Bonding and Organic and Inorganic Reactivity of Metal-Coordinated Phosphinoenolates and Related Functional Phosphine-Derived Anions

Braunstein, Pierre

doi:10.1021/cr050993p

Cited by 127 publications

(95 citation statements)

References 124 publications

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“…It was rapidly found that when this ligand is coordinated to a transition metal, either j , weak bases being sufficient as a result of the enhanced acidity of the PCH 2 protons upon coordination [26]. This observation appeared very promising, in particular in view of the remarkable properties of nickel complexes containing such phosphino-enolate and related ligands in catalytic ethylene oligomerization, which form the basis of the industrial Shell Higher Olefin Process (SHOP) .…”

Section: Metal Complexes With Po-type Ligandsmentioning

confidence: 99%

“…À were shown to carry significant electronic density at the a-PCH carbon and this was evidenced by reactions with a number of organic and inorganic electrophiles [26]. A remarkably facile reversible binding reaction of CO 2 by a Pd(II) complex under ambient conditions was discovered and its application to the catalytic telomerization of butadiene with CO 2 [50,51], and carbon-carbon bond formation by insertion of organic isocyanates RN=C=O into the a-PC-H bond [52] were some of the outcome of these investigations.…”

Section: O)oet]mentioning

confidence: 99%

“…A remarkably facile reversible binding reaction of CO 2 by a Pd(II) complex under ambient conditions was discovered and its application to the catalytic telomerization of butadiene with CO 2 [50,51], and carbon-carbon bond formation by insertion of organic isocyanates RN=C=O into the a-PC-H bond [52] were some of the outcome of these investigations. Extensions to isoelectronic or closely related metalloligands demonstrated the potential of these often air-stable but reactive systems [26,53]. Furthermore, reactions with metal electrophiles provided novel rational entries into homo-and heterodinuclear chemistry [26].…”

Section: O)oet]mentioning

confidence: 99%

“…Extensions to isoelectronic or closely related metalloligands demonstrated the potential of these often air-stable but reactive systems [26,53]. Furthermore, reactions with metal electrophiles provided novel rational entries into homo-and heterodinuclear chemistry [26]. …”

Section: O)oet]mentioning

confidence: 99%

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Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Danopoulos

Braunstein

2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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Dedicated to the memory of Yves Chauvin, a most remarkable and visionary man and scientist, with gratitude for our scientific and non-scientific conversations and a very fruitful and enjoyable collaboration.Abstract -Two major aspects of coordination/organometallic chemistry are discussed in this article: (i) the use of functional chelating ligands to stabilize metal complexes while allowing easy stereodifferentiation within the coordination sphere and (ii) the choice of suitable ligands to stabilize challenging 'underligated' metal complexes with electronically highly unsaturated metal centres, thus potentially displaying unusual reactivity. In both cases, the relevance to homogeneous catalysis will be discussed.Résumé -Contrôle de la sphère de coordination des métaux par les ligands : structures, réacti-vité et catalyse -Deux aspects majeurs de la chimie de coordination/organométallique sont discutés dans cet article : d'une part, l'utilisation de ligands chélatants fonctionnels pour stabiliser des complexes métalliques en permettant une différenciation stéréoélectronique aisée au sein de la sphère de coordination et, d'autre part, la sélection de ligands adaptés à la stabilisation de complexes métalliques sous-coordinés dont les centres métalliques sont hautement insaturés électroniquement et donc potentiellement le siège d'une réactivité inhabituelle. Dans les deux cas, nous évoquerons la pertinence de ces approches en catalyse homogène.

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Section: Metal Complexes With Po-type Ligandsmentioning

confidence: 99%

Section: O)oet]mentioning

confidence: 99%

Section: O)oet]mentioning

confidence: 99%

Section: O)oet]mentioning

confidence: 99%

See 2 more Smart Citations

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Danopoulos

Braunstein

2016

Oil Gas Sci. Technol. – Rev. IFP Energies nouvelles

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“…The reaction of PPh 2 Cl with primary amines in the presence of NEt 3 represents a simple and efficient synthetic method for the preparation of a-aminophosphines. [1] The commercial availability of a large number of functionalized amines facilitates the fine tuning of the stereoelectronic properties of this class of ligands.…”

Section: Introductionmentioning

confidence: 99%

Phosphino‐Aminothiazoline Platinum(II) and Platinum(II)/Gold(I) Complexes: Structural, Chemical and Vapoluminescent Properties

Pattacini

Giansante

Ceroni

et al. 2007

Chemistry A European J

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Phosphino-amino-thiazolines and -thiazoles can exist in solution in two tautomeric forms, in which the N-H proton involves the endo-cyclic or exo-cyclic nitrogen atom. The two tautomers show different reactivities toward alcoholysis; the imino form degrades more rapidly. Their bischelated platinum complexes were studied in the solid state by single crystal X-ray diffraction. Thus, the unique stereoelectronic features of the [Pt(PN(th))] (PN(th)=diphenylposphino-aminothiazoline) moiety were revealed. The complex cis-[Pt(PN(th))(2)] reacts with gold(I) salts to yield dimetallic compounds, the molecular structures of which have been determined by X-ray diffraction. Solid cis-[Pt(PN(th))(2)] shows vapoluminescent properties if exposed to alcohol vapors. A combined photophysical and crystallographic investigation has been carried out to clarify the unprecedented rigidochromic role of the alcohol in this phenomenon.

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Synthesis of Metal Enolato Complexes

Vicente

2010

Patai's Chemistry of Functional Groups

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Introduction Synthesis from Ketones, Aldehydes and Esters Synthesis from Ketenes, Isocyanates and Acyl Halides Synthesis from Carbon Monoxide and Carbonyl Complexes Synthesis via Cleavage of Ethers and Related Compounds Synthesis from Oxo, Hydroxo or Alkoxo Complexes Oxygenation Reactions Miscellaneous Reactions Acknowledgments

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Bonding and Organic and Inorganic Reactivity of Metal-Coordinated Phosphinoenolates and Related Functional Phosphine-Derived Anions

Abstract: ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 200 leading journals. To access a ChemInform Abstract, please click on HTML or PDF.

Cited by 127 publications

References 124 publications

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Ligand Control of the Metal Coordination Sphere: Structures, Reactivity and Catalysis

Phosphino‐Aminothiazoline Platinum(II) and Platinum(II)/Gold(I) Complexes: Structural, Chemical and Vapoluminescent Properties

Synthesis of Metal Enolato Complexes

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