The addition of donors to (dadi)Ti(THF) (1-THF, dadi = [{−CH═N(1,2-C₆H₄)N(2,6-ⁱPr₂–C₆H₃)}₂]ⁿ) afforded the adducts [(dadi)Ti(L/X)]^m (1-L, m = 0, N₂CPh₂; m = −1, X = Cl^–, N₃^–, OⁱPr^–, CH₃^–, ^neoPe^–, CH═CH₂^–, CCPh^–, CCTMS^–, H(D)⁻). In all adducts, the chelate was in the (dadi)^4– redox state. For certain anions, evidence for intimate binding of the Li⁺ counterion was explored spectroscopically. Treatment of 1-THF with PhHCN₂, yielded {PhC₃H₃(-NC₆H₄-2-NAr)₂}Ti(THF) (3, Ar = 2,6-ⁱPr₂–C₆H₃), which contains a cyclopropanated dadi ligand. The mechanism was explored by calculations, and the addition of Ph₂CN₂ to 3 produced a nacnac derivative, {PhC(CHNC₆H₄-2-NAr)₂}Ti(η²-HNNCPh₂) (4, Ar = 2,6-ⁱPr₂–C₆H₃), generated via hydrogen transfer from the cyclopropane.

中文翻译：

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[（dadi）Ti（L / X）] ^m的络合物揭示了氧化还原非纯和逐步将碳插入碳-碳键中

给（dadi）Ti（THF）（1 - THF ，dadi = [{-CH═N（1,2-C ₆ H ₄）N（2,6- ⁱ Pr ₂ –C ₆ H ₃） } ₂ ] ⁿ）得到加合物[（dadi）Ti（L / X）] ^m（1 -L，m = 0，N ₂ CPh ₂ ; m = -1，X = Cl ^–，N ₃ ^–，O ⁱ PR ^-，CH ₃ ^- ，^新Pe的^-，CH = CH ₂ ^-，CCPh^–，CCTMS ^–，H（D）⁻）。在所有加合物中，螯合物均处于（大地）^4-氧化还原状态。对于某些阴离子，通过光谱法研究了Li ⁺抗衡离子紧密结合的证据。用PhHCN ₂处理1 -THF ，得到{PhC ₃ H ₃（-NC ₆ H ₄ -2-NAr）₂ } Ti（THF）（3，Ar = 2,6- ⁱ Pr ₂ –C ₆ H ₃） ，其中包含环丙烷化的dadi配体。通过计算探索了机理，并添加了Ph ₂CN ₂至3制备的nacnac衍生物，{光子晶体（CHNC ₆ ħ ₄ -2-NAR）₂ }的Ti（η ² -HNNCPh ₂）（4中，Ar = 2,6-^我镨₂ -C ₆ ħ ₃），通过环丙烷的氢转移产生的。