Cobalt Phosphino-α-Iminopyridine-Catalyzed Hydrofunctionalization of Alkenes: Catalyst Development and Mechanistic Analysis
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https://figshare.com/articles/dataset/Cobalt_Phosphino-_-Iminopyridine-Catalyzed_Hydrofunctionalization_of_Alkenes_Catalyst_Development_and_Mechanistic_Analysis/3749415
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资源简介：
A family of CoCl2(PNpy) complexes were prepared, where
PNpy = 2-iminopyridyl-phosphine ligands derived from aminoalkyl and
aminoaryl phosphines and 2-keto- and 2-formylpyridines. Reduction
of CoCl2(PNpy) complexes in the presence of PPh3 gave CoH(PNpy)(PPh3) and CoMe(PNpy)(PPh3),
which were active for hydrofunctionalization of alkenes. According
to DFT calculations, the CoMe(PNpy)(PPh3) complexes are
best described as Co(II) derivatives of the anion [PNpy]−, with a labile PPh3 coligand. Metalation of Na[Ph2PC2NHpy] gave the dimers [CoCl(Ph2PC2NHpy)]2. Monomeric complexes catalyze hydrosilylation of
1-octene with Ph2SiH2, with the CoCl2(iPr2PC3NHpy)/2NaBEt3H system exhibiting the highest rate and selectivity for anti-Markovnikov
product. In situ NMR studies established the following: (i) silanes
protonolyze catalyst precursors to give the Co-silyl complexes Co(SiR3)(Ph2PC6H4NPhpy)(PPh3), (ii) alkenes compete with PPh3 to give Co(SiHPh2)(Ph2PC6H4NPhpy)(η2-alkene), (iii) ethylene inserts into the Co–Si bond
to give Co(CH2CH2SiR3)(Ph2PC6H4NPhpy)(PPh3).
创建时间：
2016-09-06
