Synthesis, solid-state structures and reduction reactions of heteroleptic Ge(II) and Sn(II) β-ketoiminate complexes

Article abstract of DOI:10.1515/znb-2017-0098

A series of new heteroleptic divalent germaniun and tin complexes of the general type L^1,4GeN(SiMe₃)₂ (1, 2) and L^1-4SnN(SiMe₃)₂ (3-6) were synthesized by reaction of β-ketimines L^1-4<

Full text of DOI:10.1515/znb-2017-0098

Z. Naturforsch. 2017; aop
Jessica Wiederkehr, Christoph Wölper and Stephan Schulz*
Synthesis, solid-state structures and reduction
reactions of heteroleptic Ge(II) and Sn(II)
β-ketoiminate complexes
https://doi.org/10.1515/znb-2017-0098
to steadily increase with increasing atomic number as
can already be seen when comparing the group 14 dihal-
ides. While PbCl , SnCl and GeCl ꢀ·(dioxane) are stable
Received June 16, 2017; accepted July 20, 2017
2
2
2
Abstract: A series of new heteroleptic divalent germaniun
and tin complexes of the general type L GeN(SiMe ) (1, 2)
compounds in solution and in the solid state, SiCl was
1
,4
2
3
2
only recently isolated as a carbene-stabilized compound
1
−4
and L SnN(SiMe ) (3–6) were synthesized by reaction of
3
2
IPr-SiCl2 (IPrꢀ=ꢀ1,3-bis(2,6-iPr )imidazol-2-ylidene) [6, 7].
1−4
2
β-ketimines L H with Ge[N(SiMe ) ] and Sn[N(SiMe ) ] ,
3
2
2
3 2 2
In addition, detailed reactivity studies of these heavier
carbenes clearly revealed differences to carbenes, which
mainly result from their different electronic structure. The
ground state of H C: is a triplet, whereas H M: (Mꢀ=ꢀSi, Ge,
respectively. The reaction of 3 with the strong Mg(I)
5
1
5
reductant L Mg yielded the heteroleptic complex L MgL 7
after ligand transfer from tin to magnesium, whereas anal-
4
4
2
2
ogous reactions of L GeN(SiMe ) 2 and L SnN(SiMe ) 6
3
2
3 2
Sn, Pb) show a singlet ground state, resulting in an empty p
orbital and a filled s orbital. According to quantum chemi-
cal calculations, the singletꢀ−ꢀtriplet energy differences
5
with L Mg occurred with formation of insoluble precipi-
tates, transfer of the amido substituent from the group
1
4 metal to magnesium and subsequent formation of the
ΔEST [ΔE ꢀ=ꢀE(triplet)ꢀ−ꢀE(singlet)] steadily increase from
5
ST
heteroleptic magnesium complex L MgN(SiMe ) (8). 1–8
3
2
−
14.0 (Mꢀ=ꢀC), 16.7 (Mꢀ=ꢀSi), 21.8 (Mꢀ=ꢀGe), 24.8 (Mꢀ=ꢀSn) to
1
13
119
were characterized by heteronuclear NMR ( H, C, Sn)
and IR spectroscopy, elemental analysis and single-crys-
−1
finally 34.8 (Mꢀ=ꢀPb) kcal mol [8]. In addition, the relative
stabilities of the monomeric metal organic species R M:
4
1
5
2
tal X-ray diffraction (L SnN(SiMe ) 6, L MgL 7).
3
2
(
Mꢀ=ꢀC–Pb; Rꢀ=ꢀalkyl, aryl) compared to the correspond-
Keywords: germanium; β-ketiminate; tin; X-ray crystal ing dimeric species, R Mꢀ=ꢀMR , was also found to increase
structure.
2
2
with increasing atomic number of the tetrele atom.
The first stable metal organic germylenes and stan-
nylenes [(Me Si) CH] M (Mꢀ=ꢀGe, Sn) were reported by
th
3
2
2
Dedicated to: Professor Dietrich Gudat on the occasion of his 60
birthday.
Lappert et al. [9–11] almost 40 years ago. Since then, a large
variety of compounds of this type have been synthesized,
and in particular N,N′-chelating organic substituents
including sterically bulky amidinate, guanidinate and β-
diketiminate ligands as well as N,O chelating substituents
have been successfully used for the stabilization of the
1
Introduction
The interest in heavier homologues of carbenes (R C:) desired class of compounds [12–22]. These compounds are
2
has steadily increased over the last two decades and as of interest since they can both react as Lewis base due to
a result, large numbers of silylenes (R Si:), germylenes the presence of an electron lone pair and as Lewis acid
2
(
R Ge:), stannylenes (R Sn:), and plumbylenes (R Pb:) due to an empty (acceptor) orbital. They have been widely
2 2 2
have been synthesized and structurally characterized applied in different reactions with organic substrates and
[
1–5]. The stability of these divalent species, where the in catalysis [23, 24], in particular tin complexes contain-
II
formal oxidation state of the tetrele atom is M , was found ing N,N′- and N,O-chelating ligands have been shown to
exhibit promising activities in ring-opening polymeriza-
tion (ROP) of cyclic esters [25–27]. In addition, they can
*
Corresponding author: Stephan Schulz, Institute of Inorganic
serve as suitable starting reagents in reduction reactions
for the synthesis of low-valent, including cluster-type,
compounds. For instance, the treatment of the heterolep-
Chemistry, University of Duisburg-Essen, and Center for
Nanointegration Duisburg-Essen (Cenide), 45117 Essen, Germany,
Tel.: +49 0201-1834635, Fax: + 49 0201-1834635,
tic β-diketiminate complex [HC(CMeNAr) ]SnCl with KC or
E-mail: stephan.schulz@uni-due.de
2
8
LiAlH resulted in the formation of the homoleptic complex
Jessica Wiederkehr and Christoph Wölper: Institute of Inorganic
Chemistry, University of Duisburg-Essen, 45117 Essen, Germany
4
[HC(CMeNAr) ] Sn [28], while reactions of the heteroleptic
2
2
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ꢀꢀꢀꢀꢁꢀJ. Wiederkehr et al.: Reactions of heteroleptic Ge(II) and Sn(II) β-ketoiminate complexes
4
amidotin chlorides {Sn[N(dipp)SiMe R](μ-Cl)} (dippꢀ=ꢀ2,6- C(Me)NCH CH CH NMe , L ꢀ=ꢀOC(Me)C(H)C(Me)N(dipp)) at
2
2
2
2
2
2
iPr C H ; Rꢀ=ꢀMe, Ph) with Li[BHs-Bu ] yielded two large ambient temperature. The reactions proceeded smoothly
2
6
3
3
metalloid Sb clusters [Sn {SnN(dipp)SiMe R)} ] contain- with elimination of the amine HN(SiMe ) and subsequent
15
9
2
6
3 2
ing unprecedented body-centered metal cores [29]. Bulky formation of the expected heteroleptic β-ketiminate com-
amido substituents generally show potential in the sta- plexes (Scheme 2) in high yields (67–96%).
