Back-bonding

between an
electron-poor, high-
oxidation-state
metal and poor π-
acceptor ligand in a
uranium(v)–
dinitrogen complex

Erli Lu, Benjamin E. Atkinson   , Ashley J. Wooles,

Josef T. Boronski   , Laurence R. Doyle, Floriana
Tuna, Jonathan D. Cryer, Philip J. Cobb, Inigo J.
Vitorica-Yrezabal, George F. S. Whitehead   , Nikolas
Kaltsoyannis    and Stephen T. Liddle   *

REYNALDO MARLES
 INDEX

• Abstract
• Results and discussion
• The Synthesis
• Analysis of the reaction
• Structural characterization
• Spectroscopic and magnetic characterization
• Spectroscopic and magnetic characterization
RAMAN
• Discussion
• Conclusions
 Abstract

• A fundamental bonding model in coordination and organometallic

chemistry is the synergic, donor–acceptor interaction between a metal and
a neutral π-acceptor ligand, in which the ligand σ donates to the metal,
which π back-bonds to the ligand. This interaction typically involves a
metal with an electron-rich, mid-, low- or even negative oxidation state and
a ligand with a π* orbital. Here, we report that treatment of a uranium–
carbene complex with an organoazide produces a uranium(v)–bis(imido)–
dinitrogen complex, stabilized by a lithium counterion. This complex, which
was isolated in a crystalline form, involves an electron-poor, high-
oxidation-state uranium(v) 5f 1 ion that is π back-bonded to the poor π-
acceptor ligand dinitrogen. We propose that this is made possible by a
combination of cooperative heterobimetallic uranium–lithium effects and
the presence of suitable ancillary ligands that render the uranium ion
unusually electron rich. This electron-poor back-bonding could have
implications for the field of dinitrogen activation.
Results and discussion
The Synthesis
 The Synthesis

Treatment of 1 with one equivalent of 1-adamantylazide (AdN3) in benzene resulted

in an immediate effervescence of N2 and the red solution turning black. After
workup, blackish-red crystals of [U(BIPMTMS)(NAd)2(μ-η1 :η1 -N2)(Li-2,2,2-
cryptand)]

were obtained from toluene in a 28% crystalline yield (by uranium content) Complex
2 was formed irrespective of whether the reaction was conducted under N2 or Ar,
which suggests that the coordinated N2 derives from the azide. Analysis of the
reaction mother liquor by NMR spectroscopy revealed that more than one uranium-
containing product was formed.
 The Synthesis

The by-products resisted all attempts to isolate and characterize them, but hydrolysis
of the mother liquor and analysis by NMR spectroscopy and chromatographic methods
reveals the presence of BIPMTMSH2, Me3SiCH2PPh2 and LiCl-2,2,2-cryptand in an
approximate 1:2:1 ratio.
This gives a mass balance for the reaction and accounts for the superficially low yield
of 2, as the theoretical maximum in a scenario in which sacrificial uranium-containing
by-products form is substantially lower than 100%. The reaction that produces 2 is
clearly complex and most probably involves ligand scrambling, but 2 was consistently
the sole isolable uranium complex from multiple reactions.
 Analysis of the reaction

mother liquor by NMR spectroscopy revealed that more than one

uranium-containing product was formed

The by-products resisted all attempts to isolate and characterize them

but hydrolysis of the mother liquor and analysis by NMR spectroscopy

and chromatographic methods reveals the presence of BIPMTMSH2,
Me3SiCH2PPh2 and LiCl-2,2,2-cryptand in an approximate 1:2:1
Structural characterization
 Structural characterization

The solid state molecular structure of 2 was determined by X-ray crystallographic

studies in the figure.

The salient feature of 2 is the presence of a molecule of N2 that bridges between

uranium and lithium ions, the latter of which is encapsulated within a 2,2,2-cryptand
ligand in an irregular six-coordinate geometry.

The coordination sphere of uranium is completed by a tridentate BIPMTMS carbene

ligand trans to the N2 ligand and two mutually trans-imido units, which results in a
distorted octahedral geometry.
Spectroscopic and magnetic
characterization

The NMR spectra that could be obtained for 2,

noting its poor solubility once isolated, are well
resolved and essentially within diamagnetic ranges
 Spectroscopic and magnetic
characterization RAMAN

Fig. Computed potential energy surface scans of the relative energy (kJ mol−1 ) versus the U1-N1 distance (Å) of 2. ‘XRD’ and ‘relaxed’
calculations are on the full molecule 2. ‘Core’ is the model shown in Supplementary Fig. (2 core). PBE and MP2 calculations are spin-unrestricted
(UPBE, UMP2). Both spin restricted (RHF) and unrestricted (UHF) calculations were performed. RASSCF is spin restricted. All the scans are rigid,
that is, in which all the geometric parameters of the non-hydrogen atoms are frozen, other than the U1–N1 distance, except the relaxed/UPBE
scan, in which all other geometric parameters are optimized at each point. For the rigid scans on 2 core, the hydrogen atom positions are
optimized at each point of the scan.
 Discussion

Back bonding in complex 2 arises in an electron-poor, high-oxidation-state

complex, which involves the poor π-acceptor N2 and a single electron in a 5f
orbital — which is one of the least radially expanded orbitals, and therefore
seems an unlikely candidate for this bonding scenario to occur.

We propose two factors that maybe responsible for this unusual situation. First,
the heterobimetallic uranium–lithium combination may cooperatively assist in
trapping the N2, and certainly heteropolymetallic cooperative effects are
increasingly being recognized as crucial to binding and activating N2 in
heterogeneous Haber–Bosch chemistry
 Discussion

The uranium ion in 2 is bonded to two imido ligands and the tridentate BIPMTMS
carbene ligand.
 Conclusions

To conclude, we found that the reaction of a uranium–carbene

complex with an organoazide results in the isolation of a crystalline
uranium(v)–bis(imido)–dinitrogen complex.

This complex features a +5 high-oxidation state metal classically back-bonded

to a neutral π-acceptor ligand,and this is despite formally involving an
electronpoor metal with only one valence electron, 5f 1
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