In:
European Journal of Inorganic Chemistry, Wiley, Vol. 2020, No. 35 ( 2020-09-22), p. 3359-3369
Abstract:
The cationic pincer‐type complexes [Ir I (CN Me C)L]X {CN Me C = [2,6‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene]‐3,5‐dimethylpyridine, L = CO, X = PF 6 4 ; L = CH 3 CN, X = PF 6 5 ; L = pyridine, X = BAr F 4 , Ar F = 3,5‐bis‐trifluoromethyl‐phenyl 6 }, that were obtained from [Ir I (CN Me C)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 CH 2 Cl 2 to cis ‐[Ir III (CN Me C)(CH 2 Cl)Cl 2 ] ( 7 ) and with PhICl 2 to mer ‐[Ir III (CN Me C)Cl 3 ] ( 8 ). The ruthenium derivatives trans ‐[Ru II (CNC)Cl 2 L] {CNC = [2,6‐bis(2,6‐diisopropylphenyl)imidazol‐2‐ylidene] ‐pyridine, L = pyridine, 10 } and [Ru II (CNC)(η 2 ,η 2 ‐nbd)](X) 2 . 2L (nbd = 2,5‐norbornadiene, L = CH 3 CN, X = BF 4 11 ), were prepared by the reaction of cis‐trans ‐[RuCl 2 (nbd)(py) 2 ] and trans ‐ cis ‐[RuCl 2 (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 ‐[Ru II (CNC)Cl 2 L] (L = PPh 3 ) by azido ligands gave cis ‐[Ru II (CNC)(N 3 ) 2 L] (L = PPh 3 , 12 ), which by photolytic cleavage of the coordinated N 3 failed to produce well‐defined complexes.
Type of Medium:
Online Resource
ISSN:
1434-1948
,
1099-0682
DOI:
10.1002/ejic.v2020.35
DOI:
10.1002/ejic.202000429
Language:
English
Publisher:
Wiley
Publication Date:
2020
detail.hit.zdb_id:
1475009-0
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