Synthetic and structural investigations on the reactivity of the Cd-I bond in [ICd{Zr2(OPri)9}] to construct new mixed-metal alkoxides

Article abstract of DOI:10.1021/om301053b

New mixed-metal alkoxides of general formula [XCd{Zr₂(OPr ⁱ)₉}]_n (X = -C₂F₅, -C₆F₅, -C₆F₄-4-H, -NO₃, -NCO, -SO₃CF₃, -O₂CCF₃, -O ₂CC₂F₅, -O₂CCH₃, -ClO₄, -CN, -SO₄; n = 1, 2) were obtained by the scission of the Cd-I bond in the iodo heterobimetallic isopropoxide [ICd{Zr ₂(OPrⁱ)₉}] (1), whereby the underlying synthetic strategies involve metathesis reactions with silver salts or Lewis acid-base interactions between the Bronsted acid [Zr(OPr ⁱ)₄(HOPrⁱ)]₂ and bis(fluoroorgano)cadmium (Cd(R_f)₂) compounds. The new compounds were characterized by multinuclear NMR spectroscopy, elemental analysis, and mass spectrometry. The results of X-ray diffraction analysis of [(F₅C₆)Cd{Zr₂(OPrⁱ)₉}] (2), [(4-H-F₄C₆)Cd{Zr₂(OPrⁱ) ₉}] (3), [(F₅C₂)Cd{Zr₂(OPr ⁱ)₉}]₂ (4), [(ONO₂)Cd{Zr ₂(OPrⁱ)₉}]₂ (5), [(CH ₃CO₂)Cd{Zr₂(OPrⁱ)₉}] (6), [(O₂ClO₂)(H₅C₃N)Cd{Zr ₂(OPrⁱ)₉}] (7), [(μ-O₂ClO ₂)Cd{Zr₂(OPrⁱ)₉}]₂ (8), [(μ-O₂CCF₃)Cd{Zr₂(OPrⁱ) ₈(O₂CCF₃)}]₂ (9), [(μ-O ₂CC₂F₅)Cd{Zr₂(OPrⁱ) ₈(O₂CC₂F₅)}]₂ (10), [(μ(O,N)-OCN)Cd{Zr₂(OPrⁱ)₉}]₂ (11), and [(μ-O₂SOCF₃)Cd{Zr₂(OPr ⁱ)₉}]₂ (12) revealed the molecular framework to be formally constituted by tetradentate coordination of a nonaisopropoxo dizirconate unit, {Zr₂(OPrⁱ)₉}^-, to a CdX⁺ unit. In solution and in the solid state, 1-7 exist as monomers, whereas compounds 8-12 form dimers.

Full text of DOI:10.1021/om301053b

Article
pubs.acs.org/Organometallics
Synthetic and Structural Investigations on the Reactivity of the Cd−I
Bond in [ICd{Zr2(OPri)9}] to Construct New Mixed-Metal Alkoxides
Corinna Hegemann,† Wieland Tyrra,† Jorg-Martin Neudorfl,‡ and Sanjay Mathur*,†
̈
̈
†Institute of Inorganic Chemistry and ‡Institute of Organic Chemistry, Department of Chemistry, University of Cologne, Greinstrasse
6, 50939 Cologne, Germany
S
* Supporting Information
ABSTRACT: New mixed-metal alkoxides of general formula
[XCd{Zr2(OPri)9}]n (X = −C2F5, −C6F5, −C6F4-4-H, −NO3,
−NCO, −SO3CF3, −O2CCF3, −O2CC2F5, −O2CCH3,
−ClO4, −CN, −SO4; n = 1, 2) were obtained by the scission
of the Cd−I bond in the iodo heterobimetallic isopropoxide
[ICd{Zr2(OPri)9}] (1), whereby the underlying synthetic
strategies involve metathesis reactions with silver salts or Lewis
acid−base interactions between the Brønsted acid [Zr-
(OPri)4(HOPri)]2 and bis(fluoroorgano)cadmium (Cd(Rf)2) compounds. The new compounds were characterized by
multinuclear NMR spectroscopy, elemental analysis, and mass spectrometry. The results of X-ray diffraction analysis of
[(F5C6)Cd{Zr2(OPri)9}] (2), [(4-H-F4C6)Cd{Zr2(OPri)9}] (3), [(F5C2)Cd{Zr2(OPri)9}]2 (4), [(ONO2)Cd{Zr2(OPri)9}]2 (5),
[(CH3CO2)Cd{Zr2(OPri)9}] (6), [(O2ClO2)(H5C3N)Cd{Zr2(OPri)9}] (7), [(μ-O2ClO2)Cd{Zr2(OPri)9}]2 (8), [(μ-O2CCF3)-
Cd{Zr2(OPri)8(O2CCF3)}]2 (9), [(μ-O2CC2F5)Cd{Zr2(OPri)8(O2CC2F5)}]2 (10), [(μ(O,N)-OCN)Cd{Zr2(OPri)9}]2 (11),
and [(μ-O2SOCF3)Cd{Zr2(OPri)9}]2 (12) revealed the molecular framework to be formally constituted by tetradentate
coordination of a nonaisopropoxo dizirconate unit, {Zr2(OPri)9}−, to a CdX+ unit. In solution and in the solid state, 1−7 exist as
monomers, whereas compounds 8−12 form dimers.
INTRODUCTION
■
The chemistry of M−O−C derivatives represents a cutting
edge frontier of chemical research, especially due to the
increasing importance of molecular heterometallic systems as
potential precursors enabling phase-selective synthesis of
multimetallic oxide materials by atomic scale mixing of cations.1
A large number of heterometallic alkoxides which can be used
as single-source precursors for the synthesis of oxide ceramics
are known in the literature.2 In addition to homoleptic
(MM′(OR)x), heteroleptic (MM′(OR)x(X)y where X = OAc,
OR′, halide), and oxo alkoxide species (MM′O(OR)x or
MM′(OR)x(X)y), alkoxide derivatives with different metal
combinations and up to three different metals3 in a single
molecule show the rich synthetic and structural chemistry of
metal alkoxides.4 However, structural data on heterometallic,
fluorinated molecular alkoxides have not been reported so far,
which motivated us to investigate the metathesis of the metal−
halogen bond in [ICd{Zr2(OPri)9}] (1).3
The iodocadmium zirconium isopropoxide is an interesting
starting material, due to its monomeric nature in the solid state,
solution, and gas phases imparted by the strong tetradentate
chelation of the {Zr2(OPri)9} unit (Figure 1) that endows
stability to the triangular “CdZr2” framework, making 13 a
viable synthon to construct new bi- and trimetallic alkoxide
derivatives by the metathesis of the Cd−I bond.
In comparison to the large number of homometallic mixed-
ligand compounds,6 structurally characterized examples of
heterometallic heteroleptic derivatives with fluorinated ligands
Figure 1. Tetradentate coordination mode of {M2(OR)9}− units in
heterometallic alkoxides.5
or weakly coordinating anions (WCA) have been less
investigated. In this work, a series of alkoxide derivatives of
the type [XCd{Zr2(OPri)9}], where X represents fluorinated or
other ligands, were synthesized as synthons to construct novel
heterotrimetallic alkoxides or to obtain new heterobimetallic
systems as possible precursors to metal oxides or oxyfluorides.
RESULTS AND DISCUSSION
■
Heterobimetallic derivatives of the general formula [XCd-
{Zr2(OPri)9}] were accessible by salt elimination and Lewis
acid−base condensation reactions, as depicted in Scheme 1.
Reactions of 13 with Silver Compounds. The reactions
between trimethylperfluoroorganosilanes and silver(I) fluoride
offered a convenient access to perfluoroorganosilver(I)
Received: November 6, 2012
Published: March 5, 2013
© 2013 American Chemical Society
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Scheme 1. Synthetic Routes to Complexes 2−14
compounds, as reported for reactions with the trifluoromethyl
and pentafluorophenyl groups in propionitrile and other N-
donor solvents.7
HC(OPri)3, as the major product. Both compounds were
1
unambiguously identified by H, 13C, and 19F NMR spectros-
copy. It is noteworthy that no spectroscopic evidence was
found for the missing link in this process, CHF(OPri)2, in
either the present investigation or in previous studies.11 HF
produced during the process is consumed by the [Cd-
{Zr2(OPri)9}]− framework to plausibly form “[Cd-
{Zr2(OPri)9−nFn}]” or related clusters of indefinite composition
and to release HOPri.
In order to elucidate the chemical nature of Cd−I bonds, 13
was reacted with various silver derivatives (AgC6F5, AgC6F4-4-
H, AgNO3, AgSO3CF3, AgO2CCF3, AgO2CC2F5, AgC2F5,
AgO2CCH3, AgCN, AgClO4, Ag2SO4, and AgOCN) in a
mixture of propionitrile, toluene, and heptane by stirring the
reaction mixtures at room temperature for 12 h. Given the low
propensity of silver to form strong Ag−O bonds and the facile
elimination of AgI, reactions are pushed to completion,
indicating this approach to be an interesting pathway toward
salt-elimination reactions in alkoxide chemistry.
Table 1. I−Cd Bond Lengths in Known Cd Compounds or
Ions3,8
Cd−I bond, Å
[ICd{Zr (OPri)9}] + AgR ⎯⎯⎯⎯→ [RCd{Zr (OPri)9}]
[ICd{Zr2(OPri)9}] (1)
∑ cov radii
2.637(4)
2
2
−AgI
2.83
∑ ion radii
3.03
The elimination of silver salts is a more effective strategy, due
to the low solubility of AgI in common organic solvents, which
makes it a better leaving group than alkali-metal halides or
[NMe4] halides. A survey of some Cd−I bond lengths
described in the literature shows the Cd−I bond in 13
(2.637(4) Å) to be one of the shortest in comparison to those
in other iodo-cadmium derivatives structurally characterized so
far (Table 1), indicating a uniquely strong Cd−I interaction in
1,3 which was supported by mass spectrometric data.
