Angewandte
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Coordination Chemistry
Synthesis and Reactivity of an Anionic Diazoolefin
Bastiaan Kooij, Zhaowen Dong, Farzaneh Fadaei-Tirani, Rosario Scopelliti, and
Kay Severin*
Abstract: Bent (hetero)allenes such as carbodicarbenes
and carbodiphosphoranes can act as neutral C-donor
ligands, and diverse applications in coordination
chemistry have been reported. N-Heterocyclic diazoole-
fins are heterocumulenes, which can function in a similar
fashion as L-type ligands. Herein, we describe the
synthesis and the reactivity of an anionic diazoolefin.
This compound displays distinct reactivity compared to
neutral diazoolefins, as evidenced by the preparation of
diazo compounds via protonation, alkylation, or silyla-
tion. The anionic diazoolefin can be employed as an
ambidentate, X-type ligand in salt metathesis reactions
with metal halide complexes. Extrusion of dinitrogen
was observed in a reaction with PCl(NiPr2)2, resulting in
a stable phosphinocarbene.
Allenes and heteroallenes of the general formula L=C=L
can adopt a bent geometry if the capping groups L are
strongly electron-donating (Figure 1a).[1] Bent
(hetero)allenes feature high-lying occupied molecular orbi-
tals with σ and π symmetry, and they have been described as
carbon(0) compounds with two lone pairs of electrons
(‘carbones’).[2]
Carbodiphosphoranes are a widely studied sub-class of
bent allenes (Figure 1b).[2,3] The first carbodiphosphorane,
Ph3P=C=PPh3, was reported by Ramirez and co-workers in
1961.[4] Since then, the properties of carbodiphosphoranes
have been investigated extensively.[2,3] They represent strong
C-donor ligands, which are able to bind to a wide range of
transition metal complexes and main group Lewis acids.
The formal replacement of one or both PR3 groups in
carbodiphosphoranes with N-heterocyclic carbenes (NHCs)
[*] B. Kooij, F. Fadaei-Tirani, R. Scopelliti, K. Severin
Institut des Sciences et Ingénierie Chimiques, Ecole Polytechnique
Fédérale de Lausanne (EPFL)
1015 Lausanne (Switzerland)
E-mail: kay.severin@epfl.ch
Z. Dong
Key Laboratory of Green Chemistry and Technology of Ministry of
Education, College of Chemistry, Sichuan University
29 Wangjiang Road, 610064 Chengdu (P. R. China)
© 2023 The Authors. Angewandte Chemie International Edition
published by Wiley-VCH GmbH. This is an open access article under
the terms of the Creative Commons Attribution Non-Commercial
NoDerivs License, which permits use and distribution in any med-
ium, provided the original work is properly cited, the use is non-
commercial and no modifications or adaptations are made.
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Figure 1. General resonance structures of bent (hetero)allenes (a) and
selected examples (b). The molecular structure of the anionic
diazoolefin described herein (Dipp = 2,6-C6H3iPr2) (c).
gives carbophosphinocarbenes and carbodicarbenes, respec-
tively (Figure 1b). The existence of carbodicarbenes was
predicted by Frenking in 2007,[5] and their isolation was
achieved shortly after by Bertrand and co-workers.[6,7]
Carbophosphinocarbenes of type (NHC) = C=PR3 were
introduced by the group of Ong in 2020.[8] Similar to
carbodiphosphoranes, NHC-based bent allenes are strong
C-donor ligands for transition metal complexes, and first
applications in catalysis have been reported.[2d,9] Further-
more, carbodicarbenes were used in the context of main
group element chemistry.[10]
The combination of an NHC and a dinitrogen capping
group gives a diazoolefin, which was predicted to display a
bent geometry.[11] This prediction was recently corroborated
by the isolation of N-heterocyclic diazoolefins (Fig-
ure 1b).[12–14] Crystallographic analyses revealed bent hetero-
cumulene structures, and metal coordination was achieved
via the exocyclic carbon atom.
A common feature of monodentate L=C=L ligands is
the ability to act as neutral C-donor ligands. Below, we
describe the synthesis of an anionic diazoolefin. The
negative charge allows its utilization as an X-type ligand in
salt metathesis reactions. Furthermore, it was found to
display a distinct reactivity when compared to the previously
reported diazoolefins.
Our study was inspired by work from the Robinson and
Tamm groups. In 2010, the Robinson group reported the
synthesis of an anionic dicarbene by lithiation of an
imidazol-2-ylidene at C4 position.[15] The lithiation opened
the possibility to introduce electrophiles at the backbone of

