A Comparative Study On The Reactivity Of Azido Pd Complexes And Sodium Azide Toward Organic Isocyanide And Isothiocyanate

At present,the construction of novel complexes with excellent properties is a hot topic in the field of coordination chemistry.The Pd element is located in the VIII group of the fourth cycle,and the outermost electron configuration is 4d¹⁰.It is easy to form azide palladium complexes with azide ions.Sodium azide is an inorganic azide salt that can ionize azide anions and react with reactive halides to form unstable organic azide compounds.Nitrile is a very important compound,which has both nucleophilic and electrophilic properties.It has a similar reactivity with cabbeen and is a good free radical acceptor.-S-C=N isothiocyanate,it has an isomer of-N=C=S,with the structure of the compound and the azide group [3+2]-cycloaddition reaction of azide palladium complexes and isothiocyanate reaction,chlorine bridged palladium complexes,sodium azide and ethyl isothiocyanate.For the one pot reaction,through a comparative study on two kinds of reactions,find the inherent law.The synthesis of novel nitrogen heterocyclic compounds with bridged azido complexes has been an important direction for researchers to study.The azido bridges in the metal azide complexes have good reactivity,and a comparative study of their reactivity with the basic reactants provides a new approach for us.A novel azido bridged palladium clathrate complex has been synthesized.It is important to study the reactivity of several kinds of materials with azido bridged PD clathrate complexes.In this paper the chlorine bridged palladium complexes and sodium azide and isocyanide,isorhodanic by one pot reaction and palladium complexes with azide bridge isocyanide,isorhodanic reaction compared to the effects of different reaction methods,effects of different proportions of products.In addition,we also synthesized the azide bridged palladium cage compounds,the three phenyl phosphine,1,5-two?two phenyl phosphine?-butane,1,4-two?two phenyl phosphine?-butane,organic isocyanide,isorhodanic,imidazole,1-methyl imidazole reaction,so as to study the azide bridged palladium cage compound reaction.Specific work is as follows:1.Firstly,the synthesis of chloro bridged palladium complexes was studied [Pd{C,N-?²-?4-MeO?C₆H₃CH=NC₆H₃-2,6-i-Et₂}??-Cl?₂]₂?1?,and bridged azide palladium complex[Pd{C,N-?²-?4-MeO?C₆H₃CH=NC₆H₃-2,6-i-Et₂}??-N₃?]₂?2?Com pound 2 and isorhodanic by 1:2 reaction to obtain compounds[??-SCN₄-C₂H₅?Pd{C,N-?²-?4-MeO?C₆H₃CH=NC₆H₃-2,6-i-Et₂}]₂?4?,then the compounds 1 and isothiocyanate,sodium azide according to the reaction ratio of 1:2:2 reaction of the compound [??-N?C₂H₅?-CSN₃?Pd{C,N-?²-?4-MeO?C₆H₃CH=NC₆H₃-2,6-i-Et₂}]₂?3?.Through the comparison of the above two kinds of different ways of reaction time on reaction results;and the reaction was 2 and isocyanide according to 1:2 reaction of the compound [??-N=C=N-C₆H₃-2,6-Me₂??-N₃??Pd{C,N-?²-?4-Me O?C₆H₃CH=NC₆ H3-2,6-i-Et₂}]₂?6?,compound 1 and isocyanide,azide sodium?1:2:2?reaction of the compound [??-N=C=N-C₆H₃-2,6–Me₂??-N₃??Pd{C,N-?²-?4-MeO?C₆H₃CH=NC₆H₃-2,6-i-Et₂}]₂?5?,by comparing the above two kinds of different ways of reaction time on reaction results;compound 2 and isonitrile in proportion to 1:4 generating compounds[Pd{C,N-?²-?4-MeO?C₆H₃CH=NC₆H₃-2,6-i-Et₂}?CN4-C₆H₃-2,6-Me₂??C N-C₆H₃-2,6-Me₂?]?7?,by changing the proportion of isocyanide,to study the influence on the reaction mechanism;in order to respond to the above several in-depth research,design and response:.Substance 1 reacts with 1:2 to form compounds [Pd{C,N-?²-?4-MeO?C₆H₃CH=NC₆H₃-2,6-i-Et₂}?CN-C₆H₃-2,6-Me₂?Cl]?8?,and when the ratio is 1:4,the product is [Pd{?4-OMe?C₆H₃CH=NC₆H₃-2,6-i-Et₂}?CN-C₆H₃-2,6-Me₂?₂Cl]?9?.Compound 8 is reacted with sodium azide?1:1?to form compound 10,reacting compound 9 with sodium azide?1:1?to form a compound?11?.It is hoped that an intermediate can be synthesized by this reaction method to study the reaction mechanism of the compound 1-7.The above compounds were characterized by IR and 1H NMR spectra.The compounds 3 and 7 were determined by X-ray single crystal diffraction,and their fine crystalline structure was analyzed.2.synthesis of caged compounds[Pd₆?SC₄H₃CH=NC₆H₃-2,6-i-Er₂?₄??-N₃?8?N₃?₄]?12?.The three phenyl phosphine reaction of red brown and orange crystal crystal 13,14,and 1,4-respectively with two compounds?two phenyl phosphate?butane,1,5-two?two phenyl phosphate?butane,2,6-two methyl phenyl isocyanide,ethyl isothiocyanate,imidazole,1-methyl imidazole reaction to investigate reaction the caged compounds through its reaction with these substances.The above compounds have been characterized by infrared spectroscopy.The compounds 13 and 14 have been determined by X-ray single crystal diffraction,and the single crystal structure of compound 14 has been analyzed.