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.
| 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 | |
| Publication status | Published - Jan 1 2019 |
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Keywords
- hydrosilylation
- hydroboration
- Nickel
- coordination compounds
- homogeneous catalysis
ASJC Scopus subject areas
- Inorganic Chemistry
Cite this
POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities. / Gudun, Kristina; Segizbayev, Medet; Adamov, Assyl; Plessow, Philipp; Lyssenko, Konstantin; Balanay Padayhag, Mannix; Khalimon, Andrey.
In: Dalton Transactions, Vol. 48, No. 5, 10.1039/C8DT04854A, 01.01.2019, p. 1732-1746.Research output: Contribution to journal › Article
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TY - JOUR
T1 - POCN Ni(II) pincer complexes: synthesis, characterization and evaluation of catalytic hydrosilylation and hydroboration activities
AU - Gudun, Kristina
AU - Segizbayev, Medet
AU - Adamov, Assyl
AU - Plessow, Philipp
AU - Lyssenko, Konstantin
AU - Balanay Padayhag, Mannix
AU - Khalimon, Andrey
PY - 2019/1/1
Y1 - 2019/1/1
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
UR - http://www.scopus.com/inward/record.url?scp=85060806182&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85060806182&partnerID=8YFLogxK
U2 - 10.1039/C8DT04854A
DO - 10.1039/C8DT04854A
M3 - Article
VL - 48
SP - 1732
EP - 1746
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 5
M1 - 10.1039/C8DT04854A
ER -