Deprotonation and reductive addition reactions of hypervalent aluminium dihydride compounds containing substituted pyrrolyl ligands with phenols, ketones, and aldehydes

Article abstract of DOI:10.1039/b908164j

The reactivities of [C₄H₂N(CH₂NMe ₂)₂]AlH₂ (1) with primary and secondary amines, phenols, ketones, and phenyl isothiocyanate were examined. Reactions of 1 with one or two equivalents of 2,

Full text of DOI:10.1039/b908164j

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www.rsc.org/dalton | Dalton Transactions
Deprotonation and reductive addition reactions of hypervalent aluminium
dihydride compounds containing substituted pyrrolyl ligands with phenols,
ketones, and aldehydes†
I-Chun Chen,a Shi-Mau Ho,a Ya-Chi Chen,a Che-Yu Lin,a Ching-Han Hu,a Cheng-Yi Tu,a Amitabha Datta,a
Jui-Hsien Huang*a and Chia-Her Linb
Received 23rd April 2009, Accepted 30th July 2009
First published as an Advance Article on the web 20th August 2009
DOI: 10.1039/b908164j
The reactivities of [C4H2N(CH2NMe2)2]AlH2 (1) with primary and secondary amines, phenols, ketones,
and phenyl isothiocyanate were examined. Reactions of 1 with one or two equivalents of
2,6-dichloroaniline in methylene chloride generated [C4H2N(CH2NMe2)2]AlH(NHC6H3-2,6-Cl2) (2)
and [C4H2N(CH2NMe2)2]Al(NHC6H3-2,6-Cl2)2 (3), respectively, following hydrogen elimination.
Similarly, the reactions of 1 with one or two equivalents of carbazole afforded
[C4H2N(CH2NMe2)2]AlH(NC12H8) (4) or [C4H2N(CH2NMe2)2]Al(NC12H8)2 (5) by deprotonating the
acidic N–H of carbazole. Reacting 1 with one equivalent of 2,6-diisopropylphenol in diethyl ether
formed an aluminium phenoxo compound [C4H2N(CH2NMe2)2]AlH(OC6H3-2,6-iPr2) (6), by
deprotonation of phenol as well with the elimination of one equivalent hydrogen. Further reaction of 6
with one equivalent of 2,4,6-trimethylacetophenone in methylene chloride generated
i
=
[C4H2N(CH2NMe2)2]Al(OC6H3-2,6- Pr2)[OC( CH2)(C6H2-2,4,6-Me3)] (7) by deprotonating the methyl
proton of the acetophenone. Similar deprotonation occurred when 1 reacted with two equivalents of
2,4,6-trimethylacetophenone in methylene chloride to generate [C4H2N(CH2NMe2)2]Al[OC-
=
( CH2)(C6H2-2,4,6-Me3)]2 (8). Compounds [C4H2N(CH2NMe2)2]Al(OCHPh2)2 (9), and
[C4H2N(CH2NMe2)2]Al(SCHNPh)2 (10) could also be obtained by reacting 1 with two equivalents of
benzophenone and phenyl isothiocyanate, respectively through hydroalumination. The 1H NMR
spectra of 10 showed broad signals for the CH2N and NMe2 groups, which represent dynamical
fluctuations of the molecules in solution state. The estimated energy barrier (DGc‡) from the coalescence
temperature for the fluctuation was estimated at 17.1 Kcal mol-1. The solid-state structures of
compounds 2, 3, 5, 7, 9, and 10 have been determined.
molecules, as shown in Scheme 1. It shows that the hydride acts
Introduction
as a strong base and abstracts one proton from phenol3 or amine4
The reactivities of metal hydrides were widely studied and reviewed
to yield an aluminium alkoxide or an amide compound. The
periodically.1 For more than three decades transition-metal hy-
reaction temperature, the stoichiometry of the reactants, and the
drides have held the limelight. This is understandable in view of
steric demand of the substituents were found to play key roles in
what degree of oligomerization was attained.5 The reduction of
carbonyl compounds by complex metal hydride reducing agents
is one of the most important reactions of organic compounds. In
the part played by M–H bonds in the organometallic chemistry
of the transition metals, particularly in catalytic processes. Early
transition metal hydride derivatives are thought to be responsible
for a plethora of organic transformations, catalytic cycles and
olefin polymerization intermediates, or deactivation products.2
Among these metal hydrides, aluminium hydrides have been
extensively used because of their versatility, high reactivity and
inexpensiveness. Aluminium hydride compounds can undergo
proton abstraction or nucleophilic reductive addition with organic
this connection, the hydride can also act as a nucleophilic reagent
6
=
attacking C O, an important significance of the high degree of p-
facial diastereoselectivity. The hydride also takes part in initiating
different hydroalumination reactions with CN,7 NCE (where E =
O, S),8 and unsaturated alkenes and alkynes.9 Power et al. have
reported that the reaction of a bulky alkane [Mes*AlH2]2 (Mes* =
2,4,6-t-Bu3C6H2) with nitriles RCN (R = Me, t-Bu, Mes) gives the
ortho-metalated dimers, cis- and trans-[AlC6H2-2,4-t-Bu2-6-CMe2-
aDepartment of Chemistry, National Changhua University of Education,
Changhua, 50058, Taiwan
2
CH2{m -N(H)CH2R}]2.10 Different alumoxanes have also been
bDepartment of Chemistry, Chung-Yuan Christian University, Chun-Li 320,
Taiwan. E-mail: juihuang@cc.ncue.edu.tw
previously reported,11 mediated by controlled hydrolysis of alu-
minium alkyls or organoaluminium hydrides with water or reactive
oxygen-containing species. Several hydroalumination reactions
have been investigated before either involving trialkylaluminiums
† CCDC reference numbers 721352 (2), 721534 (3), 721356 (5), 721355 (7),
721354 (9), and 721353 (10). For crystallographic data in CIF or other
electronic format see DOI: 10.1039/b908164j
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=
Scheme 1 (a) Proton abstraction (b) Nucleophilic reductive addition (c) Reactions of Al–H with organic molecules containing C O groups.
or dialkylaluminium hydrides with dialkylaluminium acetylides12
or using bis-alkynyl alcohols having an adjacent stereogenic center
which provides access to stereo-defined tert-alcohols.13 The reac-
tivity of two sterically bulky amidines, ArNC(R)N(H)Ar [Ar =
2,6-diisopropylphenyl; R = H (HFiso); tBu, (HPiso)] towards alu-
minium have examined before14 and the structural motif generated
by the prepared complexes are rationalized in terms of the steric
bulk of the amidinate ligands and electronic properties of metal.