Cleavage of Cd−C Bonds by Lewis Acid−Base
Interactions. On the basis of earlier reports on the formation
of Cd(C6F5)X9 by reactions between HX and Cd(C6F5)2,7c we
have studied the reaction between Cd(C6F5)2 and [Zr-
(OPri)4(HOPri)]2.10 For the synthesis of fluoroorgano
derivatives of 1,3 both salt metathesis with Ag salts and acidic
cleavage of cadmium−carbon bonds by [Zr(OPri)4(HOPri)]2
were applied to the synthesis of 2 (Scheme 1) in high yields.
[CdI3]−
2.708(1), 2.717(1), 2.741(1)
Multinuclear NMR Analysis. The assignment of the
isopropoxy groups in 1−14 (Table 2) was achieved using a
combination of 1D and 2D (1H,1H-COSY, 1H,13C-HSQC,
1H,13C-HMBC, H,1H-NOESY) NMR experiments. The 113Cd
1
signals were detected either by direct methods or by inverse
1H,113Cd-HMQC experiments optimized for 40 Hz. In
particular, 113Cd NMR acts as a sensitive probe for monitoring
the changes in cadmium coordination sphere12 and the nature
of the ligands.13 The chemical shifts of 113Cd NMR as a
function of the nature of the ligands are plotted in Scheme 2.
While compounds 1, 2, 5−10, 12, and 14 displayed a rigid
behavior in solution at ambient temperature, allowing the
assignment of the terminal as well as bridging OPri groups on
Zr, the doubly bridged (μ2-Zr2) OPri groups, and the μ2 OPri
(Cd−Zr) and μ3 OPri (Cd−Zr2) units, compounds 3, 4, 11,
and 13 displayed a fluxional behavior, which prevented a
distinct assignment of all signals even at low temperatures
(down to −70 °C).
[Zr(OPri)4(HOPri)]2 + Cd(Rf)2
⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯⎯→ [(Rf)Cd{Zr (OPri)9}]
2
−RfH,−HOPri
In comparison to the deceptively simple spectroscopic
In contrast to the reaction of Cd(C6F5)2 and [Zr-
(OPri)4(HOPri)]2, which proceeded selectively to form 2, the
Cd(CF3)2·(glyme) adduct reacted differently to form [(F3C)-
Cd{Zr2(OPri)9}] with concomitant formation of HCF2OPri
and HF, followed by successive substitution of fluorine for
isopropoxy groups at the CF3 group still bonded to Cd, giving
finally a reaction mixture of difluoromethyl isopropyl ether,
HCF2OPri, as the minor product and triisopropyl orthoformate,
pattern generally observed for fluxional alkoxide molecules,14
as seen for the derivatives 3, 4, 11, and 13, the H and 13C
1
NMR spectra of other derivatives are indicative of a rigid
structural pattern existing in solution.3,15 For instance, the
1
room-temperature H NMR spectra of 2 in toluene-d8 showed
four doublets for the methyl groups in an integrative ratio of
2:1:4:2 corresponding to the nine OPri groups, in the region of
1.66−1.21 ppm. The signals of the methine protons were
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1
Table 2. H NMR Chemical Shifts and Assignment (Figure 2) for All Compounds
μ2-CdZr−CH and
μ3-Zr2Cd−CH/
integrative ratio
terminal Zr−CH/
μ2-Zr2−CH/
terminal Zr−CH3/
μ2-Zr2−CH3/
μ2-CdZr−CH3 and μ3-Zr2Cd−CH3/
integrative ratio
integrative ratio
integrative ratio
integrative ratio
integrative ratio
1
2
4.46/4
4.55/1
4.68 and 4.86/2
and 2
1.37/24
1.45/6
1.59 and 1.66/12 and 12
4.41/6
4.52/1
(4.41) and
4.59/2
1.37/24
1.42/6
1.21 and 1.66/12 and 12
3
4.52/5
4.69 and 4.77/4
1.40/30
1.45/∼24
1.34/12
1.38/24
1.4/30
1.61 and 1.77/24
1.46/∼30
1.59 and 1.41/24
1.53 and 1.75/24
1.7 and 1.6/12 and 12
1.56 and 1.6/12 and 12
1.57/12
4
4.56/∼7
4.43/4
4.69/∼2
4.59 and 4.63/4
4.7 and 4.72/4
5
4.47/1
4.55/1
4.5/1
1.4/18
1.48/6
6
4.51/4
7
4.5/4
4.6/2
4.6/2
4.55/4
4.7/2
4.7/2
8
4.41/4
4.5/1
1.32/24
1.28/24
1.4/6
9
4.34 and 4.44/5
4.45 and 4.49/5
4.41/∼6
4.42/4
1.36/18
10
11
12
13
14
4.59 and 4.66/4
1.35/24 1.41/6 1.32/∼36
1.39 and 1.64/24
4.55/∼3
1.55/∼18
1.52 and 1.67/12 and 12
1.9 and 1.7/24
4.45/1
4.57 and 4.67/4
4.69 and 4.8/4
4.88/2
1.3/24
1.36/6
1.45/6
4.59 and 4.64/5
4.49/4
1.42 and 1.64/30
1.38/24
4.58 and 4.73/3
1.77 and 1.73/24
Scheme 2. 113Cd NMR Shifts of Compounds 1−14
observed as three multiplets centered at δ 4.59, 4.52, and 4.41
ppm with the integrative ratio 2:1:6; the last signal results from
an overlapping of two septets, as elucidated by 2D NMR
experiments. As found in the ambient- and variable-temperature
NMR studies of derivatives [ICd{M2(OPri)9}] (M = Sn, Ti, Zr,
Hf)3,15a and other related complexes,5a,15b the observed
spectroscopic pattern and the trend of chemical shifts vs
connectivities of the isopropoxy groups is a peculiar feature of
complexes based on a tetradentate {M2(OPri)9}− unit.15c The
number and relative total intensities of the spectroscopic
patterns of 2, 5−10, 12, and 14 were comparable with those of
1,3 and in all cases the spectroscopic pattern could be
interpreted in a tetradentate coordination mode for cadmium
(see Table 2 and the Supporting Information). The 13C NMR
spectral data for all derivatives were consistent with the type of
group(s) attached to the metal centers.
The coordination of the fluorinated ligand was elucidated by
1H,19F-HOESY NMR experiments as shown in Figure 2 for
compound 2.
For compounds 9 and 10 the solution NMR spectroscopic
data are similar and are not in line with the solid-state
structures. They exhibited four multiplets in the region 4.66−
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1
Figure 2. H−19F-HOESY NMR spectrum of 2 (room temperature, benzene-d6).
4.34 ppm, whereby the methine protons of terminal and
bridging OPri groups showed overlapping resonances. Similar
observations were made for the methyl protons in the region
1.64−1.28 ppm. The broad resonances in 19F NMR spectra
indicate oligomeric structures and a dynamic behavior in
solution, as shown in Figure 3.
{Zr2(OPri)9}− unit.16 For compounds 11, 13, and 14 mostly
ions resulting from the {Zr2(OPri)9}− unit16 were detectable.
TG/DTA Analysis. TG/DTAs were carried out in sealed
aluminum cartridges under a N2 atmosphere in order to
observe the decomposition without any additional source of
oxygen. TGA of complexes 2−6, 9, and 13 show just one major
decomposition step mostly in the range 190−270 °C, indicating
a decomposition to the oxide material with about 40−50 wt %
residues left at 600 °C, whereby the theoretical residue is about
40 wt %. For compounds 8, 10, and 12 a similar residue occurs
via a two- or multiple-step decomposition, whereas 7 and 11
decompose with ca. 60 wt % residues left at 600 °C. Given the
susceptibility of the new compounds towards atmospheric
moisture, a handling error in the TGA analyses needs to be
taken into account; also the formation of metal fluorides in F-
containing ligands cannot be completely ruled.
X-ray Diffraction Analysis. The crystallographic data of
compounds 2−12 are summarized in the Supporting
Information, as well as illustrations of the molecular structures
of 3−5, 8, and 10.
Colorless crystals suitable for X-ray diffraction studies were
obtained at room temperature from a mixture of dichloro-
methane and toluene for compound 2, a benzene solution for
compounds 3, 5−8, and 10, and a toluene solution at −12 °C
for 4, 9, 11, and 12.
The central core of all molecules comprised a heterometallic
CdZr2 triangle capped by two μ3-OPri ligands; cadmium bore
different ligand units, whereas each zirconium possessed two
terminal isopropoxide ligands. Each side of the trimetallic
planar core is bridged by a μ2-OPri group. The local
coordination environment around cadmium resembles a
distorted trigonal bipyramid, with two oxygen atoms occupying
the axial coordination sites. The Zr−O distances within the
{Zr2(OPri)9}− unit show the gradual variation (Zr−O
(terminal) < Zr−(μ2-OZr) (doubly bridging, μ2) < Zr−(μ3-
OZr) (triply bridging, μ3)) commonly observed in the confacial
bioctahedral structures of the lanthanide, actinide, and early-
transition-metal alkoxides.17 The bond lengths of μ2-OPri
ligands fall into two classes, depending on whether a Zr−O−
Zr or Zr−O−Cd linkage is present. The structurally
characterized heterometallic alkoxides based on the
{M2(OR)9}− unit generally show a trend in which the length
of the bonding interaction of the alkoxide oxygen of the
{M2(OR)9}− unit to the coordinated metal atom increases with
Figure 3. Proposed structure in solution for 9 and 10 (Rf = −O2CCF3,
−O2CC2F5).
In contrast to the stereochemically rigid [ICd{Zr2(OPri)9}]
(1),3 the 1H and 13C NMR spectra of [(F5C2)Cd{Zr2(OPri)9}]
(4), [(μ(O,N)-OCN)Cd{Zr2(OPri)9}]2 (11), [(NC)-
CdZr2(OPri)9]n (13), and [(4-H-F4C6)Cd{Zr2(OPri)9}] (3)
at 20 °C are deceptively simple, indicating a rapid alkoxide site
exchange in solution. The fluxional behavior decelerated upon
lowering the temperature, but even −70 °C did not suffice to
completely freeze the motion of ligands in compounds 3, 4, 11,
and 13. However, the observed solution 113Cd NMR chemical
1
shifts as well as the pattern of the H NMR spectra closely
resemble those observed for [ICd{Zr2(OPri)9}] (1),3 indicating
a similar binding mode (tetradentate) of the {Zr2(OPri)9}− unit
to Cd in all cases. The fluorine NMR spectra, as well as the
proton NMR spectra, of [(4-H-F4C6)Cd{Zr2(OPri)9}] (3)
showed it to be a pyridine adduct, which again supports the
proposed fluxional behavior in solution.