Communications
the NHC. The Tamm group described two years later the
coupling of lithiated NHCs with B(C6F5)3, resulting in the
formation of carbenes with weakly coordinating borate side
groups.[16] These anionic carbenes were subsequently used
with great success in transition metal and main group
element chemistry.[17]
We wanted to explore if one can use a Robinson/Tamm-
like approach for the synthesis of anionic diazoolefins. For
our investigations, we used an N-heterocyclic diazoolefin
with 2,6-C6H3iPr2 (Dipp) wing-tip groups (1).[12] Reactions of
1 with nBuLi in diethyl ether resulted in the formation of
the lithiated diazoolefin 2 in 92 % yield (Scheme 1). The
metalation was corroborated by the loss of symmetry in the
1
H NMR spectrum of 2. A structural analysis of 2 by single-
crystal X-ray diffraction (XRD)[18] confirmed that deproto-
nation had occurred at the heterocycle. There are two
distinct Li + cations in crystalline 2: one is coordinated to
two imidazole heterocycles and to one diethyl ether
molecule, and the other is coordinated to the ylidic C-atom,
to the terminal N-atom of one diazo group, and to one
diethyl ether molecule. The bridging binding mode of Li +
gives rise to a one-dimensional coordination polymer (Fig-
ure 2). In line with the presence of two distinct N2 groups in
solid 2 (terminal and bridging), we observed two ν(N2)
bands in the IR spectrum at 2023 and 1971 cm 1. In the solid
state, the lithiated diazoolefin 2 is stable at room temper-
ature for at least two weeks.
The reaction of 2 with BPh3 resulted in the formation of
the anionic diazoolefin 3, which could be isolated in 79 %
yield (Scheme 1). The borate group in 3 gave rise to an 11B
NMR signal at 8.8 ppm. As in the case of 2, one can
observe two sets of 1H and 13C{1H} NMR signals for the
chemically distinct Dipp groups. The 1H NMR spectrum
indicated the presence of two diethyl ether molecules, which
were taken into account when calculating the yield.
Scheme 1. Synthesis of the anionic diazoolefin 3 by reaction of 1 with
first nBuLi and then BPh3.
Figure 2. Molecular structures of 2 (part of the 1D polymer) and of 3 as
determined by single-crystal XRD. Ellipsoids are drawn at 30 % (2) or
40 % (3) probability, respectively. Hydrogen atoms are not shown for
clarity.
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Single crystals of the lithium salt were obtained by
layering a THF solution of 3 with pentane, and an XRD
analysis was performed.[18] In the solid-state, the lithium
cation binds to the terminal nitrogen of the diazo group and
to three THF molecules. There are two independent
diazoolefin anions in the asymmetric unit with related
structural parameters. The C C N bent angle of the C2N2
group (126.52(2) and 128.9(3)°) is slightly larger than what
was observed for the neutral starting material 1 (121.3(3)°).
Noticeable differences are also found for the C N2 (3:
1.241(3) and 1.207(4) Å; 1: 1.285(5) Å) and the N N bond
lengths (3: 1.168(3) and 1.178(4) Å; 1: 1.147(5) Å). However,
the lengths of the exocyclic C CN2 bonds are similar (3:
1.400(3) and 1.388(4) Å; 1: 1.397(5) Å). We observed one
ν(N2) band in the IR spectrum of solid 3 at 2085 cm 1.
The electronic structure of 3 was analyzed by density
functional theory (DFT) calculations at the M06-2X/6-311 +
G(d,p) level of theory.[19] For comparison, we have per-
formed calculations on the neutral diazoolefin 1, the isolated
anion in 3, and the ion-paired salt 3 with [Li(THF)3] + bound
to the terminal N-atom (for details, see the Supporting
Information). The introduction of a negative charge was
found to have a small effect on the electronic structure of
the heterocumulene unit. More pronounced changes were
found for the ion-paired salt 3. The bound lithium ion
induces a polarization of the CN2 group, with a charge
redistribution from the ylidic carbon to the terminal nitro-
gen atom (Figure S87). The calculated Wiberg bond indices
reflect the experimentally observed shortening of the C N2
bond and the lengthening of the N N bond (Table S12).
Reactivity studies with 3 quickly revealed its distinct
chemical behavior. For the neutral diazoolefin 1, we had
observed that methanol mediates a head-to-tail-dimerization
to give a quinoidal tetrazine.[20,21] No dimerization was
observed for the anionic diazoolefin 3. Instead, the addition
of methanol gave the diazo compound 4 in 92 % yield
(Scheme 2).
The protonated diazoolefin 4 can be described as a
zwitterionic vinyl diazonium compound.[22] However, an
XRD analysis of 4[18] showed a rather long C CHN2 bond
(1.432(2) Å), suggesting a significant single bond character
(for details, see the Supporting Information). Therefore,
compound 4 has strong diazoalkane character (Scheme 2).
In line with the description as a diazoalkane, we observed a
ν(N2) band in the IR spectrum of 4 at 2086 cm 1. This value
is lower than what was reported for donor-stabilized vinyl
diazonium salts such as [(EtO)2C=CHN2]SbCl6 (2181 and
Scheme 2. Synthesis of the diazo compounds 4, 5 and 6.

