Halogenomercury salts of sterically crowded triazenides - Convenient starting materials for redox-transmetallation reactions

Article abstract of DOI:10.1002/zaac.200900482

Diaryl-substituted triazenides Ar(Ar')N₃HgZ [Ar/Ar' = Dmp/Mph, X = Cl (2a), Br (3a), I (4a); Ar/Ar' = Dmp/Tph, X = Cl (2b), I (4b) with Mph = 2-MeSC₆H₄, Mes = 2,4,6-Me₃C₆H ₂, Tph = 2',4',6'

Full text of DOI:10.1002/zaac.200900482

ARTICLE
DOI: 10.1002/zaac.200900482
Halogenomercury Salts of Sterically Crowded Triazenides – Convenient
Starting Materials for Redox-Transmetallation Reactions
Sven-Oliver Hauber,[a] Jang Woo Seo,[a] and Mark Niemeyer*[a]
Keywords: Magnesium; Mercury; Redox transmetallation; Triazenide ligands; Ytterbium
Abstract. Diaryl-substituted triazenides Ar(Ar')N3HgX [Ar/Ar'
=
ytterbium
in
tetrahydrofuran
afforded
the
triazenides
Dmp/Mph, X = Cl (2a), Br (3a), I (4a); Ar/Ar' = Dmp/Tph, X = Cl Dmp(Tph)N3MX(thf) (5b: M = Mg, X = I; 6b: M = Yb, X = Cl) in
(2b), I (4b) with Mph = 2-MesC6H4, Mes = 2,4,6-Me3C6H2, Tph = good yield. All new compounds were characterized by melting point,
2',4',6'-triisopropylbiphenyl-2-yl and Dmp = 2,6-Mes2C6H3] were syn- 1H and 13C NMR spectroscopy and for selected species by IR spectro-
thesized by salt-metathesis reactions in ethyl ether from the readily scopy or mass spectrometry. In addition, the solid-state structures of
available starting materials Ar(Ar')N3Li and HgX2. These compounds triazenides 2a, 2b, 3a, 4b, 5b and 6b were investigated by single-
may be used for redox-transmetallation reactions with rare-earth or crystal X-ray diffraction.
alkaline earth metals. Thus, reaction of 4b or 2b with magnesium or
In this paper, we describe the synthesis and characterization
Introduction
of several halogenomercury triazenides. These compounds are
The design and development of alternative ligand systems,
useful transfer reagents for redox transmetalation reactions
which are able to stabilize monomeric metal complexes while
with electropositive elements such as rare-earth or alkaline
provoking novel reactivity, remains one of the most intensively
earth metals. As a proof of principle the reaction of halogeno-
studied areas of organometallic chemistry [1]. Exploration of
mercury triazenides with magnesium or ytterbium metal was
this field is driven by the potential use of these complexes
examined.
in catalysis and organic synthesis. Examples of monoanionic
chelating N-donor ligands that have received much recent at-
tention include the β-diketiminate [2] and the amidinate [3]
Results and Discussion
ligand systems. Much less attention has been given to the
closely related triazenides [4]. We recently succeeded in the
preparation of derivatives of aryl-substituted, sterically
crowded triazenido ligands that are bulky enough to prevent
undesirable ligand redistribution reactions [5–8]. These ligands
were used to stabilize the first examples of structurally charac-
terized aryl compounds of the heavier alkaline earth metals
calcium, strontium, and barium [5] and unsolvated pentafluo-
rophenyl organyls of the divalent lanthanides ytterbium and
europium [9]. We also examined the unusual “inverse” aggre-
gation behavior of alkali metal triazenides in their solid-state
structures that can be traced back to a different degree of
metal···π-arene interactions to pending aromatic substituents
[6]. A series of homologous potassium and thallium complexes
crystallizes in isomorphous cells and consists of the first exam-
ples of isostructural molecular species reported for these ele-
ments [10].
Synthesis
Diaryl-substituted halogenomercury triazenides Ar(Ar')N3HgX
[Ar/Ar' = Dmp/Mph, X = Cl (2a), Br (3a), I (4a); Ar/Ar' = Dmp/
Tph, X = Cl (2b), I (4b) with Mph = 2-MesC6H4, Mes = 2,4,6-
Me3C6H2, Tph = 2',4',6'-triisopropylbiphenyl-2-yl and Dmp =
2,6-Mes2C6H3] were synthesized by salt-metathesis reactions in
ethyl ether from the readily available starting materials
Ar(Ar')N3Li and HgX2 (Scheme 1). After crystallization from n-
heptane, the yellow compounds were isolated in moderate or
good yields (56–90 %).
The triazenides are air-stable in the solid-state for days and
decompose with evolution of gas in the range 152–194 °C.
Since the used triazenide ligands show an asymmetric substitu-
tion pattern, the existence of isomers with different Hg–N co-
ordination modes, such as η1-NNNAr(Ar'), η1-NNNAr(Ar') or
η2-NNNAr(Ar'), should be possible in principle. However, in
1
the H and 13C NMR spectra only one set of signals is ob-
* PD Dr. M. Niemeyer
E-Mail: mn@lanth.de
served for each compound, which indicates either the absence
of different isomers or, more probably, fast exchange on the
NMR time scale between them. In the IR spectra the asymmet-
ric N–N=N and N–N=N vibration modes νas of the deproto-
nated triazenide ligand appear as medium or strong bands in
the range 1163–1169 cm–1 and 1405–1423 cm–1, which indi-
[a] Institut für Anorganische und Analytische Chemie
Johannes Gutenberg-Universität Mainz
Duesbergweg 10–14
55128 Mainz, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.200900482 or from the
author.
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© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 636, 750–757

Halogenomercury Salts of Sterically Crowded Triazenides
ing Information. Pertinent bond parameters are summarized in
Table 1 and Figure 3 and Figure 4.
