Arene-ruthenium complexes with phosphanylferrocenecarboxamides bearing polar hydroxyalkyl groups-synthesis, molecular structure, and catalytic use in redox isomerizations of allylic alcohols to carbonyl compounds

Article abstract of DOI:10.1002/ejic.201200733

Phosphanylferrocenecarboxamide Ph₂P-fc-CONHCH₂CH ₂OH (1, fc = ferrocene-1,1′-diyl) and its newly synthesized congeners, Ph₂P-fc-CONHCH(CH₂OH)₂ (2) and Ph₂P-fc-CONHC(CH₂OH)₃ (3), were converted to a series of (η⁶-arene)ruthenium complexes [(η⁶- arene)RuCl₂(L-κP)] 5-7, where arene is benzene, p-cymene, and hexamethylbenzene and L = 1-3. All compounds were characterized by multinuclear NMR and IR spectroscopy, by mass spectrometry, and by elemental analysis. The molecular structures of 2, 3, 3O (a phosphane oxide resulting from the oxidation of 3), 5c·CH₂Cl₂, and 6c·Et₂O were determined by single-crystal X-ray diffraction analysis. The ruthenium complexes were further evaluated as catalysts in the redox isomerization of allyl alcohols to carbonyl compounds. Complex [(η⁶-p-cymene) RuCl₂(1-κP)] (5b) proved to be a particularly attractive catalyst, being both readily available and catalytically active. Substrates with unsubstituted double bonds were cleanly isomerized with this catalyst in 1,2-dichloroethane (0.5 mol-% Ru, 80 °C), whereas for those bearing substituents at the double bond (particularly in the position closer to the OH group) lower conversions and selectivities were achieved. A similar trend was noted when pure water was used as the solvent, except that the best results (complete conversion with 2 mol-% Ru) were seen for 1,3-diphenylallyl alcohol, the most hydrophobic substrate.

Full text of DOI:10.1002/ejic.201200733

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FULL PAPER
DOI: 10.1002/ejic.201200733
Arene–Ruthenium Complexes with Phosphanylferrocenecarboxamides Bearing
Polar Hydroxyalkyl Groups – Synthesis, Molecular Structure, and Catalytic
Use in Redox Isomerizations of Allylic Alcohols to Carbonyl Compounds
[a]
[a]
[a]
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Jirí Schulz, Ivana Císarová, and Petr Stepnicka*
Dedicated to the memory of Professor Jaroslav Podlaha
Keywords: Metallocenes / Structure elucidation / Isomerization / Phosphane ligands / Ruthenium
Phosphanylferrocenecarboxamide
Ph2P–fc–CONHCH2-
allyl alcohols to carbonyl compounds. Complex [(η6-p-cy-
mene)RuCl2(1-κP)] (5b) proved to be a particularly attractive
catalyst, being both readily available and catalytically active.
Substrates with unsubstituted double bonds were cleanly
isomerized with this catalyst in 1,2-dichloroethane (0.5 mol-
% Ru, 80 °C), whereas for those bearing substituents at the
double bond (particularly in the position closer to the OH
group) lower conversions and selectivities were achieved. A
similar trend was noted when pure water was used as the
solvent, except that the best results (complete conversion
with 2 mol-% Ru) were seen for 1,3-diphenylallyl alcohol, the
most hydrophobic substrate.
CH2OH (1, fc = ferrocene-1,1Ј-diyl) and its newly synthesized
congeners, Ph2P–fc–CONHCH(CH2OH)2 (2) and Ph2P–fc–
CONHC(CH2OH)3 (3), were converted to a series of (η6-
arene)ruthenium complexes [(η6-arene)RuCl2(L-κP)] 5–7,
where arene is benzene, p-cymene, and hexamethylbenzene
and L = 1–3. All compounds were characterized by multinu-
clear NMR and IR spectroscopy, by mass spectrometry, and
by elemental analysis,. The molecular structures of 2, 3, 3O
(a phosphane oxide resulting from the oxidation of 3),
5c·CH2Cl2, and 6c·Et2O were determined by single-crystal
X-ray diffraction analysis. The ruthenium complexes were
further evaluated as catalysts in the redox isomerization of
Rather surprisingly, only a handful of such modified do-
nors have been reported for the practically very successful
phosphanylferrocene ligands.[3,4] Pugin et al. prepared chi-
ral phosphanylferrocene donors (Josiphos analogues) bear-
ing polar, solvent-directing imidazolium and polycarboxyl-
ate tags.[5] We have recently reported several polar ferro-
cene-based amidophosphane donors prepared by the conju-
gation of 1Ј-(diphenylphosphanyl)ferrocene-1-carboxylic
acid (Hdpf; Scheme 1)[6] with aminosulfonic acids,[7] amino
acids,[8] or hydroxyalkyl-substituted amines.[9] Since phos-
phanylamides bearing hydroxyalkyl substituents have only
few precedents, even among simple (organic) ligands,[10–12]
we set out to extend our earlier study focused on ligand
1[9,13] (Scheme 1) toward the structurally related bis- and
tris(hydroxymethyl)methanamine derivatives 2 and 3.
Introduction
Phosphanyl-carboxamides are versatile ligands, having
manifold applications in catalysis.[1] The possibility of a
practically unlimited combination of various molecular
fragments achieved by amide coupling makes phosphanyl-
carboxylic amides structurally very flexible and can be ad-
vantageously utilized in the preparation of purpose-tailored
donors. In such compounds, the phosphanyl moiety typi-
cally acts as a metal binding site, whereas the amide moiety
is used to impart the desired property, to increase the affin-
ity of these donors and their complexes toward a particular
solvent or phase, or to do both. For instance, a number of
ligands have been designed by using this approach, which
were used in transition-metal-catalyzed reactions performed
in ionic liquids, water, and mixed-solvent aqueous reaction
media.[1,2]
[a] Department of Inorganic Chemistry, Faculty of Science,
Charles University in Prague,
Hlavova 2030, 12840 Prague, Czech Republic
Fax: +420-221-951-253
E-mail: stepnic@natur.cuni.cz
Homepage: http://web.natur.cuni.cz/~stepnic/
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejic.201200733.
