The Electrophilic Phosphinidene Complex i Pr 2 N–P Fe(CO) 4 Trapped by Alkynes

Wit, Jan B. M.; Eijkel, Gerno T. van; Schakel, Marius; Lammertsma, Koop

doi:10.1016/s0040-4020(99)00782-6

Cited by 37 publications

(10 citation statements)

References 19 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This is not the case with the intramolecular example described in Scheme (8). This is not the case with the intramolecular example described in Scheme (8).…”

Section: Insertion Into Si-h and B-h Bondsmentioning

confidence: 81%

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

Mathey

Duan

2016

Dalton Trans.

View full text Add to dashboard Cite

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.

show abstract

“…This is not the case with the intramolecular example described in Scheme (8). This is not the case with the intramolecular example described in Scheme (8).…”

Section: Insertion Into Si-h and B-h Bondsmentioning

confidence: 81%

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

Mathey

Duan

2016

Dalton Trans.

View full text Add to dashboard Cite

show abstract

“…16 Recently, complexes of the electrophilic aminophosphinidene i Pr 2 N-P were synthesized and in some cases the X-ray structures determined. 17,18 Now we report our successful synthesis of the first metal complex containing a terminally bonded R 2 P-P ligand. The reaction of t Bu 2 P-P(SiMe 3 )Li?2THF with a solution of Cp 2 ZrCl 2 and PPhMe 2 (molar ratio 1 : 2 : 10) in DME and crystallization from pentane yields [{Zr(PPhMe 2 )Cp 2 }(g-P-P t Bu 2 )] (2), the zirconium complex with a terminally bonded t Bu 2 P-P ligand in 44% yield together with t Bu 2 P-P(SiMe 3 ) 2 and other products which were identified by 31 P NMR spectroscopy.…”

Section: [Cpmentioning

confidence: 98%

A new synthetic entry to phosphinophosphinidene complexes. Synthesis and structural characterisation of the first side-on bonded and the first terminally bonded phosphinophosphinidene zirconium complexes [μ-(1,2∶2-η-^tBu₂PP){Zr(Cl)Cp₂}₂] and [{Zr(PPhMe₂)Cp₂}(η¹-P–P^tBu₂)]

et al. 2004

View full text Add to dashboard Cite

The reactions of lithiated diphosphanes with transition metal chlorides constitute a new general entry to phosphinophosphinidene complexes: the reaction of Cp2ZrCl2(Cp = C5H5) with tBu2P-P(SiMe3)Li (molar ratio approximately 1:1) yields [mu-(1,2:2-eta-tBu2P=P)[Zr(Cl)Cp2]2]; the reaction of Cp2ZrCl2 with tBu2P-P(SiMe3)Li (molar ratio approximately 1:2) and an excess of PPhMe2 in DME yields the first terminally bonded phosphinophosphinidene complex, [[Zr(PPhMe2)Cp2](eta1-P-PtBu2)].

show abstract

“…The electrophilicity of this tetracarbonyl(phosphanylidene)iron complex appears to be lower than that of its [M(CO) 5 ] counterparts. It has been trapped by allenes and alkynes [45], but does not react with alkenes.…”

Section: Generation Of Electrophilicmentioning

confidence: 99%

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

Mathey

Huy

Marinetti

2001

HCA

225

View full text Add to dashboard Cite

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.

show abstract

The Electrophilic Phosphinidene Complex i Pr 2 N–P Fe(CO) 4 Trapped by Alkynes

Cited by 37 publications

References 19 publications

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

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

A new synthetic entry to phosphinophosphinidene complexes. Synthesis and structural characterisation of the first side-on bonded and the first terminally bonded phosphinophosphinidene zirconium complexes [μ-(1,2∶2-η-^tBu₂PP){Zr(Cl)Cp₂}₂] and [{Zr(PPhMe₂)Cp₂}(η¹-P–P^tBu₂)]

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

Contact Info

Product

Resources

About

The Electrophilic Phosphinidene Complex i Pr 2 N–P Fe(CO) 4 Trapped by Alkynes

Cited by 37 publications

References 19 publications

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

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

A new synthetic entry to phosphinophosphinidene complexes. Synthesis and structural characterisation of the first side-on bonded and the first terminally bonded phosphinophosphinidene zirconium complexes [μ-(1,2∶2-η-tBu2PP){Zr(Cl)Cp2}2] and [{Zr(PPhMe2)Cp2}(η1-P–PtBu2)]

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

Contact Info

Product

Resources

About

A new synthetic entry to phosphinophosphinidene complexes. Synthesis and structural characterisation of the first side-on bonded and the first terminally bonded phosphinophosphinidene zirconium complexes [μ-(1,2∶2-η-^tBu₂PP){Zr(Cl)Cp₂}₂] and [{Zr(PPhMe₂)Cp₂}(η¹-P–P^tBu₂)]