Size Matters: Synthesis of Group 13 Metal-Substituted Dipnictanes by E-C Bond Homolysis

Article abstract of DOI:10.1002/ejic.202000747

Pnictanes Cp*(Ph)ECl (E = As 1, Sb 2; Cp* = C₅Me₅) react with group 13 diyls LM (M = Al, Ga, In; L = HC[C(Me)N(Dip)]₂, Dip = 2,6-iPr₂C₆H₃) with oxidative addition of the E-Cl bond to a unique series of metalylpnictanes [L(Cl)M](Ph)ECp* (E = As, M = Al 3, Ga 4, In 5; E = Sb, M = Al 6, Ga 7, In 8). Thermal treatment of 4 and 6–8 results in homolytic E-C bond scission with Cp* radical liberation, yielding the corresponding dipnictanes {[L(Cl)M](Ph)E}₂ (E = As, M = Ga 9; E = Sb, M = Al 10, Ga 11, In 12). Compounds 1–12 were characterized by NMR (¹H, ¹³C) and IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction (3–12).

Full text of DOI:10.1002/ejic.202000747

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Element–Carbon Bond Homolysis | Very Important Paper |
Size Matters: Synthesis of Group 13 Metal-Substituted
Dipnictanes by E-C Bond Homolysis
Christoph Helling,[a] Christoph Wölper,[a] and Stephan Schulz*[a]
Dedicated to Prof. Hans J. Breunig on the occasion of his 75th birthday.
Abstract: Pnictanes Cp*(Ph)ECl (E = As 1, Sb 2; Cp* = C5Me5) E-C bond scission with Cp* radical liberation, yielding the corre-
react with group 13 diyls LM (M
HC[C(Me)N(Dip)]2, Dip = 2,6-iPr2C6H3) with oxidative addition of M = Al 10, Ga 11, In 12). Compounds 1–12 were characterized
the E-Cl bond to
unique series of metalylpnictanes by NMR (1H, 13C) and IR spectroscopy, elemental analysis, and
=
Al, Ga, In;
L
=
sponding dipnictanes {[L(Cl)M](Ph)E}2 (E = As, M = Ga 9; E = Sb,
a
[L(Cl)M](Ph)ECp* (E = As, M = Al 3, Ga 4, In 5; E = Sb, M = Al 6, single-crystal X-ray diffraction (3–12).
Ga 7, In 8). Thermal treatment of 4 and 6–8 results in homolytic
Introduction
R2E· and loosely-bound dipnictanes [R2E]2 were observed in so-
lution, whereas in the solid-state only the dimeric species were
found (Figure 1b).[5,6] Consequently, the use of sterically even
more encumbering ligands R totally prevented dimerization
and enabled the isolation of monomeric pnictanyl radicals R2E·
in the solid-state even for the heaviest group 15 elements (Fig-
ure 1 c),[8] as was successfully demonstrated by the isolation of
[L(X)Ga]2E· (E = As, Sb, Bi; X = Cl, Br, I)[9] (L = HC[C(Me)N(Dip)]2,
Dip = 2,6-iPr2C6H3) and [O{Si(Me2)N(Ar)}2]Bi· (Ar = Dip, 2,6-
(CHPh2)2-4-tBuC6H2).[10] The detection of discrete monomeric
radicals {H2CC(SiMe3)2}2E· (E = P, As)[11] in the solid-state further
emphasizes the delicate influence of the ligand's characteristics,
as only equilibria were observed for [{(Me3Si)2CH}2E]2 (E = P,
As),[5] containing a strongly related but less rigid ligand, and
[{H2CC(SiMe3)2}2E]2 (E = Sb, Bi),[6] comprising the heavier group
In 1760, Louis Claude Cadet de Gassicourt discovered tetra-
methyldiarsane [Me2As]2, historically known as cacodyl, which
not only represents the first organometallic compound but also
the first molecule containing heavier group 15 elements in the
unfavorable divalent oxidation state.[1] About 170 years later,
Paneth reported on the heavier group 15 homologues,
[Me2Sb]2 and [Me2Bi]2, which formed in reactions of free methyl
radicals with antimony and bismuth mirrors, respectively.[2]
However, it was not until the 1980s that the interest in this
research field was reignited by systematic studies on the syn-
thesis, structure, and reactivity of compounds containing
covalent E–E bonds (E = Sb, Bi),[3] demonstrating the inherent
weakness of E–E bonds in tetraorganyldipnictanes [R2E]2 (R =
Me, Et, Ph) toward homolytic E–E bond cleavage.[4]
The decisive influence of the steric bulk of the substituents
R on the E–E bond formation/homolysis behavior of R2E radicals
was recognized already in 1976 for P and As,[5] and more re-
cently for Sb and Bi.[6] Small substituents such as Me, Et, and Ph
favor the formation of dipnictanes [R2E]2, which form dimeric
structures containing E–E bonds both in the solid and solution-
state (Figure 1a).[7] By employing sterically more demanding
alkyl ligands R such as bis-trimethylsilyl-methyl (Me3Si)2CH and
chelating [(Me3Si)2CCH2]2, reversible E–E bond dissociation/
association equilibria between monomeric pnictanyl radicals
15 homologues, which possess enlarged covalent radii (rcov
=
1.11 (P), 1.21 (As), 1.40 (Sb), 1.51 (Bi) Å).[12]
[a] C. Helling, Dr. C. Wölper, Prof. Dr. S. Schulz
Institute of Inorganic Chemistry and Center for Nanointegration Duisburg-
Essen (CENIDE), University of Duisburg-Essen,
Universitätsstraße 5-7, 45141 Essen, Germany
E-mail: stephan.schulz@uni-due.de
https://www.uni-due.de/ak_schulz/index_en.php
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejic.202000747.
© 2020 The Authors. Published by Wiley-VCH GmbH. · This is an open access
article under the terms of the Creative Commons Attribution License, which
permits use, distribution and reproduction in any medium, provided the
original work is properly cited.
Figure 1. Schematic representation of the influence of (a) small, (b) intermedi-
ate, and (c) large ligands on E–E bond formation behavior of R2E· radicals
(E = P, As, Sb, Bi).
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Our long-term interest in the reactivity of LM (M = Al,[13] Cp*SbPh2 in moderate yield (67 % based on pure 2), which
Ga,[14] In[15]) towards heavy group 15 element compounds of could possibly stem from partial ligand redistribution during
As, Sb, and Bi has led to the isolation of several compounds the reaction. Recrystallization proved unsuccessful due to the
with unusual bonding motifs, including dipnictenes,[16] tetra- similar solubilities of 2 and the impurities.
pnictabicyclo[1.1.0]butanes,[8,17] gallapnictenes,[8,18] and afore-
In contrast, the analogous reaction of PhBiCl2 with KCp*
mentioned pnictogen-centered radicals,[9] respectively, all of
yielded only BiPh3 and Cp*2 together with a metallic precipitate,
which containing electropositive and sterically demanding
[L(X)Ga] ligands (X = F, Cl, Br, I, OR, NR2). Very recently, we re-
ported on heteroleptic stibanyl radicals [L(Cl)Ga](R)Sb· (R =
whereas the expected compound Cp*(Ph)BiCl was not isolated.
These findings are most likely caused by the inherent weakness
of Bi–C bonds and reflects the high thermal instability of
Bi–Cp* compounds.[21] Compounds 1 and 2 are thermally stable
yellow and orange solids, respectively, and exhibit the expected
resonances in their 1H and 13C{1H} NMR spectra. The C5Me5 pro-
tons appear as single resonances in both cases and are shifted
to lower field for the heavier congener (δ(C5Me5) = 1.59 (1), 1.73
(2)), while two (1) and three (2) signals are observed for the
C6H5 protons.
Syntheses of Metalylpnictanes [L(Cl)M](Ph)ECp*. Pnic-
tanes 1 and 2 were subsequently reacted with one equivalent
of LM (M = Al, Ga, In) (Scheme 2). In oxidative addition reactions
with LM, the starting materials were readily consumed within
minutes at ambient temperature, whereas the reaction of LIn
and 1 required stirring overnight to achieve complete conver-
sion. In all cases the reactions gave rise to a single product
as shown by 1H NMR spectroscopic analyses of the reaction
mixtures.[22] After work-up, [L(Cl)M](Ph)ECp* (E = As, M = Al 3,
Ga 4, In 5; E = Sb, M = Al 6, Ga 7, In 8) were isolated as pale
yellow to orange crystalline solids in moderate yields. The for-
mation of 3–8 is essentially quantitative, however, purification
by crystallization or washing results in lower yields. The isola-
tion of compounds 3–8 is remarkable, since reactions of LGa
with Cp*(2,6-Mes2C6H3)SbCl and Cp*(Dip)SbCl containing steri-
cally more demanding aryl substituents resulted in immediate
elimination of the Cp* moiety.[19,20] Moreover, analogous reac-
tions with LAl and LIn yielded intractable mixtures of products.
Compounds 3–8 display a unique series of rare, fully unsym-
metrically substituted group 13 metalylpnictanes.
B[N(Dip)CH]2, 2,6-Mes2C6H3 I, N(Dip)SiMe3; Mes
= 2,4,6-
Me3C6H2), which were synthesized by insertion reactions of LGa
into the Sb–Cl bonds of Cp*(R)SbCl (Cp* = C5Me5). The reactions
proceeded with concomitant Cp* radical liberation, and the dis-
tinct influence of the boryl, aryl, and amide ligands on the elec-
tronic structure of the resulting radicals was demonstrated.[19]
Substitution of R in Cp*(R)SbCl by sterically less demanding
ligands R′ gave rise to the formation of Sb hydrides
[L(Cl)Ga](R′)SbH (R′ = Dip II, N(SiMe3)2, OB[N(Dip)CH]2) upon re-
action with LGa, which was accompanied by elimination of
1,2,3,4-tetramethylfulvene.[20] The astonishing difference in
these reactions is clearly induced by the ligands R/R′, hence we
became interested in further reducing the steric demand of the
aryl ligands in Cp*(2,6-Mes2C6H3)SbCl and Cp*(Dip)SbCl and
probing the reactivity towards LM as well as in extending the
studies to the group 15 homologues, As and Bi. We herein re-
port on the synthesis and characterization of [L(Cl)M](Ph)ECp*
(M = Al, Ga, In; E = As, Sb) and their transformation into group
13 metal-substituted dipnictanes {[L(Cl)M](Ph)E}2 by thermally-
induced E–C bond homolysis.
Results and Discussion
Syntheses of Pnictanes Cp*(Ph)ECl. We employed buried
volume (Vbur) calculations in our previous studies to evaluate
the “size” of ligands and to study their role on the reaction
mechanism. Employing the sterically demanding 2,6-Mes2C6H3
ligand (Vbur = 36.8 %) resulted in Cp* radical liberation with
generation of I,[19] while introduction of the Dip ligand (Vbur
=
30.8 %) resulted in 1,2,3,4-tetramethylfulvene elimination with
formation of II,[20] respectively. To study the influence of a less
bulky aryl ligand at the group 15 element on the reaction
progress, a Ph group (Vbur = 20.7 % (Sb), Figure S1) was ex-
pected to be suitable.