Scheme 1.
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FULL PAPER
This work describes the preparation and structural char- mass spectra that show abundant pseudomolecular ions
acterization of the new phosphanylferrocene hydroxyalkyl- ([M – H]–). The NMR spectra of 2 and 3 comprise signals
substituted amides 2 and 3 and of (η6-arene)ruthenium of the 1Ј-(diphenylphosphanyl)ferrocen-1-yl group and the
complexes featuring compounds 1–3 as P-monodentate li- amide pendants. It is noteworthy that the positions of the
gands. Also reported are the results of catalytic tests of the 1H, 13C{1H}, and 31P{1H} NMR signals of the former moi-
Ru complexes in the redox isomerization of allylic alcohols ety are practically identical with those found for 1. Differ-
to carbonyl compounds.
ences are seen for the signals of the NHCH3–n(CH2OH)n
groups, which shift to the lower field in both 1H and
13C{1H} NMR spectra upon increasing the substitution at
the α-C atom (i.e., with increasing n). The presence of the
amide moiety is clearly manifested in the IR spectra
through characteristic amide I (ca. 1620 cm–1), amide II (ca.
1540 cm–1), and νNH bands (3260–3300 cm–1).
Results and Discussion
Synthesis and Structural Characterization of the Ligands
The (2-hydroxyethyl)-substituted amide 1 was obtained
by the amide coupling of Hdpf with (2-hydroxyethyl)amine
upon the action of 1-ethyl-3-[(3-dimethylamino)propyl]-
carbodiimide and 1-hydroxybenzotriazole as reported ear-
lier.[9a] Amides 2 and 3, completing the series of structurally
Molecular Structures of Compounds 2, 3, and 3O
Single crystals of 2 and 3 suitable for X-ray diffraction
related ligands, have been prepared similarly (Scheme 2) by analysis were grown from ethyl acetate/hexane. The same
the direct reaction of Hdpf with an excess of the respective procedure also afforded crystals of phosphane oxide 3O, a
amine in the presence of 2-ethoxy-1-(ethoxycarbonyl)-1,2- compound resulting from the slow oxidation of the parent
dihydroquinoline (EEDQ) as an amide coupling agent and phosphane 3 with air. This compound was prepared inten-
4-(dimethylamino)pyridine (DMAP) as a base in pyridine tionally by the reaction of 3 with hydrogen peroxide (see
solvent. The coupling agent was chosen mainly to avoid an Exp. Sect.). Views of the molecular structures of 2, 3, and
undesired formation of esters.[14,15] This procedure afforded 3O are presented in Figures 1, 2, and 3, respectively. Se-
amides 2 and 3 in good yields (40 and 56%, respectively) lected geometric data are summarized in Table 1.
after isolation by column chromatography and subsequent
crystallization from ethyl acetate/hexane. Alternatively,
compound 3 was synthesized from the active pentafluoro-
phenyl ester 4[9a,16] and 2-amino-2-(hydroxymethyl)prop-
ane-1,3-diol (TRIS; route B in Scheme 2). However, this re-
action performed in the presence of DMAP in DMF at
room temperature afforded the amide with a considerably
lower isolated yield (27%).
Figure 1. PLATON plot of the molecular structure of compound
2 showing the atom labeling scheme and displacement ellipsoids at
the 30% probability level.
The ferrocene moieties in 2, 3, and 3O are regular, show-
ing marginal variations in the individual Fe–C distances
and, accordingly, tilt angles of only approximately 1°. The
structures differ by the orientation of the substituents at-
tached to the ferrocene moiety. As indicated by the torsion
angles τ in Table 1, the cyclopentadienyl rings in 2 and 3
adopt a conformation close to anticlinal eclipsed (ideal
Scheme 2. Synthesis of amides 2 and 3. Legend: EEDQ = 2-ethoxy-
value: τ = 144°) and synclinal eclipsed (ideal value: τ = 72°),
1-(ethoxycarbonyl)-1,2-dihydroquinoline, EDC
= 1-[3-(dimeth-
respectively, whereas in 3O they assume an intermediate
orientation. In all three cases, the amide substituents are
rotated out of the plane of their bonding cyclopentadienyl
ylamino)propyl]-3-ethylcarbodiimide, DMF = N,N-dimethylform-
amide, DMAP = 4-(dimethylamino)pyridine.
The formulations of amides 2 and 3 were confirmed by ring Cp1. The largest deviation from a coplanar arrange-
elemental analyses and by electrospray ionization (ESI) ment is seen for compound 3 (see φ angle in Table 1). Other-
2
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Ru Complexes with Phosphanylferrocenecarboxamide Ligands
Table 1. Selected geometric data for 2, 3, and 3O [distances in Å
and angles in °].
Parameter[a]
2
3
3O[b]
Fe–C
2.037(2)–
2.053(3)
1.651(1)
1.643(1)
1.0(1)
2.022(3)–
2.047(3)
1.641(1)
1.639(1)
1.3(2)
2.032(2)–
2.071(2)
1.6597(9)
1.658(1)
0.9(1)
(range)
Fe–Cg1
Fe–Cg2
tilt
τ
152.4(2)
1.477(3)
1.239(2)
1.347(2)
79.2(2)
121.4(1)
1.482(3)
1.236(2)
1.346(3)
123.4(2)
11.1(2)
C1–C11
C11–O1
C11–N
1.478(3)
1.242(3)
1.344(3)
123.8(2)
24.7(3)
O1–C11–N 122.3(2)
φ
17.8(2)
1.805(3)
C6–P
1.821(3)
1.775(2)
[a] Definition of the ring planes: Cp1 = C(1–5), Cp2 = C(6–10);
Cg1 and Cg2 are the centroids of the rings Cp1 and Cp2. Tilt =
dihedral angle subtended by planes Cp1 and Cp2; τ = torsion angle
C1–Cg1–Cg2–C6. φ is the dihedral angle of planes Cp1 and
{C11,N,O1}. [b] Further data: P–O1P 1.456(2) Å.
