Evidence for Silica Surface Three- and Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts

Layal F. Yaacoub; Maha A. Aljuhani; Abdesslem Jedidi; Manal S. Al-Harbi; Walid Almaksoud; Wiebke Wackerow; Edy Abou-Hamad; Jeremie Pelletier; Mohamad El Eter; Luigi Cavallo; Jean-Marie Basset

doi:10.1021/acs.organomet.0c00246

Evidence for Silica Surface Three- and Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts

Layal F. Yaacoub, Maha A. Aljuhani, Abdesslem Jedidi, Manal S. Al-Harbi, Walid Almaksoud, Wiebke Wackerow, Edy Abou-Hamad, Jeremie Pelletier, Mohamad El Eter, Luigi Cavallo, Jean-Marie Basset

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Abstract

The single-site silica-supported group IV metal amido complex [Ti(NMe2)4] gives the tris(amido)-supported fragment [(=Si−O−)Ti(−NMe2)3], which transforms into a three-membered metallacycle (called a metallaaziridine) by an αH transfer between two amido ligands. When the three-membered metallacycle reacts with 1-octene, it gives a five-membered metallacycle by insertion of the double bond into the M−C bond of the metallaziridine. These two metallacycles, key intermediates in the catalytic cycle of the hydroaminoalkylation of terminal olefins, were isolated and fully characterized following the surface organometallic chemistry (SOMC) concept and procedures. This paper shows that surface organometallic chemistry can be used to identify and fully characterize three- and five-membered metallacycles of Ti in the hydroaminoalkylation of olefins.

Original language	English (US)
Journal	Organometallics
DOIs	https://doi.org/10.1021/acs.organomet.0c00246
State	Published - Jun 30 2020

Bibliographical note

KAUST Repository Item: Exported on 2020-10-01
Acknowledgements: The King Abdullah University of Science and Technology (KAUST) supported the research. The authors acknowledge core lab at KAUST for their assistance. L.C. and A.J. are grateful to the KAUST Supercomputing Laboratory for the resources. A.J. thank High-Performance Computing Center (AZIZ supercomputer) for the support.

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10.1021/acs.organomet.0c00246

https://repository.kaust.edu.sa/bitstream/10754/663954/1/acs.organomet.0c00246.pdf

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Yaacoub, L. F., Aljuhani, M. A., Jedidi, A., Al-Harbi, M. S., Almaksoud, W., Wackerow, W., Abou-Hamad, E., Pelletier, J., El Eter, M., Cavallo, L., & Basset, J.-M. (2020). Evidence for Silica Surface Three- and Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts. Organometallics. https://doi.org/10.1021/acs.organomet.0c00246

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title = "Evidence for Silica Surface Three- and Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts",

abstract = "The single-site silica-supported group IV metal amido complex [Ti(NMe2)4] gives the tris(amido)-supported fragment [(=Si−O−)Ti(−NMe2)3], which transforms into a three-membered metallacycle (called a metallaaziridine) by an αH transfer between two amido ligands. When the three-membered metallacycle reacts with 1-octene, it gives a five-membered metallacycle by insertion of the double bond into the M−C bond of the metallaziridine. These two metallacycles, key intermediates in the catalytic cycle of the hydroaminoalkylation of terminal olefins, were isolated and fully characterized following the surface organometallic chemistry (SOMC) concept and procedures. This paper shows that surface organometallic chemistry can be used to identify and fully characterize three- and five-membered metallacycles of Ti in the hydroaminoalkylation of olefins.",

author = "Yaacoub, {Layal F.} and Aljuhani, {Maha A.} and Abdesslem Jedidi and Al-Harbi, {Manal S.} and Walid Almaksoud and Wiebke Wackerow and Edy Abou-Hamad and Jeremie Pelletier and {El Eter}, Mohamad and Luigi Cavallo and Jean-Marie Basset",