Cp*(Ph)AsCl (1) and Cp*(Ph)SbCl (2) were synthesized analo-
gously to Cp*(Dip)SbCl[19] by reactions of PhECl2 with KCp*
(Scheme 1). Arsane 1 was obtained in a high purity and high
yield (81 %), whereas stibane 2 was only isolated in approxi-
mately 85 % purity (1H NMR) as a mixture with Cp*SbCl2 and
Scheme 2. Synthesis of compounds 3–8.
Compounds 3–8 are sensitive towards air and moisture but
can be stored in isolated crystalline form at ambient tempera-
ture under inert atmosphere for weeks without decomposition.
In hydrocarbon solution, arsanes 3–5 show no signs of decom-
position, whereas stibanes 6–8 slowly decompose at ambient
temperature when stored for extended periods of time (vide
1
infra). The H NMR spectrum of 3 at ambient temperature (Fig-
ure S8) only exhibits very broad signals, presumably due to par-
tially restricted dynamic processes in solution. At elevated tem-
1
peratures (+80 °C), the H NMR spectrum of 3 (Figure S9) sug-
Scheme 1. Synthesis of Cp*(Ph)AsCl (1) and Cp*(Ph)SbCl (2).
gests free rotation of the As(Ph)Cp* moiety about the Al–As
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bond as only four doublets corresponding to the CHMe2 are isomorphous and crystallize in the monoclinic space groups
present, while the C5Me5 resonances are strongly broadened P21/c and P21/n with four molecules in the unit cell, whereas 5
and thus not observed. At –20 °C, the dynamic processes are crystallizes in the orthorhombic space group Pna21 with four
fully inhibited, affording a spectrum containing sharp and well- molecules in the unit cell (Table S1).
resolved signals (Figure S10), which is in accordance to those
of compounds 4–8 at ambient temperature. The H NMR spec-
The molecular structures of metalylpnictanes 3–8 each fea-
ture group 15 centers adopting a trigonal-pyramidal coordina-
tion sphere and distorted tetrahedral coordinated group 13
centers. Selected bond lengths and angles are summarized in
Table 1. The M–E bond lengths successively increase in the or-
der of Ga–As < Al–As < In–As < Ga–Sb < Al–Sb < In–Sb, in
good agreement with the sum of the calculated covalent radii
(Σrcov(Ga–As) = 2.45 Å, Σrcov(Al–As) = 2.47 Å, Σrcov(In–As) =
2.63 Å, Σrcov(Ga–Sb) = 2.64 Å, Σrcov(Al–Sb) = 2.66 Å, Σrcov(In–
Sb) = 2.82 Å).[12] Moreover, the M–E bond lengths are in accord-
ance with previously reported bond lengths in [L(X)M]-substi-
tuted pnictanes, dipnictenes and pnictanyl radicals (Al–As
2.4501(7) Å, 2.4554(7) Å;[16a] Ga–As 2.3957(5)-2.5197(3) Å;[16a,18c]
Al–Sb 2.6586(7) Å, 2.7169(7) Å;[24] Ga–Sb 2.5478(6)–2.8458(13)
Å;[19,25] In–Sb 2.7250(4)-2.8340(2) Å[9c]). The As1–C40(Ph) bond
lengths in 3–5 are comparable to those of Al and Ga-substi-
1
tra of 3–8 each support the asymmetric substitution pattern at
the pnictogen atoms, resulting in eight doublets, four septets,
and two singlets corresponding to the CHMe2, CHMe2, and
NCMe protons of the ꢀ-diketiminate ligand L, respectively,
which is in accordance to Sb hydrides [L(Cl)Ga](R′)SbH.[20] The
singlet γ-CH resonances of ligand L appear at 5.00 (3), 4.94 (4),
4.86 (5), 5.00 (6), 4.94 (7), and 4.85 (8) ppm, thus showing a
dependence on the coordinated metal M, whereas no influence
of the pnictogen atom E was observed. The C6H5 substituents
exhibit three distinct resonances corresponding to the ortho,
meta, and para hydrogen atoms in the range from 6.60 to
7.02 ppm, indicating free rotation around the E–C(Ph) bond.
Interestingly, the C5Me5 protons of the Cp* ligands show five
1
distinct resonances in the H NMR spectra of arsanes 3–5 con-
sistent with a fixed η1(σ) coordination, whereas only a single
resonance was observed for stibanes 6–8, indicating facile [1,5]
sigmatropic rearrangements of the η1-bound Cp* moieties,[23]
as was previously observed in related Cp*-substituted stib-
anes.[9b,9c] This behavior is most likely caused by an increased
inter-ligand steric congestion, restricting [1,5] sigmatropic rear-
rangements in case of 3–5 (vide infra). The obviously higher
activation barrier for such processes in arsanes 3–5 furthermore
points to slightly stronger As–Cp* bonds in 3–5 compared to
the Sb–Cp* bonds in 6–8,[9a,18c] and the observation of five dis-
tinct C5Me5 resonances in 3–5 reflects the asymmetric nature
of the As coordination sphere. The 13C{1H} NMR spectra of pnic-
tanes 3–8 are consistent with their molecular structures and in
line with the conclusions drawn from the 1H NMR spectra.
tuted arsanes Tmp2AlAsPh2 (1.953 Å, 1.966 Å; Tmp
N[C(Me)2CH2]CH2),[26] (Mes*AlAsPh)3 (1.957(8) Å, 1.971(7) Å,
1.959(7) Å, Mes*
2,4,6-tBu3C6H2),[27] and (Tip2Ga)2AsPh
=
=
(1.950(7) Å, Tip = 2,4,6-iPr2C6H2),[28] while the Sb1–C40(Ph)
bond lengths in 6–8 compare well to those of I (2.1716(16)
Å),[19] II (2.1804(18) Å, 2.1748(18) Å),[20] and [L(Cl)Ga]Sb(Cl)Dip
(2.1891(11) Å, 2.1725(13) Å).[9a] In the whole series, the Cp* li-
gands adopt a η1(σ) coordination mode as already indicated by
NMR spectroscopic studies of 3–5 and as observed for
LGaAsCp*[18c] and [L(X)M]Sb(X)Cp* (M = Ga, In; X = Cl, Br, I).[9b,9c]
The E1–C30(Cp*) bond lengths agree well with those of
LGaAsCp* (2.0477(17) Å, 2.0567(15) Å),[18c] [C5(4-tBuC6H4)5]AsCl2
(2.0590(18) Å),[29] and [L(X)M]Sb(X)Cp* (2.2325(12)-2.2441(16)
Å),[9b,9c] respectively. Within the arsanes 3–5 and stibanes 6–8,
Single-crystals of 3–8 suitable for X-ray diffraction analysis respectively, the C30–E1–C40 angles slightly widen, whereas
were obtained from saturated solutions in n-hexane (3, 4, 5, 8) the C30–E1–M1 and C40–E1–M1 angles become considerably
or benzene (6, 7) upon storage at ambient temperature over- more acute, leading to an overall decrease of the sum of bond
night (Figure 2, Figures S39–S42). Compounds 3, 4, and 6–8 are angles at E1, Σꢀ(E1), from 3 to 8. This demonstrates the general
Figure 2. Molecular structures of 3 and 8 in the solid-state. Hydrogen atoms were omitted for clarity. Displacement ellipsoids are drawn at 50 % probability
level.
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Table 1. Selected bond lengths [Å] and angles [°] of compounds 3–8.
3
4
5[a]
6
7
8
M1–E1
M1–Cl1
M1–N1/2
2.4681(3)
2.1613(4)
2.44153(19)
2.2327(3)
2.6034(5)
2.3976(8)
2.156(4), 2.155(4)
2.036(5)
1.946(5)
98.6(2)
108.97(16)
102.46(15)
130.78(3)
2.6945(4)
2.1670(5)
1.9029(10), 1.8955(9)
2.2824(11)
2.1539(13)
95.65(4)
110.11(3)
100.53(3)
120.771(17)
2.6443(2)
2.2349(3)
1.9631(10), 1.9507(9)
2.2770(12)
2.1476(13)
96.01(5)
108.29(3)
99.60(4)
2.7899(2)
2.4140(4)
2.1612(11), 2.1463(11)
2.2746(14)
2.1500(15)
96.95(5)
104.50(4)
97.42(4)
1.9021(9), 1.8937(9) 1.9520(9), 1.9628(10)
E1–C30 (Cp*) 2.0638(10)
2.0641(12)
1.9518(13)
97.92(5)
111.76(3)
103.59(4)
127.255(10)
E1–C40 (Ph)
C30–E1–C40
C30–E1–M1
C40–E1–M1
E1–M1–Cl1
E1–M1–N1/2
Σꢁ(E1)
1.9537(11)
97.49(4)
114.06(3)
105.37(3)
124.752(15)
123.173(11)
110.35(3), 118.04(3)
303.90(12)
125.051(12)
113.02(3), 120.68(3)
298.87(13)
108.44(3), 112.28(3) 109.67(3), 114.53(3)
316.92(10) 313.27(12)
119.53(11), 106.45(10) 108.71(3), 115.74(3)
310.0(5) 307.29(10)
[a] Values given for the major component (80 %) of the disordered As(Ph)Cp* moiety only.
tendency of heavier group 15 elements to adopt bond angles reactions of two equivalents of LGa with Cp*ECl2 (E = As, Sb),
approaching 90° in accordance with a decreasing hybridization resulting in the formation of the gallaarsene LGaAsCp* and stib-
tendency when comparing arsanes 3–5 with stibanes 6–8. Fur- anyl radical [L(Cl)Ga]2Sb·, respectively.[9b,18c] Moreover, these re-
thermore, the decreasing bond angles indicate a release of sults emphasizes that homolytic As–Cp* bond cleavage with
steric strain due to increasingly elongated N–M, M–E, and E–C formation of reduced As species is generally feasible. In addi-
bond lengths in the series of 3–8, as was reported for ETip3, tion, the photochemically-induced E–Cp* bond homolysis of
EMes3, and EPh3 (E = As, Sb).[30] The C30–E1–C40 bond angle metalylpnictanes 3–8 by UV irradiation was probed. However,
widening with increasing N–M, M–E, and E–C distances can be the reactions were found to proceed less selective than under
rationalized by a decreasing steric pressure induced by the thermolytic conditions, most likely due to facilitated M–E bond
flanking Dip substituents of the ꢀ-diketiminate ligand L.
