Stabilized germylenes based on diethylenetriamines and related diamines: Synthesis, structures, and chemical properties

Article abstract of DOI:10.1002/ejic.201200363

A series of novel, low-valent germanium compounds 2a-2j based on four diethylenetriamines 1a-1d, (methyl)bis(pyrrol-2-ylmethyl)amine (1e), N,N'-(sulfanediyldibenzene-2,1-diyl)bis(pentafluoroaniline) (1f), N,N'-(oxydibenzene-2,1-diyl)bis(pentafluoroaniline) (1g), and (pentafluorophenyl)amines 1i and 1j have been obtained either by the reaction of Ge[N(SiMe₃)₂]₂ with various diamines (1a-1e) or by the metathesis reaction of [GeCl₂·dioxane] with lithium amides. The oxidative insertion (with halogenation reagents, MeI, disulfides), [1+4] cycloaddition, and oxidation reactions of the synthesized germylenes were investigated. The compositions and structures of the novel compounds were established by elemental analysis, ¹H and ¹³C NMR spectroscopy, and X-ray diffraction analysis (germylenes 2b, 2i, 2j, Ge ⁴⁺ compounds 5b, 7a, 7b, 8, 10, 11). All the synthesized germylenes are monomeric. A series of novel, low-valent germanium compounds have been obtained by the reaction of Ge[N(SiMe₃)₂]₂ with various diamines or by the metathesis reaction of [GeCl₂· dioxane] with lithium amides. The oxidative insertion, [1+4] cycloaddition, and oxidation reactions of the synthesized germylenes were investigated. All the synthesized germylenes are monomeric. Copyright

Full text of DOI:10.1002/ejic.201200363

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DOI: 10.1002/ejic.201200363
Stabilized Germylenes Based on Diethylenetriamines and Related Diamines:
Synthesis, Structures, and Chemical Properties
Mengmeng Huang,[a,b] Marina M. Kireenko,[a] Kirill V. Zaitsev,*[a] Yuri F. Oprunenko,[a]
Andrei V. Churakov,[c] Judith A. K. Howard,[d] Elmira Kh. Lermontova,[c,e] Denis Sorokin,[e]
Thomas Linder,[e] Jörg Sundermeyer,*[e] Sergey S. Karlov,*[a] and Galina S. Zaitseva[a]
Keywords: Germanium / N-ligands / X-ray diffraction / Amines / Lithium
A series of novel, low-valent germanium compounds 2a–2j
based on four diethylenetriamines 1a–1d, (methyl)bis(pyrrol-
ive insertion (with halogenation reagents, MeI, disulfides),
[1+4] cycloaddition, and oxidation reactions of the synthe-
2-ylmethyl)amine (1e), N,NЈ-(sulfanediyldibenzene-2,1-diyl)- sized germylenes were investigated. The compositions and
bis(pentafluoroaniline) (1f), N,NЈ-(oxydibenzene-2,1-diyl)bis- structures of the novel compounds were established by ele-
(pentafluoroaniline) (1g), and (pentafluorophenyl)amines 1i
and 1j have been obtained either by the reaction of Ge[N-
(SiMe3)2]2 with various diamines (1a–1e) or by the metathesis
mental analysis, 1H and 13C NMR spectroscopy, and X-ray
diffraction analysis (germylenes 2b, 2i, 2j, Ge4+ compounds
5b, 7a, 7b, 8, 10, 11). All the synthesized germylenes are mo-
reaction of [GeCl2·dioxane] with lithium amides. The oxidat- nomeric.
to donate additional lone-pair electrons, such as a Cp li-
Introduction
gand and neutral N and O atoms (π-donating –OR and
–NR2 groups). The electron stabilization may be a result of
an additional transannular interaction of the metal centre
with a donor group. Note that diamidogermylenes and
dialkoxy(aryloxy)germylenes are sufficiently stable to be
studied as “usual” molecular substances by appropriate
techniques.
At the same time, germylenes of the formulae Ge(OR)2
and M(NR2)2 are able to exist in the dimeric state with the
metal atoms of one monomeric unit forming an additional
bond with an O or N atom of the other unit. Typically,
these dimers are less reactive than monomeric “heavier”
carbenes.
Among the diamidogermanium(II) derivatives, two-coor-
dinate Arduengo-type N-heterocyclic germylene (NHGe)
compounds are widely known.[3] The reactivities of these
compounds have been studied to a much greater extent than
those of other diamidogermylenes. In addition, the stabili-
ties and reactivities of NHGes are very different to those
of other divalent amino-substituted derivatives of group 14
elements.
In our opinion, the dianions of diethylenetriamines,
RN(CH2CH2N–RЈ)2, are very promising ligands for the sta-
bilization of monomeric structures of germylenes for the
following reasons: (1) the possible additional transannular
interaction with the nitrogen atom of the ligand and (2) the
possibility of easily designing the structures of such ligands,
for example replacing the H atoms of NH groups with dif-
ferent substituents. The latter allows the electron properties
of the central atom to be changed by varying the electron
Compounds containing low-valent group 14 elements
have attracted interest as models for highly important deriv-
atives of electron-deficient carbon analogues of carbenes. In
addition, the study of silylenes, germylenes, and stannylenes
is also important because of their use as catalysts in organic
processes such as ring-opening polymerization (ROP)[1] and
as precursors for the synthesis of superconducting materials
by metal-organic chemical vapor deposition (MOCVD)
processes.[2] In general, these compounds are very reactive,
thus additional stabilization is required. Usually, the stabili-
zation of an electron-deficient center is realized by ligand
design, balancing the inverse relationship between stability
and reactivity. Two different approaches may be marked
out: thermodynamic and/or kinetic stabilization of the reac-
tive vacant p-orbital of the low-valent group 14 element.
Bulky substituents in the ligand lead to kinetic stabilization,
whereas thermodynamic stabilization arises from the struc-
ture of the ligand, with some groups possessing the ability
[a] Chemistry Department, Moscow State University,
B-234 Leninskie Gory, 119991 Moscow, Russian Federation
Fax: +7-495-932-8846
E-mail: sergej@org.chem.msu.ru
zaitsev@org.chem.msu.ru
[b] Department of Chemistry, Zhengzhou University,
University Road 7, Zhengzhou 450052, P. R. China
[c] Institute of General and Inorganic Chemistry, Russian Academy
of Sciences,
Leninskii pr. 31, 119991 Moscow, Russia
[d] Department of Chemistry, University of Durham,
South Road, Durham, DH1 3LE, United Kingdom
[e] Fachbereich Chemie, Philipps-Universität Marburg,
Hans-Meerwein-Strasse, 35032 Marburg/Lahn, Germany
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properties of these substituents. We also suppose that the germylenes such as [GeCl2·1,4-dioxane] and the dilithium
stabilization of the low-valent centre bound to these ligands salts[8] of the corresponding triamines.
should be achieved not only by electronic effects but also by
Germylenes 2a–e were synthesized under mild conditions
kinetic factors, namely due to bulky substituents at nitrogen by the first method (Scheme 1). The yields of the target
atoms covalently bound to the atom of the group 14 ele- products were 40–60% and depended on the nature of the
ments. To date, only two divalent derivatives of group 14 ligand. In addition, 2a was obtained in 24% yield by reac-
elements containing diethylenetriamine as a ligand have tion of the dilithium salt of amine 1a and [GeCl2·dioxane].
been described. These are MeN(CH2CH2NSiMe3)2Sn and This shorter synthetic protocol does not require the isola-
MeN(CH2CH2NiPr)2Sn.[4] No germanium analogues have tion of intermediates, but it gives a lower yield of 2a
yet been prepared. There is only one example of a germyl- (Scheme 2).
ene derivative stabilized by N2N coordination, [MeSi(μ-
NtBu)2SiMe(tBuN)2]Ge.[5]
In this paper we describe the synthesis and chemical
properties of the new germylenes 2a–e with N2N coordina-
tion based on diethylenetriamine ligands 1a–e, the struc-
tural determination of the compounds obtained and their
structure–property correlations. Germylenes 2f–j based on
a set of novel chelating bis(diarylamido) ligands were pre-
pared for comparison. This work forms a part of our stud-
ies on the synthesis and investigation of “heavy carbene”
analogues stabilized by polydentate ligands.[6]
Results and Discussion
Germylene Synthesis
There are two general approaches to the preparation of
the target diamidogermylenes. The first is based on the
transamination of diethylenetriamine ligands with amino-
germylenes such as Lappert’s germylene, Ge[N(SiMe3)2]2.[7]
The second approach consists of using complexes of dihalo-
Scheme 2. Synthesis of germylenes 2a and 2f by using dilithium
salts of the corresponding amines.
In contrast to the complexes based on the ligands 1a–c
and 1e, the complex derived from N-silylated amine 1d is
very unstable. The generation of complex 2d during the re-
action was determined only by NMR spectroscopy
(Scheme 1).
We also tested the lithium salt metathesis route for the
preparation of closely related germylenes based on aromatic
diamines 1f and 1g, which are easily prepared by the nucleo-
Scheme 1. Synthesis of germylenes 2a–e by the transamination re-
action.
Scheme 3. Synthesis of germylenes 2i and 2j by using the lithium salts of the corresponding amines.
2
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Germylenes Based on Diethylenetriamines and Related Diamines
philic aromatic amidation of C6F6. Interestingly, although Ge(NR1R2)2 (NR1R2
=
2,2,5,5-tetramethylpiperidyl,
germylene 2f with an additional sulfur donor group could TMP).[12] The Ge–N bond lengths in 2i and 2j are within
be prepared, the corresponding germylene 2g with an oxy- the range found for other Ge2+ amides (1.87–1.91 Å).[10–12]
gen donor could not be prepared neither by the reaction of The N–Ge–N angle in 2j [97.88(9)°] is larger than that in 2i
the dilithium salt of 1g with [GeCl2·dioxane] nor by trans- [83.45(14)°]. This can be attributed to greater steric inter-
amination between Ge[N(SiMe3)2]2 and 1g (Scheme 2).
ligand repulsion in 2j. However, both of these angles are
Furthermore, diamidogermylenes 2i and 2j with two-co- smaller than those [105.26(8)–111.4(5)°] observed in other
ordinate germanium atoms were synthesized by lithium salt Ge2+ amides[10–12] due to sterically less hindered ligands.
metathesis with lithium (pentafluorophenyl)amides 1i and
1j, respectively (Scheme 3). The complexes 2i and 2j contain
no additional intra- or intermolecular bonding interactions
and they are sufficiently stable to study their molecular
structures by XRD analysis.
Germylene Molecular Structures
The subvalent GeII centers in the two diamagnetic com-
pounds 2i and 2j are stabilized by the weak π-interactions
between the electron pairs of the anionic nitrogen donor
atoms and the vacant orbital at the central atom. In ad-
Figure 2. Molecular structure of 2i. ORTEP diagram with elipsoids
drawn at the 50% probability level; hydrogen atoms have been
dition, the empty orbital at Ge in 2i should be stabilized by
the electron density of the nonfluorinated aromatic system,
as discussed in similar systems by Arduengo et al.[9] On the
other hand, the lone pair on GeII seems to be particularly
well stabilized by the highly fluorinated amide ligands with
relatively high electronegativity.
omitted for clarity. Selected interatomic distances [Å] and angles
[°]: N(1)–Ge 1.887(2), N(1A)–Ge(1) 1.887(2); N(1)–Ge(1)–N(1A)
83.45(14); N(1A)–Ge(1)–N(1)–C(1) –0.3(2), N(1A)–Ge(1)–N(1)–
C(5) –174.94(18).
