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The emerging chemistry of the aluminyl anion

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Cite this: Chem. Commun., 2023,
59, 503
Received 3rd November 2022,
Accepted 7th December 2022
DOI: 10.1039/d2cc05963k
rsc.li/chemcomm
Martyn P. Coles *a and Matthew J. Evansb
The chemistry of low valent p-block metal complexes continues to elicit interest in the research
community, demonstrating reactivity that replicates and in some cases exceeds that of their more widely
studied d-block metal counterparts. The introduction of the first aluminyl anion, a complex containing a
formally anionic Al(I) centre charge balanced by an alkali metal (AM) cation, has established a platform
for a new area of chemical research. The chemistry displayed by aluminyl compounds is expanding
rapidly, with examples of reactivity towards a diverse range of small molecules and functional groups
now reported in the literature. Herein we present an account of the structure and reactivity of the
growing family of aluminyl compounds. In this context we examine the structural relationships between
the aluminyl anion and the AM cations, which now include examples of AM = Li, Na, K, Rb and Cs. We
report on the ability of these compounds to engage in bond-breaking and bond-forming reactions,
which is leading towards their application as useful reagents in chemical synthesis. Furthermore we
discuss the chemistry of bimetallic complexes containing direct Al–M bonds (M = Li, Na, K, Mg, Ca, Cu,
Ag, Au, Zn) and compounds with Al–E multiple bonds (E = NR, CR2, O, S, Se, Te), where both classes of
compound are derived directly from aluminyl anions.

a
School of Chemical of Physical Sciences, Victoria University of Wellington, PO Box
600, Wellington, 6012, New Zealand. E-mail: martyn.coles@vuw.ac.nz
b
School of Chemistry, Monash University, Melbourne, Victoria, Australia
1. Introduction
1.1 Neutral, monometallic complexes of aluminium(I)
The synthesis of neutral compounds containing aluminium in
the +1 oxidation state can be traced back to the 1940’s with the
isolation of binary compounds AlX (X = Cl, Br, I).1 It was not until
techniques for manipulating these meta-stable compounds were
developed that the chemistry was able to be explored in detail,2

Martyn Coles received his BSc Matthew Evans studied at Victo-

and PhD from Durham Univer-
sity in the UK, working with
Professor Vernon Gibson. After
post-doctoral work at the Univer-
sity of Iowa (with Professor
Richard Jordan) and University
of California, Berkeley (with
Professor T. Don Tilley) he
started his first independent job
at the University of Sussex. He is
currently a Professor of Inorganic
Martyn P. Coles Chemistry at Victoria University
of Wellington – Te Herenga Waka
in New Zealand. His research interests focus on the synthesis and
reactivity of low-valent main group compounds, with a particular
passion for the group 13 elements (Al, Ga In) and the heavier group
15 elements (Sb and Bi).
Matthew J. Evans
lie in the isolation of low-valent main-group complexes for small
molecule activation.
ria University of Wellington – Te
Herenga Waka in New Zealand,
where he received his BSc degree
in Chemistry in 2018. Following a
research year with Associate Pro-
fessor J. Robin Fulton, he com-
pleted his PhD degree in 2022
under Professor Martyn Coles
and Dr Mathew Anker. Matthew
currently works at Monash Uni-
versity in Australia as a postdoc-
toral researcher for Prof. Came-
ron Jones. His research interests

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3,5-iPr2C6H),14 and the carbazolyl-substituted example IX.15

Although the chemistry of these species is at an early stage, both
classes of complex have already demonstrated interesting
reactivity,16 including oxidative addition, cycloaddition and appli-
cations in coordination chemistry.

1.2 Low valent group 13 analogues of N-heterocyclic

carbenes
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Inspired by the extensive chemistry of carbenes, in which a

divalent carbon centre is supported by a dianionic ligand set to
afford a neutral complex of the general formula X2C, researchers
have explored the chemistry of isoelectronic group 13 element
(E) analogues (Fig. 2). To maintain an isoelectronic relationship
with carbenes, atom E is present in the +1 oxidation state and
the dianionic supporting ligand therefore generates an overall
negative charge, resulting in the boryl (E = B), aluminyl (E = Al),
gallyl (E = Ga) and indyl (E = In).17 Although a large number of
predominantly bidentate ligands have been applied to this area,
the N,N 0 -chelating scaffold is commonly encountered in both
carbene and the group 13 complexes, and the following discus-
sion will therefore be restricted to such systems.
The first group 13 system to be investigated within this context
was the gallyl anion [Ga(HCNtBu)2] Xa, isolated with the [K(18-c-6)-
Fig. 1 Low valent Al(I) compounds based on cyclopentadienyl (I–IV) and
b-diketiminate (BDI, V–VII) ligand systems, and aluminylenes VIII and IX.
(THF)2]+ (18-c-6 = 18-crown-6) counter-ion.18 Subsequent work
extended this chemistry to the N-Dipp substituted analogue
[Ga(HCNDipp)2] Xb, isolated as either a dimer incorporating
with the first breakthrough in the practical synthesis of isolable [K(Et2O)]+ or [K(dme)]+ cations, or as the isolated anion with a
Al(I) compounds being the reaction of AlCl with MgCp*2, affording [K2(18-c-6)3]+ cation.19 The lightest member of the series, the boryl
[AlCp*]4 (Ia, Fig. 1).3 It was subsequently shown that Ia could also anion [B(HCNDipp)2] XI was initially isolated as the [Li(dme)]2-
be accessed by the reduction of Cp*AlCl2 with potassium,4 bridged dimer, containing a direct B–Li bond.20 Examples of
circumventing the need for specialist equipment required for monomeric lithium boryls have since been reported,21 and the
handling AlX species. ‘AlCp*’ exists as the tetramer Ia in the dimeric borylpotassium complex [K{B(HCNDipp)2}]2 XII has
solid-state but undergoes a temperature dependant dissociation recently joined the family of boryls.22
into monomeric AlCp* units Ib in solution, a feature that has
been exploited in its reactivity, illustrated by its ability to act as a
ligand at transition metal centres.5 It also exists as monomer Ib in
the gas phase.6 The area of cyclopentadienyl Al(I) chemistry has
subsequently been extended to other derivatives, with the bulky
systems [C5(CH2Ph)5] (II),7 and [1,2,4-R3C5H2] (R = SiMe3 (III),8
tBu (IV)9) successfully shifting the equilibrium such that the
momomeric forms dominate.
The next major advance in Al(I) chemistry was the synthesis
of the monomeric complex Al(BDIDipp) (V, BDIDipp = [HC{C(Me)-
(NDipp)}2]), isolated from the reduction of the diiodide
precursor by potassium.10 Despite the extensive chemistry of BDI-
ligands, only two other Al-BDI compounds are known. Al(tBuBDIDipp)
VI incorporates tBu groups into the ligand framework,11 whereas
the new ‘‘superbulky’’ derivative Al(BDIDipep) (VII) replaces the
nitrogen substituents with 2,6-diisopentylphenyl (Dipep) groups.12
The rich chemistry of both Cp- and BDI-derived Al(I) systems have
been the subject of several detailed review articles.13
A noteworthy addition to the family of Al(I) compounds con-
sists of a one coordinate Al-centre in an aluminylene complex.
Fig. 2 (a) The relationship between neutral carbenes and the group 13
Two classes of aluminylene have been presented, the ter-phenyl boryl, aluminyl, gallyl and indyl anions. (b) Examples of gallyl (X), boryl
alanediyl derivative Al(AriPr8) (VIII, AriPr8 = 2,6-(2,4,6-iPr3C6H2)2- (XI, XII) and indyl (XIII, XIV) anions (dme = dimethoxyethane).

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Although the parent aluminyl and indyl anions, [Al(HCNH)2]

[In(HCNH)2] had been studied computationally,23 it was not
until 2018 that we reported the first indyl anion.24 In this study
we showed that the dianionic bis(amidodimethyl)disiloxane
ligand [O(SiMe2NDipp)2]2 (NON), which we had used in our
earlier work with low valent bismuth,25 stabilised both the
lithium indyl (NON)In–Li(THF)3 XIII that contains an In–Li
bond, and the potassium indyl [K(crypt-222)][In(NON)] (crypt-
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222 = [2.2.2]cryptand) that has a naked indyl anion with a two-

