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Issue 6, 2017
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The pyrrole ring η2-hapticity bridged binuclear tricarbonyl Mo(0) and W(0) complexes: catalysis of regioselective hydroamination reactions and DFT calculations

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Abstract

Following the report of the ferrocene structure, metal complexes containing the heteroatom-substituted cyclopentadienyl (Cp) analogue, that is the η5 pyrrolyl ligand, have been reported. While the Cp ligand continues to be a favorite ligand in organometallics, the transition metal chemistry of the pyrrolyl ligand is still in the developing stage. In view of this, we carried out the reaction between the multidentate ligand 2,3,4,5-tetrakis(3,5-dimethylpyrazolylmethyl)pyrrole (LH) and Mo(CO)6 or [W(CO)3(CH3CN)3] and isolated two new binuclear tricarbonyl Mo(0) and W(0) complexes, [Mo2(CO)6(μ–η22-LH4N)] (1) and [W2(CO)6(μ–η22-LH4N)] (2). Their X-ray structural analyses showed that the metal centers are bridged by the double bonds of the central pyrrole ring (μ–η22), a rarely observed coordination mode. Interestingly, complex 1 is a catalyst precursor for the hydroamination reactions of phenylacetylene with a series of secondary amines at room temperature offering the regioselectively formed anti-Markovnikov product in excellent yields. In addition, DFT calculations were performed to understand the bonding nature of the pyrrole ring in 1 and 2 and to estimate the energy of six different conformations of LH.

Graphical abstract: The pyrrole ring η2-hapticity bridged binuclear tricarbonyl Mo(0) and W(0) complexes: catalysis of regioselective hydroamination reactions and DFT calculations

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Supplementary files

Article information


Submitted
24 Nov 2016
Accepted
09 Jan 2017
First published
10 Jan 2017

Dalton Trans., 2017,46, 1840-1847
Article type
Paper

The pyrrole ring η2-hapticity bridged binuclear tricarbonyl Mo(0) and W(0) complexes: catalysis of regioselective hydroamination reactions and DFT calculations

V. K. Jha, G. Mani, Y. R. Davuluri and A. Anoop, Dalton Trans., 2017, 46, 1840
DOI: 10.1039/C6DT04458A

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