Fluorinated bismuth alkoxides: From monomers to polymers and oxo-clusters

Article abstract of DOI:10.1039/b715623e

A series of new bismuth fluoroalkoxide compounds have been prepared through the treatment of 1,1,1,3,3,3-hexafluoro-2-propanol with BiAr₃ (where Ar = Ph, p-Tol). Reactions were conducted without the use of any additional solvent and the reaction products distilled or extracted with non-polar or polar Lewis base solvents. Structural analyses reveal that under variable reaction conditions the interaction of BiAr₃ with (CF₃) ₂CHOH can give a mixture of bismuth complexes with varying degrees of substitution, cluster formation and aggregation. Compounds [Bi(OCH(CF ₃)₂)₃(pyr)₂] (2) (pyr = pyridine), [Bi(OCH(CF₃)₂)₃(thf)₃] (3) (thf = tetrahydrofuran), [Bi₂(OCH(CF₃)₂) ₃(dabco)₃] (4) (dabco = 1,4-diazabicyclo[2.2.2]octane), [PhBi(OCH(CF₃)₂)₂]_n (5), [Bi ₂O(OCH(CF₃)₂)₄(C₇H ₈)]₂ (6) (C₇H₈ = toluene), [Bi ₉O₇(OCH(CF₃)₂)₁₃] (7), [Bi₂O(OCH(CF₃)₂)₄(Et ₂O)]₂ (8), [Bi₂O(OCH(CF₃) ₂)₄(thf)]₂ (9) and [Bi₂O(OCH(CF ₃)₂)₄(tmeda)₂] (10) (tmeda = N,N,N′,N′-tetramethylethylenediamine) have been fully characterised including by single crystal X-ray diffraction. The Royal Society of Chemistry.

Full text of DOI:10.1039/b715623e

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www.rsc.org/dalton | Dalton Transactions
Fluorinated bismuth alkoxides: from monomers to polymers and oxo-clusters†
Philip C. Andrews,* Peter C. Junk, Iryna Nuzhnaya and Leone Spiccia
Received 10th October 2007, Accepted 25th February 2008
First published as an Advance Article on the web 26th March 2008
DOI: 10.1039/b715623e
A series of new bismuth fluoroalkoxide compounds have been prepared through the treatment of
1,1,1,3,3,3-hexafluoro-2-propanol with BiAr3 (where Ar = Ph, p-Tol). Reactions were conducted
without the use of any additional solvent and the reaction products distilled or extracted with non-polar
or polar Lewis base solvents. Structural analyses reveal that under variable reaction conditions the
interaction of BiAr3 with (CF3)2CHOH can give a mixture of bismuth complexes with varying degrees
of substitution, cluster formation and aggregation. Compounds [Bi(OCH(CF3)2)3(pyr)2] (2) (pyr =
pyridine), [Bi(OCH(CF3)2)3(thf)3] (3) (thf = tetrahydrofuran), [Bi2(OCH(CF3)2)3(dabco)3] (4) (dabco =
1,4-diazabicyclo[2.2.2]octane), [PhBi(OCH(CF3)2)2]n (5), [Bi2O(OCH(CF3)2)4(C7H8)]2 (6) (C7H8 =
toluene), [Bi9O7(OCH(CF3)2)13] (7), [Bi2O(OCH(CF3)2)4(Et2O)]2 (8), [Bi2O(OCH(CF3)2)4(thf)]2 (9) and
[Bi2O(OCH(CF3)2)4(tmeda)2] (10) (tmeda = N,N,Nꢀ,Nꢀ-tetramethylethylenediamine) have been fully
characterised including by single crystal X-ray diffraction.
stabilities, solubilities and volatilities.20,21 Whitmire and co-workers
Introduction
has shown that oxo-cluster formation is prevalent in bismuth
phenolate chemistry, e.g. [Bi9O7(OC6F5)13],7 while Mehring and co-
Metal–organic and organometallic bismuth compounds are well
known for undergoing facile hydrolysis and/or oxidation, often
workers have proposed some basic principles which describe the
forming cluster compounds containing ligand encapsulated BixOy
growth pattern of metal–organic bismuth oxo-clusters of varying
cores. The various processes by which this can occur results in
nuclearity from their detailed structural study of bismuth siloxides,
e.g. [Bi22O26(OSiMe2 Bu)14].2 The main challenge, however, remains
t
many bismuth compounds being highly insoluble and poorly
characterised. Recently, though, the synthesis and structural
the ability to control hydrolysis rates and cluster size.
characterisation of these oxo-clusters has attracted significant
The approach we have adopted is to utilise the hydrophobic na-
attention since they constitute a class of compound with pre-
ture of fluoro groups in attempting to control the hydrolysis of bis-
formed Bi–O bonds which are highly sought after as precursors
muth alkoxides and thereby engineer smaller, more hydrolytically-
to materials containing defined phases of Bi2O3.1–10 Bismuth oxide
stable, oxo-clusters than those observed for ethoxide or the
has a number of important properties, such as its refractive index,
siloxides. In addition, fluorinated compounds have the potential to
dielectric permittivity, large energy band gap, and photocon-
ductivity, that make it attractive in a variety of applications;11
act as single source precursors for the deposition of fluorine-doped
oxide films, e.g. high quality F–SnO2 films have recently been
obtained from organotin fluorocarboxylates,22 and this provides
an additional impetus for our current study. Whitmire and co-
workers have previously described the structure of the thf-solvated
planar dimer [Bi(OCH(CF3)2)2(l-OCH(CF3)2)(thf)]2 synthesised
from the metathesis reaction of BiCl3 and NaOCH(CF3)2 in thf.23
It was reported that attempts to form the alkoxide from BiPh3
in refluxing toluene were unsuccessful. Since there are definite
synthetic advantages in using BiAr3 as an organometallic synthon,
such as air/moisture stability and low toxicity,17 we have re-
examined the reaction with (CF3)2CHOH focusing primarily on
a ‘solvent-free’ approach which has recently proved successful in
the synthesis of bismuth carboxylates.24,25 In addition, we have
compared this method with the use of a non-polar solvent medium
and the addition of coordinating Lewis base solvents.
for example, in the formulation of composite oxides for fer-
roelectric films, high Tc superconductors Bi2Sr2CaCu2O8,12,13 in
electrolytes with high ionic conductivity and in cost minimisation
in the production of solid oxide fuel cells (SOFCs).14,15 Due
to the high refractive index of 2.4 and an ability to form
colourless coatings, it is also useful for infrared reflective coat-
ings on glass.16 As precursors to both the oxide and to oxo-
clusters, bismuth alkoxides are excellent candidates. However,
although general preparative routes have been described in the
literature,17 there are only rare examples where they have been fully
structurally-characterised; e.g. bismuth subethoxide is a large oxo-
cluster, [Bi8(OEt)24(EtOH)]·(EtOH),18 while [Bi(Ph3CO)3(thf)]19
and [Bi(OCHMe2CH2OMe)3]20 are mononuclear. The ability of
the bismuth(III) cation to achieve high coordination numbers
means attempts to synthesise simple mononuclear bismuth alkox-
i
ides, such as Bi(OR)3 (R = Me, Et, Pr), leads invariably to
the formation of polymeric complexes which display limited
Results and discussion
The various outcomes from treating 1,1,1,3,3,3-hexafluoro-2-
propanol (pKa = 9.3) with BiAr3 in the absence of a solvent,
with a non-polar solvent medium, and in the presence of polar
Lewis base solvents are summarised in Schemes 1, 2 and 3. These
show the reproducible formation of fluorinated bismuth alkoxides
School of Chemistry, Monash University, Clayton, Melbourne, Vic 3800,
Australia. E-mail: phil.andrews@sci.monash.edu.au; Fax: +61 (0)3)
9905 4597; Tel: +61 (0)3 9905 5509
† CCDC reference numbers 637419–663327. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/b715623e
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Scheme 1 Synthesis of compounds 1–4.
