English
 
Help Privacy Policy Disclaimer
  Advanced SearchBrowse

Item

ITEM ACTIONSEXPORT

Released

Journal Article

Reactivity studies on [Cp′MnX(thf)]2: manganese amide and polyhydride synthesis

MPS-Authors
/persons/resource/persons237695

Römelt,  Michael
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

/persons/resource/persons216825

Neese,  Frank
Research Department Neese, Max Planck Institute for Chemical Energy Conversion, Max Planck Society;

External Resource
No external resources are shared
Fulltext (public)
There are no public fulltexts stored in PuRe
Supplementary Material (public)
There is no public supplementary material available
Citation

Maekawa, M., Römelt, M., Daniliuc, C. G., Jones, P. G., White, P. S., Neese, F., et al. (2012). Reactivity studies on [Cp′MnX(thf)]2: manganese amide and polyhydride synthesis. Chemical Science, 3(10), 2972-2979. doi:10.1039/C2SC20737K.


Cite as: http://hdl.handle.net/21.11116/0000-0007-E5B4-B
Abstract
The sterically encumbered 1,2,4-(Me3C)3C5H2 (Cp′) ligand allows the synthesis of stable high spin mono(cyclopentadienyl) manganese complexes [Cp′MnX(thf)]2 (X = Cl, Br, I; 1-X). Thermal stabilities of 1-X toward ligand redistribution to [Cp2′Mn] (2) and MnX2 depend on the bridging halide ligand. The kinetic stability of 1-I in solution even at elevated temperatures is noteworthy. Complexes 1 are useful starting materials for further functionalizations. Metathesis of 1-Cl with [LiN(SiMe3)2(OEt2)]2 yields the 13 valence-electron (VE) complex, [Cp′MnN(SiMe3)2] (3), while the manganese polyhydride cluster, [{Cp′Mn}4{MnH6}], was formed in the reaction of 1-I and KHBEt3. The 17 VE [MnH6]4− core of 4 is effectively shielded by four high spin [Cp′Mn]+ units. Magnetic susceptibility studies on 4 suggest weak electron exchange coupling between the spin carriers, but the spin state of the central [MnH6]4− fragment remained ambiguous. Therefore, the electronic structure of 4 was also analyzed by broken symmetry (BS) DFT calculations, which provided strong evidence for a low spin [MnH6]4− unit in agreement with previous spectrochemical studies performed on [FeH6]4−.