Communications
2155 cm 1),[23] and it falls in the range of diazoalkanes (2050–
2150 cm 1).[24] The diazoalkane character of 4 was corrobo-
rated by the results of DFT calculations. The Wiberg bond
index of the C CN2 bond is 1.12, indicating a pronounced
single bond character.
A unique reactivity of the anionic diazoolefin 3 was also
noted in the reaction with methyl iodide. Methylation of the
neutral diazoolefin 1 results in a dimerization.[20] In contrast,
when MeI was added to a solution of 3 in benzene, the
alkylation product 5 was formed in high yield (Scheme 2).
The structure of 5 could be established by an XRD
analysis,[18] and the structural parameters are similar to what
was found for 4.
The reaction of 3 with trimethylsilyl chloride (TMSCl)
proceeded analogously to what was observed for MeI: the
silylated diazo compound 6 was obtained in 62 % yield
(Scheme 2). With a length of 1.461(4) Å, the C CN2 bond of
6 is slightly longer than that of 4, and the CN2TMS group is
tilted with respect to the imidazole plane (N C-C-Ndihedral =
35°). These crystallographic data suggest that the diazoal-
kane description is even more relevant for 6, when
compared to 4.
Next, we investigated the coordination chemistry of 3.
First evidence that 3 could be used as an X-type ligand was
obtained in a reaction with AuCl(PPh3). A salt metathesis
reaction in benzene gave the linear gold(I) complex 7 in
87 % yield (Scheme 3). An XRD analysis[18] showed that the
anionic diazoolefin acts as a C-donor and that the diazo
moiety remains intact. The C Au bond length of 2.053(3) Å
is comparable to what was observed for the adduct between
AuCl and the neutral diazoolefin 1 (Au C = 2.008(3) Å).[12]
The reaction of 3 with the dimer [RhCl(COD)]2
(0.44 equiv; COD = 1,5-cyclooctadiene) in benzene gave
complex 8, which was isolated in nearly quantitative yield
Scheme 3. Synthesis of the complexes 7–10. The reactions were
performed in benzene or toluene at RT. The structures of the products
are based on XRD analyses. Ellipsoids are drawn at 50 % probability.
Co-crystallized solvent molecules (1 × benzene for 9, 1 × Et2O for 10)
and hydrogen atoms are omitted for clarity.
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(Scheme 3). Crystalline 8 shows two independent complexes
in the asymmetric unit.[18] For both complexes, one can
observe a close contact between Rh and the ipso-carbon
atom of one Dipp wing-tip group (Rh···C = 2.515(7) Å;
Rh’···C’ = 2.474(7) Å). As a consequence, the coordination
environment around Rh can be described as pseudo-square
planar. Similar interactions between Rh and a Dipp group
(‘π-face donation’)[25] were observed for RhI(COD) com-
plexes with thione and selenone ligands derived from N-
heterocyclic carbenes.[26]
Coordination of the diazoolefin via the terminal nitrogen
atom was observed in complex 9, which was formed in 67 %
yield by combining IrCl(CO)(PPh3)2 with 3 in benzene
(Scheme 3). Diazoolefins generally act as carbon
donors,[12,13,27] although N-coordination was reported for the
kinetic adduct of B(C6F5)3 and a neutral mesoionic
diazoolefin.[13c] Thus far, complex 9 serves as the only
example of an N-bound diazoolefin ligand in a transition
metal complex.[28] A possible explanation for the unusual
coordination mode is the presence of two PPh3 in cis
position. The steric demand of these phosphine ligands
could disfavor a C-coordination of the diazoolefin.
The CN2 group in 9 is bound in a bent fashion (N N-Ir =
150.52(10)°). With 2.054(1) Å, the Ir N bond is significantly
longer than what was found for the diazo complexes IrCl-
(N2C5Cl4)(PPh3)2 (Ir N = 1.824(6) Å)[29] and IrCl(N2C5Cl4)-
(SbiPr3)2 (Ir N = 1.79(1) Å)[30] The ν(N2) IR band in solid 9
appears at 2029 cm 1 and the ν(CO) band at 1965 cm 1.
Having established that 3 can function as an ambiden-
tate, X-type ligand for transition metal complexes, we
decided to perform some initial tests regarding its reactivity
with main group element compounds.
Combining 3 with GeCl2(dioxane) in benzene at room
temperature afforded the two-coordinate germylene 10 as a
red solid in high yield (Scheme 3). The product was found to
display good stability: a solution of 10 in benzene showed
only minor decomposition after 24 h (RT, inert atmos-
phere). The GeII center in crystalline 10 adopts the expected
bent geometry (C Ge-C = 92.91(10)°), with Ge C bond
lengths of 2.033(2) and 2.046(3) Å.[18] The closest structural
analogue to 10 is a two-coordinate germylene with N-
heterocyclic vinyl ligands, which was reported by Rivard and
co-workers.[31] However, this compound shows shorter
Ge C bonds (1.849(4) Å).
In all compounds discussed thus far, the diazoolefin 3 is
bound intact, that is without loss of dinitrogen. However,
spontaneous extrusion of N2 is possible, as observed in the
reaction of 3 with PCl(NiPr2)2. Substitution of chloride by 3
along with cleavage of N2 gave the coupling product 11 in
82 % yield (Scheme 4).
Crystalline 11[18] shows a planar P atom (Σ α = 359.9°), a
short C P bond (1.540(1) Å), and the C C P unit is only
slightly bent (170.95(10)°). These structural features imply
significant π-donation of the phosphorous to the adjacent
carbon atom. Accordingly, there is an important contribu-
tion of the heterocumulene structure A[32] to the electronic
situation in 11 (Scheme 4). However, compound 11 can also
be described as a phosphinocarbene (Scheme 4, B).[33] In
fact, similar structural parameters were found for a phosphi-

