Synthesis and single crystal x-ray structures of cationic zinc β-diketiminate complexes

Article abstract of DOI:10.1002/zaac.201300119

The cationic zinc complex [L¹Zn][Al(OC(CF₃) ₃)₄] (1) (L¹ = {[(2,4,6-Me₃-C ₆H₂)NC(Me)]₂CH}) bearing a weakly coordinating aluminate anion was obtained from reaction of L¹ZnCl with Li[Al(OC(CF₃)₃)₄]. In addition, base-stabilized zinc cations [L^1/2Zn(base)₂][X] (2-5) (L² = {[(2,6-iPr₂-C₆H₃)NC(Me)]₂CH}; X = [Al(OC(CF₃)₃)₄], [B(C₆F ₅)₄]) containing weakly coordinating anions and different Lewis bases (dimethylaminopyridine (dmap), tert-butylpyridine (tBuPy)) were synthesized and structurally characterized. Moreover, the solid-state structures of L¹ZnMe (6) and the neutral base-stabilized complexes tBuPy-Zn(Cl)L¹ (7) and base-Zn(Me)L² (base = dmap 8, tBuPy 9) are reported and compared with those of 2-5. Preliminary studies showed that 1 is catalytically activity in lactide polymerization at 160 °C. Copyright

Full text of DOI:10.1002/zaac.201300119

Job/Unit: Z13119
/KAP1
Date: 14-05-13 18:14:48
Pages: 8
ARTICLE
DOI: 10.1002/zaac.201300119
Synthesis and Single Crystal X-ray Structures of Cationic Zinc
β-Diketiminate Complexes
Christoph Scheiper,[a] Stephan Schulz,*[a] Christoph Wölper,[a] Dieter Bläser,[a] and
Joachim Roll[b]
Dedicated to Professor Heinrich Nöth on the Occasion of His 85th Birthday
Keywords: Cations; Zinc; X-ray analysis
Abstract. The cationic zinc complex [L1Zn][Al(OC(CF3)3)4] (1) pyridine (tBuPy)) were synthesized and structurally characterized.
(L1 = {[(2,4,6-Me3–C6H2)NC(Me)]2CH}) bearing a weakly coordinat-
Moreover, the solid-state structures of L1ZnMe (6) and the neutral
ing aluminate anion was obtained from reaction of L1ZnCl with base-stabilized complexes tBuPy-Zn(Cl)L1 (7) and base-Zn(Me)L2
Li[Al(OC(CF3)3)4]. In addition, base-stabilized zinc cations
(base = dmap 8, tBuPy 9) are reported and compared with those of
[L1/2Zn(base)2][X] (2–5) (L2 = {[(2,6-iPr2–C6H3)NC(Me)]2CH}; X = 2–5. Preliminary studies showed that 1 is catalytically activity in
[Al(OC(CF3)3)4], [B(C6F5)4]) containing weakly coordinating anions lactide polymerization at 160 °C.
and different Lewis bases (dimethylaminopyridine (dmap), tert-butyl-
lysts for the copolymerization of CO2 and epoxides.[12] The β-
Introduction
diketiminato ligands of the type [HC{C(Me)NR}2] are almost
The ring opening polymerization of lactide has become a
ideal ligands for the synthesis of tailor-made catalysts since
very active research field in the last decade,[1,2] since polylac-
their steric demand as well as electronic properties can be pre-
tides have received considerable interest due to their biode-
cisely controlled by variation of the organic substituents R
gradable properties.[3] Unfortunately, the commercially used
bound to the imine centers.
catalyst, SnOct2, causes problems in the biomedical field due
Based on the experimental finding, that zwitterionic
to its toxicity.[2,4] As a consequence, there is an increasing de-
mand in the development of new catalysts, which are non-toxic
and of low cost, hence leading to the synthesis of very active
zinc, aluminum, magnesium or lanthanide catalysts.[5–8]
Organozinc-based catalysts have been investigated for a
long time. Early studies of Dittrich and Schulz reported on the
use of ZnMe2, AlMe3 and SnCl4 in the lactide polymeriza-
tion,[9] whereas Kricheldorf et al. later on introduced more
tris(pyrazolyl)borate complexes are active polymerization cata-
lysts,[13] Hayes et al. suggested, that the activity of metal com-
plexes in the lactide polymerization can be increased by use
of more electropositive metals.[14] Aside from changing the
metal atom, the acidity of a cationic metal complex is also
higher than its neutral form, hence promoting facile coordina-
tion of lactide. Cationic metal complexes have been shown
to be effective catalysts in the ring-opening polymerization of
active aluminum alkoxides.[10] However, it was the pioneering
lactones,[15] whereas lactide polymerization has been studied
work of Coates et al., that clearly set the focus on neutral
to a lesser extent.[16]
zinc alkoxide complexes based on monoanionic β-diketiminato
Structurally characterized cationic complexes containing co-
ligands. Complexes of this type were found to show a very
ordinatively saturated zinc atoms are well known,[17] whereas
high activity and also stereoselectivity in lactide polymeriza-
the number of structurally characterized threefold coordinated
tion.[11] Moreover, these complexes are also promising cata-
cationic zinc complexes was limited for a long time to Boch-
mann cationic zinc diazadiene complexes (Scheme 1, type
* Prof. Dr. S. Schulz
I).[15b,f] Recently, Hayes et al. synthesized threefold coordi-
Fax: +49-201-1833830
E-mail: stephan.schulz@uni-due.de
nated cationic zinc complexes based on mono(phosphinimine)-
dibenzofuran and bis(phosphinimine)dibenzofuran pincer-type
[a] Faculty of Chemistry
University of Duisburg-Essen
Universitätsstr. 5–7
ligands (type II), which also contained weakly coordinating
anions.[18,19] Unfortunately, these cationic alkylzinc complexes
of the type [LZnR]+ (R = Me, Ph) were found to be almost
inactive for the polymerization of lactide. However, the steric
demand of the organic ligand bound to the imine center as well
45141 Essen, Germany
[b] Westfälische Hochschule
University of Applied Sciences, Organometallic Chemistry
August-Schmidt-Ring 10
45665 Recklinghausen, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201300119 or from the author. as the alkyl group bound to the zinc atom were found to play
Z. Anorg. Allg. Chem. 0000, ᭿,(᭿), 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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C. Scheiper, S. Schulz, C. Wölper, D. Bläser, J. Roll
ARTICLE
a crucial role on the catalytic activity of the complex. For in-
stance, the cationic complex VI containing the sterically less
demanding Pipp-substituent (Pipp = p-isopropyl phenyl) and a
zinc-lactate moiety was found to polymerize 200 equiv. of lact-
ide within 50 min at ambient temperature.[20] In contrast, the
sterically less demanding Ph-substituted complex IV is unex-
pectedly less active than VI, most likely due to electronic ef-
fects.[21] The phenyl group on the N-aryl rings reduces the
electron donating capacity of the ligand, whereby the zinc cen-
ter in IV is more electropositive and reduces its polymerization
activity. The exchange of the bulky phenyl ligands at the phos-
phorus atoms by sterically less demanding ethyl groups yielded
V,[22] which showed an increased catalytic activity. 200 equiv.