Syntheses of Dipnictanes {[L(Cl)M](Ph)E}2. In order to en-
force homolytic E-Cp* bond cleavage reactions and subsequent
formation of {[L(Cl)M](Ph)E} species, solutions of compounds
3–8 were treated at elevated temperatures (75–95 °C) for differ-
ent time intervals and the reaction progress was monitored by
1H NMR spectroscopy (Scheme 3).
cleavage.
Compounds 9–12 are uncommon heteroleptic metal-substi-
tuted dipnictanes and further demonstrate the wide-ranging
utility of the E–C bond homolysis approach for the synthesis
of low-oxidation state group 15 compounds. They are air- and
moisture-sensitive and stable in the solid-state and in hydro-
carbon solution at ambient temperature under inert gas atmos-
phere. The 1H NMR spectra each feature the expected resonan-
ces for the organic ligands, L and Ph, in a 1:1 molar ratio. Similar
to metalylpnictanes 3–8, the metal-substituted dipnictanes 9–
12 exhibit eight doublets, four septets, and two singlets corre-
sponding to the CHMe2, CHMe2, and NCMe protons of ligand
L, respectively, which are partially overlapping. This splitting is
characteristic of heteroleptic metalylpnictanes of the type
[L(X)M]E(R)Y (R = Cp*, Y = Cl, Br, I; R = R′, Y = H).[9c,20] The
singlets corresponding to the γ-CH resonances of ligand L (9
4.86, 10 4.95, 11 4.87, 12 4.82) are slightly shifted to higher
field compared to 3–8 and show the same trend depending on
the group 13 metal M. The three resonances assigned to the
ortho, meta, and para hydrogen atoms of the C6H5 substituents
appear in the range from 6.44 to 6.94 ppm and are thus slightly
upfield shifted compared to those in 3–8. A variable-tempera-
Scheme 3. Synthesis of dipnictanes 9–12.
Metalylstibanes 6–8 all show selective secession of a Cp*
1
radical, as judged by the presence of Cp*2 in the H NMR spec-
tra, which slowly degrades at elevated temperatures into
1,2,3,4-tetramethylfulvene and Cp*H,[31] and formation of a new
diamagnetic species containing ꢀ-diketiminate ligand L. After
crystallization, metal-substituted distibanes {[L(Cl)M](Ph)Sb}2
(M = Al 10, Ga 11, In 12) were isolated as yellow crystalline
solids in moderate yields. In contrast, mixtures of unidentified
ligand L containing species were observed in the 1H NMR spec-
tra upon thermal treatment of metalylarsanes 3–5 and only the
thermolysis of compound 4 yielded the corresponding diarsane
1
ture (VT) H NMR spectroscopic study up to 80 °C showed no
indication of E–E bond dissociation of the dipnictanes into
monomeric pnictanyl radicals [L(Cl)M](Ph)E·, suggesting
strong E–E interaction, potentially supported by inter-ligand
dispersion forces (vide infra). Moreover, the 13C{1H} NMR spectra
are in accordance with the molecular structures.
a
The solid-state molecular structures of 9–12 were deter-
{[L(Cl)Ga](Ph)As}2 (9), which was isolated as a pale yellow solid mined by X-ray diffraction, confirming the presence of E–E
in low yield. This behavior reflects the stronger As–Cp* bonds bonded species (Figure 3a), Figure S43). Single-crystals were
compared to Sb–Cp* bonds,[9a] resulting in a competitive situa- obtained from saturated solutions in toluene (9) and benzene
tion between M–As bond activation and As–Cp* bond scission (10–12) at 0 °C and ambient temperature, respectively. Distib-
under these conditions as was previously reported by us for anes 10 and 11 are isomorphous and crystallize in the mono-
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clinic space group C2/c with four molecules in the unit cell and triclinic space group P1¯ with two virtually identical but crystal-
the molecule placed on a two-fold rotation axis, whereas the lographically independent molecules (9.1, 9.2) and four mole-
indium complex 12 crystallizes together with one disordered cules of toluene in the asymmetric unit, one of which is disor-
molecule of benzene in the orthorhombic space group Pbca dered. Selected bond lengths and angles of compounds 9–12
with eight entities in the unit cell. Diarsane 9 crystallizes in the are summarized in Table 2.
Figure 3. (a) Molecular structures of 9, 10 and 12 in the solid-state. Hydrogen atoms were omitted for clarity and only one (9.2) of the two independent
molecules of 9 is shown. Displacement ellipsoids are drawn at 50 % probability level. (b) Newman-type projections of 9, 10 and 12 along the E–E bond
(proximal [L(Cl)M](Ph)E black, distal [L(Cl)M](Ph)E grey). Dip groups were omitted for clarity. (c) Intramolecular inter-ligand CH/π and H/H (below 3 Å)
contacts (red dashed lines) in the solid-state structures of 9, 10 and 12.
Table 2. Selected bond lengths [Å] and angles [°] of compounds 9–12.
9.1[a]
9.2[a]
10[b]
11[b]
12[a]
E–E
M–E
M–Cl
2.4470(4)
2.4426(3)
2.8139(4)
2.6674(7)
2.1594(7)
2.8209(4)
2.6255(3)
2.2208(6)
2.8358(3)
2.4357(4), 2.4414(4)
2.2202(5), 2.2180(5)
1.9644(13), 1.9499(14),
1.9619(13), 1.9585(13)
1.9619(17), 1.9606(17)
107.48(5), 107.91(5)
98.632(14), 98.672(15)
103.77(5), 104.47(5)
2.4282(4), 2.4249(4)
2.2151(5), 2.2167(5)
1.9502(13), 1.9611(14),
1.9570(14), 1.9672(13)
1.9568(16), 1.9533(19)
109.50(5), 111.21(5)
98.558(12), 98.807(12)
103.95(5), 103.72(6)
2.7805(3), 2.7739(3)
2.4092(5), 2.4111(5)
2.1578(16), 2.1516(16),
2.1647(15), 2.1381(15)
2.153(2), 2.1479(19)
94.59(5), 97.85(5)
94.293(6), 97.257(6)
102.69(6), 96.00(5)
120.911(14), 131.133(14)
127.05(4), 110.83(4),
120.67(4), 108.38(4)
291.57(12), 291.10(11)
25.44(8)
M–N
1.9040(16), 1.9010(16)
1.9581(17), 1.9531(16)
E–C(Ph)
E–E–C(Ph)
E–E–M
C(Ph)–E–M
E–M–Cl
2.1684(19)
114.05(5)
105.433(17)
93.62(5)
2.163(2)
114.33(6)
102.796(10)
93.62(6)
118.662(17), 118.905(17) 116.413(16), 116.992(16) 115.47(3)
116.784(18)
108.76(4), 124.97(4),
108.52(4), 123.92(4)
309.88(12), 311.05(12)
37.59(7)
178.24(1)
169.84(2)
125.40(4), 109.84(4),
128.81(4), 105.74(4)
312.00(12), 313.96(13)
40.97(8)
175.73(1)
172.27(2)
E–M–N
109.36(5), 119.74(5)
110.73(5), 122.58(5)
Σꢀ(E)
C(Ph)–E–E–C(Ph)
M–E–E–M
313.10(12)
47.13(11)
155.36(2)
27.83(4)
72.10
310.74(13)
43.39(12)
156.61(1)
28.86(3)
74.23
174.80(1)
160.75(2)
92.04
Cl–M/M–Cl
Ct–E–E–Ct[c]
90.09
88.37
[a] C(Ph) = C59, C65. [b] C(Ph) = C30. [c] Ct = C(Ph)–M bond centroid.
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Complexes 9–12 each adopt anti-periplanar arrangements of the small Ph ligand (Vbur
= 20.7 %), dimeric distibane
the sterically demanding [L(Cl)M] ligands with respect to the {[L(Cl)Ga](Ph)Sb}2 (11) was obtained upon thermal treatment of
E–E bonds with almost planar M2E2 moieties as judged by the insertion product [L(Cl)Ga](Ph)SbCp* (7). Compound 7 displays
an interesting intermediate, suggesting that compounds I, II,
and 11 are generally formed via intermediates [L(Cl)Ga]-
(Ar)SbCp* and hence allowing an insight into the underlying
reaction mechanism.[9] In all cases, relatively high selectivities
are observed, further indicating a strict mechanistic pathway.
The varying steric demand is furthermore reflected in the
M–E–E–M torsion angles, which approach 180°. The Ph substitu-
ents adopt a syn,syn orientation with rather acute C–E–E–C tor-
sion angles (Figure 3b), which is particularly pronounced in 12,
showing an almost eclipsed conformation. A similar orientation
of o-C6H4(CHNDip) and Me groups was observed in distibanes
[32]
{Sb[o-C6H4(CHNDip)]2}2
and [Sb(Me)(2,6-Mes2C6H3)]2.[33]
From the Ct–E–E–Ct torsion angles (Ct = M–C(Ph) bond reaction temperatures necessary to achieve conversion of start-
centroid) synclinal conformations of the dipnictanes 9–12 are ing materials. Radical I is formed at 80 °C, whereas hydride II
disclosed,[34] which is supposedly a result of maximized inter- and insertion product 7 are readily formed at ambient tempera-
ligand dispersion forces in form of short H/H and CH/π con- ture. Our studies prove that sterically demanding aryl ligands
tacts (Figure 3c).[16c] Such interactions could furthermore coun-
teract the dissociation of the dipnictanes into monomeric pnict-
anyl radicals at elevated temperatures. Interestingly, in 10 and
11 very short H/H distances (10 1.98 Å; 11 1.93 Å) between
the o-H atoms of the Ph ligands (H31/H31′) are observed. The
orientation of the L and Cl ligands at M with respect to the
almost planar M2E2 moiety is strikingly different (Figure 3b), as
the Cl atoms in distibanes 10 and 11 are almost perpendicular
require elevated reaction temperatures to overcome the
increased steric hindrance and form insertion products
[L(Cl)Ga](Ar)SbCp*, as was proven with the synthesis of I. Cp*
elimination from the insertion products is then facilitated by a
sterically more demanding environment due to the increased
steric pressure, which is why the formation of 11 requires heat-
ing to 75 °C, whereas II forms already at ambient temperature.
For both aryl ligands, 2,6-Mes2C6H3 and Ph, Cp* radical elimi-
to this plane and syn oriented, whereas the Cl atoms in distib- nation is observed and compounds I and 11 behave analo-
anes 9 and 12 are almost in-plane arranged and anti-aligned, gously to the scheme depicted in Figure 1c and Figure 1a, re-
spectively. In remarkable contrast, elimination of 1,2,3,4-tetra-
methylfulvene and formation of hydride II is observed in case
of intermediate sized Dip ligand instead of a temperature-
dependent dissociation/association equilibrium between stib-
anyl radicals and distibanes as shown in Figure 1b (Scheme 4).
