Issue 37, 2018

Reversible coordination of N2 and H2 to a homoleptic S = 1/2 Fe(i) diphosphine complex in solution and the solid state

Abstract

The synthesis and characterisation of the S = 1/2 Fe(I) complex [Fe(depe)2]+[BArF4] ([1]+[BArF4]), and the facile reversible binding of N2 and H2 in both solution and the solid state to form the adducts [1·N2]+ and [1·H2]+, are reported. Coordination of N2 in THF is thermodynamically favourable under ambient conditions (1 atm; ΔG298 = −4.9(1) kcal mol−1), while heterogenous binding is more favourable for H2 than N2 by a factor of ∼300. [1·H2]+[BArF4] represents a rare example of a well-defined, open-shell, non-classical dihydrogen complex, as corroborated by ESR spectroscopy. The rapid exchange between N2 and H2 coordination under ambient conditions is unique for a paramagnetic Fe complex.

Graphical abstract: Reversible coordination of N2 and H2 to a homoleptic S = 1/2 Fe(i) diphosphine complex in solution and the solid state

Supplementary files

Article information

Article type
Edge Article
Submitted
23 Apr 2018
Accepted
17 Jul 2018
First published
18 Jul 2018
This article is Open Access

All publication charges for this article have been paid for by the Royal Society of Chemistry
Creative Commons BY license

Chem. Sci., 2018,9, 7362-7369

Reversible coordination of N2 and H2 to a homoleptic S = 1/2 Fe(I) diphosphine complex in solution and the solid state

L. R. Doyle, D. J. Scott, P. J. Hill, D. A. X. Fraser, W. K. Myers, A. J. P. White, J. C. Green and A. E. Ashley, Chem. Sci., 2018, 9, 7362 DOI: 10.1039/C8SC01841C

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