of lactide were polymerized within 20 min at ambient tempera-
ture, clearly demonstrating the crucial role of steric and elec-
tronic effects on the resulting catalytic activity. Very recently,
cationic zinc complexes containing both threefold and fourfold
coordinated zinc atoms were successfully used in polymeriza-
tion reactions.[16f, g,19–23] Threefold coordinated cationic com-
plexes of type VII are active in lactide polymerization and
trimethylene carbonate polymerization.[16g] In addition, the
base-stabilized complex VIII was found to polymerize ε-cap-
rolactone without the need of additional initiators such as
alcohols.[23]
Scheme 2. Synthetic routes to cationic β-diketiminate zinc complexes.
CH2Cl2 upon warming to 40 °C and precipitates slowly as
colorless crystalline solid upon cooling to ambient tempera-
1
ture. H and 13C NMR spectra of 1 show two sets of reso-
nances due to the Mesnacnac ligand, most likely indicating the
coordination of one mesityl group to the electrophilic zinc cat-
ion as was observed in the solid-state structure of the neutral
amidinate complex [tBuC(NDipp)2ZnMe].[27] Unfortunately,
numerous attempts to grow suitable crystals for a single-crystal
X-ray diffraction study failed, to date.
Since the solubility of the cationic zinc β-diketiminate com-
plexes [L1/2Zn]+[Anion]– was expected to be increased by co-
ordination of strong Lewis bases to the electrophilic zinc atom,
we reacted L1ZnCl and L2ZnMe with M[Al{OC(CF3)3}4]
(M = Li, Ag) and Ph3C[X] [X1 = [Al{OC(CF3)3}4], X2
=
[B(C6F5)4], respectively, in the presence of two equivalents of
either 4-dimethylaminopyridine (dmap) or tBuPy. The progress
of reaction with Ph3C[X], which was given by the formation of
1
Ph3CMe, can be in situ monitored by H NMR spectroscopy.
Base-stabilized [L1Zn(dmap)2][Al{OC(CF3)3}4] (2) and
[L2Zn(base)2][X1/2] (L2 = {[(2,6-iPr2–C6H3)NC(Me)]2CH}
(Dippnacnac); X1 = [Al{OC(CF3)3}4], base = tBuPy (3), X2 =
[B(C6F5)4], base = dmap (4), tBuPy (5)) were obtained in high
yields (Ͼ 80%). The resonances of the Lewis bases (dmap,
tBuPy) are shifted toward higher (CH) and lower field (CH3)
compared to those of the “free” bases. Moreover, the relative
intensity of the resonances due to the anionic β-diketiminato
group and the Lewis bases (dmap, tBuPy) of 1:2 indicates the
formation of stable bis adducts in solution. Complexes 2–5,
which are soluble in organic solvents such as CH2Cl2, toluene
or benzene, do not show any sign of decomposition over a
period of several days.
Scheme 1. Catalytically active cationic zinc complexes.
Herein, we report on the synthesis of base-free and base-
stabilized cationic zinc complexes based on β-diketiminato li-
gands. The latter were also structurally characterized by single-
crystal X-ray diffraction. Furthermore, the catalytic activity of
[L1Zn][Al{OC(CF3)3}4] (1) in the ring opening polymerization
of lactide was investigated (Scheme 2).
2–5 were structurally characterized by single-crystal X-ray
diffraction (Figure 1, Figure 2). The complexes, which show
almost identical structural parameters (Table 1), each consist
Results and Discussion
L1ZnCl (L1 = {[(2,4,6-Me3–C6H2)NC(Me)]2CH}[24]) reacts of a twofold base-stabilized zinc cation and the respective
with one equivalent of [M(Al(OC(CF3)3)4)] (M = Li, Ag), anion, which shows no interactions to the cationic zinc center.
which contains a weakly coordinating perfluorinated alkoxy- The zinc centers in the cations adopt a tetrahedral coordination
aluminate anion,[25,26] with subsequent formation of sphere as was previously reported for cationic zinc complex-
[L1Zn][Al{OC(CF3)3}4] (1) in high yield. 1 is soluble in es.[26,32,16h] Analogous findings were observed for the corre-
2
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Synthesis and Single Crystal X-ray Structures of Cationic Zinc β-Diketiminate Complexes
sponding neutral base-stabilized complexes tBuPy-Zn(Cl)L1 ZnN2C3 rings in 2–5 are within the typical range as reported
(7) and base-Zn(Me)L2 (base = dmap 8, tBuPy 9), which have by us and others.[29] The C–N and C–C bond lengths within
been prepared by equimolar reaction of L1ZnCl and L2ZnMe the β-diketiminate backbones are almost identical compared to
with the corresponding Lewis base and structurally charac- those of the neutral base stabilized complexes tBuPy-Zn(Cl)L1
terized in order to compare their structural parameters with (7), dmap-Zn(Me)L2 (8), and tBuPy-Zn(Me)L2 (9) (Table 2).
those of 2–5. In contrast, L1ZnMe (6) exhibits a threefold-
Table 2. Central bond lengths /Å and bond angles /° of [L1ZnMe] (6)
coordinated zinc atom.[29c]
and base-stabilized, neutral zinc complexes tBuPy-Zn(Cl)L1 (7) as
well as base-Zn(Me)L2 (base = dmap 8, tBuPy 9).