coordinate indium. The latter anion was also isolated as the
dimeric potassium indyl, [K{In(NON)}]2 XIV.26
In this Feature Article we describe the research on the
synthesis and structures of the current family of aluminyl
anions, focussing on the characteristics of the supporting
ligand and the nature and extent of the interactions between
the anion and the counter cation. We have also discussed the
reactivity of aluminyls with a range of functional groups in the
context of bond breaking and bond forming reactions. Furthermore,
given that aluminyls provide facile entry into a class of bimetallic
complex containing unsupported Al–M bonds, we have examined
the ability of these compounds to promote a range of small
molecule activation processes. Finally, since the aluminyls have
also provided a stable environment for the formation of Al–E
multiple bonds, we have included a discussion on these new
functional groups in the context of small molecule activation. This
updated report compliments and extends earlier reviews on the
chemistry of the aluminyl anion.13a,27
2. Synthesis and structures of
aluminyls
2.1 N,N 0 -(Diamido) aluminyl anions
The first potassium aluminyl compound, [K{Al(xanthNON)}]2 1
was isolated in 2018, using the 4,5-bis(2,6-diisopropylanilido)-
2,7-di-tert-butyl-9,9-dimethylxanthene ([xanthNON]2) as a che-
lating diamido ligand scaffold (Fig. 3).28 Shortly after this report
we described the preparation of the potassium aluminyl
[K{Al(NON)}]2 2.29 Analysis of 1 and 2 by single crystal X-ray
diffraction confirmed that the aluminium centres in 1 are
three-coordinate with a dative O-Al interaction stabilising
the formally anionic aluminium centre, whereas the alumi-
nium centres in 2 are strictly two-coordinate.
Subsequent to these reports, potassium compounds contain-
ing seven-membered N,N 0 -(diamido) aluminyl anions with an
alkyl-bridged bis(dimethylsilylamido) ligand [{CH2SiMe2NAr}2]2
([NC2NAr]2, Ar = Dipp, Mes), [K{Al(NC2NDipp)}]2 3Dipp,30 and
[K{Al(NC2NMes)}]2 3Mes,31 were prepared using an analogous pro-
cedure to that employed for the synthesis of 1 and 2. The amido
substituent has an effect on this chemistry, demonstrated during
the synthesis of 3Dipp and 3Mes. The major product after reacting
the NMes precursor (NC2NMes)Al–I with excess potassium for
3 days was the dialumane (NC2NMes)Al–Al(NC2NMes),31 whereas
under the same experimental conditions the corresponding reac-
tion with the NDipp analogue afforded the fully reduced Al(I)
aluminyl 3Dipp.30
Fig. 3 Potassium N,N 0 -(diamido)aluminyl compounds supported by
[xanthNON]2 (1), [NON]2 (2), [NC2NAr]2 (3Ar, Ar = Dipp, Mes) and
[BDIAr-H]2 (4Ar, Ar = Dipp, Dipep) ligands.
The potassium aluminyl [K{Al(BDIDipp-H)}]2 4Dipp was isolated
during an attempt to boost the reactivity of the well-known Al(I)
compound Al(BDIDipp) (V)10 through the addition of potassium
bases, K[R] (R = CH2SiMe3, N{SiMe3}2).32 Instead of forming
the anticipated K[Al(BDIDipp)(R)] compounds, deprotonation
of a methyl group of the ligand backbone occurred generating
the diamido ligand, [DippNC(Me)QC(H)C(QCH2)(NDipp)]2
(BDIDipp-H) in 4Dipp. An analogous reaction of the NDipep
substituted precursor Al(BDIDipep) (VII) with K[R] was shown to
be solvent dependant.12 In hexane the reaction forms exclusively
the potassium aluminyl [K{Al(BDIDipep-H)}]2 4Dipep, whereas in
benzene a mixture of 4Dipep and a ligand C–H activation product
was formed.
2.2 C,N-(Alkyl)(amido) and C,C 0 -(dialkyl)aluminyl anions
It is established that the substituents adjacent to the low-valent
C-atom directly influence the electronic structure of carbenes.33
Accordingly, chelating C,N-(alkyl)(amido)-and C,C 0 -(dialkyl)
ligands have been used to form potassium aluminyls with
different electronic properties. The ligands [(Me3Si)2C(CH)2NAd]2
([CSiNAd]2),34 and [{H2CC(SiMe3)2}2]2 ([{CSi}2]2),35 form five-
membered heterocycles with C,N- and C,C 0 -coordination at
aluminium, respectively (Fig. 4). In contrast to the potassium
N,N 0 -(diamido) aluminyls 1–4, these compounds are synthe-
sized by the potassium reduction of the corresponding dialu-
manes (CSiNAd)Al–Al(CSiNAd) and ({CSi}2)Al–Al({CSi}2), affording
[K(12-c-4)2][Al(CSiNAd)] (5, 12-c-4 = 12-crown-4) and ({CSi}2)Al–
K(tol)2 (6, tol = toluene) after the appropriate work-up. A DFT
study on the electronic structures of 5 and 6 confirm that
incorporating less electron withdrawing alkyl-groups at alumi-
nium raises the energy of the HOMO relative to the diamido

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Fig. 4 Potassium and lithium C,N-(Alkyl)(Amido) and C,C 0 -(Dialkyl) alu-
minyls supported by [CSiNAd]2 (5, Si = SiMe3, Ad = 1-adamantyl), [{CSi}2]2
0
(6) and [{bo2e-CAr N}]2 (9, Ar 0 = 3,5-tBu2C6H3).
derivatives 1, 2 and 3Dipp, although the HOMO–LUMO energy
gap remains similar in all five examples.27
2.3 Beyond potassium in aluminyl chemistry
The use of potassium as the active reductant in the preparation
of 1–6 led to the exclusive formation of the corresponding
potassium aluminyls. However, inspired by the established
phenomenon of alkali-metal mediated (AMM) reactivity,36 in
which a group 1 metal works synergistically with another metal
(in this case the aluminium) to gain entry into reaction path-
ways that may not otherwise proceed efficiently,37 we sought to
extend the family of alkali metal (AM) aluminyls to other group
1 derivatives.
2.3.1 Lithium and sodium aluminyls. Lithium and sodium
aluminyls have been prepared via two different synthetic
approaches: (i) the direct reaction of Al(III) iodide precursors
with the group 1 metal as reductants, or (ii) by a metathesis
reaction of the isolated potassium aluminyls with a group 1
metal salt. We have demonstrated that (NON)Al–I reacts with an
excess of Li or Na metal to afford the corresponding lithium and
sodium aluminyl complexes, [Li{Al(NON)}]2 7 and [Na{Al(NON)}]2
8, respectively.38 Interestingly this approach is unsuccessful in
obtaining aluminyl anions supported by the [xanthNON]2 ligand,
with the attempted lithium reduction of (xanthNON)Al–I affording
Al–N cleavage products, and the corresponding reaction
with sodium giving exclusively the dialumane, (xanthNON)Al–
Al(xanthNON).39 A new C,N-(alkyl)(amido) aluminyl anion
has recently been reported incorporating a more robust
bicyclo[2.2.2]oct-2-ene (bo2e) backbone.40 As for the synthesis
of 7, the direct reduction of the Al(III) iodide precursor with
lithium powder afforded the lithium aluminyl, isolated from
0
Et2O as (bo2e-CAr N)Al–Li(Et2O)2 9 (Ar 0 = 3,5-tBu2C6H3).
Using the metathesis protocol, the lithium aluminyl (xanth-
NON)Al–Li(Et2O)2 10 was synthesized by reacting 1 and lithium
iodide in diethyl ether.39 A similar methodology reacting 4Dipp
with Li[BPh4] or Na[BPh4] gives the corresponding lithium
and sodium aluminyl compounds, isolated as (BDIDipp-H)Al–
Li(Et2O)2 11 and (BDIDipp-H)Al–Na(Et2O)(TMEDA) 12.41
2.3.2 Rubidium and caesium aluminyls. In collaboration
with Mulvey and co-workers, we have now accessed aluminyl
compounds incorporating the heavier alkali metals Rb and Cs,
completing the first series of aluminyls [AM{Al(NON)}]2 for
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AM = Li, Na, K, Rb and Cs.42 The synthesis involved the
reduction of (NON)Al–I using graphitic RbC8 or CsC8, affording
[Rb{Al(NON)}]2 13 and [Cs{Al(NON)}]2 14, respectively. A similar
approach has since completed the series of [AM{Al(BDIDipp-H)}]2
compounds for [Rb{Al(BDIDipp-H)}]2 15 and [Cs{Al(BDIDipp-H)}]2
16.41 Although the reactions that form 15 and 16 proceed using
benzene or toluene solvent, the best yields were achieved using a
solvent-free ball-milling process involving mixtures of Al(BDIDipp)
and RbC8 or CsC8.
2.4 Structural classification of aluminyl compounds
As the development of aluminyl compounds has progressed,
different structural types have been identified that can be
grouped depending on the nature and extent of the cation:
anion interactions. Whilst this area has mainly focused on
solid-state structures determined by X-ray diffraction, the facile
conversion between different structural types (e.g. in the
presence of a coordinating solvent) means that consideration
of the state of the aluminyl in solution is an important and in
some cases crucial consideration when studying the reactivity
of these species. Indeed, as the chemistry of these systems is
explored, the role of the alkali metal in directing or even
controlling reaction pathways is becoming evident. We have
therefore classified the aluminyl compounds into the following
structural types.
2.4.1 Contacted dimeric pairs (CDPs). X-Ray crystallography
has shown that the potassium aluminyls 1,28 2,29 3Ar (Ar =
Dipp,30 Mes31) and 4Ar (Ar = Dipp,32 Dipep12) exist as contacted
dimeric pairs (CDPs) in the solid-state, in which the two alumi-
nyl anions are linked by flanking K  p(arene) interactions
(Fig. 3). Diffusion ordered spectroscopy (DOSY) NMR experi-
ments on these systems are consistent with retention of these
associated dimeric structure in solution. In addition, the CDP
motif has now been structurally verified for the series of
[AM{Al(NON)}]2 (AM = Li 7, Na 8, Rb 13 and Cs 14),38,42 and
the [BDIDipp-H]2 systems [AM{Al(BDIDipp-H)}]2 (AM = Li 17, Na
18, Rb 15 and Cs 16),41 where heating samples of the initially
isolated (BDIDipp-H)Al–Li(Et2O)2 11 and (BDIDipp-H)Al–Na-
(Et2O)(TMEDA) 12 to 70 1C under vacuum afforded the corres-
ponding CDPs [Li{Al(BDIDipp-H)}]2 17 and [Na{Al(BDIDipp-H)}]2
0
18. The same conversion was achieved when (bo2e-CAr N)Al–
Li(Et2O)2 9 was recrystallized from hexane, forming the CDP
0
[Li{Al(bo2e-CAr N)}]2 19.40
The relative orientation of the aluminyl anions within the
dimer varies with the alkali metal and supporting ligand, and
three sub-types of CDP have emerged from structural analysis
(Fig. 5). The lithium and sodium aluminyls 7, 8, 17, 18 and 19
form ‘slipped’ CDPs in which the distances from the Al to the
AM (dAl  AM) are significantly different (range DdAl  AM = 0.40–
0.62 Å).38,40,41 DFT calculations show that a single Al–AM bond
exists within these ‘slipped’ CDPs, in contrast with the heavier
congeners (AM = K, Rb, Cs) that form ‘symmetric’ or ‘twisted’
dimers with the Al atoms engaging in contacts to both AM
cations (vide infra).
In our initial assessment of the structures of Rb and Cs
CDPs 13 and 14, we noted that the aluminyl heterocycles were
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Fig. 5 Three structural sub-types noted for the contacted dimeric pairs
CDPs of alkali metal aluminyls.
‘twisted’ with respect to one another. The angle y between the
least squares plane defined by Al–N–Si–O–Si–N were 66.55(4)1
(AM = Rb) and 66.31(5)1 (AM = Cs), which we ascribed to the
steric influence of the large Rb+ and Cs+ cations. However,
the relative orientations of the aluminyl heterocycles within the
Rb and Cs CDPs 15 and 16 are strictly coplanar (y = 01) due to a
crystallographic inversion centre, suggesting that other ligand:AM
interactions or packing effects also contribute to the overall
structure.
2.4.2 Monomeric ion pairs (MIPs). The lack of aromatic
substituents in the dialkyl ligand framework [{CSi}2]2 precludes
the formation of stabilizing K  p(arene) interactions that are
important in the formation of CDP structures. In this case, the
(dialkyl)-aluminyl compound is as isolated as the toluene sol-
vated species, 6.35 We refer to this structure type as a monomeric
ion pair (MIP), which is characterised by unsupported, highly
polar Al–AM bonds between the anionic and cationic compo-
nents of the aluminyl compound (Fig. 6).
Fig. 6 Aluminyls that have been characterised as monomeric ion pairs
(MIPs) in the solid-state.
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Our initial lithium reduction reactions were performed in
Et2O, affording a crude white solid after removal of the solvent.
When gently heated under vacuum during the work-up procedure,
we noted a distinct colour change to yellow and the final product
was identified as the CDP 7. Curious as to the identity of the
colourless product initially formed, we redissolved a sample of 7
in Et2O, from which we were able to isolate the lithium MIP,
(NON)Al–Li(Et2O)2 20. An analogous result was obtained with
the sodium analogue 8, affording (NON)Al–Na(Et2O)2 21. These
different structures exist in equilibrium in solution, and we
showed that, in addition to heating under vacuum, the CDPs
were fully regenerated when the MIPs were dissolved in a large
excess of non-coordinating solvents such as hexane or toluene.
We have investigated the interconversion between CDPs and
the corresponding MIPs for the aluminyl anions [Al(NON)] in
more detail, using a range of donor molecules (Scheme 1). The
addition of THF to the CDPs 7 and 8 affords the THF adducts,
(NON)Al–AM(THF)3 (22, AM = Li; 23, AM = Na).43 We were
unable to reform the CDPs from these MIPs, consistent with the
increased s-donor property of THF resulting in stronger AM–O
bonds. We were also unable to obtain the corresponding
potassium MIP from the reaction of 2 with THF, prompting
us to examine the role of the bidentate donor ligand TMEDA. In
this case, the full series of MIPs for Li, Na and K were accessed,
in (NON)Al–AM(TMEDA)n (24, AM = Li, n = 1; 25, AM = Na, n = 2; 26,
AM = K, n = 2).43 A similar approach using 18-crown-6 (18-c-6) as a
multidentate donor ligand forms the MIP (NC2NDipp)Al–K(18-c-6)
27 from the CDP 3Dipp.31 This work has recently been complimen-
ted by the demonstrated interconversion of 9 2 19,40 11 2 17
and 12 2 18.41
2.4.3 Separated ion pairs (SIPs). A third structure type for
the aluminyls was noted in the initially synthesized potassium
(alkyl)(amido) aluminyl 5.34 The addition of 12-crown-4 during
Scheme 1 The conversion of Li (7), Na (8) and K (2) CDPs to MIPs using
Et2O, THF and TMEDA. Note for simplicity, the CDP is shown as the
symmetric variant.
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[Li(TMEDA)2][Al(NON)] 33. Structural characterisation of both

