Alkyne Hydroamination and Trimerization with Titanium Bis(phenolate)pyridine Complexes: Evidence for Low-Valent Titanium Intermediates and Synthesis of an Ethylene Adduct of Titanium(II)

Handle URI:
http://hdl.handle.net/10754/597488
Title:
Alkyne Hydroamination and Trimerization with Titanium Bis(phenolate)pyridine Complexes: Evidence for Low-Valent Titanium Intermediates and Synthesis of an Ethylene Adduct of Titanium(II)
Authors:
Tonks, Ian A.; Meier, Josef C.; Bercaw, John E.
Abstract:
A class of titanium precatalysts of the type (ONO)TiX2 (ONO = pyridine-2,6-bis(4,6-di-tert-butylphenolate); X = Bn, NMe2) has been synthesized and crystallographically characterized. The (ONO)TiX2 (X = Bn, NMe2, X2 = NPh) complexes are highly active precatalysts for the hydroamination of internal alkynes with primary arylamines and some alkylamines. A class of titanium imido/ligand adducts, (ONO)Ti(L)(NR) (L = HNMe2, py; R = Ph, tBu), have also been synthesized and characterized and provide structural analogues to intermediates on the purported catalytic cycle. Furthermore, these complexes exhibit unusual redox behavior. (ONO)TiBn2 (1) promotes the cyclotrimerization of electron-rich alkynes, likely via a catalytically active TiII species that is generated in situ from 1. Depending on reaction conditions, these TiII species are proposed to be generated through Ti benzylidene or imido intermediates. A formally TiII complex, (ONO)Ti II(η2-C2H4)(HNMe2) (7), has been prepared and structurally characterized. © 2013 American Chemical Society.
Citation:
Tonks IA, Meier JC, Bercaw JE (2013) Alkyne Hydroamination and Trimerization with Titanium Bis(phenolate)pyridine Complexes: Evidence for Low-Valent Titanium Intermediates and Synthesis of an Ethylene Adduct of Titanium(II). Organometallics 32: 3451–3457. Available: http://dx.doi.org/10.1021/om400080g.
Publisher:
American Chemical Society (ACS)
Journal:
Organometallics
Issue Date:
24-Jun-2013
DOI:
10.1021/om400080g
Type:
Article
ISSN:
0276-7333; 1520-6041
Sponsors:
We thank Lawrence Henling and Dr. Michael Day for assistance with the X-ray studies. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). This work has been supported by USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431) and by the KAUST Center-In-Development at King Fahd University of Petroleum and Minerals (Dhahran, Saudi Arabia).
Appears in Collections:
Publications Acknowledging KAUST Support

Full metadata record

DC FieldValue Language
dc.contributor.authorTonks, Ian A.en
dc.contributor.authorMeier, Josef C.en
dc.contributor.authorBercaw, John E.en
dc.date.accessioned2016-02-25T12:40:43Zen
dc.date.available2016-02-25T12:40:43Zen
dc.date.issued2013-06-24en
dc.identifier.citationTonks IA, Meier JC, Bercaw JE (2013) Alkyne Hydroamination and Trimerization with Titanium Bis(phenolate)pyridine Complexes: Evidence for Low-Valent Titanium Intermediates and Synthesis of an Ethylene Adduct of Titanium(II). Organometallics 32: 3451–3457. Available: http://dx.doi.org/10.1021/om400080g.en
dc.identifier.issn0276-7333en
dc.identifier.issn1520-6041en
dc.identifier.doi10.1021/om400080gen
dc.identifier.urihttp://hdl.handle.net/10754/597488en
dc.description.abstractA class of titanium precatalysts of the type (ONO)TiX2 (ONO = pyridine-2,6-bis(4,6-di-tert-butylphenolate); X = Bn, NMe2) has been synthesized and crystallographically characterized. The (ONO)TiX2 (X = Bn, NMe2, X2 = NPh) complexes are highly active precatalysts for the hydroamination of internal alkynes with primary arylamines and some alkylamines. A class of titanium imido/ligand adducts, (ONO)Ti(L)(NR) (L = HNMe2, py; R = Ph, tBu), have also been synthesized and characterized and provide structural analogues to intermediates on the purported catalytic cycle. Furthermore, these complexes exhibit unusual redox behavior. (ONO)TiBn2 (1) promotes the cyclotrimerization of electron-rich alkynes, likely via a catalytically active TiII species that is generated in situ from 1. Depending on reaction conditions, these TiII species are proposed to be generated through Ti benzylidene or imido intermediates. A formally TiII complex, (ONO)Ti II(η2-C2H4)(HNMe2) (7), has been prepared and structurally characterized. © 2013 American Chemical Society.en
dc.description.sponsorshipWe thank Lawrence Henling and Dr. Michael Day for assistance with the X-ray studies. The Bruker KAPPA APEXII X-ray diffractometer was purchased via an NSF CRIF:MU award to the California Institute of Technology (CHE-0639094). This work has been supported by USDOE Office of Basic Energy Sciences (Grant No. DE-FG03-85ER13431) and by the KAUST Center-In-Development at King Fahd University of Petroleum and Minerals (Dhahran, Saudi Arabia).en
dc.publisherAmerican Chemical Society (ACS)en
dc.titleAlkyne Hydroamination and Trimerization with Titanium Bis(phenolate)pyridine Complexes: Evidence for Low-Valent Titanium Intermediates and Synthesis of an Ethylene Adduct of Titanium(II)en
dc.typeArticleen
dc.identifier.journalOrganometallicsen
dc.contributor.institutionCalifornia Institute of Technology, Pasadena, United Statesen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.