Incorporation of coinage metal-NHC complexes into heptaphosphide clusters

Article abstract of DOI:10.1039/d0dt03119d

Cu(i) and Au(i) ions, capped with an N-heterocyclic carbene (NHC), react with (TMS)3P7 (TMS = trimethyl-silyl) to afford an η4-coordinated anion [NHCDippCu-P7(TMS)]- and a neutral trinuclear complex (NHCDippAu)3P7. Protecting the P7 cage with the TMS groups is instrumental in controlling the course of these reactions. This journal is

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Incorporation of Coinage Metal‐NHC Complexes into
Heptaphosphide Clusters
Minyoung Jo,a Jingbai Li,b Alina Dragulescu‐Andrasi,a Andrey Yu. Rogachev*b and Michael
Received 00th January 20xx,
Accepted 00th January 20xx
Shatruk*a
DOI: 10.1039/x0xx00000x
Cu(I) and Au(I) ions, capped with an N‐heterocyclic carbene (NHC),
react with (TMS)3P7 (TMS = trimethyl‐silyl) to afford an η4‐
coordinated anion [NHCDippCu‐P7(TMS)]– and a neutral trinuclear
complex (NHCDippAu)3P7. Protecting the P7 cage with the TMS
groups is instrumental in controlling the course of these reactions.
Polyphosphides represent a fascinating group of anionic species
with diverse structural motifs, afforded by the propensity of
phosphorus atoms to form homonuclear bonds.1 While the
structural chemistry of polyphosphides has been dominated by
materials prepared via solid‐state synthesis,1,2 the potential for
further expansion of this chemistry via solution protocols
remains underexplored. The Baudler group pioneered research
into soluble polyphosphides 1970‐80s.3 Recently, however, a
renaissance in the solution chemistry of polyphosphides has
been driven by the interest in using them as ligands and building
blocks for assembly of larger supramolecular structures.4‐7
Scheme 1 Typical coordination modes of the P 37– anion.
but the η4‐coordination generally leads to partial disruption of
the P–P bonds. Many such reactions, especially with transition
metal ions, are difficult to control due to decomposition of the
polyphosphide or fast precipitation of amorphous products.
A possible approach to improve the control over the
reactivity of the P73– cage is to protect its two‐bonded P atoms.
Despite the growth in the number of known structures that
contain polyphosphide fragments, it is challenging to control
reactivity of these highly fluxional anionic cages that are also air‐
For example, a few reports showed an improved stability of a
and moisture‐sensitive. Soluble polyanions P –, P 3–, P
4–, P16
14
2–
,
functionalized cage, (TMS)3P7 (TMS = trimethylsilyl).28‐32
5
7
4– have been established,3,8‐13 but only P 3– has
3–
P
21
, and P
26
7
Reactions of (TMS)3P7 with MCp*‐containing precursors (M =
Fe, Co) led to the disruption of the P7‐based structure and
insertion of metals in the P–P bonds,25 while reactions with
been functionalized via alkylation,14‐17 protonation,18,19 and
metalation.20‐26 Similar reactions with other polyphosphides are
2– 27
.
lacking, except for a single report on the alkylation of P
16
triphos‐M (triphos = 1,1,1‐ tris(diphenylphosphinomethyl)‐
Thus, it is desirable to devise new reaction pathways to expand
the solution chemistry of these structurally diverse anions.
The P73– anion exhibits high basicity and nucleophilicity due
to three formal negative charges localized on the two‐bonded
phosphorus atoms (Scheme 1).6 A number of complexes with
the P7 anion have been reported, with the cage coordinated
to the metal center in η1, η2, or η4 fashion (Scheme 1).20‐26 The
η1‐ and η2‐coordination preserve the nortricyclane structure,
ethane; M = Co, Ni) also disrupted the cage and yielded a metal‐
coordinated cyclic triphosphirene unit.33
The disruption of the nortricyclane cage in the reactions of
(TMS)3P7 with Fe‐, Co‐, and Ni‐containing precursors might be a
result of the stronger bonding between the open‐shell metal
cations and the phosphorus atoms. Using a weaker bonding,
closed‐shell d10 transition metal ion, capped with a stable co‐
3–
ligand, might help preserve the structural integrity of the P
7
cage. Metal complexes with N‐heterocyclic carbenes (NHCs)
have been studied as catalysts in many organic reactions, which
are typically initiated by a simple salt metathesis.34‐36 We
envisaged that a reaction between NHC‐MCl (M = Cu, Au) and
(TMS)3P7 should lead to a similar metathesis, resulting in
elimination of the chloride and the formation of M–P bonds. A
a. Department of Chemistry and Biochemistry, Florida State University, Tallahassee,
FL 32306, United States. E‐mail: mshatruk@fsu.edu
b. Department of Cnmhemistry, Illinois Institute of Technology, 3101 South
Dearborn St, Chicago, IL 60616, United States. E‐mail: arogache@iit.edu
Electronic Supplementary Information (ESI) available: [details of any supplementary
information available should be included here]. See DOI: 10.1039/x0xx00000x
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precedent for such bonding was offered by coordination of the
NHC‐M fragments to the white phosphorus molecule, P4.37
The challenge of taming polyphosphides as synthons or
ligands is heightened by the limited commercial availability of
white phosphorus, commonly considered as a more reactive
form of the element, better suited for solution chemistry. In this
vein, our group has recently reported a breakthrough in the
access to polyphosphides in solution by nucleophilic activation
of shelf‐stable red phosphorus in non‐protic solvents.38, 39 In the
present work, we solubilized red phosphorus by treating it with
Na in refluxing tetrahydrofuran (THF). The solid Na3P7 that
formed after 24 h was redissolved in dimethoxyethane (DME)
and treated with (TMS)Cl to obtain a TMS‐protected structure
Fig. 1 31P‐NMR spectra monitoring progress of the reaction
between (TMS)3P7 and NHCDippCuCl vs. the stoichiometry.
