Syntheses, characterizations, and crystal structures of β-diketiminato compounds of pentafluorophenyl group 12 derivatives, HC{[C(Me)N(C6H3-2,6-i-Pr2)]2}MC 6F5 (M = Zn, Cd)

Article abstract of DOI:10.1002/zaac.200300075

The reactions of H₂C[C(Me)N(C₆H ₃-2,6-i-Pr₂)]₂ ((DPP)₂NacNacH) and Zn(C₆F₅)₂·2 EtCN or Cd(C ₆F₅)₂·2 MeCN in a molar ratio of approximately 1:1 selectively gave the derivatives (DPP) ₂NacNacMC₆F₅ (M = Zn, Cd) in excellent yields. No reaction was observed between (DPP)₂NacNacH and Hg(C ₆F₅)₂ under similar conditions. Reactions with Hg(C₆F₅)OCOMe yielded the products of dismutation, Hg(C₆F₅)₂ and Hg(OCOMe)₂. (DPP) ₂NacNacZnC₆F₅ crystallises as a 1:1 adduct with THF with two independent molecules per unit cell (triclinic, P1 (no. 2)). The zinc atom is tetrahedrally surrounded by the chelating ligand, the pentafluorophenyl group and one THF molecule. A similar situation is found in the 1:1 adduct of (DPP)₂NacNacCdC₆F₅ and DMF (monoclinic, P2₁/n (no. 14)), while in the donor-free compound (CDCl₃ and H₂O co-crystallize) the cadmium atom is nearly ideally trigonal planar co-ordinated (orthorhombic, Pbnm (no. 62)).

Full text of DOI:10.1002/zaac.200300075

Syntheses, Characterizations, and Crystal Structures of β-Diketiminato
Compounds of Pentafluorophenyl Group 12 Derivatives,
HC{[C(Me)N(C6H3-2,6-i-Pr2)]2}MC6F5 (M ؍ Zn, Cd)
Said Aboulkacem, Wieland Tyrra*, and Ingo Pantenburg
Cologne/Germany, Institute of Inorganic Chemistry of the University
Received March 17th, 2003.
Abstract. The reactions of H2C[C(Me)N(C6H3-2,6-i-Pr2)]2
((DPP)2NacNacH) and Zn(C6F5)2 · 2 EtCN or Cd(C6F5)2 · 2 MeCN
in a molar ratio of approximately 1:1 selectively gave the derivatives
(DPP)2NacNacMC6F5 (M ϭ Zn, Cd) in excellent yields. No reac-
tion was observed between (DPP)2NacNacH and Hg(C6F5)2 under
similar conditions. Reactions with Hg(C6F5)OCOMe yielded the
products of dismutation, Hg(C6F5)2 and Hg(OCOMe)2.
zinc atom is tetrahedrally surrounded by the chelating ligand, the
pentafluorophenyl group and one THF molecule. A similar situation
is found in the 1:1 adduct of (DPP)2NacNacCdC6F5 and DMF
(monoclinic, P21/n (no. 14)), while in the donor-free compound
(CDCl3 and H2O co-crystallize) the cadmium atom is nearly ideally
trigonal planar co-ordinated (orthorhombic, Pbnm (no. 62)).
(DPP)2NacNacZnC6F5 crystallises as a 1:1 adduct with THF with
¯
two independent molecules per unit cell (triclinic, P1 (no. 2)). The
Keywords: Cadmium; N-Ligands; Pentafluorophenyl; Zinc
Synthesen, Charakterisierungen und Kristallstrukturen von β-Diketiminato-
Verbindungen der Pentafluorphenylverbindungen der Elemente der Gruppe 12,
HC{[C(Me)N(C6H3-2,6-i-Pr2)]2}MC6F5 (M ؍ Zn, Cd)
Inhaltsübersicht. Die Reaktionen von H2C[C(Me)N(C6H3-2,6-i-Pr2)]2
((DPP)2NacNacH) und Zn(C6F5)2 · 2 EtCN bzw. Cd(C6F5)2
2)). Das Zinkatom in dieser Verbindung ist tetraedrisch durch den
Chelatliganden, die Pentafluorphenylgruppe und ein THF-Molekül
koordiniert. Eine vergleichbare Koordination wird in dem Addukt
aus (DPP)2NacNacCdC6F5 und DMF (monoklin, P21/n (Nr. 14))
gefunden, wohingegen in der Donator-freien Verbindung (CDCl3
und H2O kokristallisieren) das Cadmiumatom nahezu ideal trigo-
nal planar koordiniert ist (orthorhombisch, Pbnm (Nr. 62)).
