Terminal aminophosphinidene complexes. A new approach

Mercier, François; Deschamps, Bernard; Mathey, François

doi:10.1021/ja00207a016

Cited by 81 publications

(52 citation statements)

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“…Another route to these phosphinidene complexes involves the thermal decomposition of some selected phosphirane complexes. It has been used to generate aminophosphanylidene [41] and vinylphosphinidene complexes [42] (Eqn. 2).…”

Section: Generation Of Electrophilicmentioning

confidence: 99%

Electrophilic Terminal-Phosphinidene Complexes: Versatile Phosphorus Analogues of Singlet Carbenes

Mathey

Huy

Marinetti

2001

HCA

225

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In memory of Professor Luigi M. Venanzi, a highly respected inorganic chemist Electrophilic and nucleophilic terminal-phosphinidene complexes are compared in terms of electronic structures and reactivities. Various precursors of the unstable electrophilic species [RÀPÀM] (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 OÀH, NÀH, and activated CÀH 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.

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Section: Generation Of Electrophilicmentioning

confidence: 99%

Electrophilic Terminal-Phosphinidene Complexes: Versatile Phosphorus Analogues of Singlet Carbenes

Mathey

Huy

Marinetti

2001

HCA

225

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“…[1] However, this chemistry remains very limited in scope and has never led to any synthetic development. In 1982, [2] a first efficient precursor of terminal phosphinidene complexes [RP-M] (M = Cr(CO) 5 , Mo(CO) 5 , W(CO) 5 ) was introduced. In 1982, [2] a first efficient precursor of terminal phosphinidene complexes [RP-M] (M = Cr(CO) 5 , Mo(CO) 5 , W(CO) 5 ) was introduced.…”

Section: Introductionmentioning

confidence: 99%

Activation of A–H bonds (A = B, C, N, O, Si) by using monovalent phosphorus complexes [RP→M]

Mathey

Duan

2016

Dalton Trans.

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The available data on the activation of A-H sigma bonds by electrophilic terminal phosphinidene complexes are reviewed. Theoretical computations allow us to rationalize the experimental results. It appears that a successful insertion needs an initial interaction between the phosphinidene and the A-H bond, such as a donor-acceptor complex with a lone pair, a Coulombic interaction due to a negative charge on A or H, or a proximity effect.

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“…The ESI-MS/MS experiments also offer insight into the stability of the three-membered reaction products, which may either undergo decomplexation of the transition-metal group to afford unique phosphirane ligands [23] or serve as precursors to phosphinidenes by [1 + 2] retroaddition. [24] CID of mass-selected propene adduct 6 a with 70 mTorr argon caused complete loss of the W(CO) 5 unit to render metal-free phosphirane 8 a (Figure 3 C), thereby simultaneously confirming that 6 a is not a loosely bound ion-molecule complex. On the other hand, CID of bicyclic 7 a with argon gas led exclusively to regeneration of phosphinidene 3 a by elimination of 1,4-dioxene (Figure 3 D).…”

Section: J-mentioning

confidence: 84%

Reactive Intermediates: A Transient Electrophilic Phosphinidene Caught in the Act

Jansen

Samuels

Couzijn

et al. 2010

Chemistry A European J

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Phosphinidene complexes [L n M=P À R] [1] are fascinating reagents akin to the isoelectronic carbenes [L n M=CR 2 ] [2] that have made a stunning impact on the preparative and industrial scale syntheses of small molecules and polymeric materials. It is tempting to extend the relationship for lowvalent species that is based on the similar electronegativities of the element phosphorus and the diagonally related carbon to these transition-metal complexes.[3] It has already been established that phosphinidene complexes can be classified as electrophilic (Fischer-type) or nucleophilic (Schrock-type) at phosphorus depending on the nature of the ligands L; [4] electron-withdrawing ligands with strong pacceptor capacity (e.g., CO) reduce the charge concentration on the phosphorus atom and therefore enhance its electrophilicity, whereas strong s-donor ligands (e.g., Cp) increase the electron density at phosphorus and thereby increase its nucleophilic properties. Proper characterisation of these complexes assists in understanding their chemical potential.

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Terminal aminophosphinidene complexes. A new approach

Cited by 81 publications

References 0 publications

Electrophilic Terminal-Phosphinidene Complexes: Versatile Phosphorus Analogues of Singlet Carbenes

Electrophilic Terminal-Phosphinidene Complexes: Versatile Phosphorus Analogues of Singlet Carbenes

Activation of A–H bonds (A = B, C, N, O, Si) by using monovalent phosphorus complexes [RP→M]

Reactive Intermediates: A Transient Electrophilic Phosphinidene Caught in the Act

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