6
7
8
9
Zn–N1/2
1.946(2)
1.9842(12) 2.023(2)
2.0423(11)
2.0251(10)
2.1464(11)
–
1.9825(14)
1.3178(15)
1.3279(16)
1.4130(17)
1.4051(18)
93.90(4)
1.9596(16) 1.9803(12) 2.028(2)
–
–
1.946(2)
1.327(2)
1.336(3)
1.408(3)
1.399(3)
Zn–Namine
Zn–Cl
Zn–C
N1–C1
N2–C3
C1–C2
C2–C3
2.0699(12) 2.097(2)
2.2074(4)
–
–
1.995(3)
1.3251(18) 1.331(3)
1.3243(18) 1.327(3)
1.410(2)
1.407(2)
97.48(5)
1.410(3)
1.403(4)
94.62(9)
N1–Zn1–N2 96.02(7)
Zn1–N1–C1 123.42(13) 120.27(9)
Zn1–N2–C3 122.69(13) 120.61(9)
122.30(18) 122.85(8)
122.07(17) 121.60(9)
C1–C2–C3 128.62(18) 129.12(13) 130.0(2)
128.98(11)
In contrast, the neutral complexes 7–9 show slightly elon-
gated Zn–N bond lengths compared to those of the cationic
complexes 2–5, most likely resulting from the increased elec-
trophilicity of the cationic zinc atoms and due to higher ionic
bonding contributions, as well as slightly larger Zn–N–C bond
angles. L1ZnMe (6), which only contains a threefold-coordi-
nated zinc atom, shows almost identical bonding parameters
compared to the cationic complex 2. Moreover, the Zn–N bond
lengths compare very well with the values obtained from DFT
calculations for L1ZnMe (2.0025, 2.0018)[29c] and L2ZnMe
(1.9480(18), 1.9429(18) Å], respectively.[24] The Zn–Namine
bond lengths to the coordinating Lewis bases are significantly
longer as was expected (Table 1).
Figure 1. Crystal structure of [L1Zn(dmap)2][Al{OC(CF3)3}4] (2). All
hydrogen atoms and alternative site of the disorder have been omitted
for clarity. Ellipsoids are drawn at 50% probability level.
Figure 2. Crystal structure of [L2Zn(tBuPy)2][B(C6F5)4] (5). All hy-
drogen atoms as well as the solvent molecule were omitted for clarity.
Ellipsoids are drawn at 50% probability level. The relative orientation
of the ions does not resemble their orientation in the asymmetric unit.
Preliminary Polymerization Studies
Initial studies demonstrated the capability of complex 1 to
serve as catalyst in ring opening polymerization (ROP) of
lactide (Scheme 3).
Table 1. Central bond lengths /Å and bond angles /° of
[L1Zn(dmap)2][Al{OC(CF3)3}4] (2), [L2Zn(tBuPy)2][Al{OC(CF3)3}4]
(3), [L2Zn(dmap)2][B(C6F5)4] (4), and [L2Zn(tBuPy)2][B(C6F5)4] (5).
2
3
4
5
Zn–N1/2
1.9595(18)
1.9638(17)
1.9947(17)
2.0488(18)
1.328(3)
1.327(3)
1.404(3)
1.404(3)
1.955(3)
1.956(4)
2.060(4)
2.020(4)
1.331(5)
1.321(5)
1.401(6)
1.408(6)
1.9723(8)
1.9682(18)
1.9935(18)
2.0540(19)
1.333(3)
1.318(3)
1.400(3)
1.422(3)
1.9562(13)
1.9602(14)
2.0257(14)
2.0417(14)
1.332(2)
1.328(2)
1.408(2)
1.409(2)
Zn–Namine
N1–C1
N2–C3
C1–C2
C2–C3
Scheme 3. Ring opening polymerization of lactide by use of bulk 1.
Since 1 is not soluble in organic solvents at room tempera-
ture, its catalytic activity could not be investigated at ambient
temperature. However, 1 is active in bulk polymerization at
160 °C, converting 200 equivalents of lactide within 8 min into
polylactide. The molecular weight (MW; 1.2ϫ105 g·mol–1)
N1–Zn1–N2 97.50(7)
Zn1–N1–C1 119.12(15)
Zn1–N2–C3 118.74(15)
C1–C2–C3 128.7(2)
99.19(14) 98.75(7)
99.19(6)
118.5(3)
119.2(3)
129.7(4)
116.46(14)
117.42(15)
129.6(2)
117.83(11)
119.01(11)
129.43(15)
The bonding parameters of the β-diketiminate ligand frame- and polydispersity index (PDI; 1.73) of the resulting lactide
works as well as the Zn–N bond lengths of the six-membered was determined by gel permeation chromatography (GPC) in
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
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C. Scheiper, S. Schulz, C. Wölper, D. Bläser, J. Roll
ARTICLE
[[L1Zn(dmap)2][Al{OC(CF3)3}4] (2): L1ZnCl (0.22 g, 0.5 mmol) was
dissolved in CH2Cl2 (40 mL). Ag(Al(OC(CF3)3)4 (0.54 g, 0.5 mmol)
and dmap (0.12 g, 1.0 mmol) were added and the resulting mixture
was stirred for 18 h at room temperature. The solution was filtered,
concentrated to 5 mL and stored at –30 °C. Colorless crystals of 2 were
formed within 24 h (0.72 g, 89%). Elemental analysis calcd. (%) for
C53H49N6ZnAlO4F36: C 39.5, H 3.1, N 5.2; found: C 39.6, H 3.3, N
hexafluoroisopropanol (HFIP) with 0.05 m potassiumtrifluor-
acetate (KTFAc) at 23 °C (flow 1 mL·min–1) using a refractive
index detector (RI).