Scheme 2 Synthesis of compounds 5–7.
Scheme 3 Synthesis of compounds 5, 6, 8–10.
and oxo-alkoxides displaying varying degrees of complexation,
substitution and hydrolysis.
was then used as the precursor for further complexes containing
solvated Lewis donor molecules. Dissolution of 1 into pyridine and
thf produced crystalline 2 and 3, respectively, and the addition of a
slight stoichiometric excess of dabco (i.e. 2.5 : 1) resulted in crystals
of 4.
NMR studies on the product from the analogous reaction
with BiPh3 showed it to be a mixture of 1 and an additional
compound containing a residual Ph group. This was identified
by lowering the reaction temperature to 90 ◦C, resulting in the
isolation of the bis-substitution complex, [PhBi(OCH(CF3)2)2]n, 5,
as the main product. The difficulty in removing the third Ph group,
in comparison with p-Tol, is perhaps not surprising given previous
Both BiPh3 and Bi(p-Tol)3 were used as the organometallic syn-
thon in the synthetic procedures, producing, in some cases, slightly
different outcomes. Unsolvated bismuth hexafluoroisopropoxide 1
was synthesised under solvent free conditions from Bi(p-Tol)3 and
a slight excess of pre-dried (CF3)2CHOH after heating together
under a N2 atmosphere at 120 ◦C overnight. Removal of all
the volatile compounds in vacuo left only a thick, oily residue
which could be distilled under high vacuum to give a colourless
crystalline solid, identified as compound 1, in a yield of 64%. The
crystalline solid has a melting point of 50–52 ◦C. This compound
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reports indicating that activated phenyl rings are known to
undergo electrophilic protolysis more easily than those which
are not.26 In addition, DSC and TGA measurements in previous
studies on the solvent free formation of bismuth carboxylates has
shown that the third Ph group is cleaved at temperatures well above
that required for the first two.24,25
solution to slowly evaporate in air over a period of two weeks,
producing a large crop of colourless crystals. Independent unit cell
measurements on ten randomly selected crystals identified them
all as the Bi9 oxo-cluster 7. No other Bi containing compounds
or clusters were found, and the homogeneity of the sample was
supported by elemental analysis. This, we believe, provides a
reproducible method for the synthesis of well defined bismuth
oxo-clusters of a regular composition and size.
The prominence of oxo-species in reactions conducted under
reflux highlight the sensitivity of the bismuth alkoxides to hydrol-
ysis and indicate that a high temperature solvent free approach is
preferable in minimising contact with adventitious moisture.
On isolation, with the notable exception of 7, the crystalline
materials remain slightly air and moisture sensitive, and undergo
further slow decomposition into insoluble white powders of
varying composition. Loss of solvent for compounds 3, 6, 8 and 9
manifests itself in changes to their solubility. Compounds 5, 6, 7,
8 and 9 are not soluble in toluene after high vacuum drying, but
are soluble in thf and dmso.
An important observation at this point is that the reaction
stoichiometry is also crucial. The volatility of the alcohol dictates
that strict stoichiometric reactions of 3 : 1 alcohol–BiAr3 require
a closed system for solvent free reactions. However, although suc-
cessful, these have an associated risk of explosion. In attempting
to avoid this we have found that the most desirable approach
is to use an excess of alcohol under reflux and N2 with the
reaction mixture heated ◦(to ca. 120 ◦C) well above the boiling
point of the alcohol (59 C). Under these conditions the molten
and solubilised BiAr3 remains constantly in contact with hot
alcohol, which acts both as a reactant and a constantly renewing
solvent medium. This bypasses recognised problems of solvent
free reactions of heat dissipation and low molecular transport.
As such, the term solvent-free as perhaps generally understood is
not strictly applicable here but is interpreted as being conducted
without the use of an additional third party solvent medium.
When these conditions are taken into consideration the best
procedure for the synthesis of the volatile unsolvated compound
1 in high yield and purity is using Bi(p-Tol)3 with an excess of
pre-dried alcohol (5 equiv.) under reflux and N2 at 120 ◦C.
The direct reaction of BiPh3 with 4 equiv. of (CF3)2CHOH,
in which the alcohol was not pre-dried, led to the formation
and isolation by toluene extraction of the dinuclear oxo species
[Bi2O(OCH(CF3)2)4(C7H8)]2, 6, as the major product. In addition,
the oxo-cluster [Bi9O7(OCH(CF3)2)13], 7, was also obtained but in
low yield strongly suggesting that the solutions are mixtures and
that differing stages of decomposition occur simultaneously giving
varying degrees of complex nuclearity.
It is possible for cluster formation to occur by three processes:
simple hydrolytic cleavage of the Bi–OR bond, thermally pro-
moted ether elimination, and protolysis of a residual activated Bi–
C bond. It would appear that under entirely anhydrous conditions
(90 ◦C solvent free and toluene reflux) that the main isolable
product in the reaction of (CF3)2CHOH with BiAr3 is the di-
substituted polymer 5. The dimer 6, therefore, most likely arises
due to partial hydrolysis of this polymer and suggests the favoured
formation pathway is via Bi–C cleavage, as has been previously
reported for bis-substituted bismuth carboxylates.27 When the
analogous reaction was conducted with dried alcohol, but this
time in a strict stoichiometric 3 : 1 ratio under reflux in dried
toluene, the only compounds obtained were 5 as the main product
and 6 as the minor, suggesting that 7 could possibly be the
stable end product of hydrolysis. When the analogous reaction
was conducted with an excess of pre-dried (CF3)2CHOH the only
complex isolated after removal of all volatiles and extraction into
toluene was compound 6. Alternatively, extraction with diethyl
ether or with thf led to crystallisation of the analogous complexes
[Bi2O(OCH(CF3)2)4(Et2O)]2, 8, and [Bi2O(OCH(CF3)2)4(thf)]2, 9,
respectively. The subsequent addition of 2 equiv. of the bidentate
N donor tmeda to 6 led to the formation and isolation of crystals
of 10, [Bi2O(OCH(CF3)2)4(tmeda)2].
Reaction products were analysed through single crystal X-ray
diffraction studies, 1H, 13C and 19F NMR spectroscopy, elemental
analyses and mass spectrometry. The sensitivity of the compounds
towards hydrolysis made obtaining accurate and reproducible
elemental analysis data for some of the compounds difficult and
also meant that mass spectrometry tended to provide data on only
oxidised forms of the compounds.
Since the complexes are poorly soluble in non-polar solvents
NMR studies were conducted in d8-thf, for complexes 2–6, and
in d6-dmso for complexes 3, 7–10. A variable temperature study
recording both the 1H and 19F resonances in the range 30 to
−80 ◦C, was undertaken on the unsolvated compound 1 in d8-
1
toluene. For the H NMR spectrum the coalescence of the well
defined septet for CH was observed on lowering the temperature,
resul◦ting in the detection of a single broad main resonance at
−80 C. Similar results were observed for the 19F NMR spectrum,
where the initial doublet coalesces to a singlet at −80 ◦C. In
comparison to the free alcohol all the complexes display a shift
to higher frequency for the propyl H on formation of the bismuth
alkoxide. In d8-toluene the CH proton in the unsolvated compound
1 appears as a single well defined septet resonating at d 5.35 (cf.
free alcohol at 3.31), and is observed at higher frequency, d 5.53,
in d8-thf, which not unexpectedly corresponds to that observed for
the thf solvate, 3, in the same solvent. Spectra of the analogous
complexes with pyridine, 2, and dabco, 4, in d8-thf also show
similar signals at d 5.64 and 5.54, respectively. The 19F NMR
spectra show the expected doublet for 1 in d8-toluene at d −76.0
and for 3 in d8-thf at d −75.4, however, in d8-thf both 4 and
2 give singlets at d −75.4 and −73.5, respectively, suggesting a
higher degree of fluxionality in solution. This ligand fluxionality
at ambient temperature is also evident in the spectra of the unusual
asymmetric complexes 6, 8 and 9, and 10. In the solid state these
four complexes have both bridging and terminal alkoxides as well
as two different coordination environments for each of the Bi
centres, however, only one resonance is observed for each complex
in the 1H and 19F spectra.
