Patent EP-2338593-A1 (EP)
Inventor: MOLT OLIVER
IPC: B01J31/22
Filed: 2007-01-09
Abstract: 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). 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. [Image] [Image].