Synthesis of Camphor-Derived Bis(pyrazolylpyridine) Rhodium(III) Complexes: Structure-Reactivity Relationships and Biological Activity

Journal article


Publication Details

Author(s): Petrovic A, Milutinovic MM, Petri ET, Zivanovic M, Milivojevic N, Puchta R, Scheurer A, Korzekwa J, Klisuric OR, Bogojeski J
Journal: Inorganic Chemistry
Publication year: 2019
Volume: 58
Journal issue: 1
Pages range: 307-319
ISSN: 0020-1669
eISSN: 1520-510X


Abstract


Two novel rhodium(III) complexes, namely, [Rh
III
(X)Cl
3
] (X = 2 2,6-bis((4S,7R)-7,8,8-trimethyl-4,5,6,7-tetrahydro-1H-4,7-methanoindazol-3-yl)pyridine or 2,6-bis((4S,7R)-1,7,8,8-tetramethyl-4,5,6,7-tetrahydro-1H-4,7-methanoindazol-3-yl)pyridine), were synthesized from camphor derivatives of a bis(pyrazolylpyridine), tridentate nitrogen-donor chelate system, giving [Rh
III
(H
2
L∗)Cl
3
] (1a) and [Rh
III
(Me
2
L∗)Cl
3
] (1b). A rhodium(III) terpyridine (terpy) ligand complex, [Rh
III
(terpy)Cl
3
] (1c), was also synthesized. By single-crystal X-ray analysis, 1b crystallizes in an orthorhombic P2
1
2
1
2
1
system, with two molecules in the asymmetric unit. Tridentate coordination by the N,N,N-donor localizes the central nitrogen atom close to the rhodium(III) center. Compounds 1a and 1b were reactive toward l-methionine (l-Met), guanosine-5′-monophosphate (5′-GMP), and glutathione (GSH), with an order of reactivity of 5′-GMP > GSH > l-Met. The order of reactivity of the Rh
III
complexes was: 1b> 1a > 1c. The Rh
III
complexes showed affinity for calf thymus DNA and bovine serum albumin by UV-vis and emission spectral studies. Furthermore, 1b showed significant in vitro cytotoxicity against human epithelial colorectal carcinoma cells. Since the Rh
III
complexes have similar coordination modes, stability differences were evaluated by density functional theory (DFT) calculations (B3LYP(CPCM)/LANL2DZp). With (H
2
L∗) and (terpy) as model ligands, DFT calculations suggest that both tridentate ligand systems have similar stability. In addition, molecular docking suggests that all test compounds have affinity for the minor groove of DNA, while 1b and 1c have potential for DNA intercalation.


FAU Authors / FAU Editors

Korzekwa, Jana
Lehrstuhl für Anorganische und Allgemeine Chemie
Puchta, Ralph PD Dr.
Professur für Paläontologie (Schwerpunkt Faziesanalyse)
Scheurer, Andreas Dr.
Lehrstuhl für Anorganische und Allgemeine Chemie


External institutions with authors

University of Kragujevac
University of Novi Sad


How to cite

APA:
Petrovic, A., Milutinovic, M.M., Petri, E.T., Zivanovic, M., Milivojevic, N., Puchta, R.,... Bogojeski, J. (2019). Synthesis of Camphor-Derived Bis(pyrazolylpyridine) Rhodium(III) Complexes: Structure-Reactivity Relationships and Biological Activity. Inorganic Chemistry, 58(1), 307-319. https://dx.doi.org/10.1021/acs.inorgchem.8b02390

MLA:
Petrovic, Angelina, et al. "Synthesis of Camphor-Derived Bis(pyrazolylpyridine) Rhodium(III) Complexes: Structure-Reactivity Relationships and Biological Activity." Inorganic Chemistry 58.1 (2019): 307-319.

BibTeX: 

Last updated on 2019-19-08 at 13:08