US EPA

4072361 

Journal Article 

Utilizing the TEMPO Radical in Zirconocene Cation and Hydrido Zirconocene Chemistry 

Liu, Y; Kehr, G; Daniliuc, CG; Erker, G 

2017 

1 

Organometallics
ISSN: 0276-7333
EISSN: 1520-6041 

36 

17 

3407-3414 

10.1021/acs.organomet.7b00558 

WOS:000410715800027 

https://www.scopus.com/inward/record.uri?eid=2-s2.0-85029184943&doi=10.1021%2facs.organomet.7b00558&partnerID=40&md5=d5cd0034fea9542381ad9c3780e935b2
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Dimethylzirconocene reacts with 2 molar equiv of the persistent radical TEMPO to give the Cp2Zr(Me)OTMP complex 12 with formation of TEMPOMe. Methyl anion abstraction from 12 with B(C6F5)(3) generates the [Cp2ZrOTMP+] cation 13 (with the [MeB(C6F5)(3)](-) anion) that undergoes a typical intramolecular frustrated Zr+/N Lewis pair (FLP) reaction with phenylacetylene. With (PBu3)-Bu-t it reacts as an intermolecular Zr+/P FLP trapping carbon dioxide. Complex 12 reacts with HB(C6F5)(2) also by methyl anion abstraction to form the mu-H bridged tight ion pair Cp2ZrOTMP(mu-H)BMe(C6F5)(2) (19). It serves as a Cp2Zr(H)OTMP zirconocene hydride source in the reaction with CO2, giving the respective [Zr] (mu-formate) [B] complex [B]. With carbon monoxide it forms the Zr-(eta(2)-acetaldehyde)[B] complex 30 by transfer of both the hydride and the methyl anion from the Zr/B pair to the carbon atom of the CO molecule.