1
bilization of low-valent main group metal and transition
The H NMR spectra of 1–6 show the expected reso-
metal complexes including multiply-bonded and cluster- nances of the chelating β-ketiminate unit (CH, NCMe,
type species [30] as was previously shown for terphenyl OCMe) and the expected resonances of the silyl groups
4
[31–34] and silyl substituents [35–38].
between 0.30 ppm (L SnN(SiMe ) 6) and 0.45 ppm
3
2
1
We recently demonstrated that (trip Sn) (tripꢀ=ꢀ2,4,6- (L SnN(SiMe ) 3). Additional resonances due to the
2
2
3 2
iPr C H ) reacts with the strong Mg(I) reductant (LMg) β-ketoiminate-imine-substituents (NR) were recorded. In
3
6
2
2
(
Lꢀ=ꢀHC[C(Me)N(dipp)] ) with Sn–C bond cleavage and the case of 2 and 6, two well separated septets and four
2
formation of the novel metalloid tin cluster Sn trip [39]. distinguished doublets (Supporting information, Figs. S1,
1
0
8
We therefore became interested to extend these reduction S19) with a relative intensity of 3:3:6:6:6:6 for the diaste-
reaction studies to divalent heteroleptic germanium and reotopic protons of the dipp substituent were observed,
1
tin compounds containing a sterically demanding, chelat- while the H NMR spectra of 1 and 3–5 show two multi-
ing β-ketiminate ligand, which was expected to be rather plets of equal relative intensity for the methylene protons
strongly bonded and to be able to stabilize low-valent Ge of the ethylamino and propylamino group (CH CH NR ,
2
2
2
and Sn cluster species through its high steric demand, as CH CH CH NR Rꢀ=ꢀMe, Et, Figs. S4, S7, S11, S15). These
2
2
2
2
well as a weakly bonded bis(trimethylsilyl)amide ligand findings either result from the chirality of the molecules
as rather weakly bonded leaving group.
due to the pseudo-tetrahedral environment of the Ge
Herein we report on the synthesis of a series of het- and Sn atoms or point to a hindered rotation around
eroleptic divalent germanium and tin β-ketiminate amide the N–Cipso single bond (2, 6), according to which the iPr
1−4
complexes of the general type L EN(SiMe ) (Eꢀ=ꢀGe, groups become magnetically inequivalent, or a coordi-
3
2
Sn). The β-ketiminate ligands either contain a sterically nation of the sidearm NR group in solution to the Lewis
2
demanding substituent attached to the coordinating N acidic germanium and tin atom (1, 3–5), respectively.
1
19
atom or an alkyl group with a terminal NR moiety, which The Sn NMR resonances of 3–6 were detected in the
2
4
may serve as pendant side-arm donor and can further range between −89 ppm (L SnN(SiMe ) 6) and −221 ppm
3
2
1
coordinate to the metal center. Selected complexes were (L SnN(SiMe ) 3).
3
2
then investigated in reduction reactions with a strong
Mg(I) reductant.
Orange crystals of 6 suitable for an X-ray structure
determination were obtained after storage of a concen-
trated solution of 6 in n-hexane at −30°C. Compound 6
crystallizes in the monoclinic space group P2 /n with one
1
molecule in the asymmetric unit (Fig. 1).
2
Results and discussion
The central tin atom is coordinated by a chelating
4
−
β-ketiminato ligand L and one amide ([N(SiMe ) ] ) ligand.
1,4
3 2
The germanium L GeN(SiMe ) (1, 2) and tin β-
3
2
This leads to a trigonal pyramidal environment of the tin
atom. Even though the Sn1–N1 bond (see caption Fig. 1) is
longer than the average Sn–N bond in β-ketiminato com-
plexes [40, 41], this value is still within the typical range.
The Sn1–O1 bond length also is equal to the average value
derived from the database, whereas the Sn1–N2 bond is
longer than the average but well within the typical range
1−4
ketiminate complexes L SnN(SiMe ) (3–6) were syn-
3
2
thesized (Scheme 1) by reaction of equimolar amounts
of E[N(SiMe ) ] (Eꢀ=ꢀGe, Sn) with the corresponding β-
3
2
1
2
−4
1
ketimines L H (L ꢀ=ꢀOC(Me)C(H)C(Me)NCH CH NMe ,
2
2
2
2
3
L ꢀ=ꢀOC(Me)C(H)C(Me)NCH CH NEt ,
L ꢀ=ꢀOC(Me)C(H)
2
2
2
−
of Sn–N bonds to [N(SiMe ) ] ligands [42]. This elonga-
3
2
tion may be attributed to the high steric demand of the
SiMe groups. The three bonds are roughly perpendicular
3
with N/O–Sn–N bond angles ranging between 84.52(5)°
and 99.77(5)°. The central NOC unit of the β-ketiminato
3
ligand is almost planar (r.m.s. deviation from best plane
0.0192 Å) and the tin atom is slightly shifted from this plane
Scheme 1:ꢀSynthesis of the complexes 1–6.
