Synthesis and structural characterization of low-valent group 14 metal complexes based on aminobisphenol ligands

Article abstract of DOI:10.1016/j.ica.2017.02.024

Aminobisphenol supported germylenes (1a–3a), stannylenes (1b–3b) and plumbylenes (1c–3c) were synthesized by reaction of Lappert's tetrylenes, [(Me₃Si)₂N]₂M (M?=?Ge, Sn, Pb), with corresponding aminobisphenols R¹

Full text of DOI:10.1016/j.ica.2017.02.024

Accepted Manuscript
Research paper
Synthesis and structural characterization of low-valent Group 14 metal com-
plexes based on aminobisphenol ligands
Kirill V. Zaitsev, Ekaterina A. Kuchuk, Andrei V. Churakov, Mger A.
Navasardyan, Mikhail P. Egorov, Galina S. Zaitseva, Sergey S. Karlov
PII:
S0020-1693(16)30665-X
http://dx.doi.org/10.1016/j.ica.2017.02.024
ICA 17450
DOI:
Reference:
To appear in:
Inorganica Chimica Acta
Received Date:
Revised Date:
Accepted Date:
10 October 2016
9 January 2017
16 February 2017
Please cite this article as: K.V. Zaitsev, E.A. Kuchuk, A.V. Churakov, M.A. Navasardyan, M.P. Egorov, G.S.
Zaitseva, S.S. Karlov, Synthesis and structural characterization of low-valent Group 14 metal complexes based on
aminobisphenol ligands, Inorganica Chimica Acta (2017), doi: http://dx.doi.org/10.1016/j.ica.2017.02.024
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Synthesis and structural characterization of low-valent
Group 14 metal complexes based on aminobisphenol ligands
a,b,*
b
a,b b,c
Ekaterina A. Kuchuk, Andrei V. Churakov, Mger A. Navasardyan,
c
Kirill V. Zaitsev,
a,b
a,b
Mikhail P. Egorov, Galina S. Zaitseva, and Sergey S. Karlov
a
Chemistry Department, Moscow State University, B-234 Leninskie Gory, 119991 Moscow,
Russia
b
c
*
N.D.Zelinsky Institute of Organic Chemistry, Russian Acad. Sci., Leninskii pr., 47, 119991
Moscow, Russia
Institute of General and Inorganic Chemistry, Russian Acad. Sci., Leninskii pr., 31, 119991
Moscow, Russia
Corresponding Author: zaitsev@org.chem.msu.ru
Keywords: aminobisphenol; tetrylene; germylene; stannylene; plumbylene; rhenium carbonyl
complex
Abstract: Aminobisphenol supported germylenes (1a-3a), stannylenes (1b-3b) and plumbylenes
(
1c-3c) were synthesized by reaction of Lappert’s tetrylenes, [(Me
3
Si)
, 1-3 (1: R = Et, R = Me; 2:
2
(Py-2), R = t-Bu). X-Ray diffraction analysis revealed different
2
N]
2
M (M = Ge, Sn, Pb),
1
2
1
2
with corresponding aminobisphenols R N(CH
2
C
6
H
2
(OH)(t-Bu)R )
2
1
2
1
2
R = Et, R = t-Bu; 3: R = CH
coordination mode for germylene 3a and stannylene 3b with additional nitrogen donor in the
structure of the ligand. Germylene 1a was converted to the rhenium complex 1aa by the reaction
5
with Re(CO) Br.
1
. Introduction
The isolation of the stable heavier carbene analogues, such as dialkyl and diamido
substituted derivatives of germanium, tin and lead in the seventies of the last century [1], has led
to significant increase of interest in these species and since then several reviews have appeared
containing information on their synthesis and intriguing chemical properties [2].
At present it is generally accepted that most of these compounds are stable enough to be
handled as “usual” molecular substances with application of appropriate techniques and have
1

different stability depending on the structure of the ligands bound to metal atom. The low-valent
metal centre may be stabilized by two possible ways. The first way is a thermodynamic
(
(
electron) stabilization including electron donation by oxygen or nitrogen containing groups
covalently or coordinatively bound to metal centre) into an empty p-orbital of the metal. The
second way is a kinetic stabilization carried out by introduction of sterically demanding groups
to the M atom.
At the same time it is clear that excessive stabilization lowers reactivity. For example, as
was recently shown for transition metal complexes with bulky carbene ligands, their catalytic
activity is reduced in comparison with less sterically encumbered congeners [3]. It is therefore
important to keep a balance between sufficient stability and a suitable reactivity.
The electronic structure of “heavy carbenes” allows them to possess dual reactivity. Thus,
on the one side due to the electron deficiency their reactivity is enhanced so they may be used as
precursors for synthesis of various organometallic compounds and intermediates via insertion
into different σ-bonds and addition to π-bonds [4]. On the other side due to the lone electron pair,
especial interest may arise from application of such derivatives as ligands in coordination
chemistry. Recently several scientific groups successfully applied heavier carbene analogues as
initiators in the ring-opening polymerization of lactide [5].
In order to gain more insight into structure and reactivity of 14 group heavier carbene
analogues our group and Jurkschat group prepared several series of germylenes and stannylenes
based on N,N,O-alkoxyamidoamine [6] (type A), N,N,N-diamidoamine [7] (types B, C) and
O,N,O-ligands
(substituted
diethanolamine
derivatives
(types
D,
E)
and
di(hydroxyalkyl)pyridines (type F)) (Chart 1) which turned out to be monomeric or dimeric [8].
It should be noted that the third known type of stannylene structure (polymeric with bridging O
atoms) has been established only in a single compound (type G) [8f].
2