species confirmed non interactions between the AM and the Al,
confirming these species as SIPs.

3. Reactivity of aluminyl anions

3.1 Aluminyls as nucleophiles
A defining feature of aluminyls is their nucleophilic
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Fig. 7 Aluminyls characterised as separated ion pairs (SIPs) in the solid- character,27 illustrated by the reactions of 1,28 3Dipp,31 and 635
state. with organic nucleophiles such as MeOTf and MeI, affording
the corresponding aluminium(III) methyl compounds. This
reactivity has been exploited in the synthesis of new bimetallic
the work-up formed the separated ion pair (SIP) [K(12-c-4)2]- complexes via a salt metathesis route with metal halide
[Al(CSiNAd)] 5, in which the potassium cation is isolated from substrates.
the aluminyl anion (Fig. 7). 3.1.1 Synthesis of bimetallic Al–M complexes. Bimetallic
The ability to form SIPs from CDPs has also been investi- compounds accessed from aluminyls generally contain
gated for the aluminyl anions [Al(xanthNON)], [Al(NON)] and unsupported Al–M bonds that are reminiscent of the Al–AM
[Al(NC2NDipp)]. For the potassium aluminyl CDPs 1, 2 and bonds in the MIPs (see Section 2.4.2), including examples of
3Dipp, the addition of [2.2.2]cryptand (crypt-222) sequesters the Al–Mg, Al–Al, Al–Ca, Al–Cu, Al–Zn, Al–Y,45 Al–Ag and Al–Au
potassium cations to form the SIPs [K(crypt-222)][Al(xanthNON)] (Fig. 9).46 The ability of these compounds to activate small
28,44 [K(crypt-222)][Al(NON)] 29,43 and [K(crypt-222)][Al(NC2NDipp)]
30.31 The addition of an excess of 18-crown-6 to 3Dipp also gives
rise to a SIP, with formula [K(18-c-6)]1.5[Al(NC2NDipp)] 31.31
Crystallographic analysis confirms that in each case there are
no contacts between the cationic and anionic components, effec-
tively releasing the ‘naked’ aluminyls for reactivity.
To date, we have isolated the only examples of SIPs for
lithium and sodium aluminyls (Fig. 8).43 As for the potassium
aluminyl, the addition of [2.2.2]cryptand to CDP 8 afforded the
SIP, [Na(crypt-222)][Al(NON)] 32. To form the lithium SIP, we
crystallised a sample of CDP 7 directly from TMEDA, affording

Fig. 9 Bimetallic complexes derived from aluminyls. NHCiPr = N,N 0 -

Fig. 8 Examples of the different structural type for the sodium aluminyl diisopropyl-4,5-dimethyl-2-ylidene; IPr = N,N 0 -bis(2,6-diisopropylphenyl)-
Na[Al(NON)]. (a) Slipped contacted dimeric pair [Na{Al(NON)}]2 (8), (b) imidazol-2-ylidene; Me2CAAC = 1-(2,6-diisopropylphenyl)-3,3,5,5-tetrame-
Monomeric ion pair (NON)Al–Na(TMEDA)2 (25), (c) Separated ion pair, thylpyrrolidin-2-ylidene; CyCAAC = 2-[2,6-bis(1-methylethyl)phenyl]-3,
[Na(crypt-222)][Al(NON)] (32). 3-dimethyl-2-azaspiro[4.5]dec-1-ylidene.