The low relative Lewis acidity of the bismuth centre means that
donor ligands tend to be only weakly bound in the complexes,
particularly the O based donors, and this is reflected in the ease
with which these ligands can be lost on drying. As a result, good
That the cluster 7 is indeed the likely end point of hydrolysis
was confirmed by solubilizing 6 in toluene and allowing the
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elemental (C, H, N) analyses were only obtained on isolated
crystalline samples of those compounds which have no donor
ligands or contain only the more strongly bonded N based ligands,
namely 1, 2, 5, 7 and 10. Complexes 3, 4 and 6 gave slightly less
accurate results, while repeated attempts with 8 and 9 did not give
satisfactory analyses.
The melting points of compounds 1, 2, and 5 are sharp and
relatively low indicating their potential for use as precursors in
CVD processes. In contrast, the oxo-cluster 7 and oxo-dimers
6, 8, 9 only display evidence of decomposition to grey solids.
◦
Compound 1 has melting point of 50–52 C and can be purified
by distillation (118 ◦C at 0.5 mm Hg). Compound 3 melts between
57–59 ◦C while the disubstituted polymer 5 is slightly higher at 95–
97 ◦C. For compound 7 decomposition occurs above 250 ◦C, while
for oxo-dimers it is varies in region from 150 to 200 ◦C. Crystals
of compounds 4 and 10 display broad melting ranges, 131–135
and 70–75 ◦C, respectively, perhaps indicating some compositional
change in the compounds at these temperatures.
Solid state structures
Fig. 2 Molecular structure of the monomer◦ [Bi(OCH(CF3)2)3(thf)3],
Details of the crystallographic data for compounds 2–10 are given
in the Experimental section.
˚
3. Selected bond lengths (A) and angles ( ): Bi(1)–O(1) 2.155(3),
Bi(1)–O(2) 2.118(3), Bi(1)–O(3) 2.116(4), Bi(1)–O(4) 2.588(4),
Bi(1)–O(5) 2.760(4), Bi(1)–O(6) 2.708(4); O(3)–Bi(1)–O(2) 92.03(14),
O(3)–Bi(1)–O(1) 88.91(14), O(2)–Bi(1)–O(1) 90.01(14), O(2)–Bi(1)–O(4)
96.55(14), O(1)–Bi(1)–O(4) 161.51(13), O(3)–Bi(1)–O(6) 153.02(13),
O(4)–Bi(1)–O(6) 83.68(12), O(2)–Bi(1)–O(5) 161.72(14), O(5)–Bi(1)–O(1)
89.00(14), O(6)–Bi(1)–O(5) 87.89(13), O(3)–Bi(1)–O(4) 73.64(12).
Compound 2, [Bi(OCH(CF3)2)3(pyr)2], crystallises as
a
mononuclear species in the trigonal space group P32 with one
whole molecule comprising the asymmetric unit, shown in Fig. 1.
The environment around the bismuth atom is a square pyramid
with two N-bound pyridine molecules and two fluoroalkoxide
ligands comprising the basal plane with bond distances of Bi(1)–
˚
˚
O(1) 2.184(3) A, Bi(1)–O(3) of 2.135(3) A and Bi(1)–N(1) of
Compound 3, [Bi(OCH(CF3)2)3(thf)3], crystallises as a mononu-
clear species in the monoclinic space group P21/c with one
molecule comprising the asymmetric unit, shown in Fig. 2. In
contrast to 2, Bi(1) is six-coordinate with three fluoroalkox-
ide ligands and three thf molecules residing in an octahedral
arrangement about Bi. The thf and fluoroalkoxide ligands are
bound in meridional positions relative to each other. The Bi–
˚
˚
2.734(4) A, Bi(1)–N(2) 2.520(4) A. The remaining fluoroalkoxy
ligand resides in the apical position with a shorter Bi–O(2) bond
distance of 2.097(3) A. The closest contact to the Bi that resides
in the basal plane is a fluorine atom which lies at a distance of
3.260 A which quite plausibly is a weak contact.
˚
˚
˚
Oalk distances average 2.13 A while the Bi–Othf distances are
˚
significantly longer, averaging 2.68 A. The bond angles for all
O–Bi–O are in the range 161.72(14)–73.64(12)◦. Specifically, the
Oalk–Bi1–Oalk range 88.91(14)◦–92.03(14)◦, while the Othf–Bi1–
Othf range from 83.68(12)◦–90.05(14)◦. The trans Oalk–Bi1–Othf
constitute the very obtuse angles. The Bi–Oalk bond lengths
for monomeric compounds 2 and 3 are longer than previously
˚
reported for other monomers [Bi(OC6H3Me2-2,6)3] 2.091(5) A (av.)
and for [Bi(OSiPh3)3(thf)3] 2.04(1) A.28 The related dimeric species
˚
[Bi(OCH(CF3)2)2(l-OCH(CF3)2)(thf)2]2 has only one thf ligand
coordinated to each five coordinate Bi centre, with two bridging
alkoxide ligands.23 This dimer most likely forms to compensate the
low bismuth coordination environment. Bi–Oalk bond distances in
the dimer are comparable with those found in 3 (Bi–Oalk av. 2.12
˚
A), while not surprisingly the Bi–Othf bond distance is slightly
˚
shorter at 2.575(8) A.
Compound 4, [Bi2(OCH(CF3)2)6(dabco)3], crystallises as a
dinuclear complex in the monoclinic space group P21/c with
two Bi(OCH(CF3)2)3 units bridged by an N,Nꢀ-bound dabco
comprising the asymmetric unit. The structure is shown in Fig. 3.
Each bismuth atom is five coordinate with an alkoxy ligand
in the apical position and two alkoxide ligands and two dabco
Fig. 1 Molecular structure of the monomer [Bi(OCH(CF3)2)3(pyr)2], 2.
Selected angles (◦): O(2)–Bi(1)–N(2) 77.99(13), O(2)–Bi(1)–N(1) 77.08(13),
O(2)–Bi(1)–O(1) 88.50(12), O(2)–Bi(1)–O(3) 88.69(14), N(2)–Bi(1)–N(1)
88.26(13), O(3)–Bi(1)–O(1) 82.60(12), O(3)–Bi(1)–N(2) 81.15(13),
O(1)–Bi(1)–N(1) 104.42(13).
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˚
˚
Bi atoms, with Bi(1)–N(1) 2.580(8) A and Bi(2)–N(6) 2.851(8) A.
Interestingly, the shorter bridging Bi–N distances are associated
with longer Bi–Nterminal distances, and vice versa.