Recently, Gladfelter et al, reported volatile aluminium dihydrides,
H2Al[N(CH2CH2NMe2)2] and H2Al[N(CH2CH2NMe2)2]AlH3,15
stabilized with a tridentate nitrogen ligand, [N(CH2CH2NMe2)2]-,
having stability for use in chemical vapor deposition and related
applications. The relative basicity of hydride to the acidity of
organic molecules determines the types of reactions. For example,
the reactions of aluminium hydrides with ketones (Scheme 1c)
proceed either via proton abstractions or via nucleophilic reductive
addition depending on the relative acidity of the reactants and the
availability of the ketone proton sources. We have been interested
in hydroalumination reactions and have been pursuing this topic in
our present article. Herein, the reactions of monomeric aluminium
dihydride compounds containing substituted tridentate pyrrolyl
ligands with primary and secondary amines, phenols, ketones and
phenyl isothiocyanate have been discussed. Proton abstraction
and reductive addition products were both observed while the
aluminium dihydrides react with ketones. All the products were
investigated in detail by multinuclear NMR spectroscopy (1H, 13C)
and six compounds were also characterized by single-crystal X-ray
diffraction.
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Scheme 2 Deprotonation reactions of aluminium dihydride with primary and secondary amines.
phenoxide compound [C4H2N(CH2NMe2)2]AlH(OC6H3-2,6-iPr2)
Results and discussion
(6) via the elimination of one equivalent of hydrogen (Scheme 3).
Syntheses and characterization
1
The H NMR spectrum of 6 exhibits one singlet for the NMe2
The reactions of [C4H2N(CH2NMe2)2]AlH2 (1) with primary and
secondary amines, phenols, ketones, and phenyl isothiocyanate
are described. Due to the strong basic characteristics, the alu-
minium dihydride compound 1 shows a strong reactivity towards
functional organic molecules. Reaction of 1 with one equivalent
of 2,6-dichloroaniline in methylene chloride generated an alu-
minium hydride compound [C4H2N(CH2NMe2)2]AlH(NHC6H3-
2,6-Cl2) (2) via hydrogen elimination (Scheme 2). Similarly,
[C4H2N(CH2NMe2)2]AlD(NHC6H3-2,6-Cl2) (2-D) can be ob-
tained from the reaction of 1-D with one equivalent of 2,6-
dichloroaniline. The 1H NMR spectrum of 2 shows one resonance
for the NMe2 fragments and two doublets for the CH2N fragments.
The IR spectrum shows the Al–H absorption at 1851 cm-1 and the
corresponding Al–D absorption for compound 2-D at 1344 cm-1
(calculation at 1333 cm-1). While with the reaction between two
equivalents of 2,6-dichloroaniline and 1, an aluminium diamide
compound [C4H2N(CH2NMe2)2]Al(NHC6H3-2,6-Cl2)2 (3) can be
isolated. Compound 3 exhibits a planar symmetry with the
1H NMR spectra of CH2N and NMe2 fragments appeared as
two singlets at d 3.83 and 2.44, respectively.
fragments at d 2.42 and two doublets for CH2N at d 3.63
and 3.75. The IR spectrum of 6 also shows an absorption at
1853 cm-1 due to the Al–H stretching frequency. The Al–H of
6 can further deprotonate the b-proton of ketones to form an
aluminium enolate compound. Reacting 6 with one equivalent
of 2,4,6-trimethylacetophenone in methylene chloride gener-
i
=
ated [C4H2N(CH2NMe2)2]Al(OC6H3-2,6- Pr2)[OC( CH2)(C6H2-
2,4,6-Me3)] (7) in 84% yield (Scheme 3). The 1H NMR signals for
7 shows one resonance at d 2.38 and two doublets at d 3.57 and
3.64 for NMe2 fragments and CH2N fragments, respectively. The
=
signals for the methylene protons of the enolate Al-O-C( CH2)-Ar
show two singlets at d 4.08 and 4.38 with no 2JHH geminal coupling
found. The result differs from previous literature where the two
methylene protons are coupled to each other.16 Compound 1 can
also deprotonate the b-proton of ketones. Reaction of 1 with two
equivalents of 2,4,6-trimethylacetophenone in methylene chloride
=
generated [C4H2N(CH2NMe2)2]Al[OC( CH2)(C6H2-2,4,6-Me3)]2
(8). Again, the 1H NMR signals for the methylene protons of the
=
enolate CH2 COAr showed two singlets at d 3.99 and 4.46 with no
2JHH coupling found. A Gated-Decoupled 13C NMR spectrum of
8 shows two doublets of the methylene carbon due to its coupling
with two different geometrical methylene protons and a 2-D
1H–13C HSQC spectrum also proved the correlation of methylene
carbon (d 91.4) with two singlets of the methylene protons (d
3.99 and 4.46). A reasonable mechanism for the deprotonation
reaction is shown in Scheme 4. The reaction of 1 with 2,4,6-
Similarly, the reactions of 1 with one or two equivalents of
carbazole generated [C4H2N(CH2NMe2)2]AlH(NC12H8) (4) and
[C4H2N(CH2NMe2)2]Al(NC12H8)2 (5), respectively (Scheme 2).
1
The H NMR spectra of 4 and 5 both show two singlets (d 1.87
and 2.58 for 4; d 1.55 and 2.35 for 5) for the NMe2 fragments and
two doublets (d 3.70 and 3.79 for 4; d 3.65 and 4.47 for 5) for the
CH2N fragments. The IR spectrum of 4 in solid KBr shows an
absorption at 1830 cm-1 for the Al–H stretching.
The aluminium dihydride compound 1 shows strong ba-
sicity which results in the deprotonation of phenol and the
b-proton of ketones. Reaction of 1 with one equivalent of
2,6-diisopropylphenol in diethyl ether afforded an aluminium
1
trimethylacetophenone can be monitored by H NMR spectra
showing the deprotonation occurs along with the elimination of
hydrogen which has been observed at d 4.64. Similar observations
could be established concerning the use of 1-D where HD signals
appeared at d 4.64 as a triplet with the JHD coupling constant of
42.6 Hz.
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Scheme 3 Deprotonation of aluminium dihydride with phenol and ketone.
Scheme 4 The possible reaction mechanism for the deprotonation reactions of 1 with 2¢,4¢,6¢-trimethylacetophenone.
