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Reactions of an anionic chelate phosphane/borata-alkene ligand with [Rh(nbd)Cl]2, [Rh(CO)2Cl]2 and [Ir(cod)Cl]2.


ABSTRACT: Borata-alkenes can serve as anionic olefin equivalent ligands in transition metal chemistry. A chelate ligand of this type is described and used for metal coordination. Deprotonation of the Mes2P(CH2)2B(C6F5)2 frustrated Lewis pair in the ?-CH[B] position gave the methylene-bridged phosphane/borata-alkene anion. It reacted with the [Rh(nbd)Cl] or [Rh(CO)2Cl] dimers to give the respective neutral chelate [P/C[double bond, length as m-dash]B][Rh] complexes. The reaction of the [P/C[double bond, length as m-dash]B]- anion with [Ir(cod)Cl]2 proceeded similarly, only that the complex underwent a subsequent oxidative addition reaction at the mesityl substituent. Both the resulting Ir(iii)hydride complex 15 and the P/borata-alkene Rh system 12 were used as hydrogenation catalysts. The [P/C[double bond, length as m-dash]B(C6F5)2]Rh(nbd) complex 12 served as a catalyst for arylacetylene polymerization.

SUBMITTER: Watanabe K 

PROVIDER: S-EPMC7654189 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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Reactions of an anionic chelate phosphane/borata-alkene ligand with [Rh(nbd)Cl]<sub>2</sub>, [Rh(CO)<sub>2</sub>Cl]<sub>2</sub> and [Ir(cod)Cl]<sub>2</sub>.

Watanabe Kohei K   Ueno Atsushi A   Tao Xin X   Škoch Karel K   Jie Xiaoming X   Vagin Sergei S   Rieger Bernhard B   Daniliuc Constantin G CG   Letzel Matthias C MC   Kehr Gerald G   Erker Gerhard G  

Chemical science 20200619 28


Borata-alkenes can serve as anionic olefin equivalent ligands in transition metal chemistry. A chelate ligand of this type is described and used for metal coordination. Deprotonation of the Mes<sub>2</sub>P(CH<sub>2</sub>)<sub>2</sub>B(C<sub>6</sub>F<sub>5</sub>)<sub>2</sub> frustrated Lewis pair in the α-CH[B] position gave the methylene-bridged phosphane/borata-alkene anion. It reacted with the [Rh(nbd)Cl] or [Rh(CO)<sub>2</sub>Cl] dimers to give the respective neutral chelate [P/C[double bond  ...[more]

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