·
2 MeCN in einem molaren Verhältnis von ungefähr 1:1 führen se-
lektiv zu den Verbindungen (DPP)2NacNacMC6F5 (M ϭ Zn, Cd)
in sehr guten Ausbeuten. Zwischen (DPP)2NacNacH und
Hg(C6F5)2 werden unter ähnlichen Bedingungen keine Reaktionen
beobachtet. Umsetzungen mit Hg(C6F5)OCOMe führen zu Dismu-
tierungen in Hg(C6F5)2 und Hg(OCOMe)2.
(DPP)2NacNacZnC6F5 kristallisiert als 1:1 Addukt mit THF mit
¯
zwei unabhängigen Molekülen je Elementarzelle (triklin, P1 (Nr.
Introduction
Results and Discussion
Two more or less general pathways for the synthesis of
Ar2NacNac element compounds have been established in
the literature: (i) halide substitutions using compounds of
general formula Ar2NacNacM (M ϭ alkali metal) and (ii)
acidolysis of organoelement compounds [8].
Zn(C6F5)2 [1] and especially Cd(C6F5)2 [2] compounds have
turned out to be good nucleophilic pentafluorophenyl
group transfer reagents in very different types of reactions.
Especially reactions of Cd(C6F5)2 and H-acidic reagents,
HX, were investigated primarily yielding C6F5H and deriva-
tives with a Cd(C6F5)X moiety [3Ϫ6]. With this knowledge,
we investigated the reaction behaviour of M(C6F5)2
(M ϭ Zn, Cd, Hg) and the widely used β-diketimine,
(DPP)2NacNacH [7].
We decided to use the second synthetic pathway to inves-
tigate the behaviour of bis(pentafluorophenyl)group 12 de-
rivatives, M(C6F5)2 (M ϭ Zn, Cd, Hg) towards the well-
established derivative, (DPP)2NacNacH (Scheme 1).
In the case of the zinc and cadmium compounds, the re-
actions proceeded selectively to yield the expected deriva-
tives (DPP)2NacNacMC6F5 (M ϭ Zn, Cd) in very good
yields. The reactions were terminated when the integrative
ratio of (DPP)2NacNacMC6F5 (M ϭ Zn, Cd) and C6F5H
was 1:1 and no signals of the starting materials were de-
tected in the 19F NMR spectra. No reaction was observed
treating Hg(C6F5)2 and (DPP)2NacNacH in different sol-
vents even at elevated temperatures (EtCN, 50 °C).
* Dr. Wieland Tyrra
Institut für Anorganische Chemie
Universität zu Köln
Greinstr. 6
D-50939 Köln
E-mail: tyrra@uni-koeln.de
Z. Anorg. Allg. Chem. 2003, 629, 1569Ϫ1574
DOI: 10.1002/zaac.200300075
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S. Aboulkacem, W. Tyrra, I. Pantenburg
the reaction as shown in Eq. (1), while (DPP)2NacNacH
was recovered unchanged.
(DPP)2NacNacMC6F5 (M ϭ Zn, Cd) were isolated as
colourless moisture sensitive compounds and characterized
by EI mass spectrometry, 19F, 13C, 1H and 113Cd NMR
spectroscopy as well as elemental analyses.
1
13C and H NMR values are consistent with those re-
Scheme 1 Reactions of M(C6F5)2 and (DPP)2NacNacH
ported for a variety of related compounds ((DPP)2Nac-
NacM) [e.g. 9Ϫ13], while 19F and 13C NMR data of the
C6F5 group were found in the expected regions [e.g. 1, 2, 4,
5, 14]. The 113Cd NMR signal of (DPP)2NacNacCdC6F5
was shifted significantly from that of the starting material
(Ϫ237 ppm vs. Ϫ466 ppm [15]).
