Reversible modulation of the redox characteristics of acid-sensitive molybdenum and tungsten scorpionate complexes.

Title Reversible modulation of the redox characteristics of acid-sensitive molybdenum and tungsten scorpionate complexes.
Authors A.J. Heyer; P.J. Shivokevich; S.L. Hooe; K.D. Welch; D. Harman; C.W. Machan
Journal Dalton Trans
DOI 10.1039/c8dt00598b
Abstract

The large-scale synthesis of the scorpionate ligand Ttz (hydrotris(1,2,4-triazol-1-yl)borate) is reported as well as syntheses of Group VI complexes K[M(L)(CO)3] and M(L)(NO)(CO)2 (L = Ttz or Tp (hydrotris(pyrazol-1-yl)borate), M = Mo or W). The redox characteristics of the metal in these Ttz complexes are shown to be reversibly modulated by interactions between the exo-4-N lone pairs of the triazolyl rings and Brønsted or Lewis acids. The basicity of the scorpionate ligand in [M(Ttz)(CO)3]- is quantified (pKaH2O values range from 1.1 to 4.6) and found to be dependent on both the oxidation state and identity of the metal. In the presence of Brønsted acids, the observed redox behavior for the one-electron oxidation of the Group VI metal center is consistent with a proton-coupled electron transfer (PCET). Indeed, for both Mo and W derivatives, a one-electron oxidation decreases the pKa by ?3.5 units.

Citation A.J. Heyer; P.J. Shivokevich; S.L. Hooe; K.D. Welch; D. Harman; C.W. Machan.Reversible modulation of the redox characteristics of acid-sensitive molybdenum and tungsten scorpionate complexes.. Dalton Trans. 2018;47(18):63236332. doi:10.1039/c8dt00598b

Related Elements

Molybdenum

See more Molybdenum products. Molybdenum (atomic symbol: Mo, atomic number: 42) is a Block D, Group 6, Period 5 element with an atomic weight of 95.96. Molybdenum Bohr ModelThe number of electrons in each of molybdenum's shells is [2, 8, 18, 13, 1] and its electron configuration is [Kr] 4d5 5s1. The molybdenum atom has a radius of 139 pm and a Van der Waals radius of 209 pm. In its elemental form, molybdenum has a gray metallic appearance. Molybdenum was discovered by Carl Wilhelm in 1778 and first isolated by Peter Jacob Hjelm in 1781. Molybdenum is the 54th most abundant element in the earth's crust. Elemental MolybdenumIt has the third highest melting point of any element, exceeded only by tungsten and tantalum. Molybdenum does not occur naturally as a free metal, it is found in various oxidation states in minerals. The primary commercial source of molybdenum is molybdenite, although it is also recovered as a byproduct of copper and tungsten mining. The origin of the name Molybdenum comes from the Greek word molubdos meaning lead.

Tungsten

See more Tungsten products. Tungsten (atomic symbol: W, atomic number: 74) is a Block D, Group 6, Period 6 element with an atomic weight of 183.84. The number of electrons in each of tungsten's shells is [2, 8, 18, 32, 12, 2] and its electron configuration is [Xe] 4f14 5d4 6s2. Tungsten Bohr ModelThe tungsten atom has a radius of 139 pm and a Van der Waals radius of 210 pm. Tungsten was discovered by Torbern Bergman in 1781 and first isolated by Juan José Elhuyar and Fausto Elhuyar in 1783. In its elemental form, tungsten has a grayish white, lustrous appearance. Elemental TungstenTungsten has the highest melting point of all the metallic elements and a density comparable to that or uranium or gold and about 1.7 times that of lead. Tungsten alloys are often used to make filaments and targets of x-ray tubes. It is found in the minerals scheelite (CaWO4) and wolframite [(Fe,Mn)WO4]. In reference to its density, Tungsten gets its name from the Swedish words tung and sten, meaning heavy stone.

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