Figure 1. Molecular structure of 2a, showing thermal ellipsoids at the
30 % probability level and the numbering scheme. Hydrogen atoms
and minor parts of disordered groups have been omitted for clarity.
Scheme 1. Synthesis of compounds 2a–6d.
cates a mainly localized π-electron system [4a]. These values
are similar to the corresponding vibrations in the protonated
ligands [Dmp(Tph)N3H (1a): 1143/1473 cm–1; Dmp(Mph)N3H
(1b): 1169/1472 cm–1], whereas strong absorptions in the
range 1230–1295 cm–1 are indicative for the triazenides acting
as chelating ligands [5, 6, 9, 10].
In order to test the propensity of the halogenomercury tria-
zenides to act as transfer reagents for redox transmetalation
reactions with rare-earth or alkaline earth metals, we examined
the reaction of 4b with magnesium turnings in tetrahydrofu-
ran as solvent. After an induction period of several hours, dep-
osition of finely divided mercury was observed and stirring
was continued for a total of 3 days. Removal of solvent and
crystallization from n-heptane afforded the deep yellow trans-
metalation product Dmp(Tph)N3MgI(thf) (5b) in 68 % yield.
A similar reaction between the chloromercury triazenide 2b
and ytterbium chips gave the heteroleptic complex
Dmp(Tph)N3YbCl(thf) (6b) in 77 % yield. Although this com-
position together with the oxidation state of the metal was con-
firmed by single-crystal X-ray diffraction (see below) we could
not obtain a reasonable NMR spectrum due to some paramag-
netic impurities that proved difficult to separate by crystalliza-
tion.
Figure 2. Molecular structure of 4b, showing thermal ellipsoids at the
30 % probability level and the numbering scheme. Hydrogen atoms
and minor parts of disordered groups have been omitted for clarity.
The Dmp- and Mph-substituted halogenomercury triazenides
2a and 3a crystallize in isomorphous cells in the space group
¯
P1. Attempts to grow X-ray quality crystals of the iodo deriva-
tive 4a were unsuccessful. Structurally characterized mercury
triazenides have been limited so far to several unsolvated [11]
and solvated bis(diaryltriazenido) species [12], a mercury ni-
Solid-State Structures
Compounds 2a, 2b, 3a, 4b, 5b, and 6b were characterized trate [13] and two heterobimetallic complexes [14]. Very re-
by X-ray crystallography and the molecular structures of 2a, cently, the structural characterization of a donor-stabilized
4b, 5b, and 6b are shown in Figure 1, Figure 2, Figure 3, and mercury chloride was reported [15]. For 2a and 3a the size of
Figure 4. Further molecular plots are provided in the Support- the η1-bonded triazenide ligands enforces the formation of
Z. Anorg. Allg. Chem. 2010, 750–757
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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751

S.-O. Hauber, J. Woo Seo, M. Niemeyer
ARTICLE
Table 1. Selected bond lengths /Å, angles /deg and torsion angles /deg
for the triazenes Ar(Ar')N3HgX.
2a
Dmp/Mph/Cl Dmp/Mph/BrDmp/Tph/Cl Dmp/Tph/I
2.2847(13) 2.404(2) 2.2880(15) 2.5543(6)
3a
2b
4b
Ar/Ar'/X
M–X
M–N3
2.090(3)
2.638(3)
2.856(3)
1.253(4)
1.335(4)
2.972(4)
3.255(4)
3.141(4)
2.946
2.153(12)
2.641(11)
2.862(11)
1.237(15)
1.321(16)
2.975(14)
3.297(15)
3.125(15)
2.950
2.084(4)
2.737(4)
2.895(4)
1.267(5)
1.328(5)
2.917(5)
3.221(5)
3.172(5)
2.920
2.100(4)
2.674(4)
2.864(4)
1.289(6)
1.322(6)
3.049(5)
3.425(6)
3.245(5)
3.068
M···N1
M···N2
N1–N2
N2–N3
M···C41
M···C42
M···C46
M···X3
X–M–N3
174.64(9)
N2–N1–C11–C16 50.4(5)
N2–N3–C31–C36 –28.8(5)
173.2(3)
51.1(1.7)
–29(2)
175.71(11) 175.58(12)
–42.0(6)
13.7(6)
–36.2(8)
18.3(7)
Figure 3. Molecular structure of 5b, showing thermal ellipsoids at the
30 % probability level and the numbering scheme. Hydrogen atoms
have been omitted for clarity. Selected bond lengths /Å, angles /deg
and torsion angles /deg: Mg–N1 = 2.074(3), Mg–N3 = 2.112(3),
Mg···N2 = 2.537(3), Mg–I = 2.6424(13), Mg–O51 = 1.975(2), N1–
N2 = 1.319(3), N2–N3 = 1.314(3), O51–Mg–I = 111.87(8), N2···Mg–
I = 117.61(7), N2···Mg–O51 = 129.39(10), N1–Mg–N3 = 61.92(9),
2.090(3) Å (2a) and 2.153(12) Å (3a) are similar or slightly
longer than the corresponding distances in three structurally
characterized homoleptic mercury triazenides [2.060(5)–
2.077(4) Å] [11], a triazenidomercury nitrate [2.101(8) Å] [13]
and a donor-stabilized triazenidomercury chloride [2.075(4) Å]
N1–N2–N3 = 109.8(2), N2–N1–C11–C16 = –17.2(4), N2–N3–C31– [15]. Much longer distances are observed to the Dmp-bonded
C36 = 45.6(4).
nitrogen atom N1 and the central nitrogen atom N2 with values
> 2.63 Å and > 2.85 Å, respectively. Within the triazenido li-
gand cores, the rather different N1–N2 and N2–N3 distances
of 1.253(4)/1.335(4) Å (2a) and 1.237(15)/1.321(16) Å (3a)
are in agreement with the observed η1-N-bonding mode. The
different steric properties of the biphenyl- and m-terphenyl
substituents give rise to a different conformation with respect
to the central N3 plane. The C6H4 ring of the biphenyl moiety
adopts a roughly coplanar arrangement (N2–N3–C31–C36
–28.8(5) [2a], –29(2) [3a]), whereas the central C6H3 plane of
the terphenyl substituent is significantly more tilted (N2–N1–
C11–C16 50.4(5) [2a], 51.1(1.7) [3a]) to minimize repulsive
interactions between N2 and one of the Mes rings (C61→C66).
