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

Kristina A Gudun; Medet Segizbayev; Assyl Adamov; Philipp N Plessow; Konstantin A Lyssenko; Mannix P Balanay; Andrey Y Khalimon

doi:10.1039/c8dt04854a

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

Dalton Trans. 2019 Feb 7;48(5):1732-1746. doi: 10.1039/c8dt04854a. Epub 2019 Jan 14.

Authors

Kristina A Gudun¹, Medet Segizbayev¹, Assyl Adamov¹, Philipp N Plessow², Konstantin A Lyssenko³, Mannix P Balanay¹, Andrey Y Khalimon⁴

Affiliations

¹ Department of Chemistry, School of Science and Technology, Nazarbayev University, 53 Kabanbay Batyr Avenue, Astana 010000, Kazakhstan. andrey.khalimon@nu.edu.kz.
² Institute of Catalysis Research and Technology (IKFT), Hermann-von-Helmholtz-Platz 1, D-76344 Eggenstein-Leopoldshafen, Germany.
³ Department of Chemistry, M. V. Lomonosov Moscow State University, Leninskie Gory 1-3, Moscow 119991, Russia and Plekhanov Russian University of Economics, Stremyanny per. 36, Moscow 117997, Russia.
⁴ Department of Chemistry, School of Science and Technology, Nazarbayev University, 53 Kabanbay Batyr Avenue, Astana 010000, Kazakhstan. andrey.khalimon@nu.edu.kz and The Environment & Resource Efficiency Cluster, Nazarbayev University, Astana, 53 Kabanbay Batyr Avenue, Astana 010000, Kazakhstan.

PMID: 30637425
DOI: 10.1039/c8dt04854a

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.