Generation of TiII alkyne trimerization catalysts in the absence of strong metal reductants

Xin Yi See; Evan P. Beaumier; Zachary W. Davis-Gilbert; Peter L. Dunn; Jacob A. Larsen; Adam J. Pearce; T. Alex Wheeler; Ian A. Tonks

doi:10.1021/acs.organomet.7b00096

Generation of Ti^II alkyne trimerization catalysts in the absence of strong metal reductants

Xin Yi See, Evan P. Beaumier, Zachary W. Davis-Gilbert, Peter L. Dunn, Jacob A. Larsen, Adam J. Pearce, T. Alex Wheeler, Ian A. Tonks

Chemistry (Twin Cities)

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

31 Scopus citations

Abstract

Low-valent Ti^II species have typically been synthesized by the reaction of Ti^IV halides with strong metal reductants. Herein we report that Ti^II species can be generated simply by reacting Ti^IV imido complexes with 2 equiv of alkyne, yielding a metallacycle that can reductively eliminate pyrrole while liberating Ti^II. In order to probe the generality of this process, Ti^II-catalyzed alkyne trimerization reactions were carried out with a diverse range of Ti^IV precatalysts.

Original language	English (US)
Pages (from-to)	1383-1390
Number of pages	8
Journal	Organometallics
Volume	36
Issue number	7
DOIs	https://doi.org/10.1021/acs.organomet.7b00096
State	Published - Apr 10 2017

Bibliographical note

Funding Information:
Financial support was provided by the University of Minnesota (start-up funds, Heisig/Gleysteen fellowship for T.A.W.), the ACS Petroleum Research Fund (ACS-PRF 54225-DNI3) and the National Institutes of Health (1R35GM119457). Departmental equipment was purchased via grants from the NSF (MRI 1224900) (Bruker-AXS D8 Venture diffractometer) and the NIH (S10OD011952) (NMR Facility) with matching funds from the University of Minnesota.

Publisher Copyright:
© 2017 American Chemical Society.

Publisher link

10.1021/acs.organomet.7b00096

http://europepmc.org/articles/pmc5497852

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title = "Generation of TiII alkyne trimerization catalysts in the absence of strong metal reductants",

abstract = "Low-valent TiII species have typically been synthesized by the reaction of TiIV halides with strong metal reductants. Herein we report that TiII species can be generated simply by reacting TiIV imido complexes with 2 equiv of alkyne, yielding a metallacycle that can reductively eliminate pyrrole while liberating TiII. In order to probe the generality of this process, TiII-catalyzed alkyne trimerization reactions were carried out with a diverse range of TiIV precatalysts.",

author = "See, {Xin Yi} and Beaumier, {Evan P.} and Davis-Gilbert, {Zachary W.} and Dunn, {Peter L.} and Larsen, {Jacob A.} and Pearce, {Adam J.} and Wheeler, {T. Alex} and Tonks, {Ian A.}",

note = "Funding Information: Financial support was provided by the University of Minnesota (start-up funds, Heisig/Gleysteen fellowship for T.A.W.), the ACS Petroleum Research Fund (ACS-PRF 54225-DNI3) and the National Institutes of Health (1R35GM119457). Departmental equipment was purchased via grants from the NSF (MRI 1224900) (Bruker-AXS D8 Venture diffractometer) and the NIH (S10OD011952) (NMR Facility) with matching funds from the University of Minnesota. Publisher Copyright: {\textcopyright} 2017 American Chemical Society.",

year = "2017",

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doi = "10.1021/acs.organomet.7b00096",

language = "English (US)",

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T1 - Generation of TiII alkyne trimerization catalysts in the absence of strong metal reductants

AU - See, Xin Yi

AU - Beaumier, Evan P.

AU - Davis-Gilbert, Zachary W.

AU - Dunn, Peter L.

AU - Larsen, Jacob A.

AU - Pearce, Adam J.

AU - Wheeler, T. Alex

AU - Tonks, Ian A.

N1 - Funding Information: Financial support was provided by the University of Minnesota (start-up funds, Heisig/Gleysteen fellowship for T.A.W.), the ACS Petroleum Research Fund (ACS-PRF 54225-DNI3) and the National Institutes of Health (1R35GM119457). Departmental equipment was purchased via grants from the NSF (MRI 1224900) (Bruker-AXS D8 Venture diffractometer) and the NIH (S10OD011952) (NMR Facility) with matching funds from the University of Minnesota. Publisher Copyright: © 2017 American Chemical Society.

PY - 2017/4/10

Y1 - 2017/4/10

N2 - Low-valent TiII species have typically been synthesized by the reaction of TiIV halides with strong metal reductants. Herein we report that TiII species can be generated simply by reacting TiIV imido complexes with 2 equiv of alkyne, yielding a metallacycle that can reductively eliminate pyrrole while liberating TiII. In order to probe the generality of this process, TiII-catalyzed alkyne trimerization reactions were carried out with a diverse range of TiIV precatalysts.

AB - Low-valent TiII species have typically been synthesized by the reaction of TiIV halides with strong metal reductants. Herein we report that TiII species can be generated simply by reacting TiIV imido complexes with 2 equiv of alkyne, yielding a metallacycle that can reductively eliminate pyrrole while liberating TiII. In order to probe the generality of this process, TiII-catalyzed alkyne trimerization reactions were carried out with a diverse range of TiIV precatalysts.

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