Conclusions
1
5.5. H NMR (300 MHz, CD2Cl2, 25 °C): δ = 1.80 (s, 6 H, β-CCH3),
The base-free cationic zinc complex [L1Zn][Al{OC(CF3)3}4]
(1) is accessible by reactions of [L1ZnCl] with
M[Al{OC(CF3)3}4] (M = Li, Ag). In contrast, reactions
of [L2ZnMe] with Ph3CX1/2 in the presence of two
1.88 (s, 12 H, o-CH3), 2.31 (s, 6 H, p-CH3), 3.05 (s, 12 H, N(CH3)2),
3
5.01 (s, 1 H, γ-CH), 6.40 (d, JHH = 7.2 Hz, 4 H, C(3)-Hdmap) 6.82 (s,
3
4 H, m-H), 7.11 (d, JHH = 7.2 Hz, 4 H, C(2)-Hdmap). 13C NMR
(75 MHz, CD2Cl2, 25 °C): δ = 17.9 (o-CH3), 20.4 (β-CCH3), 20.6 (p-
CH3), 39.0 (N(CH3)2), 93.8 (γ-C), 107.1 (C(3)dmap), 121.2 (q, JCF
=
equivalents of
complexes
a
Lewis base yielded base-stabilized
[L1Zn(dmap)2][Al{OC(CF3)3}4]
(2),
293.3 Hz, CF3), 129.3 (m-C), 131.6 (o-C), 134.4 (p-C), 144.2 (i-C),
147.3 (C(2)dmap), 155.5 (C(4)dmap), 168.6 (β-CCH3). 19F NMR
(282 MHz, CD2Cl2, 25 °C): δ = –75.7
[L2Zn(t-BuPy)2][Al{OC(CF3)3}4] (3) [L2Zn(dmap)2][B(C6F5)4]
(4), and [L2Zn(t-BuPy)2][B(C6F5)4] (5), respectively, which
were fully characterized including single-crystal X-ray analy-
ses. [L1Zn][Al{OC(CF3)3}4] 1 is an active lactide polymeriza-
tion catalyst in its bulk form at 160 °C. Detailed studies on the
catalytic activity of 1 as well as of base-stabilized complexes
2–5 in ROP of lactide are currently under investigation.
[L2Zn(tBuPy)2][Al{OC(CF3)3}4] (3): L2ZnMe (0.25 g, 0.5 mmol)
was dissolved in CH2Cl2 (40 mL). Ph3C(Al(OC(CF3)3)4 (0.61 g,
0.5 mmol) and tBuPy (0.14 g, 1.0 mmol) were added and the resulting
mixture was stirred for 18 h at room temperature. The solvent was
removed at reduced pressure and the colorless solid extracted with n-
pentane (20 mL). 3 was obtained after storage at –30 °C as colorless
crystals (0.68 g, 79%). Elemental analysis calcd. (%) for
C63H67N4ZnAlO4F36: C 44.0, H 3.9, N 3.3; found: C 45.6, H 4.0, N
Experimental Section
3
3.0. 1H NMR (300 MHz, CD2Cl2, 25 °C): δ = 0.52 (d, JHH = 6.8 Hz,
1
3
2
12H, CH(CH3 )2), 1.14 (d, JHH = 6.8 Hz, 12H, CH(CH3 )2), 1.33 (s,
General: All manipulations involving air-sensitive materials were per-
formed using standard vacuum techniques and inert gas atmosphere
(argon, Ͻ 0.3 ppm O2) or in a glove box (MBraun Unilab V2.0). Sol-
vents were carefully dried (CH2Cl2) with CaH2, degassed and stored
in Teflon-sealed glass vessel over appropriate drying agents (molecular
sieve). L1ZnR (R = Me (6), Cl),[29c] L2ZnR (R = Me, Cl),[24,30]
3
18H, C(CH3)3), 1.95 (s, 6H, β-CCH3), 2.90 (sept, JHH = 6.8 Hz, 4H,
CH(CH3)2), 5.15 (s, 1H, γ-CH), 7.19–7.28 (6H, m/p-H), 7.47 (d, JHH
= 6.4 Hz, 4H, C(3)-HPy), 7.52 (d, JHH = 6.4 Hz, 4H, C(2)-HPy). 13C
NMR (75 MHz, CD2Cl2, 25 °C): δ = 23.2 (CH(CH3 )2), 23.5 (β-
CCH3), 24.0 (CH(CH3 )2), 28.3 (CH(CH3)2), 29.7 (C(CH3)3), 35.6
3
3
1
2
(C(CH3)3), 94.5 (γ-C), 121.3 (q, JCF = 293.3 Hz, CF3), 123.6 (C(3)Py),
124.4 (m-C), 126.5 (p-C), 142.2 (o-C), 143.0 (i-C), 148.2 (C(2)Py),
167.4 (C(4)Py), 170.5 (β-CCH3). 19F NMR (282 MHz, CD2Cl2, 25 °C):
δ = –75.7.
M[Al{OC(CF3)3}4] (M
=
Li, Ag),[25] Ph3C[Al{OC(CF3)3}4],[31]
Li[B(C6F5)4],[32] and Ph3C[B(C6F5)4][32] were synthesized according
to literature methods. 1H, 13C and 19F NMR spectra were collected
with a Bruker Advance 300 spectrometer and are referenced to internal
CD2Cl2 (1H: δ = 5.36, 13C: δ = 53.4 ppm) and external CCl3F (19F:
δ = 0.31 ppm). Elemental analyses were performed at the Labor für
Elementaranalyse of the University of Duisburg-Essen. GPC data, the
average molar mass (Mn) and molar mass distribution (Mw/Mn) were
obtained on a gel permeation chromatography (GPC) in hexafluoroiso-
propanol (HFIP) with 0.05 m potassiumtrifluoracetate (KTFAc) at
23 °C (flow rate 1 mL· min–1). Three column (PSS-PFG 1000; 300;
100 Å, 7 μm) were used in combination with a refractive index and
diode array detector and calibrated with polymethylmethacrylate. The
polymer samples were dissolved in HFIP (3.4 mg· mL–1) at 23 °C.
