| 摘要 |
<p>#CMT# #/CMT# Preparation of cyclometalated transition metal-carbene complex (I) comprises reacting a ligand precursor (III) with a base and an auxiliary reagent comprising at least a metal salt of silver, mercury, antimony, magnesium, boron or aluminum (step A), or with a basic auxiliary reagent comprising at least a metal such as silver, mercury, antimony, magnesium, boron or aluminum (step B). #CMT# : #/CMT# Preparation of cyclometalated transition metal-carbene complex (I) of formula (((L) m)((K 1>) o-M 1>-(carbene) n)) comprises reacting a ligand precursor of formula (III) with a base and an auxiliary reagent comprising at least a metal salt of silver, mercury, antimony, magnesium, boron or aluminum (step A), or with a basic auxiliary reagent comprising at least a metal such as silver, mercury, antimony, magnesium, boron or aluminum (step B), where (III) reacts with a base, an auxiliary reagent and a metal complex comprising at least a metal (M 1>) (step A) or (III) reacts with a basic auxiliary reagent and a metal complex containing at least a metal (M 1>) (step B). M 1> : metal atom such as Ir, Pt, Rh, Os (all preferred), Co, Ni, Pd, Fe, Ru, Cr, Mo, W, Mn, Tc, Re, Cu or Au; L : mono- or di- anionic ligand, which is optionally mono- or bi- dentate; K 1> : neutral mono- or bi- dentate ligand; carbene : carbene ligand of formula (II); n : greater than 1, preferably 2 (and the carbene ligand in (I) is n with greater than 1 or different); m : 0 or >=1 and the ligand (L) in m is greater than 1 or different; o : 0 or greater than 1, where the number of ligand K 1> in o is greater than 1 or different; Do 1> : donor atoms such as P, N, O, S (all preferred) C or Si; Do 2> : donor atoms such as C, N, P, O or S; r : 2 (if Do 1> is Si), 1 (if Do 1> is N or P) or 0 (if Do 1> is O or S); s : 2 (if Do 2> is C), 1 (if Do 2> is N or P) or 0 (if Do 2> is O or S); X : spacer such as silylene, alkylene, (hetero)arylene, alkynylene, alkenylene, NR 13>, PR 14>, B 1>R 15>, O, S, SO, SO 2, CO, CO-O, O-CO or (CR 16>R 17>) w, where one or more adjacent groups of (CR 16>R 17>) is replaced by NR 13>, PR 14>, B 1>R 15>, O, S, SO, SO 2, CO, CO-O or O-CO; w : 2-10; R 13>-R 17> : H, alkyl, (hetero)aryl, alkenyl or alkynyl; p, q : 0 or 1; either Y 1>, Y 2> : H or C such as alkyl-, (hetero)aryl-, alkynyl- or alkenyl; or Y 1>, Y 2> : form a bridge between Do 1> and nitrogen atom and exhibits at least two atoms, in which at least one is a carbon atom; Y 3> : H, alkyl, (hetero)aryl, alkynyl, alkenyl or H-(((R 3>) s-Do 2>) q)(R 2>)-C=C(R 1>)(X) p-CH 3 (where Y 3> and Y 2> are connected together over a bridge, which is alkylene, arylene, heteroarylene, alkynylene, alkenylene, NR 25>, PR 26>, BR 27>, O, S, SO, SO 2, SiR 32>R 33>, CO, CO-O, O-CO or (CR 28>R 29>) y); y : 2-10; R 25>-R 29>, R 32>, R 33> : H, alkyl, aryl, heteroaryl, alkenyl or alkynyl; either R 1>, R 2> : H, alkyl-, aryl-, heteroaryl-, alkynyl or alkenyl; or R 1>R 2> : a bridge with 3-5 atoms, where one or two atoms are heteroatoms and the remaining atoms are carbon atoms, so that the group forms a 5-6 membered ring (optionally exhibits one double bond in addition to already available double bonds- or two further double bonds in 6 or 7 membered ring, optionally substituted with alkyl- or aryl and/or groups with donor- or acceptor effect, and optionally contains a heteroatom), where Y 1> and R 1> are connected together over a bridge, which is alkylene, arylene, heteroarylene, alkynylene, alkenylene, NR 18>, PR 19>, BR 20>, O, S, SO, SO 2, SiR 30>R 31>, CO, CO-O, O-CO or (CR 21>R 22>) x, where one or more non-adjacent group (CR 21>R 22>) is replaced by NR 18>, PR 19>, BR 20>, O, S, SO, SO 2, SiR 30>R 31>, CO, CO-O or O-CO; x : 2-10; R 3>, R 18>-R 22>, R 30>, R 31> : H, alkyl, aryl, heteroaryl, alkenyl or alkynyl; Q -> : monoanionic counter ion, preferably halogen, pseudohalogen, BF 4 ->, BPh 4 ->, PF 6 ->, AsF 6 -> or SbF 6 ->; and G : H (when Do 2> is C), or H or a free electron pair (when Do 2> is N,S, O or P). Where the sum of n, m and o is an oxidation state and coordination number of the used metal atom and of the denticity of the carbene ligand, and depends on L, K 1> and the charge of the carbene ligand with the condition that n is at least 1. #CMT#[Image]#/CMT# #CMT#[Image]#/CMT# #CMT#USE : #/CMT# The auxiliary reagent with a base is useful for the preparation of (I) (claimed). (I) is useful in