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

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Item Summary

Title: Bis[pentamethyl(cyclopentadienyl)]uranium(IV) complexes of S,S diphenylsulfilimine
Authors: Ariyaratne, Kanahara A.N.S.
Issue Date: 1992
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.
Description: Thesis (Ph. D.)--University of Hawaii at Manoa, 1992.
Includes bibliographical references (leaves 242-252).
Microfiche.
xxi, 252 leaves, bound ill. 29 cm
URI/DOI: http://hdl.handle.net/10125/9511
Rights: All UHM dissertations and theses are protected by copyright. They may be viewed from this source for any purpose, but reproduction or distribution in any format is prohibited without written permission from the copyright owner.
Appears in Collections:Ph.D. - Chemistry



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