Electron Impact Mass Spectrometry. EI mass spectra
(20 eV) of compounds 2−10 and 12 reveal comparable
fragmentation patterns, with [XCd{Zr2(OPri)8}]+ being the
predominant fragment. This observation further supports the
stability of the CdZr2 unit. Further peaks of lower intensities are
mostly ions deriving from the decomposition of the
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each successive bridging, which is due to the loss of electron
density at the alkoxide oxygen.5b
[(F5C6)Cd{Zr2(OPri)9}] (2), [(4-H-F4C6)Cd{Zr2(OPri)9}] (3), and
[(F5C2)Cd{Zr2(OPri)9}] (4). Compound 2 (Figure 4) and 3
Figure 5. Molecular structure of [(CH3CO2)Cd{Zr2(OPri)9}] (6)
(170 K). The displacement ellipsoids are drawn at the 30% probability
level; methyl carbons and hydrogen atoms of the isopropyl groups are
omitted for clarity. Selected lengths (Å) and angles (deg): Cd1−O10
= 2.276(3), Cd1−O11 = 2.276(3), Cd1−O1 = 2.319(3), Cd1−O2 =
2.292(3), Cd1−O3 = 2.388(2), Cd1−O4 = 2.360(2), Zr−O =
1.920(3)−2.261(3); O10−Cd1−O11 = 57.25(12), O1−Cd1−O10 =
104.37(13), O2−Cd1−O11 = 110.66(12), O1−Cd1−O11 =
107.58(12), Zr1−O4−Cd1 = 91.27(9), Zr2−O4−Cd1 = 91.17(9).
Figure 4. Molecular structure of [(F5C6)Cd{Zr2(OPri)9}] (2) (100
K). Displacement ellipsoids are drawn at the 30% probability level;
methyl carbons and hydrogen atoms of the isopropyl groups are
omitted for clarity. Selected lengths (Å) and angles (deg): Cd1−C1 =
2.158(5), Cd1−O1 = 2.352(3), Cd1−O2 = 2.377(3), Cd1−O3 =
2.326(3), Cd1−O4 = 2.330(3), Zr−O = 1.921(3)−2.318(3); O1−
Cd1−C1 = 112.12(14), O2−Cd1−C1 = 112.35(14), O3−Cd1−C1 =
151.74(14), O4−Cd1−C1 = 142.64(15), O1−Cd1−O4 = 71.61(10),
O2−Cd1−O4 = 71.18(10), O4−Cd1−O3 = 65.63(10), Zr1−O4−
Cd1 = 92.78(10), Zr2−O4−Cd1 = 91.36(10).
nitrate heterometal alkoxide derivative based on a
{M2(OPri)9}− unit. Similar to the case for compound 5, the
acetate group in 6 was found to coordinate cadmium in a
bidentate mode.
[(O2ClO2)(H5C3N)Cd{Zr2(OPri)9}] (7) and [(μ-O2ClO2)Cd-
{Zr2(OPri)9}]2 (8). The perchlorate derivative 8 crystallized
similarly to 12 (Figure 7) as a dimer bridged by the perchlorate
unit in the monoclinic space group P21/c (No. 14), whereas the
monomeric propionitrile adduct 7 crystallized in the triclinic
crystallized isostructurally in the orthorhombic space group
Pbca (No. 61), whereas compound 4 crystallized in the
orthorhombic spacegroup Pnma (No. 62). The molecular
structures of 2−4 closely resemble that of the parent
compound [ICd{Zr2(OPri)9}] (1)3 in terms of the binding
mode of the {M2(OR)9}− unit to the central metal CdII in a
similar tetradentate manner.
space group P1 (No. 2) (Figure 6).
̅
In contrast to the case for compound 8, dimerization in 7 can
be prevented through addition of propionitrile to the reaction
mixture so that one propionitrile molecule coordinates to the
cadmium atom. The Cd−O contact of the second oxygen atom
of the perchlorate group is relatively long with a Cd1−O13
distance of 2.797 Å.
As indicated by the multinuclear NMR studies, 2−4 exist in
the solid state as monomers where the cadmium atom bears a
terminal fluorophenyl/fluoroethyl unit and a {Zr2(OPri)9}−
unit binding in a 4-fold fashion via two triply (μ3) and two
doubly (μ2) bridging isopropoxy groups. The steric bulk of the
fluorophenyl groups prevents 2 and 3 from dimerization, and
thus they differ from the dimeric complex [ClCd{Zr2(OPri)9}]2
described by Mehrotra et al.18
[(μ-O2SOCF3)Cd{Zr2(OPri)9}]2 (12). Compound 12 crystal-
lized in the monoclinic space group P21/c (No. 14) with four
molecules in the unit cell (Figure 7). The bond lengths and
angles in 12 show only minor differences; in comparison to the
pentacoordinated Cd centers in 2−4, the presence of a bridging
triflate unit leads to a strongly distorted octahedral config-
uration around Cd.
[(ONO2)Cd{Zr2(OPri)9}] (5) and [(CH3CO2)Cd{Zr2(OPri)9}]
(6). Compound 5 crystallized in the monoclinic space group
P21/n with four molecules in the unit cell (Supporting
Information). Compound 6 crystallized in the triclinic space
[(μ(O,N)-OCN)Cd{Zr2(OPri)9}]2 (11). Compound 11 crystal-
lized in the monoclinic space group P21/c (no. 14) (Figure 8).
The molecular structure of 11 represents, to the best of our
knowledge, the first structurally characterized example of a
cyanate-capped bimetallic alkoxide based on a {M2(OPri)9}−
unit. The cyanate unit bridges the two CdZr2 units via an end-
to-end coordination, to form the dimeric framework.
[(μ-O2CCF3)Cd{Zr2(OPri)8(O2CCF3)}]2 (9) and [(μ-O2CC2F5)-
Cd{Zr2(OPri)8(O2CC2F5)}]2 (10). In contrast to the case for the
nonfluorinated acetate derivative 6, the solid-state structural
group P1 (No. 2) (Figure 5).
̅
In the solid-state structure of 5, the NO3− group coordinates
to cadmium in a bidentate mode with Cd−O contacts of 2.298
Å and a rather acute O−Cd−O angle (55.02°). The N−O
bond lengths of 1.235−1.243 Å do not significantly vary from
each other. 5 represents the first structurally characterized
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Figure 8. Molecular structure of [(μ(O,N)-OCN)Cd{Zr2(OPri)9}]
(11). The displacement ellipsoids are drawn at the 30% probability
level; methyl carbons and hydrogen atoms of the isopropyl groups are
omitted for clarity. Selected lengths (Å) and angles (deg): Cd1−O10
= 2.306(10), Cd1−N1 = 2.193(11), O1−Cd1 = 2.313(8), O2−Cd1 =
2.310(8), O3−Cd1 = 2.378(6), O4−Cd1 = 2.407(7), Zr−O =
1.911(8)−2.272(6); O4−Cd1−O10 = 163.8(3), O4−Cd1−N1 =
106.2(4), N1−C1−O10 = 173.7(15), N1−Cd1−O10 = 89.9(5), O4−
Cd1−O2 = 70.8(3), O4−Cd1−O1 = 71.4(3), Zr1−O3−Cd1 =
91.0(2), Zr2−O3−Cd2 = 91.1(2).
Figure 6. Molecular structure of [(O2ClO2)(H5C3N)Cd{Zr2(OPri)9}]
(7) (170 K). The displacement ellipsoids are drawn at the 30%
probability level; methyl carbons and hydrogen atoms of the isopropyl
groups are omitted for clarity. Selected lengths (Å) and angles (deg):
Cd1−N1 = 2.282(2), Cd1−O10 = 2.388(3), Cl1−O10 = 1.436(3),
Cl1−O13 = 1.439(3), O2−Cd1 = 2.3017(19), O1−Cd1 =
2.3024(17), O3−Cd1 = 2.4617(17), O4−Cd1 = 2.3024(17), Zr−O
= 1.9194(19)−2.3176(17); O2−Cd1−N1 = 109.24(8), O2−Cd1−
O10 = 129.82(9), O13−Cl1−O10 = 104.1(2), O1−Cd1−O4 =
73.32(7), O2−Cd1−O = 72.59(6), O4−Cd1−O3 = 64.90(6), Zr1−
O4−Cd1 = 92.17(6), Zr2−O4−Cd1 = 93.36(6).
Figure 9. Molecular structure of [(μ-O2 CCF3 )Cd-
{Zr2(OPri)8(O2CCF3)}]2 (9) (293 K). The displacement ellipsoids
are drawn at the 30% probability level; methyl carbons and hydrogen
atoms of the isopropyl groups are omitted for clarity. Selected lengths
(Å) and angles (deg): Cd1−O12 = 2.197(6), Cd1−O11 = 2.192(5),
Cd1−O1 = 2.151(5), Cd1−O2 = 2.147(4), Zr1−O9 = 2.230(5), Zr2−
O10 = 2.224(5), Zr−Oalkoxide = 1.902(5)−2.209(4); O2−Cd1−O11 =
108.4(2), O2−Cd1−O12 = 105.9(2), O11−C1−O12 = 130.3(8),
O3−Zr1−O9 = 84.53(17).
Substitution of metal alkoxides is usually performed by
reaction with protic compounds (HY) in which the proton of
HY is transferred to an OR group with subsequent elimination
of ROH. In a similar manner, an alkoxo group could be
transferred to the R′C(O) moiety of the anhydride
accompanied by the formation of an ester. However, in these
cases neither a protic compound nor an anhydride was involved
in the reaction; accidental exposure to moisture cannot be
totally excluded. Neither water nor ester could be detected in
the reaction mixture. Solution NMR spectroscopic data are not
in line with the solid-state structure, but the proposed behavior
in solution (Figure 3) could explain the preferred formation of
these species in the solid state.