Figure 2. PLATON plot of the molecular structure of compound
3. Displacement ellipsoids are drawn at the 30% probability level.
wise, the molecular structures compare well with those
determined for other uncoordinated Hdpf-based
amides.[7,8a,9a,17]
In their crystals, compounds 2, 3, and 3O form compli-
cated supramolecular arrays through hydrogen-bonding in-
teractions of their polar amide pendants. In the case of 2,
the individual molecules combine into centrosymmetric
pairs by forming O2–H2O···O1 hydrogen bonds (Figure 4,
a; for parameters, see Table 2). These dimers, stabilized by
intramolecular C8–H8···O3 contacts, are connected to
proximal molecules by means of N–H1N···O2 and C2–
H2···O3 interactions to form layers oriented parallel to the
bc plane (Figure 4, b). The assembly is further stabilized by
O3–H3O···P contacts (Figure 4, c) directed above and be-
Figure 3. PLATON plot of the molecular structure of phosphane low the mentioned dimeric units (the O3 atom acts already
oxide 3O. Displacement ellipsoids are drawn at the 30% probability
level.
as an acceptor for two C–H bonds). This rather peculiar
interaction is manifested by a distinct electron density peak
Figure 4. Packing diagrams for compound 2. (a) View of the hydrogen-bonded dimeric motif in the structure of 2; (b) full view showing
the same dimeric unit and its interactions with adjacent molecules; (c) O–H···P contacts between molecules related by elemental translation
along the y axis. For clarity, only OH and NH hydrogen atoms and pivotal carbon atoms from the phenyl rings (in parts a and b) are
shown. The hydrogen bonds are indicated with dashed lines (for parameters, see Table 2). In part c, the green lines connect the phosphorus
atoms with the refined electron density maxima (see Exp. Sect.).
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in an appropriate position, which corresponds to the lone
electron pair at the phosphorus (see Exp. Sect.). Although
considerably weaker than the conventional O···H–O and
O···H–N hydrogen bonds operating in the structure of 2,
the P···H–O interactions have been documented by spectro-
scopic measurements[18] and can be detected in the crystal
structures of other hydroxyphosphanes (including ferro-
cene-based ones[19]) and adducts formed from phosphanes
and alcohols.[20] It is also noteworthy that the basic dimeric
motif in 2 as well as its interactions with adjacent molecules
are the same as those found in the structure of 1, from
which 2 actually differs by the added CH2OH arm, which
enters into the O–H···P interactions with molecules located
above and below the dimeric unit.
Table 2. Hydrogen bond parameters for 2, 3, and 3O.[a]
D–H···A[b]
D···A distance [Å]
D–H···A angle [°]
Figure 5. Section of a hydrogen-bonded array in the structure of 3.
For clarity, only the OH and NH hydrogens are shown and the
bulky (phosphanyl)ferrocenyl moieties were replaced with black
squares.
Compound 2
N–H1N···O2i
O2–H2O···O1ii
O3–H3O···Piii
C2–H2···O3iv
C8–H8···O3 (I)
3.103(2)
2.745(2)
3.282(2)
3.126(3)
3.317(3)
163
163
155
132
166
dimers are further connected to adjacent dimer units by O–
H···O=C interactions, forming double stranded ribbons ori-
ented along the c axis. Some C–H···O contacts (Table 2)
operate synergistically with these conventional hydrogen
bonds.
Compound 3
N–H1N···O2 (I)
N–H1N···O2v
2.778(3)
2.952(3)
2.675(2)
2.582(3)
2.679(2)
107
157
168
152
165
O2–H2O···O4vi
O3–H3O···O1 (I)
O4–H4O···O3vii
Compound 3O
N–H1N···O2viii
O2–H2O···O1Pviii
O3–H3O···O1Pviii
O4–H4O···O1ix
C3–H3···O4x
3.236(2)
2.755(2)
2.695(2)
2.780(2)
3.254(2)
3.288(2)
3.444(3)
3.465(3)
170
163
161
157
153
142
169
157
C5–H5···O2viii
C8–H8···O1ix
C9–H9···O3ix
[a] D = donor, A = acceptor. [b] Symmetry operations, i: 1 – x, y –
1/2, 3/2 – z; ii: 1 – x, 2 – y, 1 – z; iii: x, y + 1, z; iv: x, 3/2 – y, z –
1/2; v: 1 – x, –1 – y, –z; vi: 2 – x, –1 – y, –z; vii: 2 – x, –y, –z, viii:
2 – x, –y, 1 – z; ix: 2 – x, –y, 2 – z; x: x – 1, y, z. (I) denotes an
intramolecular contact.
Figure 6. Hydrogen-bonded ribbons in the structure of 3O. Only
OH and NH hydrogen atoms and pivotal carbon atoms from the
phenyl rings are shown for clarity.
The crystal packing of 3 is also dominated by hydrogen-
bonding interactions of the amide moieties but lacks sup-
portive C–H···O contacts (Figure 5). Each amide unit of 3
forms a closed array with its inversion-related counterpart,
where the H1N and O2 atoms act as bifurcated hydrogen-
bond donors and acceptors, respectively.[21] Combined with
additional inter- and intramolecular hydrogen bonds
formed by the remaining OH groups, the O–H···O and N–
H···O interactions give rise to sheets oriented along the ab
plane. The bulky (phosphanyl)ferrocenyl moieties extend
above and below these sheets and thus encase these polar
sheets.[22]
Synthesis and Structural Characterization of (η6-Arene)RuII
Complexes
Ligands 1–3 were employed in the preparation of the (η6-
arene)RuII complexes 5–7 (Scheme 3). These complexes
As expected, the polarized P=O group[23] in 3O takes
part in hydrogen bonding (Figure 6). The individual mole-
cules assemble into pairs around an inversion centers
through N–H···OH and O–H···O=P hydrogen bonds. These Scheme 3.