Compounds 6, [Bi2(l3-O)(OCH(CF3)2)2(l-OCH(CF3)2)2(C7H8)]2,
8, [Bi2(l3-O)(OCH(CF3)2)2(l-OCH(CF3)2)2(Et2O)]2, and 9,
[Bi2(l3-O)(OCH(CF3)2)2(l-OCH(CF3)2)2(thf)]2, crystallise as
dimeric tetranuclear species (Fig. 4, 5 and 6, respectively) in
the monoclinic space group P21/n for compound 6 and triclinic
space group P-1 for compounds 8 and 9. In compound 6, Bi(1) is
five-coordinate with one terminal alkoxy ligand, two l2-alkoxo
ligands and two l3-oxo ligands in its highly distorted coordination
environment. Bi(2) is formally only four coordinate, with one
terminal alkoxy ligand and being bound by two other alkoxy
ligands that bridge to Bi(1) and its symmetry generated partner
and one l3-oxo ligand that bridges to Bi(1) and its symmetry
generated partner. However, Bi(2) also interacts with a toluene
molecule that terminates polymerisation of the species in a
more tightly bound fashion than the Bi–arene interactions in
compound 5. The Bi · · · C distances in compound 6 indicate the
Fig. 3 Molecular structure of the dimer [Bi2(OCH(CF3)2)6(dabco)3], 4.
◦
˚
Selected bond lengths (A) and angles ( ): Bi(1)–O(1) 2.196(6), Bi(1)–O(2)
2.089(6), Bi(1)–O(3) 2.131(6), Bi(2)–O(4) 2.189(6), Bi(2)–O(5) 2.074(6),
Bi(2)–O(6) 2.139(7); N(3)–Bi(2)–N(6) 98.9(2), N(3)–Bi(2)–O(6) 75.1(2),
N(3)–Bi(2)–O(4) 155.8(2), N(3)–Bi(2)–O(5) 84.0(2), N(4)–Bi(1)–N(1)
100.5(2), N(4)–Bi(1)–O(2) 76.5(2), N(4)–Bi(1)–O(3) 165.8(2), N(4)–
Bi(1)–O(1) 101.1(2).
2
toluene is bound in an g -arene fashion (Bi(2)–C(17,18), 3.481,
˚
3.555 A) which is reminiscent of the distances in Davidson’s
6
˚
g -C7H8 complex (Bi–C distances average 3.542 A) where the
ligands forming a close to planar basal plane. All of the Bi–Oalk
toluene presumably resides at the optimal distance from Bi.29
˚
bond lengths are in the range 2.196(6)–2.074(6) A. In contrast,
The interaction between Bi and the toluene molecule could
be realistically considered to be an g -arene interaction if the
the Bi–Ndabco bond distances are highly asymmetrical and show
4
˚
a difference from shortest to longest of 0.41 A. The bridging
distances quoted by Deacon et al. are taken into consideration
dabco ligand is not symmetrically bound to both Bi atoms (Bi(1)–
(Bi–C 3.721, 3.898 A).30 In contrast, there is a significant difference
˚
˚
˚
N(4) 2.988(8) A and Bi(2)–N(3) 2.628(8) A). Also, the terminally
bound dabco ligands are not equally bound to their respective
in the centroid distance for Bi to the toluene ring in compound 6,
˚
Fig. 4 Molecular structure of the oxo-bridged dimer [Bi2(l3-O)(OCH(CF3)2)2(l-OCH(CF3)2)2(C7H8)]2, 6. Selected bond lengths (A) and angles
(◦): Bi(1)–O(1) 2.080(4), Bi(1)–O(5) 2.159(4), Bi(1)–O(2) 2.528(5), Bi(2)–O(2) 2.342(4), Bi(2)–O(3) 2.060(4), Bi(2)–O(4) 2.263(5), Bi(2)–O(5)
2.095(4); O(5)–Bi(1)–O(2) 134.38(14), O(2)–Bi(2)–O(5) 69.54(16), Bi(1)–O(2)–Bi(2) 101.06(17), Bi(1)–O(5)–Bi(2) 124.3(2), O(1)–Bi(1)–O(5) 91.14(16),
O(3)–Bi(2)–O(5) 94.83(17), O(3)–Bi(2)–O(4) 92.66(17). Symmetry operations: ‘x, y, z’; ‘−x + 1/2, y + 1/2, −z + 1/2ꢀ; ‘−x, −y, −z’; ‘x − 1/2, −y − 1/2,
z − 1/2ꢀ.
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◦
˚
Fig. 5 Molecular structure of the oxo-bridged dimer [Bi2(l3-O)(OCH(CF3)2)2(l-OCH(CF3)2)2(Et2O)]2, 8. Selected bond lengths (A) and angles ( ):
Bi(2)–O(6) 2.084(4), Bi(2)–O(4) 2.456(5), Bi(2)–O(5) 2.138(4), Bi(1)–O(4) 2.438(4), Bi(1)–O(5) 2.115(4), Bi(1)–O(3) 2.072(5), Bi(1)–O(1) 2.738(5),
Bi(1)–O(2) 2.218(4); O(6)–Bi(2)–O(4) 86.85(17), O(5)–Bi(2)–O(4) 68.00(16), O(4)–Bi(1)–O(5) 68.69(16), O(3)–Bi(1)–O(4) 86.48(17), O(3)–Bi(1)–O(2)
94.34(18), O(1)–Bi(1)–O(3) 80.57(18), Bi(2)–O(4)–Bi(1) 99.71(17), Bi(2)–O(5)–Bi(1) 123.2(2). Symmetry operations: ‘x, y, z’; ‘−x, −y, −z’.
◦
˚
Fig. 6 Molecular structure of the oxo-bridged dimer [Bi2(l3-O)(OCH(CF3)2)2(l-OCH(CF3)2)2(thf)]2, 9. Selected bond lengths (A) and angles ( ):
Bi(1)–O(1) 2.082(6), Bi(1)–O(2) 2.133(6), Bi(1)–O(3) 2.439(7), Bi(2)–O(3) 2.465(6), Bi(2)–O(2) 2.110(7), Bi(2)–O(4) 2.219(7), Bi(2)–O(5) 2.073(6),
Bi(2)–O(6) 2.672(7); Bi(2)–O(3)–Bi(1) 99.0(2), Bi(2)–O(2)–Bi(1) 123.1(3), O(3)–Bi(1)–O(2) 68.7(2), O(3)–Bi(2)–O(2) 68.5(2), O(1)–Bi(1)–O(2) 92.4(3),
O(5)–Bi(2)–O(2) 94.1(3), O(4)–Bi(2)–O(2) 71.1(2), O(6)–Bi(2)–O(5) 82.8(2), O(6)–Bi(2)–O(3) 136.3(2), O(6)–Bi(2)–O(4) 83.3(2). Symmetry operations:
‘x, y, z’; ‘−x, −y, −z’.
2562 | Dalton Trans., 2008, 2557–2568
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◦
˚
˚
3.566 A, and in similar interactions in other related complexes,
Bi–Obr 2.077 A and an angle for Bi(1)–O(3)–Bi(2) of 110.3(3) .
Each bismuth centre is five coordinate and has two fluoroalkoxide
˚
˚
2.96(4) A in [{Bi(OC6F5)3(C7H8)}2]·2(C7H8) and 3.073 A in
[Bi4(l4-O)(l-OC6F5)6{l3-OBi(l-OC6F5)3}2(C7H8)]·3(C7H8).7,23
The overall tetranuclear cluster is relatively planar with 10
atoms residing in a raft with four alkoxy groups equatorially
displaced from the plane and two directed above and two
below the plane; maximum deviation from the least squares
plane defined by Bi(1), Bi(2), O(2), O(4) and O(5) and their
˚
ligands with a Bi–O bonding range of 2.146(7)–2.300(7) A, and an
asymmetrically bonding tmeda molecule with one short and one
long interaction, for Bi(1) Bi(1)–N(2) 2.532(8) A and Bi(1)–N(1)
2.991 A, respectively, and for Bi(2) Bi(2)–N(4) 2.542(8) A and
˚
˚
˚
˚
Bi(2)–N(3) 2.982 A, respectively. The coordination environment
around both bismuth atoms is a distorted square based pyramid.