[L2Zn(dmap)2][B(C6F5)4] (4): L2ZnMe (0.25 g, 0.5 mmol) was dis-
solved in CH2Cl2 (40 mL). Ph3C(B(C6F5)4) (0.46 g, 0.5 mmol) and
two equivalents of dmap (0.12 g, 1.0 mmol) were added and the re-
sulting mixture was stirred for 18 h at 60 °C. The solvent was removed
at reduced pressure and the resulting light green powder extracted with
n-pentane. 4 was obtained as colorless crystalline solid after storage
at –30 °C for 24 h (0.61 g, 86%). Elemental analysis calcd. (%) for
C67H61N6ZnBF20: C 57.2, H 4.4, N 6.0; found: C 61.3, H 4.5, N 4.9.
3
1H NMR (300 MHz, CD2Cl2, 25 °C): δ = 0.67 (d, JHH = 6.78 Hz, 12
1
3
2
H, CH(CH3 )2), 1.15 (d, JHH = 6.8 Hz, 12 H, CH(CH3 )2), 1.89 (s, 6
3
H, β-CCH3), 3.04 (s, 12 H, N(CH3)2), 3.04 (sept, JHH = 6.8 Hz, 4 H,
[L1Zn][Al{OC(CF3)3}4] (1): L1ZnCl (0.43 g, 1.0 mmol) and
Li(Al(OC(CF3)3)4 (0.97 g, 1.0 mmol) were dissolved in CH2Cl2
(50 mL) and heated to 60 °C for 1 h. The resulting suspension was hot
filtered and the solvent of the filtrate was removed at reduced pressure
to give 1 as a colorless solid (1.11 g, 81%). Elemental analysis calcd.
(%) for C39H29N2ZnAlO4F36: C 34.3, H 2.1, N 2.1; found: C 37.5, H
3
CH(CH3)2), 5.04 (s, 1 H, γ-CH), 6.40 (d, JHH = 6.80 Hz, 4H, C(3)-
Hdmap), 7.10 (d, 3JHH = 6.80 Hz, 4H, C(2)-Hdmap), 7.20–7.28 (6H, m/p-
H). 13C NMR (75 MHz, CD2Cl2, 25 °C): δ = 23.4 (CH(CH3 )2), 23.5
1
2
(β-CCH3), 24.0 (CH(CH3 )2), 28.3 (CH(CH3)2), 39.0 (N(CH3)2), 94.0
(γ-C), 107.2 (C(3)dmap), 124.1 (m-C), 129.0 (p-C), 134.6 (i-C6F5),
137.9 (m-C6F5), 142.4 (o-C), 143.7 (i-C), 146.5 (p-C6F5), 147.5
(C(2)dmap), 149.7 (o-C6F5), 155.4 (C(4)dmap), 169.7 (β-CCH3). 19F
NMR (282 MHz, CD2Cl2, 25 °C): δ = –167.6, –163.8, –133.1.
1
2.8, N 2.0. H NMR (300 MHz, CD2Cl2, 27 °C): δ = 1.54 (s, 3 H, β-
1
1
2
CCH3 ), 1.76 (s, 6 H, o-CH3 ), 1.86 (s, 6 H, o-CH3 ), 2.06 (s, 3 H, β-
2
1
2
CCH3 ), 2.46 (s, 3 H, p-CH3 ), 2.47 (s, 3 H, p-CH3 ), 3.98 (s, 1 H, γ-
CH), 6.82 (s, 2 H, m-H1), 6.91 (s, 2 H, m-H2). 13C NMR (75 MHz, [L2Zn(tBuPy)2][B(C6F5)4] (5): L2ZnMe (0.25 g, 0.5 mmol) was dis-
solved in CH2Cl2 (40 mL). Ph3C(B(C6F5)4) (0.46 g, 0.5 mmol) and
20.9 (β-CCH3 ), 22.9 (p-CH3 ), 24.9 (p-CH3 ), 95.1 (γ-C), 121.2 (q, tBuPy (0.14 g, 1.0 mmol) were added and the resulting mixture was
1
2
1
CD2Cl2, 25 °C): δ = 17.4 (o-CH3 ), 17.6 (o-CH3 ), 20.7 (β-CCH3 ),
2
1
2
JCF = 292.3 Hz, CF3), 127.6 (m-C1), 129.3 (m-C2), 130.3 (o-C1), 131.5
stirred for 18 h at room temperature. The solvent was removed at
(o-C2), 133.9 (p-C1), 137.3 (p-C2), 138.7 (i-C1), 143.0 (i-C2), 169.9 reduced pressure and the colorless solid extracted with n-pentane
(β-C1CH3), 183.7 (β-C2CH3). 19F NMR (282 MHz, CDCl3, 25 °C): (20 mL). 5 was obtained as colorless crystalline solid after storage
δ = –75.4.
