Interconversion of Molybdenum Imido and Amido Complexes by Proton Coupled Electron Transfer.

Title Interconversion of Molybdenum Imido and Amido Complexes by Proton Coupled Electron Transfer.
Authors P.James Chirik; M. Bezdek
Journal Angew Chem Int Ed Engl
DOI 10.1002/anie.201708406
Abstract

Interconversion of the molybdenum amido [(PhTpy)(PPh2Me)2Mo(NHtBuAr)][BArF24] [PhTpy = 4'-Ph-2,2',6',2"-terpyridine; tBuAr = 4-tert-butyl-C6H4; ArF24 = (C6H3-3,5-(CF3)2)4)] and imido [(PhTpy)(PPh2Me)2Mo(NtBuAr)][BArF24] complexes has been accomplished by proton coupled electron transfer (PCET). Tert-butylphenoxyl radical was used as an oxidant and the non-classical ammine complex [(PhTpy)(PPh2Me)2Mo(NH3)][BArF24] as the reductant. The amido N-H BDFE formed and cleaved in the sequence was experimentally bracketed between 45.8 and 52.3 kcal/mol, in agreement with a DFT-computed value of 48 kcal/mol. The N-H BDFE in combination with electrochemical data eliminate proton transfer as the first step in the N-H bond forming sequence and favor initial electron transfer or concerted pathways.

Citation P.James Chirik; M. Bezdek.Interconversion of Molybdenum Imido and Amido Complexes by Proton Coupled Electron Transfer.. Angew Chem Int Ed Engl. 2018. doi:10.1002/anie.201708406

Related Elements

Molybdenum

42 Mo 95.960000000 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.

Related Forms & Applications

Organometallics
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