organic light-emitting diode, mobile phones and laptops. #CMT#ADVANTAGE : #/CMT# The process provides (I) in good yield. #CMT#ORGANIC CHEMISTRY : #/CMT# Preferred Process: The process takes place in the presence of a solvent, preferably aprotic solvent such as dioxane, butanone, tetrahydrofuran, toluol, xylol, dimethyl formamide, acetonitrile, dimethyl sulfoxide, N-methylpyrrolidone or pyridine at 60-200, preferably 70-150[deg]C. Preferred Components: In step A, the ratio of the metal (M 1>); ligand precursor (III); base and auxiliary reagent is 1:1-10:1-10:0.5-15, preferably 1:1-2:1-2:1-1.5. In step B, the ratio of the metal (M 1>), ligand precursor (III); base and auxiliary reagent is 1:1-10:0.5-5, preferably 1:1-3:0.5-1.5. The auxiliary reagent in (step A) contains silver such as silver tetrafluoroborate, silver nitrate, silver hexafluorophosphate, silver hexafluoroarsenate, silver hexafluoroantimonate, silver thiocyanate, silver sulfate, silver cyanate, silver trifluoroacetate, silver perchlorate and/or silver trifluoromethanesulfonate. The basic auxiliary reagent in (step B) contains silver such as silver(II)oxide (preferred), silver carbonate, silver acetate and/or silver sulfide. The base (in step A) is potassium hexamethyldisilazane, sodium hexamethyldisilazane, lithium hexamethyldisilazide, potassium tert.butoxide, sodium tert.butoxide, lithium tert.butoxide, sodium hydride, potassium acetate, sodium acetate, lithium acetate, triethyl amine, butyl lithium, RMghal, potassium hydroxide, sodium hydroxide, lithium hydroxide, cesium carbonate, potassium carbonate, sodium carbonate, lithium carbonate, pyridine and/or 1,8-diazabicyclo[5.4.0]undec-7-ene. R : alkyl, aryl or alkenyl. #CMT#DEFINITIONS : #/CMT# Preferred Definitions: M 1> : Ir (I) (preferred) or Ir (III); carbene : 10 carbene ligands of formula (a-e) (where one of the remainders of R 1> 2> is connected over a bridge with: R 4> or R 5> or the carbon atom with which R 4> and R 5> connected, R 8> or the carbon atom with which R 8> is connected, R 1> 0> or one of the carbon atoms with which R 1> 0> is connected, and R 1> 1> or the carbon atom with which R 1> 1> is connected, and the bridges are alkylene, arylene, heteroarylene, alkynylene, alkenylene, NR 1> 8>, PR 1> 9>, BR 2> 0>, O, S, SO, SO 2, SiR 3> 0>R 3> 1>, CO, CO-O, O-CO or (CR 2> 1>R 2> 1>) x, where one or more adjacent groups of (CR 2> 1>R 2> 2>) is replaced by NR 1> 8>, PR 1> 9>, BR 2> 0>, O, S, SO, SO 2, SiR 3> 0>R 3> 1>, CO, CO-O or O-CO); Z, Za, Zb : CH or N; either R 1> 2>, R12a : alkyl-, (hetero)aryl-, alkynyl- or alkenyl; or 2R 1> 2>R12a : annealed ring optionally containing at least a heteroatom or a residue with a donor- or acceptor active substance; t, t1 : 0-4 ; R 4>-R 9>, R 1> 1>, R11a : H, alkyl, (hetero)aryl, alkynyl, alkenyl or a residue with a donor- or acceptor substance; either R 1> 0> : alkyl, (hetero)aryl, alkynyl or alkenyl; or 2R 1> 0> : annealed ring optionally containing at least a heteroatom or a residue with a donor or acceptor substance; x : 2-10; R 1> 6>, R 1> 9>-R 2> 2>, R 3> 0>, R 3> 1> : H, alkyl, (hetero)aryl, alkenyl or alkynyl; and Y 3> : H, alkyl, (hetero)aryl, alkynyl, alkenyl. When t and/or t1 are greater than 1, then R 1> 2> and/or R12a is same or different. #CMT#EXAMPLE : #/CMT# Dry dimethyl formamide (1500 ml); 4-fluoro-cyanobenzene (72.67 g); imidazole (61.2 g) and sodium hydride (21.6 g) were mixed and heated at 100[deg]C and stirred for 4 hours. The obtained reaction mixture was poured on water and extracted with dichloromethane. The organic phase was dried at 60[deg]C to obtain 1-(4-cyanophenyl)imidazole (94 g). 1-(4-Cyanophenyl)imidazole (56 g) was cooled using an aqueous free tetrahydrofuran (560 ml) and reacted with methyliodide (234.2 g), stirred for 48 hours and heated at 70[deg]C to obtain 1-(4-cyanophenyl)-3-methylimidazolium iodide (81.54 g). A suspension of 1-(4-cyanophenyl)-3-methylimidazolium iodide (5 equivalent) in dioxane was reacted with potassium-bis(trimethylsilyl) amide (5 equivalent) in toluol (0.5 M) under argon within 30 minutes to obtain a suspension of 1,5-cyclooctadiene-iridium(I)chloride dimer (0.5 equivalent) and silver tetrafluoroborate (1 equivalent) in dioxane. Subsequently the reaction mixture was heated at 70[deg]C at two hours and 22 hours, and stirred to obtain mer-tris-[1-(4'-cyanophenyl)-3-methylimidazol-2-yliden-C 2>,C 2>]iridium(III) (58%).</p> |