Again, no 19F NMR spectroscopic evidence for the for-
mation of (DPP)2NacNacHgC6F5 was found in 1:2 reac-
tions of Hg(C6F5)OCOMe (19F-NMR (C6D6): δ ϭ Ϫ117.9,
5
3JHg,F ϭ 565 Hz, F-2,6; Ϫ152.0, JHg,F ϭ 28 Hz, F-4;
4
Ϫ160.0, JHg,F ϭ 185 Hz, F-3,5) and (DPP)2NacNacH.
EI mass spectra (20 eV) exhibit the molecular peaks
Hg(C6F5)2 (19F-NMR (C6D6): δ ϭ Ϫ119.7, JHg,F
ϭ
[(DPP)2NacNacZnC6F5]ϩ (m/z
ϭ
650 [M]ϩ
ϭ
3
4
434 Hz, F-2,6; Ϫ152.1, F-4; Ϫ159.8, JHg,F ϭ 113 Hz,
[C35H41F5N265Zn]ϩ; 100 %) and [(DPP)2NacNacCdC6F5]ϩ
F-3,5)) and Hg(OCOMe)2 were identified as products of
(m/z ϭ 698 [M]ϩ ϭ [C35H41F5N2112Cd]ϩ; 40 %) as well as
Table 1 Crystal Data and Structure Refinement Parameters for (DPP)2NacNacZnC6F5 · THF (I), (DPP)2NacNacCdC6F5 · DMF (II) and
(DPP)2NacNacCdC6F5 (III).
I
II
III
empirical formula
crystal system
space group
a / pm
b / pm
c / pm
C78H98F10N4O2Zn2
triclinic
P1 (no. 2)
C38H48F5N3OCd
monoclinic
P21/n (no. 14)
986.2(1)
1665.1(1)
2324.5(2)
C36H41F5N2OCl3Cd
orthorhombic
Pbnm (no. 62)
1088.8(1)
1743.8(2)
1983.3(2)
¯
1272.7(1)
1597.5(2)
1811.9(2)
84.54(1)
89.36(1)
88.63(1)
3.666(1)
2
α / deg
β / deg
95.57(1)
γ / deg
volume / nm3
Z
3.726(1)
4
3.766(1)
4
formula mass
ρcalc / g cmϪ3
µ / mmϪ1
absorption correction
1444.34
1.308
0.728
770.19
1.373
0.644
831.46
1.467
0.848
numerical
numerical
numerical
transmission max / min
θ range / deg
total data collected
index range
0.7334 / 0.9295
1.60Ϫ29.64
70290
Ϫ17 Յ h Յ 17
Ϫ22 Յ k Յ 22
Ϫ25 Յ l Յ 24
20429
0.8259 / 0.9500
2.51Ϫ27.33
57492
Ϫ12 Յ h Յ 12
Ϫ21 Յ k Յ 21
Ϫ30 Յ l Յ 29
8320
5670
0.7439 / 0.9253
2.05Ϫ27.38
40069
Ϫ14 Յ h Յ 13
Ϫ22 Յ k Յ 22
Ϫ25 Յ l Յ 25
4325
unique data
observed data
diffractometer
radiation
temperature / K
Rmerg
9208
2389
STOE Image Plate Diffraction System
Mo-Kα (Graphit-Monochromator, λ ϭ 71.073 pm)
170(2)
0.0751
170(2)
0.0524
170(2)
0.1168
R indexes [I>2σI]
R1 ϭ 0.0415
wR2 ϭ 0.0798
R1 ϭ 0.1159
wR2 ϭ 0.0951
0.954
R1 ϭ 0.0347
wR2 ϭ 0.0786
R1 ϭ 0.0572
wR2 ϭ 0.0849
1.049
R1 ϭ 0.0599
wR2 ϭ 0.1423
R1 ϭ 0.1087
wR2 ϭ 0.1613
1.069
R indexes (all data)
goodness of fit (Sobs
)
goodness of fit (Sall
no. of variables
F(000)
)
0.744
870
1520
Ϫ0.996 / 0.520
0.917
626
1592
Ϫ0.676 / 0.636
0.877
313
1692
Ϫ1.001 / 1.213
largest difference map
hole / peak [e 10Ϫ6pmϪ3
]
2
2 1/2
R1 ϭ Σ ʈFoΗϪΗFcʈ / Σ ΗFoΗ, wR2 ϭ [ Σ w ( ΗFoΗ2ϪΗFcΗ2
)
/ Σ w ( ΗFoΗ2
)
]
,
S2 ϭ [ Σ w ( ΗFoΗ2ϪΗFcΗ2
)
/ (n-p) ]1/2, with w ϭ 1 / [σ2 (Fo)2 ϩ (0,0427·P)2] for I,
2
w ϭ 1 / [σ2 (Fo)2 ϩ (0,1000·P)2] for III and w ϭ 1 / [σ2 (Fo)2 ϩ (0,0529·P)2] for II were P ϭ (Fo ϩ 2Fc2) / 3. Fc* ϭ k Fc [1ϩ0,001 · ΗFcΗ2 λ3 / sin(2θ)]Ϫ1/4
.