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J. Wiederkehr et al.: Reactions of heteroleptic Ge(II) and Sn(II) β-ketoiminate complexesꢂꢁꢀꢀꢀꢂ3
Scheme 2:ꢀSchematic drawing of the complexes 1–6.
−
[
0.330(3) Å] in the direction away from the [N(SiMe ) ]
3 2
group. This may again be explained by the high steric
demand of the SiMe groups. Two short intramolecular
3
contacts (C21–H21cꢀ·ꢀ·ꢀ·ꢀO1 2.46 Å, C22–H22aꢀ·ꢀ·ꢀ·ꢀO1 2.67 Å)
support the conformation of the molecule.
The potential capability of these heteroleptic com-
plexes 1–6 to serve as starting reagents in reduction reac-
tions for the synthesis of metalloid tin and germanium
clusters was exemplarily investigated in the reaction of
1
5
L SnN(SiMe ) 3 with the strong Mg(I) reductant [L Mg]
3
2
2
5
(
L ꢀ=ꢀ(dipp)NC(Me)C(H)C(Me)N(dipp)) [43, 44]. However,
in addition to the formation of a black insoluble precipi-
tate, most likely elemental tin, which clearly proves the
reduction of 3, we observed the formation of the het-
Fig. 1:ꢀSolid-state structure of 6. Non-H atoms are shown as
displacement ellipsoids at 50% probability levels, H atoms
are omitted for clarity except for those engaged in intramo-
lecular interactions. Selected bond lengths (Å) and angles
1
5
eroleptic complex L MgL 7, which is formed by a ligand
5
transfer reaction of L from the tin to the magnesium
atom. Comparable results were obtained from the reac-
(
deg): Sn(1)–O(1) 2.1067(13), Sn(1)–N(2) 2.1264(14), Sn(1)–N(1)
.2656(14); O(1)–Sn(1)–N(2) 96.93(5), O(1)–Sn(1)–N(1) 84.52(5),
5
4
4
tions of [L Mg] with L GeN(SiMe ) 2 and L SnN(SiMe ) 6,
2
3
2
3 2
2
which both yielded the known β-diketiminato magnesium
N(2)–Sn(1)–N(1) 99.77(5), C(1)–O(1)–Sn(1) 129.62(11), C(3)–N(1)–
C(6) 120.89(13), C(3)–N(1)–Sn(1) 125.19(11), C(6)–N(1)–Sn(1)
5
1
amide L MgN(SiMe ) 8 as was demonstrated by in situ H
3
2
NMR spectroscopy [45]. In contrast to the reactions with 3,
1
13.58(10), Si(2)–N(2)–Si(3) 124.61(8), Si(2)–N(2)–Sn(1) 119.45(7),
Si(3)–N(2)–Sn(1) 110.92(7), C(21)–H(21)cꢁ·ꢁ·ꢁ·ꢁO(1) 131.8, C(22)–H(22) which occurred with transfer of the β-ketiminato ligand L1
aꢁ·ꢁ·ꢁ·ꢁO(1) 126.7.
to the magnesium atom, the reaction with 2 and 6 led to
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ꢀꢀꢀꢀꢁꢀJ. Wiederkehr et al.: Reactions of heteroleptic Ge(II) and Sn(II) β-ketoiminate complexes
a transfer of the bis(trimethylsilyl)amido moiety from the [91.64(3)°] than the ideal value of 120°. Since Mg is on the
group 14 metal center to magnesium. Again, both reactions same plane with N1 and N3/N3′ (r.m.s. deviation 0.000 Å
proceeded with formation of insoluble precipitates, most and 0.0049 Å, resp.) the other equatorial bond angles nec-
likely elemental germanium and tin, as well as the forma- essarily have to be larger than the ideal value. Mg1 is on
1
1
tion of additional products according to in situ H NMR the plane of the NOC backbone of L [deviation from best
3
spectroscopy. Unfortunately, these compounds could not plane 0.016(5) Å and 0.350(3) Å, resp.], but significantly
5
be identified so far. However, these reactions clearly show off the plane of the N C backbone of L [deviation from
2
3
that both Ge–N and Sn–N bonds can be cleaved by reac- best plane 0.9809(10) Å]. The bond lengths match well
tion with the strong Mg(I) reductant.
with results from the CSD [46]. As was expected the more
Crystals of 7 suitable for a single crystal X-ray diffrac- weakly coordinated side-arm donor N4 shows an elon-
tion study were obtained after storage of a solution of 7 in gated bond to Mg1.
n-hexane for 2 d at −30°C (Fig. 2).
Compound 7 crystallizes in the monoclinic space
group C2/c with the molecule placed on a general posi-
3
Conclusion
5
tion. The central Mg atom is coordinated by one L and
1
one L ligands both in a chelating fashion. The resulting
1,4
Heteroleptic divalent germanium L GeN(SiMe ) (1, 2)
3
2
environment of the Mg atom is best described as distorted
trigonal bipyramidal, in which O1 and N4 adopt the apical
positions. The corresponding bond angle however devi-
ates approximately 20° from the expected linearity. The
distortion also manifests itself in the bond angles in the
equatorial positions. The N1–Mg1–N2 bond angle is deter-
mined by the bite angle of the ligand and is thus smaller
1
−4
and tin complexes L SnN(SiMe ) (3–6) are easily acces-
3
2
1
−4
sible by amide elimination reactions of β-ketimines L H
with Ge[N(SiMe ) ] and Sn[N(SiMe ) ] , respectively,
3
2
2
3 2 2
under mild reaction conditions. 3 reacts with the strong
5
Mg(I) reductant L Mg with transfer of the β-ketiminate
1
ligand (L ) from tin to magnesium and formation of the
1
5
heteroleptic complex L MgL 7, whereas analogous reduc-
4
4
tion reactions of L GeN(SiMe ) 2 and L SnN(SiMe ) 6
3
2
3 2
occurred with transfer of the amido substituent and for-
mation of the known heteroleptic magnesium complex
5
L MgN(SiMe ) (8).