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molecules is an active area of research, with key results
described below.
The monoanionic ligands [BDIAr] (Ar = Mes, Dipp) have
been utilised to support the partner metal in a series of Al–M
compounds, (xanthNON)Al–M(BDIMes) (34, M = Mg;28 35, M =
Zn),39 accessed via a metathesis route with the corresponding
(BDIMes)M–I reagents. More recently, an alternative (higher
yielding) route to 34 was presented,39 involving the reduction
of (xanthNON)Al–I with Jones’ Mg(I) reagent, [(BDIMes)Mg]2.47
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Related chemistry with potassium aluminyls 2 and 3Dipp have
afforded (NON)Al–M(BDIMes) (36, M = Mg; 37, M = Zn48) and
(NC2NDipp)Al–M(BDIDipp) (38, M = Mg; 39, M = Ca30)
compounds.
The bulky phosphine ligand PtBu3 has been used to stabilise
a series of (xanthNON)Al–M(PtBu3) complexes of the coinage
metals (40, M = Cu;49 41, M = Ag;49 42, M = Au50) and the alkyl
bridged derivative (NC2NDipp)Al–Cu(PtBu3) 43.51 Related com-
pounds were isolated using carbenes as the neutral ligand,
affording a series of (NC2NDipp)Al–M(NHC) (44, M = Cu, NHC =
NHCiPr;52 45, M = Ag, NHC = NHCiPr;51 46, M = Au, NHC =
NHCiPr;51 47, M = Cu, NHC = IPr51) and (NC2NDipp)Al–M(CAAC)
(48, M = Cu, CAAC = Me2CAAC;52 49, M = Ag, CAAC = CyCAAC51).
3.1.2 Reactivity of Al–M complexes with CO2. The reported
reactivity of these bimetallic complexes (Type-A, Scheme 2) has
focussed largely on the reduction of CO2. In this respect, the
reactions of the coinage metal complexes with CO2 have been
Scheme 2 General reaction scheme summarizing the conversion of
carbon dioxide CO2 to carbonate [CO3]2 promoted by bimetallic com-
plexes derived from aluminyls. Type-A = bimetallic complex; Type-B =
dioxocarbene complex; Type-C = m-oxo complex; Type-D = carbonate
complex.
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studied experimentally and using computational methods.53
Initial reports on the reaction of the Al–Au system 42 with CO2
identified the product as the dioxocarbene (xanthNON)Al(O2C)
Au(PtBu3) 50 (Type-B), with crystallographic analysis confirming a
m-1k2O,O0 :2kC-bonding mode for the CO2-unit formed by the
reductive insertion of CO2 into the Al–Au bond.50 This result has
since been obtained with other Al–M compounds, affording the
related dioxocarbenes for M = Cu: (NC2NDipp)Al(O2C)Cu(PtBu3) 51,
(NC2NDipp)Al(O2C)Cu(NHCiPr) 52, (NC2NDipp)Al(O2C)Cu(Me2CAAC)
53; M = Ag: (xanthNON)Al(O2C)Ag(PtBu3) 54, (NC2NDipp)Al(O2C)
Ag(NHCiPr) 55; M = Au: (NC2NDipp)Al(O2C)Au(NHCiPr) 56.49,51,52
When the CO2 reduction reaction was attempted with the
Al–Cu compound 40, rather than affording the dioxocarbene
the product was identified as the carbonate (xanthNON)Al(O2-
CO)Cu(PtBu3) 57, with a m-1k2O,O 0 :2kO00 -bonding mode for the
carbonate identified by X-ray crystallography (Type-D).49 The
propensity of the (xanthNON)Al–M(PtBu3) systems to form
the carbonate complexes was investigated further, with the
results following the decrease in M–O bond strength and
increase in M–C bond strength as the group 11 metal varies
from copper to gold. Hence, under 1 atmosphere of CO2, the
Al–Cu system 40 forms the carbonate 57 at 78 1C, while the
Al–Ag converted to the carbonate (xanthNON)Al(O2CO)Ag(PtBu3)
58 over 24 h at 80 1C and the reaction of the Al–Au compound
stopped after the initial insertion to form 50 (even when exposed
to additional CO2 under forcing conditions).49 The formation of
analogous carbonate species has since been observed when the
dioxocarbene 51 was heated to 60 1C in an atmosphere of CO2,
affording (NC2NDipp)Al(O2CO)Cu(PtBu3) 59.51
Examination of the conversion of the dioxocarbene to the
carbonate using computational analysis has identified a rate
determining step involving the extrusion of CO, to form an
intermediate m-oxo bridged species (Type-C).49,51 This was
supported experimentally for the (xanthNON)Al–M(PtBu3) system,
where the reaction of the silver aluminyl 41 with N2O formed the
spectroscopically identified (xanthNON)Al(m-O)Ag(PtBu3), which
reacted with CO2 to form the expected carbonate product 58.49
Unfortunately in this case, the proposed oxo-intermediate was
too thermally sensitive to be isolated.
We have recently examined the reactivity of Al–Zn and Al–Mg
compounds 36 and 37 with CO2.48 During this study we found
that the Al–Zn compound reacts to form the dioxocarbene
(NON)Al(O2C)Zn(BDIMes) 60, with the same Type-B regiochem-
istry as that observed in the previous examples. In contrast, the
Al–Mg compound immediately forms a carbonate complex
(Type-D), which was isolated as the trimetallic compound
[Al(NON)(O2CQO)]2[Mg(THF)4] 61, most likely the product of
a Schlenk-type ligand redistribution. To investigate whether the
Al–Mg and Al–Zn bimetallic compounds 36 and 37 allowed
access to the intermediate m-oxo species (Type-C), reactions
were performed with N2O. The products formed were shown to
contain the predicted bridging oxo-unit, (NON)Al(m-O)Zn-
(BDIMes) 62 (Fig. 10a) and (NON)Al(m-O)Mg(BDIMes) 63, verified
through a X-ray diffraction study. Furthermore, we showed that
both species react with additional CO2 to form the carbonates 61
(M = Mg) and (NON)Al(O2CQO)Zn(BDIMes) 64 (M = Zn, Fig. 10b),
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Fig. 10 (a) Crystal structure of the m-oxo complex (NON)Al(m-
O)Zn(BDIMes) 62. (b) Crystal structure of the carbonate complex, (NON)-
Al(O2CO)Zn(BDIMes) 64.
demonstrating that the m-oxo compounds are intermediates in
the conversion of CO2 to [CO3]2.
3.1.3 Reactivity of Al–M complexes towards other
substrates. In related studies, Al–M bimetallic complexes (M =
Cu, Ag, Au) have been reacted with carbodiimides,
RNQCQNR.39,49–52 The resulting products show two possible
bonding modes for the inserted carbodiimide (Scheme 3). For
example, the reaction of the Al–Cu compound 48 with diiso-
propylcarbodiimide (DIC) gave a m-1k2N,N 0 :2kC-bonding mode
(Type-E) in (NC2NDipp)Al({iPrN}2C)Cu(Me2CAAC) 65, which is an
analogous bonding mode to the CO2 insertion product 53.
However, under the same conditions, the NHC supported
Al–Cu compound 44 gave the insertion product (NC2NDipp)
Al({iPrN}2C)Cu(NHCiPr) 66 with a m-1k2N,C:2kN 0 -bonding mode
(Type-F).51,52 Further studies concluded that the divergent
reactivity leading to products with Type-E and Type-F coordina-
tion, demonstrated an ambiphilicity of the Al–Cu bond that was
dependent on the identity of the carbene co-ligand in the
bimetallic starting material.52
Scheme 3 General reaction scheme summarizing the different bonding
modes for the products of carbodiimide insertion into Al–M bonds.
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Scheme 4 Alkyne insertion and related chemistry of the bimetallic Al–Cu
compound, (xanthNON)Al–Cu(PtBu3) 40.
The reactivity profile of (xanthNON)Al–Cu(PtBu3) 40 has
recently been extended to the insertion of internal alkynes into
Al–Cu bonds (Scheme 4).54 The symmetrical substrate 3-hexyne
afforded (xanthNON)Al(m-EtCQCEt)Cu(PtBu3) 67, initially formed
as the syn-product that thermally isomerises to the anti-product
upon gentle heating. Insertion of the non-symmetrical 1-phenyl-
1-pentyne substrate afforded (xanthNON)Al(m-nPrCQCPh)-
Cu(PtBu3) 68. Analysis of the product showed a mixture of two
regioisomers for the syn-product, with the major product having
the alkyl substituent geminal to the aluminium. The reaction of
the insertion products 67 and 68 with CO was shown to be
selective for the syn-isomers affording (xanthNON)Al{m-EtCQC(Et)
CQO}Cu(PtBu3) 69 and (xanthNON)Al{m-nPrCQC(Ph)CQO}
Cu(PtBu3) 70, believed to be due to interactions with the prox-
imal aluminium centre.
3.2 Oxidative addition to aluminyls
The key to unlocking catalytic activity for many main group
metal systems is the ability to control the redox activity. Under-
standing the oxidative addition to reduced metal centres, and
onwards work towards developing reductive elimination steps
will open the opportunity to establish catalytic cycles reminiscent
of those dominant in transition metal chemistry.55 The thermo-
dynamically favoured two-electron oxidation of Al(I) to Al(III) is a
common reaction for aluminyls, and the oxidative addition of
substrates via the cleavage of s-bonds has been documented for
all systems.
3.2.1 Oxidative addition of H2. Initial work with aluminyl
compound 1 demonstrated the cleavage of H–H bonds and
oxidative addition of dihydrogen to afford [K{Al(xanthNON)
(H)2}]2 71 (Scheme 5).28 This reaction has also been studied
computationally.56 Experimentally, full conversion of 1 to 71
occurred over 5 days at room temperature under 2 bar
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Scheme 5 Oxidative addition of H2 bonds to potassium (1 and 2), sodium
(8) and lithium (20) aluminyls.
atmosphere pressure, with the isolated dihydroaluminate pro-
duct crystallizing as the dimer. Subsequently, we investigated the
reaction of H2 with the series of lighter alkali metal aluminate
compounds, using the MIP 20 (for solubility purposes), and the
potassium and sodium CDPs 2 and 8, respectively.38 We found
that more forcing conditions were required to effect oxidative
addition of H2 for the NON-system, and performed the reactions
at 100 1C under 1.5 bar of H2. Using the time taken to achieve
50% conversion (t1/2) as an approximation of the rate of reaction,
the relative order Li (t1/2 = 1.5 days)c Na (t1/2 = 6 days) 4 K (t1/2 =
12 days) was observed. The compounds were isolated as the
dimers [Na{Al(NON)(H)2}]2 72 and [K{Al(NON)(H)2}]2 73,
although to obtain a pure compound for the lithium complex
it was necessary to crystallize the product from Et2O, affording
(NON)Al(m-H)2Li(Et2O)2 74.
3.2.2 Oxidative addition of E–H bonds. The oxidative
addition of element-hydrogen (E–H) bonds has been investigated
for acidic (N–H, O–H), hydridic (Si–H) and non-polar (P–H, C–H)
bonds (Scheme 6). Cleavage of N–H bonds was demonstrated
when 5 was exposed to excess ammonia, affording the amido
complex [K(12-c-4)2][Al(CSiNAd)(H)(NH2)] 75.34 The reaction of 1
and 2 with DippNH2 afforded the corresponding dimeric anilido
product [K{Al(xanthNON)(H)(NHDipp)}]2 76,57 and the mono-
Scheme 6 Oxidative addition of E–H bonds to aluminyls.
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meric ether adduct, [K(Et2O)2][Al(NON)(H)(NHDipp)] 77,58
respectively. Compounds 2 and 5 also undergo the oxidative
addition of a hydridic E–H bond from PhSiH3, giving [K(12-c-
4)2][Al(CSiNAd)(H)(SiH2Ph)] 78,34 and [K(Et2O)][Al(NON)(H)
(SiH2Ph)] 79,58 respectively. We have also shown that 2 will
undergo oxidative addition with P–H and O–H bonds with
MesPH2 and Ar*OH (Ar* = 2,6-tBu2-4-MeC6H3) to give [K(Et2O)2]
[Al(NON)(H)(PHMes)] 80 and K[Al(NON)(H)(OAr*)] 81.58
3.2.3 Oxidative addition of C–H bonds. In contrast to
Al(BDIDipp) that is known to be stable in aromatic solvents
benzene and toluene,59 the reaction of aluminyl compounds
with sp2 C–H bonds has been realised in several systems
(Scheme 7). It was initially discovered that the oxidative
addition of a C–H bond of benzene to 1 occurred over 4 days
at 57 1C to afford the (hydrido)(phenyl) aluminate product,
[K2{Al(xanthNON)(H)(C6H5)}]2 82.28 The more reactive dialkyl
aluminyl 6 formed the corresponding oxidative addition
product [K(tol)2][Al({CSi}2)(H)(C6H5)] 83 in 2.5 hours at room
temperature.35 In contrast, we have found that only the cae-
sium CDP 14 is able to activate aromatic substituents for
the NON-aluminyl system, requiring temperatures of 80 1C for
5 days to give the corresponding product, Cs[Al(NON)(H)(C6H5)]
84.42
The reaction of 4Dipp with benzene was reportedly ‘‘very
slow’’ at 20 1C. However it was found that in this case, rather
than forming the corresponding (hydrido)(phenyl) oxidative
addition product analogous to 82–84, when gently heated to
35 1C for a week the para-phenylene product K2[1,4-{Al(BDIDipp-H)
(H)}2(C6H4)] 85 was formed.32 The analogous double activation
product has been identified as one of the products formed during
the decomposition of the corresponding Cs-CDP 16 in benzene,
which was crystallographically identified as the THF-adduct,
[Cs(THF)2]2[1,4-{Al(BDIDipp-H)(H)}2(C6H4)] 86.41
The incorporation of a methyl substituent on the C6-ring
promotes competing oxidative addition pathways involving the
aromatic or aliphatic C–H bonds (Scheme 8). A mixture of the
Scheme 7 Oxidative addition of C–H bonds of benzene to potassium
(1, 4Dipp, 6) and caesium (14, 16) aluminyls.
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reaction of aluminyls 1 and 2 with ethylene under ambient

conditions (1 bar, room temperature) form the corresponding
aluminacyclopropanes [{K(C6H6)}{Al(xanthNON)(Z2-C2H4)}]2
95, and [{K(C6H6)}{Al(NON)(Z2-C2H4)}]2 96,64 consistent with
44

a (1+2) cycloaddition of the aluminyl to the CQC double bond.

Analytical data show that the C2H4 protons resonate at high
field (95, dH = 0.70; 96, dH = 1.40 in C6D6 and dH = 0.81 in
THF-D8) in the 1H NMR spectrum, and the C–C bond lengths
are B20% longer than in ethene (95, 1.598(2) Å; 96, 1.587(2) Å/
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1.596(2) Å), suggesting an activated system.