Chart 1. The examples of germylenes and stannylenes based on N,N,O-, N,N,N- and O,N,O-
ligands
It was found that in the case of monomeric derivatives insertion reactions cleanly proceed
leading to the expected products with increased M atom oxidation state. In contrast, the reactions
of dimeric derivatives often result in mixtures of unidentified compounds.
As a part of our program to prepare novel tetrylenes and investigate their structure and
reactivity, we report herein the synthesis and structural characterization of germylenes 1a-3a,
stannylenes 1b-3b and plumbylenes 1c-3c based on aminobisphenol ligands of different types, 1-
3, without (1, 2) or with pendant pyridine ring (3). In our opinion, such ligands may prove to be
very convenient for stabilization of monomeric structures of the tetrylenes as they enable both
steric protection by bulky tert-butyl groups and thermodynamic stabilization by additional
transannular interaction with nitrogen atom of the ligands. In spite of this, aminobisphenols were
not previously used as ligands for tetrylenes (except for a ligand with two aminobisphenol
moieties bridged by an ethylene spacer which was used for preparation of complex with two tin
centers [9]), while these compounds established themselves as suitable ones for preparation of
plethora of metal complexes [10]. The structure of germylene 3a and stannylene 3b based on the
same ligand 3 was studied by X-ray diffraction, and the different structural modes were found
for Ge and Sn compounds. For preliminary investigation of reactivity of prepared compounds,
complexation reaction of 1a with Re(CO)
5
Br was performed what led to CO substitution in the
Re coordination sphere and formation of novel complex 1aa containing Ge-Re bond.
2
2
. Experimental
.1. General remarks
All manipulations were performed under a dry, oxygen-free argon atmosphere using
standard Schlenk techniques. Solvents were dried by standard methods and distilled prior to use:
toluene and n-hexane were refluxed over Na and then distilled; THF and diethyl ether were
stored over KOH, refluxed over Na/benzophenone and then distilled. Starting materials were
synthesized according to the literature procedures: 2 [11], 3 [12], [(Me
3
Si)
2
N] Ge,
2
[
(Me
3
Si)
2
N]
2
Sn, [(Me
3
Si)
2
N]
2
Pb [1b]. C
6
D
6
(distilled over sodium) and CDCl
3
(distilled over
1
13
119
CaH
2
) are obtained from Deutero GmbH. H (400.13 MHz), C (100.6 MHz) and Sn (149.2
MHz) NMR spectra were recorded on a Bruker Avance 400 or Agilent 400-MR spectrometers at
3

1
13
room temperature (if otherwise stated). H and C chemical shifts are reported in ppm relative to
Me Si as external standard. Elemental analyses were carried out in the Microanalytical
4
Laboratory of the Chemistry Department of the Moscow State University. Mass spectrometry
with ionization ESI-HRMS was performed at the Chemistry Department of Moscow State
University. Samples were introduced into the high-resolution mass spectrometer Orbitrap Elite
with electrospray ionization source via a syringe pump at a flow rate of 1-3 microliter per min.
2
2
2
.2.
Syntheses
.2.1. Synthesis of ligands
.2.1.1. Synthesis of ligand 1
In a flask 2-tert-butyl-4-methylphenol (3.97 g, 24.20 mmol), 36 % aqueous formaldehyde (1.62
ml, 19.40 mmol), 70 % aqueous EtNH (0.78 ml, 12.10 mmol) and 10 ml of methanol were
2
placed. Solution was refluxed for 23 h, and then all volatile materials were removed under
reduced pressure. Orange oil obtained was dissolved in petroleum ether and left for slow
evaporation of the solvent until crystals of compound 1 were formed. Crystals were thoroughly
washed with n-hexane and dried in vacuo. Compound 1 was obtained as a white solid. It may be
o
1
recrystallized from n-hexane for further purification. M.p. 109-110 С.Yield 2.28 g (47%). H
NMR (400.13 MHz, CDCl ): δ = 1.16 (t, J = 7.1 Hz, 3H, CH CH ), 1.40 (s, 18H, C(CH ), 2.25
s, 6H, CH -Ar), 2.63 (q, J = 7.1 Hz, 2H, CH CH ), 3.65 (s, 4H, NCH Ar), 6.72-6.77 (m, 2H,
Ar), 6.98-7.05 (m, 2H, Ar) ppm. C NMR (100.6 MHz, CDCl ): δ =11.0 (CH CH ), 20.8 (CH
Ar), 29.6 (C(CH ), 34.6 (C(CH ), 47.0 (CH CH ), 56.2 (NCH Ar), 122.4, 127.3, 128.1,
28.8, 136.8, 152.5 (Ar) ppm. Anal. Calcd. for C26 (397.5934): C, 78.54; H, 9.89; N,
.52. Found: C, 78.53; H, 9.61; N, 3.79 %.
3
2
3
3 3
)
(
3
2
3
2
1
3
3
2
3
3
-
3
)
3
3
)
3
2
3
2
1
3
H39NO
2
2
.2.1.2. Synthesis of ligand 2
1
3
The synthesis had been carried out as reported in the literature [11]. C NMR (100.6 MHz,
CDCl ): δ = 11.1 (CH CH ), 29.7, 31.6 (2C(CH ), 34.2, 34.9 (2C(CH ), 47.2 (CH CH ), 56.6
Ar), 121.6, 123.5, 125.0, 136.0, 141.5, 152.4 (Ar) ppm. Anal. Calcd. for C32
481.7528): C, 79.78; H, 10.67; N, 2.91. Found: C, 79.62; H, 10.38; N, 3.02 %.
3
2
3
3
)
3
3
)
3
2
3
(
(
NCH
2
H51NO
2
4