3–
(Scheme S1), with the goal to stabilize the P7 anion against
disruption under action of transition metal ions. The 31P{1H}
NMR spectrum of the product showed three resonances that
matched the chemical shifts reported for (TMS)3P7 (Fig. 1a).31
The reaction of (TMS)3P7 with NHCDippCuCl in THF at room
temperature was monitored by 31P NMR spectroscopy, showing
a gradual consumption of the heptaphosphide precursor as the
amount of NHCDippCuCl increased (Fig. 1). A pure intermediate
product was observed at the (TMS)3P7:NHCDippCuCl = 1:0.7 ratio
(Fig. 1c), while a new product began to form as the amount of
NHCDippCuCl further increased. Finally, at the 1:3 ratio of starting
materials, only a pure second product was observed (Fig. 1f).
The dark‐red solution obtained in the end was used to
crystallize the final product. The single‐crystal X‐ray diffraction
revealed the crystal structure of complex 1, [NHCDipp‐Cu‐
NHCDipp]+[NHCDippCu‐P7(TMS)]–. Thus, instead of the envisioned
trinuclear complex, in which all TMS groups would have been
replaced by the NHC‐Cu(I) units, we observed the formation of
a compound containing both a complex cation and a complex
anion. The 1:3 ratio of (TMS)3P7 to NHCDippCuCl required to
complete the reaction is justified by the ratio of P7 to NHCDipp in
the structure of 1. Obviously, 1/3 of the Cu(I) ions are lost to the
CuCl byproduct, which precipiates in the course of the reaciton:
Fig. 2 The [NHCDippCu(η4‐P7)(TMS)]– anion in the structure of 1.
Thermal ellipsoids are shown at 50% probability level. The
counter‐ion and hydrogen atoms are omitted for clarity. The full
asymmetric unit is shown in Fig. S1. Selected bond lengths (Å):
Cu–P6, 2.366(3); Cu–P1, 2.416(3); Cu–P3, 2.470(4); Cu–P4,
2.482(4) Å; P1–P2, 2.204(5); P2–P3, 2.254(5), P1–P3, 2.368(5).
of which the Cu(I) ion exhibits η2‐coordination to the P4
molecule. The longer Cu–P distances in 1 can be attributed both
to the larger coordination number of Cu(I) and to the bulkiness
of the NHC ligand. In turn, the Cu–C distance to the carbene
decreased from 1.953 Å in NHCDippCuCl44 to 1.907(7) Å in 1.
The nature of bonding was studied with DFT calculations.
