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Publications in Scientific Journals:

J. Pecak, W. Eder, B. Stöger, S. Realista, P. Martinho, M.J. Calhorda, W. Linert, K. Kirchner:
"Synthesis, Characterization, and Catalytic Reactivity of {CoNO}8 PCP Pincer Complexes";
Organometallics, 39 (2020), 2594 - 2601.



English abstract:
The reaction of coordinatively unsaturated Co(II) PCP pincer complexes with nitric oxide leads to the formation of new, air-stable, diamagnetic mono nitrosyl compounds. The synthesis and characterization of five- and four-coordinate Co(III) and Co(I) nitrosyl pincer complexes based on three different ligand scaffolds is described. Passing NO through a solution of [Co(PCPNMe-iPr)Cl], [Co(PCPO-iPr)Cl] or [Co(PCPCH2-iPr)Br] led to the formation of the low-spin complex [Co(PCP-iPr)(NO)- X] with a strongly bent NO ligand. Treatment of the latter species with (X = Cl, Br) AgBF4 led to chloride abstraction and formation of cationic square-planar Co(I) complexes of the type [Co(PCPiPr)( NO)]+ featuring a linear NO group. This reaction could be viewed as a formal two electron reduction of the metal center by the NO radical from Co(III) to Co(I), if NO is counted as NO+. Hence, these systems can be described as {CoNO}8 according to the Enemark−Feltham convention. X-ray structures, spectroscopic and electrochemical data of all nitrosyl complexes are presented. Preliminary studies show that [Co(PCPNMe-iPr)(NO)]+ catalyzes efficiently the reductive hydroboration of nitriles with pinacolborane (HBpin) forming an intermediate {CoNO}8 hydride species.


"Official" electronic version of the publication (accessed through its Digital Object Identifier - DOI)
http://dx.doi.org/10.1021/acs.organomet.0c00167


Created from the Publication Database of the Vienna University of Technology.