Aluminium dihydride compound, 1 undergoes hydroalu-
mination reactions (reductive addition) with benzophenone
and PhNCS resulting in aluminium alkoxides and thio-
carbamate compounds (Scheme 5). While compound 1 re-
acting with two equivalents of benzophenone, compound
[C4H2N(CH2NMe2)2]Al(OCHPh2)2 (9) was obtained through hy-
droalumination and the 1H and 13C NMR spectra are also
matched with the structure assignments. Reaction of 1 with
two equivalents of phenyl isothiocyanate in diethyl ether gener-
ates [C4H2N(CH2NMe2)2]Al(SCHNPh)2 (10) in 61% yield. The
1H NMR spectrum of 10 showed broad signals for both CH2N
and NMe2 representing a dynamical fluctuation for 10 in solution.
fragments at d 9.13 and 9.46, four doublets for the coordinated
and un-coordinated CH2N fragments at d 2.09, 2.90, 3.60, and
4.14, and two singlets for the coordinated NMe2 at d 2.54 and
2.83 and one singlet for the un-coordinated NMe2 at d 1.61.
On raising the temperature, signals broadened and coalescence
occurred at ca. 295 K, eventually becoming two singlets for the
CH2N and NMe2 at the fast limit. The estimated energy barrier17
from the coalescence temperature for the fluctuation DGc‡ is ca.
17.1 kcal mol-1. A possible fluxional mechanism is shown in
Scheme 6. Due to the steric congestion of 10, the two NMe2
fragments are coordinated to the aluminium center in an on–off
mode followed by a rotation along the aluminium pyrrolyl nitrogen
bond. A fluxional mechanism through the NCS fragments is ruled
out due to the formation energy concern. An energy profile of
the fluxional via calculation is shown in Fig. 2. With regard to
1
Variable temperature H NMR spectra were therefore recorded
from 230 to 330 K and shown in Fig. 1. At the slow limit of
the fluctuation (250 K), there are two singlets for the NCHS
8634 | Dalton Trans., 2009, 8631–8643
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Fig. 1 Variable temperature NMR spectra of compound 10 in CDCl3 using a 300 MHz NMR spectrometer showing the temperature range from 250 to
320 K.
Fig. 2 The energy profile for compound 10 at different geometries via calculation. Geometry 1 was adopted directly from the X-ray single crystal
structure; 2, the NMe2 fragments away from the aluminium center; 3–8, rotation along the aluminium–N (pyrrolyl) bond.
the diagram, the geometry 1 is adopted directly from an X-ray
single crystal structure and is considered a stable conformation.
This is also consistent with the calculated results. The Al–NaMe2
bond dissociation energy is 14.7 kcal mol-1 (geometry 2) and
the rotation of the Al–N (pyrrolyl) bond needs an additional
6 kcal mol-1 (geometries 3–7) making the total fluxional energy
20.7 kcal mol-1.
Description of molecular structures of compounds 2, 3, 5, 7, 9, and
10
The solid-state structures of compounds 2, 3, 5, 7, 9, and 10
have been determined and molecular structures are shown in
Fig. 3–8. The summary of crystal data collection along with the
refinement parameters and selected bond lengths and angles are
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Scheme 5 Hydroalumination reactions of aluminium dihydride with ketone, and PhNCS.
Scheme 6
listed in Table 1 and 2, respectively. Two independent molecules are
found in one unit cell for compound 3; however, their structures
are similar and only one molecule has been discussed here. The
crystal 5 contains a methylene chloride molecule in the lattice
which has been omitted in the molecular diagram. In summary,
a schematic drawing of the crystal structures of 2, 3, 5, 7 and
9 have been represented in Fig. 9. Compounds 2, 3, 5, 7, and
9, all adopt a distorted trigonal bipyramidal geometry with the
two NMe2 fragments occupying the axial positions. The sterically
hindered 2 exhibits an asymmetrical geometry into which two
NMe2 fragments pointed away from the bulkier arylamide group
where as the NMe2 fragments in 3, 5, 7, and 9 show equally
arranged conformation in the structures (see Fig. 9). All the
structures have similar Al–N(pyrrolyl) and Al–N(dimethylamino)
groups to the aluminium center (74.42(7)–79.44(7)◦) remain in
a similar range.
The molecular structure of 10 possesses a pseudo-octahedral ge-
ometry with the three axes occupying by N(pyrrolyl)–S(PhNCS),
N(NMe2)–N(PhNCS), and N(PhNCS)–S(PhNCS) to form the
angles of 164.33(5)◦, 158.62(6)◦, and 161.52(5)◦, respectively. The
bonding modes of isothiocyanate to the aluminium atom have
been reported in the literature.20 The tridentate pyrrolyl ligand only
coordinates to the aluminium center through pyrrolyl nitrogen
and one NMe2 fragment leaving another NMe2 fragment dangling
outside the coordination sphere. This arrangement also causes a
dynamical fluxionality.
Summary
˚
bond lengths, which are in the range of 1.8308(12)–1.8453(13) A
˚
and 2.1872(17)–2.4171(18) A, respectively and agreed with the
The reactivities of [C4H2N(CH2NMe2)2]AlH2 (1) with primary
and secondary amines, phenols, ketones, and phenyl isothio-
cyanate were investigated and generalized different modes of
deprotonation and hydroalumination reactions along with NMR
previously reported literature.18,19 The bulkiness of aryloxide and
arylamide ligands have little effect in consideration of the bond
lengths. Again, the bite angles of dimethylamino and pyrrolyl
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Fig. 3 The molecular structure of 2, the ellipsoids were drawn at 50% probability level and all hydrogen atoms were omitted for clarity.
spectroscopic data analyses. We have chosen [C4H2N-
(CH2NMe2)2]AlH2 as a starting material because of its strong
basicity and high reactivity towards functional organic molecules.
It is also remarkable to draw our attention to monomeric
compounds of the types mentioned above not only because of
their underexplored structural chemistry but also due to the
fact that monomeric compounds usually show higher volatilities
compared to heterocyclic or cage compounds. Our next attempt
is mainly to study the hydroalumination reactions of different
organic molecules using asymmetric tridentate pyrrolyl ligands.
(d 7.24, 77.0) and C6D6 (d 7.15, 128.0). Elemental analyses were
performed on a Heraeus CHN-OS Rapid Elemental Analyzer at
the Instrument Center, NCHU. [C4H2N(CH2NMe2)2]AlH2 was
prepared according to a previously reported procedure.21 All the
chemicals (Aldrich, Acros) were used as received.
