The [Rh(Xantphos)]+ catalyzed hydroboration of diphenylacetylene using trimethylamine-borane

Maximilian Dietz; Alice Johnson; Antonio Martínez-Martínez; Andrew S. Weller

doi:10.1016/j.ica.2019.03.032

The [Rh(Xantphos)]⁺ catalyzed hydroboration of diphenylacetylene using trimethylamine-borane

Maximilian Dietz, Alice Johnson, Antonio Martínez-Martínez, Andrew S. Weller^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The rhodium(I) complex [Rh(κ³-P,O,P-Xantphos)(η²-PhC≡CPh)][BAr^F₄] (Ar^F = 3,5-(CF₃)₂C₆H₄) is an effective catalyst for the cis-selective hydroboration of the alkyne diphenylacetylene using the amine-borane H₃B·NMe₃. Detailed mechanistic studies, that include initial rate measurements, full simulation of temporal profiles for a variety of catalyst and substrate concentrations, and speciation experiments, suggest a mechanism that involves initial coordination of alkyne and a saturation kinetics regime for amine-borane binding. The solid-state molecular structure of a model complex that probes the proposed resting state is also reported, [Rh(κ³-P,O,P-Xantphos)(NCMe)(η²-PhC≡CPh)][BAr^F₄].

Original language	English
Pages (from-to)	9-13
Number of pages	5
Journal	INORGANICA CHIMICA ACTA
Volume	491
Early online date	21 Mar 2019
DOIs	https://doi.org/10.1016/j.ica.2019.03.032
Publication status	Published - 1 Jun 2019

Bibliographical note

Keywords

Amine borane
Hydroboration
Mechanism
Rhodium

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10.1016/j.ica.2019.03.032

The[Rh(Xantphos)]+catalyzedhydroborationofdiphenylacetyleneusingtrimethylamine-borane
© 2019 The Authors.
Final published version, 1.13 MBLicence: CC BY

Cite this

@article{cee59acbd50840328fa5d910ee7201a0,

title = "The [Rh(Xantphos)]+ catalyzed hydroboration of diphenylacetylene using trimethylamine-borane",

abstract = "The rhodium(I) complex [Rh(κ3-P,O,P-Xantphos)(η2-PhC≡CPh)][BArF4] (ArF = 3,5-(CF3)2C6H4) is an effective catalyst for the cis-selective hydroboration of the alkyne diphenylacetylene using the amine-borane H3B·NMe3. Detailed mechanistic studies, that include initial rate measurements, full simulation of temporal profiles for a variety of catalyst and substrate concentrations, and speciation experiments, suggest a mechanism that involves initial coordination of alkyne and a saturation kinetics regime for amine-borane binding. The solid-state molecular structure of a model complex that probes the proposed resting state is also reported, [Rh(κ3-P,O,P-Xantphos)(NCMe)(η2-PhC≡CPh)][BArF4].",

keywords = "Amine borane, Hydroboration, Mechanism, Rhodium",

author = "Maximilian Dietz and Alice Johnson and Antonio Mart{\'i}nez-Mart{\'i}nez and Weller, {Andrew S.}",

note = "{\textcopyright} 2019 The Authors. ",

year = "2019",

month = jun,

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doi = "10.1016/j.ica.2019.03.032",

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T1 - The [Rh(Xantphos)]+ catalyzed hydroboration of diphenylacetylene using trimethylamine-borane

AU - Dietz, Maximilian

AU - Johnson, Alice

AU - Martínez-Martínez, Antonio

AU - Weller, Andrew S.

PY - 2019/6/1

Y1 - 2019/6/1

N2 - The rhodium(I) complex [Rh(κ3-P,O,P-Xantphos)(η2-PhC≡CPh)][BArF4] (ArF = 3,5-(CF3)2C6H4) is an effective catalyst for the cis-selective hydroboration of the alkyne diphenylacetylene using the amine-borane H3B·NMe3. Detailed mechanistic studies, that include initial rate measurements, full simulation of temporal profiles for a variety of catalyst and substrate concentrations, and speciation experiments, suggest a mechanism that involves initial coordination of alkyne and a saturation kinetics regime for amine-borane binding. The solid-state molecular structure of a model complex that probes the proposed resting state is also reported, [Rh(κ3-P,O,P-Xantphos)(NCMe)(η2-PhC≡CPh)][BArF4].

AB - The rhodium(I) complex [Rh(κ3-P,O,P-Xantphos)(η2-PhC≡CPh)][BArF4] (ArF = 3,5-(CF3)2C6H4) is an effective catalyst for the cis-selective hydroboration of the alkyne diphenylacetylene using the amine-borane H3B·NMe3. Detailed mechanistic studies, that include initial rate measurements, full simulation of temporal profiles for a variety of catalyst and substrate concentrations, and speciation experiments, suggest a mechanism that involves initial coordination of alkyne and a saturation kinetics regime for amine-borane binding. The solid-state molecular structure of a model complex that probes the proposed resting state is also reported, [Rh(κ3-P,O,P-Xantphos)(NCMe)(η2-PhC≡CPh)][BArF4].

KW - Amine borane

KW - Hydroboration

KW - Mechanism

KW - Rhodium

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