The University of Manchester Research
Dipnictogen f-Element Chemistry: A Diphosphorus
Uranium Complex
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10.1021/jacs.1c02482
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Du, J., Hunger, D., Seed, J., Cryer, J., King, D. M., Wooles, A., van Slageren, J., & Liddle, S. (2021). Dipnictogen f-
Element Chemistry: A Diphosphorus Uranium Complex. Journal of the American Chemical Society.
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Download date:02. Feb. 2026
Dipnictogen f-Element Chemistry: A Diphosphorus Uranium Com-
plex
Jingzhen Du,a David Hunger,b John A. Seed,a Jonathan D. Cryer,a David M. King,c Ashley J. Wooles,a
Joris van Slageren,b and Stephen T. Liddlea,*
a
Department of Chemistry, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK. b Institute of Physical
Chemistry, University of Stuttgart, Pfaffenwaldring 55, D-70569 Stuttgart, Germany. c School of Chemistry, University of
Nottingham, University Park, Nottingham, NG7 2RD, UK. *e-mail: [Link]@[Link]
Supporting Information Placeholder
ABSTRACT: The first isolation and structural characterization of an f-element dinitrogen complex was reported in
1988, but an f-element complex with the first heavier group 15 homolog diphosphorus has to date remained unknown.
Here, we report the synthesis of a side-on bound diphosphorus complex of uranium(IV) using a 7l3-(dimethyla-
mino)phosphadibenzonorbornadiene-mediated P-atom transfer approach. Experimental and computational characteriza-
tion reveals that the diphosphorus ligand is activated to its dianionic (P2)2- form, and that in-plane U-P p-bonding domi-
nates the bonding of the U(µ-h2:h2-P2)U unit and this is supplemented by a weak U-P interaction of d symmetry. A
preliminary reactivity study demonstrates conversion of this diphosphorus complex to unprecedented uranium cyclo-P3
complexes, suggesting in situ generation of transient, reactive phosphido species.
As the first heavier Group 15 homolog of dinitrogen, N2, there Since the PDBN unit is quite sterically demanding we tested
is burgeoning interest in the chemistry of diphosphorus, P2.1-18 the reaction of 1 with H-PDBN (2),25 Scheme 1, but consistently
Though N2 is terrestrially abundant, P2 is not, and the stable mo- isolated the diuranium(IV)-phosphinidiide complex [{(Tren-
lecular form of phosphorus is P4, with P2 only relevant >1100 TIPS
)UIV}2(µ-PH)] (3),31 that was previously prepared from
K.19-26 Thus, there has been interest in constructing and stabiliz- deprotonating [(TrenTIPS)UIV(PH2)] with benzyl potassium and
ing P2 using main group species and transition metals by acti- treating with [(TrenTIPS)UIV(THF)][BPh4].31 Whilst P-catena-
vation of P4,1-3 carbonylation of the (OCP)- anion,4,5 or P-P bond tion did not occur, this establishes PH-group transfer from the
formation from phosphido,17,23 or diphosphorus-azide ana- PDBN platform in f-element chemistry. The PH unit is evi-
logs.8,9 Recently, the 7l3-phosphadibenzonorbornadiene dently not sterically demanding enough to prevent coordination
(PDBN) group emerged as an elegant platform for accessing a of a second uranium, possibly favored over P-P catenation due
P2-synthon and as a promising reagent for P-atom transfer.20-26 to comproportionation between the likely uranium(V)-phos-
However, the established main group and transition metal P2 phinidene intermediate and uranium(III). We thus increased the
chemistries1-18 contrast starkly to the situation for the f-ele- steric protection, and examined the reaction of 1 with Me2N-
ments. The first f-element N2 complex was the lanthanide spe- PDBN (4),21,24 since p-donor P-substituents promote P-group
cies [{(h5-C5Me5)2SmIII}2(µ-h2:h2-N2)],27 and the first actinide transfer by stabilization of the phosphinidene moiety.20-26 Treat-
N2 complex was [{(TrenDMBS)UIV}2(µ-h2:h2-N2)] (TrenDMBS = ment of 1 with Me2N-PDBN resulted in precipitation of dark
{N(CH2CH2NSiMe2But)3}3-).28 However, P2 analogs have re- red crystals of [{(TrenTIPS)UIV}2(µ-h2:h2-P2)] (5), Scheme 1,
mained unknown, reflecting the capricious nature of P4 activa- and a brown solution. Work up of the mother liquor gave brown
tion and the paucity of rational methods to generate P2 at f-ele- crystals of the uranium(IV)-amide complex [(Tren-
TIPS
ments. )UIV(NMe2)] (6), accounting for the fate of the NMe2 group.
