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Examining the Generality of Metal-Ligand Cooperativity Across a Series of First-Row Transition Metals: Capture, Bond Activation, and Stabilization.

ABSTRACT: We outline the generality and requirements for cooperative N₂H₄ capture, N-N bond scission, and amido stabilization across a series of first-row transition metal complexes bearing a pyridine(dipyrazole) ligand. This ligand contains a pair of flexibly tethered trialkylborane Lewis acids that enable hydrazine capture and M-NH₂ stabilization. While the Lewis acids are required to bind N₂H₄, the identity of the metal dictates whether N-N bond scission can occur. The redox properties of the M(II) bis(amidoborane) series of complexes were investigated and reveal that ligand-based events prevail; oxidation results in the generation of a transiently formed aminyl radical, while reduction occurs at the redox-active pyridine(dipyrazole) ligand.

SUBMITTER: Kiernicki JJ

PROVIDER: S-EPMC7340558 | biostudies-literature | 2020 Jul

REPOSITORIES: biostudies-literature

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Examining the Generality of Metal-Ligand Cooperativity Across a Series of First-Row Transition Metals: Capture, Bond Activation, and Stabilization.

Kiernicki John J JJ Zeller Matthias M Szymczak Nathaniel K NK

Inorganic chemistry 20200618 13

We outline the generality and requirements for cooperative N2H4 capture, N-N bond scission, and amido stabilization across a series of first-row transition metal complexes bearing a pyridine(dipyrazole) ligand. This ligand contains a pair of flexibly tethered trialkylborane Lewis acids that enable hydrazine capture and M-NH2 stabilization. While the Lewis acids are required to bind N2H4, the identity of the metal dictates whether N-N bond sc ...[more]

PMID: 32551605

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Project description:Aspartate carbamoyltransferase (ATCase) is a large dodecameric enzyme with six active sites that exhibits allostery: its catalytic rate is modulated by the binding of various substrates at distal points from the active sites. A recently developed method, bond-to-bond propensity analysis, has proven capable of predicting allosteric sites in a wide range of proteins using an energy-weighted atomistic graph obtained from the protein structure and given knowledge only of the location of the active site. Bond-to-bond propensity establishes if energy fluctuations at given bonds have significant effects on any other bond in the protein, by considering their propagation through the protein graph. In this work, we use bond-to-bond propensity analysis to study different aspects of ATCase activity using three different protein structures and sources of fluctuations. First, we predict key residues and bonds involved in the transition between inactive (T) and active (R) states of ATCase by analysing allosteric substrate binding as a source of energy perturbations in the protein graph. Our computational results also indicate that the effect of multiple allosteric binding is non linear: a switching effect is observed after a particular number and arrangement of substrates is bound suggesting a form of long range communication between the distantly arranged allosteric sites. Second, cooperativity is explored by considering a bisubstrate analogue as the source of energy fluctuations at the active site, also leading to the identification of highly significant residues to the T ↔ R transition that enhance cooperativity across active sites. Finally, the inactive (T) structure is shown to exhibit a strong, non linear communication between the allosteric sites and the interface between catalytic subunits, rather than the active site. Bond-to-bond propensity thus offers an alternative route to explain allosteric and cooperative effects in terms of detailed atomistic changes to individual bonds within the protein, rather than through phenomenological, global thermodynamic arguments.

Dataset Information

Examining the Generality of Metal-Ligand Cooperativity Across a Series of First-Row Transition Metals: Capture, Bond Activation, and Stabilization.

Publications

Examining the Generality of Metal-Ligand Cooperativity Across a Series of First-Row Transition Metals: Capture, Bond Activation, and Stabilization.

Similar Datasets

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