Synthesis of Alkoxides, Imidos, Thiolates, and Phosphides of Uranium and investigation of their Metal Ligand bonds

Author:

Paul, Edward Louis

Degree Grantor:

University of California, Santa Barbara. Chemistry

Degree Supervisor:

Trevor W. Hayton

Place of Publication:

[Santa Barbara, Calif.]

Publisher:

University of California, Santa Barbara

Creation Date:

2016

Issued Date:

2016

Topics:

Chemistry

Keywords:

Uranium,
Alkoxide,
Pnictogen, and
Phosphorus

Genres:

Online resources and Dissertations, Academic

Dissertation:

M.S.--University of California, Santa Barbara, 2016

Description:

Addition of 2 equiv of Ph3COH to UO2[NR 2]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 KOCPh 3. Addition of 2 equiv of Ph3CSH to UO2[NR 2]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)O 2" and formation of KSCPh3. Finally, reduction of UO 2(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(mu- N)(CH2SiMe2N(SiMe3))U(N(SiMe 3)2)2] in the presence of 18-crown-6 resulted in the formation of [Na(18-crown-6)][(N(SiMe3)2) 2U(mu- N)(SeCH2SiMe2N(SiMe3))U( N(SiMe3)2)2]. Addition of Te to [Na(DME)3][(N(SiMe3)2)2U(mu-N)(CH 2SiMe2N(SiMe3))U(N(SiMe3)2) 2] in the presence of 18-crown-6 generates Na(18-crown-6)][(N(SiMe 3)2)2U(mu- N)(TeCH2SiMe 2N(SiMe3))U(N(SiMe3)2)2]. Treatment of [Na(DME)3][(N(SiMe3)2) 2U(mu- N)(CH2SiMe2N(SiMe3))U(N(SiMe 3)2)2] with 1 equiv of 1-azidoadamantane results in the formation of [Na(DME)3][(N(SiMe3)2) 2(C10H15N)U(mu- 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 I 2 in the presence of bipyridine (bipy) generates U(NCPh3)I 2(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(mu-eta2:eta 2-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)][((SiMe 3)2U)2(mu-eta5:eta 5-P5].

Physical Description: