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Synthesis of Alkoxides, Imidos, Thiolates, and Phosphides of Uranium and Investigation of their Metal Ligand Bonds

  • Author(s): Paul, Edward
  • Advisor(s): Hayton, Trevor W
  • et al.
Abstract

Addition of 2 equiv of Ph3COH to UO2[NR2]2(THF)2 (R = SiMe3) generates the U(VI) bis-alkoxide complex UO2(OCPh3)2(THF)2. Reduction of UO2(OCPh3)2(THF)2 with 2 equiv of KC8 results in the reduction of the complex to “U(IV)O2” and formation of KOCPh3. Addition of 2 equiv of Ph3CSH to UO2[NR2]2(THF)2 generates the U(VI) bis-thiolate complex UO2(SCPh3)2(THF)2. The reduction of UO2(SCPh3)2(THF)2 with 2 equiv of KC8 results in the reduction of the complex to “U(IV)O2” and formation of KSCPh3. Finally, reduction of UO2(SCPh3)2(THF)2 with 1 equiv of Cp*2Co results in the reduction of the complex to “U(IV)O2” and formation of [Cp*2Co][SCPh3].

Addition of 1 equiv of 1-azidoadamantane to U(NR2)3 (R = SiMe3) generates (AdN)U(NR2)3. The U(V) imido complexes (AdN)U(NR2)3 and (RN)U[N(R)2]3, along with the U(V) oxo (O)U(NR2)3 were characterized utilizing UV-Visible spectroscopy and SQUID magnetometry to quantify the f-orbital participation in the U-N and U-O multiple bonds.

Addition of Se to [Na(DME)3][(N(SiMe3)2)2U(μ- N)(CH2SiMe2N(SiMe3))U(N(SiMe3)2)2] in the presence of 18-crown-6 resulted in the formation of [Na(18-crown-6)][(N(SiMe3)2)2U(μ- N)(SeCH2SiMe2N(SiMe3))U(N(SiMe3)2)2]. Addition of Te to [Na(DME)3][(N(SiMe3)2)2U(μ-N)(CH2SiMe2N(SiMe3))U(N(SiMe3)2)2] in the presence of 18-crown-6 generates Na(18-crown-6)][(N(SiMe3)2)2U(μ- N)(TeCH2SiMe2N(SiMe3))U(N(SiMe3)2)2]. Treatment of [Na(DME)3][(N(SiMe3)2)2U(μ- N)(CH2SiMe2N(SiMe3))U(N(SiMe3)2)2] with 1 equiv of 1-azidoadamantane results in the formation of [Na(DME)3][(N(SiMe3)2)2(C10H15N)U(μ- N)(CH2SiMe2N(SiMe3))U(N(SiMe3)2)2].

Addition of 4 equiv of LiNHCPh3 to UCl4, along with 1 equiv of I2 generates U(NCPh3)I2THF2. Treatment of UCl4 with 4 equiv of LiNHCPh3 and 1 equiv of I2 in the presence of bipyridine (bipy) generates U(NCPh3)I2(bipy)2. Addition of 12 equiv of KC8 to 7 equiv of P4 in the presence of 18-crown-6 results in [K(18-crown-6)]3[P7]. Treatment of U(NR2)3 with 0.33 equiv of [K(18-crown-6)]3[P7] results in [K(18-crown- 6)][((SiMe3)3U)2(μ-η2:η2-P2] . Addition of 0.5 equivalents of [K(18-crown-6)]3[P7] to U(NR2)3 (R = SiMe3) generates [K(2,2,2-cryptand)][((SiMe3)2U)2(μ-η5:η5-P5].

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