3
2
4
Experimental section
All manipulations were performed under Ar. Solvents
were carefully dried with Na/K and degassed prior to use.
5
[
[
L Mg] was prepared according to literature methods
2
1
13
1
119
1
43, 44]. H NMR, C{ H} and Sn{ H} NMR spectra were
recorded with a Bruker DMX 300 spectrometer and
1
13
are referenced to internal C D H ( H: δꢀ=ꢀ7.16 ppm; C:
6
5
1
19
1
δꢀ=ꢀ128.0 ppm) and Me Sn ( Sn{ H}) [47]. IR spectra were
4
recorded with an ALPHA-T FTIR spectrometer equipped
with a single-reflection ATR sampling module. Melting
points were measured in sealed capillaries. Elemental
analyses were performed at the Elementaranalyse Labor
of the University of Essen.
Fig. 2:ꢀSolid-state structure of 7. Non-H atoms are shown as
displacement ellipsoids at 50% probability levels, H atoms and
a second orientation of the disordered side-arm are omitted for
clarity. Selected bond lengths (Å) and angles (deg): Mg(1)–O(1)
1
.9903(7), Mg(1)–N(1) 2.1055(8), Mg(1)–N(2) 2.1144(8), Mg(1)–N(3′)
.152(8), Mg(1)–N(3) 2.166(4), Mg(1)–N(4) 2.2669(9); O(1)–
Mg(1)–N(1) 94.26(3), O(1)–Mg(1)–N(2) 93.25(3), N(1)–Mg(1)–N(2)
2
9
1.64(3), O(1)–Mg(1)–N(3′) 85.5(2), N(1)–Mg(1)–N(3′) 126.55(12),
1–4
4
.1 General synthesis of β-ketimines L H
N(2)–Mg(1)–N(3′) 141.80(12), O(1)–Mg(1)–N(3) 84.58(10), N(1)–
Mg(1)–N(3) 137.20(6), N(2)–Mg(1)–N(3) 131.17(6), O(1)–Mg(1)–N(4)
1
−4
The β-ketimine ligands L H with different additional
1
60.99(3), N(1)–Mg(1)–N(4) 98.89(3), N(2)–Mg(1)–N(4) 100.01(3),
N(3′)–Mg(1)–N(4) 75.6(2), N(3)–Mg(1)–N(4) 76.44(10).
side-arm donors where synthesized according to the
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J. Wiederkehr et al.: Reactions of heteroleptic Ge(II) and Sn(II) β-ketoiminate complexesꢂꢁꢀꢀꢀꢂ5
following general procedure, which is slightly modified 3.06 (sept, 3J ꢀ=ꢀ6.9 Hz, 2 H, CH(CH ) ), 5.25 (s, 1 H, CH),
H,H
3 2
regarding the literature procedures using the correspond- 12.09 (s, 1 H, NH).
1
2
ing (di)amine (L H: N,N-dimethylethylenediamine, L H:
3
N,N-diethylethylenediamine, L H: 3-(dimethylamino)-
4
1–4
1
-propylamine, L H: 2,6-diisopropylaniline) [48–50]. L H 4.2 General synthesis of germanium
1
,4
were obtained as orange liquids in almost quantitative
yield.
complexes L GeN(SiMe )
3
2
1
4
A solution of LH (L H: 0.216 g, 1.3 mmol; L H: 0.330 g,
1
.3 mmol) in 10 mL of hexane was added slowly to a solu-
1
4
.1.1 L H
tion of Ge[N(SiMe ) ] (0.500 g, 1.3 mmol) in 10 mL of
3
2 2
hexane at 0°C and stirred for 2 h. The solution was then
N,N-Dimethylethylenediamine (9.92 mL, 0.091 mol) was allowed to warm to ambient temperature and stirred for
added to acetyl acetone (10.26 mL, 0.100 mol). The mixture another 2 h. All volatiles were removed in vacuum and 1
1
was stirred at ambient temperature for 3 h and L H was and 2 were obtained after extraction of the solid residue
isolated as an orange liquid after removal of the volatiles with toluene and evaporation of the solvent under vacuum
in vacuum. Yield: 15.3 g, (99%). – Elemental analysis: as a red-brown waxy (1) and orange crystalline compound
calcd. (found): H 62.5 (61.9), C 10.7 (10.8), N 14.5 (14.6). (2), respectively.
– 1
H NMR (300 MHz, C D , 25°C): δꢀ=ꢀ1.86 (s, 6 H, OCCH
6 6 3
3
and NCCH ), 2.18 (s, 6 H, N(CH ) ), 2.38 (t, JH,Hꢀ=ꢀ6.3 Hz, 2
3
3 2
3
H, CH CH NMe ), 3.24 (m, J ꢀ=ꢀ6.3 Hz, 2 H, CH CH NMe ),
2
2
2
H,H
2
2
2
1
4
.2.1 L GeN(SiMe ) 1
3
2
4
.88 (s, 1 H, CH), 10.71 (s, 1 H, NH). – IR (ATR): νꢀ=ꢀ2943,
2
861, 2819, 2767, 1609, 1564, 1513, 1440, 1285, 1193, 1110,
Yield: 0.501 g (96%). – Elemental analysis: calcd. (found):
−1
1
019, 732, 652 cm .
