Studies On Cyclization Chemistry Of The Brideged P/Al Or N/Al FLPs With Organic Multiple Bond Molecules

These are three sections of the research studies in this thesis.The first part focuses on synthesis and characterization of the amino group-linked P/Al FLP and the reaction chemistry with diverse alkynes.The second part gives a continuation study on the reaction chemistry of the P/Al FLP with mutiple bond-containing organic molecules such as alkene,cumulene,azobenzol,nitrile,isonitrile,isocyanate,ketone and azidoadamantane.In the meantime,synthesis and reactivity studies of the other amino group-linked P/B FLP and phenyl-linked P/Ge and P/Si FLPs were performed as well in this section.The third part explores the reaction chemistry of the aluminium hydride having an N/Al FLP character with azidoadamantane and tert-buty1 isonitrile molecules.The work done herein is detailed as follows.I.Synthesis and characterization of the amino group-linked P/Al FLP and reaction chemistry with diverse alkynes.Using 2,6-iPr2C6H3NH2 as starting material,a four-step,one-pot reaction including double lithiation.and double salt-elimination way has been proved to be efficient to synthesize the amino group-linked P/Al FLP compound[Ph2PN(2,6-iPr2C6H3)AlEt2]2(1)that was finally obtained in a high yield.Compound 1 was detailedly studied whether in the solid state or in solution,which exhibits a dimer structure as proven by X-ray diffraction single-crystal analysis.In solution,it is prone to disocciation to form a tetrahyrofuran adduct Ph2PN(2,6-iPr2C6H3)Alt2(THF)or an N-heterocyclic carbene coordination compound Ph2PN(2,6-iPr2C6H3)AlEt2[C(N-iPrCMe)2].The reaction chemistry of compound 1 was performed with diverse alkyne molcules.1 reacted with disubstituted alkynes to produce heterocyclic compounds[Ph2PN(2,6-iPr2C6H3)AlEt2](CR=CR)[R = Me(2),Ph(3)],and with PhC≡CEt,however,to give two products[Ph2PN(2,6-iPr2C6H3)AlEt2](CPh=CEt)(4a)and[Ph2PN(2,6-iPr2C6H3)AlEt2](CEt=CPh)(4b).The reactions of 1 with other alkynes that have two different substituent groups afforded the sole product,and they were[Ph2PN(2,6-iPr2C6H3)AlEt2](CR1=CR2)[R1,R2 = CO2Et,Ph(5);SiMe3,Ph(6);PPh2,Ph(7);CO2Et,Et(8)].The reactions of 1 with mono-substituted alkynes were also carried out,which genernate the sole compound as[Ph2PN(2,6-iPr2C6H3)AlEt2](CR1=CR2)[R1,R2= SiMe3,H(9);H,OEt(10);H,nC4H9(11)].Finally,1 reacted with a diyne PhC=C-C=CPh to form compound[Ph2PN(2,6-iPr2C6H3)AlEt2][C(C≡CPh)=CPh)](12).All of the compounds 2-12 have been characterized by NMR(1H,13C,31P,1H-13C HMBC and 1H-13C HSQC),CHN elemental analysis as well as thermal property melting point measurement,of which compounds 2,4a,6,9,11 and 12 were further studied by X-ray single-crystal diffraction.The NBO analysis of these alkynes employed was again conducted,and the calculation results by the charge difference of the two carbon atoms of the C≡C triple bond of the alkynes could prove reaction mechanism by the regioselective[3+2]dipolar cycloaddition under a matched electronic interaction between 1 and the alkyne substrate.This reaction way can be comparable to that of the well-known click reaction occurred between the azide and the alkyne which often worked under the catalysis of the transistion metals.Compound 1 is of strong dipolarity,which does not require an additional catalysis to fufil the[3+2]dipolar cycloaddition.All of the compounds 2-12 were formed as a zwitterionic AIC2NP heterocyclopentene.Ⅱ.The reaction chemistry of amino group-linked P/Al FLP 1 with other multiple bond-containing organic moleculesCompound 1 reacted with o-BrC6H4CH=CH2 to give product[Ph2PN(2,6-iPr2C6H3)AlEt2](CH2CH-o-BrC6H4)(13)and with H2C=C=CMe2 to[Ph2PN(2,6-iPr2C6H3)AlEt2][CH2C(=CMe2)](14).Both 13 and 14 are the AIC2NP heterocycle.Further reaction of 1 with PhN=NPh to form an AlN3P heterocycle[Ph2PN(2,6-iPr2C6H3)AlEt2](NPhNPh)(15).When the reaction was performed with iPrN=C=NiPr,an AICN2P heterocycle compound[Ph2PN(2,6-iPr2C6H3)AlEt2][N(iPr)C(=NzTPr)](16)was obtained.Another AICN2P heterocycle[Ph2PN(2,6-iPr2C6H3)AlEt2][N=C-4-BrC6H4](17)was achieved from the reaction with p-BrC6H4C≡N.The AlCNOP heterocycles[Ph2PN(2,6-iPr2C6H3)AlEt2][OC(=NtBu)](18)and[Ph2PN(2,6-iPr2C6H3)AlEt2](O=CPPh2)(19)were smoothly yielded from the reactions of 1 with the respective tBuN=C=O and Ph2C=O.In the end,compound 1 reacted with tBuN=C to generate a four-membered AlCNP heterocycle[Ph2PN(2,6-iPr2C6H3)AlEt2](C=NtBu)(20),and with N3Ad to give a four-membered AIN2P heterocycle[Ph2PN(2,6-iPr2C6H3)AlEt2][N(N=NAd)](21).All of the compounds 13-21 have been characterized by NMR(1H,13C,31P,1H-13C HMBC and 1H-13C HSQC),and CHN elemental analysis as well as thermal property melting point measurement,of which compounds 13-18 were further studied by X-ray single-crystal diffraction.The NBO analysis of these multiple bond-containing substrates was again conducted,and the calculation results by the charge difference of the two atoms of the multiple bonds involved in the reaction could also prove the reaction mechanism by the regioselective[3+2]dipolar cycloaddition under a matched electronic interaction for the formation of 13-19.For the formation of 20 and 21,the reactions might proceed through a[3+1]dipolar cycloaddition because the tBuN=C behaves as carbene analogue while another substrate N3Ad is a nitrene located at the terminal N atom due to arrangement in the reaction toward 1.This section also explored the synthesis and reaction chemistry of the amino group-linked P/B FLP Ph2PN(2,6-iPr2C6H3)BC8Hi4(22)and the phenyl group-linked P/Ge FLP o-C6H4PPh2Ge(C6F5)3(23),P/Si FLP o-C6H4PPh2SiMe2C1(24),o-C6H4PPh2SiCl3(25)and o-C6H4PPh2SiMe2H(26).Ⅲ.The reaction chemistry of an aluminium hydride that has an N/Al FLP character.The reaction of[(o-TMP-C6H4)AlH(μ-H)]2(27)with N3Ad was carried out,which however,gave a mixture of products.By means of the crystalloization,compound(RAlNNN-Ad)3(R = o-TMP-C6H4)(28)was able to be isolated,which was confirmed by the X-ray single-crystal diffraction study.The reaction of 27 with tBuN=C was also performed,which afforded a mixture of products as well.A try by the step crystallization successfully led to an isolation of compound R3A13H(CH=NtBu)(CH2NtBu)2(R = o-TMP-C6H4,29)that was identified by X-ray single-crystal diffraction.Both of these two reactions were complex,and the plausible mechanism for each was discussed.