A Sacrificial Iminato Ligand in the Catalytic Cyanosilylation of Ketones Promoted by Organoactinide Complexes

Hemanta Deka; Natalia Fridman; Moris S. Eisen

doi:10.1021/acs.inorgchem.1c03646

A Sacrificial Iminato Ligand in the Catalytic Cyanosilylation of Ketones Promoted by Organoactinide Complexes

Hemanta Deka, Natalia Fridman, Moris S. Eisen^*

^*Corresponding author for this work

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

7 Scopus citations

Abstract

Four new complexes containing the bis(pentamethylcyclopentadienyl)thorium(IV) moiety, Cp*₂Th(L1)(Me) (Th2), Cp*₂Th(L2)(Me) (Th3), Cp*₂Th(L1)Cl (Th5), and Cp*₂Th(L2)Cl (Th6), were synthesized in quantitative yields via the protonolysis reaction of the metallocene precursor complexes Cp*₂Th(Me)₂ (Th1) and Cp*₂Th(Me)Cl (Th4) and the respective six- and seven-membered N-heterocyclic neutral imine ligands L1H and L2H. The molecular structures of all the complexes were established by single-crystal X-ray structure analyses. The synthesized complexes along with the precursor complexes were employed as catalysts for the cyanosilylation reaction of ketones with trimethylsilyl cyanide (Me₃SiCN). The removal of the iminato ligand is necessary to trigger the reaction, allowing the formation of the active catalyst.

Original language	English
Pages (from-to)	3598-3606
Number of pages	9
Journal	Inorganic Chemistry
Volume	61
Issue number	8
DOIs	https://doi.org/10.1021/acs.inorgchem.1c03646
State	Published - 28 Feb 2022
Externally published	Yes

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title = "A Sacrificial Iminato Ligand in the Catalytic Cyanosilylation of Ketones Promoted by Organoactinide Complexes",

abstract = "Four new complexes containing the bis(pentamethylcyclopentadienyl)thorium(IV) moiety, Cp*2Th(L1)(Me) (Th2), Cp*2Th(L2)(Me) (Th3), Cp*2Th(L1)Cl (Th5), and Cp*2Th(L2)Cl (Th6), were synthesized in quantitative yields via the protonolysis reaction of the metallocene precursor complexes Cp*2Th(Me)2 (Th1) and Cp*2Th(Me)Cl (Th4) and the respective six- and seven-membered N-heterocyclic neutral imine ligands L1H and L2H. The molecular structures of all the complexes were established by single-crystal X-ray structure analyses. The synthesized complexes along with the precursor complexes were employed as catalysts for the cyanosilylation reaction of ketones with trimethylsilyl cyanide (Me3SiCN). The removal of the iminato ligand is necessary to trigger the reaction, allowing the formation of the active catalyst.",

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T1 - A Sacrificial Iminato Ligand in the Catalytic Cyanosilylation of Ketones Promoted by Organoactinide Complexes

AU - Deka, Hemanta

AU - Fridman, Natalia

AU - Eisen, Moris S.

PY - 2022/2/28

Y1 - 2022/2/28

N2 - Four new complexes containing the bis(pentamethylcyclopentadienyl)thorium(IV) moiety, Cp*2Th(L1)(Me) (Th2), Cp*2Th(L2)(Me) (Th3), Cp*2Th(L1)Cl (Th5), and Cp*2Th(L2)Cl (Th6), were synthesized in quantitative yields via the protonolysis reaction of the metallocene precursor complexes Cp*2Th(Me)2 (Th1) and Cp*2Th(Me)Cl (Th4) and the respective six- and seven-membered N-heterocyclic neutral imine ligands L1H and L2H. The molecular structures of all the complexes were established by single-crystal X-ray structure analyses. The synthesized complexes along with the precursor complexes were employed as catalysts for the cyanosilylation reaction of ketones with trimethylsilyl cyanide (Me3SiCN). The removal of the iminato ligand is necessary to trigger the reaction, allowing the formation of the active catalyst.

AB - Four new complexes containing the bis(pentamethylcyclopentadienyl)thorium(IV) moiety, Cp*2Th(L1)(Me) (Th2), Cp*2Th(L2)(Me) (Th3), Cp*2Th(L1)Cl (Th5), and Cp*2Th(L2)Cl (Th6), were synthesized in quantitative yields via the protonolysis reaction of the metallocene precursor complexes Cp*2Th(Me)2 (Th1) and Cp*2Th(Me)Cl (Th4) and the respective six- and seven-membered N-heterocyclic neutral imine ligands L1H and L2H. The molecular structures of all the complexes were established by single-crystal X-ray structure analyses. The synthesized complexes along with the precursor complexes were employed as catalysts for the cyanosilylation reaction of ketones with trimethylsilyl cyanide (Me3SiCN). The removal of the iminato ligand is necessary to trigger the reaction, allowing the formation of the active catalyst.

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SN - 0020-1669

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 8

ER -

A Sacrificial Iminato Ligand in the Catalytic Cyanosilylation of Ketones Promoted by Organoactinide Complexes

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