POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities

Kristina Gudun; Medet Segizbayev; Assyl Adamov; Philipp Plessow; Konstantin Lyssenko; Mannix Balanay Padayhag; Andrey Khalimon

doi:10.1039/C8DT04854A

POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities

Kristina Gudun
, Medet Segizbayev
, Assyl Adamov
, Philipp Plessow
, Konstantin Lyssenko
, Mannix Balanay Padayhag
, Andrey Khalimon

Department of Chemistry

Institute of Catalysis Research and Technology (IKFT)
Lomonosov Moscow State University
Nazarbayev University

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

51 Citations (Scopus)

Abstract

A series of iminophosphinite POCN pincer Ni(ii) complexes, (POCN)NiMe and (POCN)NiL_n(BX₄) (L = CH₃CN, n = 0, 1; X = F, Ph, C₆F₅), have been developed and subjected to catalytic hydrosilylation of alkenes, aldehydes and ketones and hydroboration of carbonyl compounds. The stoichiometric reactivity of (POCN)NiMe and (POCN)Ni(BF₄) with PhSiH₃ and HBPin suggests that catalytic reactions proceed via the hydride intermediate (POCN)NiH. With regard to reactions with HBPin, efficient and mild hydroboration of a variety of carbonyl compounds, including highly chemoselective hydroboration of benzaldehyde in the presence of other common potent reductive functional groups, such as alkenes, alkynes, esters, amides, nitriles, nitro compounds and even ketones, and the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary and secondary amides to borylated amines were demonstrated for (POCN)NiMe.

Original language	English
Article number	10.1039/C8DT04854A
Pages (from-to)	1732-1746
Number of pages	14
Journal	Dalton Transactions
Volume	48
Issue number	5
DOIs	https://doi.org/10.1039/C8DT04854A https://doi.org/10.1039/c8dt04854a
Publication status	Published - Jan 1 2019

Funding

This work was supported by Nazarbayev University through the NU Research University Development Program (grant to AYK 2016023). MPB also thanks the Ministry of Education and Science of the Republic of Kazakhstan (grant AP05134515). PNP acknowledges support by the state of Baden-Württemberg through bwHPC (bwunicluster and JUSTUS, RV bw17D011) and financial support from the Helmholtz Association.

UN SDGs

This output contributes to the following UN Sustainable Development Goals (SDGs)

SDG 7 Affordable and Clean Energy
SDG 9 Industry, Innovation, and Infrastructure
SDG 12 Responsible Consumption and Production

Keywords

hydrosilylation
hydroboration
Nickel
coordination compounds
homogeneous catalysis

ASJC Scopus subject areas

Inorganic Chemistry

Access to Document

Cite this

Gudun, K., Segizbayev, M., Adamov, A., Plessow, P., Lyssenko, K., Balanay Padayhag, M., & Khalimon, A. (2019). POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities. Dalton Transactions, 48(5), 1732-1746. Article 10.1039/C8DT04854A. https://doi.org/10.1039/C8DT04854A, https://doi.org/10.1039/c8dt04854a

Gudun, K, Segizbayev, M, Adamov, A, Plessow, P, Lyssenko, K, Balanay Padayhag, M & Khalimon, A 2019, 'POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities', Dalton Transactions, vol. 48, no. 5, 10.1039/C8DT04854A, pp. 1732-1746. https://doi.org/10.1039/C8DT04854A, https://doi.org/10.1039/c8dt04854a

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title = "POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities",

abstract = "A series of iminophosphinite POCN pincer Ni(ii) complexes, (POCN)NiMe and (POCN)NiLn(BX4) (L = CH3CN, n = 0, 1; X = F, Ph, C6F5), have been developed and subjected to catalytic hydrosilylation of alkenes, aldehydes and ketones and hydroboration of carbonyl compounds. The stoichiometric reactivity of (POCN)NiMe and (POCN)Ni(BF4) with PhSiH3 and HBPin suggests that catalytic reactions proceed via the hydride intermediate (POCN)NiH. With regard to reactions with HBPin, efficient and mild hydroboration of a variety of carbonyl compounds, including highly chemoselective hydroboration of benzaldehyde in the presence of other common potent reductive functional groups, such as alkenes, alkynes, esters, amides, nitriles, nitro compounds and even ketones, and the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary and secondary amides to borylated amines were demonstrated for (POCN)NiMe.",

