Heins Spencer P, Wolczanski Peter T, Cundari Thomas R, MacMillan Samantha N
Cornell University , Dept. Chemistry & Chemical Biology , Baker Laboratory , Ithaca , NY 14853 , USA . Email:
University of North Texas , Dept. of Chemistry , CASCaM , Denton , TX 76201 , USA . Email:
Chem Sci. 2017 May 1;8(5):3410-3418. doi: 10.1039/c6sc05610e. Epub 2017 Mar 6.
Application of the diamide, diimine {-CH[double bond, length as m-dash]N(1,2-CH)N(2,6-Pr-CH)} ((dadi) ) ligand to titanium provided adducts (dadi)TiL (-L ; L = THF, PMePh, (CNMe)), which possess the redox formulation [(dadi)]Ti(iv)L , and 22 πe (4 + 2). Related complexes containing titanium-ligand multiple bonds, (dadi)Ti[double bond, length as m-dash]X ( [double bond, length as m-dash]X; X = O, NAd), exhibit a different dadi redox state, [(dadi)]Ti(iv)X, consistent with 20 πe (4). The Redox Non-Innocence (RNI) displayed by dadi impedes binding by CO, and permits catalytic conversion of AdN + CO to AdNCO + N. Kinetics measurements support carbonylation of [double bond, length as m-dash]NAd as the rate determining step. Structural and computational evidence for the observed RNI is provided.
将二酰胺、二亚胺{-CH[双键，长度为中划线]N(1,2 - CH)N(2,6 - Pr - CH)}（(dadi) ）配体应用于钛得到加合物(dadi)TiL （-L ；L = THF、PMePh、(CNMe)），其具有氧化还原形式[(dadi)]Ti(iv)L ，以及22个π电子（4 + 2）。含有钛 - 配体多重键的相关配合物(dadi)Ti[双键，长度为中划线]X（[双键，长度为中划线]X；X = O、NAd）表现出不同的dadi氧化还原态[(dadi)]Ti(iv)X，与20个π电子（4）一致。dadi 表现出的氧化还原非无害性（RNI）阻碍了CO的配位，并允许将AdN + CO催化转化为AdNCO + N。动力学测量支持[双键，长度为中划线]NAd的羰基化作为速率决定步骤。提供了观察到的RNI的结构和计算证据。
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