Based on these observations, we propose that in the reaction
of LGa and Cp*(Dip)SbCl, the kinetically less stabilized radical
[L(Cl)Ga](Dip)Sb· (II-H) is formed initially by Cp* radical elimina-
tion from intermediate [L(Cl)Ga](Dip)SbCp*, which subsequently
abstracts a hydrogen atom from one methyl group of the Cp*
radical, leading to thermodynamically stable Sb hydride II and
1,2,3,4-tetramethylfulvene. The hydrogen abstraction from the
Cp* radical is slower than the dimerization of two
[L(Cl)Ga](Ar)Sb· radicals, which is why in case of 11 only the
distibane and no corresponding Sb hydride is observed.
as deduced by the Cl– M/M–Cl torsion angles. The As–As and
Sb–Sb bond lengths are close to the lower limits observed for
non-bridged diarsanes (range 2.417–2.592 Å)[35] and distibanes
(range 2.792–3.030 Å),[36] respectively, thus showing typical
E–E single bonds with no indication of a peculiar bond weak-
ness induced by steric congestion, as was observed in
[{(Me3Si)2CH}2As]2 and [{H2CC(SiMe3)2}2Sb]2.[6] Moreover, the
[5]
M–E, M–Cl, M–N, and E–C(Ph) bond lengths in dipnictanes 9–
12 compare well to those of compounds 3–8. Distibanes 10–
12 show a gradually decreasing sum of bond angles at the Sb
centers, Σꢀ(E), from 10 over 11 to 12, which is in line with the
observations made in the series of metalylstibanes 6–8, show-
ing a strain release by uncompressing the M2Sb2Ph2 moiety due
to increasing N–M and M–Sb bond lengths. For comparison, the
sum of bond angles at the As centers in diarsane 9 are close to
those in distibanes 10 and 11, whereas the overall conforma-
tion of diarsane 9 is similar to that of distibane 12.
Compounds 9–12 belong to the very short list of structurally
characterized metal-substituted dipnictanes. Aside from
homoleptic germyl- and stannyl-substituted distibanes
[(Me3Ge)2Sb]2[37] and [(Me3Sn)2Sb]2,[38] there are only two addi-
tional examples: the homoleptic bis iron-substituted diarsane
[39]
[CpFe(CO)2(Ph)As]2
as well as the diarsenide-dione bridged
complex, [Et3P(Cl)Pt{tBu(O)C}As]2,[40] respectively.
Influence of aryl ligand bulk on product formation. By
systematic variation of the steric demand of the aryl ligand in
Cp*(Ar)SbCl (Ar = 2,6-Mes2C6H3, Dip, Ph) different reaction out-
comes in reactions with LGa were observed. The sterically over-
crowded ligand 2,6-Mes2C6H3 (Vbur = 36.8 %) allowed for the
formation and isolation of monomeric Sb-centered radical
[L(Cl)Ga](2,6-Mes2C6H3)Sb· (I) in both solution and solid-
state.[19] Reduction of steric demand by replacing the terphenyl
ligand by an intermediate sized Dip ligand (Vbur = 30.8 %) led to
the isolation of Sb hydride [L(Cl)Ga](Dip)SbH (II).[20] Employing
Scheme 4. Influence of the aryl ligand bulk on the formation of radicals,
hydrides, and distibanes.
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residue was extracted with n-hexane (30 mL). Volatiles were re-
moved from the filtrate in vacuo, yielding a yellow solid. Yield:
0.52 g (1.61 mmol, 81 %). Mp: 56 °C. Anal. Calcd. for C16H20AsCl:
The proposed mechanism is further supported by quantum
chemical calculations, indicating that Sb–C bond cleavage and
Sb–H bond formation proceed sequentially rather than con-
certed,[9c] for which reason the formation of II can be regarded
as a stepwise ꢀ-H elimination. These observations further em-
phasize the crucial role of steric demand for the formation of
pnictanyl radicals and dipnictanes. By changing the steric char-
acteristics of just one of the two ligands in {[L(Cl)Ga](Ar)Sb}n
(Ar = 2,6-Mes2C6H3, n = 1; Ar = Ph, n = 2) by about 15 % of
buried volume, discrimination between isolable Sb-centered
radicals and distibanes is obtained.
1
C, 59.55; H, 6.25; found C, 58.7; H, 6.18. H NMR (400.1 MHz, C6D6):
δ 7.37 (m, 2 H, m-C6H5), 7.03 (m, 3 H, o-C6H5 & p-C6H5), 1.59 (s, 15
H, C5(CH3)5). 13C{1H} NMR (100.6 MHz, C6D6): δ = 143.5 (i-C6H5),
131.3 (m-C6H5), 129.7 (p-C6H5), 127.7 (o-C6H5), 11.6 (C5(CH3)5)
(C5(CH3)5 not observed). IR (neat): ν = 3055, 2969, 2912, 2853, 1616,
˜
1432, 1378, 1273, 1064, 997, 738, 692, 592, 467, 434 cm–1
.
Synthesis of Cp*(Ph)SbCl (2). A solution of PhSbCl2 (0.54 g,
2.00 mmol) in Et2O (10 mL) was added at ambient temperature to
a stirred suspension of KCp* (0.35 g, 2.00 mmol) in Et2O (15 mL)
and the resulting yellow-orange suspension was stirred for 30 min-
utes. The solvent was removed under reduced pressure and the
residue was extracted with n-hexane (30 mL). Volatiles were re-
moved from the filtrate in vacuo, yielding a yellow-orange solid.
Yield: 0.58 g (1.57 mmol, 79 %). Mp: 77 °C. Anal. Calcd. for
Conclusion
Oxidative addition reactions of diyls LM with Cp*-substituted
pnictanes 1 and 2 yield complexes 3–8, which represent a full
series of rare asymmetric metalylpnictanes. Compounds 4 and
6–8 were subsequently transformed into heteroleptic metal-
substituted dipnictanes 9–12 by thermally induced E–Cp* bond
homolysis. This study leads to a deeper understanding of the
individual steps in the reaction mechanism, resulting in the
formation of Sb-centered radicals [L(Cl)Ga](R)Sb·[19] and Sb
hydrides [L(Cl)Ga](R′)SbH.[20] The radicals and hydrides are ex-
pected to form via initial formation of insertion products
[L(Cl)Ga](Ar)SbCp* and subsequent Sb–Cp* bond homolysis fol-
lowed by H atom abstraction in case of the hydrides. The reac-
tion mechanism is largely influenced by the steric demand of
the substituents and hence the stability of intermediates and
products. Moreover, the scope of the E-Cp* bond homolysis
approach for the synthesis of reduced group 13 metal-substi-
tuted group 15 compounds was extended to Al and In-based
ligands, while demonstrating that E–Cp* scission is in principle
applicable to the lighter pnictogen As as well.
C
16H20ClSb: C, 52.00; H, 5.46; found C, 51.7; H, 5.26. 1H NMR
(400.1 MHz, C6D6): δ 7.57 (dd, JHH = 8.0, 1.4 Hz, 2 H, m-C6H5), 7.20
3
(t, JHH = 7.1 Hz, 2 H, o-C6H5), 7.13 (m, 1 H, p-C6H5), 1.73 (s, 15 H,
C5(CH3)5). 13C{1H} NMR (100.6 MHz, C6D6): δ = 153.8 (i-C6H5), 133.6
(m-C6H5), 129.9 (p-C6H5), 129.1 (o-C6H5), 122.9 (C5(CH3)5), 11.2
(C5(CH3)5). IR (neat): ν = 3060, 2961, 2910, 2854, 1429, 1378, 1299,
˜
1059, 1018, 794, 728, 692, 589, 448, 442 cm–1
.
Synthesis of [L(Cl)Al](Ph)AsCp* (3). Benzene (1.0 mL) was added
to a mixture of LAl (50 mg, 0.1125 mmol) and 1 (36 mg,
0.1125 mmol) at ambient temperature and the resulting pale-yellow
solution was stirred for 15 minutes. Volatiles were removed in vacuo
and the residue was dissolved in n-hexane (1.5 mL). Storage of the
solution at ambient temperature for 12 h afforded pale yellow ana-
lytically pure crystals of 3. Yield: 42 mg (0.0547 mmol, 49 %). Mp:
174 °C (dec.). Anal. Calcd. for C45H61AlAsClN2: C, 70.44; H, 8.01; N,
3.65; found C, 70.1; H, 8.35; N, 3.49. 1H NMR (300.1 MHz, Tol-d8,
–20 °C): δ 7.19 (dd, JHH = 7.6, 1.8 Hz, 1 H, C6H3(iPr)2), 7.14 (m, 1 H,
C6H3(iPr)2), 7.08 (dd, JHH = 7.6, 1.8 Hz, 1 H, C6H3(iPr)2), 6.81 (m, 3 H,
C6H5), 6.73 (dd, JHH = 7.6, 1.2 Hz, 1 H, C6H3(iPr)2), 6.65 (m, 3 H,
C6H5 & C6H3(iPr)2), 6.51 (dd, JHH = 7.6, 1.2 Hz, 1 H, C6H3(iPr)2), 4.93
3
(s, 1 H, γ-CH), 3.73 (sept, JHH = 6.7 Hz, 1 H, CH(CH3)2), 3.63 (sept,
Experimental Section
3
3JHH = 6.7 Hz, 1 H, CH(CH3)2), 3.47 (sept, JHH = 6.7 Hz, 2 H,
CH(CH3)2), 2.12 (s, 3 H, C5(CH3)5), 2.06 (s, 3 H, C5(CH3)5), 1.79 (d,
General Procedures. All manipulations were carried out under an
atmosphere of purified argon using standard Schlenk and glovebox
techniques. n-Hexane and diethyl ether (Et2O) were dried with a
MBraun Solvent Purification System and benzene was distilled from
Na/K alloy. Deuterated benzene was dried with activated molecular
sieves (4 Å) and degassed prior to use. Starting materials LAl,[13]
LGa,[14] LIn,[15] PhAsCl2,[41] PhSbCl2,[42] and KCp*[43] were prepared
according to literature procedures. NMR spectra (δ in ppm) were
recorded using a Bruker Avance DPX 300 (1H 300.1 MHz, 13C{1H}
75.5 MHz) or a Bruker Avance Neo 400 (1H 400.1 MHz, 13C{1H}
100.6 MHz) spectrometer and were referenced to internal C6D5H
(1H δ = 7.16, 13C δ = 128.06) or C6D5CD2H (1H δ = 2.08, 13C δ =
20.43). IR spectra were recorded in a glovebox with an ALPHA-T
FT-IR spectrometer equipped with a single-reflection ATR sampling
module. Microanalyses were performed at the elemental analysis
laboratory of the University of Duisburg-Essen. Melting points were
measured in wax-sealed glass capillaries under argon atmosphere
using a Thermo Scientific 9300 apparatus and are uncorrected.