4
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Ru Complexes with Phosphanylferrocenecarboxamide Ligands
were readily synthesized through bridge-cleaving reactions bound arene ring and the phosphanyl-substituted cyclopen-
of the respective chloride dimers [(η6-arene)RuCl2]2 with tadienyl ring (Cp2) are mutually rotated by approximately
stoichiometric amounts of the corresponding phosphanyl- 20°.[27] The ferrocene cyclopentadienyl rings are tilted by
ferrocene ligands and were purified by column chromatog- approximately 6° and their substituents adopt an anticlinal
raphy.
eclipsed conformation (cf. the ideal value: τ = 144°). Like
The coordination of the ligands 1–3 to the (C6H6)Ru and the free ligands, the complexes form hydrogen-bonded sup-
(p-cymene)Ru fragments results in a characteristic shift of ramolecular assemblies in the solid state. Diagrams de-
1
one H NMR signal assigned to ferrocene-CH protons to picting the crystal packing of 5c·CH2Cl2 and 6c·Et2O are
a higher field (δH = 3.17–3.72 ppm). In the case of presented in the Supporting Information (Figures S1 and
(C6Me6)Ru complexes, this signal is not observed because S2).
of extensive broadening, which probably reflects a hindered
molecular mobility resulting from spatial interactions of the
bulky Ru-bound arene and the (phosphanyl)ferrocenyl moi-
ety. Similar features have been observed in the spectra of
[(η6-arene)RuCl2(L)] complexes with other phosphanylfer-
rocenecarboxamides (L).[8d] The 31P{1H} NMR spectra of
5–7 comprise singlet resonances at δP = 16–20 ppm,[24]
whereas the ESI MS spectra of 5–7 are dominated by ions
resulting from a simultaneous elimination of Cl– and HCl,
[M – Cl – HCl]+.
The molecular structures of the solvates 5c·CH2Cl2 and
6c·Et2O were determined by single-crystal X-ray diffraction
analysis (Figures 7 and 8; Table 3). Both compounds pos-
sess the expected three-legged piano stool structures, similar
to the one earlier determined for [(η6-p-cymene)RuCl2-
(Hdpf-κP)].[25] The Cl–Ru–Cl and Cl–Ru–P angles do not
depart much from the 90° angle expected for a pseudo-octa-
Figure 8. PLATON plot of the complex molecule in the structure
hedral structure, in which the arene ligand occupies one tri-
gonal face of the octahedron. On the other hand, the Cg–
Ru–Cl and Cg–Ru–P angles, involving the centroid of the
benzene ring (Cg), differ significantly from each other (Cg–
Ru–Cl 123–126°; Cg–Ru–P 134–135°),[26] which reflects un-
like steric demands of the chloride and the phosphanylfer-
rocene ligands. Despite this distortion, however, only a neg-
ligible slanting of the piano-stool structure is seen, as indi-
cated by the dihedral angle of the basal plane {Cl1,Cl2,P}
and the η6-arene ring being 4.33(8)° and 5.8(1)° for
5c·CH2Cl2 and 6c·Et2O, respectively. The planes of the Ru-
of 6c·Et2O. Displacement ellipsoids are drawn at the 30% prob-
ability level.
Table 3. Selected geometric data for 5c·CH2Cl2 and 6c·Et2O [dis-
tances in Å and angles in °].
Parameter[a]
5c·CH2Cl2
6c·Et2O
Ru–Cl1
Ru–Cl2
Ru–P
Ru–C (range)
Cl1–Ru–Cl2
Cl1–Ru–P
Cl2–Ru–P
Fe–Cg1
Fe–Cg2
tilt
2.4232(6)
2.4228(6)
2.3443(5)
2.202(2)–2.271(3)
88.13(2)
85.29(2)
85.99(2)
1.651(1)
1.654(1)
6.1(1)
2.4132(6)
2.4141(7)
2.3569(6)
2.211(3)–2.252(3)
88.13(2)
83.59(2)
85.76(2)
1.650(1)
1.649(1)
5.6(2)
τ
143.0(2)
1.236(3)
1.344(3)
121.7(2)
13.7(3)
141.9(2)
1.239(3)
1.335(3)
121.3(3)
4.9(3)
C11–O1
C11–N
O1–C11–N
φ
[a] Definition of the ring planes: Cp1 = C(1–5), Cp2 = C(6–10);
Cg1 and Cg2 are the centroids of the rings Cp1 and Cp2. Tilt:
dihedral angle subtended by the planes Cp1 and Cp2; τ is the tor-
sion angle C1–Cg1–Cg2–C6. φ denotes the dihedral angle of the
planes Cp1 and {C11,N,O1}.
Catalytic Tests
The transition-metal-catalyzed isomerization of allylic
alcohols to saturated carbonyl compounds represents a syn-
thetically useful, atom-economical process, the importance
Figure 7. PLATON plot of the complex molecule in the structure
of 5c·CH2Cl2. Displacement ellipsoids are drawn at the 30% prob-
ability level.
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of which has been growing over the last decade.[28] In recent better than the related complex obtained from the parent
years, the main effort was focused on the development of carboxyphosphane,
[(η6-p-cymene)RuCl2(Hdpf-κP)],[25]
efficient catalytic systems that promote this reaction under which gave only 23% conversion under identical conditions
mild conditions and in short reaction times.[29,30] The pro- (80 °C, 1 h).
gress achieved in turn allowed for the development of vari-
Table 4. Results of catalytic tests, achieved with the (η6-arene)RuII
complexes 5–7 in the model isomerization reaction of 1-octen-3-ol
ous tandem processes (e.g., isomerization and C–C coupling
or isomerization and C–F bond formation)[29b] and even an
to octan-3-one performed at 80 °C in 1,2-dichloroethane.[a]
asymmetric variant of this reaction.[31,32] Water as a green
Ligand/arene
Catalyst/yield[b] [%]
solvent with specific properties[33] and has been used advan-
tageously as a medium for this reaction has often been em-
ployed together with RuII and RuIV catalysts.[34] Recent ap-
plications of arene–ruthenium(II) complexes of the type
[(η6-arene)RuCl2(L)], where L stands for a hydrophilic li-
gand,[35] prompted us to test our ruthenium complexes 5–7
as defined catalyst precursors for this reaction.