Figure 7. Molecular structure of [(μ-O2SOCF3)Cd{Zr2(OPri)9}]2
(12) (293 K). The displacement ellipsoids are drawn at the 30%
probability level; methyl carbons and hydrogen atoms of the isopropyl
groups are omitted for clarity. Selected lengths (Å) and angles (deg):
Cd1−O10 = 2.256(4), Cd1−O11 = 2.234(5), O11−S1′ = 1.439(4),
O10−S1 = 1.433(4), Cd1−O2 = 2.259(4), Cd1−O3 = 2.385(4),
Cd1−O4 = 2.410(4), Zr−O = 1.894(5)−2.274(4); O2−Cd1−O10 =
117.26(17), O2−Cd1−O11 = 97.57(17), O3−Cd1−O10 =
104.65(15), O3−Cd1−O11 = 167.87(15), O3−Cd1−O1 =
71.93(14), O3−Cd1−O2 = 72.03(15), Zr1−O3−Cd1 = 91.45(15),
Zr2−O3−Cd1 = 90.50(14).
mode of the perfluorinated acetate derivatives 9 (Figure 9) and
10 is changed due to the replacement of the μ2-Zr2 isopropoxy
group by a perfluorocarboxylate ligand.
The most probable sequence of reactions leading to the
formation of such clusters is that one or more alkoxo ligands
are replaced by carboxylato ligands in the first step, followed by
esterification of the liberated alcohol.
CONCLUSION
■
In the present study the syntheses of new Cd−Zr bimetallic
alkoxides based on mixed-ligand systems are reported. In view
of the volatility of these compounds, they are potential
precursors for deposition of bimetallic oxides by means of
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TG/DTAs were recorded on a TGA/DSC 1 STARe system by
Mettler with a GC 100 gas controller. Samples were placed in an
aluminum cartridge (HEKAtech GmbH, 5 × 12 mm) and sealed. The
measurements were performed under a 25 mL N2 flow between 40
and 630 °C with a heating rate of 5 °C/min.
chemical vapor deposition. In addition, they are interesting
starting materials for the construction of heterotrimetallic
alkoxides. We have demonstrated new synthetic approaches for
combining M−O−C and M−C derivatives and the introduc-
tion of fluorinated ligands. The present investigations represent
the beginning of an elusive class of mixed-ligand heterometallic
systems. Further studies to establish the generality of the results
are currently underway.
The reactions of silver fluoride and trimethyl-
(perfluoroorgano)silanes offer a convenient and general
approach to the synthesis of perfluoroorganosilver(I) com-
pounds. The low toxicity of silver and the ease of recycling
make silver compounds attractive for further studies in the field
of organic and element-organic synthesis. Finally, it is
conceivable that the successful use of argentates to synthesis
such heteroleptic heterometallic isopropoxides is an interesting
example of incorporating fluorine in a molecular alkoxide
assembly, and the extension of this strategy to other metal
combinations may provide access to the designing of “single-
source” precursors.
Data collections for X-ray crystal structure determination for
compounds 3−12 were performed on a STOE IPDS I/II
diffractometer using graphite-monochromated Mo Kα radiation (λ =
0.71073 Å). The data were corrected for Lorentz and polarization
effects. A numerical absorption correction based on crystal-shape
optimization was applied for all data.23a The programs used in this
work are Stoe’s X-Area,23b including X-RED and X-Shape for data
reduction and absorption correction,23c and the WinGX suite of
programs,23d including SIR-9223e and SHELXL-9723f for structure
solution and refinement. The hydrogen atoms were placed in idealized
positions and constrained to ride on their parent atom. The last cycles
of refinement included atomic positions for all atoms, anisotropic
thermal parameters for all non-hydrogen atoms and isotropic thermal
parameters for all hydrogen atoms. Graphics for publication were
prepared using DIAMOND.23g
X-ray diffractograms of compound 2 were measured on a Nonius
Kappa-CCD diffractometer with Mo Kα radiation (λ = 0.71073 Å),
and DENZO was used for data reduction. The structure was solved by
direct methods (SHELXS-9723h). SHELXL-9723f was used for full-
matrix least-squares refinement on F2. All non-hydrogen atoms were
refined anisotropically. All hydrogen atoms were placed in geometri-
cally idealized positions and refined using the riding model.
EXPERIMENTAL SECTION
■
Chemicals and Methods. All reactions were performed under a
nitrogen atmosphere using a modified Stock vacuum line, taking the
utmost precautions to prevent adventitious hydrolysis. All reaction
vessels were stored in a drying oven at 140 °C before use. Solvents
were purified by reported methods.19 Ammonia was dried by
condensation over sodium at −70 °C.
Selected crystallographic data for compounds 2−12 are given in
Tables 1−3 in the Supporting Information. CCDC 922612−922622
contain 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.
ZrCl4 was purchased from Merck and dried under vacuum prior to
use. [Zr(OPri)4(HOPri)]2 was prepared by following the ammonia
method, as described in the literature.10 Also, the educts Cd-
(C6F5)2·2EtCN7c and Ag(C6F5)·EtCN7c (when not prepared in
situ), Me3SiC6F5,20 Me3SiC2F5,20 and Me3SiC6F4-4-H21 were synthe-
sized according to published procedures. Me3SiCF3, silver penta-
fluoropropionate (AgO2CC2F5), silver cyanide (AgCN) and silver
acetate (AgCO2CH3) were purchased from ABCR. Silver(I) fluoride
(AgF) was purchased from Apollo Scientific Ltd., silver triflate
(AgSO3CF3) and pyridine were obtained from Acros, and CdI2, Cd
powder, silver sulfate (Ag2SO4), and benzene were purchased from
Merck. Silver(I) acetate (AgOCOCF3) was received from Solvay Fluor
and Derivate. Silver perchlorate (AgClO4) and silver cyanate
(AgOCN) were purchased from Alfa Aesar; silver nitrate (AgNO3)
was obtained from AppliChem. All chemicals were used as received.
NMR spectra were recorded with a Bruker AVANCE II 300
spectrometer at 298 K with NMR spectroscopic frequencies (external
standards) as follows: 13C, 75.5 MHz (TMS); 19F, 282.4 MHz
(CCl3F); 1H, 300.1 MHz (TMS); 113Cd, 66 MHz (Cd(CH3)2, 50% v/
v CDCl3). On a Bruker Avance 400 spectrometer at 298 K, NMR
spectroscopic frequencies (external standards) were as follows: 13C,
Synthesis of Precursors. [Zr(OPri)4(HOPri)]2. This compound was
prepared according to the literature procedure.10 Anal. Found (calcd)
for C30H72O10Zr2 (775.34): C, 46.93 (46.47); H, 9.43 (9.36). 1H
NMR (400.13 MHz, toluene-d8, 228 K; δ/ppm): 6.45 (mbr, Δ1/2 = 175
Hz, 2H, OH), 5.20 (m, 2H, μ2 OCH(CH3)2), 4.48 (m, 4H, axial
OCH(CH3)2), 4.57 (m, 4H, terminal OCH(CH3)2), 1.70 (d, 12H, μ2
OCH(CH3)2), 2.40 (d, 24H, axial OCH(CH3)2), 1.48 (d, 24H,
terminal OCH(CH3)2). 13C{1H} NMR (100.61 MHz, toluene-d8,
228K; δ/ppm): 71.3 (μ2 OCH(CH3)2), 68.3 (axial OCH(CH3)2), 70.2
(terminal OCH(CH3)2), 24.9 (μ2 OCH(CH3)2), 26.0 (axial OCH-
(CH3)2), 27.6 (terminal OCH(CH3)2). 1H NMR (300.1 MHz,
benzene-d6, 298 K; δ/ppm): 1.50 (d, 60H, OCH(CH3)2), 4.68 (m,
12H, OCH(CH3)2). 13C{1H} NMR (75.5 MHz, benzene-d6, 298 K; δ/
ppm): 69.0 (OCH(CH3)2), 26.2 (OCH(CH3)2). EI-MS (20 eV; m/z
(%)): 821 (47, [Zr3(OC3H7)9]+), 719 (6, [Zr3O2(OC3H7)7]+), 593 (5,
[Zr3O3(OC3H7)4(OC2H4)3]+), 325 (5, [Zr(OC3H7)3(OC3H6)]+), 311
(100, [Zr(OC3H7)3(OC2H4)]+), 267 (12, [Zr(OC3H7)3]+), 253 (7,
[Zr(OC3H7)2(OC2H4)]+), 45 (11, [OC2H5]+). Mp: 120−123 °C
(glass capillary).
Iodocadmium Nonaisopropoxydizirconium [ICd{Zr2(OPri)9}] (1).
This compound was prepared by the reported method.3 1H NMR
(300.1 MHz, benzene-d6, 298 K; δ/ppm): 4.86 (m, 2H, μ3
OCH(CH3)2), 4.68 (m, 2H, μ2 OCH(CH3)2 (CdZr)), 4.55 (m, 1H,
μ2 OCH(CH3)2 (ZrZr)), 4.46 (m, 4H, terminal OCH(CH3)2), 1.66
(d, 12H, μ3 OCH(CH3)2), 1.59 (d, 12H, μ2 OCH(CH3)2 (CdZr)),
1.45 (d, 6H, μ2 OCH(CH3)2 (ZrZr)), 1.37 (d, 24H, terminal
OCH(CH3)2). 13C{1H}-NMR (75.5 MHz, benzene-d6, 298 K; δ/
ppm): 70.2 (μ3 OCH(CH3)2), 70.3 (μ2 OCH(CH3)2 (CdZr)), 70.7
(μ2 OCH(CH3)2 (ZrZr)), 71.9 (terminal OCH(CH3)2), 27.2 (μ3
OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)), 26.5 (μ2 OCH(CH3)2
(ZrZr)), 26.9 (terminal OCH(CH3)2). 113Cd NMR (66 MHz,
benzene-d6, 298 K; δ/ppm): −593. Mp: 223 °C dec (glass capillary).
