Synthesis and Reduction of Heteroleptic Bis(cyclopentadienyl) Uranium(III) Complexes.

Heteroleptic U(III) complexes supported by bis(cyclopentadienyl) frameworks have been synthesized to examine their suitability as precursors to U(II) complexes. The newly synthesized (C 5 Me 5 ) 2 U(OC 6 H 2 t Bu 2 -2,6-Me-4), (C 5 Me 5 ) 2 U(OC 6 H 2 Ad 2 -2,6- t Bu-4) (Ad = 1-adamantyl), (C 5 Me 5 ) 2 U(C 5 H 5 ), and (C 5 Me 5 ) 2 U(C 5 Me 4 H) are compared with (C 5 Me 5 ) 2 U[N(SiMe 3 ) 2 ], (C 5 Me 5 ) 2 U[CH(SiMe 3 ) 2 ], and (C 5 Me 5 )U[N(SiMe 3 ) 2 ] 2 . An improved synthesis of (C 5 Me 5 ) 2 U(μ-Ph) 2 BPh 2 was developed, which was used to synthesize (C 5 Me 5 ) 2 U(C 5 Me 4 H). Since the X-ray crystal structure of (C 5 Me 5 ) 2 U(OC 6 H 2 t Bu 2 -2,6-Me-4) contained two very different molecules in the asymmetric unit with 115.7(5)° and 166.0(5)° U-O-C ipso angles, the (C 5 Me 4 H) 2 U(OC 6 H 2 t Bu 2 -2,6-Me-4) and (C 5 Me 5 ) 2 Ce(OC 6 H 2 t Bu 2 -2,6-Me-4) analogues were synthesized and characterized by X-ray diffraction for comparison. Electrochemical studies in THF with a 100 mM [ n Bu 4 N][BPh 4 ] supporting electrolyte showed U(IV)/U(III) and U(III)/U(II) redox couples for all the heteroleptic complexes except (C 5 Me 5 ) 2 U(C 5 H 5 ). Chemical reduction of all heteroleptic compounds formed dark blue solutions characteristic of U(II) when reacted with KC 8 at -78 °C, but none formed isolable U(II) complexes. The targeted U(II) complexes, [(C 5 Me 5 ) 2 U(OC 6 H 2 t Bu 2 -2,6-Me-4)] 1- , {(C 5 Me 5 ) 2 U[CH(SiMe 3 ) 2 ]} 1- , [(C 5 Me 5 ) 2 U(C 5 H 5 )] 1- , and [(C 5 Me 5 ) 2 U(C 5 Me 4 H)] 1- , were analyzed by density functional theory, and a 5f 3 6d 1 electron configuration was found to be the ground state in each case.