One interesting feature in the solid-state structures of 2a and
3a is the presence of an additional metal···η3-π-arene contact
to the (C41→C46) Mes ring of the flanking Mph group with
relatively short Hg···C distances in the range 2.972(4)–
3.255(4) Å (2a) or 2.975(14)–3.297(15) Å (3a) and corre-
sponding Hg···centroid (X3) separations of 2.946 Å and
2.950 Å, respectively. The propensity of mercury to interact
with aromatic groups is now well documented. Examples are
packing complexes of mercury perfluoroaryls with arenes {e.g.
Hg3(o-C6F4)3(arene) [16] or Hg(C6F5)2(arene) [17]} and inter-
or intramolecular contacts between mercury and arene rings of
aryl substituents in organometallic [e.g. Hg(CH2Ph)2 [18a] or
HgDmp2 [18b]) or coordination compounds (e.g. weak inter-
molecular coordination in mercury triazenides: [11, 12]) with
typical Hg···C distances in the range 3.15–3.50 Å. Considera-
bly shorter mercury···arene interactions are observed in arene
complexes of inorganic mercury salts [Hg2(O2CCF3)4(η2-
Figure 4. Molecular structure of dimeric 6b, showing thermal ellip-
soids at the 30 % probability level and the numbering scheme. Hydro-
gen, methyl carbon and isopropyl carbon atoms have been omitted for
clarity. Selected bond lengths /Å, angles /deg and torsion angles /deg:
Yb1–N1 = 2.439(6), Yb1–N3 = 2.530(6), Yb2–N4 = 2.440(6), Yb2–
N6 = 2.547(6), Yb1–Cl1 = 2.751(2), Yb1–Cl2 = 2.782(2), Yb2–Cl1 =
2.783(2), Yb2–Cl2 = 2.732(2), Yb1–O1 = 2.390(6), Yb2–O2 =
2.387(6), Yb1···C26 = 3.032(8), Yb1···C25 = 3.085(9), Yb2···C72 =
3.023(8), Yb2···C73 = 3.198(8), N1–Yb1–N3 = 51.5(2), N4–Yb2–
N6 = 51.52(19), Cl1–Yb1–Cl2 = 80.89(6), Cl1–Yb2–Cl2 = 81.20(6),
Yb1–Cl1–Yb2 = 98.59(7), Yb2–Cl2–Yb1 = 99.08(7), N2–N1–C11–
C16 = 14.3(12), N2–N3–C41–C46 = –47.0(9), N5–N4–C61–C66 =
12.1(11), N5–N6–C91–C96 = –44.1(9).
strictly monomeric compounds in which the metal atoms show C6Me6)2] (2.56, 2.58 Å) [19a] or Hg(arene)2(MCl4)2] [M = Ga,
a linear coordination by the Mph-bonded nitrogen atom N3 Al; arene = C6H5Me, C6H5Et, 1,2-C6H4Me2, 1,2,3-C6H3Me3]
and one halogen atom, respectively. The Hg–N3 distances of (2.27–2.74 Å) [19b].
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Z. Anorg. Allg. Chem. 2010, 750–757

Halogenomercury Salts of Sterically Crowded Triazenides
In contrast to isomorphous 2a and 3a, the Dmp- and Tph- ces reflect the lower donor ability of the triazenide relative to
substituted halogenomercury triazenides 2b and 4b crystallize the amidinate and β-diketiminate ligands.
¯
in different cell settings in the space group P1 and P21/n, re-
Triazenido ytterbium chloride (6b) crystallizes as a dimer,
spectively. Figure 2 shows the molecular structure of the iodo and its molecular structure is shown in Figure 4. In the dimeric
complex 4b. The average Hg–N3 distances of 2.084(4) Å [2b] units the metal atoms are bridged by chlorine atoms, therefore
or 2.100(4) Å [4b] to the η1-coordinate triazenide ligand are forming a central, almost planar Yb2Cl2 ring. The dimers have
very close to the corresponding values in the previously dis- non-crystallographic symmetry close to C2 with the twofold
cussed compounds. Additional metal···η3-π-arene are observed axis running perpendicular to the Yb2Cl2 core. However, the
to the Trip ring (C41→C46) of the flanking biaryl group. With symmetry is broken by slight but significant conformational
Hg···C distances of 2.917(5)–3.221(5) Å and a Hg···centroid differences between the two halves and the presence of four
separation of 2.920 Å these secondary interactions are stronger additional co-crystallized toluene molecules that are located in
for the chloro than for the iodo (3.049(5)–3.425(6) Å / solvent accessible cavities of the structure. Each ytterbium
3.068 Å) derivative.
