二吡唑硼酸金属配合物的合成表征与催化性能研究无机化学专业论文.docxVIP

ABSTRACTThree ABSTRACT Three bis(pyrazolyl)borate ligands were sleeted to react with CoCl2，NiCl2，Ni(acac)2， CuCl2，Cu(PPh3)2N03(I)，ZnCl2，ZrCl4 and TICl4 to produce corresponding complexes， respectively．Eight compounds were characterized by single—crystal X—ray diffraction．An of them show weak intramolecular C—H M interactions which call be assigned as agosfic or anagostic and preagostic interactions． In the past decades，transition metal organometallic complexes have been found to show some unusual bonding modes．One typical example is the agosfic interaction．In addition， non。agostic and anagostic or preagostic are complementary terms used to describe systems that，while showing similar close C-H M proximity,are not considered truly agosfic in nature． Agostic interactions are often used to active inert C—H bonds，and thus facilitate new reactions． The dissertation demonstrates the first example of designed catalysts based on the agostic interaction and the catalytic property of three new copper(I)complexes．It mainly includes the following parts： A novel methodology is reported for the hi曲ly yield synthesis of bis(pyrazolyl)borate ligands[(BBN)BpK]一(R=H，Me，1Pr)through one—pot reactions by mixing commercially available 9-BBN dimer(BBN=9-borabicyclo[3．3．1]nonane)，HpzR(3．substitued pyrazole) and metal hyarides(sodium hydride or potassium hydride)． Bis(pyrazolyl)borate ligand[(BBN)Bp]‘(1)reacted with Ni(acac)2，CuCl2 and ZnCl2 at 2：1 molar ratio leading to bis(pyraz01y1)borate complexes Ni[(BBN)Bp]2(4)，Cu[(BBN)Bp]2 (5)and Zn[(BBN)Bp]2(6)in hie#yields，respectively．The reactions of(BBN)Bp(1)with I equiv．of ZrCl4 or,TICl4 in THF affords the complex[(BBN)BplZrCl3·THF(9)or, 【(BBN)Bp]TiCIs(10)．Treatment of 1 with Cu(PPh3)2N03(I)in toluene at room temperature gave the copper complex【(BBN)Bp]Cu(PPh3)2(7)．1 reacted with Ni(acac)2，Ni(acac)2 and Napz at 1：1：1 molar ratio in CH2C12 resulting in binuclear complex Ni2[(BBN)Bp]2(pz)2(11)． All complexes are characterized by elementa