2
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β-Diketiminato Compounds of Pentafluorophenyl Group 12 Derivatives
Table 2 Selected Internuclear Distances / pm and Angles / deg for
I, II and III
(DPP)2NacNacZnC6F5 · THF (I)
Zn 1 Ϫ N 1
Zn 1 Ϫ N 2
Zn 1 Ϫ C 4
Zn 1 Ϫ O 1
N 1 Ϫ C 1
C 1 Ϫ C 2
C 2 Ϫ C 3
C 3 Ϫ N 2
199.3(2)
197.9(2)
201.1(2)
221.0(2)
132.9(3)
140.1(4)
140.3(3)
133.9(3)
N 1 Ϫ Zn 1 Ϫ N 2
N 1 Ϫ Zn 1 Ϫ C 4
N 2 Ϫ Zn 1 Ϫ C 4
C 4 Ϫ Zn 1 Ϫ O 1
O1 Ϫ Zn 1 Ϫ N 1
O 1 Ϫ Zn 1 Ϫ N 2
Zn 1 Ϫ N 1 Ϫ C 1
N 1 Ϫ C 1 Ϫ C 2
C 1 Ϫ C 2 Ϫ C 3
C 2 Ϫ C 3 Ϫ N 2
N 3 Ϫ Zn 2 Ϫ N 4
N 3 Ϫ Zn 2 Ϫ C 8
N 4 Ϫ Zn 2 Ϫ C 8
C 8 Ϫ Zn 2 Ϫ O 2
O 2 Ϫ Zn 2 Ϫ N 3
O 2 Ϫ Zn 2 Ϫ N 4
Zn 2 Ϫ N 3 Ϫ C 5
N 3 Ϫ C 5 Ϫ C 6
C 5 Ϫ C 6 Ϫ C 7
C 6 Ϫ C 7 Ϫ N 4
98.9(1)
128.3(1)
126.5(1)
100.1(1)
96.5(1)
97.4(1)
118.7(2)
124.6(2)
130.4(2)
124.1(2)
98.6(1)
127.3(1)
126.8(1)
100.4(1)
96.8(1)
Zn 2 Ϫ N 3
Zn 2 Ϫ N 4
Zn 2 Ϫ C 8
Zn 2 Ϫ O 2
N 3 Ϫ C 5
C 5 Ϫ C 6
C 6 Ϫ C 7
C 7 Ϫ N 4
199.3(2)
197.9(2)
201.3(2)
220.3(2)
133.7(3)
140.0(4)
140.3(3)
133.1(3)
98.7(1)
118.5(2)
124.4(2)
130.6(2)
124.2(2)
Fig. 1 Coordination around Zn 1 (compound I) with the atomic
labeling scheme (H-atoms are omitted for clarity, the coordination
around Zn 2 is almost the same (confer Table 2)). Thermal ellips-
oids are shown at 50% probability.