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author = "Kristina Gudun and Medet Segizbayev and Assyl Adamov and Philipp Plessow and Konstantin Lyssenko and \{Balanay Padayhag\}, Mannix and Andrey Khalimon",

note = "Funding Information: This work was supported by Nazarbayev University through the NU Research University Development Program (grant to AYK 2016023). MPB also thanks the Ministry of Education and Science of the Republic of Kazakhstan (grant AP05134515). PNP acknowledges support by the state of Baden-W{\"u}rttemberg through bwHPC (bwunicluster and JUSTUS, RV bw17D011) and financial support from the Helmholtz Association. Publisher Copyright: {\textcopyright} 2019 The Royal Society of Chemistry.",

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AU - Gudun, Kristina

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AU - Plessow, Philipp

AU - Lyssenko, Konstantin

AU - Balanay Padayhag, Mannix

AU - Khalimon, Andrey

N1 - Funding Information: This work was supported by Nazarbayev University through the NU Research University Development Program (grant to AYK 2016023). MPB also thanks the Ministry of Education and Science of the Republic of Kazakhstan (grant AP05134515). PNP acknowledges support by the state of Baden-Württemberg through bwHPC (bwunicluster and JUSTUS, RV bw17D011) and financial support from the Helmholtz Association. Publisher Copyright: © 2019 The Royal Society of Chemistry.

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N2 - A series of iminophosphinite POCN pincer Ni(ii) complexes, (POCN)NiMe and (POCN)NiLn(BX4) (L = CH3CN, n = 0, 1; X = F, Ph, C6F5), have been developed and subjected to catalytic hydrosilylation of alkenes, aldehydes and ketones and hydroboration of carbonyl compounds. The stoichiometric reactivity of (POCN)NiMe and (POCN)Ni(BF4) with PhSiH3 and HBPin suggests that catalytic reactions proceed via the hydride intermediate (POCN)NiH. With regard to reactions with HBPin, efficient and mild hydroboration of a variety of carbonyl compounds, including highly chemoselective hydroboration of benzaldehyde in the presence of other common potent reductive functional groups, such as alkenes, alkynes, esters, amides, nitriles, nitro compounds and even ketones, and the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary and secondary amides to borylated amines were demonstrated for (POCN)NiMe.

AB - A series of iminophosphinite POCN pincer Ni(ii) complexes, (POCN)NiMe and (POCN)NiLn(BX4) (L = CH3CN, n = 0, 1; X = F, Ph, C6F5), have been developed and subjected to catalytic hydrosilylation of alkenes, aldehydes and ketones and hydroboration of carbonyl compounds. The stoichiometric reactivity of (POCN)NiMe and (POCN)Ni(BF4) with PhSiH3 and HBPin suggests that catalytic reactions proceed via the hydride intermediate (POCN)NiH. With regard to reactions with HBPin, efficient and mild hydroboration of a variety of carbonyl compounds, including highly chemoselective hydroboration of benzaldehyde in the presence of other common potent reductive functional groups, such as alkenes, alkynes, esters, amides, nitriles, nitro compounds and even ketones, and the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary and secondary amides to borylated amines were demonstrated for (POCN)NiMe.

KW - hydrosilylation

KW - hydroboration

KW - Nickel

KW - coordination compounds

KW - homogeneous catalysis

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POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities

Abstract

Funding

UN SDGs

Keywords

ASJC Scopus subject areas

Access to Document

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Fingerprint

2018 NU Research Day

Brock University

Cite this

POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities

Abstract

Funding

UN SDGs

Keywords

ASJC Scopus subject areas

Access to Document

Other files and links

Fingerprint

Activities

2018 NU Research Day

Brock University

Cite this