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Conformation controlled stepwise hydride shuffling from the metal to the ligand backbone

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Abstract

The benzo annulated cycloheptatriene PCP pincer ruthenium hydrido dicarbonyl complex syn-2 was prepared in one step by treatment of the ligand 1 with Ru3(CO)12. Protonation of syn-2 with the superacid [H(Et2O)2][BArF24] {[BArF24] = tetrakis[bis(trifluoromethyl)phenyl]borate} initiates the highly stereoselective hydrogenation of one of the double bonds in the cycloheptatriene backbone. This results in the formation of the pentacoordinate cationic 16-electron dicarbonyl ruthenium complex 3. Hydrogenation of 3 with LiAlH4 generates the hydride complexes syn-4 and anti-4 which after protonation allow isolation of the symmetric 5. In 5 a second double bond of the cycloheptatriene backbone was hydrogenated. Complex 5 was also obtained directly by the reaction of 3 with hydrogen (1 bar). Storage of 5 under a hydrogen atmosphere yields two pairs of η2-H2 complexes (syn-7, anti-7) which are in a tautomeric equilibrium with their corresponding dihydrides (syn-8, anti-8). A stepwise transfer of the hydrides to the ligand backbone can be deduced from the distribution of deuterium along the seven membered ring after applying the deuterated reagents (D+, D2). The observed stereochemistry suggests that the hydride transfer is controlled by conformational constraints.

Graphical abstract: Conformation controlled stepwise hydride shuffling from the metal to the ligand backbone

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Supplementary files

Article information


Submitted
20 Apr 2020
Accepted
09 May 2020
First published
11 May 2020

Dalton Trans., 2020, Advance Article
Article type
Paper

Conformation controlled stepwise hydride shuffling from the metal to the ligand backbone

N. R. Wiedmaier, H. Speth, G. Leistikow, K. Eichele, H. Schubert, H. A. Mayer and L. Wesemann, Dalton Trans., 2020, Advance Article , DOI: 10.1039/D0DT01431A

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