Biomaterial Database

Quantitation of the ligand effect in oxo-transfer reactions of dioxo-Mo(VI) trispyrazolyl borate complexes. 2013

Partha Basu, and Brian W Kail, and Andrew K Adams, and Victor N Nemykin

Department of Chemistry and Biochemistry, Duquesne University, Pittsburgh, PA 15228, USA. basu@duq.edu

The oxygen atom transfer reactivity (OAT) of dioxo-Mo(VI) complexes of hydrotrispyrazolyl borate (hydrotris(3,5-dimethylpyrazolyl)borate, Tp(Me2); hydrotris(3-isopropylpyrazol-1-yl)borate, Tp(iPr)) with tertiary phosphines (PMe(3), PMe(2)Ph, PEt(3), PEt(2)Ph, PBu(n)(3), PMePh(2), or PEtPh(2)) has been investigated. In acetonitrile, these reactions proceed via the formation of a phosphoryl intermediate complex that undergoes a solvolysis reaction. We report the synthesis and characterization of several phosphoryl complexes. The rates of formation of phosphoryl complexes and their solvation were determined by spectrophotometry. The rates of the reactions and the properties of the phosphoryl species were investigated using the Quantitative Analysis of Ligand Effect (QALE) methodology. The results show that, at least in this system, the first step of the reaction is controlled primarily by the steric factor, and in the second step, both electronic and steric factors are important. We also analyzed the effect of ligands on the reaction rate i.e., Tp(Me2)vs. Tp(iPr).

UI	MeSH Term	Description	Entries
D007700	Kinetics	The rate dynamics in chemical or physical systems.
D008024	Ligands	A molecule that binds to another molecule, used especially to refer to a small molecule that binds specifically to a larger molecule, e.g., an antigen binding to an antibody, a hormone or neurotransmitter binding to a receptor, or a substrate or allosteric effector binding to an enzyme. Ligands are also molecules that donate or accept a pair of electrons to form a coordinate covalent bond with the central metal atom of a coordination complex. (From Dorland, 27th ed)	Ligand
D008982	Molybdenum	A metallic element with the atomic symbol Mo, atomic number 42, and atomic weight 95.95. It is an essential trace element, being a component of the enzymes xanthine oxidase, aldehyde oxidase, and nitrate reductase.	Molybdenum-98,Molybdenum 98
D009942	Organometallic Compounds	A class of compounds of the type R-M, where a C atom is joined directly to any other element except H, C, N, O, F, Cl, Br, I, or At. (Grant & Hackh's Chemical Dictionary, 5th ed)	Metallo-Organic Compound,Metallo-Organic Compounds,Metalloorganic Compound,Organometallic Compound,Metalloorganic Compounds,Compound, Metallo-Organic,Compound, Metalloorganic,Compound, Organometallic,Compounds, Metallo-Organic,Compounds, Metalloorganic,Compounds, Organometallic,Metallo Organic Compound,Metallo Organic Compounds
D010084	Oxidation-Reduction	A chemical reaction in which an electron is transferred from one molecule to another. The electron-donating molecule is the reducing agent or reductant; the electron-accepting molecule is the oxidizing agent or oxidant. Reducing and oxidizing agents function as conjugate reductant-oxidant pairs or redox pairs (Lehninger, Principles of Biochemistry, 1982, p471).	Redox,Oxidation Reduction
D010100	Oxygen	An element with atomic symbol O, atomic number 8, and atomic weight [15.99903; 15.99977]. It is the most abundant element on earth and essential for respiration.	Dioxygen,Oxygen-16,Oxygen 16
D010720	Phosphines	Inorganic or organic compounds derived from phosphine (PH3) by the replacement of H atoms. (From Grant & Hackh's Chemical Dictionary, 5th ed)
D011720	Pyrazoles	Azoles of two nitrogens at the 1,2 positions, next to each other, in contrast with IMIDAZOLES in which they are at the 1,3 positions.
D001881	Borates	Inorganic or organic salts and esters of boric acid.	Borate
D012997	Solvents	Liquids that dissolve other substances (solutes), generally solids, without any change in chemical composition, as, water containing sugar. (Grant & Hackh's Chemical Dictionary, 5th ed)	Solvent