To gain more insight into the bonding, the X-ray crystal
structures of 2b, 2i, and 2j were determined. Their molecu-
lar structures are shown in Figures 1, 2 and 3. They are all
monomeric in the solid state. Compounds 2i and 2j each
possess a two-coordinate germanium atom, as in the pre-
viously studied Ge[N(SiMe2R)2]2 (R = Me,[10] iPr[11]) and
Figure 3. Molecular structure of 2j. ORTEP diagram with elipsoids
drawn at the 50% probability level. Selected interatomic distances
[Å] and angles [°]: N(1)–Ge 1.871(2), N(2)–Ge(1) 1.877(2); N(1)–
Ge(1)–N(2) 97.88(9).
For germylene 2b, the primary coordination environment
of the Ge atom is formed by two covalently bonded nitro-
gen atoms and one dative-bonded nitrogen atom and may
be treated as a trigonal pyramid with a lone pair in one
vertex. To the best of our knowledge, this is the first exam-
ple of an X-ray-studied monomeric germylene with an N2N
coordination environment. One can compare the NǞGe
bond in 2b with that in a monomeric compound with a
tricoordinate germanium atom having an O2N coordination
environment, Py(CH2CPh2O)(CH2CMe2O)Ge.[13] The
NǞGe bond length [2.112(2) Å] in 2b is similar to that in
Py(CH2CPh2O)(CH2CMe2O)Ge [2.110(1) Å].[13] The cova-
lent bonds Ge(1)–N(1) [1.943(2) Å] and Ge(1)–N(3)
[1.984(2) Å] are longer than those in diamides with two-
coordinate germanium atoms Ge[N(SiMe3)2]2 [Ge–N
Figure 1. Molecular structure of 2b. ORTEP diagram with elipsoids
drawn at the 50% probability level; hydrogen atoms have been
omitted for clarity. Selected interatomic distances [Å] and angles
[°]: N(1)–Ge 1.943(2), N(2)–Ge(1) 2.112(2), N(3)–Ge(1) 1.984(2);
N(1)–Ge(1)–N(3) 102.48(10), N(1)–Ge(1)–N(2) 83.11(10), N(3)–
Ge(1)–N(2) 82.36(10).
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1.876(5) Å avg.],[10] Ge[TMP]2 [Ge–N 1.89(1) Å avg.],[12] 2i,
and 2j (see above). The elongation is caused by an ad-
ditional intramolecular interaction in 2b. The Ge(1)–N(2)
bond is nearly perpendicular to the N(1)–Ge(1)–N(3) plane,
which allows the ideal interaction of the nitrogen lone-pair
electron with the vacant Ge orbital. The five-membered cy-
cles –Ge(1)–N(1)–C(7)–C(8)–N(2)– and –Ge(1)–N(3)–
C(17)–C(16)–N(2)– adopt “envelope” conformations,
whereas the eight-membered ring –Ge(1)–N(1)–C(7)–C(8)–
N(2)–C(16)–C(17)–N(3) has a “boat-chair” conformation.
Scheme 5. Halogenation of germylene 2a by reaction with GeCl4.
Germylenes can also undergo another type of reaction
by insertion into C–Hal bonds. In particular, for the charac-
terization of “heavy carbenes” the reaction with methyl iod-
ide is often used.[15a,16] However, in addition, a number of
papers have been published concerned with a three-compo-
nent reaction between germylenes, organic substrate, and
RX (R = Ph, tBu, Me; X = I, Br, Cl) as a novel method
of C–H activation in quite inert organic substrates such as
alkanes, alkenes, and alkynes and even a regioselective reac-
tion in ethers and nitriles.[17]
The iodogermanes 5a and 5b were easily obtained by the
oxidative addition of MeI (Scheme 6) and fully charac-
terized by spectroscopic methods. The product 5b was also
characterized by X-ray diffraction analysis (Figure 4). Only
one example of a reaction of methyl iodide and a germyl-
ene, in which the germanium atom is bonded to two nitro-
gen atoms, has been described,[16b] but the molecular struc-
ture of the resulting iodogermane, [HC(CMeNAr)2]Ge-
Me2(I) (Ar = 2,6-iPr2C6H3), was not studied by X-ray
analysis.
Germylene Reactivity
As systematic reactivity studies of germylenes are still a
focus of interest, we investigated the classic reactions of
germylene chemistry, such as insertion, oxidative addition,
and cycloaddition reactions, for the compounds obtained
in this work.
One of the best known reactions of such compounds is
the oxidative halogen addition, which results in GeIV deriv-
atives.[13,14] In this work the reactions of monomeric
germylenes 2a and 2f with bromine were investigated
(Scheme 4). Compounds 2a and 2f reacted with bromine at
room temperature by the insertion of the germylenes into
the Br–Br bond to give the expected dibromides in high
yields.
Scheme 6. Oxidative addition of MeI to germylenes 2a,b.
The germanium atom in 5b is present in a distorted bi-
pyramidal environment. The I(1)–Ge(1)–X(eq) [X = equa-
torial substituent N(11), N(21), C(1)] bond angles are in
the range 92.99(10)–94.48(9)° and approach the idealized
bipyramidal value of angles between axial and equatorial
substituents (90°). The Ge–N bond lengths in germylene 2b
have an average value of 1.964(2) Å and the shorter Ge–N
Scheme 4. Halogenation of germylenes 2a and 2f with bromine.
The halogenation of “heavy carbenes” may be performed bond length [1.856(3) Å] in 5b is a result of the higher oxi-
not only with halogens but also with other halogen-contain- dation state of germanium in this complex. The Ge–C bond
ing derivatives. Several examples of such reactions have length in 5b is 1.940(3) Å and is typical of a Ge–C single
been described.[4,14,15] MeN(CH2CH2NSiMe3)2Sn reacts bond, and the Ge–I bond length of 2.7599(5) Å is similar to
with BiCl3, the tin atom abstracting two chlorine atoms the Ge–I bond length in (acac)GeI [acac = acetylacetonato;
from the trichloride to form MeN(CH2CH2NSiMe3)2- 2.7360(3) Å].[18] However, the Ge–I bond in 5b is longer
SnCl2.[4] If PCl3 was used for halogenation, the ionic com- than the usual Ge–I bond length.[17b] This fact can be ex-
–
plex [MeN(CH2CH2NSiMe3)2P+SnCl3 ] was formed.[4] In plained by the formation of a transannular interaction.
contrast, Veith’s germylene Me2Si(NtBu)2Ge reacts with
PCl3 by a three-fold insertion into the P–Cl bonds to form ide by insertion of Ge into the C–Br bond.[19] Unfortu-
[Me2Si(NtBu)2Ge(Cl)]3P. [14]
nately, our efforts to carry out the reaction between 2a and
We studied for the first time the reaction of germylenes allyl bromide failed due to unselective side-reactions.
It is known that [GeBr2·C4H8O2] reacts with allyl brom-
with GeCl4 as halogenating reagent. The pentacoordinated
We investigated the reactions of our germylenes with
germanium derivative 4 with an oxidation number 4+ was both diphenyl and diethyl disulfide (Scheme 7).[15a] It was
obtained (Scheme 5). The main driving force for the reac- found that the structure of the disulfide determines the be-
tion is the formation of the insoluble polymeric [GeCl2]n havior of the germylenes in question. Germylene 2b reacted
with the product 4 bearing a transannular interaction.
easily at –40 °C with diphenyl disulfide to form the corre-
4
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Germylenes Based on Diethylenetriamines and Related Diamines
(Scheme 8), which is formed by the oxidation of a mixture
of the two germylenes 2a and Ge[N(SiMe3)2]2 with molecu-
lar oxygen. The structure of 7a was studied by X-ray analy-
sis (Figure 5). The result also confirms that 1,3-digerma-
dioxetane is formed via germanone. Instead of oxygen, tri-
methylamine N-oxide has recently been widely used.[22]
Scheme 8. Formation of complex 7a.
Figure 4. Molecular structure of 5b. ORTEP diagram with elipsoids
drawn at the 50% probability level; hydrogen atoms have been
omitted for clarity. Selected interatomic distances [Å] and angles [°]:
N(1)–Ge(1) 2.166(3), N(11)–Ge(1) 1.858(3), N(21)–Ge(1) 1.854(3),
C(1)–Ge(1) 1.940(3), I(1)–Ge(1) 2.7599(5); N(21)–Ge(1)–N(11)
121.13(14), N(21)–Ge(1)–C(1) 116.52(15), N(11)–Ge(1)–C(1)
121.03(15), N(21)–Ge(1)–N(1) 81.52(11), N(21)–Ge(1)–N(11)
121.13(14), N(11)–Ge(1)–N(1) 81.55(11), C(1)–Ge(1)–N(1)
95.80(12), N(21)–Ge(1)–I(1) 93.97(9), N(11)–Ge(1)–I(1) 94.48(9),
C(1)–Ge(1)–I(1) 92.99(10), N(1)–Ge(1)–I(1) 171.18(7).
sponding disulfide adduct 6. But this was not the case with
diethyl disulfide even under irradiation with ultraviolet
light. This can be attributed to the greater strength of the
S–S bond in diethyl disulfide compared than in diphenyl
disulfide. The relative reactivities of the germylenes based
on diethylenetriamines with disulfides are similar to those
found earlier for germanium(II) dialkanolamine deriva-
tives.[6]
Figure 5. Molecular structure of 7a. ORTEP diagram with elipso-
ids drawn at the 50% probability level; hydrogen atoms have been
omitted for clarity. Selected interatomic distances [Å] and angles
[°]: Ge(1)–N(2) 1.8555(16), Ge(1)–N(1) 1.8485(15), Ge(1)–N(3)
2.1542(15), Ge(1)–O(1) 1.8463(12), Ge(1)–O(2) 1.8128(13), Ge(1)–
Ge(2) 2.6370(3), Ge(2)–N(5) 1.8366(15), Ge(2)–N(4) 1.8411(15),
Ge(2)–O(1) 1.7856(12), Ge(1)–O(2) 1.7968(12); O(2)–Ge(1)–O(1)
85.37(5), O(2)–Ge(1)–N(1) 118.71(7), O(1)–Ge(1)–N(1) 99.62(6),
O(2)–Ge(1)–N(2) 119.70(7), O(1)–Ge(1)–N(2) 101.99(6), N(1)–
Ge(1)–N(2) 118.66(7), O(2)–Ge(1)–N(3) 88.02(6), O(1)–Ge(1)–N(3)
173.27(6), N(1)–Ge(1)–N(3) 82.47(6), N(2)–Ge(1)–N(3) 82.40(6),
N(1)–Ge(1)–Ge(2) 116.51(5), N(2)–Ge(1)–Ge(2) 118.12(5), N(3)–
Ge(1)–Ge(2) 130.84(4), O(1)–Ge(2)–O(2) 87.66(6), O(1)–Ge(2)–
N(5) 118.98(6), O(2)–Ge(2)–N(5) 113.65(6), O(1)–Ge(2)–N(4)
113.85(6), O(2)–Ge(2)–N(4) 108.58(6), N(5)–Ge(2)–N(4) 111.59(7),
N(5)–Ge(2)–Ge(1) 128.27(5), N(4)–Ge(2)–Ge(1) 119.60(5), Ge(2)–
O(1)–Ge(1) 93.10(6), Ge(2)–O(2)–Ge(1) 93.86(6).