2
2
.2.2. Synthesis of germylenes
.2.2.1. Synthesis of germylene 1a
A solution of the ligand 1 (1.12 g, 2.82 mmol) in toluene (10 ml) was added to a stirred solution
of [(Me Si) N] Ge (1.11 g, 2.82 mmol) in toluene (5 ml). The solution gradually lost its intensive
3
2
2
orange color and became almost colorless. After stirring overnight all volatile materials were
removed under reduced pressure, n-hexane (5 ml) was added to the residue obtained and the
1
solid formed was filtered off to give 1a as a white solid. Yield 0.92 g (70%). H NMR (400.13
MHz, C
H, CH
2d, J = 1.9 Hz, each 2H, Ar) ppm. C NMR (100.6 MHz, C
CH -Ar), 30.4 (C(CH ), 34.9 (C(CH ), 49.9 (CH CH ), 53.4 (NCH
29.0, 141.1, 154.6 (Ar) ppm. Anal. Calcd. for C26 Ge (468.2164): C, 66.70; H, 7.97; N,
.99. Found: C, 66.46; H, 7.93; N, 3.03 %.
6
D
6
): δ = 0.60 (t, J = 7.2 Hz, 3H, CH
2
CH
3
), 1.70 (s, 18H, C(CH
3
)
3
), 2.24 (q, J = 7.2 Hz,
Ar), 6.47, 7.29
, ppm): δ = 7.9 (CH CH ), 21.1
Ar), 123.9, 127.7, 128.9,
2
2
CH ), 2.25 (s, 6H, CH -Ar), 2.95, 3.21 (2d, J = 12.4 Hz, each 2H, NCH
3
3
2
13
(
(
6
D
6
2
3
3
3
)
3
3
)
3
2
3
2
1
2
H37NO
2
2
.2.2.2. Synthesis of germylene 2a
Analogously to 1a starting from 2 (0.80 g, 1.67 mmol) in toluene (10 ml) and [(Me
3 2 2
Si) N] Ge
(
0.66 g, 1.67 mmol) in toluene (5 ml). After addition of n-hexane (5 ml) and filtration 2a was
1
obtained as a white solid. Yield 0.39 g (42%). H NMR (400.13 MHz, C
Hz, 3H, CH CH ), 1.38, 1.72 (2s, each 18H, C(CH ), 2.24 (q, J = 7.2 Hz, 2H, CH
.25 (2d, J = 12.4 Hz, each 2H, NCH Ar), 6.75, 7.61 (2d, J = 2.3 Hz, each 2H, Ar) ppm. C
NMR (100.6 MHz, C ): δ = 8.0 (CH CH ), 30.5, 32.0 (C(CH ), 34.4, 35.3 (C(CH ), 50.1
Ar), 123.4, 125.0, 125.1, 140.5, 141.2, 154.5 (Ar) ppm. Anal. Calcd. for
Ge (552.3759): C, 69.58; H, 8.94; N, 2.54. Found: C, 69.64; H, 9.01; N, 2.48 %.
6
D
6
): δ = 0.6 (t, J = 7.2
2
3
3
)
3
2
CH ), 2.99,
3
1
3
3
2
6
D
6
2
3
3
)
3
)
3 3
(
CH
2
CH
3
), 54.0 (NCH
2
C
32
H49NO
2
2
.2.2.3. Synthesis of germylene 3a
Analogously to 1a starting from 3 (0.87 g, 1.59 mmol) in toluene (10 ml) and [(Me
3 2 2
Si) N] Ge
(
0.63 g, 1.59 mmol) in toluene (5 ml). After staying overnight white precipitate was formed. The
volume of solvent was reduced to approximately 3 ml, then n-hexane (4 ml) was added. After
1
filtration 3a was obtained as a white solid. Yield 0.85 g (87%). H NMR (400.13 MHz, C
6
D
6
): δ
Ar), 3.68 (s,
Py) 6.45-6.55 (m, 2H, Py), 6.83-6.92 (m, 3H, Py and Ar), 7.62 (d, J = 2.5 Hz, 2H, Ar),
=
1.34, 1.76 (2s, each 18H, C(CH
H, NCH
.27-8.34 (m, 1H, Py) ppm. C NMR (100.6 MHz, C
3
)
3
), 3.63, 3.82 (2d, J = 12.6 Hz, each 2H, NCH
2
2
8
2
1
3
6
D
6
): δ = 30.6, 31.9 (C(CH
3
)
3
), 34.3, 35.3
5

(
C(CH
3
)
3
), 54.5, 59.3 (NCH
41.1, 149.6, 153.2, 155.0 (Py and Ar) ppm. Anal. Calcd. for C36
0.26; H, 8.19; N, 4.55. Found: C, 70.14; H, 7.87; N, 4.34 %.
2
Ar and NCH
2
Py), 122.9, 123.7, 125.0, 125.8, 125.9, 135.8, 140.4,
1
7
50 2 2
H N O
Ge (615.4344): C,
2
2
.2.3. Synthesis of stannylenes
.2.3.1. Synthesis of stannylene 1b
Analogously to 1a starting from 1 (0.65 g, 1.65 mmol) in toluene (10 ml) and [(Me
3
Si)
2
N] Sn
2
(
0.73 g, 1.66 mmol) in toluene (5 ml). After evaporation of the solvent the residue was treated
1
with n-hexane (4 ml) and solid was filtered to afford 1b as a white solid. Yield 0.45 g (54%). H
NMR (400.13 MHz, C ): δ = 0.57 (t, J = 7.3 Hz, 3H, CH CH ), 1.70 (s, 18H, C(CH ), 2.14
q, J = 7.3 Hz, 2H, CH CH ), 2.27 (s, 6H, CH -Ar), 3.00, 3.25 (2d, J = 12.6 Hz, each 2H,
NCH Ar), 6.48, 7.31 (2d, J = 2.2 Hz, each 2H, Ar) ppm. C NMR (100.6 MHz, C
.4 (CH CH ), 21.0 (CH -Ar), 30.4 (C(CH ), 35.0 (C(CH ), 50.0 (CH CH ), 54.7 (NCH
23.7, 126.2, 129.1, 129.8, 140.8, 156.8 (Ar) ppm. Sn NMR (149.2 MHz, C
6
D
6
2
3
3 3
)
(
2
3
3
1
3
2
6
D
6
, ppm): δ =
Ar),
9
1
2
3
3
3
)
3
3
)
3
2
3
2
119
6
D
6
): δ = -420.4
+
+
+
(
s) ppm. ESI-HRMS: Found: [M+Na] =538.1896, [M
2
+Na] =1051.3598. Calculated: [M+Na] =
+
538.1743, [M
2
+Na] = 1051.3882. Anal. Calcd. for C26
H37NO
2
Sn (514.2864): C, 60.72; H, 7.25;
N, 2.72. Found: C, 60.61; H, 7.32; N, 2.63 %.
2
.2.3.2. Synthesis of stannylene 2b
Analogously to 1a starting from 2 (0.77 g, 1.61 mmol) in toluene (15 ml) and [(Me
3
Si)
2
N] Sn
2
(
0.71 g, 1.61 mmol) in toluene (5 ml). After filtration and washing with n-hexane (5 ml) 2b was
1
obtained as a white solid. Yield 0.61 g (64%). H NMR (400.13 MHz, C
Hz, 3H, CH CH ), 1.39, 1.73 (2s, each 18H, C(CH ), 2.16 (q, J = 7.2 Hz, 2H, CH
.30 (2d, J = 12.4 Hz, each 2H, NCH Ar), 6.75, 7.62 (2d, J= 2.5 Hz, each 2H, Ar) ppm. C
NMR (100.6 MHz, C ): δ = 9.4 (CH CH ), 30.4, 32.0 (C(CH ), 34.3, 35.3 (C(CH ), 50.1
Ar), 123.2, 125.1, 125.9, 139.7, 140.2, 156.7 (Ar) ppm. Sn NMR
6
D
6
): δ = 0.56 (t, J = 7.2
2
3
3
)
3
2
CH ), 3.06,
3
13
3
2
6
D
6
2
3
3
)
3
3 3
)
1
19
(
(
CH
149.2 MHz, C
.25; N, 2.34. Found: C, 64.52; H, 8.24; N, 2.33 %.
2
CH
3
), 55.3 (NCH
2
6
D
6
): δ = - 422.7 (s) ppm. Anal. Calcd. for C32
H
49NO
2
Sn (598.4459): C, 64.22; H,
8
2
.2.3.3. Synthesis of stannylene 3b
6