1
C 41.9 (41.9), H 7.7 (7.4), N 10.2 (10.0). – H NMR (300 MHz,
C D , 25°C): δꢀ=ꢀ0.44 (s, 18 H, Si(CH ) ), 1.38 (s, 3 H, NCCH ),
6
6
3
3
3
1
.67 (s, 3 H, OCCH ), 2.01 (s, 6 H, N(CH ) ), 2.34 (m, 2 H,
2
3 3 2
CH CH NMe ), 3.07 (m, 1 H, CH CH NMe ), 3.42 (m, 1 H,
4
.1.2 L H
2
2
2
2
2
2
1
3
CH CH NMe ), 4.60 (s, 1 H, CH). – C NMR (75 MHz, C D ,
1
2
2
2
6
6
Yield: 18.0 g, (100%). – H NMR (300 MHz, C D , 25°C):
6
6
2
5°C): δꢀ=ꢀ5.2 (Si(CH ) ), 20.6 (NCCH ), 25.2 (OCCH ), 45.1
3 3 3 3
δꢀ=ꢀ0.86 (t, 6 H, N(CH CH ) ), 1.46 (s, 3 H, NCCH ), 1.82 (s,
2
3
2
3
(
CH CH NMe ), 45.6 (CH CH N(CH ) ), 58.1 (CH CH NMe ),
2 2 2 2 2 3 2 2 2 2
3
H, OCCH ), 2.38 (m, 6 H, overlapping signals CH CH N-
3
2
2
9
9.3 (CH), 168.0 (NCCH ), 174.7 (OCCH ). – IR (ATR):
3
3
3
(
CH CH ) ), 3.06 (m, J ꢀ=ꢀ6.8 Hz, 1 H, CH CH NEt ), 3.32
2 3 2 H,H 2 2 2
νꢀ=ꢀ2962, 2819, 2769, 1738,1610,1575, 1513, 1455, 1259, 1088,
3
(
m, J ꢀ=ꢀ6.8 Hz, 1 H, CH CH NEt ), 4.70 (s, 1 H, CH).
H,H
2
2
2
−1
1
015, 864, 795, 702, 540, 397 cm .
3
4
.1.3 L H
4
4
.2.2 L GeN(SiMe ) 2
3
2
Yield: 15.9 g, (95%). – Elemental analysis: calcd. (found): H
1
6
5.2 (64.7), C 10.6 (10.2), N 15.2 (15.0). – H NMR (300 MHz, Yield: 0.581 g, (91%). – Elemental analysis: calcd. (found):
3
1
C D , 25°C): δꢀ=ꢀ1.63 (m, J ꢀ=ꢀ7.3 Hz, 2 H, CH CH CH NMe ), C 54.1 (53.6), H 7.9 (8.5), N 5.1 (5.3). – H NMR (300 MHz,
6
6
H,H
2
2
2
2
3
1
.87 (s, 6 H, OCCH and NCCH ), 2.12 (s, 6 H, N(CH ) ), 2.24 C D , 25°C): δꢀ=ꢀ0.31 (s, 18 H, Si(CH ) ), 0.96 (d, JH,Hꢀ=ꢀ6.8 Hz,
3 3 3 2 6 6 3 3
3
3
3
(
t, J ꢀ=ꢀ6.9 Hz, 2 H, CH CH CH NMe ), 3.23 (q, JH,Hꢀ=ꢀ6.5 Hz, 3 H, CH(CH ) ), 1.01 (d, J ꢀ=ꢀ6.8 Hz, 3 H, CH(CH ) ), 1.30 (s,
H,H 2 2 2 2 3 2 H,H 3 2
3
2
H, CH CH CH NMe ), 4.88 (s, 1 H, CH), 10.78 (s, 1 H, NH). – 3 H, NCCH ), 1.33 (d, J ꢀ=ꢀ6.9 Hz, 3 H, CH(CH ) ), 1.41 (d,
2 2 2 2 3 H,H 3 2
3
IR (ATR): νꢀ=ꢀ2944, 2860, 2817, 2766, 1608, 1574, 1511, 1439, JH,Hꢀ=ꢀ6.9 Hz, 3 H, CH(CH ) ), 1.74 (s, 3 H, OCCH ), 3.18 (sept,
3
2
3
−
1
3
3
1
295, 1260, 1097, 1016, 795, 734, 637 cm .
JH,Hꢀ=ꢀ6.8 Hz, 1 H, CH(CH ) ), 3.29 (sept, JH,Hꢀ=ꢀ6.9 Hz, 1 H,
3 2
CH(CH ) ), 4.86 (s, 1 H, CH), 7.02–7.11 ppm (3 H, m/p-CH,
3
2
1
3
overlapped with solvent signal). – C NMR (75 MHz, C D ,
6
6
4
4
.1.4 L H
25°C): δꢀ=ꢀ5.5 (Si(CH ) ), 23.1, 24.3, 24.5, 24.7, 24.8, 25.4, 27.7,
3 3
2
8.8, 97.3 (backbone-CH), 124.3 (m-CH), 124.6 (m-CH), 139.1
1
Yield: 21.2 g, (90%). – H NMR (300 MHz, C D , 25°C): (p-CH), 142.6 (p-CH), 142.8 (arom. dipp-CH), 169.8 (NCCH ),
6
6
3
3
3
δꢀ=ꢀ1.17 (d, J ꢀ=ꢀ6.9 Hz, 6 H, CH(CH ) ), 1.25 (d, JH,Hꢀ=ꢀ7.0 Hz, 176.1 (OCCH ). – IR (ATR): νꢀ=ꢀ3058, 2960, 2900, 2868, 1597,
H,H
3
2
3
6
H, CH(CH ) ), 1.65 (s, 6 H, NCCH ), 2.10 (s, 6 H, OCCH ), 1572, 1507, 1460, 1441, 1386, 1364, 1324, 1257, 1243, 1217,
3 2 3 3
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ꢀꢀꢀꢀꢁꢀJ. Wiederkehr et al.: Reactions of heteroleptic Ge(II) and Sn(II) β-ketoiminate complexes
1
176, 1099, 1056, 1017, 913, 866, 833, 789, 770, 758, 703, 670, 1286, 1248, 1200, 1176, 1124, 1065, 1015, 928, 883, 837, 821,
−1
−1
6
30, 618, 555, 510, 445, 411 cm .
