Synthesis of novel POCN pincer complexes of Nickel (II) and their use as hydrosilylation and hydroboration catalysts

Medet Segizbayev, Kristina Gudun, Georgii I. Nikonov, Andrey Khalimon

Research output: Contribution to conferenceAbstract

13 Downloads (Pure)

Abstract

The chemistry of unsymmetrical pincer complexes with different side-arm donors, such as PXN, is known but little studied. Such an unsymmetrical substitution in the sidearm
positions of pincer ligands allows for fine-tuning of stability vs. catalytic activity of pincer complexes, often affecting the selectivity of catalytic transformations.
A series of unsymmetrical 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 catalytic 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 the 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, were demonstrated for (POCN)NiMe. We also report the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary and
secondary amides to borylated amines.
Original languageEnglish
Publication statusPublished - Nov 5 2019
Event52nd Inorganic Discussion Weekend - University of Ontario Institute of Technology, Oshawa, Canada
Duration: Nov 8 2019Nov 10 2019
https://science.ontariotechu.ca/inorganicdiscussion/index.php

Conference

Conference52nd Inorganic Discussion Weekend
Abbreviated titleIDW 2019
CountryCanada
CityOshawa
Period11/8/1911/10/19
Internet address

Fingerprint

Hydrosilylation
Nickel
Amides
Carbonyl compounds
Alkenes
Ketones
Catalysts
Olefins
Nitro Compounds
Nitriles
Alkynes
Catalyst selectivity
Aldehydes
Hydrides
Functional groups
Amines
Catalyst activity
Esters
Substitution reactions
Tuning

Keywords

  • Nickel
  • hydroboration
  • hydrosilylation
  • Reduction
  • Aldehydes
  • ketones
  • Amides
  • Base metals
  • pincer ligands

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry
  • Catalysis

Cite this

Segizbayev, M., Gudun, K., Nikonov, G. I., & Khalimon, A. (2019). Synthesis of novel POCN pincer complexes of Nickel (II) and their use as hydrosilylation and hydroboration catalysts. Abstract from 52nd Inorganic Discussion Weekend, Oshawa, Canada.

Synthesis of novel POCN pincer complexes of Nickel (II) and their use as hydrosilylation and hydroboration catalysts. / Segizbayev, Medet; Gudun, Kristina; Nikonov, Georgii I.; Khalimon, Andrey.

2019. Abstract from 52nd Inorganic Discussion Weekend, Oshawa, Canada.

Research output: Contribution to conferenceAbstract

Segizbayev, M, Gudun, K, Nikonov, GI & Khalimon, A 2019, 'Synthesis of novel POCN pincer complexes of Nickel (II) and their use as hydrosilylation and hydroboration catalysts', 52nd Inorganic Discussion Weekend, Oshawa, Canada, 11/8/19 - 11/10/19.
Segizbayev M, Gudun K, Nikonov GI, Khalimon A. Synthesis of novel POCN pincer complexes of Nickel (II) and their use as hydrosilylation and hydroboration catalysts. 2019. Abstract from 52nd Inorganic Discussion Weekend, Oshawa, Canada.
Segizbayev, Medet ; Gudun, Kristina ; Nikonov, Georgii I. ; Khalimon, Andrey. / Synthesis of novel POCN pincer complexes of Nickel (II) and their use as hydrosilylation and hydroboration catalysts. Abstract from 52nd Inorganic Discussion Weekend, Oshawa, Canada.
@conference{fa56fb31514e4ad8a4e39fc17bec6e1f,
title = "Synthesis of novel POCN pincer complexes of Nickel (II) and their use as hydrosilylation and hydroboration catalysts",
abstract = "The chemistry of unsymmetrical pincer complexes with different side-arm donors, such as PXN, is known but little studied. Such an unsymmetrical substitution in the sidearmpositions of pincer ligands allows for fine-tuning of stability vs. catalytic activity of pincer complexes, often affecting the selectivity of catalytic transformations.A series of unsymmetrical 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 catalytic 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 the 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, were demonstrated for (POCN)NiMe. We also report the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary andsecondary amides to borylated amines.",
keywords = "Nickel, hydroboration, hydrosilylation, Reduction, Aldehydes, ketones, Amides, Base metals, pincer ligands",
author = "Medet Segizbayev and Kristina Gudun and Nikonov, {Georgii I.} and Andrey Khalimon",
year = "2019",
month = "11",
day = "5",
language = "English",
note = "52nd Inorganic Discussion Weekend, IDW 2019 ; Conference date: 08-11-2019 Through 10-11-2019",
url = "https://science.ontariotechu.ca/inorganicdiscussion/index.php",

}

TY - CONF

T1 - Synthesis of novel POCN pincer complexes of Nickel (II) and their use as hydrosilylation and hydroboration catalysts

AU - Segizbayev, Medet

AU - Gudun, Kristina

AU - Nikonov, Georgii I.

AU - Khalimon, Andrey

PY - 2019/11/5

Y1 - 2019/11/5

N2 - The chemistry of unsymmetrical pincer complexes with different side-arm donors, such as PXN, is known but little studied. Such an unsymmetrical substitution in the sidearmpositions of pincer ligands allows for fine-tuning of stability vs. catalytic activity of pincer complexes, often affecting the selectivity of catalytic transformations.A series of unsymmetrical 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 catalytic 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 the 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, were demonstrated for (POCN)NiMe. We also report the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary andsecondary amides to borylated amines.

AB - The chemistry of unsymmetrical pincer complexes with different side-arm donors, such as PXN, is known but little studied. Such an unsymmetrical substitution in the sidearmpositions of pincer ligands allows for fine-tuning of stability vs. catalytic activity of pincer complexes, often affecting the selectivity of catalytic transformations.A series of unsymmetrical 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 catalytic 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 the 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, were demonstrated for (POCN)NiMe. We also report the first example of base metal catalyzed hydroboration of amides, including mild direct hydroborative reduction of primary andsecondary amides to borylated amines.

KW - Nickel

KW - hydroboration

KW - hydrosilylation

KW - Reduction

KW - Aldehydes

KW - ketones

KW - Amides

KW - Base metals

KW - pincer ligands

M3 - Abstract

ER -