The fully‐relaxed optimized geometry of [NHCDippCu‐P7(TMS)]–
converged to an η2‐coordination (Fig. S16a), which is different
from the crystal structure. Therefore, we used the experimental
geometry, in which only H atoms were optimized. The total
bonding energy is equal to –88.83 kcal/mol, including –150.03
kcal/mol of the total interaction energy (Eint) between
(TMS)P72–and [NHCDipp‐Cu(I)]+ and +61.20 kcal/mol of the
preparation energy (Eprep). The latter describes changes in
geometry of interacting fragments upon going from isolated
species to components of the aggregate. Energy decomposition
analysis (EDA)45,46 was used to quantify attractive electrostatic
(Eelstat), orbital (Eorb), and repulsive Pauli (EPauli) bonding
components, which were equal to –262.78, –57.61, and +170.35
kcal/mol, respectively. The Natural Bond Orbital analysis47 was
used to quantify contributions from different P atoms. The
(TMS)3P7 + 3 NHCDippCuCl  2 (TMS)Cl + CuCl +
[NHCDipp‐Cu‐NHCDipp][NHCDippCu‐P7(TMS)] (1)
The structure of 1 contains a (TMS)P72– cluster bound to the
Cu(I) centre in the η4‐fashion (Fig. 2). Such coordination mode
of phosphorus clusters is generally favoured for early transition
metals and accompanied by a distortion of the polyphosphide
cage and cleavage of a P–P bond. Such situation is observed, for
example, in [Fe(HP7)2]2– (Scheme 1b)21 and[η4‐P7Cr(CO)3]3–
(Scheme 1c).26 In contrast, late transition metals tend to engage
in η2‐coordination with P7 3–, without a significant distortion of
the polyphosphide anion (e.g., [P7PtH(PPh3)2]2– in Scheme 1e40).
Despite the η4‐coordination of P73– to the Cu(I) centre in 1,
we do not observe any dramatic distortion or cleavage of the P–
P bonds. The bonds in the basal triangle (Fig. 2) do not form an
equilateral triangular, in contrast to the structure of (TMS)3P7
with nearly identical basal P–P bonds (2.213‐2.215 Å).41 We
attribute this rather weak distortion of the basal triangle to the
3–
softer nature of interaction between P7 and the closed‐shell
2–
(TMS)P7 revealed notable donor behavior of P1, P3, P4, and
Cu(I) ion. The Cu–P bonds are longer as compared to 2.307 Å in
P6 atoms through the 3s and 3p orbitals that interact with the
acceptor 4s orbital of Cu(I), to give a total stabilization energy of
201.78 kcal/mol (Table S2 and Fig. S17). The 3p(P4) → 4s(Cu)
P4CuGaCl4 or the range of 2.336‐2.342 Å in [Cu(P4)2]+,43 in both
42
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and 3p(P6) → 4s(Cu) interactions are the strongest (51.56 and
64.64 kcal/mol, respectively), which might explain why the DFT
optimization converged to the η2‐coordination. Weak π‐back‐
donation occurs from the 3d orbital of Cu(I) to the P1–P3 σ*‐
orbital (6.66 kcal/mol), which agrees with the shortened Cu–C
distance in the crystal structure of 1. Analysis of electron density
by means of Quantum Theory of Atoms In Molecules48 revealed
only three bond critical points (BCPs) formed between the P3,
P4, and P6 atoms and Cu (Fig. S18). The lack of a BCP in the Cu–
P1 bond can be explained by coalescence of the aimed BCP with
another critical point, resulting in a non‐nuclear attractor
between the P1 and P6 atoms due to the non‐optimized
geometrical configuration. Thus, the hapticity in the target
system is best described as asymmetrical η4 coordination.
The 31P{1H} NMR spectrum of 1 revealed four independent
multiplets at 1.8, –89.4, –98.7, and –141.7 ppm, with the 1:2:2:2
intensity ratio (Fig. 1f). The assignment of resonances was aided
by analysis of a 31P‐31P COSY spectrum (Fig. S2). Compared to
the spectrum of (TMS)3P7, which showed three resonances with
an intensity ratio of 3:1:3 (Fig. 1a), the spectrum of 1 reflects the
lower symmetry of the η4‐coordinated P7. A similar AAˊBBˊCCˊX‐
type spectrum was observed for [η4‐HP7Cr(CO)3]2–.23
Fig.
3
(a) The proposed DFT‐optimized structure of the
intermediate observed in the reaction between (TMS)3P7 and
NHCDippCuCl. The H atoms are omitted for clarity. (b) The
experimental 31P{1H} NMR chemical shifts observed at the 1:0.7
ratio of the reactants and the calculated chemical shifts.
Neither the calculated nor the crystal structure geometry of
the [NHCDippCu‐P7(TMS)]– anion allowed us to reproduce the
experimental 31P‐NMR spectrum of 1. The DFT‐optimized
geometry, with or without implicit solvent, showed an η2‐
coordination, which may explain the disagreement between the
calculated and experimental chemical shifts (Fig. S16). Although
the crystal structure has an asymmetric η4‐coordination, we
hypothesize that the solution structure undergoes dynamic
changes in the η4‐coordination, most likely, balancing between
two extremes of the η2‐coordination of the Cu(I) center to the
P1‐P3‐P4‐P6 face. This hypothesis is supported by the
observation of two disordered components of the η4‐
coordinated P7 cage in the crystal structure of 1 (Fig. S1b).
