Janus POCOP Pincer Complexes of Nickel
Posted on 2018-10-19 - 20:29
A phosphinite-based
dinickel pincer complex, {2,3,5,6-(iPr2PO)4C6}Ni2Cl2,
is synthesized by heating a mixture of 1,2,4,5-tetrahydroxybenzene, iPr2PCl, NiCl2, and
Et3N at 150 °C in a microwave reactor or refluxing
1,2,4,5-(iPr2PO)4C6H2 with NiCl2 and Et3N at 175–250 °C in a flask. Substitution of chlorides
by hydrides (from LiAlH4 or LiEt3BH) and methyl
groups (from MeLi) generates {2,3,5,6-(iPr2PO)4C6}Ni2H2 and {2,3,5,6-(iPr2PO)4C6}Ni2Me2, respectively.
Protonation of the methyl complex with HCO2H gives {2,3,5,6-(iPr2PO)4C6}Ni2(OCHO)2. Spectroscopic and crystallographic
data of these Janus POCOP pincer complexes are compared to those of
the analogous mononuclear complexes {2,6-(iPr2PO)2C6H3}NiX (X =
Cl, H, Me, and OCHO). The hydride complex {2,3,5,6-(iPr2PO)4C6}Ni2H2 reacts with phenylacetylene and CO2 to give insertion
products. It also catalyzes the reduction of CO2 with catecholborane
(HBcat) to yield CH3OBcat and catBOBcat with a turnover
frequency of 7.5 min–1. The stoichiometric and catalytic
activities of {2,3,5,6-(iPr2PO)4C6}Ni2H2 are compared
to those of {2,6-(iPr2PO)2C6H3}NiH.
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Wellala, Nadeesha
P. N.; Dong, Hai T.; Krause, Jeanette A.; Guan, Hairong (2018). Janus POCOP Pincer Complexes of Nickel. ACS Publications. Collection. https://doi.org/10.1021/acs.organomet.8b00619
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AUTHORS (4)
NW
Nadeesha
P. N. Wellala
HD
Hai T. Dong
JK
Jeanette A. Krause
HG
Hairong Guan
CATEGORIES
- Biochemistry
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