Reversible Complexation of Lewis Bases to Low-Coordinate Fe(II), Co(II), and Ni(II) Amides: Influence of the Metal, Donor Ligand, and Amide Substituent on Binding Constants

Chun-Yi Lin, James C. Fettinger, Philip P. Power

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The binding constants of several monodentate Lewis bases (L) having different donor atoms [L = tetrahydrofuran (THF), tetrahydrothiophene (THT), pyridine, 4-(dimethylamino)pyridine (DMAP), PMe3, PCy3, and 1,3-bis(1,3,5-trimethylphenyl)imidazol-2-ylidene (IMes)] to the linear two-coordinate bis(amido) transition-metal complexes, M{N(SiMe3)Dipp}2 [M = Fe (1), Co (2), and Ni (3)] were determined by electronic absorption spectroscopy. In addition, 1H NMR spectroscopy was used to study the complexation of M{N(SiMe3)Dipp}2 by THF. The binding constants of the less bulky amido complexes [M{N(SiMe3)2}2]2 (M = Fe or Co; the nickel species is unstable) were also measured and found to bind THF 102-103 times more strongly than M{N(SiMe3)Dipp}2. Furthermore, unlike the corresponding -N(SiMe3)Dipp complexes, where the iron species are more strongly complexed than those of cobalt, the --N(SiMe3)2 species [Co{N(SiMe3)2}2]2 displayed a higher binding constant to THF than [Fe{N(SiMe3)2}2]2, which is in agreement with the stronger association of the [Co{N(SiMe3)2}2]2 dimer in comparison to that of its iron analogue. The binding strengths of the ligands to 1-3 were found to be in the order of DMAP > pyridine > PMe3 > PCy3 ≈ IMes > THF > THT, and those of the respective metals were in the order of Fe > Co > Ni.

Original languageEnglish
Pages (from-to)9892-9902
Number of pages11
JournalInorganic Chemistry
Volume56
Issue number16
DOIs
Publication statusPublished - 2017 Aug 21

Fingerprint

Lewis Bases
Lewis base
tetrahydrofuran
Complexation
Amides
amides
Metals
Ligands
pyridines
ligands
metals
Iron
iron
Coordination Complexes
Cobalt
Nickel
Absorption spectroscopy
imidazoles
Dimers
Nuclear magnetic resonance spectroscopy

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{9182f84184fc4445815026218243c39d,
title = "Reversible Complexation of Lewis Bases to Low-Coordinate Fe(II), Co(II), and Ni(II) Amides: Influence of the Metal, Donor Ligand, and Amide Substituent on Binding Constants",
abstract = "The binding constants of several monodentate Lewis bases (L) having different donor atoms [L = tetrahydrofuran (THF), tetrahydrothiophene (THT), pyridine, 4-(dimethylamino)pyridine (DMAP), PMe3, PCy3, and 1,3-bis(1,3,5-trimethylphenyl)imidazol-2-ylidene (IMes)] to the linear two-coordinate bis(amido) transition-metal complexes, M{N(SiMe3)Dipp}2 [M = Fe (1), Co (2), and Ni (3)] were determined by electronic absorption spectroscopy. In addition, 1H NMR spectroscopy was used to study the complexation of M{N(SiMe3)Dipp}2 by THF. The binding constants of the less bulky amido complexes [M{N(SiMe3)2}2]2 (M = Fe or Co; the nickel species is unstable) were also measured and found to bind THF 102-103 times more strongly than M{N(SiMe3)Dipp}2. Furthermore, unlike the corresponding -N(SiMe3)Dipp complexes, where the iron species are more strongly complexed than those of cobalt, the --N(SiMe3)2 species [Co{N(SiMe3)2}2]2 displayed a higher binding constant to THF than [Fe{N(SiMe3)2}2]2, which is in agreement with the stronger association of the [Co{N(SiMe3)2}2]2 dimer in comparison to that of its iron analogue. The binding strengths of the ligands to 1-3 were found to be in the order of DMAP > pyridine > PMe3 > PCy3 ≈ IMes > THF > THT, and those of the respective metals were in the order of Fe > Co > Ni.",
author = "Chun-Yi Lin and Fettinger, {James C.} and Power, {Philip P.}",
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Reversible Complexation of Lewis Bases to Low-Coordinate Fe(II), Co(II), and Ni(II) Amides : Influence of the Metal, Donor Ligand, and Amide Substituent on Binding Constants. / Lin, Chun-Yi; Fettinger, James C.; Power, Philip P.

