The Evolution of Terminal Allylphosphinidene Pentacarbonyltungsten Complex
14 May 2014-Phosphorus Sulfur and Silicon and The Related Elements (Taylor & Francis)-Vol. 189, pp 908-913
TL;DR: The authors showed that terminal allylphosphinidene pentacarbonyltungsten complex 1 can evolve either by intramolecular P + C˭C cycloaddition or by [1,2] H C to P shift to give 2 or 6.
Abstract: DFT computations suggest that terminal allylphosphinidene pentacarbonyltungsten complex 1 can evolve either by intramolecular P + C˭C cycloaddition or by [1,2] H C to P shift to give 2 or 6. Upon thermolysis of the 7-allyl-7-phosphanorbornadiene precursor, the transient complex 1 gives two diastereomeric dimers 4a,b deriving from a head-to-tail P + C˭C intermolecular cycloaddition and another dimer 5 deriving from the [4 + 1] cycloaddition of 1 with 6, followed by an intramolecular hydrophosphination.
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01 Jan 2022
TL;DR: The proliferation of group VI metal carbonyl complexes continued in the primary literature during the 2006-2020 period covered by this contribution as discussed by the authors , and the exciting fundamental discoveries disclosed during this period promise further fruitful work in this area.
Abstract: The proliferation of group VI metal carbonyl complexes continued in the primary literature during the 2006–2020 period covered by this contribution. The general robustness of group VI metal tetracarbonyl and pentacarbonyl fragments lend themselves to their incorporation into complexes with a wide variety of ligands, containing a plethora of different group VI metal–element bonds. The classical application of group VI metal carbonyl fragments as electronic reporters of ancillary ligand donor ability via infrared spectroscopy remains a contemporary motivation for the preparation of these complexes. The exploration of group VI metal isocyanide complexes enjoyed a resurgence during 2006–2020, and the exciting fundamental discoveries disclosed during this period promise further fruitful work in this area.
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TL;DR: In this article, various precursors of the unstable electrophilic species [R−P−M] (M=Cr, Mo, W(CO)5 and Fe(CO), Fe(Co)4) are discussed.
Abstract: Electrophilic and nucleophilic terminal-phosphinidene complexes are compared in terms of electronic structures and reactivities. Various precursors of the unstable electrophilic species [R−P−M] (M=Cr, Mo, W(CO)5 and Fe(CO)4) are discussed. The addition reactions of the electrophilic phosphinidene complexes with Lewis bases, insertion reactions into O−H, N−H, and activated C−H bonds, and cycloaddition reactions with double and triple bonds are described, as well as some rearrangements and autocondensations. Various applications to the synthesis of new organophosphorus molecules are discussed and techniques available for demetallation are given.
197 citations
TL;DR: A selection of recent advances in metal complexes bearing terminal phosphido or phosphinidene ligands in the stoichiometric and catalytic preparation of phosphorus-element bonds are described.
Abstract: Metal complexes bearing terminal phosphido or phosphinidene ligands have become versatile tools in the stoichiometric and catalytic preparation of phosphorus–element bonds. This Perspective describes a selection of recent advances in this field, and certain emphasis has been placed on reactions that vary from what has been previously observed. Some of the general reactivity trends and mechanistic understanding in these metal-mediated reactions that has emerged are also described. Much of what is chronicled herein comes from a flux of reports over the last decade describing unique metal-mediated phosphorus–element bond formation reactions that are likely to stimulate further discoveries.
183 citations
TL;DR: In this article, the versatile carbene-like chemistry of electrophilic phosphinidene complexes (R−P=MLn) with C = C, C≡C, C=X, and X = N, O, S, Si, and P) bonds and aromatics is discussed.
162 citations
TL;DR: The description of the first stable electrophilic terminal phosphinidene complexes, new precursors for the widely used transient [RP-M(CO)5] complex, new substituents at phosphorus, new reactions and new decomplexation techniques, and a different approach is proposed for stabilizing singlet phosphinidenes by formation of adducts with nitrogen bases.
Abstract: Electrophilic terminal phosphinidene complexes can be seen as singlet phosphinidenes stabilized by complexation with electron withdrawing metallic centers. They allow the development of an original P(I) chemistry whose latest results are summarized. These include the description of the first stable electrophilic terminal phosphinidene complexes, new precursors for the widely used transient [RP–M(CO)5] complexes (M = Cr, Mo, W), new substituents at phosphorus, new reactions and new decomplexation techniques. Finally, a different approach is proposed for stabilizing singlet phosphinidenes by formation of adducts with nitrogen bases such as N-methylimidazole. The resulting zwitterions are potentially equivalent to singlet nucleophilic phosphinidenes. Their synthetic potential remains to be explored.
159 citations
TL;DR: Preparation des complexes phosphinidene RP=M(CO) 5 qui reagissent in situ avec les olefines pour donner des complexes of phosphirane as discussed by the authors.
123 citations