Preparation of the complexes
Complex 2. A solution of 1 (0.50 g, 2.39 mmol) in 15 mL
methylene chloride was cooled to -78 ◦C, and a 2,6-dichloroaniline
(0.40 g, 2.39 mmol)/methylene chloride (15 mL) solution was
added dropwise via cannula. The solution then was warmed to
-20 ◦C and stirred for 15 min. The pale yellow solution then was
vacuum dried to yield an off-white solid powder. The solid was
recrystallized from a diethyl ether/methylene chloride solution
Experimental
Physical measurements and materials
1
All reactions were performed under a dry nitrogen atmosphere
using standard Schlenk techniques or a glove box. Toluene,
diethyl ether, and tetrahydrofuran were dried by refluxing over
sodium benzophenone ketyl. CH2Cl2 was dried over P2O5. All
solvents were distilled and stored in solvent reservoirs which
to yield colorless crystals of 2 (0.61 g, 68.5% yield). H NMR
2
(CDCl3): 2.43 (s, 12H, NMe2), 3.57, 3.80 (dd, JHH = 13.8 Hz,
4H, CH2N), 3.85 (s, 1H, NH), 5.92 (s, 2H, pyrrole CH), 6.37 (t,
1H, p-Ph CH), 7.10 (d, 2H, m-Ph CH). 13C NMR (CDCl3): 47.1
(q, JCH = 138 Hz, NMe2), 59.6 (t, JCH = 138 Hz, CH2N), 104.3
(d, JCH = 166 Hz, pyrrole CH), 114.6 (d, JCH = 165 Hz, phenyl
CH), 120.8 (s, phenyl, Cipso), 127.9 (d, JCH = 163 Hz, phenyl CH),
130.8 (s, pyrrole Cipso), 146.5 (s, phenyl, Cipso). IR (KBr) for Al-H:
1851 cm-1. Anal. Calcd for C16H23N4Cl2Al: C, 52.04; H, 6.28; N,
˚
contained 4 A molecular sieves and were purged with nitrogen.
1H and 13C NMR spectra were recorded on a Bruker Avance
1
300 spectrometer. Chemical shifts for H and 13C spectra were
recorded in ppm relative to the residual protons and 13C of CDCl3
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Fig. 4 The molecular structure of 3, the ellipsoids were drawn at 50% probability level and all hydrogen atoms were omitted for clarity.
Fig. 5 The molecular structure of 5, the ellipsoids were drawn at 50% probability level and all hydrogen atoms were omitted for clarity.
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Fig. 6 The molecular structure of 7, the ellipsoids were drawn at 50% probability level and all hydrogen atoms were omitted for clarity.
Fig. 7 The molecular structure of 9, the ellipsoids were drawn at 50% probability level and all hydrogen atoms were omitted for clarity.
15.17. Found: C, 51.46; H, 6.22; N: 15.35%. The correspond-
ing deuterium compound [C4H2N(CH2NMe2)2]AlD(NHC6H3-
2,6-Cl2) (2-D) was synthesized with the same method and the
NMR spectra are essentially the same as compound 2. The IR
(KBr) for Al–D: 1344 cm-1 (calculated: 1333 cm-1).
vacuum and the resulting solid was recrystallized from a diethyl
ether solution to yield colorless crystals of 3 (0.76 g, 60% yield).
1H NMR (CDCl3): 2.44 (s, 12H, NMe2), 3.83 (s, 4H, CH2N),
4.15 (s, 2H, NH), 5.93 (s, 2H, pyrrole, CH), 6.40 (t, 2H, p-Ph-
CH), 7.12 (d, 4H, m-Ph CH). 13C NMR (CDCl3): 48.0 (q, JCH
136 Hz, NMe2), 60.3 (t, JCH = 137 Hz, CH2NMe2), 105.1 (d, JCH
=
=
Complex 3. A solution of 1 (0.50 g, 2.39 mmol) in 15 mL
diethyl ether was cooled to -78 ◦C, then a 2,6-dichloroaniline
(0.79 g, 4.78 mmol)/diethyl ether (15 mL) solution was added
slowly via cannula. The solution then was warmed to -20 ◦C and
stirred for an additional 15 min. Volatiles were removed under
162 Hz, pyrrole CH), 115.2 (d, JCH = 166 Hz, phenyl CH), 120.9 (s,
phenyl Cipso), 128.2 (d, JCH = 164 Hz, phenyl CH), 130.8 (s, pyrrole
C
ipso), 146.3 (s, phenyl Cipso). Anal. Calcd for C22H26N5Cl4Al:
C, 49.92; H, 4.95; N, 13.23. Found: C, 49.33; H, 5.21; N:
13.02%.
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Table 1 Summary of data collections for compounds 2, 3, 5, 7, 10, and 11
2
3
5
7
9
10
formula
fw
C16H23AlCl2N4
369.26
monoclinic
P21/n
13.3892(4)
10.8311(4)
15.3524(4)
C22H26AlCl4N5
529.26
monoclinic
Cc
21.4849(5)
9.0569(2)
25.5170(6)
C35H36AlCl2N5
624.57
orthorhombic
Pccn
20.656(3)
36.021(7)
8.4360(14)
C33H48AlN3O2
545.72
monoclinic
P21/c
8.7168(3)
17.7020(6)
21.6908(7)
C36H40AlN3O2
573.69
triclinic
P-1
9.7181(3)
11.9863(4)
14.7312(5)
90.608(2)
107.021(2)
104.025(2)
1585.71(9), 2
1.202
C24H30AlN5S2
479.63
monoclinic
P21/c
10.2678(3)
21.9497(6)
14.2669(4)
crystal syst
space group
˚
a (A)
˚
b (A)
˚
c (A)
a (deg)
b (deg)
124.500(2)
90.4260(10)
90
106.796(2)
128.105(2)
g (deg)
3
˚
V (A ), Z
1834.83(10), 4
1.337
0.406
150(2)
776
4965.1(2), 8
1.416
0.533
150(2)
2192
6276.8(18), 8
1.322
0.269
150(2)
2624
3204.21(19), 4
1.131
0.095
150(2)
1184
2530.14(12), 4
1.259
0.267
150(2)
1016
Dcalc (Mg m-3)
Abs coeff (mm-1)
T (K)
0.100
150(2)
612
F(000)
no. of reflns
collected
no. of ind reflns
data/restraints/
params
29329
23086
35323
34891
28937
26122
4425 (Rint = 0.0257) 11124 (Rint = 0.0207) 7517 (Rint = 0.1226) 7730 (Rint = 0.0593) 7625 (Rint = 0.0475) 6099 (Rint = 0.0482)
4425/0/216
11124/2/585
7517/0/392
7730/0/363
7625/0/383
6099/0/293
Flack parameter
goodness of fit on
F2
-0.01(2)
1.057
1.037
0.918
1.023
1.047
1.057
final R indices [I > R1 = 0.0309
R1 = 0.0280
R1 = 0.0660
R1 = 0.0482
R1 = 0.0439
R1 = 0.0376
2s(I)]
wR2 = 0.0781
wR2 = 0.0644
R1 = 0.0346
wR2 = 0.1494
R1 = 0.1812
wR2 = 0.1061
R1 = 0.0879
wR2 = 0.1002
R1 = 0.0772
wR2 = 0.0885
R1 = 0.0635
R indices (all data) R1 = 0.0353
wR2 = 0.0812
wR2 = 0.0666
0.226 and -0.194
wR2 = 0.1893
0.366 and -0.645
wR2 = 0.1207
0.242 and -0.283
wR2 = 0.1120
0.259 and -0.304
wR2 = 0.0960
0.501 and -0.239
largest diff peak
0.677 and -0.708
-3
˚
and hole (e A )
Fig. 8 The molecular structure of 10, the ellipsoids were drawn at 50% probability level and all hydrogen atoms were omitted for clarity.
