Carboxylate Ligand-Induced Intramolecular C-H Bond Activation of Iridium Complexes with N-Phenylperimidine-Based Carbene Ligands

被引:37
作者
Tsurugi, Hayato [1 ]
Fujita, Shingo [1 ]
Choi, Gyeongshin [1 ]
Yamagata, Tsuneaki [1 ]
Ito, Syoji [2 ]
Miyasaka, Hiroshi [2 ]
Mashima, Kazushi [1 ]
机构
[1] Osaka Univ, Grad Sch Engn Sci, Dept Chem, Osaka 5608531, Japan
[2] Osaka Univ, Grad Sch Engn Sci, Div Frontier Mat Sci, Osaka 5608531, Japan
基金
日本科学技术振兴机构;
关键词
EFFICIENT ELECTROGENERATED CHEMILUMINESCENCE; CYCLOMETALATED IR(III) COMPLEXES; TRANSITION-METAL-COMPLEXES; CATALYZED DIRECT ARYLATION; EXCITED-STATE PROPERTIES; LIGHT-EMITTING-DIODES; HETEROCYCLIC CARBENES; ORGANIC-SYNTHESIS; ASTERISK-IR; PALLADIUM;
D O I
10.1021/om100604u
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
We report the synthesis and structure of iridium(1) complexes with N,N'-disubstituted perimidine carbene ligands and halides or carboxylate ligands. Iodo-, chloro-, and acetate-Ir(carbene)(cod) complexes were selectively prepared by changing the bases and silver salts. Intramolecular C H bond activation to prepare a cyclometalated Ir(III) complex, (C<<^>>C:)(2)Ir(OAc) (6), where C<<^>>C: is a cyclometalated perimidine carbene ligand, was achieved using a carboxylate-ligated iridium complex; otherwise, C-H activation did not proceed. Acetate-Ir(carbene)(cod) (3c) reacted with benzoic anhydride at room temperature to afford benzoate-Ir(carbene)(cod) (3d). A perimidine-carbene- and phenylpyridine-ligated Ir(III) complex, (C<<^>>C:)(C<<^>>N)Ir(OCOR) (8), where C<<^>>N is a cyclometalated phenylpyridine ligand, was isolated in good yield by mixing 3c or 3d and phenylpyridine under reflux in toluene. On the basis of the formation of 1,3-cyclooctadiene from the reaction mixture, we propose the following reaction mechanism for the intramolecular C-H activation: carboxylate-induced C-H bond activation and subsequent pyridine- or carbene-directed C-H bond oxidative addition, followed by the isomerization of 1,5-cyclooctadiene and reaction with carboxylic acid produces (C<<^>>C:)(N<<^>>C:)Ir(OCOPh). The cyclometalated complex 6 reacts with sodium acetylacetonate to form (C<<^>>C:)(2)Ir(acac) (11), which exhibits phosphorescent emission at lambda(max) = 555 nm (tau = 0.65 mu s, Phi(PL) = 0.0018) in CH2Cl2 solution at room temperature.
引用
收藏
页码:4120 / 4129
页数:10
相关论文
共 84 条
[1]   Synthesis, characterization, photophysical and electrochemical properties of new phosphorescent dopants for OLEDs [J].
Agarwal, Neeraj ;
Nayak, Pabitra K. .
TETRAHEDRON LETTERS, 2008, 49 (17) :2710-2713
[2]   Aryl-aryl bond formation by transition-metal-catalyzed direct arylation [J].
Alberico, Dino ;
Scott, Mark E. ;
Lautens, Mark .
CHEMICAL REVIEWS, 2007, 107 (01) :174-238
[3]   SIR92 - a program for automatic solution of crystal structures by direct methods [J].
ALTOMARE, A ;
CASCARANO, G ;
GIACOVAZZO, G ;
GUAGLIARDI, A ;
BURLA, MC ;
POLIDORI, G ;
CAMALLI, M .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1994, 27 :435-435
[4]   High-efficiency fluorescent organic light-emitting devices using a phosphorescent sensitizer [J].
Baldo, MA ;
Thompson, ME ;
Forrest, SR .
NATURE, 2000, 403 (6771) :750-753
[5]   Highly efficient phosphorescent emission from organic electroluminescent devices [J].
Baldo, MA ;
O'Brien, DF ;
You, Y ;
Shoustikov, A ;
Sibley, S ;
Thompson, ME ;
Forrest, SR .
NATURE, 1998, 395 (6698) :151-154
[6]   Constructing a stable carbene with a novel topology and electronic framework [J].
Bazinet, P ;
Yap, GPA ;
Richeson, DS .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (44) :13314-13315
[7]   Design of sterically demanding, electron-rich carbene ligands with the perimidine scaffold [J].
Bazinet, Patrick ;
Ong, Tiow-Gan ;
O'Brien, Julie S. ;
Lavoie, Nathalie ;
Bell, Eleanor ;
Yap, Glenn P. A. ;
Korobkov, Ilia ;
Richeson, Darrin S. .
ORGANOMETALLICS, 2007, 26 (11) :2885-2895
[8]   Stable carbenes [J].
Bourissou, D ;
Guerret, O ;
Gabbaï, FP ;
Bertrand, G .
CHEMICAL REVIEWS, 2000, 100 (01) :39-91
[9]   Investigation into the phosphorescence of a series of regioisomeric iridium(III) complexes [J].
Bronstein, Hugo A. ;
Finlayson, Chris E. ;
Kirov, Kiril R. ;
Friend, Richard H. ;
Williams, Charlotte K. .
ORGANOMETALLICS, 2008, 27 (13) :2980-2989
[10]   SIR2004:: an improved tool for crystal structure determination and refinement [J].
Burla, MC ;
Caliandro, R ;
Camalli, M ;
Carrozzini, B ;
Cascarano, GL ;
De Caro, L ;
Giacovazzo, C ;
Polidori, G ;
Spagna, R .
JOURNAL OF APPLIED CRYSTALLOGRAPHY, 2005, 38 :381-388