C6H6
p-Cymene
C6Me6
1
2
3
5a/100
6a/100
7a/29
5b/100
6b/Ͼ98
7b/55
5c/Ͼ98
6c/37
7c/27
[a] Substrate (1.0 mmol), catalyst (0.5 mol-%), KOtBu (2.5 mol-%),
1,2-dichloroethane (4 mL), 1 h at 80 °C. [b] Determined by 1H
NMR spectroscopy. The results are an average of two independent
runs.
The complexes were firstly assessed in the redox isomer-
ization of the model substrate 1-octen-3-ol (Scheme 4) by
using 0.5 mol-% of the metal catalyst and 2.5 mol-% of
KOtBu as a base. Complex 5b, obtained from the most eas-
ily accessible Ru precursor and the simplest ligand, was
chosen for the initial catalytic tests aimed at an optimiza-
tion of the reaction conditions.
When the catalyst loading was decreased to 0.25 mol-%
(at 80 °C; see Supporting Information, Table S1), the con-
versions in the model isomerization reaction decreased con-
siderably. The best results were obtained with complexes
bearing the η6-benzene ligand (5a: 38%, 6a: 49%, and 7a:
25%). Conversions achieved with all other complexes
ranged from 10 to 19%. Finally, a reaction carried out at
50 °C with 0.5 mol-% 5b showed no conversion after 1 h.
Because the course of the redox isomerization is affected
by the structure of the substrate,[28,29] the readily accessible
yet active catalyst 5b (1 or 2 mol-%) was evaluated in reac-
tions of various substituted allylic alcohols (Scheme 5). The
results collected in Table 5 for reactions in 1,2-dichloroe-
thane indicate that secondary allylic alcohols with unsubsti-
tuted double bonds are isomerized best (entries 1 and 5).
The presence of any substitutents at the double bond (par-
ticularly in the position adjacent to the OH-substituted car-
bon) of both primary and secondary allylic alcohols results
in relatively lower conversions and can also incite an unde-
sired direct oxidation of the substrate to the respective α,β-
unsaturated ketone (Scheme 5).
Scheme 4. The model redox isomerization of 1-octen-3-ol to octan-
3-one.
Gratifyingly, the model isomerization reaction selectively
produced octan-3-one with complete conversion within 1 h
in both 1,2-dichloroethane and dioxane at 80 °C. A similar
reaction in N-methylpyrrolidone afforded the ketone with
33% conversion, whereas reactions performed in N,N-di-
methylformamide, N,N-dimethylacetamide, dimethyl sulfox-
ide, propionitrile, and 1-propanol did not proceed in any
appreciable extent. The reaction in pure water afforded the
desired product with 55% conversion after 1 h (at 80 °C),
but, surprisingly, no reaction was observed in a 1:1 water–
dioxane mixture under similar conditions. The reaction in
1,2-dichloroethane did not proceed in the absence of a base.
On the other hand, the addition of any common base in a
catalytic amount (2.5 mol-% of KOtBu, KOAc, KOH,
K2CO3, or K3PO4) resulted in complete conversion within
1 h.
Scheme 5. Redox isomerization of substituted allylic alcohols.
When the same isomerization reactions were performed
A possible influence of the structure of the precatalysts
was investigated next. The results achieved with the com-
plexes 5–7 in the model reaction (0.5 mol-% Ru, 2.5 mol-% in water, surprisingly, 1,3-diphenylallyl alcohol (R1 = R3 =
KOtBu, 1,2-dichloroethane, 80 °C, 1 h) are summarized in Ph, R2 = H) was fully and cleanly converted into the corre-
Table 4. The data indicate that the catalytic performance sponding saturated ketone in 20 h (5b: 2 mol-%). A plaus-
depends on both the Ru-bound arene and the phosphane ible explanation could be the solubility of this compound,
ligand. Complexes prepared from the ligands 1 and 2 af- which is the most hydrophobic in the series and can proba-
forded the product with practically quantitative conver- bly form droplets, in which the catalyst accumulates (reac-
sions, whereas those prepared from 3 performed consider- tion “on-water”).[33e,36] Among other substrates tested, only
ably worse. The influence of the Ru-bound arene was less but-3-en-2-ol (R1 = Me, R2 = R3 = H; 17% yield) and 2-
pronounced. The best results were achieved with p-cymene methylprop-2-en-1-ol (R1 = Ph, R2 = R3 = H, 29% yield;
complexes, whereas complexes bearing C6Me6, the most both are secondary alcohols with unsubstituted double
bulky and electron-rich arene ligand, achieved the lowest bonds) were converted into the respective saturated ketones
conversions. Nonetheless, all compounds 5–7 performed in a notable extent. Other substrates substituted at the
6
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Ru Complexes with Phosphanylferrocenecarboxamide Ligands
cene-1,1Ј-diyl). IR spectra were measured with an FTIR Nicolet
Magna 650 spectrometer in the range 400–4000 cm–1. Low-resolu-
tion electrospray ionization (ESI) mass spectra were obtained with
a Bruker Esquire 3000 instrument by using methanol solutions.
