Mixed P,S‐Bidentate Ligand Featuring a λ⁴‐Phosphinine Anion and a Phosphanyl Sulfide Group − Synthesis, X‐ray Crystal Structures and Catalytic Properties of Its Chloro(cymene)ruthenium and Allylpalladium Complexes

Syntheses of Phosphinine-Based Tripodal Ligands

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1,3,2-Diazaphosphinines: New, Versatile Precursors of 1,2-Azaphosphinines and Polyfunctional Phosphinines

Cited by 100 publications

References 10 publications

Recent Developments in the Chemistry of N-Heterocyclic Phosphines

Recent Developments in the Chemistry of N-Heterocyclic Phosphines

A New Mixed P,S‐Bidentate Ligand Featuring a λ4‐Phosphinine Anion and a Phosphanyl Sulfide Group − Synthesis, X‐ray Crystal Structures and Catalytic Properties of Its Chloro(cymene)ruthenium and Allylpalladium Complexes

Syntheses of Phosphinine-Based Tripodal Ligands

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A New Mixed P,S‐Bidentate Ligand Featuring a λ⁴‐Phosphinine Anion and a Phosphanyl Sulfide Group − Synthesis, X‐ray Crystal Structures and Catalytic Properties of Its Chloro(cymene)ruthenium and Allylpalladium Complexes