Exploring the Insertion Chemistry of Tetrabenzyluranium Using Carbonyls and Organoazides
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https://figshare.com/articles/dataset/Exploring_the_Insertion_Chemistry_of_Tetrabenzyluranium_Using_Carbonyls_and_Organoazides/2407288
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The
insertion chemistry of U(CH2C6H5)4 (1) was explored with acetone, benzophenone,
mesityl azide, and 1-azidoadamantane. Using 2 equiv of acetone affords
the double-insertion product U[OC(CH3)2(CH2C6H5)]2(CH2C6H5)2(THF)2 (2), while using 4 equiv results in the tri-inserted enolate
product U[OC(CH3)2(CH2C6H5)]3[OC(CH3)CH2](THF)3 (3). Deuterium labeling
experiments aided in the assignment of 2 and 3. With 4 equiv of benzophenone, insertion at all U–C bonds
is noted, forming U[OC(C6H5)2(CH2C6H5)]4 (4)
and the THF adduct U[OC(C6H5)2(CH2C6H5)]4(THF)
(4-THF). Addition of 4 equiv of N3Mes to 1 forms the tetrakis(triazenido)uranium(IV) complex U[CH2(C6H5)NNN(Mes)-κ2N1,2][CH2(C6H5)NNN(Mes)-κ2N1,3]3 (5), while the same reaction
with 1-azidoadamantane generates the uranium(VI) trans-bis(imido) complex U(NAd)2[CH2(C6H5)NNN(Ad)-κ2N1,3]2(THF) (6). All species
were characterized by 1H NMR and infrared spectroscopy,
with select examples being structurally characterized using single-crystal
X-ray diffraction.
创建时间：
2013-06-10
