Synthesis and Characterization of a Family of POCOP Pincer Complexes with Nickel: Reactivity Towards CO2 and Phenylacetylene.
(2014) In Chemistry: A European Journal 20(37). p.11894-11902- Abstract
- A cyclohexyl-based POC sp 3OP pincer ligand (POC sp 3OP=cis-1,3-bis(di-tert-butylphosphinito)cyclohexyl) cyclometalates with nickel to generate a series of new POC sp 3OP-supported Ni(II) complexes, including the halide, hydride, methyl, and phenyl species. trans-[NiCl{cis-1,3-bis(di-tert-butylphosphinito)cyclohexane}], [(POC sp 3OP)NiCl] (1 a) and the analogous bromide complex (1 b) were synthesized and fully characterized by NMR spectroscopy and X-ray crystallography. Cyclic voltammetry measurements of 1 a and 1 b alongside their bis(phosphine) analogues [(PC sp 3P)NiCl] (2 a) and [(PC sp 3P)NiCl] (2 a) (PC sp 3P=cis-1,3-bis(di-tert-butylphosphino)cyclohexyl) indicate a reduced electron density at the metal center upon introducing... (More)
- A cyclohexyl-based POC sp 3OP pincer ligand (POC sp 3OP=cis-1,3-bis(di-tert-butylphosphinito)cyclohexyl) cyclometalates with nickel to generate a series of new POC sp 3OP-supported Ni(II) complexes, including the halide, hydride, methyl, and phenyl species. trans-[NiCl{cis-1,3-bis(di-tert-butylphosphinito)cyclohexane}], [(POC sp 3OP)NiCl] (1 a) and the analogous bromide complex (1 b) were synthesized and fully characterized by NMR spectroscopy and X-ray crystallography. Cyclic voltammetry measurements of 1 a and 1 b alongside their bis(phosphine) analogues [(PC sp 3P)NiCl] (2 a) and [(PC sp 3P)NiCl] (2 a) (PC sp 3P=cis-1,3-bis(di-tert-butylphosphino)cyclohexyl) indicate a reduced electron density at the metal center upon introducing electron-withdrawing oxygen atoms in the pincer arms. The methyl [(POC sp 3OP)NiMe] (3) and phenyl [(POC sp 3OP)NiPh] (4) complexes were formed from 1 a by reaction with the corresponding organolithium reagents. 1 a also reacts with LiAlH4 to give the hydride complex [(POC sp 3OP)NiH] (5). The methyl complex 3 reacts with phenyl acetylene to give the acetylide complex [(POC sp 3OP)NiCCPh] (6). The reactivity of compounds 3-5 towards CO2 was studied. The hydride complex 5 and the methyl complex 3 both underwent CO2 insertion to form the formate species [(POC sp 3OP)NiOCOH] (7) and acetate species [(POC sp 3OP)NiOCOCH3 ] (8), respectively, although with a higher barrier of insertion in the latter case. Compound 4 was unreactive towards CO2 even at elevated temperatures. Complexes 3-8 were all characterized by NMR spectroscopy and X-ray crystallography. (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/4615795
- author
- Jonasson, Klara LU and Wendt, Ola LU
- organization
- publishing date
- 2014
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Chemistry: A European Journal
- volume
- 20
- issue
- 37
- pages
- 11894 - 11902
- publisher
- Wiley-Blackwell
- external identifiers
-
- pmid:25080339
- wos:000341630500038
- scopus:84906949382
- pmid:25080339
- ISSN
- 1521-3765
- DOI
- 10.1002/chem.201403246
- language
- English
- LU publication?
- yes
- id
- 35a81ca8-cfec-4103-8378-f8bc0cbd8f07 (old id 4615795)
- date added to LUP
- 2016-04-01 10:05:16
- date last changed
- 2022-07-07 01:18:45
@article{35a81ca8-cfec-4103-8378-f8bc0cbd8f07,
abstract = {{A cyclohexyl-based POC sp 3OP pincer ligand (POC sp 3OP=cis-1,3-bis(di-tert-butylphosphinito)cyclohexyl) cyclometalates with nickel to generate a series of new POC sp 3OP-supported Ni(II) complexes, including the halide, hydride, methyl, and phenyl species. trans-[NiCl{cis-1,3-bis(di-tert-butylphosphinito)cyclohexane}], [(POC sp 3OP)NiCl] (1 a) and the analogous bromide complex (1 b) were synthesized and fully characterized by NMR spectroscopy and X-ray crystallography. Cyclic voltammetry measurements of 1 a and 1 b alongside their bis(phosphine) analogues [(PC sp 3P)NiCl] (2 a) and [(PC sp 3P)NiCl] (2 a) (PC sp 3P=cis-1,3-bis(di-tert-butylphosphino)cyclohexyl) indicate a reduced electron density at the metal center upon introducing electron-withdrawing oxygen atoms in the pincer arms. The methyl [(POC sp 3OP)NiMe] (3) and phenyl [(POC sp 3OP)NiPh] (4) complexes were formed from 1 a by reaction with the corresponding organolithium reagents. 1 a also reacts with LiAlH4 to give the hydride complex [(POC sp 3OP)NiH] (5). The methyl complex 3 reacts with phenyl acetylene to give the acetylide complex [(POC sp 3OP)NiCCPh] (6). The reactivity of compounds 3-5 towards CO2 was studied. The hydride complex 5 and the methyl complex 3 both underwent CO2 insertion to form the formate species [(POC sp 3OP)NiOCOH] (7) and acetate species [(POC sp 3OP)NiOCOCH3 ] (8), respectively, although with a higher barrier of insertion in the latter case. Compound 4 was unreactive towards CO2 even at elevated temperatures. Complexes 3-8 were all characterized by NMR spectroscopy and X-ray crystallography.}},
author = {{Jonasson, Klara and Wendt, Ola}},
issn = {{1521-3765}},
language = {{eng}},
number = {{37}},
pages = {{11894--11902}},
publisher = {{Wiley-Blackwell}},
series = {{Chemistry: A European Journal}},
title = {{Synthesis and Characterization of a Family of POCOP Pincer Complexes with Nickel: Reactivity Towards CO2 and Phenylacetylene.}},
url = {{http://dx.doi.org/10.1002/chem.201403246}},
doi = {{10.1002/chem.201403246}},
volume = {{20}},
year = {{2014}},
}