We previously reported that treatment of [(TrenTIPS)UIII] (1, We consistently isolate 5 and 6 in crystalline yields of 45 and
TrenTIPS = {N(CH2CH2NSiPri3)3}3-)29 with P4 in any ratio af- 34% (by U content), noting that 50% is the maximum for each
forded [{(TrenTIPS)UIV}2(µ-h5:h5-P5)] that exhibits U-P d-bond- due to the formation of 6, revealing a selective reaction.32 This
ing.30 Seeking a P-transfer reagent where reactivity could be contrasts to the formation of [{(TrenTIPS)UIV}2(µ-h5:h5-P5)],30
modulated, we drew inspiration from the PDBN family,20-26 and demonstrating that the TrenTIPS sterics do not decisively deter-
introduced its reactivity to f-element chemistry. Here, we report mine the nature of the product, and the P-delivery reagent also
the construction of P2 at uranium, the first f-element P2 complex determines the extent of P-oligomerization in the product.
over thirty years after the first N2 complex.27 Preliminary reac- The formation of 3 and 5 suggest that HP and Me2NP phos-
tivity studies show this P2 complex can be converted to uranium phinidene group transfers occur,24 with subsequent reductive P-
cyclo-P3 derivatives. The electronic structures of these P2 and N cleavage and P-P coupling mediated by uranium(III) for 5.
cyclo-P3 complexes emphasize the dominant role of p-bonding However, the formation of 5 raises the possibility that Me2N-
in these actinide complexes. PDBN is reduced by uranium(III) to (PDBN)2, analogously to
Scheme 1. Reactions of the R-PDBN reagent with R = H or NMe2 to give the parent phosphinidiide 3 or the diphosphorus complex 5 with amide 6.
Subsequent reduction of 5 with alkali metal reagents provides the derivatives 7M (M = K, Rb, Cs) and the cyclometallate 8 along with alkali metal phosphide.
Cl-PDBN reduction to (PDBN)2,21 subsequently delivering pre- to twice the double bond covalent radii of P (2.04 Å),33 and is
formed P2 to uranium. To test this, we treated 1 with (PDBN)2,21 shorter than zig-zag-and butterfly-coordinated (P2)4- units that
but find no reaction, and over time 1 is left unreacted as the are >2.11 Å,7,11,15 and approaching twice the single bond cova-
(PDBN)2 decomposes.32 This suggests that the pre-reduction lent radii of P (2.22 Å).33 Since twice the triple bond covalent
route does not operate, and that Me2NP, and by extrapolation radii of P is 1.88 Å,33 the P-P distance in 5 suggests, unusually
PH, group transfers occur, followed by P-N cleavage and di- for electropositive metals,8,11,15 the presence of (P2)2- rather than
merization of the putative phosphido to give 5. Further support (P2)4-.
for this derives from the observation that R-PDBN reagents
without phosphinidene-stabilizing p-donor R-substituents (R =
But, (BPh3)Na(OEt2)2)20,26 do not react with 1.
Figure 2. Variable-temperature SQUID magnetometry plot for 5 of the ef-
fective magnetic moment µeff (µB) per ion over the temperature range 1.8-
300 K. The line is a guide to the eye only.
The insolubility of 5 precluded NMR and UV/Vis/NIR
spectroscopic analyses, however SQUID magnetometry was
performed on a powdered sample of 5, Figure 2.32 The effective
Figure 1. Molecular structure of 5 at 150 K with selected atom labels. Dis-
magnetic moment of 5 at 300 K is 4.51 µB (3.19 µB per uranium
placement ellipsoids are set at 40% and hydrogen atoms are omitted for ion) and this falls smoothly over the temperature range reaching
clarity. 0.79 µB (0.56 µB per uranium ion) at 1.8 K and tending to zero.
