Molecules put under moderate pressure modify their conformations. When higher pressure is applied, soft bonds, like that between two metals, are also substantially affected.
A recent example from the Macchi's group is the "off-axis" Mn-Mn bond in crystalline Mn2(CO)10, investigated by synchrotron X-ray diffraction (at SLS-PSI) and by Raman spectroscopy, up to a pressure of 6 GPa (ca. 60.000 atm).
References:
-
P. Macchi, N. Casati, S. R. Evans, F. Gozzo, P. Simoncic, D. Tiana;
"An 'Off-axis' Mn-Mn bond in Mn2(CO)10 at high pressure"
Chem. Commun., 50, 12785, (2014);
doi:10.1039/C4CC90402H &
Chem. Commun., 50, 12824-12827, (2014);
doi:10.1039/C4CC04152F.
-
N. Casati, P. Macchi, A. Sironi;
"Molecular Crystals Under High Pressure: Theoretical and Experimental Investigations of the Solid-Solid Phase Transitions in [Co2(CO)6(XPh3)2] (X=P, As)"
Chemistry, Eur. J., 15, 4446-4457, (2009);
doi:10.1002/chem.200801528.
-
N. Casati, P. Macchi, A. Sironi;
"Staggered to Eclipsed Conformational Rearrangement of [Co2(CO)6(PPh3)2] in the Solid State: An X-ray Diffraction Study at High Pressure and Low Temperature"
Angew. Chem. Int. Ed., 44, 7736-7739, (2005);
doi:10.1002/anie.200502241.
|