Open AccessLow-Valent Molybdenum PNP Pincer Complexes as Catalysts for the Semihydrogenation of Alkynes
Author(s) -
Niklas F. Both,
Anke Spannenberg,
Kathrin Junge,
Matthias Beller
Publication year - 2022
Publication title -
organometallics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.231
H-Index - 172
eISSN - 1520-6041
pISSN - 0276-7333
DOI - 10.1021/acs.organomet.1c00709
Subject(s) - chemistry , diphenylacetylene , pincer movement , molybdenum , catalysis , ligand (biochemistry) , medicinal chemistry , pincer ligand , cooperativity , combinatorial chemistry , coordination sphere , polymer chemistry , stereochemistry , metal , photochemistry , inorganic chemistry , organic chemistry , biochemistry , receptor
Low-valent molybdenum PNP pincer complexes were studied as catalysts for the semihydrogenation of alkynes. For that purpose, t Bu-substituted PNP complexes PNP t Bu Mo(CO) 2 ( 6a ) and PNP t Bu Mo(CO) 3 ( 6c ) and the NNP complex NNP i Pr Mo(CO) 2 (PPh 3 ) (( rac )- 7 ) were synthesized and characterized. By utilizing the cyclohexyl-substituted complex PNP Cy Mo(CO) 2 (CH 3 CN) ( 5a ), several diphenylacetylene derivatives are transformed to the corresponding ( Z )-alkenes with good to very good diastereoselectivities (up to 91:9). Mechanistic experiments indicate an outer-sphere mechanism including metal-ligand cooperativity.