Synthesis And Structures Of Novel Silicon-Substituted And Silicon-bridged Lithium Complexes

The research work is consisted of three parts focusing on syntheses and structures of twelve novel silicon-substituted and silicon-bridged lithium complexes. Part 1.The PhCH2Si(Me)2NMe:(2a)was synthesized firstly,then the{PhCHSi(Me)2NMe2}Li(TMEDA)(2b) was synthesized by the reaction of(2a)with n-BuLi and TMEDA(1:1:1)in hexane.Then the complex{PhCHC(Bu')NSi(Me)2NMe2}Li(TMEDA)(2c)was obtained via the reaction of(2b)with Bu'CN in hexane:we also synthesized complex{(Me2N)2C=NLi}.(2d)by the reaction of complex(2b) with (Me)2NCN in the Et2O(Schemel).Thecomplexes(2b),(2e) and (2d)was characterized by X-ray.The proposedmechanisms of synthesis of complexes(2c) was also studied.The populationof eharges of complexes(2b)and(2c)were studied using the calculatedmethod in quantum chemistry.Conditions(i)hexane,24h,ca 0℃:(ii)hexane,6 h ea 25℃:(iii)Et20,sh,ca℃Part 2. The compound PhCH2Si(Me)(NMe) (3a)was synthesized in first step,then complex{PhCHSi(Me)(NMe:):}Li(TMEDA)(3b)was obtained by (3a) with n-BuLi and TMEDA (1:1:1)in hexane.Then wePh.D Dissertation-He-Ping Shi Shanxi Universitysynthesized compleX{PhCHC(B。')NSi(Me)(NMeZ)2}Li(TMEDA)(3e)using thereaetion of eomplex(3b)with Bu'CN in hexane(SehemeZ).The eomplexes(3b)and(3e)was eharaeterized byX-ray.The proPosed meehanism ofsynthesis of eomplex(3e)was studied .The population of eharges ofeomplexes(3b)and(3e)were stodied via the ealeulating method in quantumehemistry.SCheme2 Conditions(i)hexane,24h,ca℃:(11)hexane,6h ea Part 3.Silieon-bridged(PhCHZ):51(NMeZ):(4b) Were eomPounds synthesized, (PhCHZ):51(Me)NMe:(4a)and and{PhCHC(Bu')NHSi(Me)(NMeZ)NC(Bu')CHPh}Li(TMEDA)(4e) the was made eomPlex using thereaetion of(4a)withn-BuLi,TMEDA and ButCN(l:1:1:1 or 1:1:1:2)inhexane,and the complex{(PhCH),51(Me)(NMeZ)}Li2(TMEDA)2(4d)was made bythe reaetion of(4a)withn-BuLi and TMEDA(1:2:2)in hexane:we alsosynthesized eomplex{PhCHSi(PhCHZ)(NMeZ):)}Li(TMEDA)(4e)by the reaetionof eompound(4b)withn-BuLi and TMEDA(1:1:1)in hexane(Seheme 3 andSeheme4).The eomplexes(4e),(4d)and(4e)were eharaeterized.TheProPosed meehanism of synthesis of eomplexes(4e)was studied .Westudiedthe population of eharges of eomplexes(4e),(4d),(4e)using theealeulated method in quantum ehemistry.Ph.D Dissertation-He-Ping ShiShanxi UniversityConditions(i)hexane,24h,ea ooC:(11)hexane,6 h ea 25oC:Seheme4Conditiontions(i)hexane,24h,cao℃.