Synthesis And Reactivity Studies Of Nitrogen-containing Ligand Stablized Coinage Metal And ⅣA Group Complexes

The synthesis and reaction of nitrogen-containing ligands and their complexes are important in there search of coordination chemistry,and α-iminopyridine ligands and N-heterocyclic carbene ligands are typical representatives.Due to the unique "noninnocent" activity and flexible skeleton structure variability,α-iminopyridine ligands can be used to synthesize metal complexes with multiple coordination modes,but the related coordination chemistry of coin group metals has not yet been systematically studied.As another important nitrogen-containing ligand,the reactivity study of the divalent IVA group elements Si and Ge halides has always been a frontier topic in main group chemistry,but the reaction with unsaturated small molecules containing triple bond structures has not achieved great progress in recent years.In view of the above contents,this thesis mainly focuses on the following two aspects:1.Synthesis of α-iminopyridine ligand(IP)-stabilized coin group metal complexes:A series of metal complexes were prepared by the reactions of IP with metal inorganic salts CuCl,CuBr,CuI,AgSbF6 and AuCl3.Among them,the cationic part structure of compounds(IP2Cu)+(CuCl2)-(2-1)and(IP2Ag)+SbF6-(2-4)are similar,and both are double IP chelating structures.The difference between the two is that the anion of compound 2-1 is CuCl2-,while the anion of compound 2-4 is SbF6-.The compounds IP3Cu4Br4(2-2)and IP3Cu4I4(2-3)have Cu4X4(X=Br,I)clusters as the inorganic core,and no positive and negative charge separation phenomena like that in 2-1 and 2-4 occur.Compound(IP-CHPh)AuCl2(2-5)has the structure of an IP-incorporated CN fivemembered ring,while the Au in the form of[AuCl2]is at the periphery of the main structure.The[PhCH]fragment in the structure of 2-5 may arise from the activation of the solvent toluene,which is first observed in IP-metal complex reaction systems.2.Reactivity studies of NHC stabilized halogenated E(Ⅱ)(E=Si,Ge)compounds with triple bond-containing small molecule metal salts;NHC-SiI2 was heated with excess NaN3 in 1,4-dioxane,and a NHC based 1,3-butadiene radical analogue(NHCC2H2-NHC)+I-(dioxane)(3-1)was accidentally obtained,and its single-electron radical property was proved by EPR spectroscopy.3-1 can also be considered as the first C2H2 radical species stabilized by carbene.During the process of isolating compound 3-1,the reaction mixture was directly dried,and the residue was extracted with dichloromethane to obtain a triazene compound(NHC-N=N-N=NHC)+I-(3-2).The formation mechanisms of 3-1 and 3-2 are very complex.The C2H2 part in 3-1 structure may be derived from the thermo-decomposition of dioxane molecules,and the triazene part in 3-2 structure may be from the unreacted NaN3 salt.In addition,the reaction of cAAC-GeCl2 with alkynyl lithium salt TMS-C≡C-Li afforded a alkatriene-based dimer(cAAC=C=C-TMS)2(3-3).This reaction is quite different from the previously reported simple substitution reaction of carbene-stabilized halogenated Ge(Ⅱ),which may undergo the formation of cAAC-Ge(C≡CTMS)2 intermediate,the removal of metal Ge,and the formation and dimerization of[cAAC=C=C(TMS)]radical,which is also observed for the first time in NHC-Ge(Ⅱ)chemistry.