Breaking bonds and breaking rules: inert-bond activation by [(PrP)Ni]H and catalytic stereospecific norbornene dimerization
The facile carbon atom abstraction reaction by [( i Pr 3 P)Ni] 5 H 6 ( 1 ) with various terminal alkenes to give [( i Pr 3 P)Ni] 5 H 4 (μ 5 -C) ( 2 ) occurs via a common highly reactive intermediate [( i Pr 3 P)Ni] 5 H 4 ( 3 ), which was isolated by the reaction of 1 with norbornene. Temperature dep...
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| Published in | Chemical communications (Cambridge, England) Vol. 59; no. 24; pp. 3542 - 3545 |
|---|---|
| Main Authors | , , , |
| Format | Journal Article |
| Published |
21.03.2023
|
| Online Access | Get full text |
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| Summary: | The facile carbon atom abstraction reaction by [(
i
Pr
3
P)Ni]
5
H
6
(
1
) with various terminal alkenes to give [(
i
Pr
3
P)Ni]
5
H
4
(μ
5
-C) (
2
) occurs
via
a common highly reactive intermediate [(
i
Pr
3
P)Ni]
5
H
4
(
3
), which was isolated by the reaction of 1 with norbornene. Temperature dependent
1
H and
31
P{
1
H} NMR chemical shifts of 3 are consistent with a thermally populated triplet excited state only 2 kcal mol
−1
higher energy than the diamagnetic ground state. Complex 3 catalyzes the dimerization of norbornene to stereoselectively provide exclusively (
Z
) anti-(bis-2,2'-norbornylidene).
64 Electrons, singlet-triplet gap of 2 kcal mol
−1
and does inert bond activation and catalysis; that doesn't follow the rules? |
|---|---|
| Bibliography: | 2222970 For ESI and crystallographic data in CIF or other electronic format see DOI Electronic supplementary information (ESI) available: Experimental procedures and crystallographic data (PDF and CIF). CCDC and https://doi.org/10.1039/d2cc06681e 2222969 |
| ISSN: | 1359-7345 1364-548X |
| DOI: | 10.1039/d2cc06681e |