Compound 5, [PhBi(OCH(CF3)2)2(l-OCH(CF3)2)]n, crystallises
in the monoclinic space group P21/n. It is polymeric with four-
coordinate bismuth centres bound by a phenyl group and three
alkoxy groups. Two of the alkoxy groups span successive bismuth
atoms generating the linear chain polymer (Fig. 8) while the third
is a terminally bound ligand. The environment about the bismuth
atom is highly distorted and resembles an equatorial deficient
trigonal bipyramid and the polymer is reminiscent of an alternately
staggered infinite saw-horse structure. The Oaxial–Bi–Oaxial angle
is 169.9◦ (av.), the Bi(1)–O(2)–Bi(2) angle is 113.71(19)◦ and the
Cphenyl–Bi–Oequatorial angle is 86.0◦ (av.). The Oaxial–Bi–Oequatorial (range
80.02(17) to 91.95(18)◦) and Oaxial–Bi–Cphenyl (range 83.0(2) to
94.8(2)◦) angles are close to perpendicular. The low-coordinate
˚
symmetry (1 − x, 2 − y, 2 − z) partners is 0.116(2) A. An
analogous Bi4O6 structural motif has also been observed as part
of larger bismuth oxo frameworks; in the phosphonate cluster,
[Bi14O10(tBuPO3)10(tBuPO3H)2]·3(C6H6)·4(H2O),5 in the calixarene
complex, Bi8O4(tBuC8)2 (tBuC8 = p-tert-butylcalix[8]arene),10 and
in [Bi9(l-O)8(l-OH)6](ClO4)5 and its alcoholysis product [Bi9(l-
O)8(l-OEt)6(EtOH)](ClO4)5·4(EtOH).3 Compounds 8 and 9 have
similar tetranuclear structural motifs to compound 6, except Et2O
˚
replaces the arene bound toluene molecule in 8 (Bi–O, 2.711 A
(av.)) while in 9 the coordinating solvent is thf with a Bi–O distance
of 2.685 A (av.). For compounds 6, 8 and 9 the average Bi(1)–Bi(2)
distance is 3.746 (A).
Compound 10, [Bi2(l-O)(OCH(CF3)2)4(tmeda)2], crystallises as
an oxo-bridged dinuclear species in the monoclinic space group
P21/n with the bimetallic unit comprising the asymmetric unit
of the structure. The structure is shown in Fig. 7. Two bismuth
centres are linked via a l-oxo ligand with average distances of
˚
˚
2
Bi atoms have a weak g -arene interaction with a phenyl ring of
an adjacent PhBi(OCH(CF3)2)2 fragment of the polymer (Bi(1)–
˚
centroid of C(19,20) = 3.7165 A, Bi(2)–centroid of C(13,14) =
˚
3.7635 A). While these distances are reasonably long, they do
◦
˚
Fig. 7 Molecular structure of the oxo-bridged dimer [Bi2(l-O)(OCH(CF3)2)4(tmeda)2], 10. Selected bond lengths (A) and angles ( ): Bi(1)–N(2)
2.532(8), Bi(1)–O(1) 2.153(6), Bi(1)–O(2) 2.276(6), Bi(1)–O(3) 2.076(6), Bi(2)–O(3) 2.077(6), Bi(2)–N(4) 2.542(8), Bi(2)–O(5) 2.146(7), Bi(2)–O(4) 2.300(7);
O(3)–Bi(2)–O(4) 77.6(3), O(3)–Bi(2)–O(5) 93.7(3), O(3)–Bi(2)–N(4) 81.0(3), Bi(1)–O(3)–Bi(2) 110.3(3), O(3)–Bi(1)–O(1) 92.2(3), O(3)–Bi(1)–N(2) 85.7(3),
O(3)–Bi(1)–O(2) 77.9(2), N(4)–Bi(2)–O(4) 155.2(2), O(2)–Bi(1)–N(2) 158.7(2), O(2)–Bi(1)–O(1) 88.9(2), O(5)–Bi(2)–O(4) 90.7(3).
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Fig.
Polymeric structure of [PhBi(OCH(CF3)2)2(l-OCH(CF3)2)]n, 5. Selected bond lengths (A) and angles (◦): Bi(2)–C(19) 2.204(7),
˚
8
Bi(1)–C(13) 2.231(7), Bi(2)–O(4) 2.109(5), Bi(2)–O(2) 2.583(5), Bi(1)–O(2) 2.290(5), Bi(1)–O(3) 2.104(5); C(19)–Bi(2)–O(4) 87.0(2), C(13)–Bi(1)–O(3)
85.1(2), Bi(2)–O(2)–Bi(1) 113.71(19), O(1)–Bi(1)–O(2) 169.47(17), C(13)–Bi(1)–O(1) 83.0(2), O(3)–Bi(1)–O(1) 80.02(17), C(19)–Bi(2)–O(2) 83.3(2),
O(4)–Bi(2)–O(2) 82.01(17), C(13)–Bi(1)–O(2) 94.8(2), O(3)–Bi(1)–O(2) 89.53(2).
fall within the limits given in [BiPh(oxinate)2(O-dmso)]2 where the
recirculating Ar gas glove box. BiPh3 and Bi(p-Tol)3 were prepared
from reaction of the appropriate Grignard reagent with anhydrous
BiCl3 and recrystallised from ethanol. The purity was checked by
NMR spectroscopy and by melting point analysis. All solvents
were dried using a MBraun SPS-800 and stored over molecular
6
naked Bi atom has an g -arene interaction with an adjacent oxinate
29
˚
ligand at Bi–C distances between 3.55–3.81(1) A.
Compound 7, [Bi9(l3-O)7(OCH(CF3)2)4(l-OCH(CF3)2)9],
shown in Fig. 9, crystallises in the triclinic space group P-1
as an oxo-cluster with a Bi9O7 core, reminiscent of that seen
in [Bi9O7(salicylate)13(Me2CO)5]31 and with other ligated Bi9O7
clusters.2,7 Alkoxo ligands shroud the core where bismuth atoms
are arranged in an octahedral fashion with three Bi atoms
emanating from the oxo ligands that cap faces of the octahedral
core. The ranges of bond lengths for Bi–O are 2.097(3)–2.759(3)
˚
sieves (4 A). All reagents were purchased from Sigma Aldrich
and used without further purification. 1,1,1,3,3,3-hexafluoro-
2-propanol was dried under reflux with Mg and stored over
˚
molecular sieves (4 A). Infrared spectra were obtained on a Perkin
Elmer 1600 FTIR. NMR spectra were obtained with Bruker
AV200, DPX-300 and DRX400 spectrometers with chemical
shifts referenced d8-toluene or d8-thf where appropriate. Elemental
analysis was carried out by CMAS, Melbourne, Australia and the
Campbell Microanalytical Laboratory, New Zealand.
◦
˚
(A) and O–Bi–O angles in the core range 62.87(11)–169.22(11) ,
while the Bi–O–Bi angles span 91.32(11)–129.17(17)◦.
Conclusions
Synthesis and Characterisation
[Bi(OCH(CF3)2)3]n, (1)
We have shown that by using variable reaction conditions the
reaction of BiAr3 with 1,1,1,3,3,3-hexafluoro-2-propanol produces
a new series of bismuth complexes with varying degrees of substi-
tution, cluster formation, and aggregation. A volatile unsolvated
bismuth fluoroalkoxide can be isolated from the direct reaction of
(CF2)3CHOH with BiAr3. Extraction with toluene and Lewis base
solvents leads to a variety of complexed mononuclear complexes
and oxo species containing predominantly Bi2O cores. From
hydrolysis experiments the oxo-cluster containing Bi9O7 appears
to be the stable end point of hydrolysis, anticipating for the first
time a reproducible method of obtaining a stable cluster with a
predetermined cluster composition.