To investigate the onwards functionalisation of the activated
ethene, we have examined the reaction of the aluminacyclopro-
pane group in 96 with carbon monoxide, affording a series of
ethene carbonylation products (Scheme 9).64 Initial work with
dimeric 96 afforded the dialuminium product, K2[{Al(NON)
(Et)(m-OCQCHCH2)Al(NON)}] 97, containing an unprecedented
m-prop-1-ene-1,3-diyl-1k2C-1-olato-2kO ligand. To restrict the
Scheme 8 Oxidative addition of substituted arenes to potassium (1, 3Dipp,
6) aluminyls showing meta-selective and benzylic activation of C–H
reactivity to a single Al-centre, 18-crown-6 was added to 96 to
bonds. give the expected monomeric [K(18-c-6)][Al(NON)(Z2-C2H4)]
species 98. Accordingly, exposure of the aluminacyclopropane
group in 98 to CO gave the insertion product [K(18-c-6)]
meta-activated K[Al(xanthNON)(H)(3-MeC6H4)] 87 (Type-G, R 0 = [Al(NON)(CH2CH2CQO)] 99, containing the propan-1,3-diyl-
Me, R00 = H) and benzylic K[Al(xanthNON)(H)(CH2Ph)] 88 (Type-H, 1k2C-1-one ligand. This strained metallacycle underwent a
R 0 = R00 = H) products were formed in a 3 : 1 ratio when CDP 1 was thermally induced 1,2-hydrogen shift at 80 1C to afford the
heated to 80 1C in toluene for 2 days.60 In contrast, the Type-G 1-propen-1-olate compound, [K(18-c-6)(THF)2][Al(NON)(CH2-
meta-activated product K[Al({CSi}2)(H)(3-MeC6H4)] 89 formed CHQCHO)] 100.
exclusively when a sample of 6 was left at room temperature in
toluene for 12 h,61 and heating a sample of 3Dipp to 110 1C in 3.4 Aluminyl promoted oxidation chemistry
toluene for 24 h proceeded with Type-H benzylic activation to For many researchers in the area, the chemistry of aluminyls is
afford K[Al(NC2NDipp)(H)(CH2Ph)] 90.31 progressing beyond that of being an academic curiosity and
To probe the selectivity of the reaction with aluminyl com- becoming more targeted towards their application in the devel-
pound 1, the study was extended to the oxidative addition of opment of synthetically useful transformations. In this context,
xylenes and other dialkylated aromatic substrates. The reaction
with ortho-xylene (1,2-Me2C6H4) at 80 1C for 2 days exclusively
formed the benzylic activation product K[Al(xanthNON)(H)
{CH2(2-MeC6H4)}] 91 (Type-H, R 0 = Me, R00 = H), whereas
reaction with meta-xylene (1,3-Me2C6H4) under the same con-
ditions afforded a 2 : 3 mixture of meta-activated K[Al(xanthNON)
(H)(3,5-Me2C6H3)] 92 (Type-G, R 0 = R00 = Me) and benzylic
K[Al(xanthNON)(H)(CH2{3-MeC6H4})] 93 (Type-H, R 0 = H, R00 =
Me) products.60 To restrict the activation to exclusively meta-
selectively, the reaction of 1 with n-butylbenzene afforded
K[Al(xanthNON)(H)(3-nBuC6H4)] 94 (Type-G, R 0 = H, R00 = nBu).
DFT calculations performed on the reaction of 28 with n-
butylbenzene and the reaction of 6 with toluene indicated that
the activation energies required to promote meta-alumination
were lower than the competing benzylic-, ortho- and/or para-
alumination processes.60,61 Further DFT studies also revealed
the presence of Meisenheimer intermediates, consistent with a
concerted SNAr mechanism for arene C–H activation.32,44,62

3.3 Cycloaddition of aluminyls to unsaturated groups

Aluminyl compounds are known to form cycloaddition pro-
ducts with one (or more) unsaturated bonds within a substrate,
with documented examples showing addition to CRC,63 Scheme 9 Carbonylation of ethene promoted by a potassium alumina-
CQC,44,63,64 and CQN31 groups. In the simplest case, the cyclopropanes 96 and 98.

