Singlet (Phosphino)phosphinidenes are Electrophilic

Hansmann, Max M.; Jazzar, Rodolphe; Bertrand, Guy

doi:10.1021/jacs.6b04232

Cited by 155 publications

(115 citation statements)

References 60 publications

(41 reference statements)

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“…[48,49] Theu se of phosphaethynolate as source of P À has also been observed in the reaction between an unsaturated three-membered silicon ring (a cyclotrisilene) and Na(OCP) (Scheme 7). [48,49] Theu se of phosphaethynolate as source of P À has also been observed in the reaction between an unsaturated three-membered silicon ring (a cyclotrisilene) and Na(OCP) (Scheme 7).…”

Section: Angewandte Chemiementioning

confidence: 90%

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The Chemistry of the 2‐Phosphaethynolate Anion

2018

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In all likelihood the first synthesis of the phosphaethynolate anion, PCO , was performed in 1894 when NaPH was reacted with CO in an attempt to make Na(CP) accompanied by elimination of water. This reaction was repeated 117 years later when it was discovered that Na(OCP) and H are the products of this remarkable transformation. Li(OCP) was synthesized and fully characterized in 1992 but this salt proved to be too unstable to allow for a detailed investigation of its chemistry. It was not until the heavier analogues of this lithium salt were isolated, Na(OCP) and K(OCP) (both of which are remarkably stable and can be even dissolved in water), that the chemistry of this new functional group could be explored. Here we review the chemistry of the 2-phosphaethynolate anion, a heavier phosphorus-containing analogue of the cyanate anion, and describe the wide breadth of chemical transformations for which it has been thus far employed. Its use as a ligand, in decarbonylative and deoxygenative processes, and as a building block for novel heterocycles is described. In the mere twenty-six years since Becker first reported the isolation of this remarkable anion, it has become a fascinating reagent for the synthesis of a vast library of, often unprecedented, molecules and compounds.

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Section: Angewandte Chemiementioning

confidence: 90%

“…[66] Formally this reaction, which proceeds under loss of CO, can be viewed as a[3+ +1] cycloaddition of the P À anion to the P=C=Ounit. [48,49] [66] Note that this reaction does not proceed under substitution of CO by the isonitrile to give [P]ÀP=C= NR as observed with the bulky derivative with R = Ar**.…”

Section: Angewandte Chemiementioning

confidence: 96%

The Chemistry of the 2‐Phosphaethynolate Anion

2018

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“…Its isolation opened a novel avenue towards NHC–phosphinidene adducts, simply by phosphinidene addition to carbenes. In this fashion, the phosphinidene adducts of CAAC 20 [ 20· P(DAP); δ 31 P = 76.3] and less electrophilic carbenes such as imidazol‐2‐ylidene 3 [ 3· P(DAP); δ 31 P = –68.2] and benzimidazol‐2‐ylidene 9 [ 9· P(DAP); δ 31 P = –35.5] have been prepared (Scheme ), illustrating the electrophilic nature of this phosphinidene …”

Section: Synthesis Of N‐heterocyclic Carbene–phosphinidene Adductsmentioning

confidence: 98%

N‐Heterocyclic Carbene–Phosphinidene Adducts: Synthesis, Properties, and Applications

Krachko

Slootweg

2018

Eur J Inorg Chem

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Syntheses, properties, and reactivity of N‐heterocyclic carbene–phosphinidene adducts are reviewed. These adducts, formally built by combining a phosphinidene with a carbene, are characterized by high nucleophilicity at the phosphorus atom. The main types of reactivity these adducts exhibit are: Lewis‐base reactivity towards main group and organic compounds as well as transition‐metal complexes, substitution reactions at the phosphorus atom with main group compounds and transition‐metal complexes, and phosphinidene transfer reactions resulting in C–P bond cleavage. These differ substantially from the classic phosphaalkenes.

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“…While transition metal pnictides have been known since Schrock and Cummins described the first terminal phosphides in 1995, related examples for main group systems are still rare. Bertrand recently demonstrated that ligand bulk can indeed lead to the stabilisation of a terminal phosphorus atom bonded to a main group element centre in the form of a phosphino‐phosphinidene (Figure A) . The utilisation of a less bulky substituent set resulted in the formation of the phosphanyl‐diphosphene B .…”

Section: Figurementioning

confidence: 99%

Limitations of Steric Bulk: Towards Phospha‐germynes and Phospha‐stannynes

Hinz

Goicoechea

2018

Chemistry A European J

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The use of bulky aryl(silyl)amides (R) as substituents for the stabilisation of phospha-germynes and phospha-stannynes (R-Ge≡P and R-Sn≡P, respectively) is described. Such species can be transiently generated by photolysis of the phosphaketene precursors (RE(PCO); E=Ge, Sn). Utilisation of bulky amides R and R (R =Ar**NSi(OtBu) , where Ar**=2,6-bis[bis(4-tert-butylphenyl)methyl]-4-methylphenyl; R =Ar***NSi(iPr) , where Ar***=2,6-bis[bis(3,5-di-tert-butylphenyl)methyl]-4-methylphenyl) facilitates the formation of diphosphene-type dimers, [(RGe)P] and [(RSn)P] . In an effort to circumvent dimerisation, the bulkier R substituent (R =Ar***NSi(4-tert-butylphenyl) ) was employed in an analogous series of experiments. This affords cyclic germylenes and stannylenes due to insertion of the terminal phosphide into Si-C bonds of the R substituent, which in case of the stannylene could act as a trap for another R -Sn≡P moiety. All attempts to isolate terminal phosphide species were unsuccessful due to the reactivity of such compounds towards the organic periphery of the bulky amides, highlighting the limitations of highly sterically demanding functionalities.

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Singlet (Phosphino)phosphinidenes are Electrophilic

Cited by 155 publications

References 60 publications

The Chemistry of the 2‐Phosphaethynolate Anion

The Chemistry of the 2‐Phosphaethynolate Anion

N‐Heterocyclic Carbene–Phosphinidene Adducts: Synthesis, Properties, and Applications

Limitations of Steric Bulk: Towards Phospha‐germynes and Phospha‐stannynes

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