This is characteristic of isolated 3H4 uranium(IV) ions that at
The formulation of 5 was confirmed by its solid-state struc- low temperature typically adopt a magnetic singlet ground state
ture, Figure 1.32 The salient feature of 5 is that the P2 unit is that is subject to temperature independent paramagnetism.35,36
symmetrically side- not end-on bound.2-7,11-13,15,16 The unique U- We note a small plateau in the low temperature regime for c vs
P distances of 2.9441(12) and 2.9446(12) Å are longer than the T,32 but there is no evidence for anti-ferromagnetic coupling,
sum of the single bond covalent radii of U and P (2.81 Å),33 and this feature is attributed to single-ion crystal field effects.37
reflecting the bridging nature of the P2 unit in 5, but correlate to Magnetization vs field data do not saturate, confirming the ura-
the terminal U-P distance of 2.883(2) Å in [(Tren- nium(IV) formulation of 5,32 and for comparison these data are
TIPS
)UIV(PH2)].34 The P-P distance of 2.036(2) Å compares well clearly different compared to U(V)-N2 magnetic data.38,39
In order to examine the electronic structure of 5 we per- the A(pg=) combination, Figure 3b. The computed U, P2, Namide,
formed DFT calculations on the whole model of 5.32 The geom- and Namine multipole derived charge (MDC) computed charges
etry optimized quintet (5quin) spin formulation is found to be and spin densities are +3.55/-2.22, -2.80/-0.16, -1.65/+0.08,
19.59 kcal/mol lower in energy than the septet (5sept) form. and -0.78/+0.01, which, considering the amides are formally a
The bond metrics of 5quin more closely match the crystal struc- -1 charge, is consistent with the P2 unit carrying a charge of ~
ture of 5 than 5sept and are consistent with the magnetism -1.7. This implies a reduction of the P2 unit to or slightly lower
data.32 Thus, 5quin is considered to provide an appropriate, than a P=P double bond, which is confirmed by the Mayer P-P
qualitative description of the electronic structure of 5. bond order of 0.95. For comparison, the Mayer U-P bond orders
average 0.85 and the U-Namide/-Namine Mayer bond orders aver-
age 0.80/0.23, respectively.
The Raman spectrum of 5 shows a sharp peak at 589 cm-1,
and a broad feature centered at 538 cm-1.32 An analytical fre-
quencies calculation on 5quin returns a computed P-P stretch at
553 cm-1. From group theory considerations, the A1 stretch of
P2 will be Raman active but IR inactive, so the absence of any
absorption at 589 cm-1 in the IR spectrum of 5, but a cluster of
absorptions below this value, suggests that the Raman peak at
589 cm-1 represents the A1 stretching mode of the P2 unit in 5.
The discrepancy (36 cm-1) for the computed stretch is reasona-
ble given phase-changes and the harmonic approximation, lend-
ing further experimental validation of the computational model.
In comparison to spectroscopic and calculated data for P2, P2H2,
(P2)2-, and P2H4, Table 1,40,41 the data suggest that the P2 unit in
5 is moderately activated, equating to (P=P)2-, with the calcula-
tions slightly over-estimating the extent of P2 activation.
As the first member of the heavier homologs of N2, it is no-
table that the principal U-P binding mode in 5quin is of A(pg=)
character. Thus, P2 joins a family of two donor-atom p-bonded
ligands at uranium that includes N2,42 C2H4,43 As2H2,44 and
larger p-bonded ligands such as cyclobutadienyl and -pentadi-
enyl.45 In contrast, cyclo-P530 and larger h6-8-ligands46,47 adopt
d-bonding, emphasizing the greater use of 5f-orbitals for p-
bonding to small ligands that require more angular overlap,
whereas 6d-orbital participation becomes more significant for
Figure 3. a) the B(pg^) (d) symmetry combination of P2 for a C2-symmetric more expansive, less angular overlap ligands. The appearance
U2P2 unit and the corresponding computed Kohn Sham a-spin HOMO-3 of of B(pg^) (d) symmetry MO coefficients in the HOMO-3 of
5quin. b) the A(pg=) symmetry combination of P2 for a C2-symmetric U2P2 5quin is instructive regarding prior analysis of U-N2 bonding.48-
51
unit and the corresponding computed Kohn Sham a-spin HOMO-4 (the From the MO diagrams of N2 and P2 the latter has a smaller
occupied b-spin equivalent is similar) of 5quin. Hydrogen atoms are omit- HOMO-LUMO gap and the two degenerate LUMO p*-orbitals
ted from the MO plots for clarity.
