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He, Fan; Ruhlmann, Laurent; Gisselbrecht, Jean-Paul; Choua, Sylvie; Orio, Maylis; Wesolek, Marcel; Danopoulos, Andreas A.; Braunstein, Pierre
Dalton transactions : an international journal of inorganic chemistry, 2015, Letnik: 44, Številka: 39Journal Article
Deprotonation of 1-arylimidazoles (aryl = mesityl (Mes), 2,6-diisopropylphenyl (Dipp)), with n -butyl lithium afforded the corresponding derivatives (1-aryl-1 H -imidazol-2-yl)lithium ( 1a , Ar = Mes; 1b , Ar = Dipp) in good yield. Reaction of 1a with 0.5 equiv. of Ir(cod)(μ-Cl) 2 yielded two geometrical isomers of a doubly C2,N3-bridged dinuclear complex Ir(cod){μ-C 3 H 2 N 2 (Mes)-κC2,κN3} 2 ( 3 ), 3H–H , a head-to-head (H–H) isomer of C S symmetry, and 3H–T , the thermodynamically preferred head-to-tail (H–T) isomer of C 2 symmetry. The metallated carbon of the 4 electron donor anionic bridging ligands has some carbene character, reminiscent of the situation in N-metallated protic NHC complexes. Displacement of cod ligands from 3H–H and 3H–T afforded the tetracarbonyl complexes Ir(CO) 2 {μ-C 3 H 2 N 2 (Mes)-κC2,κN3} 2 4H–H and 4H–T , respectively. The reaction with PMe 3 , which gave only one complex, Ir(CO)(PMe 3 ){μ-C 3 H 2 N 2 (Mes)-κC2,κN3} 2 ( 5 ), demonstrates that the isomerization of the central core Irμ-C 3 H 2 N 2 (Mes)-κC2,κN3 2 Ir from H–H to H–T on going from 4H–H to 5 is readily triggered by phosphine substitution under mild conditions. Oxidative-addition of MeI to 5 afforded the formally metal–metal bonded d 7 –d 7 complex Ir 2 (CO) 2 (PMe 3 ) 2 (Me)I{μ-C 3 H 2 N 2 (Mes)-κC2,κN3} 2 ( 6 ). The blue Ir(C 2 H 4 ) 2 {μ-C 3 H 2 N 2 (Mes)-κC2,κN3} 2 ( 7 ) and purple Rh(C 2 H 4 ) 2 {μ-C 3 H 2 N 2 (Dipp)-κC2,κN3} 2 ( 9 ) tetraethylene complexes were also obtained with only a H–T arrangement of the bridging ligands. Although only modestly efficient in alkane dehydrogenation, complex 7 was found to be a more active pre-catalyst than 3H–T , 4H–T and 5 , probably because of the favorable lability of the ethylene ligands. From cyclic voltammetry, exhaustive coulometry and spectroelectrochemistry studies, it was concluded that 3H–T undergoes a metal-based one electron oxidation to generate the mixed-valent Ir( i )/Ir( ii ) system. The energy of the intervalence band for the orange dirhodium complex Rh(cod){μ-C 3 H 2 N 2 (Mes)-κC2,κN3} 2 ( 8 ) is shifted toward lower energies in comparison with 3H–T , reflecting the decrease of the energy with the intermetallic distance. It was concluded from the EPR study that the Ir and Rh centres contribute substantially to the experimental magnetic anisotropy and thus to the singly occupied molecular orbital (SOMO) in the mixed-valent Ir( i )/Ir( ii ) and Rh( i )/Rh( ii ) systems. The molecular structures of 3H–H , 3H–T , 8 and 9 have been determined by X-ray diffraction.
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