Bi(p-Tol)3 (2.02 g, 4.18 mmol) and (CF3)2CHOH (2.20 ml,
20.90 mmol) were heated together, without solvent, at 120 ◦C
overnight under N2 atmosphere. An oily solid was obtained which
was distilled in vacuo (118 ◦C at 0.5 mm Hg). A clear liquid is
obtained which crystallises at room temperature.
Yield 1.90 g, 64%. M.p. 50–52◦◦C.
1H NMR (200 MHz, C6D6, 30 C): d 5.4 (sep, J(F, H) = 6.05 Hz,
1H). 13C NMR (50 MHz, C6D6, 30◦C): d 68.9(p, J(C, F) = 32.7 Hz,
CH), 125.0 (q, J(C, F) = 276.4 Hz, CF3). 19F NMR (282 MHz,
C6D6, 30 ◦C): d −74.4 (d, J(H, F) = 5.9 Hz, CF3).
Experimental
Variable temperature NMR study. 1H NMR (200 MHz, d8-
toluene, 30 ◦C): d 5.35 (sep, J(F, H) = 6.05 Hz, 1H); (0 ◦C) d 5.3
(p, J(F, H) = 5.9 Hz, 1H); (−30 ◦C) d 5.22 (t, J(F, H) = 5.46 Hz,
General
◦
◦
All syntheses and compound manipulations were done using
inert atmosphere techniques under a dry N2 atmosphere and a
1H); (−60 C) d 5.12 (br s, 1H); (−80 C) d 5.06 (br s, 1H). 19F
NMR (282 MHz, d8-toluene, 30 ◦C): d −75.9 (d, J(H, F) = 5.6 Hz,
2564 | Dalton Trans., 2008, 2557–2568
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˚
Fig. 9 Molecular structure of the bismuth oxo-cluster [Bi9(l3-O)7(OCH(CF3)2)4(l-OCH(CF3)2)9], 7. Selected bond lengths (A) and angles ( ): Bi(4)–O(2)
2.282(3), Bi(4)–O(7) 2.125(3), Bi(5)–O(7) 2.199(3), Bi(5)–O(2) 2.197(3), Bi(2)–O(20) 2.214(3), Bi(1)–O(20) 2.127(3), Bi(9)–O(20) 2.150(3), Bi(3)–O(6)
2.120(3), Bi(8)–O(3) 2.207(3), Bi(1)–O(3) 2.696(3), Bi(8)–O(18) 2.221(4); O(10)–Bi(3)–O(9) 90.80(12), O(11)–Bi(3)–O(8) 85.34(12), Bi(4)–O(7)–Bi(5)
108.26(15), Bi(4)–O(2)–Bi(5) 102.96(13), O(7)–Bi(4)–O(2) 73.96(12), O(7)–Bi(5)–O(2) 74.27(12), O(18)–Bi(8)–O(3) 85.50(14), O(18)–Bi(8)–O(17)
142.82(12), Bi(2)–O(20)–Bi(1) 121.97(15), Bi(2)–O(20)–Bi(9) 110.13(15).
CF3); (0 ◦C) d −76.1 (d, J(H, F) = 6.2 Hz, CF3); (−30 ◦C) d −76.2
(d, J(H, F) = 5.6 Hz, CF3,); (−60 ◦C) d −76.3 (d, J(H, F) =
5.3 Hz, CF3); (−80 ◦C) d −76.4 (s, CF3). FT-IR (cm−1): 1289.5 (s),
1216.5 (s), 1184.9 (s), 1109.5 (s), 1086.7 (s), 893.8 (m), 853.5 (m),
799.1 (w), 793.9 (m), 722.0 (sh), 687.7 (s). Elemental analysis calc.
(%) for C9H3BiF18O3: C 15.22, H 0.43; found: C 15.26, H 0.48.
[Bi(OCH(CF3)2)3(thf)3], (3)
Compound 1 (1.00◦g, 1.41 mmol) was dissolved in thf (2.00 ml)
and stored at −30 C for four days, producing compound 3 as a
crystalline solid. The crystals were isolated by filtration and dried
in vacuo.
Yield 0.33 g, 28%. M.p. 82–86 ◦C.
1H NMR (300 MHz, d8-thf, 30 ◦C): d 5.54 (1H, m, CH). 19F
◦
[Bi(OCH(CF3)2)3(pyr)2], (2)
NMR (282 MHz, d8-thf, 30 C): d −75.4 (d, J(H, F) = 6.2 Hz,
CF3). 1H NMR (400 MHz, d6-dmso, 30 ◦C): d 1.75 (m, CH), 3.6
(m, CH), 5.65 (br s, CH). 13C NMR (100 MHz, d6-dmso, 30 ◦C):
d 25.5 (s, CH), 67.4 (s, CH), 70.4 (m, CH), 126.3 (q, J(C, F) =
281.7 Hz. CF3). Elemental analysis calc. (%) for C21H27BiF18O6:
27.23 C, 2.94 H; found: 18.60 C, 1.33 H. Calc. (%) for C9H3BiF18O3
+ 0.7(C4H8O): 18.48 C, 1.11 H.
Compound 1 (1.00 g, 1.41 mmol) was dissolved in pyridine
(2.00 ml) and stored at −30 ◦C for three days, producing
compound 2 as large flat crystals. The crystals were isolated by
filtration and dried in vacuo.
Yield 0.48 g, 40%. M.p. 57–59 ◦C.
1H NMR (300 MHz, d8-thf, 30 ◦C): d 5.64 (3H, br s, CH), 7.38
(4H, br s, CH, 2-Py), 7.77 (2H, br s, CH, 4 − Py), 8.61 (4H, br s,
CH, 3-Py). 13C NMR (75 MHz, d8-thf, 30 ◦C): d 69.4 (p, J(C,
H) = 32.2 Hz, CH), 121.6 (q, J(C, F) = 282.6 Hz, CF3), 123.1
(s, CH, 3-Py), 135.8 (s, CH, 4-Py), 147.8 (s, CH, 2-Py). 19F NMR
(282 MHz, d6-dmso, 30 ◦C): d −73.5 (s). Elemental analysis calc.
(%) for C19H13BiF18N2O3: 26.28 C, 1.51 H, 3.23 N; found: 26.17 C,
1.6 H, 3.30 N.
[Bi2(OCH(CF3)2)6(dabco)3], (4)
Dabco (0.15 g, 1.34 mmol) and compound 1 (0.26 g, 0.54 mmol)
were dissolved together in toluene and stored at −30 ◦C. After
two days crystals of compound 4 were isolated and dried in vacuo.
Yield 0.30 g, 32%. M.p. 130–135 ◦C.
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◦
1H NMR (200 MHz, d8-thf, 30 C): d 2.74 (6H, s, CH2), 5.54
(w), 852 (m), 737 (w), 684 (m). Elemental analysis calc. (%) for
C39H13Bi9F78O20: C 11.25, H 0.31; found: C 11.17, H 0.25.
(1H, m, CH). 13C NMR (50 MHz, d8-thf, 30 ◦C): d 39.1 (s, CH2),
62.3 (p, CH, J(C, H) = 31.5 Hz), 119.4 (q, CF3, J(C, F) = 282.9
Hz). 19F NMR (282 MHz, d8-thf, 30 ◦C): d −75.4 (s).