8640 | Dalton Trans., 2009, 8631–8643
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◦
˚
Table 2 (Contd.)
Table 2 Selected bond lengths (A) and angles ( ) for compounds 2, 3, 5,
7, 9 and 10
10
2
Al(1)–N(1)
Al(1)–N(4)
Al(1)–N(5)
S(1)–C(11)
1.9064(13)
1.9852(14)
2.0201(14)
1.7021(18)
1.6978(18)
99.32(6)
101.00(6)
98.15(6)
83.82(6)
Al(1)–N(2)
Al(1)–S(1)
Al(1)–S(2)
C(11)–N(4)
2.1093(14)
2.5226(6)
2.4894(6)
1.306(2)
1.302(2)
161.52(5)
68.37(4)
90.49(4)
164.33(5)
68.21(4)
90.47(4)
89.36(4)
Al(1)–N(4)
Al(1)–N(2)
Al(1)–H
N(2)–Al(1)–N(4)
N(4)–Al(1)–N(3)
N(1)–Al(1)–N(3)
1.8642(11)
1.8534(10)
1.477(17)
105.90(5)
102.86(5)
151.32(4)
Al(1)–N(1)
Al(1)–N(3)
N(4)–Al(1)–N(1)
N(1)–Al(1)–N(2)
N(2)–Al(1)–N(3)
Al(1)–N(4)–C(11)
2.2318(11)
2.2275(10)
99.20(5)
78.13(4)
78.40(4)
S(2)–C(18)
C(18)–N(5)
N(1)–Al(1)–N(4)
N(1)–Al(1)–N(5)
N(4)–Al(1)–N(5)
N(1)–Al(1)–N(2)
N(4)–Al(1)–N(2)
N(5)–Al(1)–N(2)
N(1)–Al(1)–S(2)
S(2)–C(18)–N(5)
N(4)–Al(1)–S(2)
N(5)–Al(1)–S(2)
N(2)–Al(1)–S(2)
N(1)–Al(1)–S(1)
N(4)–Al(1)–S(1)
N(5)–Al(1)–S(1)
N(2)–Al(1)–S(1)
139.92(9)
101.63(6)
158.60(6)
95.78(4)
3
Al(1)–N(4)
Al(1)–N(2)
Al(1)–N(5)
Al(1)–N(3)
1.8253(17)
1.8432(16)
1.8497(15)
2.1872(17)
2.4171(18)
136.33(7)
111.60(7)
109.64(7)
104.73(7)
79.44(7)
102.53(7)
92.51(7)
74.42(7)
88.93(7)
153.72(6)
Al(2)–N(10)
Al(2)–N(7)
Al(2)–N(9)
Al(2)–N(8)
1.8298(17)
1.8412(18)
1.8527(15)
2.1995(16)
2.3472(18)
138.67(7)
114.23(7)
105.71(8)
102.22(7)
78.93(8)
101.67(7)
93.79(7)
75.04(7)
90.67(7)
153.40(7)
116.82(13)
S(1)–C(11)–N(4)
116.49(13)
Al(1)–N(1)
Al(2)–N(6)
Complex 4. To a solution of 1 (0.50 g, 2.39 mmol) in 15 mL
tetrahydrofuran, a carbazole (0.36 g, 2.15 mmol)/tetrahydrofuran
(15 mL) solution was added at 0 ◦C slowly via cannula. The
solution was stirred at room temperature for 12 h and volatiles
were removed under vacuum to generate pale yellow solids of 4
(0.65 g, 72.6% yield). 1H NMR (CDCl3): 1.87 (s, 6H, NMe2), 2.58
(s, 6H, NMe2), 3.70, 3.79 (dd, 4H, JHH = 14.0 Hz, CH2N), 6.14 (s,
2H, pyrrole CH), 6.48 (d, 1H, phenyl CH), 7.18 (m, 3H, phenyl
CH), 7.44 (t, 1H, phenyl CH), 8.11 (m, 3H, phenyl CH). 13C NMR
(CDCl3): 46.2 (q, JCH = 136 Hz, NMe2), 48.0 (q, JCH = 136 Hz,
NMe2), 60.4 (t, JCH = 139 Hz, CH2N), 105.7 (d, JCH = 166 Hz,
N(4)–Al(1)–N(2)
N(4)–Al(1)–N(5)
N(2)–Al(1)–N(5)
N(4)–Al(1)–N(3)
N(2)–Al(1)–N(3)
N(5)–Al(1)–N(3)
N(4)–Al(1)–N(1)
N(2)–Al(1)–N(1)
N(5)–Al(1)–N(1)
N(3)–Al(1)–N(1)
N(10)–Al(2)–N(7)
N(10)–Al(2)–N(9)
N(7)–Al(2)–N(9)
N(10)–Al(2)–N(8)
N(7)–Al(2)–N(8)
N(9)–Al(2)–N(8)
N(10)–Al(2)–N(6)
N(7)–Al(2)–N(6)
N(9)–Al(2)–N(6)
N(8)–Al(2)–N(6)
5
pyrrole CH), 112.9 (d, JCH = 158 Hz, phenyl CH), 113.8 (d, JCH
=
Al(1)–N(1)
Al(1)–N(3)
1.832(3)
2.247(3)
Al(1)–N(4)
Al(1)–N(5)
N(1)–Al(1)–N(5)
N(5)–Al(1)–N(3)
N(4)–Al(1)–N(2)
N(1)–Al(1)–N(3)
N(5)–Al(1)–N(2)
1.868(3)
1.862(3)
121.99(13)
102.67(12)
99.79(11)
78.06(11)
91.76(11)
164 Hz, phenyl CH), 117.7 (d, JCH = 150 Hz, phenyl CH), 119.7
(d, JCH = 149 Hz, phenyl CH), 124.7 (d, JCH = 159 Hz, phenyl
CH), 125.2 (d, JCH = 158 Hz, phenyl CH), 125.4 (s, phenyl Cipso),
130.6 (s, pyrrole Cipso), 146.7 (s, phenyl Cipso), 147.6 (s, phenyl Cipso).