atom is bonded to two chlorine atoms, two nitrogen atoms of
Because of the different steric properties of the Dmp and a η2-bonded triazenide ligand and the oxygen atom of a THF
Tph substituents and inter-ligand repulsion the N2–N1–C11– molecule. If only one coordination site is assigned to the small-
C16 (–42.0(6) [2b], –36.2(8) [4b]) and N2–N3–C31–C36 bite angle triazenido ligands, a distorted square-planar coordi-
(13.7(6) [2b], 18.3(7) [4b]) torsion angles differ by approx. nation results for both ytterbium atoms as can be judged by
28° [2b] and 18° [4b]. Therefore, a different interaction of the the angles N2/N5–Yb1/Yb2–Cl2/Cl1 and O1/O2–Yb1/Yb2–
π-system of the central NNN fragment with that of the substi- Cl1/Cl2 that are in the range 160.3–163.8°. An additional
tuted C6H4 rings is anticipated. As in the Dmp/Mph com- metal···η2-π-arene contact to ortho and meta carbon atoms of
pounds, these conformational differences, together with steric a Mes ring of the flanking Dmp substituents with Yb···C dis-
factors, are probably responsible for the higher nucleophilicity tances of 3.023(8)–3.198(8) Å extends the coordination for
of the biphenyl-substituted nitrogen atom N3. This explanation each metal atom to tetragonal-pyramidal. The bonding of the
is supported by the observation of disordered mercury sites triazenide ligands is slightly asymmetric with shorter and
with minor site occupation factors in the range 0.017–0.039 longer Yb–N bond lengths of 2.439(6)/2.440(6) Å and
for complexes 2a, 3a and 4b that correspond to a Hg–η1-N1 2.530(6)/2.547(6) Å, respectively. The average Yb–N distance
coordination mode with bonding to the terphenyl-substituted of 2.489 Å is longer than that of the heteroleptic ytterbium
nitrogen atom (see Experimental Section and Supporting Infor- triazenide [Yb{N3(Dmp)Tph}C6F5] (2.445 Å) the currently
only structurally characterized triazenide available for compar-
ison [9]. Shorter M–N distances are observed in some tetraco-
ordinate homoleptic ytterbium amidinates (2.38–2.39 Å) [23]
and diketiminates (2.37–2.41 Å) [24] therefore reflecting the
lower coordination number and the stronger donor character of
the chelating N-donor ligands in these compounds. For 6b,
the average Yb–Cl and Yb–O bond lengths of 2.762(2) Å and
2.389(6) Å are in accordance with the presence of divalent
metal atoms. Similar values are observed for the YbII complex
[Yb{N(Dip)SiMe3}(μ-Cl)(thf)2]2 (av. Yb–Cl 2.72 Å, Yb–O
2.40 Å) [25], that features a pentacoordinate metal atom,
whereas the corresponding distances for some structurally re-
lated YbIII compounds such as [Yb{N(Ph)SiMe3}2(μ-Cl)(thf)]2
(av. Yb–Cl 2.67 Å, Yb–O 2.32 Å) [25], [Yb{N(SiMe3)2}2(μ-
Cl)(thf)]2 (av. Yb–Cl 2.68 Å, Yb–O 2.35 Å) [26a] or
mation). For these compounds the difference of the N2–N1–
C11–C16 and N2–N3–C31–C36 torsion angles is smaller than
in complex 2b which shows no disorder of the mercury atom.
In the triazenido magnesium iodide (5b) the magnesium
atom has a very distorted tetrahedral coordination with angles
in the range 61.92(9)–125.20(11)° by two nitrogen atoms N1
and N3 of a η2-bonded triazenide ligand, a chlorine atom and
the oxygen atom O51 of a THF molecule. In an alternative
description that assigns only one coordination site (represented
by the central nitrogen atom N2) to the small-bite triazenido
ligand the metal atom shows a trigonal planar coordination
with corresponding angles of 111.87(8)–129.39(10)°. With
1.319(3) Å and 1.314(3) Å the N–N distances are consistent
with delocalized bonding. The coordination of the triazenide
ligand is slightly asymmetric with Mg–N bond lengths of
2.074(3) Å and 2.112(3) Å. The average Mg–N distance of
2.093 Å is shorter than that of the six-coordinate magnesium
triazenide [Mg{N3Tol2}2(thf)2] (2.183 Å with Tol = 4-Me-phe-
nyl) the currently only structurally characterized triazenide
available for comparison [20]. Shorter Mg–N bonds but longer
Mg–I and Mg–O distances are observed in the heteroleptic
[Yb{N(tBu)SiMe2SiMe2(tBu)N}(μ-Cl)(thf)]2
(av.
Yb–Cl
2.70 Å, Yb–O 2.31 Å) [26b] are considerably shorter, as one
might expect.
β-diketiminate (Dip-nacnac)2MgI(OEt2) [Dip-nacnac
(Dip)NC(Me)C(H)C(Me)N(Dip) with Dip = 2,6-iPr2C6H3]
(Mg–N 2.040(3) Å, Mg–I 2.689(1) Å, Mg–O
=
Conclusions
=
=
=
Monomeric unsolvated triazenido mercury halides were syn-
thesized and structurally characterized for the first time. We
have shown that these compounds may be used for the prepara-
tion of triazenido magnesium and ytterbium halides. We antici-
2.010(3) Å] [21] and a number of homoleptic magnesium ami-
dinates Mg{RNC(R')NR}2 (R = tBu, R' = Ph, av. Mg–N =
2.042(2) Å [22a]; R = iPr, R' = Dmp, av. Mg–N = 2.04(1) Å
[22b]; R = Mes, R' = tBu, av. Mg–N = 2.041(3) Å [22c]; R = pate a similar reactivity for redox-transmetallation reactions
Dip, R' = Tol, av. Mg–N = 2.058(2) Å [22d]). These differen- with other alkaline earth and rare-earth elements.
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753

S.-O. Hauber, J. Woo Seo, M. Niemeyer
ARTICLE
+
MS (70eV, 430 K): m/z (%) 195.1 (38.4) [MesC6H4 ], 313.3 (100)
Experimental Section
[2,6-Mes2C6H3–H+], 341.2 (15.1) [2,6-Mes2C6H3N2+], 523.4 (10.3)
[(2,6-Mes2C6H3)(C6H4Mes)NH+], 831.3 (2.4) [M+].
