756876-44-5Relevant academic research and scientific papers
Chemical ligand non-innocence in pyridine diimine Rh complexes
Kooistra, T. Martijn,Hetterscheid, Dennis G.H.,Schwartz, Erik,Knijnenburg, Quinten,Budzelaar, Peter H.M.,Gal, Anton W.
, p. 2945 - 2952 (2008/10/09)
The formation and reactivity of pyridine diimine rhodium(I) alkyl complexes without β-hydrogens (Me, Bz, CH2SiMe3) is described. In contrast to the corresponding cobalt complexes, the rhodium complexes could not be activated to polymerise ethene. Rh ethyl complexes could not be prepared. Examples of hydrogen transfer to and from the ligand were observed, illustrating the active role the pyridine diimine ligand can play in the reactions of its complexes. Decomposition via loss of free ligand was observed in many cases, indicating that the pyridine diimine ligand is not a very suitable one for RhI.
The electronic structure of (diiminopyridine)cobalt(I) complexes
Knijnenburg, Quinten,Hetterscheid, Dennis,Martijn Kooistra,Budzelaar, Peter H. M.
, p. 1204 - 1211 (2007/10/03)
DFT calculations show that square-planar LCoIR complexes of a diiminopyridine ligand are best regarded as containing low-spin CoII antiferromagnetically coupled to a ligand radical anion. The lowest triplet state, corresponding to a 3dz2→π* excitation, is calculated to be only a few kcal/mol above the ground state, and is thermally accessible. The anomalous 1H NMR chemical shifts of the LCoR complexes are suggested to be due to thermal population of the triplet state at room temperature. Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004.