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the ability of the aluminyls to promote oxidation of small
molecules is becoming established as an important reaction
type, and the following sections detail some of the areas in
which this reaction type has been recently applied.
3.4.1 Reactivity with white phosphorus (P4). The functio-
nalisation of white phosphorus (P4) has been achieved by
aluminyl compounds 1, 3Dipp and 5 (Scheme 10). In the
presence of 18-c-6, both 1 and 3Dipp form compounds containing
a doubly reduced [P4]2 unit in the products [K(18-c-6)][Al-
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(XanthNON)(Z1 : 1-P4)] 101,65 and [K(18-c-6)][Al(NC2NDipp)(Z1 : 1-P4)]
102,66 respectively. The corresponding ether-solvated analogue,
[K(Et2O)3][Al(NC2NDipp)(Z1 : 1-P4)] 103 was obtained when the
reaction with 3Dipp was performed in ether, which forms a 1-D
polymer with intermolecular K  P interactions. This contrasts the
behaviour of the (alkyl)(amido) aluminyl 5 that extracted a single
P-atom when reacted with P4 to afford the bis-aluminyl phos-
phide, [K(12-c-4)2][{Al(CSiNAd)}2(m-P)] 104.67
The reaction of 101 with an additional 0.5 equivalents of the
CDP 1 resulted in further reduction of the phosphorus unit,
Scheme 10 Oxidation of P4 by potassium aluminyls 1, 3Dipp and 5.
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generating a linear [P4]4 ligand in K2[{Al(xanthNON)}2(m-Z2 : 2-P4)]
105. The P–P bond lengths in the bridging P4-unit of 105 indicate a
degree of p-bonding, confirmed using DFT calculations. It was also
shown that the reaction of 105 with 1 atmosphere of ammonia
liberated PH3 from the reaction and generated a mixture of
Al(xanthNON)(NH2)NH3 106 and [K{Al(xanthNON)(NH2)2}]2 107.
Under more forcing conditions the 3Dipp/P4 system was
shown to form higher P-containing oligomers. When performed
at 60 1C in THF, the [P6]4 containing product, [{K(THF)2}
{Al(NC2NDipp)}]2(m-P6) 108 was isolated in which the phosphorus
group consisted of two cyclo-P3 subunits linked by a P–P bond.
Furthermore, increasing the amount of P4 to 3 equivalents and
heating the reaction to 60 1C for 8 days gave [{K(tol)2}
{Al(NC2NDipp)(m-P16)}]2 109 containing the [P16]4 cluster.
3.4.2 Reactivity with ketones. A recent report described
a divergent series of products obtained when the aluminyl
compound 3Dipp was reacted with ketones (Scheme 11).68 Based
on previous work with in situ generated Al(BDIDipp),69 the
reaction was anticipated to proceed via reductive coupling of
two equivalents of ketone to afford the corresponding pinaco-
late structure, and indeed this is what is observed with aceto-
phenone to afford K[Al(NC2NDipp)({OC(H)Ph}2)] 110, which crystal-
lized as a single diastereoisomer. Although a reductive coupling
reaction is also observed when 3Dipp is reacted with 2 equivalents of
benzophenone, rather than forming the symmetrical pinacolate, a
C–C bond is formed between the ketyl carbon atom of one molecule
and an ortho-carbon atom of a phenyl group belonging to a second
equivalent, affording [K(THF)2][Al(NC2NDipp)(k2O,O0 ){OCPh2CH
(CHQCHCHQCH)CQCPhO}] 111. The reaction with one equiva-
lent of 2,4-dimethyl-3-pentanone afforded the potassium (hydrido)
(carboxyl)aluminate K[Al(NC2NDipp)(H){OC(iPr)QCMe2}] 112, which
corresponds to the formal oxidative addition of an enolisable
Scheme 11 Diverse reactivity of potassium aluminyl 3Dipp with ketones
acetophenone, benzophenone, 2,4-dimethyl-3-pentanone and 2,2,4,4-
tetramethyl-3-pentanone.
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iso-propyl methine proton to aluminium. To avoid this possi-
bility, one equivalent of the non-enolisable ketone 2,2,4,4-
tetramethyl-3-penanone was reacted with 3Dipp. In this case,
the product K[Al(NC2N 0 ){OC(H)tBu2}] 113 (NC2N 0 = k3N,N 0 ,C-
[DippNSiMe2(C2H4)SiMe2NC6H3iPr{C(H)MeCH2}-2,6]3) showed
a hydroalumination pathway was in operation in which the
ketone had been reduced to a [tBuC(H)O] alkoxy ligand, with
a likely source of the hydridic hydrogen originating from an
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intramolecular oxidative addition of a methine C–H bond from
an iPr substituent of a Dipp group.
3.4.3 Reactivity with carbon monoxide. Another recent
development in the application of aluminyl compounds for
the reductive coupling of small molecules via C–C bond for-
mation involves their reactivity towards carbon monoxide
(Scheme 12). We reported that when exposed to an atmosphere
of CO, the potassium aluminyl MIP 26 formed [K2{Al(NON)}2-
(C4O4)]2 114, containing a m-(k2C,O-1,4-dioxido-2,3-diolato(Z)-but-
2-en-1,4-diyl) tetraanion, with the cis-{anti,anti} configuration.70
The [C4O4]4 ligand is linear with bonds that approximate
to alternating C–C single and CQC double bonds, and the
compound crystallised as the dimer with K  O interactions join-
ing the two monomeric units. A rearrangement of the C4-chain to
form the corresponding (1,4-dioxido-2,3-diolato(E)-but-2-en-1,4-
diyl) ligand with a trans-{syn,syn} configuration in [{K(TMEDA)}
{Al(NONDipp)}]2(C4O4) 115 took place when a sample of 114 was
heated under an atmosphere of CO in the presence of TMEDA.
Scheme 12 Summary of reactions of CDPs (1 and 2) and MIPs (10 and 26) with CO, forming complexes containing [C4O4]4 (3 isomers: {114, 120}, 115,
{117, 118}), [C5O5]5 (116) and [C6O6]4 (119) and [C4O4]6 (121) ligands.
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When the CDP 2 was reacted with CO under identical conditions
to that leading to the formation of 114, and the crude product
crystallized in the presence of TMEDA, the product was identified
by X-ray crystallography as K5[K(TMEDA)][{Al(NONDipp)}4(C5O5)2]
116 containing the pentameric [C5O5]5 ligand. The synthesis of
116 was also achieved from the reaction of the MIP 24 with CO at
60 1C. Further analysis of the reaction of 2 with CO showed that it
is not selective for the formation of 114, suggesting that decom-
position or higher oligomers could be forming.
Shortly after this report, the reactivity of the CDP 1 and MIP
10 with CO was described.71 Under ambient conditions, both
aluminyl compounds promoted tetramerization of CO in the
products to afford [{K(tol)2}{Al(xanthNON)}]2(C4O4) 117 and
[{Li(Et2O)}{Al(xanthNON)}]2(C4O4) 118, respectively. X-ray crystallo-
graphy confirmed a trans-{syn,syn} configuration for the
[C4O4]4 chain, analogous to that found in 115. Interestingly,
when 117 was heated to 65 1C under CO at two atmosphere
pressure in THF, a further two equivalents of CO were incorpo-
rated to afford K[K(THF)2][Al(xanthNON)]2(C6O6) 119 containing
a novel cyclo-[C6O6]4 ligand with a C5O-pyran core. It was also
noted that a thermally induced isomerization of the trans-
{syn,syn}-C4O4 ligand in 117 to the cis-{anti,anti}-C4O4 ligand
in the new compound [K(THF)]2[{Al(xanthNON)}2(C4O4)] 120
occurred when heated to 65–70 1C in the presence of K[HBEt3].
In addition to the [C4O4]4 and [C6O6]4 ligands present in
117–120, this study contained reports of the [C4O4]6 ligand.
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Thus, whilst isolated samples of 117 were resistant to further
reduction using Li[HBEt3] or K[HBEt3], the in situ reaction of
K[HBEt3] with 1/CO afforded K4[{Al(xanthNON)}2(C4O4)(BEt3)2]
121 with the formally hexa-anionic [C4O4]6 ligand.71 To com-
plete the series of [C4O4]n ligands for n = 2, 4 and 6, the
reaction of (xanthNON)Al–I with the silver salt of the pre-formed
squarate dianion, Ag2[C4O4], was conducted, affording the
expected product, {Al(xanthNON)}2(C4O4) 122.
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3.5 Aluminium–element multiple bonds
Low valent aluminium species have previously been used to
access compounds containing Al–E multiple bonds.72 For
example, iminoalanes were synthesized from Al(BDIDipp) (V)73
or Al(tBuBDIDipp) (VI) with the N-heterocyclic carbene, 1,3-iPr2-
4,5-Me2-2-ylidene.74 Similarly, Al–E bonds (where E = O,75 S76
and Te77) have been characterised using neutral Al(I) species as
a starting reagent. The aluminyl compounds therefore offered
an alternative entry point into this area of chemistry and have
been exploited in the development of a range of Al–E multiple
bonded systems.
3.5.1 Al–NR multiple bonds. As a continuation of our
earlier work with the indyl anion [K{In(NON)}]2,26 we examined
the reaction of CDP 2 with mesityl azide as a potential route to
Al–NR multiple bonds.78 The reaction proceeded smoothly to
afford the molecular aluminium imide [K{Al(NON)(NMes)}]2 123.
Examination of the Al–Nimide bond using DFT calculations
indicated that this unit has multiple bond character but contains
a significant ionic contribution. The reactivity of the Al–NR
group was consistent with an unsaturated bond, demonstrated
by a [2+2] cycloaddition reaction with CO2 to afford the alumi-
nium carbamate, [K{Al(NON)(OC{O}NMes)}]2 124.
The analogous reactions between CDP 1 and organic
azides has been studied.57 Reaction with DippN3 afforded
[K{Al(xanthNON)(NDipp)}]2 125. Reactivity was observed with H2,
which adds across the Al–Nimide bond to afford [K{Al(xanthNON)-
(NHDipp)(H)}]2 126. Further demonstration of the high reac-
tivity of 125 was noted during the reaction with CO, forming
[K{Al(xanthNON)(OC{O}CQNDipp)}]2 127, which involved the
complete cleavage of the CO triple bond in CO.
3.5.2 Al–O multiple bonds. When exposed to 1 atm of CO2,
CDPs 1 and 2 afforded form the carbonate complexes,
[K{Al(xanthNON)(O2CQO)}]2 128,79 and [K{Al(NON)(O2CQO)}]4
129,80 respectively. The proposed mechanism parallels that
discussed for the bimetallic carbonates (Section 3.1.2), involving
intermediate aluminium oxide species that are generated by
extrusion of CO. Under more controlled conditions using N2O as
the oxidant, the target aluminium oxides (alumoxanes) were
isolated as the dimeric species [K{Al(xanthNON)(O)}]2 130 and
[K{Al(NON)(O)}]2 131. Reactions of 130 and 131 with additional
N2O afforded the corresponding cis-hyponitrites [K{Al(xanthNON)-
(O2N2)}]2 132 and [K(crypt-222)][Al(NON)(O2N2)] 133, whilst
exposure to CO2 formed carbonates 128 and 129. These results
support the proposal that an Al–Ooxide bond is initially generated in
the reactions with CO2, and the final products are consistent with a
[2+2] cycloaddition of a second molecule of CO2 to an Al–Ooxide
multiple bond.
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The highly reactive Al–Ooxide bond has also been used to pro-
mote C–C bond forming reactions (Scheme 13). The addition of
excess xylyl isonitrile (Ar‡NC, Ar‡ = 2,6-Me2C6H3) to a solution of
130 resulted in uptake of two equivalents and formation of the C–C
coupled product [K(THF)3][Al(xanthNON)(Ar‡NQC–C{O}QNAr‡)]
134.57 As part of our investigations, we reacted the alumoxane 131
with CO to form a unique ethene tetraolate ligand, [O2CQCO2]4,
in the product [K{Al(NON)(O2C)}]2 135.81 Using computational
techniques, we showed that the dimeric composition of the alumi-
nium oxide is maintained during this reaction, which proceeds via a
dioxocarbene (akin to Type-B structures) that reacts with additional
CO to form an intermediate aluminium ketene.
3.5.3 Al–S multiple bonds. Initial evidence for the formation
of the Al–S multiple bond from aluminyls was obtained when
CDP 2 was reacted with CS2, affording the trithiocarbonate
complex, [K{Al(NON)(S2CQS)}]4 136.81 As for carbonate com-
plexes 128 and 129, the implication of this result was the
formation of a transient ‘Al–S’ multiple bond that reacted with
additional CS2 in a [2+2] cycloaddition. Repeating the reaction
with CS2 at low temperature generated [K{Al(NON)(S2C)}]2 137
containing the ethene tetrathiolate anion, [S2CQCS2]4.
Although this bridging ligand is analogous to the ethene tetra-
olate anion in 135, the coordination to the two aluminium
0 0
centres is different. In 135, a m-(1kO1,1kO1 :2kO2,2kO2 ) mode
is adopted which generates two AlO2C heterocycles, whereas in
0 0
137 the ligand is m-(1kS1,1kS2 : 2kS1 ,2kS2 ) with two AlS2C2 rings.
Attempted oxidation of aluminyl 2 directly with elemental
sulfur failed to generate a terminal sulfide, instead forming the
1,2,3,4,5-tetrathiaaluminyl anion in K[Al(NON)(S4)] 138. This
prompted a ‘top down’ approach – namely the desulfurisation
reaction of 138 with PPh3, which successfully formed the target
sulfide, isolated as the tetrameric species [K{Al(NON)(S)}]4 139.
The [Al(NON)(S)] anion was also isolated as a separated ion
pair in [K(crypt-222)][Al(NON)(S)] 140.82
Given the bio-relevance of sulfur containing organic com-
pounds, we assessed the potential for 139 to be used as a
Scheme 13 Reaction of aluminium oxides ([K{Al(xanthNON)(O)}])2 130 and
[K{Al(NON)(O)}]2 131 with isonitrile Ar‡NC (128, Ar‡ = xylyl = 2,6-Me2C6H3)
and CO (129).
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reagent for the formation of new S–C bonds (Scheme 14).
Accordingly, the reaction with CO2 afforded the thiocarbonate
compound [{K(Et2O)2}{Al(NON)(SC{O}O)}]2 141, in a [2+2]
cycloaddition reaction analogous to the formation of 124.
Furthermore, we demonstrated that reaction with benzophe-
none incorporates a single equivalent in K[Al(NON)(SC{Ph2}O)]
142 containing the k2S,O-diphenylsulfidomethanolate ligand,
while two equivalents of benzaldhyde react to give the k2O,O 0 -
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thio-bis(phenylmethanolate), [K{Al(NON)({OC(H)Ph}2S)}]2 143.
3.5.4 Al–Se multiple bonds. Access to the aluminium
selenide containing a terminal Al–Se bond proved more
straight forward than the corresponding sulfide, with the direct
reaction of 2 with one equivalent of elemental selenide affording
[K(THF)][Al(NON)(Se)] 144, also structurally characterized as the
separated ion pair, [K(crypt-222)][Al(NON)(Se)] 145.83 When two
equivalent of selenium were used per aluminium, a diselenirane
compound was generated that was isolated as the [2.2.2]cryptand
complex, [K(crypt-222)][Al(NON)(k2-Se2)] 146. The terminal
selenide bond in 144 undergoes analogous C–E bond forming
reactions with carbon dioxide, benzophenone and benzaldehyde
as noted for the sulfide, forming [{K(THF)3}{Al(NON)(SeC{O}-
O)}]2 147, [K(THF)3][Al(NON)(SeC{Ph2}O)] 148 and [K{Al(NON)-
({OC(H)Ph}2Se)}]2 149, respectively (Scheme 14).
3.5.5 Al–Te multiple bonds. As for the preparation of the
selenide 144, the direct reaction of 2 with elemental tellurium
afforded the telluride, K[Al(NON)(Te)(THF)] 150 (Scheme 15).84
In contrast to 144 however, in which the THF is bound to the
potassium, the X-ray structure of 150 shows that it coordinates
to aluminium to generate a four-coordinate anion that contains
Scheme 14 Reaction of aluminium sulfide and selenide [K{Al(NON)(S)}]4
139 and [K(THF)][Al(NON)(Se)] 144 with CO2, Ph2CO and PhHCO.
516 | Chem. Commun., 2023, 59, 503–519
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Scheme 15 Synthesis of aluminium telluride 150 and its reaction with
CO2 to afford the double insertion product 151.
a structurally authenticated terminal Al–Te bond. When exposed
to an atmosphere of CO2, compound 150 reacted to form
[K(Et2O)2(THF/Et2O)][Al(NON)({OC(O)}2Te)] 151. Rather than
the [2+2] cycloaddition of a single equivalent of CO2 to the Al–E
multiple bonds noted during the formation of 124 (E = NMes),
129 (E = O), 141 (E = S) and 147 (E = Se), the reaction proceeds
directly to give the double insertion product containing the
tellurodicarbonate ligand. An intermediate complex observed
spectroscopically using 13CO2 was presumed to be the initially
formed tellurocarbonate complex containing the [OC{O}Te]2
ligand, which reacts rapidly with a second equivalent of CO2 to
generate 151.
3.5.6 Al–C multiple bonds. The reaction of the lithium
aluminyl CDP 19 with the bulky diaryldiazomethane derivative
5,5 0 -(diazomethylene)bis(1,3-di-tert-butylphenyl) has been used
to access a novel compound containing an Al–C multiple bond
(Scheme 16).40 The reaction proceeds with the initial formation
0
of the [1+2] cycloaddition product, [Li(Et2O)2][Al(bo2e-CAr N)(N2 =
CAr 0 2)] 152. This complex thermally decomposes at 40 1C with
0
loss of N2 to afford [Li(Et2O)][Al(bo2e-CAr N)(CAr 0 2)] 153, which
was crystallised as the 12-c-4 complex, [Li(12-c-4)2][Al(bo2e-
0 0
CAr N)(CAr 2)] 154. The crystal structure of 154 shows a short
Scheme 16 Formation of an Al–C multiple bond (Ar 0 = 3,5-tBu2C6H3).
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Al–CAr 0 2 bond and DFT calculations identify key MOs containing
a p-component in the Al–C bond.
Latest developments
There are two notable publications in this area that have been
published since this original manuscript was submitted. We
have continued to explore the oxidative addition of E–H bonds
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to the [AM{Al(NON)}]2 (Section 3.2.2), confirming that the
full series of alkali metal aluminyls form the (silyl)(hydrido)
product, [AM(L)n][Al(NON)(H)(SiH2Ph)] (AM(L)n = Li(Et2O) 155,
Na(Et2O) 156, K(Et2O) 79, Rb(Et2O) 157 and Cs(THF)2 158).85
Structural analysis of the isomorphous Na, K and Rb crystal
structures confirmed a tendency to form intramolecular
AM  (arene) interactions for the heavier alkali metals, noted
from a higher hapticity to the SiPh and NDipp groups.
A new addition to the family of N,N 0 -(diamido) aluminyl
anions has been reported and the chemistry of its bimetallic
complex with scandium investigated.86 The relatively simple
1,3-propanediamido ligand [DippN(CH2)3NDipp]2 ([NC3N]2)
supports the potassium aluminyl that has been isolated as the
CDP 159 and the [K(crypt-222)]+ SIP, 160 (Scheme 17). Metathesis
reactions with Sc(NR2)2Cl(THF)n (R = SiMe3, n = 1; R = iPr, n = 2)
affords the bimetallic Al–Sc complexes, (NC3N)Al–Sc(NR2)2(THF)
161 (R = SiMe3) and 162 (R = iPr). Compound 161 undergoes a
thermal (room temperature) activation of a methyl group from
SiMe3 to afford a methylene-/hydrido-bridged species 163. When
the NiPr2 derivative 162 was reacted with Ph2CHBr in benzene, a
dialuminated 1,4-cyclohexadiene product 164 was isolated that
derives from the dearomatisation of C6H6. The side product
of the reaction was identified as 1,1,2,2-tetraphenylethane and
Scheme 17 Reactions of a new potassium N,N 0 -(diamido)aluminyl
compound.
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mechanistic investigation using DFT concluded that an ionic
pathway involving the Al–Sc bimetallic complex was operating.
4. Conclusions
In the relatively brief time since their discovery, the chemistry
of aluminyls has expanded rapidly to encompass a diverse
range of reactions. Whilst aspects of aluminyl reactivity mimic
that documented with known Al(I) compounds, their enhanced
activity (compared with their neutral counterparts) and ability
to react with new substrates through the activation of otherwise
stable chemical bonds is becoming increasingly evident.
Furthermore, it is apparent that the chemistry of the aluminyl
anions cannot be considered in isolation. There is mounting
evidence that the group 1 metal cations play a fundamental role
in directing the reactivity of these systems through synergistic
interactions with many substrates. This is being developed by
expanding the family of potassium aluminyls to encompass all
stable members of group 1 metals, and through an enhanced
control of the cation and anion interactions that are present.
With these new tools in hand, the current goals of researchers
in this field involve the development of synthetically useful
transformations that will allow aluminyls to take a position at
the forefront of p-block metal chemistry.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This works was supported by Government funding from the
Marsden Fund Council, managed by the Royal Society Te
Apārangi (Grant Number: MFP-VUW2020).
References
1 W. Klemm, E. Voss and K. Geiersberger, Z. Anorg. Allg. Chem., 1948,
256, 15–24.
2 (a) M. Tacke and H. Schnoeckel, Inorg. Chem., 1989, 28, 2895–2896;
(b) M. Mocker, C. Robl and H. Schnöckel, Angew. Chem., Int. Ed.
Engl., 1994, 33, 1754–1755; (c) A. Ecker and H. Schnöckel, Z. Anorg.
Allg. Chem., 1996, 622, 149–152.
3 C. Dohmeier, C. Robl, M. Tacke and H. Schnöckel, Angew. Chem.,
Int. Ed. Engl., 1991, 30, 564–565.
4 S. Schulz, H. W. Roesky, H. J. Koch, G. M. Sheldrick, D. Stalke and
A. Kuhn, Angew. Chem., Int. Ed. Engl., 1993, 32, 1729–1731.
5 (a) S. González-Gallardo, T. Bollermann, R. A. Fischer and
R. Murugavel, Chem. Rev., 2012, 112, 3136–3170; (b) C. Gemel,
T. Steinke, M. Cokoja, A. Kempter and R. A. Fischer, Eur. J. Inorg.
Chem., 2004, 4161–4176; (c) G. Linti and H. Schnöckel, Coord. Chem.
Rev., 2000, 206–207, 285–319; (d) R. A. Fischer and J. Weiß, Angew.
Chem., Int. Ed., 1999, 38, 2830–2850.
6 A. Haaland, K.-G. Martinsen, S. A. Shlykov, H. V. Volden,
C. Dohmeier and H. Schnoeckel, Organometallics, 1995, 14,
3116–3119.
7 C. Dohmeier, E. Baum, A. Ecker, R. Köppe and H. Schnöckel,
Organometallics, 1996, 15, 4702–4706.
8 H. Sitzmann, M. F. Lappert, C. Dohmeier, C. Üffing and
H. Schnöckel, J. Organomet. Chem., 1998, 561, 203–208.
Chem. Commun., 2023, 59, 503–519 | 517