[Bi2O(OCH(CF3)2)4(Et2O)]2, (8); [Bi2O(OCH(CF3)2)4(thf)]2, (9)
and alternative synthesis of [Bi2O(OCH(CF3)2)4(C7H8)]2, (6)
FT-IR (cm−1): 1282.5 (s), 1259.2 (sh), 1179.5 (s), 1115.0 (s),
1095.8 (s), 1058.0 (s), 1018.4 (sh), 995.9 (w), 887.2 (s), 856.6 (s),
776.8 (s), 741.4 (s), 685.5 (s), 650.8 (w), 640.1 (w). Elemental
analysis calc. (%) for C36H42Bi2F36N6O6: C 24.61, H 2.41, N 4.78;
found: C 23.30, H 2.90, N 5.17.
Compound 1 was prepared as described above. The residue was
taken up separately in toluene, die◦thyl ether, and thf and the
solutions filtered and stored at −30 C for one week. Colourless
crystals of 6, 8 and 9, respectively, were obtained. The crystals
were isolated by filtration and dried over a stream of N2.
[PhBi(OCH(CF3)2)2]n, (5)
Compound 8. Yield 0.72 g, 31%.◦M.p. > 190 ◦C (decomp).
1H NMR (300 MHz, d6-dmso, 30 C): d 1.09 (6 H, t, J(H, H) =
6.99 Hz, CH3), 3.37 (4H, q, J(H, H) = 6.99 Hz, CH2), 5.1 (8 H,
br s, CH). 19F NMR (282 MHz, d8-thf, 30 ◦C): d −73.8 (s).
FT-IR (cm−1): 1371 (w), 1277 (w), 1255 (w), 1207 (m), 1169 (s),
1112 (s), 1078 (s), 889 (w), 848 (w), 738 (w), 685 (w). Elemental
analysis calc. (%) for C16H14Bi2F24O6: C 16.34, H 1.2; found: C
11.65, H 0.45. Calc. (%) for C12H4Bi2F24O5 (without Et2O): C
13.08, H 0.37.
BiPh3 (0.80 g, 1.80 mmol) and (CF3)2CHOH (0.76 ml, 7.20 mmol)
were heated together, without solvent, at 90 C overnight under
◦
an N2 atmosphere. Volatiles were then removed in vacuo. The
remaining solid was dissolved in toluene, filtered and refrigerated
at −8 ◦C. The solution produced colourless crystals of 5 after
one week.
Yield 0.65 g, 53%. M.p. 95–97 ◦C.
◦
1H NMR (300 MHz, d8-thf, 30 C): d 5.11 (2H, m, CH), 7.38
(1H, m, p-Ph), 7.93 (2H, t, J(H, H) = 7.08 Hz, m-Ph), 8.42
(2H, d, J(H, H) = 6.88 Hz, o-Ph). 13C NMR (50 MHz, d8-thf,
30 ◦C): d 63.2 (m, CH), 113.2 (q, J(C, F) = 282.35 Hz CF3),
121.5 (p-C), 124.31 (o,m-C), 126.78 (ipso-C). 19F NMR (282 MHz,
d8-thf, 30 ◦C): d −75.9 (s). MS (ESI, −ve, CH3OH, thf); m/z
[OCH(CF3)2]− 167.0 (100%), [PhBiO(CH3OH)H]− 335.0 (30%),
MS (EI, +ve, CH3OH, thf) [Ph2Bi2(OCH(CF3)2)3(thf)H]2+ 572.55
(95%). Elemental analysis calc. (%) for C12H7BiF12O2: C 23.24, H
1.14; found: C 23.50, H 1.34.
Compound 9. Yield 0.65 g, 28%. M.p. > 150 ◦C (decomp.).
◦
1H NMR (300 MHz, d6-dmso, 30 C): d 1.76 (2 H, m, CH2),
3.59 (2 H, m, CH2), 5.09 (4 H, m, CH). 19F NMR (282 MHz,
d6-dmso, 30 ◦C): d −73.3 (s).
FT-IR (cm−1): 1370 (w), 1276 (w), 1255 (w), 1207 (s), 1169 (s),
1115 (s), 1078 (s), 888 (w), 848 (m), 738 (w), 685 (m). Reasonable
elemental analysis could not be obtained.
[Bi2O(OCH(CF3)2)4(tmeda)2], (10)
[Bi2O(OCH(CF3)2)4(C7H8)]2, (6)
Tmeda (1.00 ml) was added to compound 6 (0.40 g) and the
suspension gently warmed to aid complete dissolution. On cooling
to room temperature needle-like crystals of compound 10 were
obtained. These were isolated and dried in vacuo.
BiPh3 (0.80 g, 1.80 mmol) and (CF3)2CHOH (0.76 ml, 7.20 mmol)
were heated together in toluene under reflux overnight under an N2
atmosphere. The alcohol was used as received, without any drying.
All volatiles were then removed in vacuo and the remaining solid
re-dissolved in toluene, filtered and stored at −8 ◦C for one week.
Crystals of 6 were obtained, isolated and dried in vacuo. Also
prepared from compound 1, see below for details.
Yield 0.40 g, 35% M.p. 70–75 ◦C.
◦
1H NMR (300 MHz, d6-dmso, 30 C): d 5.24 (2H, br s, CH),
2.2 (4H, s, CH2), 2.1 (12H, s, CH3). 19F NMR (282 MHz,
d6-dmso, 30 ◦C): d −73.8 (s). Elemental analysis calc. (%) for
C24H36Bi2F24N4O5: C 21.60, H 2.72, N 4.20; found: C 22.72, H
3.05, N 3.73.
Yield 1.03 g, 48%. M.p. >160 ◦C (decomp.).
1H NMR (200 MHz, d8-thf, 30 ◦C): d 5.12 (1H, br m, CH),
5.58 (4H, p, CH). 13C NMR (50 MHz, d8-thf, 30 ◦C): d 64.4
(m, CH). 19F NMR (282 MHz, d8-thf, 30 ◦C): d −74.6 (s).
MS (EI, −ve, CH3OH, thf) m/z [OCH(CF3)2]− 167.0 (100%),
[PhBiO(CH3OH)H]− 335.0 (45%). MS (ESI, +ve, CH3OH, thf)
m/z [HOBiOCH(CF3)2(C7H8)(CH3OH)]+ 517.1 (100%). FT-IR
(cm−1): 1373 (w), 1278 (w), 1210 (m), 1170 (s), 1109 (s), 1078
(s), 891 (w), 850 (m), 739 (w), 685 (m). Elemental analysis calc.
(%) for C38H24Bi4F48O10 3: C 19.11, H 1.01; found: C 17.91, H 1.09.
X-Ray crystallography†
Crystalline samples were mounted on glass fibres in viscous
hydrocarbon oil. Crystal data were collected using either an Enraf-
Nonius Kappa CCD or a Bruker X8 APEX CCD instrument with
˚
monochromated Mo Ka radiation, k = 0.71073 A. All data were
collected at 123 K, maintained using an open flow of nitrogen from
an Oxford Cryostreams cryostat. X-ray data were processed using
the DENZO program.32 Structural solution and refinement was
carried out using SHELXL-9733 utilising the graphical interface
X-Seed.34 Crystal data and refinement parameters for compounds
2–10 are presented below:
[Bi9O7(OCH(CF3)2)13], (7)
After separation of compound 6 from solution a further small
crop of crystals were obtained after ten days at −8 ◦C. These were
isolated, dried in vacuo, and analysed as [Bi9O7(OCH(CF3)2)13] 7.
Yield 0.74 g, 10%. M.p. decomp > 250 ◦C.