Table 5. Results of catalytic tests, achieved with complex 5b in the
redox isomerization of various vinyl alcohols in 1,2-dichloro-
ethane.[a]
Entry
Substrate
R1 R2
Yield [%][b]
R3
1 h
3 h
20 h
20 h[c]
1Ј-(Diphenylphosphanyl)-1-[N-(bis(hydroxymethyl)methyl)carb-
amoyl]ferrocene (2): Hdpf (1.66 g, 4.0 mmol), serinol (1.46 g,
16.0 mmol), 4-(dimethylamino)pyridine (24 mg, 0.2 mmol), and
EEDQ (1.48 g, 6.0 mmol) were dissolved in pyridine (40 mL), and
the resulting mixture was stirred first at 120 °C (temperature in the
heating bath) for 1 h and then at room temperature for 1 d. The
volatiles were removed under reduced pressure, and the solid resi-
due was purified by column chromatography over silica gel. Elution
with dichloromethane/methanol (50:1 v/v) led to the development
of three minor bands, which were discarded. The eluent was then
changed to a different dichloromethane/methanol mixture (20:1 v/
v) to elute a major orange band, which was the product. After
evaporation, the crude product was crystallized from a warm ethyl
acetate/hexane mixture (60 mL, 1:2 v/v) by slowly cooling down to
–18 °C. The resulting crystalline material was filtered off, washed
with diethyl ether and pentane, and dried under vacuum; yield
0.79 g (40 %), orange needles. 1H NMR (400.0 MHz, CDCl3,
25 °C): δ = 3.30 (br. s, 2 H, OH), 3.91 (m, 4 H, CH2O), 4.07 (m, 1
H, NHCH), 4.10 (vq, JЈ = 1.8 Hz, 2 H, CH of fc), 4.20 (vt, JЈ =
2.0 Hz, 2 H, CH of fc), 4.46 (vt, JЈ = 1.8 Hz, 2 H, CH of fc), 4.62
1
2
3
4
5
6
7
Me
H
H
Me
Ph
H
H
Me
H
H
H
H
H
H
H
Me
Me
H
Ph
Ph
11 (2)
0 (0)
8 (0)
6 (14)
42 (0)
0 (0)
13 (3)
3 (0)
14 (0)
6 (20)
49 (0)
4 (5)
17 (6)
4 (0)
18 (7)
9 (25)
67 (0)
10 (6)
39 (0)
78 (3)
7 (0)
25 (0)
23 (37)
79 (0)
30 (6)
40 (0)
Ph
0 (0)
19 (0)
[a] Substrate (1.0 mmol), catalyst 5b (1 mol-%, unless specified
otherwise), and KOtBu (5 mol-%) in 1,2-dichloroethane (4 mL) at
80 °C. [b] Determined by H NMR spectroscopy. The amount of
α,β-unsaturated ketone (oxidation product) is given in parentheses.
[c] Reactions in the presence of 2 mol-% of the Ru catalyst.
1
double bond typically achieved less than 5% conversion
(for the complete results, see Supporting Information,
Table S2.)
Conclusions
3
(vt, JЈ = 2.0 Hz, 2 H, CH of fc), 6.61 (d, JHH = 7.4 Hz, 1 H,
NH), 7.31–7.39 (m, 10 H, PPh2) ppm. 13C{1H} NMR (100.6 MHz,
Compounds 1–3 representing a complete series of struc-
turally related phosphanylferrocenecarboxamides bearing
congeneric polar hydroxyalkyl groups were utilized as P-
monodentate ligands in (η6-arene)RuII complexes of the
type [(η6-arene)RuCl2(L-κP)] (arene = benzene, p-cymene,
or hexamethylbenzene; L = 1–3). Both the ligands and their
(η6-arene)RuII complexes form complex supramolecular as-
semblies in the solid state, which are formed by means of
hydrogen-bonding interactions of their polar hydroxyamide
pendants. The complexes efficiently mediate the redox
isomerization of allylic alcohols to the respective carbonyl
compounds under moderate conditions, showing the best
results for allylic alcohols with unsubstituted double bonds.
CDCl3, 25 °C): δ = 52.53 (NCH), 63.96 (CH2O), 69.70 (CH of fc),
71.61 (CH of fc), 72.76 (d, JPC = 4 Hz, CH of fc), 74.60 (d, JPC
=
3
13 Hz, CH of fc), 76.36 (C–CONH of fc), 128.37 (d, JPC = 7 Hz,
CHmeta of PPh2), 128.93 (CHpara of PPh2), 133.41 (d, 2JPC = 20 Hz,
1
CHortho of PPh2), 137.70 (d, JPC = 6 Hz, Cipso of PPh2), 170.72
(C=O) ppm. The signal of C–P of fc was not found. 31P{1H} NMR
(161.9 MHz, CDCl , 25 °C): δ = –17.3 (s) ppm. IR (Nujol): ν =
˜
3
3300 (s), 1605 (s), 1549 (s), 1346 (m), 1307 (m), 1218 (w), 1192 (w),
1161 (m), 1092 (w), 1053 (s), 964 (w), 846 (w), 822 (w), 759 (w),
743 (m), 701 (m), 523 (m), 490 (m), 453 (m) cm–1. ESI-MS: m/z =
486 [M – H]–. C26H26FeNO3P (487.30): calcd. C 64.08, H 5.38,
N 2.88; found C 62.95, H 5.30, N 2.67. The compound tends to
incorporate diethyl ether.
1Ј-(Diphenylphosphanyl)-1-[N-(tris(hydroxymethyl)methyl)carb-
amoyl]ferrocene (3)
Experimental Section
Method A: Hdpf (1.66 g, 4.0 mmol), tris(hydroxymethyl)methyl-
amine (1.94 g, 16.0 mmol), 4-(dimethylamino)pyridine (24 mg,
0.20 mmol), and EEDQ (1.48 g, 6.0 mmol) were dissolved in pyr-
idine (40 mL), and the reaction mixture was first stirred at 120 °C
for 1 h and then at room temperature overnight. The volatiles were
removed under reduced pressure, and the solid residue was purified
by column chromatography (silica gel, dichloromethane/methanol,
50:1 v/v). The first minor band was discarded, and the following
one was collected and the solvent evaporated to afford a crude
product, which was crystallized from warm ethyl acetate/hexane
(40 mL, 1:1 v/v) by slowly cooling down to –18 °C. The obtained
crystalline material was isolated by suction, washed successively
with diethyl ether and pentane, and dried under vacuum; yield
1.16 g (56%), orange, microcrystalline solid.
Materials and Methods: All syntheses were performed under an
argon atmosphere and with exclusion of the direct daylight.
