Reaction of UCl4(THF)(4) with 1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H4Li2 produced a complex formulated as [{1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H4}UCl3][Li(THF)(4)] (1) that exhibits a nonagostic interaction between one of the carbon atoms of the central phenyl ring and the U metal center. This interaction leads to significant weakening of the corresponding C-H bond, thereby facilitating proton removal in consecutive transformations. Attempts to form trivalent uranium derivatives were carded out by reacting the same ligand dianion with in situ-prepared "UCl3". The reaction indeed afforded a trivalent species formulated as {1,3-[2,5-(i-Pr)(2)-PhNC(=CH2)](2)C6H4 }U(mu-Cl)(3)[Li(THF)(2)](2) (2). The configuration of the ligand system in this complex is similar to that in 1, with the same type of arrangement of the central phenyl ring. Further reduction chemistry with a variety of reagents and conditions was examined. Reaction of 1 with 1 equiv of lithium naphthalenide at 0 degrees C did not afford 2 but instead gave a closely related U(III) complex formulated as {1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H4}-U(THF)(mu-Cl)(2)[Li(Et2O)(2)] (3). Both of the trivalent complexes 2 and 3 reacted thermally in boiling THF, undergoing oxidation of the metal center to afford a new tetravalent compound {1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H3}U(THF)-(mu-Cl)(2)[Li(THF)(2)] (4) in which the oxidation of the trivalent center occurred at the expense of the central phenyl ring C-H bond. Reaction of 1 with 3 equiv of lithium naphthalenide at room temperature afforded {{1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H3}U(mu-Cl)(mu-[O(CH2)(3)CH2])[Li(DM E)]}[Li(DME)(3)] (5). In this species, the tetravalent metal center forms a six-membered metallacycle ring with a moiety arising from THF ring opening. Reaction in DME afforded reductive cleavage of the solvent accompanied by reoxidation of U to the tetravalent state. Reduction of 1 in DME with 2 equiv of potassium naphthalenide at room temperature gave a mixture of two compounds having very similar structures. The two different species [{1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H3}UCl-(OCH3)][Li(DME)(3)] (6a) and [{1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H3}UCl2][Li(DME)(3)] (6b) cocrystallized in a ratio very close to 1:1 within the same unit cell. The methoxide group was generated from cleavage of the DME solvent. We also attempted the reduction of 1 with a different reducing agent such as NaH in DME. After a slow reaction, a new species formulated as {1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H3}U(mu-OCH3)(3)(mu,eta(6)-Na)[eta(3) -Na(DME)] (7) was isolated in significant yield. Once again, the crystal structure revealed the presence of several methoxy groups coordinated to the U center in addition to the metalation of the ligand phenyl ring. To minimize solvent cleavage, reduction of 1 was also carded out at low temperature (-35 degrees C) and ith a larger amount (4 equiv) of lithium naphthalenide. After suitable workup, the new species {[(1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H3}U{1,3-[2,5-(i-pr)(2)PhN=C(CH3)]( 2)C6H4)][Li(DME)(THF)])center dot Et2O (8) was isolated, in significant yield. Even in this case, the uranium atom is surrounded by the expected trianionic, ring-metalated ligand. However, a second ligand unit surrounds the metal center, being bonded through a part of the pi system. Reaction of 1 with excess NaH in toluene proceeded slowly at room temperature, affording a significant yield of {[{1,3-[2,5-(i-Pr)(2)PhNC(=CH2)](2)C6H3)U{1,3-[2,5-(i-Pr)(2)PhN=C(CH3)]( 2)C6H4}{Na(DME)(2)}][Na(DME)(3)]}center dot 1/2C(7)H(8) (9) after crystallization from DME/ toluene. Similar to 8, the complex still contains one ring-metalated trianionic ligand and one intact ligand that has regained the H atoms and restored the two imine functions. Although according to their connectivities, complexes 8 and 9 could be assigned with the formal oxidation states +2 and +1, respectively, density functional theory calculations clearly indicated that these species contain additional spin density on the ligand system with the metal center in its more standard trivalent state.