(DPP)2NacNacCdC6F5 · DMF (II)
Cd Ϫ N 1
Cd Ϫ N 2
Cd Ϫ O 1
Cd Ϫ C 4
N 1 Ϫ C 1
C 1 Ϫ C 2
C 2 Ϫ C 3
C 3 Ϫ N 2
219.2(2)
221.3(2)
235.5(2)
216.9(3)
132.1(3)
141.2(4)
141.3(4)
133.1(4)
N 1 Ϫ Cd Ϫ N 2
N 1 Ϫ Cd Ϫ O 1
N 1 Ϫ Cd Ϫ C 4
N 2 Ϫ Cd Ϫ O 1
N 2 Ϫ Cd Ϫ C 4
O 1 Ϫ Cd Ϫ C 4
Cd Ϫ N 1 Ϫ C 1
Cd Ϫ N 2 Ϫ C 3
N 1 Ϫ C 1 Ϫ C 2
C 1 Ϫ C 2 Ϫ C 3
C 2 Ϫ C 3 Ϫ N 2
90.0(1)
99.1(1)
130.3(1)
95.4(1)
133.8(1)
98.5(1)
122.7(2)
121.3(2)
125.1(2)
131.3(2)
125.7(2)
of the THF molecule acting as ligand atoms. A six-mem-
bered heterocycle is build up exhibiting a boat confor-
mation with the zinc atom and the opposite carbon atom
forming prow and stern. Deviations from least square
planes (N1-C1-C3-N2 and N3-C5-C6-N4) of the two inde-
pendent units were calculated [16] to be 37.1(1) pm for Zn
1 and 35.7(1) pm for Zn2 and 10.7(3) pm for C1 and
11.6(3) pm for C5, respectively. It has to be noted that the
ring containing the atom Zn2 is significantly twisted com-
pared with that of the other independent molecule contain-
ing the atom Zn1.
(DPP)2NacNacCdC6F5 · (H2O · CDCl3) (III)
Cd Ϫ N 3
Cd Ϫ C 8
N 3 Ϫ C 6
C 6 Ϫ C 7
216.8(4)
214.5(7)
131.8(6)
141.4(6)
N 3 Ϫ Cd Ϫ N 3Ј
N 3 Ϫ Cd Ϫ C 8
N 3 Ϫ C 6 Ϫ C 7
C 6 Ϫ C 7 Ϫ C 6Ј
90.5(2)
134.8(1)
125.1(5)
131.6(7)
The zinc-nitrogen bond length of 197.9(2) and
199.3(2) pm (identical for both ZnN2C3 cores) and the an-
gle N-Zn-N 98.6(1) (98.9(1))° are in the typical range of
related zinc derivatives such as (DPP)2NacNacZnEt [10],
(DPP)2NacNacZnCϵCPh [11] and (DPP)2NacNacZnR
(R ϭ Me, Ph, t-Bu) [9]. In comparison with structural data
reported for ZnC6F5 compounds, the Zn-C bond lengths
found for I (201.1(2) (201.3(2)) pm) are in good agreement
with those reported for Zn(C6F5)2 · 2 THF [3] but as ex-
pected significantly deviate from those found for the donor-
free molecule Zn(C6F5)2 (192.6(4), 193.0(4) pm) [17]. By
contrast to the structure of Zn(C6F5)2 · 2 THF [3], the
Zn-O contact in I is significantly elongated (220.3(2)
(221.0(3)) pm vs. 209.3(2) / 211.3(3) pm [3]).
fragments known from the fragmentation of further zinc
and cadmium derivatives either containing the (DPP)2Nac-
Nac or the C6F5 moiety.
Results of Crystal Structure Analyses
Details of single crystal structure analyses of (DPP)2Nac-
NacZnC6F5 · THF (I), (DPP)2NacNacCdC6F5 · DMF (II)
and (DPP)2NacNacCdC6F5 (III) are summarized in Tables
1 and 2.
Molecular structure of (DPP)2NacNacZnC6F5 ·
THF (I)
Molecular structure of (DPP)2NacNacCdC6F5 ·
DMF (II)
¯
I (Figure 1) crystallises in the triclinic space group P1 (no.
II (Figure 2) crystallizes in the monoclinic space group
P21/n (no. 14) with four molecules per unit cell. Again as
outlined for the zinc derivative, the coordination around the
metal atom is strongly distorted tetrahedral with two nitro-
gen bonds, one carbon bond and one oxygen bond to the
2) with two independent molecules per unit cell. The coor-
dination around the zinc atom is distorted tetrahedral with
two nitrogen atoms of the chelating (DPP)2NacNac, the
ipso-carbon atom of the C6F5 group and the oxygen atom
Z. Anorg. Allg. Chem. 2003, 629, 1569Ϫ1574
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S. Aboulkacem, W. Tyrra, I. Pantenburg
Fig. 2 Asymmetric unit of II. Coordination around Cd with the
atomic labeling scheme (H-atoms are omitted for clarity). Thermal
ellipsoids are shown at 50% probability.