o
At -20 C toluene (20 ml) was added to the mixture of the ligand 3 (0.47 g, 0.86 mmol) and
(Me Si) N] Sn (0.38 g, 0.87 mmol), then solution obtained was gradually warmed to room
[
3
2
2
temperature and stirred overnight. After evaporation of the solvent the residue was treated with
n-hexane (5 ml), filtered off and washed with n-hexane (5 ml) to afford 3b as a white solid.
1
Yield 0.38 g (67%). H NMR (400.13 MHz, C
6
D
6
): δ = 1.36, 1.79 (2s, each 18H, C(CH
Ar), 3.34 (s, 2H, NCH Py), 6.14 (d, J = 8.1 Hz, 1H, Py), 6.20-
.25 (m, 1H, Py), 6.62 (d, J = 2.5 Hz, 2H, Ar), 6.68-6.74 (m, 1H, Py), 7.51 (d, J = 2.5 Hz, 2H,
3 3
) ), 3.30,
3
.54 (2d, J = 12.1 Hz, 4H, NCH
2
2
6
1
3
Ar), 7.68 (d, J = 4.6 Hz, 1H, Py) ppm. C NMR (100.6 MHz, C
6
D
6
): δ = 30.6, 32.1 (C(CH
3 3
) ),
3
1
5
4.1, 35.4 (C(CH
3
)
3
), 59.5, 62.2 (NCH
2
Ar and NCH
2
Py), 122.1, 122.3, 123.4, 124.5, 125.4,
1
19
36.7, 137.9, 139.2, 146.9, 154.2, 158.5 (Py and Ar) ppm. Sn NMR (149.2 MHz, C
6
D ): δ = -
6
+
+
14.2 (s) ppm. ESI-HRMS: Found: [M+H] = 663.2967. Calculated: [M+H] = 663.2957.
2
2
.2.4. Synthesis of plumbylenes
.2.4.1. Synthesis of plumbylene 1c
A solution of 1 (0.33 g, 0.85 mmol) in toluene (10 ml) was added to a stirred solution of
(Me Si) N] Pb (0.45 g, 0.85 mmol) in toluene (5 ml). After stirring overnight the precipitate
[
3
2
2
formed was filtered off, washed with toluene (2 ml) and dried in vacuo to give 1c as a white
1
solid. Yield 0.39 g (78%). H NMR (400.13 MHz, C
6
D
6
): δ = 0.5 (t, J = 7.1 Hz, 3H, CH
), 2.35 (s, 6H, CH -Ar), 3.37, 3.51 (2d,
Ar), 6.56 (m, 2H, Ar), 7.40 (m, 2H, Ar) ppm. C NMR (100.6
): δ = 10.3 (CH CH ), 21.0 (CH -Ar), 30.7 (C(CH ), 35.0 (C(CH ), 48.9
), 54.7 (NCH Ar), 124.6, 125.2, 128.9, 130.2, 141.4, 158.8 (Ar) ppm. Anal. Calcd. for
Pb (602.7764): C, 51.81; H, 6.19; N, 2.32. Found: C, 51.99; H, 6.19; N, 2.21 %.
2 3
CH ),
1
.73 (s, 18H, C(CH
J = 11.6 Hz, each 2H, NCH
MHz, C
3
)
3
), 2.23 (q, J = 7.1 Hz, 2H, CH
2
CH
3
3
1
3
2
6
D
6
2
3
3
3
)
3
3 3
)
(
CH
2
CH
3
2
C
26
H37NO
2
2
.2.4.2. Synthesis of plumbylene 2c
Analogously to 1c starting from 2 (0.43 g, 0.90 mmol) in toluene (10 ml) and [(Me
3
Si)
2
N]
2
Pb
(
0.48 g, 0.90 mmol) in toluene (5 ml). After filtration and washing with n-hexane (5 ml) 2c was
1
obtained as white solid. Yield 0.48 g (79%). H NMR (400.13 MHz, C
Hz, 3H, CH CH ), 1.40 (s, 18H, C(CH ), 1.75 (s, 18H, C(CH ), 2.29 (q, J = 7.0 Hz, 2H,
CH CH ), 3.44, 3.57 (2d, J = 11.4 Hz, each 2H, NCH Ar), 6.78-6.86 (m, 2H, Ar), 7.67-7.74 (m,
H, Ar) ppm. C NMR (100.6 MHz, C
6 6
D ): δ = 0.49 (t, J = 7.0
2
3
3
)
3
3 3
)
2
3
2
1
3
2
6
D
6
): δ = 10.4 (CH
2
CH
3
), 30.7, 32.2 (C(CH
3
)
3
), 34.1,
7