note = "KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The King Abdullah University of Science and Technology (KAUST) supported the research. The authors acknowledge core lab at KAUST for their assistance. L.C. and A.J. are grateful to the KAUST Supercomputing Laboratory for the resources. A.J. thank High-Performance Computing Center (AZIZ supercomputer) for the support.",

year = "2020",

month = jun,

day = "30",

doi = "10.1021/acs.organomet.0c00246",

language = "English (US)",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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Yaacoub, LF, Aljuhani, MA, Jedidi, A, Al-Harbi, MS, Almaksoud, W, Wackerow, W, Abou-Hamad, E, Pelletier, J, El Eter, M, Cavallo, L & Basset, J-M 2020, 'Evidence for Silica Surface Three- and Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts', Organometallics. https://doi.org/10.1021/acs.organomet.0c00246

TY - JOUR

T1 - Evidence for Silica Surface Three- and Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts

AU - Yaacoub, Layal F.

AU - Aljuhani, Maha A.

AU - Jedidi, Abdesslem

AU - Al-Harbi, Manal S.

AU - Almaksoud, Walid

AU - Wackerow, Wiebke

AU - Abou-Hamad, Edy

AU - Pelletier, Jeremie

AU - El Eter, Mohamad

AU - Cavallo, Luigi

AU - Basset, Jean-Marie

N1 - KAUST Repository Item: Exported on 2020-10-01 Acknowledgements: The King Abdullah University of Science and Technology (KAUST) supported the research. The authors acknowledge core lab at KAUST for their assistance. L.C. and A.J. are grateful to the KAUST Supercomputing Laboratory for the resources. A.J. thank High-Performance Computing Center (AZIZ supercomputer) for the support.

PY - 2020/6/30

Y1 - 2020/6/30

N2 - The single-site silica-supported group IV metal amido complex [Ti(NMe2)4] gives the tris(amido)-supported fragment [(=Si−O−)Ti(−NMe2)3], which transforms into a three-membered metallacycle (called a metallaaziridine) by an αH transfer between two amido ligands. When the three-membered metallacycle reacts with 1-octene, it gives a five-membered metallacycle by insertion of the double bond into the M−C bond of the metallaziridine. These two metallacycles, key intermediates in the catalytic cycle of the hydroaminoalkylation of terminal olefins, were isolated and fully characterized following the surface organometallic chemistry (SOMC) concept and procedures. This paper shows that surface organometallic chemistry can be used to identify and fully characterize three- and five-membered metallacycles of Ti in the hydroaminoalkylation of olefins.

AB - The single-site silica-supported group IV metal amido complex [Ti(NMe2)4] gives the tris(amido)-supported fragment [(=Si−O−)Ti(−NMe2)3], which transforms into a three-membered metallacycle (called a metallaaziridine) by an αH transfer between two amido ligands. When the three-membered metallacycle reacts with 1-octene, it gives a five-membered metallacycle by insertion of the double bond into the M−C bond of the metallaziridine. These two metallacycles, key intermediates in the catalytic cycle of the hydroaminoalkylation of terminal olefins, were isolated and fully characterized following the surface organometallic chemistry (SOMC) concept and procedures. This paper shows that surface organometallic chemistry can be used to identify and fully characterize three- and five-membered metallacycles of Ti in the hydroaminoalkylation of olefins.

UR - http://hdl.handle.net/10754/663954

UR - https://pubs.acs.org/doi/10.1021/acs.organomet.0c00246

UR - http://www.scopus.com/inward/record.url?scp=85087738615&partnerID=8YFLogxK

U2 - 10.1021/acs.organomet.0c00246

DO - 10.1021/acs.organomet.0c00246

M3 - Article

SN - 0276-7333

JO - Organometallics

JF - Organometallics

ER -

Evidence for Silica Surface Three- and Five-Membered Metallacycle Intermediates in the Catalytic Cycle of Hydroaminoalkylation of Olefins Using Single-Ti-Metal Catalysts

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