Anal. Found (calcd) for C27H63CdIO9Zr2 (953.53): C, 34.35 (34.01);
H, 6.89 (6.66). EI-MS (20 eV; m/z (%)): 893 (100, [ICdZ-
r2(OC3H7)8]+), 767 (8, [CdZr2(OC3H7)8]+), 653 (8,
[Zr2(OC3H7)8]+), 593 (48, [Zr3O3(OC3H7)4(OC2H4)3]+), 566 (50,
[Zr3O3(OC3H7)2(OC2H4)3]+), 441 (6, [Zr3O5(OC2H4)2]+), 368 (8,
[CdI2]+), 325 (9, [Zr(OPri)3(OC3H6)]+), 311 (80, [Zr-
1
100.61 MHz (TMS); 19F, 376.50 MHz (CCl3F); H, 400.13 MHz
(TMS); 113Cd, 88.73 MHz (Cd(CH3)2). Positive shifts denote
downfield resonances. 13C NMR chemical shifts are taken from
1D-13C-APT NMR spectra.
Microanalysis for C, H, N, and S was carried out using a Hekatech
CHNS EuroEA 3000 analyzer with helium as carrier gas. The
discrepancy between calculated and measured values can be attributed
to the high moisture sensitivity of the derivatives. The results for
compound 7, 8, 11, 13, and 14 deviate from the expected analytical
purity, and the results provided here refer to the best values obtained
after several repetitions. Mass spectra were run on a Thermo Quest
Finnigan MAT 95 using electron impact ionization with 20 eV. The
isotope patterns for comparison were calculated with the program
Isopro,22 whereby the most intensive peak of the isotope pattern is
listed. Melting and decomposition points were determined with a
HWS Mainz Laboratoriumstechnik SG 2000 apparatus in sealed 4 mm
tubes under an atmosphere of nitrogen and are uncorrected.
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(OC3H7)3(OC2H4)]+), 267 (13, [Zr(OC3H7)3]+), 253 (10, [Zr-
(OC3H7)2(OC2H4)]+), 45 (32, [OC2H5]+). Sublimation temperature:
150 °C/10−3 mbar.
4-H-tetrafluorophenylcadmium Nonaisopropoxydizirconium,
[(4-H-F4C6)Cd{Zr2(OPri)9}] (3). Yield: 1.43 g (1.47 mmol, 92.5%)
crude product (yellowish solid). H NMR (300.1 MHz, toluene-d8,
1
298 K; δ/ppm): 6.6 (m, 1H, 4-H-C6F4), 4.77 and 4.69 (overlapping m,
total integral of 4H, μ3 OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)),
4.52 (overlapping mbr, total integral of 5H, μ2 OCH(CH3)2 (ZrZr)
and terminal OCH(CH3)2), 1.77 and 1.61 (overlapping d, total
integral of 4H, μ3 OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)), 1.40
(overlapping d, total integral of 5H, μ2 OCH(CH3)2 (ZrZr) and
terminal OCH(CH3)2). 13C{1H NMR (75.5 MHz, toluene-d8, 298 K;
δ/ppm): 148.8 (C-2,6), 146.0 (C-3,5), 129.1 (C-1), 106.4 (C-4), 70.7
and 70.0 (μ3 OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)), 71.3 (μ2
OCH(CH3)2 (ZrZr) and terminal OCH(CH3)2), 26.5 and 26.3 (μ3
OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)), 26.1 (μ2 OCH(CH3)2
(ZrZr) and terminal OCH(CH3)2). 19F NMR (282.4 MHz, toluene-d8,
298 K; δ/ppm): −110.9 (m, 2 F, F-2,6), −138.1 (m, 2 F, F-3,5). 113Cd
NMR (66.0 MHz, toluene-d8, 298 K; δ/ppm): −468. Anal. Found
(calcd) for C33H64CdF4O9Zr2 (975.7): C, 40.23 (40.62); H, 6.89
( 6 . 6 1 ) . E I - M S ( 2 0 e V ; m / z ( % ) ) : 9 1 5 ( 7 0 ,
[C6F5HCdZr2(OC3H7)8]+), 766 (10, [C6F5CdZr2(OC3H7)7O]+),
651 (5, [Zr2(OC3H7)8]+), 593 (68, [Zr3O3(OC3H7)4(OC2H4)3]+),
587 (66, [C6 F4 HCdZr(OC3 H7 )4 ]+ ), 325 (8, [Zr-
(OC3H7)3(OC3H6)]+), 311 (21, [Zr(OC3H7)3(OC2H4)]+), 150 (23,
[C6F4H]+), 45 (100, [OC2H5]+). Sublimation temperature: 155 °C/
10−3 mbar.
General Procedure for the Synthesis of Ag(C2F5)·NC5H5,
Ag(C6F4-4-H)·NC5H5, and Ag(C6F5)·NC5H5. These compounds were
prepared according to the literature procedure for Ag(C6F5).7
A 0.2 g portion (1.59 mmol) of AgF was suspended in 8 mL of well-
dried pyridine at room temperature and the mixture stirred for
approximately 15 min. A 2.5 mmol amount (1.5-fold excess) of
Me3SiRf was added in one portion. Immediately a slightly exothermal
reaction started, during which a spotty silver mirror was formed.
Stirring was continued overnight. The completeness of the reaction
was monitored by 19F NMR spectroscopy, exhibiting the signals of
AgRf in addition to Me3SiF and low-intensity signals of Me3SiRf and
RfH. After decanting, all volatile components were distilled off in
vacuo (10−3 mbar) at ambient temperature, giving AgRf·NC5H6 as a
pale gray crystalline material in nearly quantitative (96%) yield.
AgC6F5·NC5H5. 19F NMR (282.4 MHz, acetonitrile-d3, 298 K; δ/
ppm): −105.8 (m, 2 F, F-2,6), −158.4 (t, 1 F, F-4), −163.1 (m, 2 F, F-
3,5).
AgC2F5·NC5H5. 19F NMR (282.4 MHz, benzene-d6, 298 K; δ/ppm):
−81.6 (sbr, 3 F, CF2CF3), −108.2 (sbr, 2 F, CF2CF3).
AgC6F4-4-H·NC5H5. 19F NMR (282.4 MHz, dichloromethane-d2,
298 K; δ/ppm): −109.8 (m, 2 F, F-2,6), −140.7 (t, 1 F, F-3,5).
General Procedure for the Synthesis of [(F5C6)Cd{Zr2(OPri)9}]
(2), [(4-H-F4C6)Cd{Zr2(OPri)9}] (3), and [(F5C2)Cd{Zr2(OPri)9}] (4).
A solution of 1.5 mmol of AgRf in pyridine was prepared in situ from
Me3SiRf and 0.2 g (1.5 mmol) of AgF. After short vacuum evaporation
to remove the formed Me3SiF, a toluene (10 mL) solution of 1.51 g
(1.5 mmol) of [ICd{Zr2(OPri)9}] (1)3 was added. Immediately a
yellow solid precipitated. After the mixture was stirred overnight and
the overlaying supernatant solution was decanted from the precipitated
AgI, all volatile components were distilled off under vacuum (1 × 10−3
mbar) at room temperature to yield the corresponding derivatives as
off-white to pale yellow solids. For all compounds, purity was checked
Pentafluoroethylcadmium Nonaisopropoxydizirconium, [(F5C2)-
Cd{Zr2(OPri)9}] (4). Yield: 1.48 g (1.57 mmol, 98.1%) crude product
1
(white solid). H NMR (400.13 MHz, benzene-d6, 298 K; δ/ppm):
4.69 (m, 2H, μ3 OCH(CH3)2), 4.56 (overlapping m, total integral of
7H, μ2 OCH(CH3)2 (CdZr) and μ2 OCH(CH3)2 (ZrZr) and terminal
OCH(CH3)2), 1.46 (overlapping d, total integral of 5H, μ3
OCH(CH3)2) and μ2 OCH(CH3)2 (CdZr) and μ2 OCH(CH3)2
(ZrZr)), 1.45 (d, 4H, terminal OCH(CH3)2). 13C{1H} NMR
(100.61 MHz, benzene-d6, 298 K; δ/ppm): 135.3 (CdCF2CF3),
122.8 (CdCF2CF3), 71.9 (μ3 OCH(CH3)2 and μ2 OCH(CH3)2
(CdZr) and μ2 OCH(CH3)2 (ZrZr)), 69.9 (terminal OCH(CH3)2),
26.7 (μ3 OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr) and μ2
OCH(CH3)2 (ZrZr) and terminal OCH(CH3)2). 19F NMR (376.5
MHz, benzene-d6, 298 K): δ = −118.9 (t, 2 F, CF2CF3), −85.4 (m, 3
F, CF2CF3). 113Cd NMR (88.73 MHz, benzene-d6, 298 K; δ/ppm):
−532. Mp: 168 °C (glass capillary) (onset of decomposition at 142
°C). Anal. Found (calcd) for C29H63CdF5O9Zr2 (945.65): C, 37.18
(36.83); H, 6.63 (6.72). EI-MS (20 eV; m/z (%)): 885 (100,
[C2F5CdZr2(OC3H7)8]+), 821 (8, [Zr3(OC3H7)9]+), 767 (20,
[CdZr2(OC3H7)8]+), 651 (7, [Zr2(OC3H7)8]+), 593 (52,
[Zr3O3(OC3H7)4(OC2H4)3]+), 559 (68, [CdZrC2F5(OC3H7)4]+),
441 (12, [Zr3O5(OC2H4)2]+), 325 (9, [Zr(OC3H7)3(OC3H6)]+),
311 (38, [Zr(OC3H7)3(OC2H4)]+). Sublimation temperature: 145
°C/10−3 mbar.
General Procedure for the Synthesis of [(ONO2)Cd-
{Zr2(OPri)9}]2 (5), [(CH3CO2)Cd{Zr2(OPri)9}] (6), [(O2ClO2)(H5C3N)-
Cd{Zr2(OPri)9}] (7), [(μ-O2ClO2)Cd{Zr2(OPri)9}]2 (8), [(μ-O2CCF3)-
C d { Z r 2 ( O P r i ) 8 ( O 2 C C F 3 ) } ] 2 ( 9 ) , [ ( μ - O 2 C C 2 F 5 ) C d -
{Zr2(OPri)8(O2CC2F5)}]2 (10), [(μ(O,N)-OCN)Cd{Zr2(OPri)9}]2 (11),
[(μ-O2SOCF3)Cd{Zr2(OPri)9}]2 (12), [(NC)Cd{Zr2(OPri)9}] (13), and
[(SO4){Cd{Zr2(OPri)9}}2] (14). One equivalent of [ICd{Zr2(OPri)9}]
(1)3 in a heptane/toluene mixture was added to a well-stirred
suspension of AgR in propionitrile/toluene. Directly after combina-
tion, a yellow precipitate was formed. The mixture was stirred for 12 h
and decanted, and the volume of the solution was reduced by slow
evaporation of all volatiles. In the synthesis of 8 and 14 no
propionitrile was involved and the reaction time was prolonged to 3
days.