755, 733, 668, 617, 501, 395 cm
3
4
.3 General synthesis of tin complexes
4.3.3 L SnN(SiMe ) 5
3
2
1
–4
L SnN(SiMe )
3
2
Yield: 1.597 g (81%). – Elemental analysis: calcd. (found):
1
2
1
A solution of LH (L H: 0.750 g, 4.4 mmol; L H: 0.451 g, C 40.8 (41.1), H 6.4 (6.5), N 9.7 (9.5). – H NMR (300 MHz,
3
4
2
.3 mmol; L H: 0.800 g, 4.3 mmol; L H: 1.000 g, 3.9 mmol) C D , 25°C): δꢀ=ꢀ0.41 (s, 18 H, Si(CH ) ), 1.46 (s, 3 H, NCCH ),
6
6
3
3
3
3
in 15 mL of hexane was added slowly to a solution of 1.52 (m, J ꢀ=ꢀ7.0 Hz, 2 H, CH CH CH NMe ), 1.81 (s, 3
H,H
2
2
2
2
Sn[N(SiMe ) ] (1.936 g, 4.4 mmol ) in 15 mL of hexane at H, OCCH ), 1.98 (s, 6 H, N(CH ) ), 2.06 (m, 2 H, CH CH -
3
2
2
3
3
2
2
2
0
°C and stirred for 2 h. The solution was allowed to warm CH NMe ), 3.08 (m, 1 H, CH CH CH NMe ), 3.39 (m, 1 H,
2 2 2 2 2 2
1
3
to ambient temperature, stirred for additional 2 h and CH CH CH NMe ), 4.69 (s, 1 H, CH). – C NMR (75 MHz, C D ,
2
2
2
2
6
6
then evaporated to dryness in vacuum. The heteroleptic 25°C): δꢀ=ꢀ4.35 (Si(CH ) ), 25.0 (NCCH ), 26.3 (OCCH ), 27.9
3
3
3
3
complexes 3–6 were obtained as red waxy (3), red-brown (CH CH CH NMe ), 43.8 (CH CH CH NMe ), 44.6 (N(CH ) ),
2
2
2
2
2
2
2
2
3 2
waxy (4, 5) and yellow-orange crystalline solids (6), 55.0 (CH CH CH NMe ), 98.4 (CH), 167.4 (NCCH ), 175.0
2
2
2
2
3
1
19
respectively, after extraction with toluene and removal of (OCCH ). – Sn NMR (111.9 MHz, C D , 25°C): δꢀ=ꢀ−133.1. –
3
6
6
all volatiles in vacuum.
IR (ATR): νꢀ=ꢀ2938, 2855, 2812, 2762, 1645, 1608, 1559, 1510,
1
1
457, 1440, 1399, 1372, 1336, 1299, 1259, 1219, 1178, 1151, 1121,
−1
096, 1061, 1039, 965, 932, 820, 803, 743, 501, 460 cm .
1
4
.3.1 L SnN(SiMe ) 3
3
2
4
Yield: 1.569 g (80%). – Elemental analysis: calcd. (found): 4.3.4 L SnN(SiMe ) 6
3
2
1
C 37.3 (37.5), H 6.8 (6.5), N 8.4 (8.2). – H NMR (300 MHz,
C D , 25°C): δꢀ=ꢀ0.46 (s, 18 H, Si(CH ) ), 1.36 (s, 3 H, NCCH ), Yield: 1.398 g (67%). – Elemental analysis: calcd. (found):
6
6
3
3
3
1
1
.86 (s, 3 H, OCCH ), 1.94 (s, 6 H, N(CH ) ), 2.25 (m, 2 H, H 51.3 (51.7), C 7.7 (8.0), N 5.3 (5.2). – H NMR (300 MHz,
3
3
2
3
CH CH NMe ), 2.70 (m, 1 H, CH CH NMe ), 2.95 (m, 1 H, C D , 25°C): δꢀ=ꢀ0.30 (s, 18 H, Si(CH ) ), 0.96 (d, JH,Hꢀ=ꢀ6.7 Hz,
2
2
2
2
2
2
6
6
3 3
13
3
CH CH NMe ), 4.72 (s, 1 H, CH). – C NMR (75 MHz, C D , 3 H, CH(CH ) ), 1.05 (d, J ꢀ=ꢀ6.8 Hz, 3 H, CH(CH ) ), 1.22
2
2
2
6
6
3
2
H,H
3 2
3
2
(
(
5°C): δꢀ=ꢀ6.6 (Si(CH ) ), 23.2 (NCCH ), 27.5 (OCCH ), 44.9 (d, J ꢀ=ꢀ6.7 Hz, 3 H, CH(CH ) ), 1.37 (s, 3 H, NCCH ), 1.43
3 3 3 3 H,H 3 2 3
3
CH CH NMe ), 47.5 (N(CH ) ), 58.2 (CH CH NMe ), 99.2 (d, J ꢀ=ꢀ6.8 Hz, 3 H, CH(CH ) ), 1.86 (s, 3 H, OCCH ), 2.99
2
2
2
3
2
2
2
2
H,H
3
3
2
3
119
3
CH), 170.2 (NCCH ), 180.9 (OCCH ). – Sn NMR (111.9 MHz, (sept, J ꢀ=ꢀ6.6 Hz, 1 H, CH(CH ) ), 3.32 (sept, JH,Hꢀ=ꢀ6.4 Hz,
3
3
H,H
3 2
C D , 25°C): δꢀ=ꢀ–221.4. – IR (ATR): νꢀ=ꢀ3055, 2952, 2860, 1 H, CH(CH ) ), 4.86 (s, 1 H, CH), 6.95–7.25 (m, 3 H, m/p-
6
6
3 2
1
3
2
819, 2770, 1646, 1603, 1567, 1508, 1455, 1422, 1393, 1340, CH, overlapped with solvent signal). – C NMR (75 MHz,
1
6
246, 1175, 1124, 1097, 1016, 927, 867, 836, 780, 780, 758, 668, C D , 25°C): δꢀ=ꢀ6.7 (Si(CH ) ), 24.2, 24.3, 24.9, 25.4, 25.6,
6
6
3
3
−1
18, 509, 411, 392 cm .