General Remarks
All manipulations were performed by using standard Schlenk tech-
niques in an inert atmosphere of purified argon and solvents freshly
distilled from sodium wire or LiAlH4. The triazenes Dmp(Mph)N3H
or Dmp(Tph)N3H [5] were synthesized as described previously. NMR
spectra were recorded in C6D6 with Bruker AM200, AC250 or AM400
instruments and referenced to solvent resonances. IR spectra were ob-
tained in the range 4000–200 cm–1 with a Perkin–Elmer paragon 1000
PC (Nujol mulls) or a Nicolet 6700 FT-IR (reflection data) spectrome-
ter. Mass spectra were recorded with a Varian MAT711 or Finnegan
MAT95 instrument. Melting points were determined under argon at-
mosphere in sealed glass tubes. No elemental analysis data for com-
pounds 2a–4b could be obtained due to mercury contamination prob-
lems. Therefore, purity of these compounds was proven by combined
NMR and mass spectrometry experiments.
Iodo-{[[N'-2-(2',4',6'-trimethyl)biphenyl]-(N'''-2,4,6,2'',4'',6''-
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (4a):
The synthesis was accomplished in a similar manner to the preparation
of 2a with use of triazene (1a) (1.10 g, 2 mmol), n-BuLi in n-hexane
(0.80 mL, 2.5 m, 2 mmol) and HgI2 (0.91 g, 2 mmol). Yield: 1.12 g
(1.17 mmol, 58 %); Mp: 192–194 °C. 1H NMR (400.1 MHz): δ =
1.63 (s, 6 H, o-CH3, biphenyl), 2.11 (s, 12 H, o-CH3, terphenyl), 2.24
(s, 3 H, p-CH3, biphenyl), 2.26 (s, 6 H, p-CH3, terphenyl), 6.73 (s, 2
H, m-Mes, biphenyl), 6.88 (s, 4 H, m-Mes, terphenyl), 6.73–7.17 (m,
7 H, various aryl-H). 13C NMR (100.6 MHz): δ = 20.3 (o-CH3, bi-
phenyl), 21.0 (o-CH3, terphenyl), 21.3 (p-CH3, terphenyl), 21.5 (p-
CH3, biphenyl), 120.1, 123.8, 126.2, 128.2, 129.0, 129.2, 129.6, 130.3
(aromatic CH), 128.3, 133.6, 135.1, 135.8, 136.5, 136.8, 137.6, 138.8,
143.6, 143.9 (aromatic C). IR (Nujol): 1716 w, 1699 w, 1611 m, 1557
w, 1436 w, 1418 w, 1316 m br, 1205 m, 1169 m br, 1099 m, 1069 w,
1026 m br, 981 m, 846 s, 806 s, 789 m, 759 s, 734 m, 688 m, 651 s,
697 m, 572 w, 511 m, 496 m, 462 m, 438 m cm–1. EI-MS (70eV,
420 K): m/z (%) 195.1 (45.4) [MesC6H4+], 313.2 (100) [2,6-
Mes2C6H3–H+], 341.2 (16.2) [2,6-Mes2C6H3N2+], 523.3 (8.2) [(2,6-
Mes2C6H3)(C6H4Mes)NH+], 897.2 (2.7).
Preparation of the Triazenido Mercury Halides
Chloro-{[[N'-2-(2',4',6'-trimethyl)biphenyl]-(N'''-2,4,6,2'',4'',6''-
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (2a):
To a stirred solution of 1a (1.10 g, 2 mmol) in ethyl ether (20 mL),
which was cooled in an ice bath was added n-BuLi in n-hexane
(0.80 mL, 2.5 m, 2 mmol) and stirring was continued for 30 min at the
same temperature. HgCl2 (0.54 g, 2.00 mmol) was afterwards added in
one portion and the resulting mixture was stirred at ambient tempera-
ture for 4 h. The volatile materials were removed under reduced pres-
sure and the remaining solid was extracted with n-heptane (20 mL).
After separation of the precipitated lithium halide by centrifugation the
filtrate was concentrated to incipient crystallization. Cooling in a
–20 °C freezer afforded 2a as yellow crystals. Yield: 0.88 g
(1.12 mmol, 56 %); Mp: 165–167 °C. 1H NMR (250.1 MHz): δ =
1.60 (s, 6 H, o-CH3, biphenyl), 2.11 (s, 12 H, o-CH3, terphenyl), 2.24
(s, 3 H, p-CH3, biphenyl), 2.26 (s, 6 H, p-CH3, terphenyl), 6.76 (s, 2
H, m-Mes, biphenyl), 6.89 (s, 4 H, m-Mes, terphenyl), 6.71–7.11 (m,
7 H, various aryl-H). 13C NMR (62.9 MHz): δ = 20.2 (o-CH3, bi-
phenyl), 21.0 (o-CH3, terphenyl), 21.2 (p-CH3, terphenyl), 21.3 (p-
CH3, biphenyl), 120.2, 123.8, 126.4, 128.3, 128.7, 129.5, 129.8, 130.3
(aromatic CH), 128.8, 132.9, 135.1, 135.7, 136.6, 136.8, 137.5, 139.2,
143.5, 143.6 (aromatic C). IR (Nujol): 1716 w, 1699 w, 1611 m, 1557
w, 1436 w, 1418 w, 1316 m br, 1206 m, 1186 m, 1164 m br, 1098 m,
1030 m br, 982 m, 911 w, 847 s, 805 ms, 790 m, 761 s, 735 m, 691
m, 652 s, 597 s, 576 m, 514 s, 499 m, 463 m, 463 m, 443 m cm–1.
Chloro-{[[N'-2-(2',4',6'-triisopropyl)biphenyl]-(N'''-2,4,6,2'',4'',6''-
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (2b):
The synthesis was accomplished in a similar manner to the preparation
of 2a with use of triazene (1b) (1.27 g, 2.00 mmol), n-BuLi in n-
hexane (0.80 mL, 2.5 m, 2 mmol) and HgCl2 (0.59 g, 2.17 mmol).