1
by CHN analysis and mass and 19F, H, and 13C NMR spectra.
Pentafluorophenylcadmium Nonaisopropoxydizirconium,
[(F5C6)Cd{Zr2(OPri)9}] (2). Yield: 1.46 g (1.47 mmol, 97.5%) crude
1
product (yellowish solid). H NMR (300.1 MHz, toluene-d8, 298 K;
δ/ppm): 4.59 (m, 2H, μ3 OCH(CH3)2 (CdZr)), 4.52 (m, 1H, μ2
OCH(CH3)2 (ZrZr)), 4.41 (overlapping m, 6H, μ2 OCH(CH3)2
(CdZr) and terminal OCH(CH3)2), 1.66 (d, 12H, μ3 OCH(CH3)2),
1.42 (d, 6H, μ2 OCH(CH3)2 (ZrZr)), 1.31 (d, 24H, terminal
OCH(CH3)2), 1.21 (m, 12H, μ2 OCH(CH3)2 (CdZr)). 13C{1H}
NMR (75.5 MHz, toluene-d8, 298 K; δ/ppm): 147.8 (C-2,6), 136.9
(C-3,5), 140.3 (C-1), 120.0 (C-4), 70.3 (μ3 OCH(CH3)2), 69.6 (μ2
OCH(CH3)2 (CdZr)), 70.1 (μ2 OCH(CH3)2 (ZrZr)), 71.8 (terminal
OCH(CH3)2), 27.1 (μ3 OCH(CH3)2), 27.1 (μ2 OCH(CH3)2
(CdZr)), 26.2 (μ2 OCH(CH3)2 (ZrZr)), 26.7 (terminal OCH-
(CH3)2). 19F NMR (282.4 MHz, toluene-d8, 298 K; δ/ppm):
−110.0 (m, 2F, F-3,5), −154.5 (m, 1F, F-4), −159.7 (m, 2F, F-2,6).
19F NMR spectra in all solvents exhibit the characteristic splitting of a
pentafluorophenyl group (AA′MM′X spin system). 113Cd NMR (66
MHz, toluene-d8, 298 K; δ/ppm): −465. Mp: 158 °C (glass capillary).
Anal. Found (calcd) for C33H63CdF5O9Zr2 (993.69): C, 40.03 (39.89);
H, 6.40 (6.39). EI-MS (20 eV; m/z (%)): 932 (100,
[C6F6CdZr2(OC3H7)7]+), 919 (8, [C6F5CdZr2(OC3H7)8]+), 820 (6,
[Zr3(OC3H7)9]+), 765 (9, [CdZr2(OC3H7)8]+), 650 (7,
[Zr2(OC3H7)8]+), 606 (55, [C6F5CdZr(OC3H7)4]+), 593 (50,
+
[ Z r
O
( O C
H
)
( O C
H
) ]
3
) , 5 6 6 ( 4 ,
3
3
3
7
4
2
4
[Zr3O3(OC3H7)2(OC2H4)3]+), 311 (43, [Zr(OC3H7)3(OC2H4)]+),
168 (10, [C6F5H]+), 45 (10, [OC2H5]+). Sublimation temperature:
140 °C/10−3 mbar.
(Nitrato)cadmium Nonaisopropoxydizirconium, [(ONO2)Cd-
{Zr2(OPri)9}] (5). Educts: [ICd{Zr2(OPri)9}] (0.34 g, 0.35 mmol),
Ag(NO3) (0.06 g, 0.35 mmol). Yield: 0.29 g (0.33 mmol, 92.6%)
Alternative Synthesis of [(F5C6)Cd{Zr2(OPri)9}] (2) through an
Acid−Base Reaction. A toluene (30 mL) solution of [Zr-
(OPri)4(HOPri)]2 (1.0 g, 1.29 mmol) was added to a well-stirred
suspension of Cd(C6F5)2·2EtCN (0.72 g, 1.29 mmol) in toluene.
Stirring was continued overnight at room temperature. The clear
solution obtained was evaporated to dryness in vacuo (1 × 10−3
mbar), giving a pale yellow solid in nearly quantitative yield (96%).
1
crude product (white solid). H NMR (300.1 MHz, benzene-d6, 298
K; δ/ppm): 4.63 and 4.59 (overlapping m, 4H, μ3 OCH(CH3)2 and μ2
OCH(CH3)2 (CdZr)), 4.47 (m, 1H, μ2 OCH(CH3)2 (ZrZr)), 4.43
(m, 4H, terminal OCH(CH3)2), 1.59 and 1.41 (overlapping d, 24H, μ3
OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)), 1.40 (overlapping d, 18H,
1661
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Organometallics
Article
μ2 OCH(CH3)2 (ZrZr) and terminal OCH(CH3)2), 1.34 (d, 12H,
terminal OCH(CH3)2). 13C{1H} NMR (75.5 MHz, benzene-d6, 298
K; δ/ppm): 70.6 (μ3 OCH(CH3)2), 69.8 (μ2 OCH(CH3)2 (CdZr)),
70.5 (μ2 OCH(CH3)2 (ZrZr)), 72.0 (terminal OCH(CH3)2), 27.0 (μ3
OCH(CH3)2) 26.4 (μ2 OCH(CH3)2 (CdZr)), 26.5 (μ2 OCH(CH3)2
(ZrZr)), 26.7 (terminal OCH(CH3)2). 113Cd NMR (66 MHz,
benzene-d6, 298 K; δ/ppm): −658. Anal. Found (calcd) for
C27H63CdNO12Zr2 (888.64): C, 36.79 (36.49); H, 7.70 (7.15); N,
1.47 (1.58). EI-MS (20 eV; m/z (%)): 828 (35, [CdZr2(NO3)-
(OC3H7)8]+), 821 (18, [Zr3(OC3H7)9O]+), 770 (44, [CdZr2(NO3)-
(OC3H7)7]+), 665 (27, [CdZr2O2(OC3H7)5(NO2)]+), 593 (40,
[Zr3O3(OC3H7)4(OC2H4)3]+), 441 (32, [Zr3O5(OC2H4)2]+), 325
(10, [Zr(OC3H7)3(OC3H6)]+), 311 (100, [Zr(OC3H7)3(OC2H4)]+),
267 (13, [Zr(OC3H7)3]+), 253 (8, [Zr(OC3H7)2(OC2H4)]+), 58 (8,
[C2H4N]+), 45 (80, [OC2H5]+). Sublimation temperature: 150 °C/
10−3 mbar.
OCH(CH3)2 (CdZr)), 70.6 (μ2 OCH(CH3)2 (ZrZr)), 72.2 (terminal
OCH(CH3)2), 27.0 (μ3 OCH(CH3)2), 26.4 (μ2 OCH(CH3)2
(CdZr)), 26.5 (μ2 OCH(CH3)2 (ZrZr)), 26.6 (terminal OCH-
(CH3)2). 113Cd NMR (66 MHz, benzene-d6, 298 K; δ/ppm): −688.
Anal. Found (calcd) for C27H63CdClO13Zr2 (926.08): C, 33.21
(35.02); H, 7.02 (6.86). EI-MS (20 eV; m/z (%)): 867 (78,
[CdZr2(ClO4)(OC3H7)8]+), 805 (45, [Zr3O(OC3H7)8(OC2H5)]+),
7 6 7 ( 8 , [ C d Z r 2 ( O C 3 H 7
)
4
]
+ ) , 5 9 3 ( 1 0 0 ,
8
+
[ Z r ( O C ( O C
O
H
)
H
) ]
3
) , 5 6 7 ( 8 ,
3
3
3
7
4
2
[Zr3O3(OC3H7)2(OC2H4)3]+), 475 (13, [(ClO4)CdZr(OC3H7)4]+),
441 (46, [Zr3O5(OC2H4)2]+), 325 (10, [Zr(OC3H7)3(OC3H6)]+), 311
(100, [Zr(OC3H7)3(OC2H4)]+), 267 (11, [Zr(OC3H7)3]+), 253 (9,
[Zr(OC3H7)2(OC2H4)]+), 58 (10, [C2H4N]+), 45 (44, [OC2H5]+).
Bis(trifluoroacetato)cadmium Octaisopropoxy(trifluoroacetato)-
dizirconium, [(μ-O2CCF3)Cd{Zr2(OPri)8(O2CCF3)}]2 (9). Educts: [ICd-
{Zr2(OPri)9}] (0.55 g, 0.58 mmol), Ag(O2CCF3) (0.14 g, 0.58 mmol).