at –30 °C for 24 h (0.67 g, 94%). Elemental analysis calcd. (%) for
4
www.zaac.wiley-vch.de
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 0000, 0–0

Job/Unit: Z13119
/KAP1
Date: 14-05-13 18:14:48
Pages: 8
Synthesis and Single Crystal X-ray Structures of Cationic Zinc β-Diketiminate Complexes
C71H67N4ZnBF20·CH2Cl2: C 57.3, H 4.5, N 3.7; found: C 56.9, H 4.6, Polymerization Studies: A mixture of freshly prepared 1 (0.0683 g,
3
N 3.5. 1H NMR (300 MHz, CD2Cl2, 25 °C): δ = 0.52 (d, JHH
=
0.05 mmol) and lactide (1.4413g, 10 mmol) was heated in the absence
of any solvent over the melting point of lactide to 160 °C for 8 min in
1
3
6.8 Hz, 12 H, CH(CH3 )2), 1.14 (d, JHH
=
6.8 Hz, 12 H,
2
CH(CH3 )2), 1.33 (s, 18 H, C(CH3)3), 1.95 (s, 6 H, β-CCH3), 2.90 a glass reactor. After cooling to room temperature the less remaining
3
(sept, JHH = 6.8 Hz, 4 H, CH(CH3)2), 5.15 (s, 1 H, γ-CH), 7.19–7.28
monomer lactide on the reactor wall was dissolved in CH2Cl2 and
separated. The crude polymer was slowly dissolved in THF (10 mL),
exposed to air and cold methanol (10 mL) was added. This solution
3
3
(6H, m/p-H), 7.47 (d, JHH = 6.4 Hz, 4H, C(3)-HPy), 7.52 (d, JHH
=
6.4 Hz, 4H, C(2)-HPy). 13C NMR (75 MHz, CD2Cl2, 25 °C): δ = 23.2
1
2
(CH(CH3 )2), 23.5 (β-CCH3), 24.0 (CH(CH3 )2), 28.3 (CH(CH3)2), was quenched in n-hexane (80 mL) and the white polymer precipi-
29.7 (C(CH3)3), 35.6 (C(CH3)3), 94.5 (γ-C), 123.6 (C(3)Py), 124.4 tation was isolated by filtration and dried in vacuo.
(m-C), 126.5 (p-C), 134.6 (i-C6F5), 137.9 (m-C6F5), 142.2 (o-C), 143.0
(i-C), 146.5 (p-C6F5), 148.2 (C(2)Py), 149.7 (o-C6F5), 167.4 (C(4)Py), Single Crystal X-ray Analyses: X-ray crystal structures were col-
170.5 (β-CCH3). 19F NMR (282 MHz, CD2Cl2, 25 °C): δ = –167.6,
–163.8, –133.1.
lected using a Bruker AXS D8 Kappa diffractometer with APEX2 de-
tector (Mo-Kα radiation, λ = 0.71073 Å) at T = 100(1) K (6 180(1) K).
The structures were solved by Direct Methods (SHELXS-97)[33] and
refined by full-matrix least-squares on F2. Semi-empirical absorption
corrections from equivalent reflections on basis of multi-scans (Bruker
AXS APEX2) were applied. All non-hydrogen atoms were refined
tBuPy-Zn(Cl)L1 (7): L1ZnCl (0.43 g, 1.0 mmol) and tBuPy (0.14 g,
1.0 mmol) were dissolved in THF (50 mL) and the resulting mixture
was stirred for 18 h at room temperature. The solution was concen-
trated to 5 mL and stored at –30 °C. Colorless crystals of 7 were anisotropically and hydrogen atoms by
formed within 24 h (0.52 g, 92%). Elemental analysis calcd. (%) for [C37H49N6Zn][AlC16F36O4], 1610.33, colorless crystal
a
riding model.[34] 2:
M
=
1
C32H42ClN3Zn: C 67.5, H 7.4, N 7.4; found: C 66.3, H 7.3, N 7.1. H
NMR (300 MHz, CD2Cl2, –80 °C): δ = 1.23 (s, 9 H, C(CH3)3), 1.41
(0.32 ϫ 0.26 ϫ 0.18 mm); monoclinic, space group P21/n; a =
13.7265(3), b = 23.7765(5), c = 20.4753(5) Å; β = 107.2980(10)°,
1
2
(s, 6 H, o-CH3 ), 1.54 (s, 6 H, o-CH3 ), 2.09 (s, 6 H, β-CCH3), 2.17 V = 6380.2(2) Å3; Z = 4; μ = 0.554 mm–1; ρber. = 1.676 g·cm–3; 89530
(s, 6 H, p-CH3), 4.76 (s, 1 H, γ-CH), 6.70 (s, 2 H, m-H1), 6.83 (s, 2
reflexes (2θmax = 57°), 16119 unique (Rint = 0.0326); Goof 1.020; 1018
parameters; largest max./ min. in the final difference Fourier synthesis
1.282 /–0.682 e·Å–3; max./ min. transmission 0.75/0.67; R1 = 0.044
H, m-H2), 7.39 (d, JHH = 5.8 Hz, 2 H, C(3)-HPy), 8.38 (d, JHH
=
3
3
5.8 Hz, 2 H, C(2)-HPy). 13C NMR (75 MHz, CD2Cl2, 25 °C): δ = 18.2
1
2
(o-CH3 ), 19.1 (o-CH3 ), 21.1 (β-CCH3), 23.4 (p-CH3), 30.5 [I Ͼ 2σ(I)], wR2 (all data) = 0.1237. Perfluoromethyl groups (C92 to
(C(CH3)3), 35.8 (C(CH3)3), 93.6 (γ-C), 122.6 (C(3)Py), 128.9 (m-C1), C94) are disordered over two sites with occupancies of 0.7 and 0.3
129.5 (m-C2), 131.6 (o-C1), 133.0 (o-C2), 134.0 (p-C), 143.0 (i-C),
149.3 (C(2)Py), 165.3 (C(4)Py), 168.3 (β-CCH3).
