Carbon-carbon vs. carbon-oxygen bond activation in 2- and 3-furonitriles with nickelElectronic supplementary information (ESI) available: Includes selected NMR spectra, GC-MS determinations of all products and crystallographic tables. The crystallographic material for compounds 7 and 11 has been deposited at the CCDC 1497182 and 1497183 respectively. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c6ra20244f
The reaction between [(dippe)NiH] 2 ( 1 ) (dippe = 1,2-bis(diisopropylphosphino)-ethane) and 2- and 3-furonitrile ( 2-FN and 3-FN ) was carried out at room temperature. Both furonitriles initially react with H 2 loss and coordinating a [Ni(dippe)] fragment to the nitrile substituent in a η 2 -C&...
Saved in:
| Main Authors | , , |
|---|---|
| Format | Journal Article |
| Language | English |
| Published |
24.10.2016
|
| Online Access | Get full text |
Cover
Loading…
| Summary: | The reaction between [(dippe)NiH]
2
(
1
) (dippe = 1,2-bis(diisopropylphosphino)-ethane) and 2- and 3-furonitrile (
2-FN
and
3-FN
) was carried out at room temperature. Both furonitriles initially react with H
2
loss and coordinating a [Ni(dippe)] fragment to the nitrile substituent in a η
2
-C&z.tbd;N way to yield complexes [(dippe)Ni(η
2
-C,N-
2-FN
)] (
2
) and [(dippe)Ni(η
2
-C,N-
3-FN
)] (
10
), respectively. After monitoring this reaction for 6 days at room temperature in the presence of a slight excess of each nitrile, the C-CN bond activation products [(dippe)Ni(CN)(η
1
-C-
2-FN
)] (
7
) and [(dippe)Ni(CN)(η
1
-C-
3-FN
)] (
11
) were observed as the main products. These complexes were fully characterized by
1
H,
31
P{
1
H} and
13
C{
1
H} NMR and by single crystal X-ray determinations. After isolation and characterization of (
7
) and (
11
), a thermal stability study was carried out, and it was found that the -C-CN bond activation is reversible at 100 °C for both compounds. Particularly, the thermolysis of complex (
7
) allowed the further production of a C-O ring opening at the furan to yield complex [(dippe)Ni(κ
2
-O,C-OCH&z.dbd;CH-CH&z.dbd;C(CN))] (
9
), which was also isolated and characterized by multinuclear NMR.
The reaction between [(dippe)NiH]
2
(
1
) (dippe = 1,2-bis(diisopropylphosphino)-ethane) and 2- and 3-furonitrile (
2-FN
and
3-FN
) was carried out at room temperature. |
|---|---|
| Bibliography: | 11 1497182 1497183 has been deposited at the CCDC 10.1039/c6ra20244f and 7 Electronic supplementary information (ESI) available: Includes selected NMR spectra, GC-MS determinations of all products and crystallographic tables. The crystallographic material for compounds respectively. For ESI and crystallographic data in CIF or other electronic format see DOI |
| ISSN: | 2046-2069 |
| DOI: | 10.1039/c6ra20244f |