Scheme 7. Insertion of germylene 2b into Ph2S2.
Germylenes are affected by oxidants such as dioxygen
and sulfur. When (ArO)2Ge reacts with sulfur, ger-
manethione compounds with a highly dipolar “Ge=S”
bond are formed, as indicated by cryoscopy.[20] The reaction
of monomeric [(Me3Si)2N]2Ge with molecular oxygen gives
rise to crystalline 1,3-digermadioxetane, [([Me3Si]2N)2Ge(μ-
O)]2, characterized by NMR and X-ray analysis.[21] It is
supposed that the 1,3-digermadioxetane results from the
germanone originally obtained. Note that in the course of
To investigate the stabilizing effect of diethylenetriamines
the purification of 2a from starting Ge[N(SiMe3)2]2 we ob- on the few germanium derivatives with a zwitterionic
tained a trace amount of mixed 1,3-digermadioxetane 7a “Ge=O” bond, we carried out the reaction between germyl-
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ene 2b and Me3NǞO (Scheme 9). As expected, the oxi-
dation product was obtained in 42% yield, and its structure
was confirmed by X-ray diffraction analysis (Figure 6).
Scheme 9. Oxidation of germylene 2b by trimethylamine N-oxide.
Figure 7. Molecular structure of 8. ORTEP diagram with elipsoids
drawn at the 50% probability level; hydrogen atoms have been
omitted for clarity. Selected interatomic distances [Å] and angles
[°]: Ge(1)–S(1) 2.2062(17), Ge(1)–S(1A) 2.2875(18), Ge(1)–N(2)
1.856(5), Ge(1)–N(1) 1.869(5), Ge(1)–N(3) 2.323(5), Ge(1)–Ge(1A)
3.124; N(2)–Ge(1)–N(1) 112.7(2), N(2)–Ge(1)–S(1) 123.50(17),
N(1)–Ge(1)–S(1) 118.52(16), N(2)–Ge(1)–S(1) 100.27(16), N(1)–
Ge(1)–S(1) 101.32(17), S(1)–Ge(1)–S(1) 91.93(6), N(2)–Ge(1)–N(3)
78.97(19), N(1)–Ge(1)–N(3) 78.9(2), S(1)–Ge(1)–N(3) 88.63(13),
S(1)–Ge(1)–N(3) 179.23(13), Ge(1)–S(1)–Ge(1) 88.07(6).
The germanium atoms in 7b and 8 and Ge(1) in 7a have
distorted trigonal-bipyramidal geometries with N(3) and
O(1) in 7a, and N(3) and O(1a) in 7b occupying the axial
positions. N(1), N(2), and O(2) in 7a, and N(1), N(2), and
O(1) in 7b form the equatorial plane. The coordination
polyhedron of Ge(2) in 7a is a distorted tetrahedron.
The Ge–O bond lengths are similar to those of the corre-
sponding bonds in {[MeSi(μ-NtBu)2SiMe(tBuN)2]Ge(μ-
O)}2 [1.809(4) and 1.825(4) Å][5] and in {[P(μ-NtBu)2P-
(tBuN)2]Ge(μ-O)}2 [1.78(1) and 1.84(1) Å].[23] The Ge–
X(ax) bond is, as expected, longer than the Ge–X(eq) [X =
O (7a,b), X = S (8)] bond in the same molecule for the Ge
atom in the trigonal-bipyramidal environment. This is in
accordance with the hypervalent bond theory.[24] The intra-
Figure 6. Molecular structure of 7b. ORTEP diagram with elipsoids
drawn at the 50% probability level; hydrogen atoms have been
omitted for clarity. Selected interatomic distances [Å] and angles
[°]: Ge(1)–O(1) 1.7844(13), Ge(1)–O(1A) 1.8313(13), Ge(1)–N(2)
1.8519(16), Ge(1)–N(1) 1.8574(16), Ge(1)–N(3) 2.1478(17), Ge(1)–
Ge(1A) 2.6524(4), O(1)–Ge(1A) 1.8313(13); O(1)–Ge(1)–O(1A)
85.64(6), O(1)–Ge(1)–N(2) 17.60(7), O(1A)–Ge(1)–N(2) 99.61(7),
O(1)–Ge(1)–N(1) 122.81(7), O(1A)–Ge(1)–N(1) 100.02(7), N(2)–
Ge(1)–N(1) 117.30(8), O(1)–Ge(1)–N(3) 89.54(6), O(1A)–Ge(1)–
N(3) 175.18(6), N(2)–Ge(1)–N(3) 82.48(7), N(1)–Ge(1)–N(3)
82.74(7), N(2)–Ge(1)–Ge(1A) 115.27(6), N(1)–Ge(1)–Ge(1A)
118.99(6), N(3)–Ge(1)–Ge(1A) 133.05(5), Ge(1)–O(1)–Ge(1A)
94.36(6).
molecular
transannular
interaction
N(3)ǞGe
[2.1542(15) Å] in 7a and [2.1478(17) Å] in 7b are similar,
but in 8, N(3)ǞGe [2.323(5) Å] is longer because of the
lower electronegativity of S as compared with O. The trans-
annular Ge···Ge separations in 7a [2.6370(3) Å] and 7b
[2.6524(4) Å] are similar, but slightly longer than in
{Ge[N(SiMe3)2]2(μ-O)}2 [2.608(1) Å] and much shorter
than twice the van der Waals radius of Ge4+ (4.30 Å). The
increase in the transannular Ge···Ge separations in 8
[3.124(5) Å] can be explained by the increasing size of the
bridged atoms in this case.
The reaction of 2a with sulfur also gave the expected
product (Scheme 10), the cyclodimer 8, which was charac-
terized by X-ray diffraction analysis (Figure 7).
The reaction of germylene 2b with water gave free ligand
1b and germanium(II) hydroxide. Evidently, the driving
force for the reaction is the formation of the precipitate of
Scheme 10. Reaction of germylene 2a with sulfur.
6
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Germylenes Based on Diethylenetriamines and Related Diamines
germanium(II) hydroxide. The interaction of germylenes
with water does not result in the four-membered cycle –M–
O–M–O–.
The reactions of germylenes with azides has been the
subject of several investigations.[20] By studying the reac-
tions of germylenes without the additional transannular in-
teraction, it was determined that different derivatives of
M4+ (azides, germoles, imines) might be obtained de-
pending on the reaction conditions and the structures of
Scheme 13. [1+4] Cycloaddition reactions of germylene 2a and 2b
with substituted chalcones.
The structures of 10 and 11 were confirmed by X-ray
the “heavy carbene” and azides. According to Barrau et analysis (Figures 8 and 9). The coordination environment
al.,[20] the reaction of (ArO)2Ge [Ar
=
2,4,6-(Me2- of the germanium atom in both 10 and 11 is trigonal-bipy-
NCH2)3C6H2] with trimethylsilyl azide, Me3SiN3, yields ramidal with O(1) and N(3) in 10, and O(1) and N(3) in 11
germanimines. The reactions of germylenes with diphenyl- in axial positions and O(2), N(1), and N(2) in 10, and N(1),
phosphoryl azide is practically unexplored.[25] We carried N(2), and C(2) in 11 in the equatorial plane. Note that in
out this reaction with germylene 2b and obtained the ex- both cycloaddition products the intramolecular transannu-
pected product 9 (Scheme 11).
lar interactions N(3)ǞGe [2.089(4) Å] in 10 and
[2.2566(17) Å] in 11 differ from that of the initial germylene
2b. Moreover, this interaction is stronger, the more electro-
negative substituents are located at the germanium atom.
This may be explained by the presence of two electronega-
tive substituents at the germanium atom in the adduct 10
and one in the product 11. The same trend was observed
for compounds MeN(CH2CH2O)2Ge(-OCH2CH2O-),[27]
HOCH2CH2N(CH2CH2O)2Ge[-OC(O)CH2CH2-],[28] and
MeN(CH2CH2O)2Ge[-OC(O)CPh2O-],[29] in which NǞGe
is 2.159(7), 2.149(6), and 2.080(3) Å respectively.
Scheme 11. Reaction of germylene 2b with (PhO)2P(O)N3.
The similarity between the results obtained in the reac-
tions with (PhO)2P(O)N3 and Me3NǞO can be explained
by the analogy of the mechanisms supposed. In the case
of diphenylphosphoryl azide, the intermediate might be an
unstable germanimine, (PhO)2P(O)–N=MR2, that dimer-
izes immediately.
Addition to unsaturated systems is a classic reaction for
“heavy carbenes”, different organic substrates with conju-
gate double bonds having being studied. We investigated a
number of similar reactions to determine the influence of
organic substrate structure on the reaction.
The reactions of different M2+ derivatives with benzil
have been studied in detail[26] and it was established that
[1+4] cycloaddition products form independently of the
structure of the “heavy carbene”. The use of germylene 2b
in such a reaction led to the expected product 10 in moder-
ate yield (Scheme 12).
Figure 8. Molecular structure of 10. ORTEP diagram with elipso-
ids drawn at the 50% probability level; hydrogen atoms have been
omitted for clarity. Selected interatomic distances [Å] and angles
[°]: Ge(1)–O(2) 1.796(3), Ge(1)–N(1) 1.836(4), Ge(1)–O(1) 1.838(3),
Ge(1)–N(2) 1.839(4), Ge(1)–N(3) 2.089(4); O(2)–Ge(1)–N(1)
Scheme 12. [1+4] Cycloaddition reaction of germylene 2b with
benzil.
124.40(16),
96.00(15),
119.51(18),
90.54(14),
O(2)–Ge(1)–O(1)
O(2)–Ge(1)–N(2)
O(1)–Ge(1)–N(2)
N(1)–Ge(1)–N(3)
89.26(14),
114.40(16),
97.79(15),
83.40(16),
N(1)–Ge(1)–O(1)
N(1)–Ge(1)–N(2)
O(2)–Ge(1)–N(3)
O(1)–Ge(1)–N(3)
Germylenes 2a and 2b reacted with chalcone and its
ferrocenyl analogues to give [1+4]-cycloaddition products
11 and 12 (Scheme 13).
179.11(14), N(2)–Ge(1)–N(3) 83.09(15).
Eur. J. Inorg. Chem. 0000, 0–0
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K. V. Zaitsev, J. Sundermeyer, S. S. Karlov et al.
FULL PAPER
transamination reactions of a range of substituted amines
and Ge[N(TMS)2]2 or by metathesis of lithiated ligand syn-
thons with [GeCl2·dioxane]. According to XRD studies,
monomeric germylenes were obtained in all cases. Three-
coordinate germylenes stabilized by an additional transan-
nular interaction showed a reactivity similar to that of their
classic two-coordinate counterparts in oxidative addition
reactions with halogenation agents (bromine and GeCl4),
methyl iodide, diphenyl disulfide, dioxygen, sulfur, and di-
phenylphosphoryl azide. Although α,β-unsaturated ketones
(benzil, chalcone, and its ferrocenyl analogues) led to the
expected [1+4]-cycloaddition products, base-stabilized
germylenes based on the diethylenetriamine backbone were
found to be unreactive towards 2,3-dimethyl-1,3-butadiene
and 1,4-di-tert-butyl-1,4-diazabuta-1,3-diene.