3
5.4 (C(CH
ppm. Anal. Calcd. for C32
.19; N, 1.97 %.
3
)
3
), 49.0 (CH
2
CH
3
), 55.3 (NCH
2
Ar), 124.1, 124.8, 126.3, 138.7, 140.7, 158.8 (Ar)
H
49NO Pb (686.9359): C, 55.95; H, 7.19; N, 2.04. Found: C, 55.71; H,
2
7
2
.2.4.3. Synthesis of plumbylene 3c
Analogously to 1c starting from the ligand 3 (0.54 g, 1.00 mmol) in toluene (10 ml) and
[
(Me
3
Si)
2
N]
2
Pb (0.53 g, 1.00 mmol) in toluene (5 ml). After filtration and washing with n-
1
hexane (5 ml) 3c was obtained as a white solid. Yield 0.54 g (74%). H NMR (400.13 MHz,
C
6
D
6
): δ = 1.41, 1.81 (2s, each 18H, C(CH
.57 (s, 2H, NCH Py), 6.27 (d, J = 7.8 Hz, 1H, Py), 6.29-6.34 (m, 1H, Py), 6.74-6.80 (m, 1H,
Py), 6.84 (d, J = 2.4 Hz, 2H, Ar), 7.58 (d, J = 4.7 Hz, 1H, Py), 7.66 (d, J = 2.4 Hz, 2H, Ar) ppm.
3
)
3
), 3.57, 3.80 (2d, J = 11.7 Hz, each 2H, NCH
2
Ar),
3
2
1
3
C NMR (100.6 MHz, C
1.9 (NCH Ar), 122.2, 124.0, 123.9, 124.5, 126.1, 137.0, 140.0, 147.3, 156.4, 160.3 (Ar and Py)
ppm. Signal of one aromatic carbon was not found. Anal. Calc. for C36 Pb (749.9933): C,
7.65; H, 6.72; N, 3.74. Found: C, 57.87; H, 6.91; N, 3.58 %.
6 6 3 3 3 3 2
D ): δ = 30.8, 32.3 (C(CH ) ), 34.0, 35.4 (C(CH ) ), 59.1 (br, CH Py),
6
2
H
50
N
2
O
2
5
2
5
.2.5. Reaction of 1a with Re(CO) Br. Synthesis of rhenium complex 1aa
5
Solid Re(CO) Br (0.096 g, 2.350 mmol) was added to 1a (0.110 g, 2.350 mmol) in toluene (10
ml) in one portion and after stirring for 30 h at 70˚C (periodically evacuating the flask to remove
CO) the amount of solvent was reduced to 2 ml, n-hexane (5 ml) was added to the residue and
1
the precipitate formed was filtered off to give 1aa as a white solid. Yield 0.09 g (45%). H NMR
(
(
400.13 MHz, C
s, 6H, CH -Ar), 3.49 (q, J = 7.0 Hz, 2H, CH
Ar), 6.17-6.24, 7.15-7.21 (2m, each 2H, Ar) ppm. C NMR (100.6 MHz, C
.3 (CH CH ), 20.8 (CH -Ar), 30.8 (C(CH ), 35.3 (C(CH ), 48.8 (CH CH ), 54.0 (NCH
19.3, 128.9, 129.4, 129.8, 140.1, 152.5 (Ar), 184.1 (CO), 185.1 (2CO), 190.2 (CO) ppm. Anal.
37BrGeNO Re (846.3678): C, 42.57; H, 4.41; N, 1.65. Found: C, 40.14; H, 4.33;
6
D
6
, 40˚C): δ = 0.50 (t, J = 7.0 Hz, 3H, CH
2 3 3 3
CH ), 1.58 (s, 18H, C(CH ) ), 2.14
3
2
CH ), 3.44-3.53, 3.68-3.92 (2m, each 2H,
3
1
3
NCH
2
6
D
6
, 68˚C): δ =
Ar),
5
1
2
3
3
3
)
3
3
)
3
2
3
2
Calc. for C30
H
6
N, 1.48 %. Found value for carbon is lower than calculated one due to possible formation of
rhenium carbide during analysis.
2
.3.
X-ray diffraction studies
8

