Synthesis of Ti Complexes Supported by an ortho-Terphenoxide Ligand and Their Applications in Alkyne Hydroamination Catalysis

Steven K. Butler; Ethan P. Ashbrook; Ian A. Tonks

doi:10.1021/acs.organomet.2c00593

Synthesis of Ti Complexes Supported by an ortho-Terphenoxide Ligand and Their Applications in Alkyne Hydroamination Catalysis

Steven K. Butler
, Ethan P. Ashbrook
, Ian A. Tonks

Chemistry (Twin Cities)

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

5 Scopus citations

Abstract

The synthesis of a series of Ti complexes of an aryl-linked bis-phenoxide ligand, 3,3″-di-tert-butyl-5,5″-dimethyl-[1,1′:2′,1″-terphenyl]-2,2″-bis(olate), (TPO)H₂, is reported. This ortho-linked terphenyl ligand builds on previously reported meta- and para-linked terphenyl-based ligands, completing the isomeric series of terphenoxide ligands. The 4-coordinate (TPO)Ti(NMe₂)₂ is an active catalyst for alkyne hydroamination with a variety of arylamines, revealing good regioselectivity in reactions with unsymmetric alkynes. Terminal alkynes such as phenylacetylene undergo additional insertion reactions with the key azatitanacyclobutene intermediates, providing further evidence that Ti aryloxide complexes are susceptible to this further reactivity.

Original language	English (US)
Pages (from-to)	1732-1739
Number of pages	8
Journal	Organometallics
Volume	42
Issue number	14
DOIs	https://doi.org/10.1021/acs.organomet.2c00593
State	Published - Jul 24 2023

Bibliographical note

Funding Information:
Financial support was provided by the National Institutes of Health (R35GM119457). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). X-ray diffraction experiments were performed with a diffractometer purchased through a grant from NSF/MRI (1229400) and the University of Minnesota.

Publisher Copyright:
© 2023 American Chemical Society.

Publisher link

10.1021/acs.organomet.2c00593

Find It

Find It at U of M Libraries

Cite this

@article{dea6f63ac68f4e1a9d49026e420fd9fb,

title = "Synthesis of Ti Complexes Supported by an ortho-Terphenoxide Ligand and Their Applications in Alkyne Hydroamination Catalysis",

abstract = "The synthesis of a series of Ti complexes of an aryl-linked bis-phenoxide ligand, 3,3″-di-tert-butyl-5,5″-dimethyl-[1,1′:2′,1″-terphenyl]-2,2″-bis(olate), (TPO)H2, is reported. This ortho-linked terphenyl ligand builds on previously reported meta- and para-linked terphenyl-based ligands, completing the isomeric series of terphenoxide ligands. The 4-coordinate (TPO)Ti(NMe2)2 is an active catalyst for alkyne hydroamination with a variety of arylamines, revealing good regioselectivity in reactions with unsymmetric alkynes. Terminal alkynes such as phenylacetylene undergo additional insertion reactions with the key azatitanacyclobutene intermediates, providing further evidence that Ti aryloxide complexes are susceptible to this further reactivity.",

author = "Butler, \{Steven K.\} and Ashbrook, \{Ethan P.\} and Tonks, \{Ian A.\}",

note = "Funding Information: Financial support was provided by the National Institutes of Health (R35GM119457). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). X-ray diffraction experiments were performed with a diffractometer purchased through a grant from NSF/MRI (1229400) and the University of Minnesota. Publisher Copyright: {\textcopyright} 2023 American Chemical Society.",

year = "2023",

month = jul,

day = "24",

doi = "10.1021/acs.organomet.2c00593",

language = "English (US)",

volume = "42",

pages = "1732--1739",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "14",

}

TY - JOUR

T1 - Synthesis of Ti Complexes Supported by an ortho-Terphenoxide Ligand and Their Applications in Alkyne Hydroamination Catalysis

AU - Butler, Steven K.

AU - Ashbrook, Ethan P.

AU - Tonks, Ian A.

N1 - Funding Information: Financial support was provided by the National Institutes of Health (R35GM119457). Instrumentation for the University of Minnesota Chemistry NMR facility was supported from a grant through the National Institutes of Health (S10OD011952). X-ray diffraction experiments were performed with a diffractometer purchased through a grant from NSF/MRI (1229400) and the University of Minnesota. Publisher Copyright: © 2023 American Chemical Society.

PY - 2023/7/24

Y1 - 2023/7/24

N2 - The synthesis of a series of Ti complexes of an aryl-linked bis-phenoxide ligand, 3,3″-di-tert-butyl-5,5″-dimethyl-[1,1′:2′,1″-terphenyl]-2,2″-bis(olate), (TPO)H2, is reported. This ortho-linked terphenyl ligand builds on previously reported meta- and para-linked terphenyl-based ligands, completing the isomeric series of terphenoxide ligands. The 4-coordinate (TPO)Ti(NMe2)2 is an active catalyst for alkyne hydroamination with a variety of arylamines, revealing good regioselectivity in reactions with unsymmetric alkynes. Terminal alkynes such as phenylacetylene undergo additional insertion reactions with the key azatitanacyclobutene intermediates, providing further evidence that Ti aryloxide complexes are susceptible to this further reactivity.

AB - The synthesis of a series of Ti complexes of an aryl-linked bis-phenoxide ligand, 3,3″-di-tert-butyl-5,5″-dimethyl-[1,1′:2′,1″-terphenyl]-2,2″-bis(olate), (TPO)H2, is reported. This ortho-linked terphenyl ligand builds on previously reported meta- and para-linked terphenyl-based ligands, completing the isomeric series of terphenoxide ligands. The 4-coordinate (TPO)Ti(NMe2)2 is an active catalyst for alkyne hydroamination with a variety of arylamines, revealing good regioselectivity in reactions with unsymmetric alkynes. Terminal alkynes such as phenylacetylene undergo additional insertion reactions with the key azatitanacyclobutene intermediates, providing further evidence that Ti aryloxide complexes are susceptible to this further reactivity.

UR - https://www.scopus.com/pages/publications/85147958702

UR - https://www.scopus.com/pages/publications/85147958702#tab=citedBy

U2 - 10.1021/acs.organomet.2c00593

DO - 10.1021/acs.organomet.2c00593

M3 - Article

C2 - 37842019

AN - SCOPUS:85147958702

SN - 0276-7333

VL - 42

SP - 1732

EP - 1739

JO - Organometallics

JF - Organometallics

IS - 14

ER -

Synthesis of Ti Complexes Supported by an ortho-Terphenoxide Ligand and Their Applications in Alkyne Hydroamination Catalysis

Abstract

Bibliographical note

Publisher link

Find It

Other files and links

Fingerprint

Cite this