Experimental Section
General: All manipulations were performed under dry, oxygen-free
argon by using standard Schlenk techniques. Solvents were dried
by standard methods and distilled prior to use. The starting materi-
als were synthesized according to literature procedures:
Ge[N(TMS)2]2,[31] [GeCl2·C4H8O2],[32] LiN(TMS)2·Et2O,[33] MeN-
(CH2CH2NHC6F5)2,[34] BnN(CH2CH2NHC6F5)2,[24b] BnN(CH2-
CH2NHTMS)2,[24b] H2(dpma),[35] TMSN(CH2CH2NHTMS)2,[36]
FcC(O)CH=CHPh,[37] HN(C6F5)2,[38] LiN(C6F5)2,[38] and N,NЈ-bis-
(pentafluorophenyl)benzene-1,2-diamine (1i).[39] MeI (Aldrich),
GeCl4 (Aldrich), Et2S2 (Aldrich), and 2,3-dimethylbuta-1,3-diene
(Aldrich) were distilled prior to use. Ph2S2 (Aldrich), S8 (Merck),
N3P(O)(OPh)2 (Merck), PhC(O)C(O)Ph (Aldrich), PhC(O)-
CH=CHPh (Aldrich), and tBuN=CHCH=NtBu (Aldrich) were
used as supplied. Me3NǞO·2H2O (Fluka) was sublimated for use.
C6D6 was obtained from Deutero GmbH and dried with sodium.
1H, 13C, and 19F NMR spectra were recorded with a Bruker Avance
400 or ARX 200 spectrometer at room temperature. 1H and 13C
chemical shifts are reported in ppm relative to Me4Si as external
standard. In 19F NMR experiments, CFCl3 was used as the exter-
nal standard. Elemental analyses were carried out by the Microana-
lytical Laboratory of the Chemistry Department of the Moscow
State University. Mass spectra (EI-MS, 70 eV) were recorded with
a Varian CH-7a device (Philipps University Marburg, Germany).
All assignments were made by reference to the most abundant iso-
topes. Infrared spectra were recorded with a Bruker IFS 88 FT
instrument, and samples were Nujol mulls between KBr plates.
Figure 9. Molecular structure of 11. ORTEP diagram with elipso-
ids drawn at the 50% probability level; hydrogen atoms have been
omitted for clarity. Selected interatomic distances [Å] and angles
[°]: Ge(1)–N(2) 1.8596(18), Ge(1)–N(1) 1.8642(17), Ge(1)–O(1),
1.8651(14), Ge(1)–C(2) 1.996(2), Ge(1)–N(3) 2.2566(17); N(2)–
Ge(1)–N(1) 117.05(8), N(2)–Ge(1)–O(1) 95.96(7), N(1)–Ge(1)–O(1)
93.04(7), N(2)–Ge(1)–C(2) 119.68(8), N(1)–Ge(1)–C(2) 122.50(8),
O(1)–Ge(1)–C(2) 89.85(7), N(2)–Ge(1)–N(3) 80.90(7), N(1)–Ge(1)–
N(3) 80.16(7), O(1)–Ge(1)–N(3) 170.05(6), C(2)–Ge(1)–N(3)
99.92(8).
We found that there was no reaction between monomeric
germylene 2b and 2,3-dimethylbutadiene neither at ambient
temperature nor after prolonged heating. In similar reac-
tions germanium(4+) compounds would be expected to
form in which the transannular bond is weak or does not
exist, because the germanium atom bonds to two donor
carbon atoms.
The digermene R2Ge=GeR2 [R = tetrakis(2-tert-butyl-
4,5,6-trimethylphenyl)], which dissociates into the germyl-
ene molecules R2Ge: in solution, reacts with 1,4-di-
isopropyl-1,4-diazabuta-1,3-diene to furnish the product
formed by the [4+1] cycloaddition of germylene to the ni-
trogen atoms.[30] Similar reactions could be expected for our
germylenes, but no reaction was observed between our do-
nor-stabilized, three-coordinate germylene 2b and 1,4-di-
tert-butyl-1,4-diazabuta-1,3-diene.
Bis{2-[(pentafluorophenyl)amino]phenyl} Thioether [S(oC6H4NH-
C6F5)2 (1f)]: nBuLi (1.6 m, 83.6 mL, 0.13 mol) in hexane was added
to a solution of HN(SiMe3)2 (21.6 g, 0.13 mol) in thf (70 mL) at
25 °C. After 20 min at 25 °C, a solution of bis(2-aminophenyl) thio-
ether (6.43 g, 30.0 mmol) in thf (60 mL) was added. The mixture
was cooled to –78 °C, and C6F6 (13.81 g, 74.0 mmol) was added
within 2 min. The brownish reaction mixture was slowly warmed
to 25 °C and stirred at room temp. until all the starting material
had been consumed (monitored by TLC, ca. 4 h). After the ad-
dition of water (200 mL) and diethyl ether (150 mL), the raw prod-
uct was extracted with diethyl ether (3ϫ 100 mL). The combined
diethyl ether phases were dried with Na2SO4, and the diethyl ether
was removed to give a brown oily solid, which was dissolved in
CH2Cl2/n-hexane (2:1) and passed through a bed of Merck silica
60 (ca. 60 g). After further extraction with this solvent mixture, all
volatiles were removed, and the residue was crystallized from hot
Conclusions
A new class of two-coordinate and donor-stabilized
three-coordinate germylenes based on (pentafluorophenyl)-
amides and diethylenetriamines have been synthesized by heptane/benzene (3:1) to yield colorless crystalline needles of 1f
8
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Germylenes Based on Diethylenetriamines and Related Diamines
(12.80 g, 78%). M.p. 178.4 °C. 1H NMR (400 MHz, C6D6): δ =
5.74 (s, 2 H, NH), 6.37 (dd, J = 8.0 and 1.2 Hz, 2 H, C6H4), 6.65
–154.21 to –154.11 (m, 2 F) ppm. MS (EI): m/z (%) = 599 (12)
[M]+, 390 (28) [M – CH2CH2NC6F5]+, 330 (7) [M – CH2NC6-
(dt, J = 7.6 and 1.3 Hz, 2 H, C6H4), 6.91 (dt, J = 8.0 and 1.5 Hz, F5Ge]+, 312 (13) [M – CH2Ph CH2NC6F5]+.
2 H, C6H4), 7.22 (dd, J = 7.8 and 1.5 Hz, 2 H, C6H4) ppm. 13C
BnN(CH2CH2NSiMe3)2Ge (2c): The procedure was analogous to
NMR (100.6 MHz, C6D6): δ = 115.3 (s, C6H4), 116.9 (t, J =
13.4 Hz, C6F5), 120.6 (s, C6H4), 122.6 (s, C6H4), 129.7 (s, C6H4),
133.2 (s, C6H4), 138.3 (dm, J = 245.1 Hz, C6F5), 138.4 (dm, J =
246.0 Hz, C6F5), 142.4 (dm, J = 247.9 Hz, C6F5), 142.9 (s, C6H4)
ppm. 19F NMR (188.2 MHz, C6D6): δ = –163.4 (t, J = 20 Hz, 2 F,
meta), –162.2 (t, J = 21 Hz, 1 F, para), –149.4 (d, J = 20 Hz, 2 F,
ortho) ppm. MS (EI): m/z (%) = 548 (23) [M]+, 365 (3) [M –
that used for 2a (Method A); reaction of BnN(CH2CH2NHTMS)2
(1c; 0.58 g, 1.73 mmol) with Ge[N(TMS)2]2 (0.68 g, 1.73 mmol) in
1
toluene (15 mL) gave 2c (0.13 g, 18%) as a yellow solid. H NMR
(400 MHz, C6D6, 25 °C): δ = 0.34 (s, 3 H, SiMe3), 1.97–2.02, 2.73–
2.78 (2 m, 4 H, NCH2), 3.12–3.17, 3.22–3.29 (2 m, 4 H, NCH2),
3.69 (s, 2 H, PhCH2), 6.93–6.94, 7.04–7.06, 7.30–7.32 (3 m, 5 H,
Ph) ppm. 13C NMR (100 MHz, C6D6, 25 °C): δ = 1.43 (SiMe3),
40.01, 49.85, 58.46, 61.01 (NCH2), 64.50 (CH2Ph), 127.15, 128.47,
129.19, 131.28 (Ph) ppm. C17H33GeN3Si2 (408.2451): calcd. C
50.01, H 8.15, N 10.29; found C 49.89, H 8.03, N 10.35.
NHC F ]+, 259 (100) [C H NHC F ]+. IR (Nujol): ν = 3385 (m,
˜
6
5
6
5
6 5
NH), 1655 (w), 1638 (w), 1524 (s), 1464 (vs), 1425 (s), 1377 (s),
1296 (s), 1232 (m), 1155 (m), 1055 (m), 981 (s), 945 (s), 866 (w), 748
(s), 735 (m), 723 (m), 671 (m), 544 (w), 434 (w) cm–1. C24H10F10N2S
(548.40): calcd. C 52.56, H 1.84, N 5.11; found C 52.59, H 2.12, N
5.09.
Me3SiN(CH2CH2NSiMe3)2Ge (2d): The procedure was analogous
to that used for 2a (Method A); Me3SiN(CH2CH2NHSiMe3)2 (1d;
0.34 g, 1.07 mmol) was treated with Ge[N(TMS)2]2 (0.42 g,
1.07 mmol) in toluene (15 mL). The reaction mixture was stirred at
room temperature. After 4 d, the volatiles were removed under vac-
uum to give an orange oil. On the basis of the NMR spectroscopic
data, the orange oil was considered to be germylene 2d, but in view
of its extreme hygroscopicity and sensitivity to oxygen our attempts
to isolate 2d in pure form failed. 1H NMR (400 MHz, C6D6,
25 °C): δ = 0.04, 0.33 (2 s, 27 H, SiMe3), 1.98–2.02, 2.30–2.37, 3.17–
3.21, 3.27–3.33 (4 m, 8 H, NCH2) ppm.
MeN(CH2CH2NC6F5)2Ge (2a)
Method A: A solution of MeN(CH2CH2NHC6F5)2 (1a; 0.46 g,
1.02 mmol) in toluene (5 mL) was added to a stirred solution of
Ge[N(TMS)2]2 (0.40 g, 1.02 mmol) in toluene (10 mL). The mixture
was stirred at room temperature for 4 d. After removal of the vola-
tiles under vacuum, diethyl ether (10 mL) was added to the residue.