As mentioned above, an intermediate product was
observed in the reaction as the (TMS)3P7 to NHCDippCuCl ratio
changed from 1:0.5 to 1:3 (Fig. 1). The 31P‐NMR spectrum of the
intermediate showed six resonances in the 2:1:1:1:1:1 intensity
ratio, which might correspond to the initial substitution of one
TMS group by NHCDippCu+. To verify this hypothesis, we carried
out DFT calculations on the structure of [NHCDippCu‐P7(TMS)2].
The geometry optimization yielded a linearly coordinated Cu(I)
complex (Fig. 3a), the 31P‐NMR spectrum of which is in excellent
agreement with the spectrum of the intermediate (Fig. 3b).
Seeking to substitute all three TMS groups, we reacted the
(TMS)3P7 cluster with a NHC‐gold precursor, keeping in mind the
strong preference of Au(I) for linear coordination. Treatment of
(TMS)3P7 with NHCDippAuCl in THF in a 1:3 stoichiometric ratio
led to the substitution of all three TMS groups by NHCDippAu+
units to afford a neutral trinuclear complex:
Fig. 4 Side (a) and top (b) views of the crystal structure of 2.
Thermal ellipsoids are shown at 50% probability level.
and the approximate axial C3v symmetry of the P7 cage impart
chirality to complex 2. The crystal structure, however, is
centrosymmetric, since the unit cell contains equal numbers of
stereoisomers with the opposite chirality (Fig. S1c).
The shape of the original seven‐atom cage in 1 is essentially
preserved, and the coordination of three NHCDippAu+ units only
causes minor perturbations to the cage geometry (Fig. 4). The P–
P bond lengths vary from 2.179(1) to 2.233(1) Å, being only
marginally longer than those in (TMS)3P7 (2.178–2.215 Å). The
Au–P bond distances of 2.314(1), 2.319(1), and 2.342(1) Å are
shorter than the Au–P bonds observed in related complexes, i.e.
2.357 and 2.349 Å in [Au2(HP7)2]2–,20 and 2.404 and 2.428 Å in
[NHCDippAu(η2‐P4)]+.37 The Au–C bond, however, is lengthened
from 1.998 Å in NHCDippAuCl49 to 2.033(4)–2.053(4) Å in 2, likely
due to steric congestion from the NHC ligands.
The 31P{1H} NMR spectrum of 2 exhibits three resonances
with an intensity ratio of 3:1:3 (Fig. S13). The spectrum is thus
very similar to the one observed for the (TMS)3P7 precursor. A
notable difference between the spectra is the shift of all three
multiplets (Fig. S19). The peaks at 0 and –99.8 ppm, assigned,
respectively, to the substituted P atoms (A) and the apex P atom
(TMS)3P7 + 3 NHCDippAuCl  3 (TMS)Cl + (NHCDippAu)3P7 (2)
A similar example is offered by P7[FeCp(CO)2]3,25 which, to the
best of our knowledge, is the only other reported case of the
three‐fold coordination of transition metals to the P7 cage. The (B) in (TMS)3P7, have been shifted downfield to 8.9 and –79.5
linear coordination of the Au(I) ions, the bulky capping ligands,
ppm in the spectrum of 2, while the peak at –156.8 ppm, due to
the basal P atoms (C) in (TMS)3P7, is shifted to –183.5 ppm in 2.
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17 M. Baudler, W. Faber and J. Hahn, Z. Anorg. Allg. Chem.,
The DFT‐optimized geometry of complex 2 agrees well with
the crystal structure. The computed Au–P bonds of 2.352 Å,
2.354 Å, and 2.357 Å are slightly longer than the experimental
values. The P–P bond lengths range from 2.189 Å to 2.227 Å,
also in accord with the experimental structure. The calculated
31P‐NMR spectra of (TMS)3P7 and 2 show an excelent agreement
with the exerimental spectra (Fig. S19).
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In summary, the use of TMS‐protected P7 cage has afforded
better control over its reactions with NHC‐d10 metal complexes,
yielding the anionic [(NHCDippCu)η4‐P7(TMS)]– and the neutral
(NHCDippAu)3P7 with unique molecular structures. Although two
isoelectronic coinage metal ions give rise to different binding
3–
modes toward the P7 cage, this difference is well justified by
established coordination preferences of the Cu(I) and Au(I) ions.
We also highlight that our facile synthetic route to produce
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DOI: 10.1039/D0DT03119D
A Me3Si-protected P7 cage reacts with N-
heterocyclic-carbene complexes of coinage
metals to yield a mononuclear Cu(I) complex
featuring a Cu(η4-P7) core and a trinuclear Au(I)
complex with linearly coordinated metal ions
attached to the P7 cluster.