Sba-15 Load Iridium, Ruthenium Heterocyclic Carbene Complexes Synthesis And Catalytic Activity Tests

N-Heterocyclic carbenes (NHCs), and their transition-metal complexes(for example:Pd, Ir, Ru, Ni,Cu), are more and more ued in oraganometallic chemistry. N-Heterocyclic carbenes are easy to synthesize and more stable. Not only used in homogeneous catalysis, but also used in heterogeneous catalysis. N-Heterocyclic carbenes Ir and Ru complexs has used for transfer hydrogenation and so on. SBA-15is one of the most useful Mesoporous, because of the good stabilization, we can load some metal complex on it. So the catalyst we get will have the homogeneous catalysis ability and easy to separated thanks for homogeneous material. In view of the broad prospect of N-Heterocyclic carbenes, this thesis describes the synthesis and catalytic study of NHCs and their metal complexes as follows:Part1:N-alkylation of amines and β-alkylation of secondary alcohols with primary alcohols was most used in organic synthesize. The traditional mothed were ues halogenated hydrocarbon. But halogenated hydrocarbon is so deleterious for us. N-heterocyclic carbene iridium complex has reported for N-alkylation of amines and (3-alkylation of secondary alcohols, it ues primary alcohols replaced halogenated hydrocarbon, low mammalian toxicity, by-product is water. Mesoporous silica (SBA-15) supported pyrimidine-substituted N-heterocyclic carbene iridium complex2a, bearing catalytic activity of organometallic moiety and water locking function of mesoporous silica, was prepared and used as a catalyst for both environmentally friendly N-alkylation of amines and β-alkylation of secondary alcohols with primary alcohols under mild conditions. Solid-state13C MAS NMR and Ir K-edge XAFS analysis revealed that the structure of iridium complex2a was retained after immobilization on SBA-15. This well-defined supported iridium complex as a catalyst can be easily recycled by simple washing without chemical treatment, and exhibited excellent recycling performance and no notable decrease in catalytic efficiency even after twelve test cycles for N-alkylation of aniline with benzyl alcohol, eight cycles for N-alkylation of different amines with different alcohols, and eight cycles for β-alkylation of1-phenylethanol with benzyl alcohol, respectively.Part2:The one major limitation of this technique is that the maximum theoretical yield is50%due to the consumption of only one enantiomer. Because of this, the unreacted enantiomer must be racemized and resubmitted to resolution conditions in order to increase this yield. If the racemization can occur concurrently with the kinetic resolution, known as Dynamic Kinetic Resolution (DKR), then theoretically100%of the racemic mixture can be converted to one enantiomer. Ruthenium has various valencies and is a not so expensive transition metal; therefore, various useful catalytic reactions for organic synthesis have been explored. Several attempts were made to utilize a ruthenium complex as the racemization catalyst effective for DKR. In this review, we describe the preparation of chiral compounds by the enzymatic resolution of secondary alcohols coupled with ruthenium-catalyzed racemization. We get a Mesoporous silica (SBA-15) supported N-heterocyclic carbene ruthedium complex3e, and found that the DKR for3e have two reason:ruthedium complex and pore canal of SBA-15.