The precipitate was filtered off to give 2a (0.27 g, 51%) as a white
solid. 1H NMR (400 MHz, C6D6, 25 °C): δ = 1.70 (s, 3 H, CH3N),
1.77–1.90 (m, 4 H, 2 NCH2), 2.94–3.05, 3.35–3.49 (2 m, 4 H, 2
NCH2C6F5) ppm. 13C NMR (100 MHz, C6D6, 25 °C): δ = 46.23
(CH3N), 50.96 (NCH2), 60.11 (NCH2C6F5) ppm. The 13C NMR
signals of the pentafluorophenyl rings were not observed under
these conditions due to poor solubility and higher-order C–F cou-
pling. 19F NMR (376.4 MHz, C6D6, 25 °C): δ = –172.94 to –172.78
(m, 1 F), –165.41 to –165.26 (m, 2 F), –154.34 to –154.25 (m, 2 F)
ppm. C17H11F10GeN3 (519.8835): calcd. C 39.27, H 2.13, N 8.08;
found C 39.30, H 2.45, N 7.82. Prolonged standing of the mother
liquor for a month led to colorless crystals of the compound
MeN(CH2CH2NC6F5)2Ge(μ-O)2Ge[N(TMS)2]2 (7a). The structure
of 7a was established by X-ray analysis.
Ge(dpma) (2e): The procedure was analogous to that used for 2a
(Method A); H2(dpma) (1e; 0.18 g, 0.97 mmol) was treated with
Ge[N(TMS)2]2 (0.38 g, 0.97 mmol) in toluene (15 mL) to give 2e
(0.09 g, 36%) as a brown solid. 1H NMR (400 MHz, C6D6, 25 °C):
δ = 1.69 (s, 3 H, CH3N), 2.97 and 3.48 (2 d, J = 13.6 Hz, 4 H,
NCH2), 5.96–6.13, 6.49–6.54, 6.88–6.93 (3 m, 6 H, pyrrole ring
protons) ppm. 13C NMR (100 MHz, C6D6, 25 °C): δ = 43.15
(CH3N), 58.52 (NCH2), 104.75, 111.98, 121.73, 133.54 (pyrrole
ring) ppm. C11H13GeN3 (259.8511): calcd. C 50.84, H 5.04, N
16.17; found C 50.98, H 5.13, N 16.06.
S(oC6H4NC6F5)2Ge (2f)
Method A: A solution of LiN(SiMe3)2·Et2O (0.62 g, 2.60 mmol) in
thf (10 mL) was added to a stirred solution of S(o-C6H4NH-
C6F5)2 (1f; 0.70 g,1.30 mmol) in thf (15 mL) at –78 °C. After warm-
ing to room temperature and stirring for 1 h, the reaction mixture
was again cooled to –78 °C, added to a suspension of [GeCl2·
C4H8O2] (0.30 g, 1.30 mmol) in thf (15 mL), and cooled to –78 °C.
The reaction mixture was stirred at room temperature overnight,
and the volatiles were removed under vacuum. Recrystallization
from toluene gave 2f (0.50 g, 63%) as a white solid. 1H NMR
(400 MHz, C6D6, 25 °C): δ = 6.07–6.10, 6.38–6.43, 6.76–6.82, 7.12–
7.13 (4 m, 8 H, aromatic protons) ppm. 13C NMR (100 MHz,
C6D6, 25 °C): δ = 115.55, 119.50, 119.76, 132.14, 132.70, 153.26
(aromatic carbon atoms) ppm. The 13C NMR signals of the penta-
fluorophenyl rings were not observed under these conditions due
to poor solubility and higher-order C–F coupling. 19F NMR
(376.4 MHz, C6D6, 20 °C): δ = –162.45 to –162.07 (m, 2 F),
–159.86 (t, 1 F), –149.00 to –148.86 (m, 1 F), –144.43 (d, 1 F) ppm.
C24H8F10GeN2S (618.9938): calcd. C 46.57, H 1.30, N 4.53; found
C 46.36, H 1.66, N 4.43.
Method B: A solution LiN(TMS)2·Et2O (0.88 g, 3.66 mmol) in thf
(10 mL) was added dropwise at –78 °C to a stirred solution of
MeN(CH2CH2NHC6F5)2 (1a; 0.82 g, 1.83 mmol) in thf (15 mL).
The reaction mixture was stirred for 1 h and then warmed to room
temperature. The reaction mixture was again cooled to –78 °C, and
[GeCl2·C4H8O2] (0.42 g, 1.83 mmol) in thf (15 mL) was added with
stirring. After stirring at room temperature for 24 h, the volatiles
were removed under vacuum. Recrystallization from toluene solu-
tion gave 2a (0.22 g, 24%) as a white solid.
BnN(CH2CH2NC6F5)2Ge (2b): The procedure was analogous to
that used for 2a (Method A) by employing BnN(CH2CH2-
NHC6F5)2 (1b; 0.81 g, 1.55 mmol) and Ge[N(TMS)2]2 (0.61 g,
1.55 mmol). Colorless crystals of 2b (0.42 g, 46%) were obtained
from a toluene solution (6 mL) at –20 °C. 1H NMR (400 MHz,
C6D6, 25 °C): δ = 1.79–1.85, 2.31–2.40 (2 m, 4 H, 2 NCH2), 3.08–
3.14 (m, 2 H, NCH2C6F5), 3.38 (s, 2 H, NCH2Ph), 3.41–3.50 (m,
2 H, NCH2C6F5), 6.73–6.76, 7.00–7.07 (2 m, 5 H, Ph) ppm. 13C
NMR (100 MHz, C6D6, 25 °C):
δ
=
51.44 (NCH2), 56.94
Method B: A solution of Ge[N(SiMe3)2]2 (0.26 g, 0.66 mmol) in tol-
uene (10 mL) was added to a stirred solution of 1f (0.36 g,
0.66 mmol) in toluene (10 mL). The progress of the reaction was
monitored by 19F NMR spectroscopy. Even after boiling the mix-
ture for 24 h, only signals from the starting materials were detected
(NCH2C6F5), 62.62 (PhCH2), 128.77, 129.35, 131.45, 131.51 (Ph)
ppm. The 13C NMR signals of the pentafluorophenyl rings were
not observed under these conditions due to poor solubility and
higher-order C–F coupling. 19F NMR (376.4 MHz, C6D6, 25 °C):
δ = –172.86 to –172.65 (m, 1 F), –165.30 to –165.14 (m, 2 F), in the spectrum.
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
9

Job/Unit: I20363
/KAP1
Date: 02-07-12 10:59:01
Pages: 14
K. V. Zaitsev, J. Sundermeyer, S. S. Karlov et al.
FULL PAPER
[oC6H4(NC6F5)2]2Ge (2i)
MeN(CH2CH2NC6F5)2GeCl2 (4): A solution of GeCl4 (0.21 g,
0.96 mmol) in toluene (5 mL) was added dropwise to a stirred solu-
tion of 2a (0.50 g, 0.96 mmol) in toluene (10 mL) at 0 °C. After
stirring at room temperature for 24 h, a white precipitate of
[GeCl2]n was separated by filtration. The precipitate was extracted
with toluene (10 mL), and the organic solutions were combined.
The volatiles were removed under vacuum, and diethyl ether
(10 mL) was added. A white solid was separated by filtration,
washed with diethyl ether (2ϫ2 mL), and dried under vacuum to
give 4 (0.30 g, 54%) as a white solid. The 1H and 13C NMR spectra
are in accord with literature data.[24b] 1H NMR (400 MHz, C6D6,
25 °C): δ = 1.93 (s, 3 H, NCH3), 1.93–1.98, 2.20–2.25 (2 m, 4 H, 2
NCH2), 2.83–2.69 (m, 4 H, 2 NCH2C6F5) ppm. 13C NMR
(100 MHz, C6D6, 25 °C): δ = 43.37 (CH3), 45.04 (NCH2), 50.99
(NCH2C6F5) ppm.
Method A: The procedure was analogous to that used for 2a
(Method B); treatment of N,NЈ-bis(pentafluorophenyl)benzene-1,2-
diamine (1i; 0.57 g, 1.30 mmol) in thf (10 mL) with a solution of
LiN(SiMe3)2·Et2O (0.62 g, 2.60 mmol) in thf (10 mL) and then
[GeCl2·C4H8O2] (0.30 g, 1.30 mmol) gave compound 2i (0.44 g,
67%) from thf (5 mL) at –20 °C. 1H NMR (400 MHz, C6D6,
25 °C): δ = 6.51–6.58, 6.92–6.98 (2 m, 4 H, C6H4) ppm. 13C NMR
(100 MHz, C6D6, 25 °C): δ = 111.60, 121.21, 139.53 (C6H4), 136.58,
139.93, 141.85, 145.24 (NC6F5) ppm. 19F NMR (376.4 MHz, C6D6,
25 °C): δ = –164.19 (br. t, 2 F), –159.65 (br. t, 1 F), –149.03 (d, 2
F) ppm. MS (EI): m/z (%) = 512 (100) [M]+.
Method B: The procedure was analogous to that used for 2a
(Method A); 1,3-bis(pentafluorophenyl)benzene-1,2-diamine (1g;
0.48 g, 1.10 mmol) was treated with Ge[N(TMS)2]2 (0.42 g,
1.10 mmol) in toluene (15 mL). The progress of the reaction was
monitored by 19F NMR spectroscopy. Even after boiling the mix-
ture for 24 h, only signals from the starting materials were detected
in the spectrum.
MeN(CH2CH2NC6F5)2Ge(Me)I (5a): A solution of MeI (0.27 g,
1.92 mmol) in toluene (5 mL) was added to a stirred solution of 2a
(0.50 g, 0.96 mmol) in toluene (10 mL). The reaction mixture was
stirred at room temperature for 4 d, and the precipitate was filtered
1
off to give 5a (0.58 g, 91%) as a white solid. H NMR (400 MHz,
C6D6, 25 °C): δ = 1.04 (s, 3 H, CH3Ge), 1.47 (s, 3 H, NCH3), 1.61–
1.71, 2.16–2.23, 2.60–2.71, 2.91–3.02 (4 m, 8 H, 2 NCH2 and 2
NCH2C6F5) ppm. 13C NMR (100 MHz, C6D6, 25 °C): δ = 22.21
(GeCH3), 43.05 (NCH3), 48.23 (NCH2), 56.26 (NCH2C6F5) ppm.
The 13C NMR signals of the pentafluorophenyl rings were not ob-
served under these conditions due to poor solubility and higher-
order C–F coupling. C18H14F10GeIN3 (611.8225): calcd. C 32.67,
H 2.13, N 6.35; found C 32.43, H 2.09, N 6.44. Crystals suitable
for single-crystal X-ray diffraction were grown from a concentrated
toluene solution.
Ge[N(C6F5)2]2 (2j)
Method A: The procedure was analogous to that used for 2a
(Method B); treatment of bis(pentafluorophenyl)amine (1j; 0.96 g,
2.75 mmol) in thf (10 mL) with a solution of LiN(SiMe3)2·Et2O
(0.66 g, 2.75 mmol) in thf (10 mL) and then GeCl2·C4H8O2 (0.32 g,
1.35 mmol) led to compound 2j (0.25 g, 24%), which was crys-
tallized from thf (6 mL) at –20 °C. 19F NMR (376.4 MHz, C6D6,
25 °C): δ = –164.19 (br. t, 2 F), –159.65 (br. t, 1 F), –149.03 (d, 2
F) ppm. The 13C NMR signals of the pentafluorophenyl rings were
not observed under these conditions due to poor solubility and
higher-order C–F coupling.