Intensity data for 3a, 3b and 1aa were measured on a Bruker SMART APEX II diffractometer
(
graphite monochromatized MoK
α
radiation, λ = 0.71073 Å) using ω-scan mode. The structures
2
were solved by direct methods and refined by full matrix least-squares on F with anisotropic
thermal parameters for all non-hydrogen atoms [13]. All H atoms were placed in calculated
positions and refined using a riding model. Details of X-ray diffraction experiments are given in
Table 1.
X-ray diffraction studies were performed at the Centre of Shared Equipment of IGIC RAS.
The crystallographic data for 3a, 3b and 1aa have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publications under the CCDC numbers 1508528-
1508530. This information may be obtained free of charge from the Cambridge Crystallographic
Data Centre via www.ccdc.cam.ac.uk/data_request/cif.
Table 1.The crystallographic data for compounds 3a, 3b and 1aa.
3
a
3b
1aa
empirical formula
C
36
H50GeN
2
O
2
C
36
H
50
N
2
O
2
Sn
C
30
6
H37BrGeNO Re
M
w
615.37
173(2)
661.47
180(2)
846.31
temperature (K)
size (mm)
150(2)
0.40 x 0.25 x
.20
0.40 x 0.17 x
0.08
0.25 x 0.20 x 0.20
0
cryst. system
space group
a (Å)
triclinic
P-1
monoclinic
monoclinic
P2
1
/c
P2 /c
1
11.4695(16)
12.7942(18)
13.971(3)
99.213(3)
110.588(3)
112.117(2)
1673.8(5)
2
11.8693(9)
10.2384(7)
28.385(2)
90
13.9716(8)
12.5033(7)
18.4706(10)
90
b (Å)
c (Å)
α (deg)
β (deg)
γ(deg)
93.147(1)
90
99.700(1)
90
3
V (Å )
3444.2(4)
4
3180.5(3)
4
Z
-3
ρ
cald(g*cm )
1.221
1.276
1.767
-
1
abs coeff. (mm )
F(000)
0.947
0.773
6.045
656
1384
1656
θ range (deg)
collected rflns.
unique rflns., Rint
2.15 – 27.00
16212
2.18 – 27.00
30231
2.20 – 28.00
32386
7302, 0.0319
7493, 0.0370
7493 / 0 / 382
7688, 0.0339
7688 / 0 / 370
data/restraints/param
s.
7302 / 0 / 382
2
Goof on F
1.052
1.029
1.041
9

final R indices
I> 2σ(I))
R
1
= 0.0366,
R
1
= 0.0265,
1
R = 0.0226,
(
wR
2
= 0.0830
wR
2
= 0.0606
wR
2
= 0.0534
R indices (all data)
R
1
= 0.0449,
R
1
= 0.0338,
1
R = 0.0288,
wR
2
= 0.0863
wR
2
= 0.0641
2
wR = 0.0554
largest diff.
peak/hole (e/Å )
0.489 / -0.377
0.452 / -0.297
0.970 / -0.480
3
3
3
. Results and discussion
.1.
Synthesis of tetrylenes
Ligands 1-3 were obtained according to the previously reported general procedure by
Mannich condensation of corresponding phenol, formalin and amine in methanol at reflux.
Ligand 1 is a novel compound. It was isolated as a white powder in 47% yield.
Among others [8h,i] the most suitable method for synthesis of M(OR)
2
is a reaction of
alkoxydesamination of [(Me Si) N] M with appropriate alcohols [8a, 14]. This reaction was
3
2
2
earlier successfully applied for the preparation of various closely related germylenes and
stannylenes based on aminodialcohols (see Chart 1). Corresponding germylenes 1a-3a,
stannylenes 1b-3b and plumbylenes 1c-3c were prepared in moderate yields by treating ligands
with amides in toluene at room temperature (Scheme 1). Such procedure is easy to perform and
the by-products formed in the course of the reaction may be easily removed under reduced
pressure.
Scheme 1. Synthesis of tetrylenes 1a-c, 2a-c and 3a-c
10

6 6
Germylenes 1-3a, stannylenes 1-3b and plumbylenes 2c, 3c are soluble in toluene, C D
and only sparingly soluble in n-hexane, while plumbylene 1c is poorly soluble in toluene and
even in THF.
3
.2.
Structure and reactivity of tetrylenes
1
13
H and C NMR spectra confirm the suggested structure of the compounds. There is one
1
set of signals in the H NMR spectra for all compounds in solution, which implies the
2 2
equivalence of both CH ArO groups in the tetrylene. Methylene protons NCH Ar become
diastereotopic and split into two doublets suggesting strong transannular interaction between
1
nitrogen atom of (-CH
2
)NR group and the metal atom. Methylene protons NCH
2
Py in tetrylenes
3a-3c appear as a singlet and are not diastereotopic. It seems that strong coordination M←NPy is
not observed in solution or there are fast dynamic processes (in NMR time scale) in solution
where this bond forms and breaks. This observation is in correlation with X-ray diffraction data
(
see below) according to which there is no contact between Ge and NPy atoms in 3a and the
Sn←NPy bond in 3b is a weak one.
As stated above, one of the most important questions in structural chemistry of tetrylenes is
a clarification of the structural mode, i.e. the establishment of the monomeric or dimeric
1
13
structure. The data obtained from H and C spectra stands for either the existence of tetrylenes
as monomer species or the presence of fast (in NMR time scale) equilibrium between monomeric
and dimeric structures. According to X-ray diffraction data for 3a we can conclude that all
studied germylenes (1a, 2a and 3a) are monomeric in solution because 3a is monomeric even in
the solid state without any Ge←NPy contact.
1
19
Sn NMR spectroscopy is a powerful tool for determination of tin coordination number.
1
19
119
The data of Sn NMR spectra obtained for 1b-3b are the following: chemical shifts of the Sn
resonance in stannylenes 1b, 2b and 3b (C solution) are -420.4, -422.7 and -514.3 ppm,
respectively, what correlates well with tetracoordinated tin atom in these compounds. These data
are in agreement with those previously found for dimeric stannylenes with NO -environment of
Sn atom (~ -450 ppm [8a]) and stannylenes with N environment (~ -530 ppm) [15]. The
chemical shift value of the Sn resonance in dimeric {[(t-BuO-µ)(Ph SiO)]Sn} (–225.79 ppm
) [16]) with tricoordinated Sn atom with O -environment is downfield shifted in
6
D
6
3
2
O
2
1
19
3
2
(
C
6
D
6
3
1
19
comparison with those for 1b-3b. We further studied the Sn NMR spectra for 1b in DMSO-d6
1
19
and in pyridine-d5. Chemical shift of the Sn NMR resonance in stannylene 1b in DMSO-d6
solution is -490.8 ppm, in pyridine-d5 solution is -482.4 ppm, respectively. One can suppose,
11

