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Zwitterionic and biradicaloid heteroatomic cyclopentane derivatives containing different group 15 elements.

ABSTRACT: The formal cyclopentane-1,3-diyl derivatives [E1(?-NTer)2({E2C} = NDmp)] (Ter = 2,6-dimesityl-phenyl, Dmp = 2,6-dimethylphenyl) were prepared by 1,1-insertion of CNDmp into the N-E2 bond of [E1(?-NTer)2E2] (E1 = N, P; E2 = P, As). The insertion does not occur for E1 = E2 = As or E2 = Sb. Dependent on the choice of formal radical centres E, either a biradicaloid or a zwitterion was obtained. The biradicaloid features a P and an As radical center and its biradical character was established by computations as well as characteristic reactivity with respect to the formation of a housane derivative and the activation of molecules bearing multiple bonds, which was demonstrated using the example of PC t Bu. In contrast, the formally N,As- and N,P-centered biradicaloids are better regarded as zwitterionic species in accord with computations and diminished reactivity, as neither housane formation nor activation of multiple bonds could be observed.

SUBMITTER: Hinz A

PROVIDER: S-EPMC5953028 | biostudies-literature | 2016 Jan

REPOSITORIES: biostudies-literature

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Zwitterionic and biradicaloid heteroatomic cyclopentane derivatives containing different group 15 elements.

Hinz Alexander A Schulz Axel A Villinger Alexander A

Chemical science 20151027 1

The formal cyclopentane-1,3-diyl derivatives [E1(μ-NTer)2({E2C} = NDmp)] (Ter = 2,6-dimesityl-phenyl, Dmp = 2,6-dimethylphenyl) were prepared by 1,1-insertion of CNDmp into the N-E2 bond of [E1(μ-NTer)2E2] (E1 = N, P; E2 = P, As). The insertion does not occur for E1 = E2 = As or E2 = Sb. Dependent on the choice of formal radical centres E, either a biradicaloid or a ...[more]

PMID: 29896358

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