BnN(CH2CH2NC6F5)2Ge(Me)I (5b): The procedure was analogous
to that used for 5a; reaction of 2b (0.70 g, 1.17 mmol) with MeI
(0.33 g, 2.34 mmol) in toluene (15 mL) gave 5b (0.51 g, 59%) as a
Method B: The procedure was analogous to that used for 2a
(Method A): bis(pentafluorophenyl)amine (1j; 0.77 g, 2.20 mmol)
was treated with Ge[N(TMS)2]2 (0.42 g, 1.10 mmol) in toluene
(15 mL). The progress of the reaction was monitored by 19F NMR
spectroscopy. Even after boiling the mixture for 24 h, only signals
from the starting materials were detected in the spectrum.
1
white solid. H NMR (400 MHz, C6D6, 50 °C): δ = 1.60 (s, 3 H,
CH3Ge), 2.19–2.36 (m, 4 H, 2 NCH2), 2.90–2.98, 3.03–3.11 (2 m,
4 H, 2 NCH2C6F5), 3.33 (s, 2 H, PhCH2), 6.70–6.74, 6.98–7.05 (2
m, 5 H, Ph) ppm. 13C NMR (100 MHz, C6D6, 50 °C): δ = 23.06
(GeCH3), 46.42 (NCH2), 48.06 (NCH2C6F5), 56.78 (PhCH2),
127.89, 128.82, 129.13, 131.25 (Ph) ppm. The 13C NMR signals of
the pentafluorophenyl rings were not observed under these condi-
tions due to poor solubility and higher-order C–F coupling.
C24H18F10GeIN3 (737.9184): calcd. C 39.06, H 2.46, N 5.69; found
C 39.23, H 2.40, N 5.50. Crystals suitable for single-crystal X-ray
diffraction were grown from a concentrated toluene solution.
MeN(CH2CH2NC6F5)2GeBr2 (3a): A solution of bromine (0.14 g,
0.87 mmol) in toluene (5 mL) was added to a stirred solution of 2a
(0.45 g, 0.87 mmol) in toluene (10 mL). The reaction mixture was
stirred at room temperature for 1 d, and the volatiles were then
removed under vacuum. Then diethyl ether (10 mL) was added to
the residue, and the precipitate was filtered off to give 3a (0.45 g,
76%) as a white solid. The 1H and 13C NMR spectra are in accord
with literature data.[24b] 1H NMR (400 MHz, C6D6, 25 °C): δ =
1.85 (s, 3 H, NCH3), 1.92–1.98, 2.14–2.20 (2 m, 4 H, 2 NCH2),
2.78–2.70 (m, 4 H, 2 NCH2C6F5) ppm. 13C NMR (100 MHz,
C6D6, 25 °C): δ = 43.64 (CH3N), 45.27 (NCH2), 50.48 (NCH2C6F5)
ppm. The 13C NMR signals of the pentafluorophenyl rings were
not observed under these conditions due to poor solubility and
higher-order C–F coupling.
BnN(CH2CH2NC6F5)2Ge(SPh)2 (6): A solution of Ph2S2 (0.21 g,
0.96 mmol) in toluene (5 mL) was added dropwise at –40 °C to a
stirred solution of 2b (0.57 g, 0.96 mmol) in toluene (10 mL). The
reaction mixture was stirred for 30 min and then warmed to room
temperature. After stirring for 4 d, the volatiles were removed under
vacuum and pentane (10 mL) was added. The precipitate was sepa-
rated by filtration, washed with pentane (2ϫ2 mL), and dried in
vacuo to give 6 (0.60 g, 77%) as a white solid. 1H NMR (400 MHz,
C6D6, 25 °C): δ = 2.41 (t, J = 5.6 Hz, 4 H, NCH2), 3.07 (t, J =
5.6 Hz, 4 H, NCH2C6F5), 4.09 (s, 3 H, PhCH2), 6.79–6.96, 6.98–
7.06, 7.34–7.42 (3 m, 15 H, 3Ph) ppm. 13C NMR (100 MHz, C6D6,
25 °C): δ = 48.53, 48.95, 57.60 (NCH2, PhCH2, NCH2C6F5),
125.61, 127.28, 128.51, 128.69, 129.28, 131.14, 133.62, 136.11 (Ph)
ppm. The 13C NMR signals of the pentafluorophenyl rings were
not observed under these conditions due to poor solubility and
higher-order C–F coupling. C35H25F10GeN3S2 (841.3193): calcd. C
51.62, H 3.09, N 5.16; found C 51.68, H 3.17, N 5.20.
S(oC6H4NC6F5)2GeBr2 (3f): By applying the same experimental
procedure as described above with 2f (0.26 g, 0.42 mmol) and bro-
mine (0.067 g, 0.42 mmol), compound 3f (0.28 g, 87%) was ob-
tained as a white solid. 1H NMR (400 MHz, C6D6, 25 °C): δ = 5.45
(s), 5.97–6.03 (m), 7.00–7.06 (dd), 7.35 (d, 8 H, aromatic protons)
ppm. 19F NMR (376.4 MHz, C6D6, 25 °C): δ = –163.00 to –162.79
(m,
2
F), –161.17 (t,
1
F), –149.45 (d,
2
F) ppm.
C24H8Br2F10GeN2S (778.802): calcd. C 37.01, H 1.04, N 3.60;
found C 36.86, H 1.24, N 3.48.
10
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Eur. J. Inorg. Chem. 0000, 0–0

Job/Unit: I20363
/KAP1
Date: 02-07-12 10:59:01
Pages: 14
Germylenes Based on Diethylenetriamines and Related Diamines
Reaction of 2a with Et2S2: The procedure was analogous to that
used for 6; compound 2a (0.27 g, 0.52 mmol) was treated with
Et2S2 (0.06 g, 0.52 mmol) in toluene (15 mL). After stirring for 4 d,
the volatiles were removed under vacuum to give a yellow solid
(0.31 g). On the basis of the NMR spectroscopic data, only starting
materials were found in the reaction mixture.
of 2b (0.74 g, 1.24 mmol) in toluene (10 mL). The reaction mixture
was stirred at room temperature for 4 d, and the volatiles were re-
moved under vacuum. Then diethyl ether (10 mL) was added to
the residue, and the precipitate was filtered off to give 10 (0.43 g,
43%) as a white solid. 1H NMR (400 MHz, C6D6, 25 °C): δ = 2.18–
2.23, 2.38–2.44 (2 m, 4 H, 2 NCH2), 2.91–2.99 (m, 4 H, 2
NCH2C6F5), 4.18 (s, 2 H,CH2Ph), 6.70–6.72, 6.82–6.86, 6.92–6.99,
7.03–7.13, 7.25–7.27, 7.65–7.68 (6 m, 15 H, 3Ph) ppm. 13C NMR
(100 MHz, C6D6, 25 °C): δ = 43.51 (NCH2), 47.79 (NCH2C6F5),
57.07 (PhCH2), 126.55, 127.06, 127.64, 128.80, 129.20, 130.87,
131.80, 135.39, 136.02, 136.55, 138.26, 139.22, 145.25, 147.72 (2 C
and 3 Ph) ppm. The 13C NMR signals of the pentafluorophenyl
rings were not observed under these conditions due to poor solubil-
ity and higher-order C–F coupling. 19F NMR (376.4 MHz, C6D6,
25 °C): δ = –148.33 to –148.17 (m, 1 F), –161.28 to –161.12 (m, 3
[BnN(CH2CH2NC6F5)2Ge]2(μ-O)2 (7): A solution of Me3NǞO
(0.04 g, 0.54 mmol) in toluene (5 mL) was added to a stirred solu-
tion of 2b (0.32 g, 0.54 mmol) in toluene (10 mL). The reaction
mixture was stirred at room temperature for 4 d. The volatiles were
removed under vacuum, and diethyl ether (10 mL) was added. The
precipitate was filtered off to give 7 (0.14 g, 42%) as a white solid.
1H NMR (400 MHz, C6D6, 25 °C): δ = 2.16–2.32, 2.41–2.54 (2 m,
4 H, 2 NCH2), 2.73–2.85, 3.15–3.28 (2 m, 4 H, 2 NCH2C6F5), 3.72
(s, 2 H, PhCH2), 6.79–6.90, 6.96–7.12 (5 H, Ph) ppm. 13C NMR
(100 MHz, C6D6, 25 °C): δ = 43.52, 47.21 (NCH2), 53.27 (CH2Ph),
128.86, 128.94, 131.31, 138.65 (Ph) ppm. The 13C NMR signals of
the pentafluorophenyl rings were not observed under these condi-
tions due to poor solubility and higher-order C–F coupling.
C46H30F20Ge2N6O2 (1223.9577): calcd. C 45.14, H 2.47, N 6.87;
found C 45.30, H 2.55, N 6.90. Crystals suitable for single-crystal
X-ray diffraction were grown from a concentrated toluene solution
of 7.
F), –164.98 to –164.86 (m,
1 F) ppm. C37H25F10GeN3O2
(806.2075): calcd. C 55.12, H 3.13, N 5.21; found C 55.48, H 3.28,
N 5.24.
MeN(CH2CH2NC6F5)2Ge-cyclo-[OC(Ph)CHCHPh] (11): Solid
(E)-PhC(O)CH=CHPh (0.09 g, 0.42 mmol) was added to a stirred
solution of 2a (0.22 g, 0.42 mmol) in toluene (10 mL). The reaction
mixture was stirred at room temperature for 7 d. The precipitate
1
was filtered off to give 11 (0.23 g, 74%) as a white solid. H NMR
(400 MHz, C6D6, 25 °C): δ = 1.45–1.52, 1.61–1.71 (2 m, 4 H, 2
NCH2), 1.79 (s, 3 H, CH3N), 2.61–2.89 (m, 4 H, 2 NCH2C6F5),
3.56 (d, J = 3.3 Hz, 1 H, CHPh), 5.40 [d, J = 3.3 Hz, 1 H,
CH=C(O)Ph], 6.87–6.99, 7.04–7.09, 7.20–7.30, 7.35–7.39 (4 m, 10
H, 2Ph) ppm. 13C NMR (100 MHz, C6D6, 25 °C): δ = 40.03
(CHPh), 41.69 (CH3N), 44.28, 44.71, 52.9, 53.14 (4 NCH2), 99.35
[CH=C(O)Ph], 124.47, 126.01, 128.61, 128.74, 129.98, 135.48,
143.38 (2 Ph), 145.38 [PhC(O)=CH] ppm. The signal of one carbon
atom was not observed; the signals of the pentafluorophenyl rings
were not observed under these conditions due to poor solubility
and higher-order C–F coupling. C32H23F10GeN3O (728.1387):
calcd. C 52.78, H 3.18, N 5.77; found C 52.58, H 3.28, N 5.58.
Crystals suitable for single-crystal X-ray diffraction were grown
from a concentrated toluene solution of 11.
