The iron hydrido complex [FeH(dppe)2]⁺: Solution and solid-state reactivity with dinitrogen

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2006

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The blue compound [FeH(dppe)2]BPh4 (1) (dppe = 1,2-bis(diphenylphosphino)ethane) is investigated by optical absorption, - vibrational, NMR and Mössbauer spectroscopy as well as magnetic susceptibility measurements. In the solid state, 1 is found to be paramagnetic (S= 1) whereas in tetrahydrofuran (thf) solution it is diamagnetic. Importantly, 1 reacts with dinitrogen in thf solution and in the solid state to give the yellow and green dinitrogen complexes 2a and 2b, respectively, both of which have the formula [FeH(N2)(dPPe)2]BPh4. Apart from their colour and optical spectroscopic properties, the dinitrogen compounds 2a and 2b also differ in their magnetic, Mössbauer and vibrational properties. The N-N stretching frequency of 2a is found at 2120 cm-1 whereas 2b exhibits an N-N stretching vibration of 2145 cm -1. Moreover, 2a is diamagnetic whereas 2b is paramagnetic. DFT is employed to determine the relative energies and structure of 1 and its dinitrogen adducts in the singlet and triplet state. © 2006 Wiley-VCH Verlag GmbH & Co. KGaA.

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The iron hydrido complex [FeH(dppe)2]+: Solution and solid-state reactivity with dinitrogen