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

23 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 - 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.

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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.",

year = "2017",

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

language = "English (US)",

volume = "36",

pages = "1383--1390",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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TY - JOUR

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.

PY - 2017

Y1 - 2017

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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