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)

Type
Article

Authors
Tonks, Ian A.
Meier, Josef C.
Bercaw, John E.

Online Publication Date
2013-06-03

Print Publication Date
2013-06-24

Date
2013-06-03

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.

Acknowledgements
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).

Publisher
American Chemical Society (ACS)

Journal
Organometallics

DOI
10.1021/om400080g

Permanent link to this record