Polymetallic Uranium Azide

and Nitride Complexes

Tanya Kumanova Todorova
Justin R. Walensky and William J. Evans
University of California, Irvine
 Uranium nitride vs. oxide
I
I
U U
I
6 O U O + 3NaN 3 2 I E I + other products ( 1)
I - 18THF I
I
O U

E = N , 1; O , 2

W. J. Evans et al. Inorg. Chem. 46, 8008 (2007)

Product [(C5Me5)U(µ-I)2]3(μ3-E) is identified by X-ray crystallography

• E = N: U4+ nitride complex derived from conversion of azide to nitride

• E = O: (U4+)2(U3+) mixed valence compound derived from adventitious

source of oxygen
 Uranium nitride vs. oxide
I
I
U U
(2)
3 UI3 + 3 KC 5 Me5 I O I
- 3 KI
I I
U

2
Hitchcock et al. Chem. Commun. 1, 82 (2008)

The two compounds have different color, crystallographic space group

and NMR spectrum: these are two different complexes.

Is theory capable in differentiating between the two pairs (nitride

vs. oxide in polymetalic uranium complexes)?
 Uranium nitride vs. oxide

U E U E
N2 (4)
U B + KC 8 E U E U
THF E U E U
E E U E

[(C5Me5)U(μ3-E)8 not identified by X-ray crystallography

U4+ nitride or U3+ oxide complex?

It could also be mixed oxide/nitride with a mixture of uranium

valences
Single crystals are not obtainable  characterization not possible
 Polymetallic Uranium Azide/Nitride

W. J. Evans et al. Inorg. Chem. 46, 8008 (2007)

W. J. Evans, S. A. Kozimor, W. J. Ziller Science 309, 1835 (2005)

Compounds dense in uranium and nitrogen: interesting as molecular

precursors to high-purity UN, a potential nuclear fuel of the future
 Computational Approach
1. DFT optimization and comparison with X-ray crystallography data
2. CASSCF/CASPT2 investigations of the electronic structure

• PBE functional & def-TZVP basis sets on all atoms (ECP on I and U)
• NBO analysis
• Turbomole 5.10 package

• ANO-RCC-VDZP on U, N, O, B, I; ANO-RCC-MB on F, C and H

• CAS: 6/21 for [(C5Me5)U(μ-I)2]3(μ3-N)] and [(C5Me5)2UN3(µ-N3)]3
7/21 for ([(C5Me5)U(μ-I)2]3(μ3-O)
14/14 for [(C6F5)3BNU(N[Me]Ph)3
• MOLCAS 7.3 package
 Uranium nitride vs. oxide

At DFT level: septet octet

At CASSCF/CASPT2:
Septet, quintet, triplet and singlet states are almost degenerate for
[(C5Me5)U(μ-I)2]3(μ3-N)]
Octet, sextet and quartet states are almost degenerate for
[(C5Me5)U(μ-I)2]3(μ3-O)]
 Uranium nitride vs. oxide

• Very good agreement with the experimental X-ray data

• The only difference is in the U – E bond lengths

U – O bond lengths are 2.208, 2.203 and 2.193 Å, being longer than
the U – N ones (2.145, 2.149 and 2.154 Å)
 Uranium nitride vs. oxide
[(C5Me5)U(μ-I)2]3(μ3-N)]:

NBO analysis: U1(5f2.03), U2(5f2.09), U3(5f2.09)

CASSCF/CASPT2: U1(5f1.99), U2(5f1.99), U3(5f1.99)

5f2  U4+ centers  U4+ nitride complex

[(C5Me5)U(μ-I)2]3(μ3-O)]:

NBO analysis: U1(5f2.34), U2(5f2.31), U3(5f2.34)

CASSCF/CASPT2: U1(5f2.97), U2(5f1.99), U3(5f1.99)

U3+, U4+, U4+  (U4+)2(U3+) mixed valence complex

Uranium nitride
 Uranium oxide

• Both structures are very ionic: no U – N and U – O interactions

• Electrons are localized only on U: linear combinations of 5f

Uranium azide: [(C5Me5)2UN3(µ-N3)]3

• Trimetallic U(IV) complex

• Each U is attached to two bridging azide

ligands and one terminal azide

• Insights into U – N (azide) bonding

existing in [(C5Me5)2U(µ-N)U(µ-N3)(C5Me5)2]4

• Very good agreement with the experimental X-ray data

• Eight septets and eight quintets are almost degenerate in energy

• Very ionic structure

Uranium azide: [(C5Me5)2UN3(µ-N3)]3
 Uranium nitride vs. oxide

U E U E
N2 (4)
U B + KC 8 E U E U
THF E U E U
E E U E

• DFT only!!! Required CAS: 16 electrons in 56 orbitals

• Differences in the U – E and U – Cnt bond lengths
• Experimental structure is E = N

E=N E=O Experiment

U–E 2.145 – 2.359 2.184 – 2.499 2.142 – 2.405
U – Cnt 2.557 – 2.600 2.488 – 2.539 2.554 – 2.573
 [(C5Me5)2U(μ-N)(C5Me5)2U(μ-N3)]4

• Mixed nitride azide complex

• Crystallizes with a 24 atom (UNUNNN)4 ring
• Near linear UNU linkages
• X-ray crystallographic studies indicate that it crystallizes both in a
pseudo-boat and a pseudo-chair form
• DFT only!!! CASSCF/CASPT2 not plausible
 Boat or Chair?

Chair Boat

• Very good agreement with experiment

• The two conformations are very flexible in their geometries
• DFT favors the boat structure by only ca. 5 kcal/mol
• The chair conformation is a local minimum
 [(C6F5)3BNU(N[Me]Ph)3

• First nitridoborate complex of uranium

• Nearly linear B – N ≡ U core
• The system is an analogue of the formally
triply bonded U(VI) organoimido complexes
(bond multiplicity value is 2.83)

CASSCF/CASPT2 study to investigate the U – N type of bonding and

to compare it with the bonding in [(C5Me5)U(µ-I)2]3(μ3-N) and
[(C5Me5)2U(µ-N)U(µ-N3)(C5Me5)2]4
 [(C6F5)3BNU(N[Me]Ph)3

The uranium nitride bonding in this complex has much more pronounced
covalent character than any of the polymetallic uranium complexes.