Communications
Scheme 4. Synthesis of 11. The structure of the product is based on an
XRD analysis. Ellipsoids are drawn at 50 % probability. Co-crystallized
solvent molecules (2 × benzene) and hydrogen atoms are omitted for
clarity.
noarylcarbene with an electron-withdrawing 2,6-
bis(trifluoro-methyl)phenyl substituent (planar P atom,
C C-P = 162.1(3)°, C P = 1.544(3) Å).[34]
A notable characteristic of the push-pull carbene 11 is its
good stability: it can be stored at room temperature as a
solid for at least 2 weeks without noticeable decomposition,
and at least for one day in solution (DCM).
We have also attempted a coupling between the neutral
diazoolefin 1 and PCl(NiPr2)2. No reaction was observed by
1
H NMR spectroscopy after 1 h (C6D6, RT), which is in
contrast to the fast reaction observed with the anionic
diazoolefin 3 (completion within 30 min). Apparently, the
elimination of LiCl is an important driving force for this
reaction.
To summarize: we have prepared an anionic diazoolefin,
3, by deprotonation and subsequent borylation of a neutral
diazoolefin. The anionic diazoolefin was found to display a
distinct reactivity when compared to its neutral counterpart
1. Notably, we were able to obtain zwitterionic diazo
compounds by protonation or alkylation of 3. In the case of
1, these reactions had resulted in the formation of dimers.[20]
The ligand properties of 3 were evaluated in reactions with
AuI, RhI, IrI, and GeII complexes. Salt metathesis reactions
gave C-bound complexes for AuI, RhI, and GeII, whereas an
unusual N-bound coordination mode was found for the IrI
complex 9. With its ability to function as an X-type ligand,
diazoolefin 3 complements the L-type behavior of ligands
such as carbodicarbenes. The isolation of the germylene 10
and the phosphinocarbene 11 suggests that 3 can also have
interesting applications in main-group element chemistry.
Acknowledgements
This work was supported by funding from the Ecole
Polytechnique Fédérale de Lausanne (EPFL), the Swiss
National Science Foundation and the Fundamental Re-
search Funds for the Central Universities, and Natural
Science Foundation of Sichuan, China (2023NSFSC1083).
We thank Louise Foltzer-De Cian for help with the synthesis
of compound 2 and Dr. Mrittika Roy, EPFL, for synthesiz-
ing IrCl(CO)(PPh3)2. Open Access funding provided by
École Polytechnique Fédérale de Lausanne.
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Conflict of Interest
The authors declare no conflict of interest.
Data Availability Statement
The data that support the findings of this study are available
in the supplementary material of this article.
Keywords: Coordination Chemistry · Diazo Compound ·
Diazoolefin · Ligand · Organometallic Chemistry
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Angewandte
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Manuscript received: June 19, 2023
Accepted manuscript online: June 30, 2023
Version of record online: ■■■, ■■■■
 15213773, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/anie.202308625, Wiley Online Library on [16/08/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
Angewandte
Communications Chemie

Communications
Coordination Chemistry

B. Kooij, Z. Dong, F. Fadaei-Tirani,

R. Scopelliti, K. Severin* e202308625

Synthesis and Reactivity of an Anionic

Diazoolefin
An anionic diazoolefin was synthesized.
It was found to display a distinct
reactivity as evidenced by the prepara-
tion of diazo compounds via protona-
tion, alkylation, or silylation. Further-
more, it can act as an ambidentate, X-
type ligand for metal complexes.

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