DMF molecule. A six-membered cadmium containing ring
is build up exhibiting a boat conformation with the cad-
mium atom and the opposite carbon atom forming prow
and stern. Deviations of the cadmium atom and the op-
posite carbon atom from a least square plane [16] are of
comparable size as determined for the zinc compound I,
35.4(1) pm for cadmium and 12.7(3) pm for carbon.
Fig. 3 Asymmetric unit of III. Coordination around Cd with the
atomic labeling scheme (H-atoms are omitted for clarity). Thermal
ellipsoids are shown at 50% probability.
While numerous zinc compounds with NacNac ligands
have been crystallographically characterised [8], only one
NacNacCd derivative has been mentioned so far [13].
Nevertheless, structural differences between (DPP)2Nac-
NacCdC6F5 · DMF and (DPP)2NacNacCd(µ-I)2Li(OEt2)2
[13] concerning the CdN2C3 core are of minor significance.
Cd-N bond lengths are found to be 219.2(2) and
221.3(2) pm, respectively. The Cd-C bond to the penta-
fluorophenyl group (216.9(3) pm) is elongated by up to
6 pm compared with donor-free Cd(C6F5)2 (210.9(3) /
211.1(3) pm) [14] but absolutely in the range of Cd-C bond
lengths of further structurally characterised Cd(C6F5) com-
pounds varying from 216 to 221 pm [3Ϫ6].
(0.0(1) pm for Cd; 0.4(8) pm for C) revealing nearly ideal
planarity for the CdN2C3 core.
The Cd-C bond length is estimated to be 214.5(7) pm,
shorter than those found for the DMF-adduct II
(216.9(3) pm) and also the Cd-N bonds are significantly
shorter (216.8(4) vs. 220.3 pm (mean value)).
Experimental Part
General methods
Schlenk techniques were used throughout all manipulations. NMR
spectra were recorded on a Bruker AC 200 spectrometer (1H, 19F,
13C) and a Bruker AMX 300 spectrometer (13C{19F}, 113Cd). Ex-
ternal standards were used in all cases (1H, 13C: Me4Si; 19F: CCl3F;
113Cd: Me2Cd). Acetone-D6 was used as an external lock (5 mm
tube) in reaction control measurements while an original sample of
the reaction mixture was measured in a 4 mm insert. Mass spectra
were run on a Finnigan MAT 95 spectrometer using the electron
impact method (20 eV). Intensities are referenced to the most inten-
sive peak of a group. Visible decomposition points were determined
using the apparatus HWS Mainz 2000. CHN analyses were carried
out with a HEKAtech Euro EA 3000 apparatus.
Molecular structure of (DPP)2NacNacCdC6F5 (III)
(CDCl3 and H2O co-crystallize)
III (Figure 3) crystallises in the orthorhombic space group
Pbnm (no. 62) with 4 molecules per unit cell. Each molecule
is characterised by a mirror plane through C3, Cd, C4 as
well as the co-crystallising solvent molecules. The CdN2C3
core as well as the C6F5 group are co-planar additionally
supporting the high symmetry of this molecule. By contrast
to the structures of I and II described above, no significant
deviation of the positions of the cadmium atom and the
opposite carbon atom from the idealised plane are observed
The following compounds were prepared according to literature
procedures: Zn(C6F5)2 · 2 EtCN [18], Cd(C6F5)2 · 2 MeCN [2],
Hg(C6F5)2 [18] and (DPP)2NacNacH [19]. Hg(C6F5)OCOMe was
received from Dipl.-Chem. F. Schulz as a gift.
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β-Diketiminato Compounds of Pentafluorophenyl Group 12 Derivatives
168 ([C6F5H]ϩ, 5 %). Zinc containing fragments are referenced to the iso-
tope 65Zn.
Single crystal structure determination
A suitable single crystal of each compound was carefully selected
under a polarizing microscope and mounted in glass capillaries.