3
3JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.62 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2),
3
1.59 (s, 3 H, CCH3), 1.56 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.51 (s, 3
H, CCH3), 1.42 (s, 3 H, C5(CH3)5), 1.35 (d, 3JHH = 6.7 Hz, 3 H, CH(CH3)2),
1.18 (d, 3JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.13 (s, 3 H, C5(CH3)5), 1.12 (d,
3
3JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.04 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2),
3
0.88 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 0.54 (s, 3 H, C5(CH3)5). 13C{1H}
NMR (75.5 MHz, Tol-d8, –20 °C): δ = 170.7 (CCH3), 170.2 (CCH3), 146.1
(C6H3(iPr)2), 144.2 (C6H3(iPr)2), 143.8 (C6H3(iPr)2), 142.0 (C6H3(iPr)2),
140.3 (C6H3(iPr)2), 139.7 (C6H3(iPr)2), 139.3 (C5(CH3)5), 137.9 (C6H5),
137.3 (C5(CH3)5), 136.8 (C6H5), 132.6 (C5(CH3)5), 131.9 (C5(CH3)5),
128.1 (C6H3(iPr)2), 125.7 (C6H3(iPr)2), 125.5 (C6H5), 125.4 (C6H5), 125.2
(C6H3(iPr)2), 124.5 (C6H3(iPr)2), 123.6 (C6H3(iPr)2), 98.7 (γ-CH), 62.1
(C5(CH3)5), 30.3 (CH(CH3)2), 30.2 (CH(CH3)2), 28.1 (CH(CH3)2), 27.8
(CH(CH3)2), 26.0 (CH(CH3)2), 25.9 (CH(CH3)2), 25.3 (CH(CH3)2), 25.2
(CH(CH3)2), 25.1 (CH(CH3)2), 24.8 (CH(CH3)2), 23.8 (CH(CH3)2), 23.8
(CCH3 & CH(CH3)2), 23.6 (CCH3), 23.0 (CH(CH3)2), 16.0 (C5(CH3)5), 12.9
(C5(CH3)5), 11.6 (C5(CH3)5), 10.9 (C5(CH3)5), 10.5 (C5(CH3)5). IR (neat):
ν = 2961, 2926, 2869, 1524, 1432, 1385, 1314, 1251, 1177, 1020,
˜
Synthesis of Cp*(Ph)AsCl (1). A solution of PhAsCl2 (0.45 g,
0.27 mL, 2.00 mmol) in Et2O (10 mL) was added at ambient temper-
ature to a stirred suspension of KCp* (0.35 g, 2.00 mmol) in Et2O
(15 mL) and the resulting pale yellow suspension was stirred for 30
937, 873, 797, 730, 692, 644, 533, 475, 421 cm–1
.
Synthesis of [L(Cl)Ga](Ph)AsCp* (4). Benzene (1.0 mL) was added
to a mixture of LGa (50 mg, 0.1026 mmol) and 1 (33 mg,
minutes. The solvent was removed under reduced pressure and the 0.1026 mmol) at ambient temperature and the resulting pale-yellow
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solution was stirred for 15 minutes. Volatiles were removed in vacuo (CH(CH3)2), 23.3 (CH(CH3)2), 17.6 (C5(CH3)5), 12.6 (C5(CH3)5), 11.3
and the residue was washed with n-hexane (2 × 1.0 mL), yielding
pure 4 in form of a colorless crystalline solid. Single-crystals of 4
were obtained from a saturated solution in hot n-hexane after stor-
age at ambient temperature for 12 h. Yield: 45 mg (0.0555 mmol,
54 %). Mp: 177 °C. Anal. Calcd. for C45H61AsClGaN2: C, 66.72; H, 7.59;
(C5(CH3)5), 10.9 (C5(CH3)5), 10.4 (C5(CH3)5) (C5(CH3)5 not observed).
IR (neat): ν = 2961, 2962, 2869, 1550, 1516, 1432, 1386, 1314, 1251,
˜
1175, 1018, 935, 852, 793, 730, 691, 589, 520, 467 cm–1
.
Synthesis of [L(Cl)Al](Ph)SbCp* (6). Benzene (1.0 mL) was added
to a mixture of LAl (50 mg, 0.1125 mmol) and 2 (42 mg,
0.1125 mmol) at ambient temperature and the resulting orange
solution was stirred for 15 minutes. The solution was slightly con-
centrated until incipient crystallization and stored at ambient tem-
perature for 12 h to yield orange analytically pure crystals of 6.
Yield: 25 mg (0.0307 mmol, 27 %). Mp: 198 °C (dec.). Anal. Calcd. for
1
N, 3.46; found C, 66.9; H, 7.61; N, 3.52. H NMR (400.1 MHz, C6D6):
δ 7.23 (m, 1 H, C6H3(iPr)2), 7.17 (m, 2 H, C6H3(iPr)2), 6.85 (dd, JHH
=
7.7, 1.4 Hz, 1 H, C6H3(iPr)2), 6.80 (m, 3 H, C6H5), 6.71 (t, 3JHH = 7.7 Hz,
1 H, C6H3(iPr)2), 6.65 (t, 3JHH = 7.4 Hz, 2 H, C6H5), 6.55 (dd, JHH = 7.7,
3
1.4 Hz, 1 H, C6H3(iPr)2), 4.94 (s, 1 H, γ-CH), 3.83 (sept, JHH = 6.7 Hz,
3
1 H, CH(CH3)2), 3.71 (sept, JHH = 6.7 Hz, 1 H, CH(CH3)2), 3.68 (sept,
C
45H61AlClN2Sb: C, 66.38; H, 7.55; N, 3.44; found C, 66.6; H, 7.51;
3
3JHH = 6.7 Hz, 1 H, CH(CH3)2), 3.41 (sept, JHH = 6.7 Hz, 1 H,
1
N, 3.72. H NMR (300.1 MHz, C6D6): δ 7.22 (m, 1 H, C6H3(iPr)2), 7.17
(m, 2 H, C6H3(iPr)2), 6.96 (dd, JHH = 7.7, 1.3 Hz, 2 H, o-C6H5), 6.91 (tt,
JHH = 7.4, 1.3 Hz, 1 H, C6H3(iPr)2), 6.84 (dd, JHH = 7.8, 1.5 Hz, 1 H,
C6H3(iPr)2), 6.76 (t, 3JHH = 7.2 Hz, 2 H, m-C6H5), 6.74 (t, 3JHH = 7.7 Hz,
1 H, p-C6H5), 6.64 (dd, JHH = 7.6, 1.4 Hz, 1 H, C6H3(iPr)2), 5.00 (s, 1
CH(CH3)2), 2.13 (s, 3 H, C5(CH3)5), 1.97 (s, 3 H, C5(CH3)5), 1.75 (d,
3
3JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.68 (s, 3 H, CCH3), 1.63 (d, JHH
=
3
6.7 Hz, 3 H, CH(CH3)2), 1.58 (s, 3 H, CCH3), 1.57 (d, JHH = 6.7 Hz, 3
3
H, CH(CH3)2), 1.37 (s, 3 H, C5(CH3)5), 1.29 (d, JHH = 6.7 Hz, 3 H,
3
3
CH(CH3)2), 1.20 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.15 (d, JHH
=
3
3
H, γ-CH), 3.74 (sept, JHH = 6.8 Hz, 1 H, CH(CH3)2), 3.64 (sept, JHH
=
6.7 Hz, 3 H, CH(CH3)2), 1.11 (d, 3JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.10 (s,
6.7 Hz, 1 H, CH(CH3)2), 3.51 (sept, 3JHH = 6.7 Hz, 1 H, CH(CH3)2), 3.46
3
3 H, C5(CH3)5), 0.95 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 0.65 (s, 3 H,
3
3
(sept, JHH = 6.7 Hz, 1 H, CH(CH3)2), 1.74 (d, JHH = 6.8 Hz, 3 H,
CH(CH3)2), 1.64 (s, 3 H, CCH3), 1.61 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2),
1.56 (br s & s, 18 H, C5(CH3)5 & CCH3), 1.50 (d, JHH = 6.7 Hz, 3 H,
CH(CH3)2), 1.38 (d, JHH = 6.8 Hz, 3 H, CH(CH3)2), 1.17 (d, JHH
C5(CH3)5). 13C{1H} NMR (100.6 MHz, C6D6): δ = 168.9 (CCH3), 168.6
(CCH3), 146.4 (C6H3(iPr)2), 144.7 (C6H3(iPr)2), 143.6 (C6H3(iPr)2), 142.0
(C6H3(iPr)2), 142.0 (C6H3(iPr)2), 141.5 (C6H3(iPr)2), 139.4 (C5(CH3)5),
137.1 (C6H5), 136.4 (C6H5), 135.9 (C5(CH3)5), 134.4 (C5(CH3)5), 133.0
(C5(CH3)5), 127.6 (C6H3(iPr)2), 126.3 (C6H5), 125.7 (C6H5), 125.7
(C6H3(iPr)2), 125.3 (C6H3(iPr)2), 124.4 (C6H3(iPr)2), 123.5 (C6H3(iPr)2),
97.3 (γ-CH), 63.9 (C5(CH3)5), 30.2 (CH(CH3)2), 30.2 (CH(CH3)2), 28.2
(CH(CH3)2), 27.9 (CH(CH3)2), 26.0 (CH(CH3)2), 25.3 (CH(CH3)2), 25.3
(CH(CH3)2), 25.2 (CH(CH3)2), 25.0 (CH(CH3)2), 24.1 (CCH3), 23.9 (CCH3),
23.9 (CH(CH3)2), 23.0 (CH(CH3)2), 16.2 (C5(CH3)5), 13.0 (C5(CH3)5), 11.5
3
3
3
3
=
3
6.7 Hz, 3 H, CH(CH3)2), 1.11 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.05
3
3
(d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 0.91 (d, JHH = 6.7 Hz, 3 H,
CH(CH3)2). 13C{1H} NMR (75.5 MHz, C6D6): δ = 170.9 (CCH3), 170.6
(CCH3), 146.5 (C6H3(iPr)2), 145.1 (C6H3(iPr)2), 143.5 (C6H3(iPr)2), 142.3
(C6H3(iPr)2), 140.4 (C6H3(iPr)2), 140.2 (C6H5), 139.7 (C6H3(iPr)2), 134.7
(C6H5), 126.2 (C6H5), 126.0 (C6H3(iPr)2), 126.0 (C6H3(iPr)2), 125.6
(C6H3(iPr)2), 124.7 (C6H3(iPr)2), 124.0 (C6H3(iPr)2), 99.0 (γ-CH), 30.8
(CH(CH3)2), 30.6 (CH(CH3)2), 28.2 (CH(CH3)2), 28.0 (CH(CH3)2), 26.2
(CH(CH3)2), 26.0 (CH(CH3)2), 25.4 (CH(CH3)2), 25.2 (CH(CH3)2), 25.0
(CH(CH3)2), 25.0 (CH(CH3)2), 24.3 (CH(CH3)2), 24.0 (CCH3), 23.9
(CH(CH3)2), 23.8 (CCH3), 12.9 (C5(CH3)5) (C5(CH3)5 not observed). IR
(C5(CH3)5), 10.8 (C5(CH3)5), 10.4 (C5(CH3)5). IR (neat): ν = 2962, 2929,
˜
2869, 1551, 1523, 1434, 1385, 1314, 1253, 1178, 1020, 938, 862, 796,
728, 692, 590, 527, 467 cm–1
.