1
Yield: 1.46 g (1.68 mmol, 84 %); Mp: 173–175 °C (dec.). H NMR
3
(400.1 MHz): δ = 0.87, 0.90 (2 × d, JHH = 6.7 Hz, 2 × 6 H, o-
3
CH(CH3)2), 1.32 (d, JHH = 6.7 Hz, 6 H, p-CH(CH3)2), 2.11 (s, 12 H,
3
o-CH3), 2.24 (s, 6 H, p-CH3), 2.47 (sep, JHH = 6.7 Hz, 2 H, o-
3
CH(CH3)2), 2.86 (sep, JHH = 6.7 Hz, 1 H, p-CH(CH3)2), 6.69 (d,
3
3JHH = 8.2 Hz, 1 H, 6-C6H4), 6.85 (t, JHH = 7.7 Hz, 1 H, 4-C6H4),
6.88 (d, 1 H, 3-C6H4), 6.90 (s, 4 H, m-Mes), 7.00 (m, 2 H, m-C6H3),
7.06 (m, 1 H, p-C6H3), 7.12 (t, 1 H, 5-C6H4), 7.14 (s, 2 H, m-Trip).
13C NMR (100.6 MHz): δ = 21.0 (o-CH3), 21.2 (p-CH3), 24.1, 24.2
(o-CH(CH3)2), 24.7 (p-CH(CH3)2), 30.5 (o-CH(CH3)2), 34.8 (p-
CH(CH3)2), 119.3 (6-C6H4), 122.9 (4-C6H4), 123.0 (m-Trip), 126.6 (p-
C6H3), 128.6 (5-C6H4), 128.8 (m-Mes), 129.8 (m-C6H3), 131.2 (3-
C6H4), 127.0, 131.3, 135.2, 135.4, 136.5, 137.7, 143.4, 144.2, 147.6,
151.1 (aromatic C).
+
Iodo-{[[N'-2-(2',4',6'-triisopropyl)biphenyl]-(N'''-2,4,6,2'',4'',6''-
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (4b):
The synthesis was accomplished in a similar manner to the preparation
of 2a with use of triazene (1b) (0.83 g, 1.30 mmol), 0.52 mL of a
EI-MS (70eV, 430 K): m/z (%) 195.0 (32.6) [MesC6H4 ], 313.2 (100)
[2,6-Mes2C6H3–H+], 341.2 (12.4) [2,6-Mes2C6H3N2+], 523.3 (3.1)
[(2,6-Mes2C6H3)(C6H4Mes)NH+], 787.3 (2.7) [M+].
Bromo-{[[N'-2-(2',4',6'-trimethyl)biphenyl]-(N'''-2,4,6,2'',4'',6''- 2.5 m n-BuLi solution in n-hexane (0.52 mL, 2.5 m, 1.3 mmol) and
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N'}mercury (3a): HgI2 (0.70 g, 1.54 mmol). Yield: 1.14 g (1.18 mmol, 90 %); Mp:
1
3
The synthesis was accomplished in a similar manner to the preparation 152 °C (dec.). H NMR (250.1 MHz): δ = 0.91, 0.92 (2 × d, JHH
=
3
of 2a with use of triazene (1a) (1.10 g, 2 mmol), n-BuLi in n-hexane 6.8 Hz, 2 × 6 H, o-CH(CH3)2), 1.31 (d, JHH = 6.8 Hz, 6 H, p-
(0.80 mL, 2.5 m, 2 mmol) and HgBr2 (0.72 g, 2 mmol). Yield: 0.98 g CH(CH3)2), 2.21 (s, 12 H, o-CH3), 2.22 (s, 6 H, p-CH3), 2.51 (sep,
(1.18 mmol, 59 %); Mp: 161–163 °C. 1H NMR (200.1 MHz): δ = 3JHH = 6.8 Hz, 2 H, o-CH(CH3)2), 2.88 (sep, JHH = 6.8 Hz, 1 H, p-
3
1.61 (s, 6 H, o-CH3, biphenyl), 2.11 (s, 12 H, o-CH3, terphenyl), 2.24 CH(CH3)2), 6.97–7.01 (m, 7 H, various aryl-H), 6.89 (s, 4 H, m-Mes),
(s, 3 H, p-CH3, biphenyl), 2.26 (s, 6 H, p-CH3, terphenyl), 6.75 (s, 2 7.11 (s, 2 H, m-Trip). 13C NMR (62.9 MHz): δ = 21.1 (o-CH3), 21.2
H, m-Mes, biphenyl), 6.89 (s, 4 H, m-Mes, terphenyl), 6.70–7.19 (m, (p-CH3), 24.2, 24.5, 24.7 (o/p-CH(CH3)2), 30.6 (o-CH(CH3)2), 34.5
7 H, various aryl-H). 13C NMR (50.3 MHz): δ = 20.2 (o-CH3, bi- (p-CH(CH3)2), 119.0, 121.8, 122.9, 123.4, 126.3, 128.3, 130.0, 131.4
phenyl), 21.0 (o-CH3, terphenyl), 21.2 (p-CH3, terphenyl), 21.3 (p- (aromatic C-H), 129.7, 134.7, 135.5, 136.4, 137.9, 143.6, 144.6, 147.5,
CH3, biphenyl), 120.2, 123.8, 126.4, 128.3, 128.8, 129.5, 130.0, 130.3, 150.7 (aromatic C); one aromatic C signal could not be observed. IR
(aromatic CH), 129.0, 133.1, 135.1, 135.1, 136.6, 136.8, 137.5, 139.0, (Nujol) 1612 s, 1592 ms, 1568 s, 1313 vs, 1288 s, 1207 s, 1189 s,
143.6 (aromatic C); one aromatic C signal could not be observed. EI- 1166 vs. br, 1092 s, 1069 ms, 1054 ms, 1003 m, 978 m, 946 w, 937
754
www.zaac.wiley-vch.de
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2010, 750–757

Halogenomercury Salts of Sterically Crowded Triazenides
Table 2. Selected Crystallographic Data for Compounds 2a, 2b, and 3aa).
