C–H Bond Activation Facilitated by Bis(phosphinoamide) Heterobimetallic Zr/Co Complexes

Hunter, Nathanael H.; Lane, Elizabeth M.; Gramigna, Kathryn M.; Moore, Curtis E.; Thomas, Christine M.

doi:10.1021/acs.organomet.1c00511

C–H Bond Activation Facilitated by Bis(phosphinoamide) Heterobimetallic Zr/Co Complexes

Journal Article · Wed Oct 20 00:00:00 EDT 2021 · Organometallics

DOI:https://doi.org/10.1021/acs.organomet.1c00511· OSTI ID:1835591

Hunter, Nathanael H. ^[1]; Lane, Elizabeth M. ^[2]; Gramigna, Kathryn M. ^[3]; ^[2]; ^[2]

The Ohio State Univ., Columbus, OH (United States); The Ohio State University
The Ohio State Univ., Columbus, OH (United States)
Brandeis Univ., Waltham, MA (United States)

The activation of C–H bonds using first-row transition metals poses a formidable challenge in the development of sustainable catalytic methods. Early/late heterobimetallic complexes provide a Lewis acidic binding site for directing groups, facilitating the activation of C–H bonds at an appended first-row transition metal center. In this work, the reactivity of the ZrIV/Co–I heterobimetallic complexes (THF)(I)Zr(XylNPⁱPr₂)₂Co(PR₃) (1-PR₃; Xyl = 3,5-dimethylphenyl; PR₃ = PMe₃, PPh₂Me) toward directed C–H bond activation is explored with pyridine and terminal alkyne derivatives. 1-PMe₃ reacts reversibly with 4-methylpyridine to afford the C–H activated complex (4-Me-C₅H₄N)(I)Zr(XylNPⁱPr₂)₂(μ-4-Me-C₅H₃N)Co(PMe₃)(H) (3-PMe₃). By using the more Lewis basic substrate 4-tert-butylpyridine, (I)Zr(XylNPⁱPr₂)2(μ-4-^tBu-C₅H₃N)Co(PMe₃)(H) (4-PMe₃) is formed irreversibly. In addition to pyridine derivatives, 1-PPh₂Me can activate the C–H bond of terminal alkynes to form (THF)(I)Zr(XylNPiPr₂)₂(μ-R'C≡C)Co(PPh₂Me)(H) (R' = Ph (5-PPh₂Me); R' = SiMe₃ (6-PPh₂Me)).

View Accepted Manuscript (DOE)

Research Organization:: The Ohio State Univ., Columbus, OH (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0019179

OSTI ID:: 1835591

Journal Information:: Organometallics, Journal Name: Organometallics Journal Issue: 21 Vol. 40; ISSN 0276-7333

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

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