Synthesis of [L(Cl)In](Ph)AsCp* (5). Benzene (1.0 mL) was added
to a mixture of LIn (50 mg, 0.0939 mmol) and 1 (30 mg,
0.0939 mmol) at ambient temperature and the resulting pale-yellow
(neat): ν = 2965, 2925, 2867, 1530, 1434, 1385, 1313, 1254, 1177,
˜
1018, 937, 873, 792, 727, 695, 465, 418 cm–1
.
solution was stirred for 24 hours. Volatiles were removed in vacuo Synthesis of [L(Cl)Ga](Ph)SbCp* (7). Benzene (1.0 mL) was added
and the residue was dissolved in n-hexane (1.5 mL). Storage of the
to a mixture of LGa (50 mg, 0.1026 mmol) and 2 (38 mg,
solution at ambient temperature for 12 h afforded pale yellow ana-
0.1026 mmol) at ambient temperature and the resulting orange
lytically pure crystals of 5. Yield: 36 mg (0.0423 mmol, 45 %). Mp: solution was stirred for 15 minutes. The solution was slightly con-
168 °C. Anal. Calcd. for C45H61AsClInN2: C, 63.20; H, 7.19; N, 3.28; centrated until incipient crystallization and stored at ambient tem-
found C, 63.4; H, 7.59; N, 3.39. 1H NMR (400.1 MHz, C6D6): δ 7.20 perature for 12 h to yield orange analytically pure crystals of 7.
(m, 1 H, C6H3(iPr)2), 7.17 (m, 2 H, C6H3(iPr)2), 6.96 (dd, JHH = 7.7,
Yield: 27 mg (0.0315 mmol, 31 %). Mp: 205 °C (dec.). Anal. Calcd. for
1.4 Hz, 1 H, C6H3(iPr)2), 6.83 (t, 3JHH = 7.7 Hz, 2 H, C6H5 & C6H3(iPr)2),
C
45H61ClGaN2Sb: C, 63.07; H, 7.18; N, 3.27; found C, 63.4; H, 7.17; N,
3
6.72 (dd, JHH = 7.7, 1.5 Hz, 2 H, C6H5), 6.66 (t, JHH = 7.6 Hz, 3 H,
3.32. 1H NMR (300.1 MHz, C6D6): δ 7.19 (m, 3 H, C6H3(iPr)2), 6.90 (m,
3
C6H5 & C6H3(iPr)2), 4.86 (s, 1 H, γ-CH), 3.86 (sept, JHH = 6.8 Hz, 1 H,
4 H, C6H5 & C6H3(iPr)2), 6.74 (m, 3 H, C6H5 & C6H3(iPr)2), 6.60 (dd,
CH(CH3)2), 3.80 (sept, 3JHH = 6.8 Hz, 1 H, CH(CH3)2), 3.60 (sept, 3JHH
=
JHH = 7.7, 1.4 Hz, 2 H, C6H5), 4.94 (s, 1 H, γ-CH), 3.79 (sept, JHH
=
=
3
6.8 Hz, 1 H, CH(CH3)2), 3.33 (sept, 3JHH = 6.8 Hz, 1 H, CH(CH3)2), 1.98 6.7 Hz, 1 H, CH(CH3)2), 3.68 (m, 2 H, CH(CH3)2), 3.42 (sept, JHH
3
(br s, 3 H, C5(CH3)5), 1.90 (br s, 3 H, C5(CH3)5), 1.72 (s, 3 H, CCH3),
6.8 Hz, 1 H, CH(CH3)2), 1.70 (d, 3JHH = 6.8 Hz, 3 H, CH(CH3)2), 1.69 (s,
3
1.68 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.63 (s, 3 H, CCH3), 1.58 (d, 3 H, CCH3), 1.63 (d, 3JHH = 6.6 Hz, 3 H, CH(CH3)2), 1.61 (s, 3 H, CCH3),
3
3
3JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.49 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2),
1.54 (d, JHH = 6.6 Hz, 3 H, CH(CH3)2), 1.53 (s, 15 H, C5(CH3)5), 1.30
3
3
3
1.40 (br s, 3 H, C5(CH3)5), 1.23 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.20
(d, JHH = 6.8 Hz, 3 H, CH(CH3)2), 1.20 (d, JHH = 6.8 Hz, 3 H,
3
3
3
(d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.18 (br s, 3 H, C5(CH3)5), 1.16 (d, CH(CH3)2), 1.15 (d, JHH = 6.8 Hz, 3 H, CH(CH3)2), 1.09 (d, JHH
=
3
3JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.14 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2),
6.7 Hz, 3 H, CH(CH3)2), 0.96 (d, 3JHH = 6.7 Hz, 3 H, CH(CH3)2). 13C{1H}
3
1.02 (d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 0.81 (br s, 3 H, C5(CH3)5).
NMR (75.5 MHz, C6D6): δ = 168.8 (CCH3), 168.6 (CCH3), 146.5
(C6H3(iPr)2), 145.1 (C6H3(iPr)2), 143.0 (C6H3(iPr)2), 142.0 (C6H3(iPr)2),
13C{1H} NMR (100.6 MHz, C6D6): δ = 169.3 (CCH3), 169.2 (CCH3), 145.1
(C6H3(iPr)2), 144.1 (C6H3(iPr)2), 143.7 (C6H3(iPr)2), 143.3 (C6H3(iPr)2), 141.9 (C6H3(iPr)2), 141.3 (C6H5), 139.4 (C6H3(iPr)2), 135.8 (C6H3(iPr)2),
142.5 (C6H3(iPr)2), 141.7 (C6H3(iPr)2), 136.9 (C6H5), 136.5 (C6H5), 127.1
(C6H3(iPr)2), 127.0 (C6H5), 126.9 (C6H3(iPr)2), 126.6 (C6H5), 125.4
126.6 (C6H3(iPr)2), 126.5 (C6H3(iPr)2), 125.6 (C6H5), 124.5 (C5(CH3)5),
124.4 (C6H3(iPr)2), 123.6 (C6H5), 97.3 (γ-CH), 30.6 (CH(CH3)2), 30.5
(C6H3(iPr)2), 125.0 (C6H3(iPr)2), 124.1 (C6H3(iPr)2), 123.6 (C6H3(iPr)2), (CH(CH3)2), 28.2 (CH(CH3)2), 28.0 (CH(CH3)2), 26.2 (CH(CH3)2), 26.1
96.6 (γ-CH), 30.1 (CH(CH3)2), 29.9 (CH(CH3)2), 28.0 (CH(CH3)2), 27.8 (CH(CH3)2), 25.3 (CH(CH3)2), 25.2 (CH(CH3)2), 25.2 (CH(CH3)2), 25.0
(CH(CH3)2), 26.3 (CH(CH3)2), 26.1 (CH(CH3)2), 25.1 (CH(CH3)2), 25.0 (CH(CH3)2), 24.1 (CH(CH3)2), 24.1 (CCH3), 23.9 (CCH3), 23.6 (CH(CH3)2),
(CH(CH3)2), 25.0 (CH(CH3)2), 24.8 (CH(CH3)2), 24.4, 24.4 (CCH3), 24.0
12.7 (C5(CH3)5). IR (neat): ν = 3061, 2964, 2925, 2867, 1553, 1526,
˜
Eur. J. Inorg. Chem. 0000, 0–0
www.eurjic.org
8
© 2020 The Authors published by Wiley-VCH GmbH

Full Paper
doi.org/10.1002/ejic.202000747
EurJIC
European Journal of Inorganic Chemistry
1435, 1392, 1316, 1260, 1177, 1108, 1021, 939, 863, 790, 728, 694, 29.6 (CH(CH3)2), 28.1 (CH(CH3)2), 28.0 (CH(CH3)2), 27.7 (CH(CH3)2),
589, 524, 450 cm–1
.
26.5 (CH(CH3)2), 25.4 (CH(CH3)2), 24.8 (CH(CH3)2), 24.7 (CH(CH3)2),
24.5 (CH(CH3)2), 24.4 (CH(CH3)2), 24.2 (CCH3), 23.9 (CCH3), 22.6
Synthesis of [L(Cl)In](Ph)SbCp* (8). Benzene (1.0 mL) was added
to a mixture of LIn (50 mg, 0.0939 mmol) and 2 (35 mg,
0.0939 mmol) at ambient temperature and the resulting orange
(CH(CH3)2). IR (neat): ν = 2959, 2925, 2864, 1527, 1435, 1385, 1316,
˜
1260, 1178, 1023, 865, 796, 730, 692, 498, 467 cm–1
.
solution was stirred for 15 minutes. Volatiles were removed in vacuo Synthesis of {[L(Cl)Al](Ph)Sb}2 (10). Benzene (1.0 mL) was added
and the residue was dissolved in n-hexane (1.0 mL). Storage of the to a mixture of LAl (50 mg, 0.1125 mmol) and 2 (42 mg,
solution at ambient temperature for 12 h afforded orange analyti- 0.1125 mmol) at ambient temperature and the resulting orange
cally pure crystals of 8. Yield: 54 mg (0.0599 mmol, 64 %). Mp:
150 °C (dec.). Anal. Calcd. for C45H61ClInN2Sb: C, 59.92; H, 6.82; N,
3.11; found C, 60.3; H, 6.85; N, 2.81. 1H NMR (300.1 MHz, C6D6):
solution was heated at 75 °C for 2 hours. The solution was slightly
concentrated until incipient crystallization and stored at ambient
temperature for 12 h to yield yellow analytically pure crystals of 10.
