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.
N1 - Publisher Copyright:
© 2017 American Chemical Society.
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
M3 - Article
C2 - 28758744
AN - SCOPUS:85027674781
SN - 0020-1669
VL - 56
SP - 9892
EP - 9902
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 16
ER -