Feature Article
9 A. Hofmann, T. Tröster, T. Kupfer and H. Braunschweig, Chem. Sci.,
2019, 10, 3421–3428.
10 C. Cui, H. W. Roesky, H.-G. Schmidt, M. Noltemeyer, H. Hao and
F. Cimpoesu, Angew. Chem., Int. Ed., 2000, 39, 4274–4276.
11 X. Li, X. Cheng, H. Song and C. Cui, Organometallics, 2007, 26,
1039–1043.
12 S. Grams, J. Mai, J. Langer and S. Harder, Organometallics, 2022, 41,
2862–2867.
13 (a) K. Hobson, C. J. Carmalt and C. Bakewell, Chem. Sci., 2020, 11,
6942–6956; (b) M. Zhong, S. Sinhababu and H. W. Roesky, Dalton
Trans., 2020, 49, 1351–1364; (c) Y. Liu, J. Li, X. Ma, Z. Yang and
Published on 08 December 2022. Downloaded by University of Liverpool on 12/30/2023 6:45:00 PM.
H. W. Roesky, Coord. Chem. Rev., 2018, 374, 387–415; (d) Y.-C. Tsai,
Coord. Chem. Rev., 2012, 256, 722–758; (e) M. Asay, C. Jones and
M. Driess, Chem. Rev., 2011, 111, 354–396; ( f ) S. Nagendran and
H. W. Roesky, Organometallics, 2008, 27, 457–492; ( g) H. W. Roesky
and S. S. Kumar, Chem. Commun., 2005, 4027–4038;
(h) M. N. Sudheendra Rao, H. W. Roesky and G. Anantharaman,
J. Organomet. Chem., 2002, 646, 4–14; (i) C. Dohmeier, D. Loos and
H. Schnöckel, Angew. Chem., Int. Ed. Engl., 1996, 35, 129–149.
14 J. D. Queen, A. Lehmann, J. C. Fettinger, H. M. Tuononen and
P. P. Power, J. Am. Chem. Soc., 2020, 142, 20554–20559.
15 (a) X. Zhang and L. L. Liu, Angew. Chem., Int. Ed., 2021, 60,
27062–27069; (b) A. Hinz and M. P. Müller, Chem. Commun., 2021,
57, 12532–12535.
16 X. Zhang, Y. Mei and L. L. Liu, Chem. – Eur. J., 2022, e202202102.
17 As noted previously (ref. 27), the recommended nomenclature for
these anions is boranyl, alumanyl, gallanyl and indinanyl (based on
uncharged EH2. See R. M. Hartshorn and A. T. Hutton, in Nomen-
clature of Inorganic Chemistry, IUPAC Recommendations 2005, IUPAC
Red Book, ed. N. G. Connelly and T. Damhus, RSC Publishing,
London, 2005, However, for consistency with the existing literature
and in agreement with most researchers in the area, we have
adopted the terms boryl, aluminyl, gallyl and indyl to describe
generic EX2 systems and their corresponding anions.
18 E. S. Schmidt, A. Jockisch and H. Schmidbaur, J. Am. Chem. Soc.,
1999, 121, 9758–9759.
19 R. J. Baker, R. D. Farley, C. Jones, M. Kloth and D. M. Murphy,
J. Chem. Soc., Dalton Trans., 2002, 3844–3850.
20 Y. Segawa, M. Yamashita and K. Nozaki, Science, 2006, 314, 113–115.
21 Y. Segawa, Y. Suzuki, M. Yamashita and K. Nozaki, J. Am. Chem. Soc.,
2008, 130, 16069–16079.
22 A. V. Protchenko, P. Vasko, M. Á. Fuentes, J. Hicks, D. Vidovic and
S. Aldridge, Angew. Chem., Int. Ed., 2021, 60, 2064–2068.
23 (a) N. Metzler-Nolte, New J. Chem., 1998, 22, 793–795;
(b) A. Sundermann, M. Reiher and W. W. Schoeller, Eur. J. Inorg.
Chem., 1998, 305–310; (c) H. M. Tuononen, R. Roesler, J. L. Dutton
and P. J. Ragogna, Inorg. Chem., 2007, 46, 10693–10706.
24 R. J. Schwamm, M. D. Anker, M. Lein, M. P. Coles and C. M. Fitchett,
Angew. Chem., Int. Ed., 2018, 57, 5885–5887.
25 R. J. Schwamm, J. R. Harmer, M. Lein, C. M. Fitchett, S. Granville
and M. P. Coles, Angew. Chem., Int. Ed., 2015, 54, 10630–10633.
26 M. D. Anker, M. Lein and M. P. Coles, Chem. Sci., 2019, 10,
1212–1218.
27 J. Hicks, P. Vasko, J. M. Goicoechea and S. Aldridge, Angew. Chem.,
Int. Ed., 2021, 60, 1702–1713.
28 J. Hicks, P. Vasko, J. M. Goicoechea and S. Aldridge, Nature, 2018,
557, 92–95.
29 R. J. Schwamm, M. D. Anker, M. Lein and M. P. Coles, Angew. Chem.,
Int. Ed., 2019, 58, 1489–1493.
30 R. J. Schwamm, M. P. Coles, M. S. Hill, M. F. Mahon, C. L. McMullin,
N. A. Rajabi and A. S. S. Wilson, Angew. Chem., Int. Ed., 2020, 59, 3928–3932.
31 R. J. Schwamm, M. S. Hill, H.-Y. Liu, M. F. Mahon, C. L. McMullin
and N. A. Rajabi, Chem. – Eur. J., 2021, 27, 14971–14980.
32 S. Grams, J. Eyselein, J. Langer, C. Färber and S. Harder, Angew.
Chem., Int. Ed., 2020, 59, 15982–15986.
33 D. Bourissou, O. Guerret, F. P. Gabbaı̈ and G. Bertrand, Chem. Rev.,
2000, 100, 39–92.
34 K. Koshino and R. Kinjo, J. Am. Chem. Soc., 2020, 142, 9057–9062.
35 S. Kurumada, S. Takamori and M. Yamashita, Nat. Chem., 2020, 12, 36–39.
36 T. X. Gentner and R. E. Mulvey, Angew. Chem., Int. Ed., 2021, 60,
9247–9262.
37 (a) J. M. Gil-Negrete and E. Hevia, Chem. Sci., 2021, 12, 1982–1992;
(b) S. D. Robertson, M. Uzelac and R. E. Mulvey, Chem. Rev., 2019,
119, 8332–8405.
518 | Chem. Commun., 2023, 59, 503–519
View Article Online
ChemComm
38 M. J. Evans, M. D. Anker, C. L. McMullin, S. E. Neale and M. P. Coles,
Angew. Chem., Int. Ed., 2021, 60, 22289–22292.
39 M. M. D. Roy, J. Hicks, P. Vasko, A. Heilmann, A.-M. Baston,
J. M. Goicoechea and S. Aldridge, Angew. Chem., Int. Ed., 2021, 60,
22301–22306.
40 C. Yan and R. Kinjo, Angew. Chem., Int. Ed., 2022, 61, e202211800.
41 S. Grams, J. Mai, J. Langer and S. Harder, Dalton Trans., 2022, 51,
12476–12483.
42 T. X. Gentner, M. J. Evans, A. R. Kennedy, S. E. Neale,
C. L. McMullin, M. P. Coles and R. E. Mulvey, Chem. Commun.,
2022, 58, 1390–1393.
43 M. J. Evans, M. D. Anker, M. G. Gardiner, C. L. McMullin and
M. P. Coles, Inorg. Chem., 2021, 60, 18423–18431.
44 J. Hicks, P. Vasko, J. M. Goicoechea and S. Aldridge, J. Am. Chem.
Soc., 2019, 141, 11000–11003.
45 K. Sugita and M. Yamashita, Chem. – Eur. J., 2020, 26, 4520–4523.
46 The aluminium-titanium complex ({CSi}2)Al(m-OiPr)2Ti(OiPr)2 has
also been isolated from an aluminyl starting reagent. In this
instance the metals do not form a direct bond but are linked by
bridging isopropoxide ligands:K. Sugita and M. Yamashita, Organo-
metallics, 2020, 39, 2125–2129.
47 S. P. Green, C. Jones and A. Stasch, Science, 2007, 318, 1754–1757.
48 M. J. Evans, G. H. Iliffe, S. E. Neale, C. L. McMullin, J. R. Fulton,
M. D. Anker and M. P. Coles, Chem. Commun., 2022, 58,
10091–10094.
49 C. McManus, J. Hicks, X. Cui, L. Zhao, G. Frenking, J. M. Goicoechea
and S. Aldridge, Chem. Sci., 2021, 12, 13458–13468.
50 J. Hicks, A. Mansikkamäki, P. Vasko, J. M. Goicoechea and
S. Aldridge, Nat. Chem., 2019, 11, 237–241.
51 H.-Y. Liu, S. E. Neale, M. S. Hill, M. F. Mahon and C. L. McMullin,
Dalton Trans., 2022, 51, 3913–3924.
52 H.-Y. Liu, R. J. Schwamm, M. S. Hill, M. F. Mahon, C. L. McMullin
and N. A. Rajabi, Angew. Chem., Int. Ed., 2021, 60, 14390–14393.
53 (a) D. Sorbelli, L. Belpassi and P. Belanzoni, J. Am. Chem. Soc., 2021,
143, 14433–14437; (b) D. Sorbelli, L. Belpassi and P. Belanzoni, Inorg.
Chem., 2022, 61, 1704–1716; (c) D. Sorbelli, L. Belpassi and
P. Belanzoni, Chem. Sci., 2022, 13, 4623–4634; (d) X. Guo, T. Yang,
Y. Zhang, F. K. Sheong and Z. Lin, Inorg. Chem., 2022, 61, 10255–10262.
54 C. McManus, A. E. Crumpton and S. Aldridge, Chem. Commun.,
2022, 58, 8274–8277.
55 T. Chu and G. I. Nikonov, Chem. Rev., 2018, 118, 3608–3680.
56 N. Villegas-Escobar, A. Toro-Labbé and H. F. Schaefer Iii, Chem. –
Eur. J., 2021, 27, 17369–17378.
57 A. Heilmann, J. Hicks, P. Vasko, J. M. Goicoechea and S. Aldridge,
Angew. Chem., Int. Ed., 2020, 59, 4897–4901.
58 M. J. Evans, M. D. Anker and M. P. Coles, Inorg. Chem., 2021, 60,
4772–4778.
59 T. Chu, I. Korobkov and G. I. Nikonov, J. Am. Chem. Soc., 2014, 136,
9195–9202.
60 J. Hicks, P. Vasko, A. Heilmann, J. M. Goicoechea and S. Aldridge,
Angew. Chem., Int. Ed., 2020, 59, 20376–20380.
61 S. Kurumada, K. Sugita, R. Nakano and M. Yamashita, Angew.
Chem., Int. Ed., 2020, 59, 20381–20384.
62 J. J. Cabrera-Trujillo and I. Fernández, Chem. – Eur. J., 2020, 26,
11806–11813.
63 K. Sugita, R. Nakano and M. Yamashita, Chem. – Eur. J., 2020, 26,
2174–2177.
64 M. J. Evans, S. E. Neale, M. D. Anker, C. L. McMullin and M. P. Coles,
Angew. Chem., Int. Ed., 2022, 61, e202117396.
65 M. M. D. Roy, A. Heilmann, M. A. Ellwanger and S. Aldridge, Angew.
Chem., Int. Ed., 2021, 60, 26550–26554.
66 M. S. Hill, M. F. Mahon, C. L. McMullin, S. E. Neale, K. G. Pearce and
R. J. Schwamm, Z. Anorg. Allg. Chem., 2022, 648, e202200224.
67 K. Koshino and R. Kinjo, Organometallics, 2020, 39, 4183–4186.
68 H.-Y. Liu, M. S. Hill and M. F. Mahon, Chem. Commun., 2022, 58,
6938–6941.
69 C. Cui, S. Köpke, R. Herbst-Irmer, H. W. Roesky, M. Noltemeyer,
H.-G. Schmidt and B. Wrackmeyer, J. Am. Chem. Soc., 2001, 123,
9091–9098.
70 M. J. Evans, M. G. Gardiner, M. D. Anker and M. P. Coles, Chem.
Commun., 2022, 58, 5833–5836.
71 A. Heilmann, M. M. D. Roy, A. E. Crumpton, L. P. Griffin, J. Hicks,
J. M. Goicoechea and S. Aldridge, J. Am. Chem. Soc., 2022, 144,
12942–12953.
This journal is © The Royal Society of Chemistry 2023