Yield: 25 mg (0.0184 mmol, 33 %). Mp: 198 °C (dec.). Anal. Calcd. for
C70H92Al2Cl2N4Sb2: C, 61.92; H, 6.83; N, 4.13; found C, 62.3; H, 7.12;
N, 3.97. 1H NMR (300.1 MHz, C6D6): δ 7.30 (t, JHH = 7.7 Hz, 2 H,
δ 7.20 (m, 1 H, C6H3(iPr)2), 7.17 (m, 2 H, C6H3(iPr)2), 7.02 (dd, JHH
=
7.8, 1.3 Hz, 2 H, C6H5), 6.95 (dd, JHH = 7.8, 1.5 Hz, 1 H, C6H3(iPr)2),
3
6.91 (tt, JHH = 7.6, 1.3 Hz, 1 H, C6H5), 6.83 (t, JHH = 7.7 Hz, 1 H,
C6H3(iPr)2), 6.78 (tt, JHH = 7.6, 1.3 Hz, 2 H, C6H5), 6.70 (dd, JHH = 7.7,
C6H3(iPr)2), 7.22 (dd, JHH = 7.7, 1.4 Hz, 2 H, C6H3(iPr)2), 7.13 (dd, JHH
7.6, 1.8 Hz, 2 H, C6H3(iPr)2), 6.94 (dd, JHH = 7.7, 1.1 Hz, 4 H, m-C6H5),
=
3
1.5 Hz, 1 H, C6H3(iPr)2), 4.85 (s, 1 H, γ-CH), 3.84 (sept, JHH = 6.8 Hz,
3
1 H, CH(CH3)2), 3.77 (sept, JHH = 6.8 Hz, 1 H, CH(CH3)2), 3.52 (sept, 6.88 (m, 6 H, p-C6H5 & C6H3(iPr)2), 6.72 (dd, JHH = 6.3, 2.8 Hz, 2 H,
3
3JHH = 6.8 Hz, 1 H, CH(CH3)2), 3.28 (sept, JHH = 6.8 Hz, 1 H,
C6H3(iPr)2), 6.66 (t, JHH = 7.5 Hz, 4 H, o-C6H5), 4.95 (s, 2 H, γ-CH),
3
3
CH(CH3)2), 1.70 (s, 3 H, CCH3), 1.62 (s, 3 H, CCH3), 1.59 (d, JHH
=
3.63 (sept, JHH = 6.7 Hz, 2 H, CH(CH3)2), 3.35 (m, 6 H, CH(CH3)2),
6.6 Hz, 3 H, CH(CH3)2), 1.54 (s, 15 H, C5(CH3)5), 1.52 (d, 3JHH = 6.6 Hz, 1.54 (s, 6 H, CCH3), 1.45 (d, JHH = 6.7 Hz, 12 H, CH(CH3)2), 1.44 (s, 6
3
3 H, CH(CH3)2), 1.46 (d, 3JHH = 6.8 Hz, 3 H, CH(CH3)2), 1.24 (d, 3JHH
=
H, CCH3), 1.29 (d, 3JHH = 6.8 Hz, 6 H, CH(CH3)2), 1.22 (d, 3JHH = 6.8 Hz,
6 H, CH(CH3)2), 1.07 (d, 3JHH = 6.7 Hz, 12 H, CH(CH3)2), 0.92 (d, 3JHH
3
6.8 Hz, 3 H, CH(CH3)2), 1.19 (d, JHH = 6.8 Hz, 6 H, CH(CH3)2), 1.11
=
(d, JHH = 6.7 Hz, 3 H, CH(CH3)2), 1.01 (d, JHH = 6.7 Hz, 3 H,
6.7 Hz, 12 H, CH(CH3)2). 13C{1H} NMR (75.5 MHz, C6D6): δ = 170.6
3
3
CH(CH3)2). 13C{1H} NMR (75.5 MHz, C6D6): δ = 169.1 (CCH3), 169.1 (CCH3), 170.2 (CCH3), 145.9 (C6H3(iPr)2), 145.3 (C6H3(iPr)2), 143.1
(CCH3), 145.4 (C6H3(iPr)2), 144.3 (C6H3(iPr)2), 143.9 (C6H3(iPr)2), 143.4 (C6H3(iPr)2), 142.4 (C6H3(iPr)2), 142.3 (C6H5), 140.5 (C6H3(iPr)2), 140.3
(C6H3(iPr)2), 142.1 (C6H3(iPr)2), 141.4 (C6H3(iPr)2), 139.9 (C6H5), 135.5
(C6H5), 127.4 (C6H5), 127.1 (C6H3(iPr)2), 125.6 (C6H3(iPr)2), 125.2
(C6H3(iPr)2), 124.1 (C6H3(iPr)2), 123.7 (C6H3(iPr)2), 96.7 (γ-CH), 30.3
(C6H3(iPr)2), 127.1 (C6H5), 125.5 (C6H3(iPr)2), 125.4 (C6H3(iPr)2), 124.6
(C6H5), 124.4 (C6H3(iPr)2), 123.9 (C6H3(iPr)2), 99.4 (γ-CH), 30.4
(CH(CH3)2), 30.0 (CH(CH3)2), 28.3 (CH(CH3)2), 27.8 (CH(CH3)2), 27.5
(CH(CH3)2), 30.1 (CH(CH3)2), 27.9 (CH(CH3)2), 27.8 (CH(CH3)2), 26.4 (CH(CH3)2), 26.2 (CH(CH3)2), 25.4 (CH(CH3)2), 25.0 (CH(CH3)2), 24.9
(CH(CH3)2), 26.2 (CH(CH3)2), 25.0 (CH(CH3)2), 24.9 (CH(CH3)2), 24.8 (CH(CH3)2), 24.9 (CH(CH3)2), 24.7 (CH(CH3)2), 23.8, 23.7 (CCH3), 23.5
(CH(CH3)2), 24.6 (CCH3), 24.4 (CCH3), 24.3 (CH(CH3)2), 23.9 (CH(CH3)2),
(CH(CH3)2). IR (neat): ν = 2964, 2925, 2866, 1531, 1435, 1383, 1314,
˜
12.9 (C5(CH3)5). IR (neat): ν = 3061, 2959, 2925, 2866, 1553, 1520,
1254, 1177, 1018, 937, 873, 797, 724, 690, 530, 468, 417 cm–1
.
˜
1435, 1395, 1316, 1266, 1175, 1099, 1021, 937, 850, 789, 728, 694,
Synthesis of {[L(Cl)Ga](Ph)Sb}2 (11). Benzene (1.0 mL) was added
to a mixture of LGa (50 mg, 0.1026 mmol) and 2 (38 mg,
0.1026 mmol) at ambient temperature and the resulting orange
520, 448 cm–1
.
Synthesis of {[L(Cl)Ga](Ph)As}2 (9). Benzene (1.0 mL) was added
to a mixture of LGa (50 mg, 0.1026 mmol) and 1 (33 mg, solution was heated at 75 °C overnight. The solution was slightly
0.1026 mmol) at ambient temperature and the resulting pale yellow concentrated until incipient crystallization and stored at ambient
solution was heated at 95 °C overnight. Volatiles were removed in temperature for 12 h to yield yellow analytically pure crystals of 11.
vacuo and the residue was dissolved in n-hexane (1.2 mL). Storage
Yield: 38 mg (0.0253 mmol, 51 %). Mp: 171 °C (dec.). Anal. Calcd. for
of the solution at 0 °C for several days afforded pure 9 in form of a
C
70H92Cl2Ga2N4Sb2: C, 58.25; H, 6.42; N, 3.88; found C, 59.4; H, 6.45;
pale yellow solid. Single-crystals of 9 were obtained from a satu- N, 3.82. 1H NMR (300.1 MHz, C6D6): δ 7.30 (t, JHH = 7.6 Hz, 4 H,
rated solution in toluene after storage at 0 °C for 12 h. Yield: 10 mg
(0.0074 mmol, 14 %). Mp: 254 °C. Anal. Calcd. for C70H92As2Cl2Ga2N4: 7.5, 1.6 Hz, 4 H, C6H3(iPr)2), 6.86 (m, 6 H, C6H5 & C6H3(iPr)2), 6.79 (m,
C, 62.29; H, 6.87; N, 4.15; found C, 62.3; H, 6.70; N, 3.94. 1H NMR
4 H, C6H5 & C6H3(iPr)2), 6.51 (m, 6 H, C6H5 & C6H3(iPr)2), 4.87 (s, 2 H,
(400.1 MHz, C6D6): δ 7.30 (t, 3JHH = 7.6 Hz, 4 H, C6H3(iPr)2), 7.21 (dd, γ-CH), 3.81 (sept, JHH = 6.7 Hz, 2 H, CH(CH3)2), 3.50 (sept, JHH
C6H3(iPr)2), 7.22 (dd, JHH = 7.7, 1.6 Hz, 4 H, C6H3(iPr)2), 7.12 (dd, JHH =
3
3
=
JHH = 7.6, 1.5 Hz, 4 H, C6H3(iPr)2), 7.11 (dd, JHH = 7.6, 1.4 Hz, 4 H,
6.7 Hz, 2 H, CH(CH3)2), 3.30 (sept, 3JHH = 6.8 Hz, 2 H, CH(CH3)2), 3.20
3
3
C6H3(iPr)2), 6.91 (d, JHH = 7.7 Hz, 4 H, o-C6H5), 6.84 (dd, JHH = 7.8,
(sept, JHH = 6.8 Hz, 2 H, CH(CH3)2), 1.56 (s, 6 H, CCH3), 1.49 (d,
1.5 Hz, 2 H, C6H3(iPr)2), 6.80 (m, 2 H, p-C6H5), 6.77 (t, JHH = 7.7 Hz, 3JHH = 6.8 Hz, 6 H, CH(CH3)2), 1.46 (d, JHH = 6.7 Hz, 6 H, CH(CH3)2),
3
3
3
3
2 H, C6H3(iPr)2), 6.53 (t, JHH = 7.7 Hz, 4 H, m-C6H5), 6.46 (dd, JHH
=
=
1.45 (s, 6 H, CCH3), 1.28 (d, JHH = 6.8 Hz, 6 H, CH(CH3)2), 1.11 (d,
3
3
7.6, 1.5 Hz, 2 H, C6H3(iPr)2), 4.86 (s, 2 H, γ-CH), 3.85 (sept, JHH
3JHH = 6.8 Hz, 6 H, CH(CH3)2), 1.08 (d, JHH = 6.7 Hz, 6 H, CH(CH3)2),
3
3
6.8 Hz, 2 H, CH(CH3)2), 3.45 (sept, 3JHH = 6.8 Hz, 2 H, CH(CH3)2), 3.21 1.05 (d, JHH = 6.8 Hz, 6 H, CH(CH3)2), 0.99 (d, JHH = 6.7 Hz, 6 H,
3
3
3
(sept, JHH = 6.8 Hz, 2 H, CH(CH3)2), 2.95 (sept, JHH = 6.8 Hz, 2 H,
CH(CH3)2), 0.89 (d, JHH = 6.7 Hz, 6 H, CH(CH3)2). 13C{1H} NMR
3
CH(CH3)2), 1.55 (d, JHH = 6.7 Hz, 6 H, CH(CH3)2), 1.49 (s, 6 H, CCH3),
(75.5 MHz, C6D6): δ = 168.8 (CCH3), 168.4 (CCH3), 145.8 (C6H3(iPr)2),
3
1.42 (d, JHH = 6.7 Hz, 6 H, CH(CH3)2), 1.37 (s, 6 H, CCH3), 1.34 (d, 145.0 (C6H3(iPr)2), 142.8 (C6H3(iPr)2), 142.0 (C6H3(iPr)2), 141.9 (C6H5 &
3
3JHH = 6.7 Hz, 6 H, CH(CH3)2), 1.09 (d, JHH = 6.7 Hz, 6 H, CH(CH3)2),
C6H3(iPr)2), 141.4 (C6H3(iPr)2), 127.5 (C6H5 & C6H3(iPr)2), 126.0 (C6H5 &
C6H3(iPr)2), 125.5 (C6H3(iPr)2), 125.1 (C6H5 & C6H3(iPr)2), 125.0 (C6H5 &
C6H3(iPr)2), 124.2 (C6H3(iPr)2), 123.6 (C6H5 & C6H3(iPr)2), 97.8 (γ-CH),
3
3
1.06 (d, JHH = 6.7 Hz, 6 H, CH(CH3)2), 0.95 (d, JHH = 6.7 Hz, 6 H,
3
3
CH(CH3)2), 0.92 (d, JHH = 6.7 Hz, 6 H, CH(CH3)2), 0.82 (d, JHH
=
6.7 Hz, 6 H, CH(CH3)2). 13C{1H} NMR (100.6 MHz, C6D6): δ = 169.0 30.3 (CH(CH3)2), 30.0 (CH(CH3)2), 28.1 (CH(CH3)2), 28.0 (CH(CH3)2),
(CCH3), 168.7 (CCH3), 145.3 (C6H3(iPr)2), 144.8 (C6H3(iPr)2), 142.8
27.7 (CH(CH3)2), 26.6 (CH(CH3)2), 25.3 (CH(CH3)2), 24.9 (CH(CH3)2),
(C6H3(iPr)2), 142.6 (C6H3(iPr)2), 141.9 (C6H3(iPr)2), 141.3 (C6H3(iPr)2), 24.8 (CH(CH3)2), 24.6 (CH(CH3)2), 24.6 (CH(CH3)2), 23.9 (CCH3), 23.8
139.6 (o-C6H5), 133.2 (i-C6H5), 127.9 (C6H3(iPr)2), 127.6 (C6H3(iPr)2),
126.9 (m-C6H5), 126.5 (p-C6H5), 125.5 (C6H3(iPr)2), 124.9 (C6H3(iPr)2),
(CCH3), 23.0 (CH(CH3)2). IR (neat): ν = 3037, 2964, 2923, 2866, 1530,
1435, 1385, 1316, 1263, 1177, 1018, 942, 863, 796, 756, 723, 687,
˜
124.4 (C6H3(iPr)2), 123.5 (C6H3(iPr)2), 98.2 (γ-CH), 30.0 (CH(CH3)2), 526, 447 cm–1
.
