CAJ | 학술논문

采用ONIOM(B3LYP/6-31G(d):AM1)方法,对β-二酮二亚胺A1配合物LAl[η~2-(CsiMe_3)_2](L=HC [(CMe)(NAr)]_2,Ar=2,6-~iPr_2C_6H_3)和LAl[η~2-(CPh)_2](L=Hc[(CMe)(NAr)]_2,Ar=2,6-~iPr_2C_6H_3)的CO插入反应进行了理论研究,并在B3LYP/6-311G(d,p)水平上分析了反应物、过渡态和产物的键合特征.结果表明:反应活化能和前线分子轨道能级差较低,该插入过程易于进行;与过渡金属原子的酰基配合物不同,主族元素Al的酰基配合物中,Al原子与酰基碳原子之间不存在σ-π仃配键,而是Al的3s轨道与酰基C原子的sp~2杂化轨道形成的电价配键,且Al的酰基配合物可能较过渡金属类似物有更高的化学活性.
채용ONIOM(B3LYP/6-31G(d):AM1)방법,대β-이동이아알A1배합물LAl[η~2-(CsiMe_3)_2](L=HC [(CMe)(NAr)]_2,Ar=2,6-~iPr_2C_6H_3)화LAl[η~2-(CPh)_2](L=Hc[(CMe)(NAr)]_2,Ar=2,6-~iPr_2C_6H_3)적CO삽입반응진행료이론연구,병재B3LYP/6-311G(d,p)수평상분석료반응물、과도태화산물적건합특정.결과표명:반응활화능화전선분자궤도능급차교저,해삽입과정역우진행;여과도금속원자적선기배합물불동,주족원소Al적선기배합물중,Al원자여선기탄원자지간불존재σ-π정배건,이시Al적3s궤도여선기C원자적sp~2잡화궤도형성적전개배건,차Al적선기배합물가능교과도금속유사물유경고적화학활성.
CO insertion into LAl[η~2-(CsiMe_3)_2](L=HC[(CMe)(NAr)]_2,Ar=2,6-~iPr_2C_6H_3)and LAl[η~2-(CPh)_2](L=HC[(CMe)(NAr)]_2,Ar=2,6-~iPr_2C_6H_3)have been studied theoretically using the ONIOM (B3LYP/6-31G(d):AMl)method.The bonding characters about the stationary points during the reactions have been explored by natural bond orbital(NBO)analysis at the B3LYP/6-311G(d,p)level.It was found that the ac-ylation reactions are facile due to their rather low activation energy barriers and considerable similarity between their frontier molecular orbitals.Furthermore,unlike transition metal elements which interact with C(O)by both σ and π bonding,the A1 atom is linked to the carbon atom by a coordinate bond involving the Al 3s orbital and the sp~2 hybridized orbital of carbon.As a result,acyl compounds of Al may be more reactive than those formed by transi-tion metals.