Abstract
A series of iron(II) hydride complexes containing diphenylphosphine ligands is reported. In the presence of five equivalents of Ph2PH, the ionic complex trans-[(Ph2PH)4Fe(H)(NCMe)](Ph2P{BH3}2) (1) with the rather unusual Ph2P{BH3}2-anion is formed, whereas with four equivalents of Ph2PH, the fluxional cis-[(Ph2PH)4Fe(H)2] (2) can be isolated under otherwise identical conditions. Furthermore, our attempts to synthesize a mixed phosphine iron(II) hydride complex resulted in the isolation of [(dppe)(Ph2PH)Fe(H)(BH4)] (3, dppe = 1,2-bis(diphenylphosphino)ethane). The behavior of complexes 1-3 in solution was investigated by 1H NOESY NMR spectroscopy and compared with those of the corresponding ruthenium complex cis-[(Ph2PH)4Ru(H)2], revealing that no chemical exchange between the hydride ligands and the P–H-proton of the coordinated Ph2PH can be observed.
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