IR (KBr) for Al–H: 1830 cm-1.
Al(1)–N(2)
2.319(3)
N(5)–Al(1)–N(4)
N(1)–Al(1)–N(2)
N(1)–Al(1)–N(4)
N(4)–Al(1)–N(3)
N(2)–Al(1)–N(3)
114.16(13)
76.39(11)
123.75(13)
93.46(12)
154.43(11)
Complex 5. Same procedure as for synthesizing 4 has been
applied. Amount used: 1, 0.50 g, 2.39 mmol; carbazole, 0.75 g,
4.49 mmol. Yield: 1.01 g, 78.2%. 1H NMR (CDCl3): 1.55 (s, 6H,
NMe2), 2.35 (s, 6H, NMe2), 3.65, 4.57 (dd, 4H, JHH = 15.0 Hz,
CH2N), 6.29 (s, 2H, pyrrole CH), 6.97 (t, 2H, phenyl CH), 7.23 (m,
10H, phenyl CH), 8.11 (m, 4H, phenyl CH). 13C NMR (CDCl3):
47.9 (q, JCH = 137 Hz, NMe2), 48.0 (q, JCH = 135 Hz, NMe2),
62.2 (t, JCH = 142 Hz, CH2N), 106.9 (d, JCH = 171 Hz, pyrrole
CH), 110.5 (d, JCH = 159 Hz, phenyl CH), 112.6 (d, JCH = 157 Hz,
7
Al(1)–N(1)
Al(1)–N(3)
Al(1)–O(2)
C(12)–C(11)
O(1)–Al(1)–O(2)
O(2)–Al(1)–N(1)
O(2)–Al(1)–N(3)
O(1)–Al(1)–N(2)
N(1)–Al(1)–N(2)
C(22)–O(1)–Al(1)
O(2)–C(11)–C(12)
C(12)–C(11)–C(13)
1.8308(12)
2.1885(14)
1.7208(11)
1.321(3)
118.97(6)
114.70(6)
100.09(6)
95.65(6)
Al(1)–N(2)
Al(1)–O(1)
O(2)–C(11)
O(1)–C(22)
O(1)–Al(1)–N(1)
O(1)–Al(1)–N(3)
N(1)–Al(1)–N(3)
O(2)–Al(1)–N(2)
N(3)–Al(1)–N(2)
C(11)–O(2)–Al(1)
O(2)–C(11)–C(13)
2.1952(14)
1.6956(12)
1.3433(18)
1.3459(18)
126.16(6)
96.24(6)
78.14(6)
92.91(6)
155.32(5)
149.89(12)
113.03(14)
phenyl CH), 117.1 (d, JCH = 159 Hz, phenyl CH), 118.6 (d, JCH
=
160 Hz, phenyl CH), 118.8 (d, JCH = 160 Hz, phenyl CH), 119.1
(d, JCH = 159 Hz, phenyl CH), 119.4 (d, JCH = 170 Hz, phenyl
CH), 119.9 (d, JCH = 159 Hz, phenyl CH), 120.2 (d, JCH = 159 Hz,
phenyl CH), 122.9 (s, phenyl Cipso), 124.4 (d, JCH = 158 Hz, phenyl
CH), 125.4 (d, JCH = 159 Hz, phenyl CH), 125.6 (d, JCH = 162 Hz,
phenyl CH), 125.8 (s, phenyl Cipso), 126.0 (s, phenyl Cipso), 131.0 (s,
pyrrole Cipso), 139.2 (s, phenyl Cipso), 145.9 (s, phenyl Cipso), 147.1
(s, phenyl Cipso). Anal. Calcd. for C34H34AlN5·CH2Cl2: C, 67.31;
H, 5.81; N, 11.21. Found: C, 67.44; H, 6.47; N, 11.34%.
77.37(6)
172.55(10)
124.68(16)
122.29(15)
9
Al(1)–O(1)
Al(1)–N(1)
Al(1)–N(3)
O(1)–Al(1)–N(2)
O(1)–Al(1)–N(3)
N(2)–Al(1)–N(3)
O(2)–Al(1)–N(1)
N(1)–Al(1)–N(3)
Al(1)–O(2)–C(24)
1.7241(10)
2.2680(14)
2.2641(14)
121.59(6)
101.91(5)
75.89(5)
94.98(5)
151.46(5)
128.06(9)
Al(1)–O(2)
Al(1)–N(2)
1.7248(10)
1.8453(13)
113.33(5)
127.08(6)
94.84(5)
99.32(5)
76.82(5)
O(1)–Al(1)–O(2)
O(2)–Al(1)–N(2)
O(2)–Al(1)–N(3)
O(1)–Al(1)–N(1)
N(2)–Al(1)–N(1)
Al(1)–O(1)–C(11)
Complex 6. A solution of 1 (3.0 g, 14.3 mmol) in 40 mL diethyl
ether was cooled to 0 ◦C, and a 2,6-diisopropylphenol (2.6 g,
14.4 mmol)/diethyl ether (40 mL) solution was added dropwise via
cannula. The solution was stirred at room temperature for another
3 h after the completion of addition. The volatiles were removed
under vacuum to yield pale yellow solid of the final product 2
135.75(9)
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Fig. 9 Schematic drawings the molecular structures of 2, 3, 5, 7, and 9 presenting the relative geometries of all crystal structures.
(4.5 g, 81% yield). 1H NMR (CDCl3): 1.16 (d, 12H, CHMe2), 2.42
(s, 12H, NMe2), 3.32 (m, 4H, CHMe2), 3.63 (d, 2H, CH2NMe2),
3.75 (d, 2H, CH2NMe2), 5.95 (s, 2H, pyrrole CH), 6.78 (t, 2H,
phenyl CH), 7.02 (d, 2H, phenyl CH). 13C NMR (CDCl3): 23.5 (q,
JCH = 125 Hz, CHMe2), 26.5 (d, JCH = 127 Hz, CHMe2), 46.9 (q,
JCH = 137 Hz, NMe2), 59.9 (t, JCH = 139 Hz, CH2NMe2), 104.3
(d, JCH = 165 Hz, pyrrolyl CH), 117.9 (d, JCH = 159 Hz, phenyl
CH), 123.0 (d, JCH = 155 Hz, phenyl CH), 130.3 (s, Cipso), 136.9
(s, Cipso), 153.2 (s, Cipso). IR (KBr) for Al–H: 1853 cm-1.