27.4, 28.3, 29.2, 98.9 (CH), 125.1 (dipp-CH), 125.3 (dipp-CH),
1
1
26.0, 141.1 (dipp-CH), 142.1 (dipp-CH), 143.7 (dipp-CH),
1
19
71.4 (NCCH ), 179.2 (OCCH ). – Sn NMR (111.9 MHz, C D ,
3
3
6
6
2
4
.3.2 L SnN(SiMe ) 4
25°C): δꢀ=ꢀ−88.8. – IR (ATR): νꢀ=ꢀ3055, 2962, 2896, 2869,
723, 1575, 1502, 1460, 1440, 1386, 1364, 1322, 1240, 1176,
3
2
1
Yield: 0.834 g (76%). – Elemental analysis: calcd. (found): 1101, 1054, 1042, 1014, 937, 864, 831, 795, 774, 758, 689, 668,
C 40.4 (41.0), H 6.5 (6.7), N 8.4 (8.7). – H NMR (300 MHz, 614, 595, 529, 506, 439, 405 cm .
1
−1
3
C D , 25°C): δꢀ=ꢀ0.43 (s, 18 H, Si(CH ) ), 0.86 (t, JH,Hꢀ=ꢀ7.1 Hz,
6
6
3 3
6
H, N(CH CH ) ), 1.46 (s, 3 H, NCCH ), 1.82 (s, 3 H, OCCH ),
2 3 2 3 3
1
5
2
.36 (m, 6 H, N(CH CH ) overlapped with CH CH NEt ), 4.4 Synthesis of L MgL 7
2
3
2
2
2
2
3
.06 (m, 1 H, CH CH NEt ), 3.32 (m, 1 H, CH CH NEt ),
2
2
2
2
2
2
13
5
4
.70 (s, 1 H, CH). – C NMR (75 MHz, C D , 25°C): δꢀ=ꢀ6.6 A mixture of 3 (94 mg, 0.2 mmol) and [L Mg] (186 mg,
6
6
2
(
(
(
Si(CH ) ), 12.0 (N(CH CH ) , 22.1 (NCCH ), 27.1 (OCCH ), 47.4 0.2 mmol) was dissolved at 0°C in 5 mL of toluene and
3 3 2 3 2 3 3
N(CH CH ) ), 48.4 (CH CH NEt ), 53.1 (CH CH NEt ), 100.2 stirred for 48 h at ambient temperature. The solvent
2
3
2
2
2
2
2
2
2
119
CH), 169.9 (NCCH ), 177.8 (OCCH ). – Sn NMR (111.9 MHz, was evaporated from the dark red-brown solution and
3
3
C D , 25°C): δꢀ=ꢀ−150.7. – IR (ATR): νꢀ=ꢀ2964, 2933, 2872, the resulting crystalline solid was dissolved in pentane.
6
6
2
809, 1647, 1608, 1565, 1510, 1467, 1438, 1397, 1372, 1341, Slightly orange crystals of 7 were formed within 2 d upon
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J. Wiederkehr et al.: Reactions of heteroleptic Ge(II) and Sn(II) β-ketoiminate complexesꢂꢁꢀꢀꢀꢂ7
storage at –30°C. Yield: 30 mg (25%). – Elemental analysis:
5
Crystal structure determinations
1
calcd. (found): C 74.7 (74.6), H 9.6 (9.7), N 9.2 (9.2). H NMR
3
(
300 MHz, C D ): δꢀ=ꢀ1.21 (d, J ꢀ=ꢀ7.4 Hz, 6 H, CH(CH ) ), The crystals of 6 and 7 were mounted on nylon loops in
6
6
HH
3 2
1
.26–1.35 (overlapping douplets, 18 H, CH(CH ) ), 1.59 (s, 3 inert oil. Data were collected on a Bruker AXS D8 Kappa
3 2
1
5
H, NCCH (L )), 1.72 (s, 6 H, CH (L )), 1.79 (s, 6 H, N(CH ) ), diffractometer with APEX2 detector (monochromated
3
3
3 2
1
1
.96 (s, 3 H, OCCH (L )), 2.78 (m, 2 H, CH CH NMe ), 3.49 MoKα radiation, λꢀ=ꢀ0.71073 Å). The structures were
3
2
2
2
(
m, 4 H, overlapping signals CH CH NMe and CH(CH ) ), solved by Direct Methods (Sꢁꢂꢃꢄꢅ-97) [51, 52] and
2 2 2 3 2
5
1
4
.89 (s, 1 H, CH (L )), 5.09 (s, 1 H, CH (L )), 7.01–7.20 (m, 3 refined anisotropically by full-matrix least-squares on
13
2
H, m/p-CH, overlapping with solvent signals). – C NMR F (Sꢁꢂꢃꢄꢃ-2014) [53–57]. Absorption corrections were
(
75 MHz, C D , 25°C): δꢀ=ꢀ21.9, 22.6, 23.5, 24.2, 24.5, 24.9, performed semi-empirically from equivalent reflections
6 6
2
5.2, 25.3, 27.4, 28.2, 28.5, 28.6, 45.4, 46.2, 59.5, 96.9 (CH), on basis of multi-scans (Bruker AXS APEX2, Tꢆꢇꢈꢉꢊꢅ).
