Novel pyrazolylphosphite- and pyrazolylphosphinite-ruthenium(II) complexes as catalysts for hydrogenation of acetophenone
(2016) In Dalton Transactions 45(34). p.13514-13524- Abstract
The new compounds and potential ligands 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyldiphenlyphosphinite (L1), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyldiethylphosphite (L2), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyl-diethylphosphite (L3) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiethylphosphite (L4) were prepared from the reaction of (3,5-(disubstituted)pyrazol-1H-yl)ethanol and the appropriate phosphine chloride. The phosphinite (L1) and phosphites (L2-L4) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L5) were reacted with [Ru(p-cymene)Cl2]2 to afford the ruthenium(ii) complexes [Ru(p-cymene)Cl2(L1)] (1), [Ru(p-cymene)Cl2(L2)] (2), [Ru(p-cymene)Cl2(L3)] (3),... (More)
The new compounds and potential ligands 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyldiphenlyphosphinite (L1), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyldiethylphosphite (L2), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyl-diethylphosphite (L3) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiethylphosphite (L4) were prepared from the reaction of (3,5-(disubstituted)pyrazol-1H-yl)ethanol and the appropriate phosphine chloride. The phosphinite (L1) and phosphites (L2-L4) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L5) were reacted with [Ru(p-cymene)Cl2]2 to afford the ruthenium(ii) complexes [Ru(p-cymene)Cl2(L1)] (1), [Ru(p-cymene)Cl2(L2)] (2), [Ru(p-cymene)Cl2(L3)] (3), [Ru(p-cymene)Cl2(L4)] (4), and [Ru(p-cymene)Cl2(L5)] (5). All ruthenium complexes were characterized by a combination of NMR spectroscopy, elemental analysis and, in selected cases, by single crystal X-ray crystallography. Complexes 1-5 and [Ru(p-cymene)Cl2(L6)] (6) (prepared from 2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L6)) were investigated as catalysts for both transfer and molecular hydrogenation of acetophenone to 1-phenylethanol. At 80 °C the percent conversion of acetophenone in transfer hydrogenation was moderate to high over 10 h (42-87%); for molecular hydrogenation acetophenone, conversions were as high as 98% in 6 h.
(Less)
- author
- Amenuvor, Gershon ; Obuah, Collins ; Nordlander, Ebbe LU and Darkwa, James
- organization
- publishing date
- 2016
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Dalton Transactions
- volume
- 45
- issue
- 34
- pages
- 11 pages
- publisher
- Royal Society of Chemistry
- external identifiers
-
- pmid:27504937
- wos:000382144300031
- scopus:84983655876
- ISSN
- 1477-9226
- DOI
- 10.1039/c6dt02164f
- language
- English
- LU publication?
- yes
- id
- cf61948f-a65a-495d-b1fc-125a2f1f3682
- date added to LUP
- 2017-02-22 15:22:03
- date last changed
- 2024-04-14 05:25:10
@article{cf61948f-a65a-495d-b1fc-125a2f1f3682, abstract = {{<p>The new compounds and potential ligands 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyldiphenlyphosphinite (L1), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyldiethylphosphite (L2), 2-(3,5-di-tert-butyl-1H-pyrazol-1-yl)ethyl-diethylphosphite (L3) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiethylphosphite (L4) were prepared from the reaction of (3,5-(disubstituted)pyrazol-1H-yl)ethanol and the appropriate phosphine chloride. The phosphinite (L1) and phosphites (L2-L4) and 2-(3,5-diphenyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L5) were reacted with [Ru(p-cymene)Cl<sub>2</sub>]<sub>2</sub> to afford the ruthenium(ii) complexes [Ru(p-cymene)Cl<sub>2</sub>(L1)] (1), [Ru(p-cymene)Cl<sub>2</sub>(L2)] (2), [Ru(p-cymene)Cl<sub>2</sub>(L3)] (3), [Ru(p-cymene)Cl<sub>2</sub>(L4)] (4), and [Ru(p-cymene)Cl<sub>2</sub>(L5)] (5). All ruthenium complexes were characterized by a combination of NMR spectroscopy, elemental analysis and, in selected cases, by single crystal X-ray crystallography. Complexes 1-5 and [Ru(p-cymene)Cl<sub>2</sub>(L6)] (6) (prepared from 2-(3,5-dimethyl-1H-pyrazol-1-yl)ethyldiphenylphosphinite (L6)) were investigated as catalysts for both transfer and molecular hydrogenation of acetophenone to 1-phenylethanol. At 80 °C the percent conversion of acetophenone in transfer hydrogenation was moderate to high over 10 h (42-87%); for molecular hydrogenation acetophenone, conversions were as high as 98% in 6 h.</p>}}, author = {{Amenuvor, Gershon and Obuah, Collins and Nordlander, Ebbe and Darkwa, James}}, issn = {{1477-9226}}, language = {{eng}}, number = {{34}}, pages = {{13514--13524}}, publisher = {{Royal Society of Chemistry}}, series = {{Dalton Transactions}}, title = {{Novel pyrazolylphosphite- and pyrazolylphosphinite-ruthenium(II) complexes as catalysts for hydrogenation of acetophenone}}, url = {{http://dx.doi.org/10.1039/c6dt02164f}}, doi = {{10.1039/c6dt02164f}}, volume = {{45}}, year = {{2016}}, }