Crystal data for compound 2. C19H13BiF18N2O3, M = 868.29,
colourless prismatic, 0.08 × 0.07 × 0.07 mm, trigonal, space
◦
1H NMR (200 MHz, d8-dmso, 30 C): d 5.58 (br s, 1H, CH).
group P32 (No. 145), a = b = 13.9674(3), c = 11.9283(3) A,
˚
19F NMR (282 MHz, d8-dmso, 30 ◦C): d −75.1 (d, J(H, F) =
5.35 Hz, CF3). FT-IR (cm−1): 1374 (w), 1357 (w), 1278 (w), 1257
(w), 1213 (m), 1173 (s), 1105 (sh), 1085 (s), 1053 (m), 996 (w), 890
V = 2015.30(8) A , Z = 3, Dc = 2.146 g cm−3, F000
=
3
˚
1230, Bruker X8 APEX CCD, 2hmax = 60.2◦, 50623 reflections
collected, 7830 unique (Rint = 0.0839). Final GooF = 0.969,
2566 | Dalton Trans., 2008, 2557–2568
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R1 = 0.0359, wR2 = 0.0522, R indices based on 6865 reflections
with I >2r(I) (refinement on F2), 388 parameters, 1 restraint. Lp
and absorption corrections applied, l = 6.712 mm−1. Absolute
structure parameter = −0.014(4).35
F2), 1315 parameters, 0 restraints. Lp and absorption corrections
applied, l = 18.988 mm−1.
Crystal data for compound 8. C32H28Bi4F48O12, M = 2352.46,
colourless prismatic, 0.09 × 0.09 × 0.08 mm, triclinic, space group
Note. There was high thermal motion on the CF3 groups.
˚
P-1 (No. 2), a = 10.1484(3), b = 15.1108(5), c = 19.1279(5) A, a =
◦
3
˚
94.013(2), b = 91.126(2), c = 91.274(2) , V = 2924.70(15) A ,
Crystal data for compound 3. C21H27BiF18O6, M = 926.41,
colourless prismatic, 0.08 × 0.06 × 0.06 mm, monoclinic, space
group P21/c (No. 14), a = 16.5066(4), b = 9.5546(2), c = 19.4747(5)
Z = 2, Dc = 2.671 g cm−3, F000 = 2160, Bruker X8 APEX CCD,
2hmax = 60.3◦, 74 379 reflections collected, 16 986 unique (Rint
=
◦
3
−3
˚
˚
0.0806). Final GooF = 1.063, R1 = 0.0528, wR2 = 0.0670, R
indices based on 12 044 reflections with I >2r(I) (refinement on
F2), 869 parameters, 0 restraints. Lp and absorption corrections
applied, l = 12.203 mm−1.
A, b = 92.201(1) , V = 3069.17(13) A , Z = 4, Dc = 2.005 g cm ,
F000 = 1784, Bruker X8 APEX CCD, 2hmax = 55.2◦, 63395
reflections collected, 7071 unique (Rint = 0.0805). Final GooF =
1.167, R1 = 0.0373, wR2 = 0.0732, R indices based on 5759
reflections with I >2r(I) (refinement on F2), 415 parameters, 0
restraints. Lp and absorption corrections applied, l = 5.888 mm−1.
Note. There was high thermal motion on the thf molecule.
Note. There was high thermal motion on the CF3 groups and
diethyl ether molecules.
Crystal data for compound 9. C32H24Bi4F48O12, M = 2348.43,
colourless prismatic, 0.08 × 0.07 × 0.08 mm, triclinic, space group
Crystal data for compound 4. C36H42Bi2F36N6O6, M = 1756.72,
colourless prismatic, 0.08 × 0.07 × 0.07 mm, monoclinic, space
group P21/c (No. 14), a = 17.123(3), b = 17.976(4), c = 19.379(4)
˚
P-1 (No. 2), a = 9.8435(3), b = 14.5758(5), c = 20.1015(7) A, a =
◦
3
˚
86.782(2), b = 86.257(2), c = 87.184(2) , V = 2870.42(17) A ,
Z = 2, Dc = 2.717 g cm−3, F000 = 2152, Bruker X8 APEX CCD,
◦
3
−3
˚
˚
A, b = 111.56(3) , V = 5547.7(19) A , Z = 4, Dc = 2.103 g cm ,
F000 = 3352, Bruker X8 APEX CCD, 2hmax = 59.1◦, 54132
reflections collected, 15296 unique (Rint = 0.1890). Final GooF =
0.965, R1 = 0.0680, wR2 = 0.1260, R indices based on 8134
reflections with I >2r(I) (refinement on F2), 775 parameters, 0
restraints. Lp and absorption corrections applied, l = 6.504 mm−1.
Note. There was high thermal motion on C22 of one dabco
molecule.
2hmax = 60.3◦, 73 105 reflections collected, 16 905 unique (Rint
=
0.1266). Final GooF = 1.028, R1 = 0.0641, wR2 = 0.1079, R
indices based on 11 118 reflections with I >2r(I) (refinement on
F2), 865 parameters, 0 restraints. Lp and absorption corrections
applied, l = 12.433 mm−1.
Note. There was high thermal motion on the CF3 groups and
thf molecules.
Crystal data for compound 10. C24H36Bi2F24N4O5, M =
1334.53, colourless prismatic, 0.09 × 0.09 × 0.05 mm, monoclinic,
space group P21/n (No. 14), a = 9.9443(3), b = 33.6528(11),
Crystal data for compound 5. C12H7BiF12O2, M = 620.16,
0.15 × 0.10 × 0.10 mm3, monoclinic, space group P21/n (No. 14),
◦
˚
a = 12.8185(2), b = 19.3178(3), c = 13.3728(3) A, b = 103.868(2) ,
◦
3
˚
˚
c = 12.6212(4) A, b = 110.258(2) , V = 3962.5(2) A , Z = 4,
3
−3
˚
V = 3214.91(10) A , Z = 8, Dc = 2.563 g cm , F000 = 2288,
Dc = 2.237 g cm−3, F000 = 2520, Bruker X8 APEX CCD, 2hmax
=
˚
Nonius Kappa CCD, Mo Ka radiation, k = 0.71073 A, T =
60.4◦, 100 981 reflections collected, 11 692 unique (Rint = 0.1512).
Final GooF = 1.093, R1 = 0.0703, wR2 = 0.1328, R indices
based on 8336 reflections with I >2r(I) (refinement on F2), 540
parameters, 0 restraints. Lp and absorption corrections applied,
l = 9.022 mm−1.
123(2)K, 2hmax = 56.4◦, 43063 reflections collected, 7764 unique
(Rint = 0.0939). Final GooF = 1.073, R1 = 0.0508, wR2 = 0.1177,
R indices based on 6446 reflections with I >2r(I) (refinement on
F2), 487 parameters, 0 restraints. Lp and absorption corrections
applied, l = 11.105 mm−1.
Crystal data for compound 6. C38H24Bi4F48O10, M = 2388.49,
colourless prismatic, 0.20 × 0.18 × 0.10 mm, monoclinic, space
group P21/n (No. 14), a = 12.7084(12), b = 12.0381(11), c =
Acknowledgements
We would like to thank the Cooperative Centre for Functional Co-
munication Surfaces (CRC Smartprint), the Monash University
Faculty of Science Postgraduate Publication Award (I. N.) and the
Australian Research Council for funding, and also acknowledge
the assistance of Dr Craig Forsyth (Monash University) for some
X-ray data manipulation.
◦
3
˚
˚
19.6916(18) A, b = 90.155(2) , V = 3012.5(5) A , Z = 2, Dc =
2.633 g cm−3, F000 = 2192, Bruker X8 APEX CCD, 2hmax
=
55.0◦, 19 964 reflections collected, 6513 unique (Rint = 0.0429).
Final GooF = 0.866, R1 = 0.0230, wR2 = 0.0587, R indices
based on 2967 reflections with I >2r(I) (refinement on F2), 452
parameters, 0 restraints. Lp and absorption corrections applied,
l = 11.847 mm−1.
References
Note. There was high thermal motion on the CF3 groups.
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