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Danopoulos, Andreas A., Braunstein, Pierre, Saßmannshausen, Jörg, Pugh, David and Wright, Joseph A. 
ORCID: https://orcid.org/0000-0001-9603-1001
(2020)
“Pincer” pyridine–dicarbene–iridium and -ruthenium complexes and derivatives thereof.
European Journal of Inorganic Chemistry, 2020 (35).
pp. 3359-3369.
ISSN 1434-1948
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Abstract
The cationic pincer-type complexes [IrI(CNMeC)L]X {CNMeC = [2,6-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]-3,5-dimethylpyridine, L = CO, X = PF6 4; L = CH3CN, X = PF6 5; L = pyridine, X = BArF4, ArF = 3,5-bis-trifluoromethyl-phenyl 6}, that were obtained from [IrI(CNMeC)Cl] (1) by displacement of the chloride ligand were structurally characterized. Complexes 4 and 5 adopt square planar, in-plane distorted geometries, and in 6 the metal environment shows substantial pyramidalization. Theoretical calculations of the cations in 4 and 6 reproduce the experimental structures and rationalize their features. 1 undergoes oxidative transformations with CH2Cl2 to cis-[IrIII(CNMeC)(CH2Cl)Cl2] (7) and with PhICl2 to mer-[IrIII(CNMeC)Cl3] (8). The ruthenium derivatives trans-[RuII(CNC)Cl2L] {CNC = [2,6-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]-pyridine, L = pyridine, 10} and [RuII(CNC)(η2,η2-nbd)](X)2. 2L (nbd = 2,5-norbornadiene, L = CH3CN, X = BF4 11), were prepared by the reaction of cis-trans-[RuCl2(nbd)(py)2] and trans-cis-[RuCl2(nbd)(pip)2] (pip = piperidine) with the ligand CNC, respectively; both adopt distorted octahedral structures. The back-bonding in 11 is comparable to that in its precursor complex, indicating minimal contribution of the NHC donors to this effect. Substitution of both chlorides in the known cis-[RuII(CNC)Cl2L] (L = PPh3) by azido ligands gave cis-[RuII(CNC)(N3)2L] (L = PPh3, 12), which by photolytic cleavage of the coordinated N3 failed to produce well-defined complexes.
| Item Type: | Article |
|---|---|
| Uncontrolled Keywords: | carbene ligands,iridium,oxidative addition,pincer complexes,ruthenium,theoretical calculations,inorganic chemistry ,/dk/atira/pure/subjectarea/asjc/1600/1604 |
| Faculty \ School: | Faculty of Science > School of Chemistry (former - to 2024) |
| UEA Research Groups: | Faculty of Science > Research Groups > Energy Materials Laboratory |
| Related URLs: | |
| Depositing User: | LivePure Connector |
| Date Deposited: | 06 Nov 2020 01:39 |
| Last Modified: | 25 Sep 2024 15:06 |
| URI: | https://ueaeprints.uea.ac.uk/id/eprint/77560 |
| DOI: | 10.1002/ejic.202000429 |
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