In: Inorganic Chemistry, Vol. 56, No. 16, 21.08.2017, p. 9892-9902.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Reversible Complexation of Lewis Bases to Low-Coordinate Fe(II), Co(II), and Ni(II) Amides

T2 - Influence of the Metal, Donor Ligand, and Amide Substituent on Binding Constants

AU - Lin, Chun-Yi

AU - Fettinger, James C.

AU - Power, Philip P.

PY - 2017/8/21

Y1 - 2017/8/21

N2 - The binding constants of several monodentate Lewis bases (L) having different donor atoms [L = tetrahydrofuran (THF), tetrahydrothiophene (THT), pyridine, 4-(dimethylamino)pyridine (DMAP), PMe3, PCy3, and 1,3-bis(1,3,5-trimethylphenyl)imidazol-2-ylidene (IMes)] to the linear two-coordinate bis(amido) transition-metal complexes, M{N(SiMe3)Dipp}2 [M = Fe (1), Co (2), and Ni (3)] were determined by electronic absorption spectroscopy. In addition, 1H NMR spectroscopy was used to study the complexation of M{N(SiMe3)Dipp}2 by THF. The binding constants of the less bulky amido complexes [M{N(SiMe3)2}2]2 (M = Fe or Co; the nickel species is unstable) were also measured and found to bind THF 102-103 times more strongly than M{N(SiMe3)Dipp}2. Furthermore, unlike the corresponding -N(SiMe3)Dipp complexes, where the iron species are more strongly complexed than those of cobalt, the --N(SiMe3)2 species [Co{N(SiMe3)2}2]2 displayed a higher binding constant to THF than [Fe{N(SiMe3)2}2]2, which is in agreement with the stronger association of the [Co{N(SiMe3)2}2]2 dimer in comparison to that of its iron analogue. The binding strengths of the ligands to 1-3 were found to be in the order of DMAP > pyridine > PMe3 > PCy3 ≈ IMes > THF > THT, and those of the respective metals were in the order of Fe > Co > Ni.

AB - The binding constants of several monodentate Lewis bases (L) having different donor atoms [L = tetrahydrofuran (THF), tetrahydrothiophene (THT), pyridine, 4-(dimethylamino)pyridine (DMAP), PMe3, PCy3, and 1,3-bis(1,3,5-trimethylphenyl)imidazol-2-ylidene (IMes)] to the linear two-coordinate bis(amido) transition-metal complexes, M{N(SiMe3)Dipp}2 [M = Fe (1), Co (2), and Ni (3)] were determined by electronic absorption spectroscopy. In addition, 1H NMR spectroscopy was used to study the complexation of M{N(SiMe3)Dipp}2 by THF. The binding constants of the less bulky amido complexes [M{N(SiMe3)2}2]2 (M = Fe or Co; the nickel species is unstable) were also measured and found to bind THF 102-103 times more strongly than M{N(SiMe3)Dipp}2. Furthermore, unlike the corresponding -N(SiMe3)Dipp complexes, where the iron species are more strongly complexed than those of cobalt, the --N(SiMe3)2 species [Co{N(SiMe3)2}2]2 displayed a higher binding constant to THF than [Fe{N(SiMe3)2}2]2, which is in agreement with the stronger association of the [Co{N(SiMe3)2}2]2 dimer in comparison to that of its iron analogue. The binding strengths of the ligands to 1-3 were found to be in the order of DMAP > pyridine > PMe3 > PCy3 ≈ IMes > THF > THT, and those of the respective metals were in the order of Fe > Co > Ni.

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U2 - 10.1021/acs.inorgchem.7b01387

DO - 10.1021/acs.inorgchem.7b01387

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