Trans Ligand Determines the Stability of Paramagnetic Manganese(II) Hydrides of the Type trans -[MnH(L)(dmpe) 2 ] + Where L is PMe 3 , C 2 H 4 , or CO.

Paramagnetic metal hydride (PMH) complexes play important roles in catalytic applications and bioinorganic chemistry. 3d PMH chemistry has largely focused on Ti, Mn, Fe, and Co. Various Mn PMHs have been proposed as intermediates in catalysis, but isolated Mn PMHs are limited to dimeric high-spin Mn structures with bridging hydrides. In this paper, a series of the first low-spin monomeric Mn PMH complexes are generated by chemical oxidation of their Mn analogues. This series is of the type -[MnH(L)(dmpe)] where the ligand L is PMe, CH, or CO [dmpe is 1,2-bis(dimethylphosphino)ethane], and the thermal stability of the Mn hydride complexes was found to be strongly dependent on the identity of the ligand. When L is PMe, the complex is the first example of an isolated monomeric Mn hydride complex. In contrast, when L is CH or CO, the complexes are only stable at low temperatures; upon warming to room temperature, the former decomposed to afford [Mn(dmpe)], accompanied by ethane and ethylene, whereas the latter eliminated H, generating [Mn(MeCN)(CO)(dmpe)] or a mixture of products including [Mn(κ-PF)(CO)(dmpe)], depending on the reaction conditions. All PMHs were characterized by low-temperature electron paramagnetic resonance (EPR) spectroscopy, and stable [MnH(PMe)(dmpe)] was further characterized by UV-vis and IR spectroscopy, Superconducting Quantum Interference Device magnetometry, and single-crystal X-ray diffraction. Noteworthy spectral properties are the significant EPR superhyperfine coupling to the hydride (∼85 MHz) and an increase (+33 cm) in the Mn-H IR stretch upon oxidation. Density functional theory calculations were also employed to gain insights into the acidity and bond strengths of the complexes. Mn-H bond dissociation free energies are estimated to decrease in the series of complexes from 60 (L = PMe) to 47 kcal/mol (L = CO).