respectively. The highest peaks of the residual electron density indicate
further disorder of this group which could not be resolved. 3:
[C47H67N4Zn][AlC16F36O4]·0.1CH2Cl2, M = 1727.56, colorless crystal
(0.30 ϫ 0.25 ϫ 0.07 mm); orthorhombic, space group Pbca; a =
dmap-Zn(Me)L2 (8): L2ZnMe (0.50 g, 1.0 mmol) and dmap (0.12 g,
1.0 mmol) were dissolved in CH2Cl2 (5 mL) and the resulting mixture 23.2213(7), b = 20.5324(6), c = 31.0581(9) Å; V = 14808.2(8) Å3;
was stirred for 18 h at room temperature. The solution was concen-
trated to 2 mL and stored at –30 °C. Colorless crystals of 8 formed
Z = 8; μ = 0.488 mm–1; ρber. = 1.550 g·cm–3; 111316 reflexes (2θmax
= 50°, Ͼ43° approx. 65% unobserved, i.e. IϽ2σ(I)), unique (Rint
=
within 24 h (0.56 g, 90%). Elemental analysis calcd. (%) for 0.0651); Goof 1.052; 1001 parameters; largest max./ min. in the final
C37H54N4Zn·CH2Cl2: C 64.7, H 8.0, N 7.9; found: C 65.1, H 7.8, N
8.3. H NMR (300 MHz, CD2Cl2, 20 °C): δ = –1.24 (s, 3 H, ZnCH3),
difference Fourier synthesis 0.860 /–0.811 e·Å–3; max./ min. trans-
mission 0.75/0.60; R1 = 0.0508 [I Ͼ 2σ(I)], wR2 (all data) = 0.1407.
The perfluoromethyl groups connected to C300 are disordered over
at least two sites. Two of them could be identified but only refined
isotropically with various restraints. The position of the residual elec-
tron density peaks suggests further sites which could not be modeled.
1
3
1
3
1.12 (d, JHH = 6.9 Hz, 12 H, CH(CH3 )2), 1.26 (d, JHH = 6.9 Hz, 12
2
H, CH(CH3 )2), 1.79 (s,
6
H, β-CCH3), 3.01 (s,
6
H,
N(CH3)2), 3.07 (sept, 3JHH = 6.9 Hz, 4 H, CH(CH3)2), 5.07 (s, 1 H, γ-
CH), 6.53 (d, 3JHH = 6.50 Hz, 2 H, C(3)-Hdmap), 7.19 (s, 6 H, m/p-H),
8.20 (d, JHH = 6.50 Hz, 2 H, C(2)-Hdmap). 13C NMR (75 MHz, The structure contains a dichloromethane molecule whose site is
3
1
CD2Cl2, 25 °C):
δ
=
–18.5 (ZnCH3), 23.3 (CH(CH3 )2), 23.4 partially occupied (about 10%) which could also only be refined iso-
2
(β-CCH3), 24.0 (CH(CH3 )2), 27.9 (CH(CH3)2), 38.9 (N(CH3)2), 94.1 tropically. Due to the poor crystal quality only the connectivity
(γ-C), 106.4 (C(3)dmap), 123.2 (m-C), 124.7 (p-C), 141.9 (o-C), 145.3
(i-C), 149.5 (C(2)dmap), 154.5 (C(4)dmap), 166.8 (β-CCH3).
of the structure model should be regarded reliable. 4:
[C43H61N6Zn][C24BF20]·CH2Cl2, M = 1491.32, colorless crystal (0.33
ϫ 0.18 ϫ 0.13 mm); triclinic, space group P1; a = 12.7348(3), b =
¯
tBuPy-Zn(Me)L2 (9): L2ZnMe (0.50 g, 1.0 mmol) and tBuPy (0.14 g,
16.5546(4), c = 17.9992(4) Å; α = 65.7970(10)°, β = 75.9020(10)°, γ
1.0 mmol) were dissolved in CH2Cl2 (5 mL) and the resulting mixture = 84.9610(10)°, V = 3356.48(14) Å3; Z = 2; μ = 0.548 mm–1; ρber.
=
=
was stirred for 18 h at room temperature. The solution was concen-
1.476 g·cm–3; 66800 reflexes (2θmax = 56°), 15951 unique (Rint
trated to 2 mL and stored at –30 °C. Colorless crystals of 9 formed
0.0228); Goof 1.043; 883 parameters; largest max./ min. in the final
within 24 h (0.58 g, 91%). Elemental analysis calcd. (%) for difference Fourier synthesis 1.097 /–1.566 e·Å–3; max./ min. trans-
C39H57N3Zn·C2H4Cl4: C 61.3, H 7.7, N 5.2; found: C 60.7, H 8.3, N
4.5. H NMR (300 MHz, CD2Cl2, 20 °C): δ = –1.23 (s, 3 H, ZnCH3),
mission 0.75/0.68; R1 = 0.0483 [I Ͼ 2σ(I)], wR2 (all data) = 0.1376.
5: [C47H67N4Zn][C24BF20]·CH2Cl2, M = 1517.39, colorless crystal
(0.38 ϫ 0.33 ϫ 0.25 mm); monoclinic, space group P21/c; a =
13.2455(2), b = 25.5145(5), c = 22.0286(4) Å; β = 105.598 (1)°, V =
7170.4(2) Å3;Z=4;μ=0.513 mm–1;ρber.=1.406 g·cm–3;108166reflexes
(2θmax = 58°), 19351 unique (Rint = 0.0258); Goof 1.087; 901 param-
eters; largest max./ min. in the final difference Fourier synthesis
1
3
1
3
1.12 (d, JHH = 6.8 Hz, 12 H, CH(CH3 )2), 1.26 (d, JHH = 6.8 Hz, 12
2
H, CH(CH3 )2), 1.35 (s, 9 H, C(CH3)3), 1.79 (s, 6 H, β-CCH3), 3.06
(sept, JHH = 6.8 Hz, 4 H, CH(CH3)2), 5.08 (s, 1 H, γ-CH), 7.19 (s, 6
H, m/p-H), 7.32 (d, JHH = 6.40 Hz, 2 H, C(3)-HPy), 8.51 (s, JHH
6.40 Hz, 2 H, C(2)-HPy). 13C NMR (75 MHz, CD2Cl2, 25 °C): δ =
3
3
3
=
–17.6 (ZnCH3), 23.0 (CH(CH3 )2), 23.2 (β-CCH3), 23.9 (CH(CH3 )2), 1.905 e·Å–3 (1.05 Å from CL2)/–1.082 e·Å–3; max./ min. transmission
27.9 (CH(CH3)2), 30.2 (C(CH3)3), 34.5 (C(CH3)3), 94.8 (γ-C), 122.6 0.75/0.65; R1 = 0.0445 [I Ͼ 2σ(I)], wR2 (all data) = 0.1290. The refine-
1
2
(C(3)Py), 123.3 (m-C), 125.1 (p-C), 141.6 (o-C), 144.5
(i-C), 149.3 (C(2)Py), 165.3 (C(4)Py), 167.3 (β-CCH3).