[MeN(CH2CH2NC6F5)2Ge]2(μ-S)2 (8): A solution of S8 (0.03 g,
0.10 mmol) in thf (10 mL) was added to a stirred solution of 2a
(0.40 g, 0.77 mmol) in thf (10 mL). The reaction mixture was
stirred at room temperature for 5 d and the volatiles were removed
under vacuum. After recrystallization from a concentrated solution
of toluene, white crystals of 8 (0.19 g, 45%) were obtained. 1H
NMR (400 MHz, C6D6, 25 °C): δ = 1.67 (s, 3 H, NCH3), 2.02–
2.10, 2.34–2.43 (2 m, 4 H, 2 NCH2), 2.73–2.83, 3.03–3.12 (2 m, 4
H, 2 NCH2C6F5) ppm. 13C NMR (100 MHz, C6D6, 25 °C): δ =
42.69 (NCH3), 45.73, 50.98 (4 NCH2) ppm. The 13C NMR signals
of the pentafluorophenyl rings were not observed under these con-
ditions due to poor solubility and higher-order C–F coupling.
C34H22F20Ge2N6S2 (1103.899): calcd. C 36.99, H 2.01, N 7.61, S
5.81; found C 36.82, H 1.95, N 7.55, S 5.97.
[BnN(CH2CH2NC6F5)2GeN=P(OPh)2O]2 (9):
A
solution of
BnN(CH2CH2NC6F5)2Ge-cyclo-[OC(Fc)CHCHPh] (12): Solid of
(E)-FcC(O)CH=CHPh (0.08 g, 0.25 mmol) was added to a stirred
solution of 2b (0.15 g, 0.25 mmol) in toluene (15 mL). The reaction
mixture was stirred at room temperature. After stirring for 7 d, the
volatiles were removed under vacuum, and diethyl ether (10 mL)
was added. The precipitate was separated by filtration, washed with
diethyl ether (2ϫ2 mL), and dried in vacuo to give 12 (0.10 g,
N3P(O)(OPh)2 (0.16 g, 0.59 mmol) in toluene (10 mL) was added
to a stirred solution of 2b (0.35 g, 0.59 mmol) in toluene (10 mL).
The reaction mixture was stirred at room temperature for 4 d. The
precipitate was filtered off to give 9 (0.27 g, 54%) as a white solid.
1H NMR (400 MHz, C6D6, 25 °C): δ = 2.29–2.44 (m, 4 H, 2
NCH2), 2.89–2.97, 3.10–3.19 (2 m, 4 H, 2 NCH2C6F5), 3.46 (s, 2
H, PhCH2), 6.72–6.83, 6.96–7.01, 7.03–7.12 (3 m, 15 H, 3Ph) ppm.
The 13C NMR spectrum was not recorded because of the low solu-
bility of 9. 31P NMR (161.98 MHz, C6D6, 25 °C): δ = –34.19 (s)
ppm. C70H50F20Ge2N8O6P2 (1686.3319): calcd. C 49.86, H 2.99, N
6.64; found C 49.95, H 2.91, N 6.51.
1
44%) as an orange solid. H NMR (400 MHz, C6D6, 25 °C): δ =
1.87–3.06 (m, 8 H, NCH2), 3.64 (d, J = 2.9 Hz, 1 H, PhCH), 3.83
(s, 5 H, C5H5), 3.86 (s, 2 H, CH2Ph), 3.69–3.79, 3.90–3.96, 4.01–
4.05, 4.09–4.14 (4 m, 4 H, C5H4), 5.12 [d, J = 2.9 Hz, 1 H,
CH=C(O)Fc], 6.65–6.70, 7.03–7.11, 7.20–7.27, 7.40–7.45 (4 m, 10
H, 2 Ph) ppm. 13C NMR (100 MHz, C6D6, 25 °C): δ = 43.28
(CHPh), 53.21, 63.54 (NCH2), 64.33, 67.11, 67.50 (C5H4), 67.90
(C5H5), 68.69 (CH2Ph), 96.49 [CH=C(O)Fc], 125.48, 127.47,
127.86, 128.66 (Ph), 130.24 [CH=C(O)Fc] ppm. The 13C NMR sig-
nals of the pentafluorophenyl rings were not observed under these
conditions due to poor solubility and higher-order C–F coupling.
C42H31F10FeGeN3O (912.1542): calcd. C 55.30, H 3.43, N 4.61;
found C 55.16, H 3.52, N 4.80.
Reaction of BnN(CH2CH2NC6F5)2Ge with H2O: H2O (0.01 g,
0.55 mmol) was added to
a stirred solution of 2b (0.15 g,
0.25 mmol) in thf (5 mL) at room temperature. After stirring for
5 d, the volatiles were removed under vacuum. Toluene (5 mL) was
added to the residue, and the precipitate was filtered. After remov-
ing all the volatiles in vacuo, a yellow oil was obtained, which cor-
responds to the starting amine 1b according to the NMR spectro-
scopic data.[24b] 1H NMR (400 MHz, C6D6, 25 °C): δ = 2.10 (t, J
= 5.8 Hz, 4 H, NCH2), 2.85–2.92 (q, 4 H, 2 NCH2C6F5), 3.06 (s,
2 H, PhCH2), 3.78 (br. s, 2 H, NHC6F5), 7.01–7.11 (m, 5 H, Ph)
ppm.
Reaction of 2b with 2,3-Dimethylbuta-1,3-diene
Method A:
A solution of 2,3-dimethylbuta-1,3-diene (0.37 g,
BnN(CH2CH2NC6F5)2Ge-cyclo-[OC(Ph)C(Ph)O]
(10):
Solid
4.50 mmol) in toluene (5 mL) was added to a stirred solution of 2b
PhC(O)C(O)Ph (0.26 g, 1.24 mmol) was added to a stirred solution
(0.27 g, 0.45 mmol) in toluene (10 mL). The mixture was stirred at
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Job/Unit: I20363
/KAP1
Date: 02-07-12 10:59:01
Pages: 14
K. V. Zaitsev, J. Sundermeyer, S. S. Karlov et al.
FULL PAPER
room temperature for 4 d or heated at reflux, and the volatiles were
removed under vacuum. On the basis of the NMR spectroscopic
data, a mixture of unidentified compounds was obtained.
vacuum to yield 0.39 g of a brown solid. On the basis of the NMR
spectroscopic data, this was a mixture of the starting materials.
X-ray Crystallography: Crystal data and details of the X-ray analy-
ses are given in Table 1. Experimental data sets were collected with
Stoe IPDS-1 (for 2b, 2i, and 2j) and Bruker SMART APEX II
(for 5b, 7a, 7b, 8, 10, and 11) diffractometers by using graphite-
monochromatized Mo-Kα radiation (λ = 0.71073 Å). The structures
were solved by direct methods (Sir97 for 2b, 2i, and 2j,[40]
SHELXS[41] for 5b, 7a, 7b, 8, 10, and 11) and refined by full-matrix
least-squares methods on F2 with anisotropic thermal parameters
for all non-hydrogen atoms (except solvent toluene molecules in 5b
and 10). All hydrogen atoms were placed in calculated positions
and refined by using a riding model. CCDC-854658 (for 2b),
-854659 (for 2i), -854660 (for 2j), -854661 (for 5b), -854662 (for
Method B:
A
solution 2,3-dimethylbuta-1,3-diene (0.37 g,
4.50 mmol) in toluene (5 mL) was added dropwise to a stirred solu-
tion of 2b (0.27 g, 0.45 mmol) in toluene (10 mL) at –78 °C. The
reaction mixture was stirred for 1 h and warmed to room tempera-
ture. After stirring for 4 d, the volatiles were removed under
vacuum. After recrystallization from toluene, 2b was obtained as a
white solid.
Reaction of 2b with tBuN=C–C=N-tBu: A solution of 2b (0.31 g,
0.52 mmol) was added to a stirred solution of tBuN=C–C=NtBu
(0.09 g, 0.52 mmol) in toluene (15 mL). The reaction mixture was
stirred at reflux for 12 h, and the volatiles were removed under 7a), -854663 (for 7b), -854664 (for 8), -854665 (for 10), and -854666
Table 1. Crystallographic data collection parameters for 2b, 2i, 2j, 5b, 7a, 7b, 8, 10, and 11.
Complex
2b
2i
2j
5b
7a
Formula
Mr
Crystal system
Space group
Z
C23H15F10GeN3
595.97
C18H4F10GeN2
510.84
orthorhombic
Pnma
C24F20GeN2
768.85
orthorhombic
Pbca
C31H26F10GeIN3 C29H47F10Ge2N5O2Si4
830.04
orthorhombic
Pbca
945.26
monoclinic
P21/n
triclinic
¯
P1
2
4
8
8
4
T [K]
a [Å]
b [Å]
c [Å]
α [°]
β [°]
293(2)
293(2)
293(2)
14.120(5)
14.123(5)
24.455(5)
90
90
90
4877(3)
2.094
1.431
32864
4772 (0.0628)
424
180(2)
12.8050(18)
21.427(3)
22.556(3)
90
90
90
6188.8(15)
1.782
2.076
56717
6747 (0.0655)
382
150(2)
7.693(5)
8.601(5)
17.731(5)
84.663(5)
80.985(5)
75.536(5)
1120.2(10)
1.767
1.469
9827
4096 (0.0588)
334
0
6.1666(12)
20.818(4)
15.324(3)
90
90
90
1967.2(7)
1.725
1.656
14500
1981 (0.0612)
143
11.0262(8)
34.270(2)
11.2722(8)
90
111.592(1)
90
3960.5(5)
1.585
1.721
γ [°]
V [Å3]
ρcalcd. [gcm–3]
μ [mm–1]
Total reflections
Unique reflections (Rint
No. of variables
Restraints
R1 [IϾ2σ(I)]
wR2 (all data)
40700
9567 (0.0317)
482
)
0
0
0
0
0.0342
0.0809
0.0387
0.1319
0.363/–1.175
0.0313
0.0715
0.364/–0.232
0.0358
0.0907
1.654/–0.782
0.0282
0.0682
0.490/–0.399
Largest diff. peak/hole [eÅ–3] 0.615/–0.792
Complex
7b
8
10
11
Formula
Mr
Crystal system
Space group
Z
C70H54F20Ge2N6O2 C34H22F20Ge2N6S2 C48.67H38.33F10GeN3O2 C35H26F10GeN3O
1536.37
triclinic
P1
1103.88
triclinic
P1
959.75
767.18
trigonal
triclinic
¯
¯
¯
¯
R3
P1
1
1
18
2
T [K]
a [Å]
b [Å]
c [Å]
α [°]
β [°]
150(2)
150(2)
150(2)
44.999(3)
44.999(3)
11.6920(18)
90
90
120
20503(4)
1.399
0.755
58502
8487 (0.1260)
515
150(2)
11.8540(11)
11.9205(12)
13.3564(13)
68.806(2)
75.749(2)
64.895(1)
1583.8(3)
1.611
1.061
13431
6753 (0.0277)
451
0
9.330(3)
10.952(3)
11.206(3)
63.389(4)
71.037(4)
66.982(4)
926.5(5)
1.978
1.875
5872
3472 (0.0438)
290
0
11.0951(6)
11.7015(6)
12.7451(6)
93.032(1)
106.189(1)
92.008(1)
1584.71(14)
1.608
1.061
15281
6909 (0.0352)
452
0
γ [°]
V [Å3]
ρcalcd. [gcm–3]
μ [mm–1]
Total reflections
Unique reflections (Rint
No. of variables
Restraints
R1 [IϾ2σ(I)]
wR2 (all data)
)
10
0.0346
0.0795
0.0627
0.1621
1.770/–1.709
0.0630
0.1876
0.686/–0.526
0.0375
0.0851
0.508/–0.455
Largest diff. peak/hole [eÅ–3] 0.438/–0.317
12
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Job/Unit: I20363
/KAP1
Date: 02-07-12 10:59:01
Pages: 14
Germylenes Based on Diethylenetriamines and Related Diamines
[18] S. R. Stobart, M. R. Churchill, F. J. Hollander, W. J. Youngs,
J. Chem. Soc., Chem. Commun. 1979, 911–912.
[19] N. A. Victorov, T. K. Gar, I. S. Nikishina, V. M. Nosova, D. A.