that in the system stannylene : donor solvent complexes of R
equilibrium with dimeric [R Sn] with the same coordination number of tin as well as with
monomeric species R Sn (coordination number of tin = 3). This supposition explains observed
2
SnꢀBase may exist in fast
2
2
2
chemical shift values in 1b characteristic for tetracoordinated tin and one set of signals for two
symmetrical parts of the ligand framework. The same situation is observed in 2b. With regard to
compound 3b we assume on the basis of chemical shift for complex 1bꢀPy-d5 that compound
3
b exists in solution most likely as monomer and coordination number 4 arises from additional
intramolecular coordination with pyridine. One more proof for monomeric structure of 3b in
solution and the existence of monomer-dimer equilibrium in stannylenes 1b and 2b is data
obtained from mass-spectrometry ESI HRMS (acetonitrile solution). In ESI spectra both
monomer ([1b+Na]: 538.1896) and dimer ([1b +Na]:1051.3882) were detected. For 3b no dimer
2
was detected. As far as plumbylenes are concerned we assume that they also exist in equilibrium.
To further investigate structure of the tetrylenes obtained in the solid state we performed
single crystal X-ray diffraction analysis. Crystals of compound 3a suitable for diffraction studies
were obtained from n-hexane/toluene solution. In 3a (Figure 1) germanium atom has a distorted
tetrahedral geometry where the electron lone pair of Ge occupies one coordination place. The
values of the O–Ge–O and N–Ge–O angles (~ 90 - 97º) exhibit the significant s-character of this
pair. It should be noted, that coordination number of Ge atom is three, and possible
intramolecular bond between nitrogen atom of the pyridine ring and germanium atom is not
observed in this compound. It turned out that germanium center in 3a is non-attractive for the
second Ge←N (i.e. with pyridine pendant group) bond formation due to the presence of lone pair
of electrons. For the germanium atom in 3a the “octet rule” is followed so the Ge←N bond is a
classical donor-acceptor interaction. The geometrical characteristics of 3a are close to those
found earlier in the related monomeric structures: [2,6-C
.827(1), 1.881(1), d(Ge–N) 2.110(1) Å) [8a], MeN(CH
d(Ge–O) 1.833(3), 1.855(3), d(Ge–N) 2.113(3) Å) [8b]. It should be noted that the d(Ge–O) in
a are close to the distances found in monomeric dialkoxygermane (Ge[OC(t-Bu) (1.83(1) Å))
5
H
3
N(CH
2
CPh
2
O)
2
]Ge (d(Ge–O)
1
2
CPh O)((R,S)-CHMeCHPhO)Ge
2
(
3
3 2
]
where the coordination number of Ge atom is 2 [17]. Thus, aminobisphenol ligands are bulky
enough to stabilize monomeric structure of germylene. At the same time it should be noted that
nowadays there are no known structures of chelated phenol stabilized germylenes. The structure
of (MesO)
2 2 2 2 2
Ge(Me NCH CH NMe ) [18] is a single compound related to ones obtained in the
course of this work.
12

Figure 1. Molecular structure of 3a. Hydrogen atoms are omitted for clarity. Selected bond
lengths (Å) and angles (deg): Ge(1)-O(2) 1.8516(13), Ge(1)-O(1) 1.8607(13), Ge(1)-N(1)
2.1614(15); O(2)-Ge(1)-O(1) 97.61(6), O(2)-Ge(1)-N(1) 93.29(6), O(1)-Ge(1)-N(1) 90.47(6).
Single crystals of stannylene 3b suitable for X-ray diffraction analysis (Figure 2) were
grown from concentrated n-hexane solution. In contrast to found for the related 3a tin atom in 3b
possesses the [3+1] coordination mode due to the formation of two transannular Sn←N
interactions: strong bond with amine N atom and weak interaction with pyridine N atom. Thus,
tin atom in 3b is more attractive than Ge atom in closely related 3a for formation of additional
week interaction between pyridine nitrogen atom and tin atom due to both larger radii and more
electropositive character of Sn than Ge. The coordination polyhedron of the Sn atom in 3b
represents a distorted tetragonal pyramid with two oxygen atoms, nitrogen atom N(2) and a lone
pair in the base of the pyramid and nitrogen atom N(1) in its vertex.
13

Figure 2. Molecular structure of 3b. Hydrogen atoms are omitted for clarity. Selected bond
lengths (Å) and angles (deg): Sn(1)-O(2) 2.0415(13), Sn(1)-O(1) 2.1136(13), Sn(1)-N(1)
2
.3192(15), Sn(1)-N(2) 2.7059(17); O(2)-Sn(1)-O(1) 91.85(5), O(2)-Sn(1)-N(1) 85.62(5), O(1)-
Sn(1)-N(1) 84.38(5), O(2)-Sn(1)-N(2) 85.25(5), O(1)-Sn(1)-N(2) 152.49(5), N(1)-Sn(1)-N(2)
8.13(5).
6
The Sn–O and Sn–N bond lengths in 3b are comparable with the same in dimeric
NCH CH OSnN
(dimeric due to an additional O→Sn bond formation) which possesses
close related O coordination environment for the tin atom (except for two coordination
[
Me
2
2
2
]
3 2
2
N
2
N→Sn bonds in 3b and one O→Sn bond and one N→Sn bond in azide) [19]. The values for
azide are Sn–O 2.125(4), O→Sn 2.225(4), N→Sn 2.505(5), N–Sn 2.220(5) Å. One should note
the presence of a very strong transannular interaction between amine N atom and tin atom in 3b;
furthermore under comparison two these structures (azide and 3b) it is possible to state that the
donor properties of the pendant Py group are sufficient to stabilize monomeric structure,
especially taking into account the smaller donor ability of phenolic oxygens in comparison with
alkylalkoxy groups. In general the structures such as 3b are very rare and this one is close to
published earlier [(Py)Sn]
2
(CH
2
N(CH
2
C
6
H
2
(O)(t-Bu)
2
)
2
[9]. It should also be noted that in
Sn] [8i] the coordination number of
closely related stannylene [Me
2
NCH CH
2
2
N(CH CMe
2
2
O)
2
2
the tin atom is also 4, but additional bond appears from dimerization of stannylene through O
atom. Thus, one can conclude, that steric hindrance and ligand structure (phenolic groups,
pendant Py group) in 3b are sufficient to prevent dimerization.
In order to investigate the ability of the tetrylenes synthesized to act as a ligand in
5
transition metal complexes the reaction of 1a with Re(CO) Br was performed (Scheme 2). The
14