ment was performed with solvent-free reflection data following
PLATON/squeeze run. A refinement of the untreated reflection data set
Z. Anorg. Allg. Chem. 0000, 0–0
© 0000 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
5

Job/Unit: Z13119
/KAP1
Date: 14-05-13 18:14:48
Pages: 8
C. Scheiper, S. Schulz, C. Wölper, D. Bläser, J. Roll
ARTICLE
produces several peaks with 2.5–7.5 e·Å–3 corresponding to a highly
disordered dichloromethane molecule. The peaks attributed to two
chlorine and one carbon atoms over two sites with occupancies factor
0.5 resulted in R1 = 0.0783. The SQUEEZE refinement revealed four
voids corresponding to 119 Å3 each. 6: C24H32N2Zn, M = 413.89, col-
orless crystal (0.38 ϫ 0.32 ϫ 0.23 mm); monoclinic, space group
P21/n; a = 8.8277(10), b = 32.260(4), c = 16.7973(18) Å; β =
[5] a) J. Börner, I. dos Santos Vieira, A. Pawlis, A. Döring, D. Kuck-
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104.955(4)°, V = 4621.6(9) Å3; Z = 8; μ = 1.072 mm–1; ρber.
1.190g·cm–3; 71621 reflexes (2θmax = 55°), 11467 unique (Rint
=
=
[6] a) K. Matsubara, C. Terata, H. Sekine, K. Yamatani, T. Harada,
K. Eda, M. Dan, Y. Koga, M. Yasuniwa, J. Polym. Sci. Part A:
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lics 2012, 31, 5252–5261.
0.0313); Goof 1.099; 487 parameters; largest max./ min. in the final
difference Fourier synthesis 0.381 /–0.541 e·Å–3; max./ min. trans-
mission 0.75/0.52; R1 = 0.0400 [I Ͼ 2σ(I)], wR2 (all data) = 0.0969.
7: C32H42ClN3Zn, M = 569.51, colorless crystal (0.38 ϫ 0.12 ϫ
¯
0.08 mm); triclinic, space group P1; a = 7.9599(2), b = 12.2162(3),
c = 16.4476(4) Å; α = 109.169 (1), β = 93.783 (1), γ = 92.229 (1),
V = 1504.28(6) Å3; Z = 2; μ = 0.929 mm–1; ρber. = 1.257 g·cm–3; 43585
reflexes (2θmax = 58°), 7808 unique (Rint = 0.0284); Goof 1.036; 334
parameters; largest max./ min. in the final difference Fourier synthesis
0.430 /–0.316 e·Å–3; max./ min. transmission 0.75/0.65; R1 = 0.0282
[I Ͼ 2σ(I)], wR2 (all data) = 0.0727. 8: C37H54N4Zn·3(CH2Cl2), M =,
¯
colorless crystal (0.37 ϫ 0.12 ϫ 0.10 mm); triclinic, space group P1;
a = 9.2948(3), b = 12.2388(4), c = 20.7088(7) Å; α = 104.079(2)°, β
= 102.4820(10)°, γ = 95.013(2)°, V = 2206.50(13) Å3; Z = 2; μ =
0.952 mm–1; ρber. = 1.317g·cm–3; 42837 reflexes (2θmax = 58°), 10961
unique (Rint = 0.0332); Goof 1.050; 460 parameters; largest max./ min.
in the final difference Fourier synthesis 1.675 /–1.260 e·Å–3; max./
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126.
0.1494. 9: C39H57N3Zn·CH2Cl2, M = 718.17, colorless crystal (0.37 ϫ
0.32 ϫ 0.23 mm); monoclinic, space group P21/n; a = 16.7558(10), b
= 13.5456(8), c = 17.8375(10) Å; β = 101.587(2)°, V = 3966.0(4) Å3;
[10] H. R. Kricheldorf, M. Berl, N. Scharnagl, Marcromol. 1988, 21,
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Z = 4; μ = 0.784 mm–1; ρber. = 1.203 g·cm–3; 50562 reflexes (2θmax
=
60°), 11425 unique (Rint = 0.0234); Goof 1.034; 415 parameters;
largest max./ min. in the final difference Fourier synthesis
0.885 /–0.736 e·Å–3; max./ min. transmission 0.75/0.67; R1 = 0.0326
[I Ͼ 2σ(I)], wR2 (all data) = 0.0928.
Supporting Information (see footnote on the first page of this article):
X-ray crystallographic data of 2–9 are given in the electronic sup-
plement. The crystallographic data (without structure factors) were
also deposited as “supplementary publication no. CCDC-91429 (2),
-914735 (3), -914731 (4), -914734 (5), -914736 (6) -914730 (7),
-914733 (8), -914732 (9) at the Cambridge Crystallographic Data Cen-
tre. These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre: CCDC, 12 Union Road, Cambridge,
CB21EZ (Fax: (+44)1223/336033; E-mail: deposit@ccdc.cam-ak.uk).
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Acknowledgments
S. Schulz likes to thank the University of Duisburg-Essen for financial
support.
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Received: February 27, 2013
Published Online: ᭿
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C. Scheiper, S. Schulz, C. Wölper, D. Bläser, J. Roll
ARTICLE
C. Scheiper, S. Schulz,* C. Wölper, D. Bläser, J. Roll .... 1–8
Synthesis and Single Crystal X-ray Structures of Cationic Zinc
β-Diketiminate Complexes
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