are lower in energy for the latter.32 P2 is thus anticipated to be a
better p-acceptor than N2, and on spatial grounds A(pg=) bond-
The top four unpaired electrons in 5quin are all a-spin and
ing will give a better overlap than B(pg^) (d) bonding. Previ-
the corresponding b-spin orbitals are vacant. Three are of es-
sentially pure 5f-character. However, the fourth highest occu- ously,48-51 for U-N2 complexes the energy of the B(pg^) MO has
been found to be variable, being influenced significantly by the
pied molecular orbital (HOMO-3) exhibits significant P2 char-
nature of the ancillary ligands,48-51 but for comparable truncated
acter (31% 3p, 69% U 5f) where the orbital coefficients exhibit
models of [{(TrenDMBS)UIV}2(µ-h2:h2-N2)]48,49 the A(pg=) and
a d-symmetry interaction, that is the B(pg^) combination for a
C2-symmetric U2P2 unit, Figure 3a. However, this interaction is B(pg^) (d) MOs are computed to sit under and above, respec-
weak since the spatial overlap is poor. The a-spin HOMO-4 tively, the four a-spin 5f electrons, which can be traced to U 5f
overlap to the former leading to stabilization, but poorer overlap
(and occupied b-spin equivalent) represents the principal U-P
for the latter leading to less stabilization.48-50 The energies of the
interaction in 5, and is of in-plane p-character from donation of
corresponding A(pg=) and B(pg^) (d) MOs for 5quin suggests
uranium (39%, 3:1 5f:6d) into a p* MO of P2 (61%, 3p), being
that again the former is better stabilized by effective U 5f and
Table 1. Selected computed properties for P2, P2H2, (P2)2-, P2H4, and 5/5quin.
Cmpda P-P Bond length and indexb,c MDCq charged MDCm spin densitye P-P Stretchf
Exp. Calc’d Mayer P U P U Exp.g Calc’d
P2 - 1.908 2.91 0 - 0 - 770-781 771
P2H2 - 2.050 1.97 +0.21 - 0 - 586-605 590
(P2)2- - 2.138 1.80 -1.00 - 0 - - 482
P2H4 - 2.256 1.03 +0.12 - 0 - 438 401
5/5quin 2.036(2) 2.080 0.95 -1.40 +3.55 -0.08 -2.22 589 553
a
All molecules geometry optimized without symmetry constraints at the LDA VWN BP86 TZP/ZORA level. b Calculated bond of interest. c Mayer bond
indices. d MDCq charge on P or U. e MDCm spin density on P or U. f Experimental and computed analytical frequencies P-P stretch.32,40,41 g Ranges reflect
shifts from different matrix isolation and vapor-phase conditions and also the cis/trans isomers of P2H2.40,41
p*-orbital overlap than the latter, but the latter is better stabi- EP/K024000/1, EP/M027015/1, EP/P001386/1, EP/S033181/1,
lized than the analogous U-N2 B(pg^) (d) MO (for comparable and EP/T011289/1), European Research Council (grant
amide ancillaries).48,49 This can be related to the energetically CoG612724), Royal Society (grant UF110005), Deutsche For-
superior p-acceptor nature of P2 compared to N2, and also that schungsgemeinschaft (SL104/10-1), Landesgraduiertenförder-
the 3p-orbitals of phosphorus may benefit from greater spatial ung Baden-Württemberg, and The University of Manchester in-
overlap with U 5f-orbitals than the 2p-orbitals of N2. cluding computational resources and associated support ser-
A preliminary reactivity study demonstrates that 5 consti- vices from the Computational Shared Facility. The Alexander
tutes a launchpad to new actinide-phosphorus motifs. Reduction von Humboldt Foundation is thanked for a Friedrich Wilhelm
with alkali metals generates the structurally authenticated cy- Bessel Research Award to S.T.L.
clo-P3 complexes [{(TrenTIPS)UIV}2(µ-h3:h3-P3)][M(arene)4]
(7M, M = K, Rb, Cs; arene = toluene or benzene), albeit in low REFERENCES
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