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Synthesis of {[L(Cl)In](Ph)Sb}2 (12). Benzene (1.0 mL) was added
to a mixture of LIn (50 mg, 0.0939 mmol) and 2 (35 mg,
0.0939 mmol) at ambient temperature and the resulting orange
solution was heated at 95 °C for 3 hours. The solution was slightly
concentrated until incipient crystallization and stored at ambient
temperature for 12 h to yield yellow analytically pure crystals of 12.
Yield: 26 mg (0.0170 mmol, 36 %). Mp: 206 °C (dec.). Anal. Calcd. for
sponding centro-symmetric space group Pnma was tried but the
best obtainable R1 was larger than 10 %. Even the anisotropic dis-
placement parameters of the parts matching the special position
were enlarged. It was not possible to refine two alternate positions,
though this model was discarded. In 9 a solvent molecule is disor-
dered. Two alternate positions could be identified and refined,
though the anisotropic displacement parameters suggest further
disorder that could not be modelled sufficiently. All phenylic bond
lengths and the angles of the methyl group were restrained to be
equal (SADI) for all solvent molecules. RIGU restraints were applied
to the anisotropic displacement parameters of the solvent mole-
cules.
C
70H92Cl2In2N4Sb2: C, 54.82; H, 6.05; N, 3.65; found C, 55.3; H, 6.05;
N, 3.56. 1H NMR (300.1 MHz, C6D6): δ 7.27 (t, JHH = 7.6 Hz, 2 H,
C6H3(iPr)2), 7.20 (dd, JHH = 7.7, 1.6 Hz, 2 H, C6H3(iPr)2), 7.11 (dd, JHH
=
7.5, 1.6 Hz, 2 H, C6H3(iPr)2), 6.96 (dd, JHH = 7.7, 1.5 Hz, 2 H,
C6H3(iPr)2), 6.88 (t, JHH = 7.6 Hz, 2 H, C6H3(iPr)2), 6.86 (dd, JHH = 7.6,
1.2 Hz, 4 H, o-C6H5), 6.72 (tt, JHH = 7.6, 1.2 Hz, 2 H, p-C6H5), 6.65
(dd, JHH = 7.6, 1.5 Hz, 2 H, C6H3(iPr)2), 6.44 (t, JHH = 7.6 Hz, 4 H, m-
Deposition Numbers 2021506 (7), –2021507 (11), - 2021508 (5),
2021509 (8), 2021510 (3), 2021511 (4), 2021512 (6), 2021513 (10),
2021514 (9), 2021515 (12) contain the supplementary crystallo-
graphic data for this paper. These data are provided free of
charge by the joint Cambridge Crystallographic Data Centre and
Fachinformationszentrum Karlsruhe Access Structures service
www.ccdc.cam.ac.uk/structures.
3
C6H5), 4.82 (s, 2 H, γ-CH), 3.81 (sept, JHH = 6.7 Hz, 2 H, CH(CH3)2),
3
3
3.70 (sept, JHH = 6.8 Hz, 2 H, CH(CH3)2), 3.28 (sept, JHH = 6.8 Hz, 2
3
H, CH(CH3)2), 3.18 (sept, JHH = 6.8 Hz, 2 H, CH(CH3)2), 1.62 (s, 6 H,
CCH3), 1.53 (s, 6 H, CCH3), 1.39 (d, 3JHH = 6.8 Hz, 6 H, CH(CH3)2), 1.32
3
3
(d, JHH = 6.7 Hz, 6 H, CH(CH3)2), 1.28, (d, JHH = 6.8 Hz, 6 H,
CH(CH3)2), 1.18, (d, JHH = 6.8 Hz, 6 H, CH(CH3)2), 1.14, (d, JHH
6.8 Hz, 6 H, CH(CH3)2), 1.13 (d, JHH = 6.8 Hz, 6 H, CH(CH3)2), 0.97
3
3
=
3
3
3
(d, JHH = 6.7 Hz, 6 H, CH(CH3)2), 0.94 (d, JHH = 6.8 Hz, 6 H,
CH(CH3)2). 13C{1H} NMR (100.6 MHz, C6D6): δ = 169.3 (CCH3), 169.2
(CCH3), 144.7 (C6H3(iPr)2), 144.4 (C6H3(iPr)2), 143.6 (C6H3(iPr)2), 142.9
(C6H3(iPr)2), 142.2 (C6H3(iPr)2), 141.8 (C6H3(iPr)2), 141.5 (C6H5), 127.3
(C6H3(iPr)2), 127.1 (C6H3(iPr)2), 126.4 (C6H5), 125.3 (C6H5), 125.1
(C6H3(iPr)2), 124.9 (C6H3(iPr)2), 124.0 (C6H3(iPr)2), 123.9 (C6H3(iPr)2),
97.0 (γ-CH), 29.8 (CH(CH3)2), 29.6 (CH(CH3)2), 28.0 (CH(CH3)2), 27.7
(CH(CH3)2), 27.0 (CH(CH3)2), 25.0 (CH(CH3)2), 25.0 (CH(CH3)2), 24.8
(CH(CH3)2), 24.5 (CH(CH3)2), 24.3 (CH(CH3)2), 24.3 (CCH3), 24.2 (CCH3),
Acknowledgments
Financial support by the University of Duisburg-Essen, the
German Research Foundation DFG (grant no. SCHU 1069/23-1),
and Evonik Industries (C. H., doctoral fellowship) is gratefully
acknowledged. Open access funding enabled and organized by
Projekt DEAL.
Keywords: Main group elements · Antimony · Arsenic ·
Heterometallic complexes · Radicals
23.4 (CH(CH3)2). IR (neat): ν = 3061, 2961, 2922, 2866, 1521, 1432,
˜
1383, 1314, 1267, 1175, 1099, 1017, 935, 852, 792, 721, 688, 635,
526, 450 cm–1
.
Single-Crystal X-ray Diffraction. Crystals of 3–12 were mounted
on nylon loops in inert oil. Crystallographic data of 3–12 were
collected on a Bruker AXS D8 Kappa diffractometer with APEX2
detector (monochromated Mo-Kα radiation, λ = 0.71073 Å) at
100(2) K and are summarized in Table S1. The structures were
solved by direct methods (SHELXS-97)[44] and refined anisotropically
by full-matrix least-squares on F2 (SHELXL-2014).[45] Absorption cor-
rections were performed semiempirically from equivalent reflec-
tions on the basis of multiscans (Bruker AXS APEX2). Hydrogen
atoms were refined using a riding model or rigid methyl groups. In
12 the benzene molecule is disordered over two positions. Its bond
length and angles were restrained to be equal (SADI) and RIGU
restraints were applied to the anisotropic displacement parameters
of its atoms. In 5 the molecule is disordered by pseudo-mirror-
symmetry. However, one of the positions is occupied by more than
80 %. The occupancy was constrained to a refined value in the final
refinement cycles to avoid correlations. A global RIGU restraint was
applied to all anisotropic displacement parameters. ISOR restraints
with σ = 0.05 were applied to the anisotropic displacement parame-
ters of the minor component. In two cases stricter sigmas were
necessary to avoid non-positive definites. The corresponding bond
lengths of the Cp* ligands were restrained to be equal (SADI). In
addition, all atoms of this ligand except for the ipso-methyl group
were restrained to lie on a mutual plane (FLAT, minor component
only). The bond lengths of the minor component's phenyl ring were
restrained to be equal to 1.39 Å (DFIX) and the angle to be all equal
(SADI). In addition, a FLAT restraint was applied. Due to the severe
disorder and the vast use of restraints and constraints bond lengths
and angles may be unreliable and should only be used carefully.
The model was refined as a 2-component inversion twin. The corre-
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Received: August 6, 2020
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Element–Carbon Bond Homolysis
C. Helling, C. Wölper,
S. Schulz* ........................................... 1–12
Size Matters: Synthesis of Group 13
Metal-Substituted Dipnictanes by
E-C Bond Homolysis
A
series
of
metalylpnictanes dipnictanes {[L(Cl)M](Ph)E}2 by thermal
Al, Ga, In; treatment. The study reveals the dis-
[L(Cl)M](Ph)ECp* (M
=
E = As Sb), which are generally acces- tinct influence of ligand size on the
sible by oxidative addition reaction of reaction mechanism and product for-
Cp*(Ph)ECl and group 13 diyls LM, is mation.
converted into the corresponding
doi.org/10.1002/ejic.202000747
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