1
13
complex 1aa was obtained in moderate yield. H, C NMR spectra in C
6 6
D were registered at
68˚C (due to reduced solubility of the complex) and it may be concluded that the overall
structure has a cis-arrangement of germylene and bromine ligands (3 signals for CO groups),
what corresponds to the XRD data.
Scheme 2. Synthesis of rhenium complex 1aa
Figure 3. Molecular structure of 1aa. Hydrogen atoms are omitted for clarity. Selected bond
lengths (Å) and angles (deg): Re(1)-C(2) 1.925(3), Re(1)-C(1) 1.965(3), Re(1)-C(4) 1.995(3),
Re(1)-C(3) 2.019(3), Re(1)-Ge(1) 2.5446(3), Re(1)-Br(1) 2.6376(3), Ge(1)-O(11) 1.8012(17),
Ge(1)-O(21) 1.8074(18), Ge(1)-N(1) 2.031(2); C(2)-Re(1)-C(1) 93.59(12), C(2)-Re(1)-C(4)
9
2.18(12), C(4)-Re(1)-C(3) 176.27(12), C(2)-Re(1)-Ge(1) 85.89(8), C(1)-Re(1)-Ge(1)
74.95(9), C(4)-Re(1)-Ge(1) 93.19(8), C(3)-Re(1)-Br(1) 86.06(9), Ge(1)-Re(1)-Br(1)
1
15

9
6.638(10), O(11)-Ge(1)-O(21) 99.33(8), O(11)-Ge(1)-N(1) 97.85(8), O(11)-Ge(1)-Re(1)
03.49(6), O(21)-Ge(1)-Re(1) 126.84(6), N(1)-Ge(1)-Re(1) 127.46(6).
1
The structure of 1aa was studied with X-ray diffraction analysis. Despite the fact that
coordination chemistry of heavier carbene analogues has experienced an exponential growth in
the past few years, the examples of such complexes of 7 Group metals (Mn, Re) are very rare
[
20]. To the best of our knowledge complex 1aa is the third structurally characterized derivative
of germanium(II) where germylene is a ligand in rhenium complex after two chlorogermylidene
complexes Cl(L)(PMe Re=Ge(Cl)C -2,6-Trip (L = CO, MeNC) [20b].
3
)
3
6
H
3
2
The molecular structure of 1aa is shown in Figure 3. According to X-ray diffraction data,
coordination polyhedron of Re atom in 1aa is a distorted octahedron, where germylene ligand
and bromine atom are in cis-positions relative to each other. The same cis-ligand arrangement in
metal coordination sphere was detected in closely related manganese complex [MnBr{Ge-(i-
Pr
distance in 1aa (2.5446(3) Å) is noticeably longer than the same distance in
Cl(L)(PMe Re=Ge(Cl)C -2,6-Trip (2.3422(4) Å, 2.3253(4) Å) cited above [20b]. The Re–
Br and Re–C bond distances in 1aa are close to the same bond distances in parent Re(CO) Br
Re–Br 2.619(2) Å, Re–C 1.889(5) (trans to Br), 1.975(5), 1.991(6) Å) [21].
2 4 2
bzam)Bu-t}(CO) ] (where i-Pr bzam = N,N′-bis(isopropyl)benzamidinate) [20a]. The Re–Ge
3
)
3
6
H
3
2
5
(
The coordination environment of the Ge atom in 1aa is formed by two covalent bonded
oxygen atoms and one dative bonded nitrogen atom and may be regarded as a trigonal pyramid
with a lone pair in one vertex. The Ge–O and Ge–N bond distances in 1aa are noticeably shorter
than those in the related 3a (free germylene) due to donation of lone electron pair from Ge atom
to vacant orbital of Re atom.
4
. Conclusions
So, we investigated a new class of heavier carbene analogues (germylenes, stannylenes
and plumbylenes) that were successfully stabilized by aminobisphenols. According to the X-ray
diffraction analysis germylenes and stannylenes with pendant nitrogen donor differ in
coordination mode. The nature of the ligand (phenolic vs. alkylalkoxy groups) and pendant donor
group (pyridinyl vs. alkylamino) strongly effects on tetrylene structure determining the
aggregation degree (monomeric or dimeric). Reaction of germylene 1a with Re(CO)
complex 1aa with Re-Ge bond.
5
Br gave
16

Acknowledgements
The authors (K.V.Z., E.A.K., A.V.C., M.P.E., G.S.Z., S.S.K.) are grateful to the Russian
Science Foundation for financial support for studies on the synthesis and structural investigation
of stable tetrylenes made as a part of the project No 14-13-01456. M.A.N. thanks the Centre of
Shared Equipment of IGIC RAS where X-ray diffraction study of 1aa was performed. K.V.Z.,
E.A.K., G.S.Z., S.S.K. acknowledge (partial) support from M.V. Lomonosov Moscow State
University Program of Development for NMR investigation of the compounds.
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Graphical abstract
23

Graphical Abstract (text part)
Aminobisphenol supported germylenes, stannylenes and plumbylenes were prepared starting
from the reaction of corresponding Lappert’s tetrylene with aminobisphenols. XRD analysis
revealed different coordination mode for germylene and stannylene with additional nitrogen
donor in the structure of the ligand. Germylene was converted to the rhenium complex in
reaction with Re(CO) Br featuring Reꢀ:Ge dative bond.
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•
•
•
Heavier carbene analogues based on aminobisphenols were successfully synthesized
Different coordination mode for Ge, Sn tetrylenes with additional N donor was found
Reaction of germylene with Re(CO) Br gives complex with Re–Ge bond
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