NMR (CDCl3): 20.5 (q, JCH = 126 Hz, o-PhMe), 20.9 (q, JCH
126 Hz, p-PhMe), 46.9 (q, JCH = 137 Hz, NMe2), 60.3 (t, JCH
=
=
139 Hz, CH2N), 91.4 (dd, JCH = 158 Hz, 158 Hz, OCCH2), 104.1
(d, JCH = 167 Hz, pyrrole CHCCH2), 128.0 (d, JCH = 150 Hz,
phenyl CH), 130.7 (s, pyrrole Cipso), 135.4 (s, phenyl Cipso), 136.0
(s, phenyl Cipso), 138.5 (s, OCCH2), 157.6 (s, phenyl Cipso).
Complex 9. A solution of 1 (0.30 g, 1.44 mmol) in 20 mL
methylene chloride was cooled to -78 ◦C, and a methylene chloride
(15 mL) solution of benzophenone (0.53 g, 2.88 mmol) was added
◦
Complex 7. A solution of 6 (0.88 g, 2.28 mmol) in 20 mL
methylene chloride was cooled to -78 ◦C, and a 2,4,6-
trimethylacetophenone (0.37 g, 2.28 mmol)/methylene chloride
(15 mL) solution was added slowly via cannula. The solution then
was stirred at -20 ◦C for 2 h after addition to be completed.
The volatiles were removed under vacuum and a white solid was
obtained (1.05 g, 84%). 1H NMR (CDCl3): 1.15 (d, 3J = 13.5 Hz,
12H, CHMe2), 2.29 (s, 3H, p-PhMe), 2.36 (s, 6H, o-PhMe), 2.38 (s,
dropwise via cannula. The solution was stirred at -20 C for 2 h
and then volatiles were removed under vacuum to yield a solid of
10 which then was recrystallized from a diethyl ether/methylene
chloride mixed solvent to generate 0.36 g (44% yield) of final
product 10. 1H NMR (CDCl3): 2.06 (s, 12H, NMe2), 3.32 (s, 4H,
NCH2), 5.91 (s, 2H, pyrrole CH), 5.91 (s, 2H, OCH), 7.17 (t, 4H,
phenyl CH), 7.26 (t, 8H, phenyl CH), 7.39 (d, 8H, phenyl CH).
13C NMR (CDCl3): 46.7 (q, JCH = 137 Hz, NMe2), 59.9 (t, JCH
138 Hz, NCH2), 77.0 (d, JCH = 139 Hz, OCH), 103.9 (d, JCH
=
12H, NMe2), 3.41 (m, 2H, CHMe2), 3.57, 3.64 (dd, 2J = 21.0 Hz,
=
3
=
J = 13.5 Hz, 4H, CH2N), 4.08 (s, 1H, OC CH2), 4.38 (s, 1H,
166 Hz, pyrrole CH), 126.3 (d, JCH = 160 Hz, phenyl CH), 126.7
(d, JCH = 158 Hz, phenyl CH), 127.9 (d, JCH = 159 Hz, phenyl
CH), 131.2 (s, pyrrole CHCN), 148.2 (s, phenyl OCHCCH). Anal.
Calcd. for C36H40N3O2Al: C: 75.37; H: 7.03; N: 7.32; Found: C:
74.50; H: 6.73; N: 6.90%.
=
OC CH2), 5.98 (s, 2H, pyrrole CH), 6.80-7.07 (m, 5H, phenyl
CH). 13C NMR (CDCl3): 20.5 (q, JCH = 126 Hz, o-PhMe), 21.0
(q, JCH = 120 Hz, p-PhMe), 24.2 (q, JCH = 125 Hz, CHMe2), 25,7
(d, JCH = 126 Hz, CHMe2), 47.3 (q, JCH = 137 Hz, NMe2), 60.6
=
(t, JCH = 138 Hz, CH2N), 91.6(dd, JCH = 159, 158 Hz, OC CH2),
Complex 10. A solution of 1 (1.00 g, 4.78 mmol) in 15 mL
104.5 (d, JCH = 166 Hz, pyrrole CH), 118 (d, JCH = 160 Hz, phenyl
CH), 123.2 (d, JCH = 155 Hz, phenyl CH), 128.0 (d, JCH = 154 Hz,
phenyl CH), 130.3 (s, pyrrole C), 135.4 (s, phenyl Cipso), 136.3 (s,
phenyl Cipso), 137.2 (s, phenyl Cipso), 138.5 (s, phenyl Cipso), 152.3
◦
diethyl ether was cooled to -78 C, and a diethyl ether (15 mL)
solution of phenyl isothiocyanate (1.30 g, 9.6 mmol) was added
dropwise via cannula. The solution was slowly warmed to –20 ◦C
and stirred for 1 h. The clear solution became cloudy with white
precipitation. The solid was filtered off and recrystallized from a
diethyl ether and methylene chloride solution to yield 1.40 g of
=
(s, OCC), 157.4 (s, OC CH2). Anal. Calcd. for C33H48N3O2Al: C,
72.63; H, 8.87; N, 7.70. Found: C, 72.87; H, 8.62; N, 7.45%.
