Hydroaminoalkylation of alkenes using transition metals complexes grafted on silica SBA15 as catalysts

Abdesslem Jedidi; Manal S Al-Harbi; Saadullah G Aziz; Osman I Osman; Luigi Cavallo

doi:10.1016/j.jmgm.2022.108281

Hydroaminoalkylation of alkenes using transition metals complexes grafted on silica SBA15 as catalysts

Abdesslem Jedidi, Manal S Al-Harbi, Saadullah G Aziz, Osman I Osman, Luigi Cavallo

Research output: Contribution to journal › Article › peer-review

2 Scopus citations

Abstract

The gas-phase hydroaminoalkylation reaction of propene catalyzed by group 4 (M = Ti, Zr and Hf) metal amido complexes [(≡Si–O-)(M(-NMe2)3] was investigated by using PBE0-D3/SVP//TZVP level of theory. The geometrical analysis traced the formation of the metallaaziridines and the azametallacyclopentanes as key intermediates in these reactions. The metallaaziridines were simulated through the activation of α-C-H bonds of the amido groups; while the azametallacyclopentanes were configured by slotting the propene double bond onto the M − C bonds of the metallaaziridines. The latter reaction was considered the rate-determining step. Thermochemical calculations showed that the order of catalytic activity is: Ti ≥ Zr > Hf; while the preference of the azametallacyclopentanes is: Hf > Zr ≥ Ti.

Original language	English (US)
Pages (from-to)	108281
Journal	Journal of molecular graphics & modelling
Volume	117
DOIs	https://doi.org/10.1016/j.jmgm.2022.108281
State	Published - Aug 17 2022

ASJC Scopus subject areas

Materials Chemistry
Spectroscopy
Physical and Theoretical Chemistry
Computer Graphics and Computer-Aided Design

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@article{da849849f3b640ebb00cc588e95623d2,

title = "Hydroaminoalkylation of alkenes using transition metals complexes grafted on silica SBA15 as catalysts",

abstract = "The gas-phase hydroaminoalkylation reaction of propene catalyzed by group 4 (M = Ti, Zr and Hf) metal amido complexes [(≡Si–O-)(M(-NMe2)3] was investigated by using PBE0-D3/SVP//TZVP level of theory. The geometrical analysis traced the formation of the metallaaziridines and the azametallacyclopentanes as key intermediates in these reactions. The metallaaziridines were simulated through the activation of α-C-H bonds of the amido groups; while the azametallacyclopentanes were configured by slotting the propene double bond onto the M − C bonds of the metallaaziridines. The latter reaction was considered the rate-determining step. Thermochemical calculations showed that the order of catalytic activity is: Ti ≥ Zr > Hf; while the preference of the azametallacyclopentanes is: Hf > Zr ≥ Ti.",

author = "Abdesslem Jedidi and Al-Harbi, {Manal S} and Aziz, {Saadullah G} and Osman, {Osman I} and Luigi Cavallo",

note = "KAUST Repository Item: Exported on 2022-09-14 Acknowledgements: The authors acknowledge with thanks the technical support and funding by the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah, under grant no. G: 388-130-38. The authors are also grateful to the HPCC (Aziz Supercomputer) for the resources. L.C. and A. J. are grateful to the KAUST Supercomputing Laboratory (Shaheen II) for the provided resources.",

year = "2022",

month = aug,

day = "17",

doi = "10.1016/j.jmgm.2022.108281",

language = "English (US)",

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pages = "108281",

journal = "Journal of molecular graphics & modelling",

issn = "1093-3263",

publisher = "Elsevier",

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TY - JOUR

T1 - Hydroaminoalkylation of alkenes using transition metals complexes grafted on silica SBA15 as catalysts

AU - Jedidi, Abdesslem

AU - Al-Harbi, Manal S

AU - Aziz, Saadullah G

AU - Osman, Osman I

AU - Cavallo, Luigi

N1 - KAUST Repository Item: Exported on 2022-09-14 Acknowledgements: The authors acknowledge with thanks the technical support and funding by the Deanship of Scientific Research (DSR), King Abdulaziz University, Jeddah, under grant no. G: 388-130-38. The authors are also grateful to the HPCC (Aziz Supercomputer) for the resources. L.C. and A. J. are grateful to the KAUST Supercomputing Laboratory (Shaheen II) for the provided resources.

PY - 2022/8/17

Y1 - 2022/8/17

N2 - The gas-phase hydroaminoalkylation reaction of propene catalyzed by group 4 (M = Ti, Zr and Hf) metal amido complexes [(≡Si–O-)(M(-NMe2)3] was investigated by using PBE0-D3/SVP//TZVP level of theory. The geometrical analysis traced the formation of the metallaaziridines and the azametallacyclopentanes as key intermediates in these reactions. The metallaaziridines were simulated through the activation of α-C-H bonds of the amido groups; while the azametallacyclopentanes were configured by slotting the propene double bond onto the M − C bonds of the metallaaziridines. The latter reaction was considered the rate-determining step. Thermochemical calculations showed that the order of catalytic activity is: Ti ≥ Zr > Hf; while the preference of the azametallacyclopentanes is: Hf > Zr ≥ Ti.

AB - The gas-phase hydroaminoalkylation reaction of propene catalyzed by group 4 (M = Ti, Zr and Hf) metal amido complexes [(≡Si–O-)(M(-NMe2)3] was investigated by using PBE0-D3/SVP//TZVP level of theory. The geometrical analysis traced the formation of the metallaaziridines and the azametallacyclopentanes as key intermediates in these reactions. The metallaaziridines were simulated through the activation of α-C-H bonds of the amido groups; while the azametallacyclopentanes were configured by slotting the propene double bond onto the M − C bonds of the metallaaziridines. The latter reaction was considered the rate-determining step. Thermochemical calculations showed that the order of catalytic activity is: Ti ≥ Zr > Hf; while the preference of the azametallacyclopentanes is: Hf > Zr ≥ Ti.

UR - http://hdl.handle.net/10754/680466

UR - https://linkinghub.elsevier.com/retrieve/pii/S1093326322001607

U2 - 10.1016/j.jmgm.2022.108281

DO - 10.1016/j.jmgm.2022.108281

M3 - Article

C2 - 35987187

SN - 1093-3263

VL - 117

SP - 108281

JO - Journal of molecular graphics & modelling

JF - Journal of molecular graphics & modelling

ER -

Hydroaminoalkylation of alkenes using transition metals complexes grafted on silica SBA15 as catalysts

Abstract

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