7.7 ( CH), 123.4, 123.6, 123.9, 124.0, 124.7, 125.9, 142.4 (dipp- Hydrogen atoms were refined using a riding model or
9
CH), 142.8 (dipp-CH), 143.5 (dipp-CH), 148.1, 161.6 (NCCH ), rigid methyl groups. Compound 6 was non-merohe-
68.3 (NCCH ), 173.2 (NCCH ), 182.7 (OCCH ). – IR (ATR): drally twinned and refined with two components against
3
1
3 3 3
νꢀ=ꢀ3053, 2959, 2922, 2865, 1621, 1581, 1537, 1516, 1458, 1430, HKLF5 data. Compound 7 contained highly disordered
400, 1337, 1312, 1261, 1225, 1172, 1098, 1052, 1014, 925, solvent of unidentifiable nature. n-pentane, n-hexane
1
8
4
41, 789, 759, 734, 699, 668, 646, 622, 596, 548, 516, 435, and toluene were used but none of these or combina-
−
1
17 cm .
tions thereof yielded a satisfying model for the residual
density. Consequently, the refinement was done using
“
solvent-free” data from a Pꢃꢉꢋꢌꢈ/SQEEZE run. Because
5
4
.5 Reaction of 2 with [L Mg]
2
the solvent could not be identified for certain it was
ignored in the sum formula. The ligands side-arm is dis-
ordered over two positions.
5
Compound 2 (15 mg, 0.03 mmol) and [L Mg] (13 mg,
2
0
.015 mmol) were dissolved at –10°C in 0.5 mL toluene
CCDC-1555595 (6) and CCDC-1555596 (7) contain the
supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
and stirred for 3 h at that temperature, slowly warmed up
to ambient temperature and stirred for additional 12 h.
Thereafter the reaction mixture was heated to 50°C for
6
h, yielding an dark solution with a black precipitate.
1
The in-situ H NMR spectrum of the solution showed the
5
formation of L MgN(SiMe ) 8 [45]. Additional signals were
either assigned to the starting reagent 2 or belong to so
3
2
far unidentified products. The formation of a black solid 6 Supporting Information
indicates the reduction of 2 to elemental germanium 8:
1
H NMR (300 MHz, C D , 25°C): δꢀ=ꢀ0.02 (s, 18 H, Si(CH ) ), H and C NMR and IR spectra of 1–7, 119Sn NMR spectra
1
13
6
6
3 3
3
3
1
1
.20 (d, J ꢀ=ꢀ6.7 Hz, 12 H, CH(CH ) ), 1.40 (d, JH,Hꢀ=ꢀ6.8 Hz, of 3–6, in situ H NMR spectra of the reduction reaction of
H,H
3 2
3
5
1
2 H, CH(CH ) ), 1.67 (s, 3 H, CH ), 3.23 (sept, JH,Hꢀ=ꢀ6.8 Hz, 2 and 6 with [L Mg] , and crystallographic data of 6 and
3
2
3
2
4
H, CH(CH ) ), 4.83 (s, 1 H, CH), 7.02–7.05 ppm (m, 6 H, 7 are given as Supporting Information available online
3
2
m/p-CH).
(https://doi.org/10.1515/znb-2017-0098).
Acknowledgments: S. Schulz thank the University of Duis-
burg-Essen for financial support. J. Wiederkehr is grateful
to the Fonds der Chemischen Industrie for a doctoral fel-
lowship. Ms. Haley Palm is acknowledge for contributing
to the experimental work.
5
4
.6 Reaction of 6 with [L Mg]2
5
6
(64 mg, 0.1 mmol) and [L Mg] (102 mg, 0.1 mmol) were
2
dissolved at –10°C in 0.5 mL of toluene and stirred for 3 h
at that temperature, resulting in the formation of a dark
brown solution and a black precipitate. The mixture was
warmed to ambient temperature and stirred for another
References
3
h, upon which the color did not change. The in-situ
1
H NMR spectrum of the reaction solution showed the for-
[
1] N. Tokitoh, T. Sasamori, in Comprehensive Inorganic Chemistry
5
mation of L MgN(SiMe ) 8. Additional signals could not
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3
2
II, 2 edition, From Elements to Applications, Vol. 1
been assigned to any known compound. The formation of
a black solid indicates the formation of elemental tin.
(
Eds.: J. Reedijk, K. Poeppelmeier), Elsevier, Amsterdam, 2013,
chapter 1.19, p. 567.
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8
ꢀꢀꢀꢀꢁꢀJ. Wiederkehr et al.: Reactions of heteroleptic Ge(II) and Sn(II) β-ketoiminate complexes
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[
[
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[
[
[
[
[
[
[
[
13] E. Ballestero-Martínez, J. Klosin, B. D. Fahlman, L. W. Pineda,
3
2
Eur. J. Inorg. Chem. 2014, 5233.
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5
15 hits. The corresponding search for the L backbone yielded
275 hit (818 bonds): average Mg–N 2.060(35) Å (1.994 to
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Z. Naturforsch.ꢂ
ꢂ2017 | Volume x | Issue x(b)
Graphical synopsis
Jessica Wiederkehr, Christoph Wölper and
Stephan Schulz
Synthesis, solid-state structures and
reduction reactions of heteroleptic Ge(II)
and Sn(II) β-ketoiminate complexes
https://doi.org/10.1515/znb-2017-0098
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