Yield: 0.32 g (0.34 mmol, 59%) crude product (white solid). 1H NMR
(300.1 MHz, benzene-d6, 298 K; δ/ppm): 4.55 (m, 4H, μ3
OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)), 4.44 and 4.34 (over-
lapping m, 5H, μ2 OCH(CH3)2 (ZrZr) and terminal OCH(CH3)2),
1.57 (d, 12H, μ3 OCH(CH3)2), 1.36 (overlapping d, 18H, μ2
OCH(CH3)2 (CdZr) and μ2 OCH(CH3)2 (ZrZr)) 1.28 (dd, 24H,
terminal OCH(CH3)2). 13C{1H} NMR (75.5 MHz, benzene-d6, 298
K; δ/ppm): 166.1 (O2CCF3), 117.4 (O2CCF3), 70.3 (μ3 OCH-
(CH3)2), 70.7 (μ2 OCH(CH3)2 (CdZr)), 70.6 (μ2 OCH(CH3)2
(ZrZr)), 72.2 (terminal OCH(CH3)2), 27.0 (μ3 OCH(CH3)2), 26.4
(μ2 OCH(CH3)2 (CdZr)), 26.5 (μ2 OCH(CH3)2 (ZrZr)), 26.6
(terminal OCH(CH3)2). 113Cd NMR (66 MHz, benzene-d6, 298 K; δ/
ppm): −650. 19F NMR (282.4 MHz, benzene-d6, 298 K; δ/ppm):
−73.3. Anal. Found (calcd; sublimed product) for C29H63CdF3O11Zr2
(939.65): C, 37.15 (37.07); H, 7.49 (6.76). EI-MS (20 eV; m/z (%)):
879 (100, [(O2 CCF3 )CdZr2 (OC3 H7 )8 ]+ ), 821 (100,
(Acetato)cadmium Nonaisopropoxydizirconium, [(CH3CO2)Cd-
{Zr2(OPri)9}] (6). Educts: [ICd{Zr2(OPri)9}] (1.14 g, 1.2 mmol),
AgOCOCH3 (0.2 g, 1.2 mmol). Yield: 1.02 g (1.15 mmol, 97.9%)
1
crude product (white solid). H NMR (300.1 MHz, benzene-d6, 298
K; δ/ppm): 4.72 and 4.70 (overlapping m, 4H, μ3 OCH(CH3)2 and μ2
OCH(CH3)2 (CdZr)), 4.55 (m, 1H, μ2 OCH(CH3)2 (ZrZr)), 4.51
(m, 4H, terminal OCH(CH3)2), 2.25 (s, 3H, O2CCH3), 1.75 and 1.53
(d, 12H, μ3 OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)), 1.48 (d
(overlapping with resonance at 1.53), 6H, μ2 OCH(CH3)2 (ZrZr)),
1.38 (dd, 24H, terminal OCH(CH3)2). 13C{1H}-NMR (75.5 MHz,
benzene-d6, 298 K; δ/ppm): 181.2 (O2CCH3), 70.6 (μ3 OCH(CH3)2),
70.2 (μ2 OCH(CH3)2 (CdZr)), 71.4 (μ2 OCH(CH3)2 (ZrZr)), 71.7
(terminal OCH(CH3)2), 26.4 (μ3 OCH(CH3)2), 27.1 (μ2 OCH-
(CH3)2 (CdZr)), 26.6 (μ2 OCH(CH3)2 (ZrZr)), 26.9 (terminal
OCH(CH3)2), 20.6 (O2CCH3). 113Cd NMR (66 MHz, benzene-d6,
298 K; δ/ppm): −643. Anal. Found (calcd) for C28H66CdO11Zr2
(885.68): C, 39.54 (39.33); H, 7.50 (7.51). EI-MS (20 eV; m/z (%)):
825 and 821 (39, [(O2 CCH3 )CdZr2 (OC3 H7 )8 ]+ and
[Zr3(OC3H7)9O]+), 768 and 767 (58, [(O2CCH3)CdZr2(OC3H7)7]+
and [CdZr2(OC3H7)8]+), 593 (12, [Zr3O3(OC3H7)4(OC2H4)3]+), 499
(11, [(O2CCH3)CdZr(OC3H7)4]+), 440 (38, [Zr3O5(OC2H4)2]+),
311 (41, [Zr(OC3H7)3(OC2H4)]+), 267 (8, [Zr(OC3H7)3]+), 45 (100,
[OC2H5]+). Sublimation temperature: 155 °C/10−3 mbar.
[Zr3(OC3H7)9O]+), 766 (17, [CdZr2(OC3H7)8]+), 593 (37,
+
[ Z r
O
( O C
H
)
( O C
H
) ]
3
) , 5 6 7 ( 9 ,
3
3
3
7
4
2
4
[Zr3O3(OC3H7)2(OC2H4)3]+), 553 (18, [(O2CCF3)CdZr-
(OC3H7)4]+), 440 (52, [Zr3O5(OC2H4)2]+), 325 (12, [Zr-
(OC3H7)3(OC3H6)]+), 311 (46, [Zr(OC3H7)3(OC2H4)]+), 45 (93,
[OC2H5]+). Anal. Found (calcd; crystallized product) for
C28H56CdF6O12Zr2 (993.58): C, 33.81 (33.85); H, 6.98 (5.68); N,
1 . 2 5 ( 0 ) . E I - M S ( 2 0 e V ; m / z ( % ) ) : 9 3 3 ( 2 8 ,
[(CO2CF3)2CdZr2(OC3H7)7]+), 879 (100, [(O2CCF3)-
CdZr2(OC3H7)8]+), 821 (100, [Zr3(OC3H7)9O]+), 766 (17,
[CdZr2(OC3H7)8]+), 593 (37, [Zr3O3(OC3H7)4(OC2H4)3]+), 553
(18, [(O2CCF3)CdZr(OC3H7)4]+), 440 (52, [Zr3O5(OC2H4)2]+), 311
(46, [Zr(OC3H7)3(OC2H4)]+), 58 (9, [C2H4N]+), 45 (93,
[OC2H5]+). Sublimation temperature: 145 °C/10−3 mbar.
Propionitrilo(perchlorato)cadmium Nonaisopropoxydizirconium,
[(O2ClO2)(H5C3N)Cd{Zr2(OPri)9}] (7). Educts: [ICd{Zr2(OPri)9}] (1.53
g, 1.6 mmol), Ag(ClO4) (0.33 g, 1.6 mmol). Yield: 1.38 g (1.41 mmol,
88%) crude product (yellowish solid). 1H NMR (300.1 MHz,
benzene-d6, 298 K; δ/ppm): 4.70 (m, 2H, μ3 OCH(CH3)2), 4.60
(m, 2H, μ2 OCH(CH3)2 (CdZr)), 4.50 (m, 1H, μ2 OCH(CH3)2
(ZrZr)), 4.50 (m, 4H, terminal OCH(CH3)2), 1.60 (d, 12H, μ3
OCH(CH3)2), 1.70 (d, 12H, μ2 OCH(CH3)2 (CdZr)), 1.40
(overlapping d, 30H, μ2 OCH(CH3)2 (ZrZr) and terminal OCH-
(CH3)2). 13C{1H} NMR (75.5 MHz, benzene-d6, 298 K; δ/ppm): 70.0
(μ3 OCH(CH3)2), 70.9 (μ2 OCH(CH3)2 (CdZr)), 70.5 (μ2
OCH(CH3)2 (ZrZr)), 72.0 (terminal OCH(CH3)2), 27.0 (μ3
OCH(CH3)2), 26.3 (μ2 OCH(CH3)2 (CdZr)), 26.6 (μ2 OCH(CH3)2
(ZrZr)), 26.7 and 26.6 (terminal OCH(CH3)2). 113Cd NMR (66
MHz, benzene-d6, 298 K; δ/ppm): −673. Anal. Found (calcd) for
C30H68CdClNO13Zr2 (981.16): C, 35.73 (36.72), H, 7.63 (6.99); N,
1.02 (1.43). EI-MS (20 eV; m/z (%)): 981 (3, [CdZr2(ClO4)-
Bis(pentafluoropropionato)cadmium Octaisopropoxy-
(pentafluoropropionato)dizirconium, [(μ-O2 CC2 F5 )Cd-
{Zr2(OPri)8(O2CC2F5)}]2 (10). Educts: [ICd{Zr2(OPri)9}] (1.781 g,
1.88 mmol), Ag(O2CC2F5) (0.506 g, 1.88 mmol). Yield: 1.01 g (1.02
1
mmol, 54%) crude product (yellowish waxy solid). H NMR (300.1
MHz, benzene-d6, 298 K; δ/ppm): 4.66 and 4.59 (overlapping m, 4H,
μ3 OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)), 4.49 and 4.45
(overlapping m, 5H, μ2 OCH(CH3)2 (ZrZr) and terminal
OCH(CH3)2), 1.64 (d, 12H, μ3 OCH(CH3)2), 1.39 and 1.41
(overlapping d, 18H, μ2 OCH(CH3)2 (CdZr) and μ2 OCH(CH3)2
(ZrZr)), 1.35 (dd, 24H, terminal OCH(CH3)2). 13C{1H} NMR (75.5
MHz, benzene-d6, 298 K; δ/ppm): 181.9 (O2CC2F5), 133.9
(O2CCF2CF3), 123.1 (O2CCF2CF3), 69.8 (μ3 OCH(CH3)2), 70.5
(μ2 OCH(CH3)2 (CdZr)), 70.4 (μ2 OCH(CH3)2 (ZrZr)), 71.8
(terminal OCH(CH3)2), 26.8 (μ3 OCH(CH3)2), 26.4 (μ2 OCH-
(CH3)2 (CdZr)), 26.5 (μ2 OCH(CH3)2 (ZrZr)), 26.6 (terminal
OCH(CH3)2). 19F NMR (282.4 MHz, benzene-d6, 298 K; δ/ppm):
−118.9 (sbr, 2F, O2CCF2CF3), −82.6 (sbr, 3F, O2CCF2CF3). 113Cd
NMR (66 MHz, benzene-d6, 298 K; δ/ppm): −651. Anal. Found
(calcd; sublimed product) for C30H63CdF5O11Zr2 (989.66): C, 36.36
(36.41); H, 7.49 (6.42). Found (calcd; crystallized product) for
C30H56CdF10O12Zr2 (1093.59): C, 34.29 (32.95); H, 4.16 (5.16). EI-
MS (20 eV; m/z (%)):1032 (50, [CdZr2(OC3H7)7(C2F5CO2)2]+),
974 (10, [CdZr2(OC3H7)6(OC2H4)(C2F5CO2)(C2F5)]+), 951 (8,
+
(NC3H7)(OC3H7)9 ] +), 951 (7, [Zr3(OC3H7)11(OCH2)]+), 901 (23,
[Zr4O4(OC3H7)8]+), 861 (6, [Zr3O(OC3H7)9(OC2H5)]+), 801 (17,
[Zr3O(OC3H7)8(OC2H5)]+), 593 (5, [Zr3O3(OC3H7)4(OC2H4)3]+),
58 (37, [C2H4N]+), 45 (100, [OC2H5]+).
