Bis[pentamethyl(cyclopentadienyl)]uranium(IV) complexes of S,S diphenylsulfilimine

Abstract

In toluene, the reaction of CP*2UCl2 with anhydrous HNSPh2 yields the neutral N-donor adduct Cp*2UCl2(HNSPh2), 1, that crystallizes in the monoclinic space group C2/c with unit cell parameters a = 23.83(3) A, b = 9.92(1) A, c = 27.29(3) A, β = 94.36(4)°, V = 6430(12) A3 , Z = 8, R = 6.77% and Rg = 7.17%. The structure was determined with 1310 unique reflections of I > 3σ. Attempts to induce the dehydrochlorination of 1 to Cp*2UCl(NSPh2), 2, were not successful. However, 2 can be prepared by the reaction of Cp*2UCl2 with one equivalent of LiNSPh2. 2 reacts with another equivalent of LiNSPh2 to give Cp*2U(NSPh2)2, 3. 2 and 3 can also be prepared by the reaction of Cp*2UCl(CH2)2PR2 with one and two equivalents of HNSPh2, respectively. 2 crystallizes in the monoclinic space group P21/n with unit cell parameters a = 12.120(5) A, b = 13.249(6) A, c = 21.644(8) A, β = 95.57(3)°, V = 3445(2) A3 , Z = 4, R = 6.55%, Rg = 8.00% for 2530 unique reflections with I > 2σ. The structure of 3 has been determined to be in the monoclinic space group C2/c with unit cell parameters a = 15.70(1) A, b = 13.00(1) A, c = 19.13(1) A, β = 92.98(6)°, V = 3898(5) A3 , Z = 4, R = 4.54%, Rg = 6.56% for 6345 unique reflections with I > 2σ. The reaction of 1 with HNSPh2H2O yields Cp*2UCl(OH) (HNSPh2), 4, that crystallizes in the monoclinic space group, P21/c with unit cell parameters a = 14.503(5) A, b = 30.10(1) A, c = 17.048(9) A, β = 102.20(3)°, V = 7273(5) A3 , Z = 8, R = 6.53%, Rg = 9.33% for 6280 unique reflections with I > 2σ. Further reaction of 4 with HNSPh2H2O forms the complex, 5. The structure of 5 has been determined to be in the triclinic space group P1 bar with unit cell parameters a = 14.093(7) A, b = 15.36(1) A, c = 16.153(5) A, α= 88.9(1)°, β = 64.56(6)°, γ= 71.88(8)°, V = 3018(3) A3 , Z = 1, R = 5.64%, Rg = 7.91% for 5008 unique reflections with I > 3σ. Based on the crystallographic data, compound 5 has been formulated as [Cp*(Cl)(HNSPh2)U- (µ3-0H)(µ2-O)2-U(Cl)(HNSPh2)2]2.