ChemComm
72 (a) D. Franz and S. Inoue, Dalton Trans., 2016, 45, 9385–9397;
(b) P. Bag, C. Weetman and S. Inoue, Angew. Chem., Int. Ed., 2018,
57, 14394–14413; (c) C. Weetman, Chem. – Eur. J., 2021, 27,
1941–1954; (d) F. Dankert and C. Hering-Junghans, Chem. Commun.,
2022, 58, 1242–1262.
73 N. J. Hardman, C. Cui, H. W. Roesky, W. H. Fink and P. P. Power,
Angew. Chem., Int. Ed., 2001, 40, 2172–2174.
74 J. Li, X. Li, W. Huang, H. Hu, J. Zhang and C. Cui, Chem. – Eur. J.,
2012, 18, 15263–15266.
75 D. Neculai, H. W. Roesky, A. M. Neculai, J. Magull, B. Walfort and
D. Stalke, Angew. Chem., Int. Ed., 2002, 41, 4294–4296.
Published on 08 December 2022. Downloaded by University of Liverpool on 12/30/2023 6:45:00 PM.
76 T. Chu, S. F. Vyboishchikov, B. Gabidullin and G. I. Nikonov, Angew.
Chem., Int. Ed., 2016, 55, 13306–13311.
77 D. Franz, T. Szilvási, E. Irran and S. Inoue, Nat. Commun., 2015,
6, 10037.
78 M. D. Anker, R. J. Schwamm and M. P. Coles, Chem. Commun., 2020,
56, 2288–2291.
This journal is © The Royal Society of Chemistry 2023
View Article Online
Feature Article
79 J. Hicks, A. Heilmann, P. Vasko, J. M. Goicoechea and S. Aldridge,
Angew. Chem., Int. Ed., 2019, 58, 17265–17268.
80 M. D. Anker and M. P. Coles, Angew. Chem., Int. Ed., 2019, 58,
18261–18265.
81 M. D. Anker, C. L. McMullin, N. A. Rajabi and M. P. Coles, Angew.
Chem., Int. Ed., 2020, 59, 12806–12810.
82 M. J. Evans, M. D. Anker, C. L. McMullin, S. E. Neale, N. A. Rajabi
and M. P. Coles, Chem. Sci., 2022, 13, 4635–4646.
83 M. D. Anker and M. P. Coles, Angew. Chem., Int. Ed., 2019, 58,
13452–13455.
84 M. J. Evans, M. D. Anker, C. L. McMullin, N. A. Rajabi and
M. P. Coles, Chem. Commun., 2021, 57, 2673–2676.
85 G. M. Ballmann, M. J. Evans, T. X. Gentner, A. R. Kennedy,
J. R. Fulton, M. P. Coles and R. E. Mulvey, Inorg. Chem., 2022, 61,
19838–19846.
86 G. Feng, K. L. Chan, Z. Lin and M. Yamashita, J. Am. Chem. Soc.,
2022, 144, 22662–22668.
Chem. Commun., 2023, 59, 503–519 | 519