Help Privacy Policy Disclaimer
  Advanced SearchBrowse




Journal Article

Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0)


Jerabek,  Paul
Centre for Theoretical Chemistry and Physics, The New Zealand Institute for Advanced Study and the Institute for Natural and Mathematical Sciences, Massey University;
Research Department Neese, Max-Planck-Institut für Kohlenforschung, 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

Vondung, L., Jerabek, P., & Langer, R. (2019). Ligands Based on Phosphine‐Stabilized Aluminum(I), Boron(I), and Carbon(0). Chemistry – A European Journal, 25(12), 3068-3076. doi:10.1002/chem.201805123.

Cite as: http://hdl.handle.net/21.11116/0000-0003-D056-1
A systematic quantum chemical study of the bonding in d6‐transition‐metal complexes, containing phosphine‐stabilized, main‐group‐element fragments, (R3P)2E, as ligands (E=AlH, BH, CH+, C), is reported. By using energy decomposition analysis, it is demonstrated that a strong M−E bond is accompanied by weak P−E bonds, and vice versa. Although the Al−M bond is, for example, found to be very strong, the weak Al−P bond suggests that the corresponding metal complexes will not be stable towards phosphine dissociation. The interaction energies for the boron(I)‐based ligand are lower, but still higher than those for two‐carbon‐based ligands. For neutral ligands, electrostatic interactions are the dominating contributions to metal–ligand bonding, whereas for the cationic ligand a significant destabilization, with weak orbital and even weaker electrostatic metal–ligand interactions, is observed. Finally, for iron(II) complexes, it is demonstrated that different reactivity patterns are expected for the four donor groups: the experimentally observed reversible E−H reductive elimination of the borylene‐based ligand (E=BH) exhibits significantly higher barriers for the protonated carbodiphosphorane (CDP) ligand (E=CH) and would proceed through different intermediates and transition states. For aluminum, such reaction pathways are not feasible (E=AlH). Moreover, it is demonstrated that the metal hydrido complexes with CDP ligands might not be stable towards reduction and isomerization to a protonated CDP ligand and a reduced metal center.