Ivaschenko, V. F. Mironov, Russ. J. Gen. Chem. 1986, 56, 1535–
1539.
(for 11) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[20] J. Barrau, G. Rima, T. E. Amraoui, J. Organomet. Chem. 1998,
570, 163–174.
[21] D. Ellis, P. B. Hitchcock, M. F. Lappert, J. Chem. Soc., Dalton
Trans. 1992, 3397–3398.
Acknowledgments
[22] P. Jutzi, H. Schmidt, B. Neumann, H. G. Stammler, Organome-
tallics 1996, 15, 741–746.
[23] I. Schranz, L. Grocholl, C. J. Carrow, L. Stahl, R. J. Staples, J.
Organomet. Chem. 2008, 693, 1081–1095.
E. K. L. gratefully acknowledges Deutscher Akademischer Aus-
tauschdienst (DAAD) for supporting
a three-month stay at
Philipps-Universität Marburg. We thank the Russian Foundation
for Basic Research (Grant 09-03-00536-a).
[24] a) Y. I. Baukov, S. N. Tandura in The chemistry of organic ger-
manium, tin and lead compounds (Ed.: Z. Rappoport), Wiley,
Chichester, 2002, vol. 2, pp. 1036–1072; b) E. Kh. Lermontova,
M. Huan, A. V. Churakov, J. A. K. Howard, M. V. Zabalov,
S. S. Karlov, G. S. Zaitseva, Dalton Trans. 2009, 4695–4702.
[25] A. Meller, G. Ossig, W. Maringgele, M. Noltemeyer, D. Stalke,
R. Herbstirmer, S. Freitag, G. M. Sheldrick, Z. Naturforsch. B
1992, 47, 162–170.
[26] a) N. Tokitoh, K. Manmaru, R. Okazaki, Organometallics
1994, 13, 167–171; b) G. Billeb, K. Bootz, W. P. Neumann, G.
Steinhoff, J. Organomet. Chem. 1991, 406, 303–308.
[27] S. N. Gurkova, A. I. Gusev, N. V. Alekseev, T. K. Gar, N. A.
Viktorov, J. Struct. Chem. 1991, 31, 833–835.
[28] a) N. V. Alekseev, S. N. Gurkova, A. I. Gusev, S. N. Tandura,
T. K. Gar, N. Y. Khromova, N. A. Viktorov, V. F. Mironov, Zh.
Obshch. Khim. 1982, 52, 2136–2137; b) S. N. Gurkova, A. I.
Gusev, N. V. Alekseev, T. K. Gar, N. Y. Khromova, N. A.
Viktorov, J. Struct. Chem. 1984, 25, 458–462.
[29] D. H. Chen, H. C. Chiang, J. Chin. Chem. Soc. 1993, 40, 373–
377.
[1]
[2]
a) T. Szyman´ska-Buzar, Coord. Chem. Rev. 2005, 249, 2195–
2202; b) M. Górski, A. Kochel, T. Szyman´ska-Buzar, J. Or-
ganomet. Chem. 2006, 691, 3708–3714.
a) T. Chen, W. Hunks, P. S. Chen, G. T. Stauf, T. M. Cameron,
C. Xu, A. G. DiPasquale, A. L. Rheingold, Eur. J. Inorg. Chem.
2009, 2047–2049; b) M. A. Malik, M. Afzaal, P. O’Brien,
Chem. Rev. 2010, 110, 4417–4446.
[3]
[4]
M. Asay, C. Jones, M. Driess, Chem. Rev. 2011, 111, 354–396.
J.-L. Fauré, H. Gornitzka, R. Réau, D. Stalke, G. Bertrand,
Eur. J. Inorg. Chem. 1999, 2295–2299.
[5]
[6]
M. Veith, S. Becker, V. Huch, Angew. Chem. 1989, 101, 1287;
Angew. Chem. Int. Ed. Engl. 1989, 28, 1237–1238.
M. Huang, M. M. Kireenko, K. V. Zaitsev, Y. F. Oprunenko,
A. V. Churakov, J. A. K. Howard, M. V. Zabalov, E. Kh. Ler-
montova, J. Sundermeyer, T. Linder, S. S. Karlov, G. S. Zait-
seva, J. Organomet. Chem. 2012, 706–707, 66–83.
[7]
[8]
a) F. E. Hahn, A. V. Zabula, T. Pape, A. Hepp, Eur. J. Inorg.
Chem. 2007, 2405–2408; b) T. Gans-Eichler, D. Gudat, K. Nat-
tinen, M. Nieger, Chem. Eur. J. 2006, 12, 1162–1173.
a) D. Matioszek, N. Katir, N. Saffon, A. Castel, Organometal-
lics 2010, 29, 3039–3046; b) A. McHeik, N. Katir, A. Castel,
H. Gornitzka, S. Massou, P. Riviere, T. Hamieh, Eur. J. Inorg.
Chem. 2008, 5397–5403.
[30] A. Arndt, H. Schafer, W. Saak, M. Weidenbruch, Z. Anorg.
Allg. Chem. 2005, 631, 1341–1342.
[31] M. J. S. Gynane, D. H. Harris, M. F. Lappert, P. P. Power, P.
Riviere, M. Riviere-Baudet, J. Chem. Soc., Dalton Trans. 1977,
2004–2009.
[32] S. P. Kolesnikov, I. S. Rogozhin, O. M. Nefedov, Bull. Acad.
Sci. USSR Div. Chem. Sci. (Engl. Transl.) 1974, 23, 2297–
2298.
[33] U. Wannagat, H. Niederprum, Chem. Ber. 1961, 94, 1540–1547.
[34] R. R. Schrock, J. Lee, L.-C. Liang, W. M. Davis, Inorg. Chim.
Acta 1998, 270, 353–362.
[9] A. J. Arduengo, R. L. Harlow, M. Kline, J. Am. Chem. Soc.
1991, 113, 361–363.
[10] R. W. Chorley, P. B. Hitchcock, M. F. Lappert, W. P. Leung,
P. P. Power, M. M. Olmstead, Inorg. Chim. Acta 1992, 198, 203–
209.
[11] A. Schnepf, Z. Anorg. Allg. Chem. 2006, 632, 935–938.
[12] M. Veith, A. Rammo, Z. Anorg. Allg. Chem. 2001, 627, 662– [36] H. C. S. Clark, G. N. Cloke, P. B. Hitchcock, J. B. Love, A. P.
[35] Y. Li, A. Turnas, J. T. Ciszewski, A. L. Odom, Inorg. Chem.
2002, 41, 6298–6306.
668.
Wainwright, J. Organomet. Chem. 1995, 501, 333–340.
[37] C. R. Hauser, J. K. Lindsay, J. Org. Chem. 1957, 22, 482–485.
[38] a) R. Koppang, Acta Chem. Scand. 1971, 25, 3067–3071; b) A.
Khvorost, P. L. Shutov, K. Harms, J. Lorberth, J. Sundermeyer,
S. S. Karlov, G. S. Zaitseva, Z. Anorg. Allg. Chem. 2004, 630,
885–889.
[13] M. Huang, E. Kh. Lermontova, K. V. Zaitsev, A. V. Churakov,
Y. F. Oprunenko, J. A. K. Howard, S. S. Karlov, G. S. Zaitseva,
J. Organomet. Chem. 2009, 694, 3828–3832.
[14] M. Veith, M. Grosser, V. Huch, Z. Anorg. Allg. Chem. 1984,
513, 89–102.
[15] a) E. Bonnefille, S. Mazires, N. El Hawi, H. Gornitzka, C. Co-
uret, J. Organomet. Chem. 2006, 691, 5619–5625; b) A.
Tzschach, M. Scheer, K. Jurkschat, Z. Anorg. Allg. Chem. 1984,
512, 177–180.
[39] M. M. Khusniyarov, E. Bill, Th. Weyhermüller, E. Bothe, K.
Harms, J. Sundermeyer, K. Wieghardt, Chem. Eur. J. 2008, 14,
7608–7622. This ligand was first obtained in 20% yield, see: A.
Khvorost, Ph. D. Thesis, Philipps-Universität Marburg, 2003.
The refined synthetic procedure and other ligand syntheses by
nucleophilic amidation of C6F6 were developed later, see: A.
Sorokin, Ph. D. Thesis, Philipps-Universität Marburg, 2006.
[40] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C.
Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R.
Spagna, J. Appl. Crystallogr. 1999, 32, 115–119.
[16] a) L. D. Silverman, M. Zeldin, Inorg. Chem. 1980, 19, 270–272;
b) Y. Ding, Q. Ma, H. W. Roesky, R. Herbst-Irmer, I. Usón,
M. Noltemeyer, H.-G. Schmidt, Organometallics 2002, 21,
5216–5220; c) C. S. Weinert, A. E. Fenwick, P. E. Fanwick, I. P.
Rothwell, Dalton Trans. 2003, 532–539.
[17] a) K. A. Miller, J. M. Bartolin, R. M. O’Neill, R. D. Sweeder,
T. M. Owens, J. W. Kampf, M. M. B. Holl, N. J. Wells, J. Am. [41] G. M. Sheldrick, SHELXL-97, Program for the Refinement of
Chem. Soc. 2003, 125, 8986–8987; b) A. E. Wetherby, C. R. Sa-
manamu, A. C. Schrick, A. DiPasquale, J. A. Golen, A. L.
Rheingold, C. S. Weinert, Inorg. Chim. Acta 2010, 364, 89–95.
Crystal Structures, University of Göttingen, Göttingen, 1997.
Received: April 12, 2012
Published Online: ᭿
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13

Job/Unit: I20363
/KAP1
Date: 02-07-12 10:59:01
Pages: 14
K. V. Zaitsev, J. Sundermeyer, S. S. Karlov et al.
FULL PAPER
Germylenes
M. Huang, M. M. Kireenko,
K. V. Zaitsev,* Yu. F. Oprunenko,
A. V. Churakov, J. A. K. Howard,
E. K. Lermontova, D. Sorokin, T. Linder,
J. Sundermeyer,* S. S. Karlov,*
G. S. Zaitseva ................................. 1–14
Stabilized Germylenes Based on Diethyl-
enetriamines and Related Diamines: Syn-
thesis, Structures, and Chemical Properties
Keywords: Germanium / N-ligands / X-ray
diffraction / Amines / Lithium
A series of novel, low-valent germanium
compounds have been obtained by the re-
action of Ge[N(SiMe3)2]2 with various di-
amines or by the metathesis reaction of
[GeCl2·dioxane] with lithium amides. The
oxidative insertion, [1+4] cycloaddition,
and oxidation reactions of the synthesized
germylenes were investigated. All the syn-
thesized germylenes are monomeric.
14
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