Planar-Locked Ru-PNN Catalysts in 1‑Phenylethanol Dehydrogenation

• Published in: Organometallics 2020-10, Vol.39 (20), p.3628-3644
• Main Authors: Fanara, Paul M, MacMillan, Samantha N, Lacy, David C
• Format: Article
• Language: English
• ISSN: 0276-7333; 1520-6041
• DOI: 10.1021/acs.organomet.0c00327

Ru-PNN pincer catalysts of the general form [{PNN}­Ru­(H)­(Cl)­(CO)] can dehydrogenate alcohols through inner- and outer-sphere mechanisms, but determining the favored path is challenging. To address this challenge, the following planar-locked quinoline-based PNN ligands, which cannot form key inner-sphere transition states and intermediates, were synthesized: 2-((ditertbutyl­phosphaneyl)­methyl)-N,N-diethylquinolin-8-amine (QNPtBu), 2-((diisopropyl­phosphaneyl)­methyl)-N,N-diethyl­quinolin-8-amine (QNPiPr), and 2-((diphenyl­phosphaneyl)­methyl)-N,N-diethyl­quinolin-8-amine (QNPPh). In addition to the quinoline-derived ligands, we also prepared the isoquinoline PNN ligand N-((1-((ditert-butylphosphaneyl)­methyl)­isoquinolin-3-yl)­methyl)-N-ethylethanamine (IsoQNP) and two known picoline- and lutidine-derived ligands 2-((ditert-butylphosphaneyl)­methyl)­pyridine (PicP) and 2-((ditert-butylphosphaneyl)­methyl)-6-methylpyridine (LutP). These six ligands were coordinated to Ru­(II) ions to prepare six new complexes of the general formulation [{L}­Ru­(H)­(Cl)­(CO)] analogous to Milstein’s PNN catalyst precursor (1PyCl). The X-ray structural, NMR, UV–vis, and FTIR spectroscopic properties of the new complexes are similar to parent complex 1PyCl and were used in catalytic 1-phenylethanol acceptor-less and transfer dehydrogenation. The comparative results demonstrate that 1Py outperforms the other catalysts. DFT reaction profiles were computed for 1Py and the planar-locked catalysts. The results suggest that 1Py has access to a lower-energy inner-sphere path, whereas the planar-locked catalysts can only proceed through a high-energy outer-sphere mechanism and may even get trapped in unreactive alkoxide sinks.