Bis(perchlorato)cadmium Nonaisopropoxydizirconium, [(μ-
O2ClO2)Cd{Zr2(OPri)9}]2 (8). Educts: [ICdZr2(OPri)9] (2.00 g, 2.1
mmol), Ag(ClO4) (0.43 g, 2.1 mmol). Yield: 1.61 g (1.74 mmol, 83%)
1
crude product (yellowish solid). H NMR (300.1 MHz, benzene-d6,
298 K; δ/ppm): 4.7 (m, 2H, μ3 OCH(CH3)2), 4.60 (m, 2H, μ2
OCH(CH3)2 (CdZr)), 4.50 (m, 1H, μ2 OCH(CH3)2 (ZrZr)), 4.41
(m, 4H, terminal OCH(CH3)2), 1.60 (d, 12H, μ3 OCH(CH3)2), 1.56
(d, 12H, μ2 OCH(CH3)2 (CdZr)), 1.40 (d, 6H, μ2 OCH(CH3)2
(ZrZr)), 1.32 (d, 24H, terminal OCH(CH3)2). 13C{1H} NMR (75.5
MHz, benzene-d6, 298 K; δ/ppm): 70.3 (μ3 OCH(CH3)2), 70.7 (μ2
1662
dx.doi.org/10.1021/om301053b | Organometallics 2013, 32, 1654−1664

Organometallics
Article
+
[ Z r ( O C
[ C d Z r 2 ( O C 3 H 7
H
)
( O C H ) ] ) ,
9 2 9
( 1 0 0 ,
(39.44); H, 7.31 (7.45); N, 2.16 (1.64). EI-MS (20 eV; m/z (%)): 821
(38, [Zr3(OC3H7)9O]+), 718 (6, [Zr3O2(OC3H7)7]+), 311 (7,
[Zr(OC3H7)3(OC2H4)]+), 58 (16, [C2H4N]+), 45 (100, [OC2H5]+).
Sulfatobis(cadmium nonaisopropoxydizirconium), [(SO4){Cd-
{Zr2(OPri)9}}2] (14). Educts: [ICd{Zr2(OPri)9}] (1.88 g, 2 mmol),
Ag2(SO4) (0.307 g, 1 mmol). Yield: 2.89 g (1.65 mmol, 82.6%) crude
3
3
7
1 1
)
2
8 ( C 2 F 5 C O 2 ) ] + ) , 8 7 1 ( 3 7 ,
[CdZr2(OC3H7)7(C2F5CO2)]+ and [Zr3O(OC3H7)9(OC2H5)]+), 847
(74, [Zr3O(OC3H7)9(OCH3)]+), 821 (24, [Zr3(OC3H7)9O]+), 766
(9, [CdZr2(OC3H7)8]+), 697 (24, [Zr2(OC3H7)6(O2CC2F5)]+), 593
( 6 9 , [ Z r 3 O 3 ( O C 3 H 7 ) 4 ( O C 2 H 4 ) 3 ] + ) , 5 6 7 ( 1 2 ,
[Zr3 O3(OC3 H7 )2 (OC2 H4 )3 ]+ ), 519 (28, ?), 440 (46,
[Zr3O5(OC2H4)2]+), 325 (13, [Zr(OC3H7)3(OC3H6)]+), 311 (38,
[Zr(OC3H7)3(OC2H4)]+), 45 (93, [OC2H5]+). Sublimation temper-
ature: 145 °C/10−3 mbar.
1
product (yellow solid). H NMR (300.1 MHz, benzene-d6, 298 K; δ/
ppm): 4.88 (m, 2H, μ3 OCH(CH3)2), 4.58 and 4.73 (overlapping m,
3H, μ2 OCH(CH3)2 (CdZr) and μ2 OCH(CH3)2 (ZrZr)), 4.49 (m,
4H, terminal OCH(CH3)2), 1.73 and 1.77 (overlapping d, 24H, μ3
OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)), 1.45 (d, 6H, μ2
OCH(CH3)2 (ZrZr)), 1.38 (d, 24H, terminal OCH(CH3)2).
13C{1H} NMR (75.5 MHz, benzene-d6, 298 K; δ/ppm): 70.6 (μ3
OCH(CH3)2), 70.4 (μ2 OCH(CH3)2 (CdZr)), 70.2 (μ2 OCH(CH3)2
(ZrZr)), 71.7 (terminal OCH(CH3)2), 26.4 (μ3 OCH(CH3)2), 27.0
(μ2 OCH(CH3)2 (CdZr)), 26.6 (μ2 OCH(CH3)2 (ZrZr)), 26.8
(terminal OCH(CH3)2). 113Cd NMR (66 MHz, benzene-d6, 298 K; δ/
ppm): −624. Anal. Found (calcd) for C54H126Cd2O22SZr4 (1749.33):
C, 37.2 (37.08); H, 7.7 (7.26); S, 0.8 (1.83). EI-MS (20 eV; m/z (%)):
Bis(cyanato)cadmium Nonaisopropoxydizirconium, [(μ(O,N)-
OCN)Cd{Zr2(OPri)9}]2 (11). Educts [ICd{Zr2(OPri)9}] (1.00 g, 1.05
mmol), Ag(OCN) (0.16 g, 1.05 mmol). Yield: 0.56 g (0.64 mmol,
61.4%) crude product (yellowish solid). 1H NMR (300.1 MHz,
benzene-d6, 298 K; δ/ppm): 4.55 (mbr, 3H, μ3 OCH(CH3)2 and μ2
OCH(CH3)2 (ZrZr)), 4.41 (mbr, 6H, μ2 OCH(CH3)2 (CdZr) and
terminal OCH(CH3)2), 1.55 (dbr, 18H, μ3 OCH(CH3)2 and μ2
OCH(CH3)2 (ZrZr)), 1.32 (dbr, 36H, μ2 OCH(CH3)2 (CdZr) and
terminal OCH(CH3)2). 13C{1H} NMR (75.5 MHz, benzene-d6, 298
K; δ/ppm): 128.0 (CdOCN), 71.0 (μ3 OCH(CH3)2 and μ2
OCH(CH3)2 (CdZr)), 71.8 (μ2 OCH(CH3)2 (ZrZr) and terminal
OCH(CH3)2), 26.5 (μ3 OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)),
26.8 (μ2 OCH(CH3)2 (ZrZr) and terminal OCH(CH3)2). 113Cd NMR
(66 MHz, benzene-d6, 298 K; δ/ppm): −581. Anal. Found (calcd) for
C28H63CdNO10Zr2 (868.65): C, 38.13 (38.72); H, 7.52 (7.31); N, 1.18
(1.61). EI-MS (20 eV; m/z (%)): 821 (8, [Zr3(OC3H7)9]+), 803 (12,
[Zr3O(OC3H7)8(OEt)]+), 766 (9, [CdZr2(OC3H7)8]+), 593 (23,
[Zr3O3(OC3H7)4(OC2H4)3]+), 440 (7, [Zr3O5(OC2H4)2]+), 311
(100, [Zr(OC3H7)3(OC2H4)]+), 267 (13, [Zr(OC3H7)3]+), 253 (11,
[Zr(OC3H7)2(OC2H4)]+), 58 (18, [C2H4N]+), 45 (100, [OC2H5]+).
Bis(trifluoromethanesulfonato)cadmium Nonaisopropoxydizir-
conium, [(μ-O2SOCF3)Cd{Zr2(OPri)9}]2 (12). Educts: [ICd-
{Zr2(OPri)9}] (0.51 g, 0.53 mmol), Ag(SO3CF3) (0.14 g, 0.53
mmol). Yield: 0.49 g (0.5 mmol, 94%) crude product (white solid). 1H
NMR (300.1 MHz, benzene-d6, 298 K; δ/ppm): 4.67 and 4.57
(overlapping m, 4H, μ3 OCH(CH3)2 and μ2 OCH(CH3)2 (CdZr)),
4.45 (m, 1H, μ2 OCH(CH3)2 (ZrZr)), 4.42 (m, 4H, terminal
OCH(CH3)2), 1.67 (d, 12H, μ3 OCH(CH3)2), 1.52 (d, 12H, μ2
OCH(CH3)2 (CdZr)), 1.36 (d, 6H, μ2 OCH(CH3)2 (ZrZr)), 1.30 (d,
24H, terminal OCH(CH3)2). 13C{1H} NMR (75.5 MHz, benzene-d6,
298 K; δ/ppm): 120.5 (SO3CF3), 70.1 (μ3 OCH(CH3)2), 71.2 (μ2
OCH(CH3)2 (CdZr)), 70.6 (μ2 OCH(CH3)2 (ZrZr)), 72.1 (terminal
OCH(CH3)2), 26.6 (μ3 OCH(CH3)2), 27.6 (μ2 OCH(CH3)2
(CdZr)), 26.9 (μ2 OCH(CH3)2 (ZrZr)), 27.0 (terminal OCH-
(CH3)2). 19F NMR (282.4 MHz, benzene-d6, 298 K; δ/ppm):
−77.1. 113Cd NMR (66 MHz, benzene-d6, 298 K; δ/ppm): −693.
Anal. Found (calcd) for C28H63CdF3O12SZr2 (975.7): C, 33.93
(34.47); H, 6.85 (6.51); S, 3.64 (3.29). EI-MS (20 eV; m/z (%)):
915 (42, [SO3CF3CdZr2(OC3H7)7]+), 857 (10, [Zr3(OC3H7)9O-
821 (88, [Zr3(OC3H7)9O]+), 719 (8, [Zr3O2(OC3H7)7]+), 593 (9,
+
[ Z r
O
( O C
H
)
( O C
H
) ]
3
) , 5 6 7 ( 8 ,
3
3
3
7
4
2
4
[Zr3O3(OC3H7)2(OC2H4)3]+), 311 (7, [Zr(OC3H7)3(OC2H4)]+), 58
(32, [C2H4N]+), 45 (100, [OC2H5]+).
ASSOCIATED CONTENT
* Supporting Information
■
S
Text, figures, tables, and CIF files giving X-ray crystallographic
data and additional analytical data (1H NMR spectra, DTA
curves and molecular structures) of all compounds. This
material is available free of charge via the Internet at http://
pubs.acs.org.
AUTHOR INFORMATION
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
■
We are thankful to the University of Cologne for financial
support. We also acknowledge the support of Ms. Silke Kremer
(Elemental Analysis), Daniela Naumann (NMR), and Astrid
Baum (MS). We are thankful to Dr. Stefan Stucky and Dr. Ingo
Pantenburg for valuable discussions and their help in the single-
crystal diffraction analyses.
REFERENCES
■
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1
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