Hdpf,[6a] 1,[9a] 4,[9a,16] [(η6-C6H6)RuCl2]2,[37] and [(η6-C6Me6)-
[38]
RuCl2]2 were prepared according to literature procedures. Other
chemicals were obtained from commercial sources (Alfa-Aesar,
Fluka, Sigma–Aldrich) and used as received. Solvents (Lachner)
used for the syntheses and catalytic tests were dried with appropri-
ate drying agents (dichloromethane, 1,2-dichloroethane, and chlo-
roform: anhydrous potassium carbonate; 1,4-dioxane: sodium
metal, acetonitrile: P2O5) and were freshly distilled under argon.
Solvents used in crystallizations and for chromatography were used
without any additional purification.
NMR spectra were recorded with a Varian Unity Inova 400 spec-
trometer. Chemical shifts (δ in ppm) are given relative to an internal
Method B: A reaction flask was charged with active ester 4 (0.58 g,
SiMe4 standard (1H and 13C) or an external standard of 85% aque- 1 mmol), tris(hydroxymethyl)methylamine (0.145 g, 1.3 mmol), and
ous H3PO4 (31P). In addition to the standard notation of the signal
multiplicity, vt and vq are used to distinguish virtual triplets and
quartets, respectively, which arise from magnetically nonequivalent
protons in the AAЈBBЈ and AAЈBBЈX spin systems (X = 31P) of
the unsymmetrically 1,1Ј-disubstituted ferrocene moiety (fc = ferro-
4-(dimethylamino)pyridine (6 mg, 0.05 mmol). Dry N,N-dimethyl-
formamide (15 mL) was added, and the resulting solution was
stirred for 20 h, after which the solvent was evaporated under vac-
uum. The solid residue was dissolved in dichloromethane (20 mL).
This solution was washed twice with a 5% aqueous solution of
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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7

Job/Unit: I20733
/KAP1
Date: 10-09-12 16:04:22
Pages: 12
ˇ
J. Schulz, I. Císarˇová, P. Steˇpnicˇka
FULL PAPER
citric acid (10 mL), a saturated aqueous solution of NaHCO3
(20 mL), and brine (20 mL), and, finally, it was dried with MgSO4.
The solvent was evaporated under vacuum, and the solid residue
was purified by column chromatography and crystallized as de-
scribed above (method A); yield 0.137 g (27%), orange, microcrys-
talline solid. 1H NMR (400.0 MHz, CDCl3, 25 °C): δ = 3.73 (d,
3JHH = 3.9 Hz, 6 H, CH2O), 4.11 (vq, JЈ = 1.8 Hz, 2 H, CH of fc),
4.23 (vt, JЈ = 2.0 Hz, 2 H, CH of fc), 4.44 (vt, JЈ = 1.8 Hz, 2 H,
CH of fc), 4.52 (unresolved t, 3 H, OH), 4.59 (vt, JЈ = 2.0 Hz, 2
H, CH of fc), 6.89 (s, 1 H, NH), 7.31–7.39 (m, 10 H, PPh2) ppm.
13C{1H} NMR (100.6 MHz, CDCl3, 25 °C): δ = 61.58 (NCCH2),
cessively with diethyl ether and pentane (10 mL each) and dried
under vacuum.
[(η6-C6H6)RuCl2(1-κP)] (5a): Yield 126 mg (86%), light, orange
powder. 1H NMR (400.0 MHz, CDCl3, 25 °C): δ = 3.24 (br. s, 2
H, CH of fc), 3.60 (br. s, 2 H, CH2N), 3.70 (br. s, 1 H, OH), 3.90
(br. s, 2 H, CH2O), 4.35 (br. s, 2 H, CH of fc), 4.64–4.70 (m, 4 H,
2
CH of fc), 5.30 (d, JPH = 0.8 Hz, 6 H, C6H6), 7.34–7.47 (m, 7 H,
PPh2 and NH), 7.69–7.80 (m, 4 H, PPh2) ppm. 31P{1H} NMR
(161.9 MHz, CDCl3, 25 °C): δ = 16.3 (s) ppm. MS (ESI+): m/z =
636 [M – H – HCl]. C31H30Cl2FeNO2PRu·1.5H2O (734.4): calcd.
C 50.70, H 4.53, N 1.91; found C 50.74, H 4.52, N 1.94.
63.36 (CH2O), 69.67 (CH of fc), 71.95 (CH of fc), 72.85 (d, JPC
=
[(η6-Cymene)RuCl2(1-κP)] (5b): Yield 131 mg (86%), ruby-red
4 Hz, CH of fc), 74.60 (d, JPC = 14 Hz, CH of fc), 76.29 (C–CONH
1
3
1
3
powder. H NMR (400.0 MHz, CDCl3, 25 °C): δ = 0.96 [d, JHH
of fc), 77.54 (d, JPC = 5 Hz, C–P of fc), 128.32 (d, JPC = 7 Hz,
CHmeta of PPh2), 128.91 (CHpara of PPh2), 133.43 (d, 2JPC = 20 Hz,
3
= 7.0 Hz, 6 H, CH(CH3)2], 1.85 (s, 3 H, CH3), 2.59 [sept, JHH
=
1
7.0 Hz, 1 H, CH(CH3)2], 3.19 (m, 2 H, CH of fc), 3.57 (virtual q,
J = 4.7 Hz, 2 H, CH2N), 3.84–3.86 (m, 2 H, CH2O), 4.46–4.47 (m,
2 H, CH of fc), 4.48–4.49 (m, 2 H, CH of fc), 4.52 (vt, JЈ = 2.0 Hz,
2 H, CH of fc), 5.10–5.14 (m, 4 H, C6H4), 7.40–7.47 (m, 6 H,
PPh2), 7.51 (t, 3JHH = 5.1 Hz, 1 H, NH), 7.77–7.83 (m, 4 H, PPh2)
ppm. The resonance of the OH proton was not seen. 31P{1H}
NMR (161.9 MHz, CDCl3, 25 °C): δ = 17.7 (s) ppm. MS (ESI+):
m/z = 692 [M – Cl – HCl]+. C35H38Cl2FeNO2PRu·H2O (768.9):
calcd. C 54.67, H 5.06, N 1.82; found C 54.37, H 5.32, N 1.74.
