Two cobalt complexes containing coordinated N-heterocyclic phosphenium (NHP(+)) ligands are synthesized using a bidentate NHP(+)/phosphine chelating ligand, [PP](+). Treatment of Na[Co(CO)4] with the chlorophosphine precursor [PP]Cl (1) affords [PP]Co(CO)2 (2), which features a planar geometry at the NHP(+) phosphorus center and a short Co-P distance [1.9922(4) Å] indicative of a Co═P double bond. The more electron-rich complex [PP]Co(PMe3)2 (3), which is synthesized in a one-pot reduction procedure with 1, CoCl2, PMe3, and KC8, has an even shorter Co-P bond [1.9455(6) Å] owing to stronger metal-to-phosphorus back-donation. The redox properties of 2 and 3 were explored using cyclic voltammetry, and oxidation of 3 was achieved to afford [[PP]Co(PMe3)2](+) (4). The electron paramagnetic resonance spectrum of complex 4 features hyperfine coupling to both (59)Co and (31)P, suggesting strong delocalization of the unpaired electron density in this complex. Density functional theory calculations are used to further explore the bonding and redox behavior of complexes 2-4, shedding light on the potential for redox noninnocent behavior of NHP(+) ligands.
This research output has an Altmetric Attention Score of 2. This is our high-level measure of the quality and quantity of online attention that it has received. This Attention Score, as well as the ranking and number of research outputs shown below, was calculated when the research output was last mentioned on 22 December 2016.
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