2a
3a
2b
Formula
C39H40ClHgN3
786.78
C39H40BrHgN3
831.24
C45H52ClHgN3
870.94
Formula weight
Color, habit
Crystal size/mm
Crystal system
Space group
a /Å
pale yellow, prism
0.35 × 0.25 × 0.20
triclinic
pale yellow, prism
0.30 × 0.25 × 0.15
triclinic
yellow, prism
0.38 × 0.35 × 0.30
triclinic
¯
¯
¯
P1
P1
P1
8.2637(18)
11.088(3)
18.861(5)
82.56(2)
89.950(19)
88.89(2)
1713.3(7)
2
8.384(6)
11.031(8)
18.944(9)
82.81(5)
89.32(5)
88.16(5)
1737(2)
2
12.401(3)
12.623(3)
15.146(3)
79.997(15)
84.084(15)
61.170(16)
2045.0(8)
2
b /Å
c /Å
α /°
β /°
γ /°
V /Å3
Z
dcalc /g·cm–3
1.525
46.00
1.589
56.10
1.414
3.862
μ /cm–1
2θ range/°
Collected data
Unique data (Rint)
Data with I > 2σ (I) (No)
No. of parameters (Np)
R1 (I > 2σ (I))b)
wR2 (all data)c)
4.0–56.0
8499
3.7–50.4
6414
3.7–54.0
9346
8035 (0.019)
7425
5975 (0.056)
4263
8923 (0.049)
7523
421
398
467
0.033
0.079
0.043
0.086
0.211
0.101
d)
GOF
1.159
1.256
1.174
Resd. dens./e·Å–3
1.61 and –1.92
3.32 and –3.34
1.99 / –1.04
2
2 2
a) All data were collected at 173 K using Mo-Kα (λ = 0.71073 Å) radiation. b) R1 = Σ(--Fo- – -Fc--).Σ (-Fo-. c) wR2 = {Σ [w(Fo –Fc ) ].
2 2
2
2 2
Σ[w(Fo ) ]}1.2. d) GOF = {Σ [w(Fo –Fc ) ]. (No–Np).
ms, 879 s, 864 m, 848 vs, 805 s, 788 s, 779 m, 764 vs, 755 vs. br,
740 s, 723 s, 692 m, 656 ms, 602 w, 594 m, 491 w cm–1.
cess of ytterbium chips (0.71 g, 4.10 mmol) and the stirred mixture
was heated for 2 min to 50 °C. A color change to brown was observed
and stirring was continued for 20 h at ambient temperature. The vola-
tile materials were removed under reduced pressure and the remaining
solid was extracted with an n-heptane/toluene 2:1 solvent mixture
(60 mL). Solid byproducts were separated by centrifugation and the
filtrate was concentrated to incipient crystallization. Storage at –10 °C
for 3 days afforded 6b·(toluene)2 as dark red crystals. Yield: 0.98 g
(0.89 mmol, 77 %); Mp: 68–180 °C (dec.); Because of paramagnetic
impurities no NMR spectra could be obtained. For the following char-
acterization the co-crystallized toluene was removed in vacuum.
C49H60ClN3OYb (915.5): C 64.36 (calcd. 64.28); H 6.73 (6.61); N 4.51
(4.59) %. IR (Nujol) 1604 s, 1581 ms, 1568 s, 1432 vs, 1360 s, 1310
s, 1291 vs, 1255 vs. br, 1232 vs. br, 1218 vs, 1178 s, 1106 ms, 1076
ms, 1056 m, 1031 vs. br, 1004 s, 953 m, 936 ms, 920 w, 908 w, 876
vs, 847 vs, 800 ms, 788 m, 781 ms, 769 s, 752 vs, 739 s, 727 vs, 694
s, 678 ms, 653 ms, 622 w, 600 w, 586 m, 576 w, 551 w, 523 m, 506
m, 464 ms, 409 w cm–1. EI-MS (70eV, 520 K): m/z (%) 195.0 (12.4)
Redox Transmetallation Reactions
Iodo-{[[N'-2-(2',4',6'-triisopropyl)biphenyl]-(N'''-2,4,6,2'',4'',6''-
hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-N',N'''}-
(tetrahydrofuran-O)-magnesium (5b): A solution of 4b (0.63 g,
1 mmol) in tetrahydrofuran (40 mL) was added to an excess of magne-
sium turnings and the mixture was stirred for 3 d at ambient tempera-
ture. The volatile materials were removed under reduced pressure and
the remaining solid was extracted with n-heptane (40 mL). Solid by-
products were separated by centrifugation and the filtrate was concen-
trated to incipient crystallization. Storage at ambient temperature for
several days afforded 5b as deep yellow crystals. Yield: 0.58 g
(0.68 mmol, 68 %); Mp: 70–120 °C (dec.). C49H60IMgN3O (858.2):
C 69.19 (calcd. 68.58); H 7.02 (7.05); N 4.87 (4.90) %. 1H NMR
3
(400.1 MHz): δ = 1.02, 1.15 1.29 (3 × d, JHH = 6.8 Hz, 3 × 6 H, o-
[MesC6H4 ], 312.1 (100) [2,6-Mes2C6H3–H+], 341.1 (6.2) [2,6-
+
+ p-CH(CH3)2), 1.11 (m, 4 H, OCH2CH2); 2.15 (s, 12 H, o-CH3), 2.21
Mes2C6H3N2 ], 607.3 (44.1) [(2,6-Mes2C6H3)(C6H4Trip)NH+], 916.4
+
3
(s, 6 H, p-CH3), 2.60 (sep, JHH = 6.8 Hz, 2 H, o-CH(CH3)2), 2.84
(14.5) [M+].