1
Complex 8. A solution of 1 (0.30 g, 1.44 mmol) in 20 mL
methylene chloride wad cooled to -20 ◦C, and a methylene chlo-
ride (15 mL) solution of 2¢,4¢,6¢-trimethylacetophenone (0.47 g,
2.89 mmol) was added dropwise via cannula. The solution was
stirred at -20 ◦C for 30 min and then volatiles were removed under
vacuum to yield a pale yellow solid of 4 (0.42 g, 55.3% yield). 1H
NMR (CDCl3): 2.25 (s, 6H, p-PhMe), 2.32 (s, 12H, o-PhMe), 2.37
(s, 12H, NMe2), 3.51 (s, 4H, CH2N), 3.99 (s, 2H, OCCH2), 4.46 (s,
10 (61% yield). H NMR (CDCl3, 240 K): 1.61 (s, 6H, NMe2),
2.09 (d, 2JHH = 14.7 Hz, 1H, CH2N), 2.54 (s, 3H, NMe2), 2.83 (s,
3H, NMe2), 2.90 (d, 2JHH = 14.2 Hz, 1H, CH2N), 3.60 (d, 2JHH
=
2
14.2 Hz, 1H, CH2N), 4.14 (d, JHH = 14.2 Hz, 1H, CH2N), 5.95
(s, 1H, pyrrole CH), 6.03 (s, 1H, pyrrole CH), 6.36 (d, 2H, phenyl
CH), 7.15 (m, 8H, phenyl CH), 9.13 (s, 1H, SCHNPh), 9.46 (s,
1H, SCHNPh). 13C NMR (CDCl3, 230 K): 46.1 (q, JCH = 129 Hz,
NMe2), 46.7 (q, JCH = 135 Hz, NMe2), 50.2 (q, JCH = 139 Hz,
NMe2), 60.2 (t, JCH = 135 Hz, CH2N), 60.7 (t, JCH = 130 Hz,
2H, OCCH2), 5.87 (s, 2H, pyrrole CH), 6.80 (s, 4H, Ph CH). 13
C
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CH2N), 104.5 (d, JCH = 168 Hz, pyrrole CH), 106.7 (d, JCH
=
2001, 40, 2011; (c) H. Zhu, Z. Yang, J. Magull, H. W. Roesky, H. -G.
Schmidt and M. Noltemeyer, Organometallics, 2005, 24, 6420; (d) R. J.
Wehmschulte and P. P. Power, J. Am. Chem. Soc., 1996, 118, 791; (e) T.
Belgardt, J. Storre, A. Klemp, H. Gornitzka, L. Ha¨ming, H.-G. Schmidt
and H. W. Roesky, J. Chem. Soc., Dalton Trans., 1995, 3747; (f) T. Bauer,
S. Schulz, H. Hupfer and M. Nieger, Organometallics, 2002, 21, 2931.
5 (a) P. J. Brothers, R. J. Wehmschulte, M. M. Olmstead, K. Ruhlandt-
Senge, S. R. Parkin and P. P. Power, Organometallics, 1994, 13, 2792;
(b) G. M. Sheldrick and W. S. Sheldrick, J. Chem. Soc. A, 1969, 2279;
(c) A. J. Downs, D. Duckworth, J. C. Machell and C. R. Pulham,
Polyhedron, 1992, 11, 1295; (d) U. Du¨michen, V. Gelbrich and J. Sieler,
Z. Anorg. Allg. Chem., 1999, 625, 262; (e) N. Kuhn, S. Fuchs and M.
Steimann, Z. Anorg. Allg. Chem., 2000, 626, 1387; (f) K. Ouzounis, H.
Riffel, H. Hess, U. Kohler and J. Weidlein, Z. Anorg. Allg. Chem., 1983,
504, 67; (g) C. -C. Chang, M. -D. Li, M. Y. Chiang, S. -M. Peng, Y.
Wang and G. -H. Lee, Inorg. Chem., 1997, 36, 1955; (h) J. F. Janik, R. L.
Wells, A. L. Rheingold and I. A. Guzei, Polyhedron, 1998, 17, 4101.
6 (a) M. Uchiyama, S. Furumoto, M. Saito, Y. Kondo and T. Sakamoto,
J. Am. Chem. Soc., 1997, 119, 11425; (b) R. T. Luibrand, I. R. Taigounov
and A. A. Taigounov, J. Org. Chem., 2001, 66, 7254; (c) J. March,
Advanced Organic Chemistry, 4th edn, Wiley, New York, 1992.
7 (a) J. A. Jensen, J. Organomet. Chem., 1993, 456, 161; (b) N. D. Reddy,
H. W. Roesky, M. Noltemeyer and H. -G. Schmidt, Inorg. Chem., 2002,
41, 2374; (c) N. D. Reddy, S. S. Kumar, H. W. Roesky, D. Vidovic, J.
Magull, M. Noltemeyer and H.-G. Schmidt, Eur. J. Inorg. Chem., 2003,
442.
162 Hz, pyrrole CH), 121.0 (d, JCH = 159 Hz, phenyl CH), 121.6
(d, JCH = 160 Hz, phenyl CH), 126.3 (d, JCH = 162 Hz, phenyl
CH), 129.2 (d, JCH = 162 Hz, phenyl CH), 129.6 (d, JCH = 161 Hz,
phenyl CH), 131.2 (s, pyrrole Cipso), 135.8 (s, pyrrole Cipso), 144.6
(s, phenyl Cipso), 146.0 (s, phenyl Cipso), 184.9 (d, JCH = 181 Hz,
SCHNPh), 189.6 (d, JCH = 179 Hz, SCHNPh). Anal. Calcd. for
C24H30N5S2Al: C, 60.10; H, 6.30; N, 14.60. Found: C, 59.92; H,
6.51; N, 14.42%.
X-Ray crystallography
The crystals were mounted on capillaries and transferred to a
goniostat and were collected at 150 K under a nitrogen stream.
Data were collected on a Bruker SMART CCD diffractometer
with graphite-monochromated Mo-Ka radiation. The structures
were solved by direct and difference Fourier methods and refined
by full matrix least-squares on F2. All non-hydrogen atoms
were refined with anisotropic displacement parameters. Crys-
tallographic computing was performed using the SHELXTL22
package of programs. All refinements were carried out by full-
matrix least squares using anisotropic displacement parameters
for all non-hydrogen atoms. All the relevant crystallographic data
and structure refinement parameters for 2, 3, 5, 7, 9 and 10 are
summarized in Table 1.
8 Y. Peng, G. Bai, H. Fan, D. Vidovic, H. W. Roesky and J. Magull, Inorg.
Chem., 2004, 43, 1217.
9 (a) G. Zweifel and J. A. Miller, Org. React., 1984, 32, 375; (b) Compre-
hensive Organic Synthesis, ed. J. J. Eisch, B. M. Trost and I. Fleming,
Pergamon, Oxford, UK, 1991, Vol. 8, 733; (c) S. S. Kumar, J. Rong,
S. Singh, H. W. Roesky, D. Vidovic, J. Magull, D. Neculai, V.
Chandrasekhar and M. Baldus, Organometallics, 2004, 23, 3496.
10 R. J. Wehmschulte and P. P. Power, Inorg. Chem., 1998, 37, 6906.
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Acknowledgements
The authors gratefully acknowledge the National Science Council
of Taiwan for the financial assistance. JHH would also like
to thank the National Changhua University of Education for
providing the X-ray facility.
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