Single-crystal X-ray data were collected on a STOE image-plate
diffractometer (IPDS II) by using graphite-monochromatised
Synthesis of (DPP)2NacNacCdC6F5
A solution of 0.21 g (0.50 mmol) (DPP)2NacNacH in 5 ml toluene
was slowly dropped to a well stirred solution of 0.30 g (0.56 mmol)
Cd(C6F5)2 · 2 MeCN in 5 ml toluene at ambient temperature. After
stirring for approximately 3 hours, the mixture became turbid and
an ochre solid began to precipitate. The reaction mixture was
stirred overnight and finally all volatile compounds were removed
in vacuo. After washing with several small portions of n-pentane
and drying in vacuo, a pale ochre solid was obtained which was
identified as (DPP)2NacNacCdC6F5. 0.30 g (86 %) (DPP)2Nac-
NacCdC6F5 were collected. No visible melting or decomposition
point was observed on heating up to 400 °C in a melting point ap-
paratus.
˚
MoKα radiation (λ ϭ 0.71073 A) operating at 50 kV and 40 mA.
Intensity data for I and II were collected at 170 K in 180 frames
with ω-scans (0 Յ ω Յ 180°; ψ ϭ 0°, 0 Յ ω Յ 180°; ψ ϭ 90°,
∆ω ϭ 2°, exposure time of 2 min for I and 4 min for II) in the 2 θ
range of 2.3 to 59.5° for I and 1.9 to 54.8° for II. The intensity
data for III were collected at 170 K in 130 frames with ω-scans (0
Յ ω Յ 180°; ψ ϭ 0°, 0 Յ ω Յ 80°; ψ ϭ 90°, ∆ω ϭ 2°, exposure
time of 5 min) in the 2 θ range of 1.9 to 54.8°. The structures were
solved by direct methods SHELXS-97 [20] and difference Fourier
syntheses. Full matrix least squares structure refinements against
͉F2͉ were carried out using SHELXL-93 [21]. Compound I crys-
¯
tallized in the triclinic space group P1 with two independent mol-
Analytical Data C35H41F5N2Cd (697.11): C 58.94 (calc. 60.30), H
6.02 (5.92), N 4.12 (4.01) %.
ecules per unit cell. The hydrogen atoms in I were placed geometri-
cally and held in the riding mode. The H atom positions for II and
III were taken from the difference Fourier card at the end of the
refinement (except the solvent molecules CDCl3 and H2O in III).
Numerical absorption corrections were applied after optimisation
of the crystal shapes (X-RED [22] and X-SHAPE [23]). The last
cycles of refinement included atomic positions for all atoms, aniso-
tropic thermal parameters for all non-hydrogen atoms and isotropic
thermal parameters for all hydrogen atoms. Details of the refine-
ments are given in Table 1 [24]. Selected internuclear distances and
angles are presented in Table 2. Deviations from least square planes
to confirm the conformations of the MN2C3 cores in all derivatives
were carried out with the program PARST97 [16].
Single crystals of (DPP)2NacNacCdC6F5 (CDCl3 and H2O co-crys-
tallise) were grown on storing unsealed NMR samples of
(DPP)2NacNacCdC6F5 in CDCl3 for several days at Ϫ30 °C. Crys-
tals of the complex with DMF were obtained on cooling a highly
diluted DMF / n-pentane solution of the donor-free derivative for
one week to Ϫ30 °C.
NMR data (CDCl3): 19F: δ ϭ Ϫ111.41 (m, 2F, F-2,6, JCd,F ϭ 116 Hz),
3
5
4
Ϫ154.78 (t, 1F, F-4, JCd,F ϭ 72 Hz), Ϫ160.81 (m, 2F, F-3,5, JCd,F
ϭ
100 Hz) ppm. 1H: δ ϭ 7.13 (m, 6H, ArH),4.93 (s, 1H, Hβ), 3.16 (sept., 4H,
CH(CH3)2), 1.79 (s, 6H, α-CH3), 1.24 (d, 12H, CH(CH3)2), 1.07 (d, 12H,
CH(CH3)2). 13C{1H}: δ ϭ 169.3 (Cα), 147.8 (C-2,6 JC,F ഠ 228 Hz), 145.2
1
1
1
(Cipso), 140.8 (Co), 140.3 (C-4, JC,F ഠ 249 Hz), 136.4 (C-3,5, JC,F
ഠ
251 Hz), 125.5 (Cp), 123.5 (Cm), 116.5 (C-1,2JC,F ഠ 61 Hz), 94.2 (Cβ), 28.0
(CHMe2), 24.3 (CHMe2), 24.1 (CHMe2), 23.4 (α-CH3).