3
(sep, JHH = 6.8 Hz, 1 H, p-CH(CH3)2), 3.06 (m, 4 H, OCH2CH2),
6.79–7.12 (m, 13 H, various aryl-H). 13C NMR (100.6 MHz): δ =
21.2, 21.6 (o/p-CH3), 24.3, 24.3, 25.0 (o/p-CH(CH3)2), 25.3
(OCH2CH2), 30.4 (o-CH(CH3)2), 34.8 (p-CH(CH3)2), 70.1(OCH2CH2),
113.8, 121.2, 121.5, 125.0, 128.9, 129.7, 130.5, (aryl CH), 123.8,
132.0, 133.9, 136.0, 139.6, 139.6, 143.9, 147.3, 148.3, 149.5 (aryl C);
one aromatic CH signal could not be observed.
X-ray Crystallographic Studies
X-ray-quality crystals were obtained as described in the Experimental
Section. Crystals were removed from Schlenk tubes and immediately
covered with a layer of viscous hydrocarbon oil (Paratone N, Exxon).
A suitable crystal was selected, attached to a glass fiber, and instantly
Bis[μ-chloro-{[[N'-2-(2',4',6'-triisopropyl)biphenyl]-(N'''- placed in a low-temperature N2-stream [27a]. All data were collected at
2,4,6,2'',4'',6''-hexamethyl-1,1':3',1''-terphen-2'-yl)]triazenido-
173 K using either a Siemens P4 (3a) or a rebuilt Syntex P21/Siemens
N',N'''}(tetrahydrofuran-O)-ytterbium] (6b): A solution of 2b P3 (2a, 2b, 4b–6b) diffractometer. Selected data collection parameters
(1.01 g, 1.15 mmol) in tetrahydrofuran (40 mL) was added to an ex- and other crystallographic data are summarized in Table 2 and Table 3.
Z. Anorg. Allg. Chem. 2010, 750–757
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
755

S.-O. Hauber, J. Woo Seo, M. Niemeyer
ARTICLE
Table 3. Selected Crystallographic Data for Compounds 4b, 5b, and 6ba).
4b
5b
(6b)2·(C7H8)3
Formula
C45H52HgIN3
962.39
yellow, prism
0.35 ! 0.25 ! 0.25
monoclinic
P21.c
8.8388(11)
21.681(3)
21.817(2)
C49H60IMgN3O
858.21
yellow, prism
0.50 ! 0.30 ! 0.15
monoclinic
P21.n
9.6393(18)
39.797(6)
12.926(2)
C119H144Cl2N6O2Yb2
2107.38
Formula weight
Color, habit
Crystal size.mm
Crystal system
Space group
a .Å
dark red, prism
0.55 ! 0.25 ! 0.15
triclinic
P1
14.079(3)
15.807(4)
25.661(7)
77.000(19)
81.487(19)
82.425(19)
5474(2)
b .Å
c .Å
α .°
ꢀ .°
93.059(10)
110.65(2)
γ .°
V .Å3
4174.9(9)
4
1.531
44.59
4640.0(13)
4
1.229
7.40
Z
2
dcalc. .g·cm–3
1.278
μ .cm–1
17.97
2θ range .deg
Collected data
Unique data (Rint)
Data with I > 2σ (I) (No)
No. of parameters (Np)
R1 (I>2σ (I))b)
wR2 (all data)c)
3.7–54.0
9692
3.5–52.0
9826
3.2–54.0
24790
9103 (0.037)
6670
9100 (0.029)
5989
23799 (0.046)
16108
471
513
1168
0.050
0.050
0.081
0.106
0.102
0.190
d)
GOF
1.214
1.359
1.450
Resd. dens..e·Å–3
1.31 . –1.44
0.54 . –0.62
3.11 . –1.13
2
2 2
a) All data were collected at 173 K using Mo-Kα (λ = 0.71073 Å) radiation. b) R1 = Σ(--Fo- – -Fc--).Σ (-Fo-. c) wR2 = {Σ [w(Fo –Fc ) ].
2 2
2
2 2
Σ[w(Fo ) ]}1.2. d) GOF = {Σ [w(Fo –Fc ) ]. (No–Np).
Calculations were carried out with the SHELXTL PC 5.03 [27b] and
SHELXL-97 [27c], program system installed on local personal comput-
ers. The phase problem was solved by direct methods and the structures
Supporting Information (see footnote on the first page of this article):
Molecular structures of 2a, 2b, 3a, 4b, 5b, and 6b showing the full
numbering scheme. Molecular plots showing the disorder in 2a, 3a,
and 4b.
2
were refined on Fo by full-matrix least-squares refinement. Absorption
corrections were applied by using semiempirical ψ-scans. Anisotropic
thermal parameters were refined for all non-hydrogen atoms, except
some carbon atoms of disordered THF molecules. The hydrogen atoms
were positioned at distances of 1.00 (CH), 0.99 (CH2) and 0.98 Å (CH3)
and refined in a riding model approximation, including free rotation for
methyl groups and variable isotropic displacement parameters. In 3a and
4b, the mercury atoms are disordered and were refined with split posi-
tions. The major occupancy (3a: 0.961, 4b: 0.983) corresponds to a η1-
N3 coordination mode whereas the minor occupancy (3a: 0.039, 4b:
0.017) is in accordance with a η1-N1 coordination. In 2a, the mercury
Acknowledgement
Support of this work by the Deutsche Forschungsgemeinschaft within
the priority program SPP 1166 (Lanthanoid-spezifische Funktionali-
täten in Molekül und Material) is gratefully acknowledged.
References
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Received: October 9, 2009
Published Online: January 29, 2010
Z. Anorg. Allg. Chem. 2010, 750–757
© 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
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