EI-MS (20 eV): m/z
ϭ
698 (Mϩ, 40 %), 683 ([M-Me]ϩ, 8 %), 418
([(DPP)2NacNacH]ϩ 32 %), 403 ([(DPP)2NacNac-Me]ϩ, 34 %), 375
([(DPP)2NacNacHϪCH(Me)2]ϩ, 8 %), 202 ([(DPP)NacNac-2 Me]ϩ 100 %),
168 ([C6F5H]ϩ, 5 %). Cadmium containing fragments are referenced to the
isotope 112Cd.
Synthesis of (DPP)2NacNacZnC6F5
A solution of 0.46 g (1.10 mmol) (DPP)2NacNacH in 5 ml CH2Cl2
was slowly dropped to a well stirred solution of 0.58 g (1.13 mmol)
Zn(C6F5)2 · 2 EtCN in 5 ml CH2Cl2 at 0 °C. The reaction mixture
was warmed to room temperature and stirred for 3 days. All volatile
components were distilled off in vacuo. The remaining colourless
solid was washed with four portions (5 ml each) of cold n-pentane
(Ϫ30 °C) to remove traces of the starting materials. The washing
liquor was disposed. The remaining residue was dissolved in 20 ml
n-pentane at room temperature, the solution directly concentrated
in vacuo to one third and stored for several days at Ϫ30 °C. After
approximately 3 days, a micro-crystalline solid began to precipitate
which was collected after disposal of n-pentane. Careful drying in
vacuo gave 0.65 g (91 %) (DPP)2NacNacZnC6F5 with a visible
melting point of 96 Ϫ 97 °C.
Acknowledgements. Generous support by Professor Dr. Dieter Nau-
mann is gratefully acknowledged. We are indebted to Dipl.-Chem.
Frank Schulz for a sample of Hg(C6F5)OCOMe.
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Analytical Data C35H41F5N2Zn (650.09): C 63.14 (calcd. 64.66),
H 6.38 (6.35), N 4.52 (4.30) %.
Single crystals of (DPP)2NacNacZnC6F5 · THF were grown on
storing an n-pentane / THF (10 :1 ϭ v/v) solution of (DPP)2Nac-
NacZnC6F5 for several days at Ϫ30 °C.
NMR data (C6D6): 19F: δ ϭ Ϫ115.11 (m, 2F, F-2,6), Ϫ154.63 (t, 1F, F-4),
Ϫ161.25 (m, 2F, F-3,5). 1H: δ ϭ 7.02 (m, 6H, ArH), 5.06 (s, 1H, Hβ), 3.23
(sept., 4H, CH(CH3)2), 1.67 (s, 6H, α-CH3), 1.24 (d, 12H, CH(CH3)2), 1.11
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1
1
143.6 (Cipso), 142.0 (Co), 140.5 (C-4, JC,F ഠ 249 Hz), 136.7 (C-3,5, JC,F
ഠ
251 Hz), 126.7 (Cp), 124.0 (Cm), 114.2 (C-1,2JC,F ഠ 61 Hz), 96.6 (Cβ), 28.6
(CHMe2), 24.1 (CHMe2), 23.9 (CHMe2), 23.6 (α-CH3).
EI-MS (20 eV): m/z ϭ 650 (Mϩ, 100 %), 635 ([M-Me]ϩ, 28 %), 418
([(DPP)2NacNacH]ϩ, 46 %), 403 ([(DPP)2NacNac-Me]ϩ, 72 %), 375
([(DPP)2NacNacHϪCHMe2]ϩ, 16 %), 202 ([(DPP)NacNac-2Me]ϩ 60 %),
Z. Anorg. Allg. Chem. 2003, 629, 1569Ϫ1574
zaac.wiley-vch.de
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
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1574
 2003 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim
zaac.wiley-vch.de
Z. Anorg. Allg. Chem. 2003, 629, 1569Ϫ1574