CHortho of PPh2), 137.74 (d, JPC = 7 Hz, Cipso of PPh2), 171.70
(C=O) ppm. 31P{1H} NMR (161.9 MHz, CDCl3, 25 °C): δ = –17.7
(s) ppm. IR (Nujol): ν = 3262 (s), 1626 (s), 1532 (s), 1351 (m), 1305
˜
(m), 1287 (w), 1192 (w), 1160 (w), 1124 (w), 1084 (w), 1055 (m),
1027 (s), 837 (w), 821 (w), 771 (w), 746 (m), 737 (m), 696 (s), 568
(w), 520 (w), 498 (m), 484 (m), 453 (w) cm–1. ESI-MS: m/z = 516
[M – H]–. C27H28FeNO4P (517.32): calcd. C 62.68, H 5.46, N 2.71;
found C 62.62, H 5.58, N 2.60.
1Ј-(Diphenylphosphanoyl)-1-[N-(tris(hydroxymethyl)methyl)carb-
amoyl]ferrocene (3O): Aqueous hydrogen peroxide (0.21 mL, 30%,
ca. 2 mmol) was added dropwise to a solution of phosphane 3
(103.5 mg, 0.2 mmol) in acetone (15 mL) with stirring and cooling
in ice. After 30 min, the reaction was quenched with a saturated
aqueous solution of sodium thiosulfate (10 mL), and the volatiles
were evaporated under vacuum. The aqueous residue was diluted
with water and extracted with dichloromethane (2ϫ 15 mL). The
organic extracts were washed with brine (1ϫ 30 mL), dried with
magnesium sulfate, and the solvents were evaporated. The product
was isolated by column chromatography (silica gel, dichlorometh-
ane/methanol, 10:1 v/v) as a yellow solid; yield 98 mg (92%). 1H
NMR (400.0 MHz, [D6]DMSO, 25 °C): δ = 3.70 (d, 3JHH = 6.0 Hz,
6 H, CH2O), 4.13 (vt, JЈ = 2.0 Hz, 2 H, CH of fc), 4.36 (vt, JЈ =
1.9 Hz, 2 H, CH of fc), 4.68 (vt, JЈ = 1.8 Hz, 2 H, CH of fc), 4.81
(vt, JЈ = 2.0 Hz, 2 H, CH of fc), 4.83 (unresolved t, J ≈ 6.0 Hz, 3
H, OH), 7.53–7.72 (m, 11 H, PPh2 and NH) ppm. 13C{1H} NMR
[(η6-C6Me6)RuCl2(1-κP)] (5c): Yield 129 mg (81%), orange powder.
1H NMR (400.0 MHz, CDCl3, 50 °C): δ = 1.67 (s, 18 H, C6Me6),
3.58 (virtual q, J = 4.9 Hz, 2 H, CH2N), 3.63 (br. s, 1 H, OH), 3.85
(virtual q, J = 5.1 Hz, 2 H, CH2O), 4.43 (br. s, 4 H, CH of fc), 4.51
(br. s, 2 H, CH of fc), 7.28–7.39 (m, 6 H, PPh2), 7.42 (br. s, 1 H,
NH), 7.72–7.90 (m, 4 H, PPh2) ppm. A resonance of two protons
at the ferrocen-1,1Ј-diyl backbone was not observed because of ex-
tensive signal broadening. 31P{1H} NMR (161.9 MHz, CDCl3,
50 °C): δ = 19.3 (bs) ppm. MS (ESI+): m/z = 720 [M – Cl –
HCl]+. C37H42Cl2FeNO2PRu (791.5): calcd. C 56.14, H 5.35, N
1.77; found C 56.02, H 5.37, N 1.67.
[(η6-C6H6)RuCl2(2-κP)] (6a): Yield 136 mg (87%), orange powder.
1H NMR (400.0 MHz, CDCl3, 25 °C): δ = 3.62 (br. s, 2 H, OH),
3
3.98 (d, JHH = 4.1 Hz, 4 H, CH2O), 4.19 (m, 1 H, CHNH), 4.38
(br. s, 2 H, CH of fc), 4.67 (br. s, 2 H, CH of fc), 4.71 (vt, JЈ =
2
1.8 Hz, 2 H, CH of fc), 5.30 (d, JPH = 0.7 Hz, 6 H, C6H6), 7.37–
(100.6 MHz, [D6]DMSO, 25 °C):
δ = 60.58 (CH2O), 62.62
7.48 (m, 7 H, PPh2 and NH), 7.67–7.81 (br. s, 4 H, PPh2) ppm. A
resonance of two protons at the ferrocen-1,1Ј-diyl backbone was
not observed because of extensive signal broadening. 31P{1H}
NMR (161.9 MHz, CDCl3, 25 °C): δ = 16.5 (s) ppm. MS (ESI+):
m/z = 666 [M – H – HCl]+. C32H32Cl2FeNO3PRu·2H2O·0.4Et2O
(780.8): calcd. C 49.84, H 4.78, N 1.79; found C 49.62, H 4.60, N
1.75.
(CNHCO), 69.99 (CH of fc), 70.57 (CH of fc), 72.61 (d, JPC
=
1
10 Hz, CH of fc), 72.91 (d, JPC = 115 Hz, C–P of fc), 74.32 (JPC
= 13 Hz, CH of fc), 79.12 (C–CONH of fc), 128.57 (2JPC = 12 Hz,
CHortho of PPh2), 130.79 (3JPC = 10 Hz, CHmeta of PPh2), 131.95
(4JPC = 2 Hz, CHpara of PPh2), 132.76 (1JPC = 107 Hz, Cipso of
PPh2), 169.08 (C=O) ppm. 31P{1H} NMR (161.9 MHz, [D6]-
DMSO, 25 °C): δ = 29.9 (s) ppm. HRMS (ESI+): calcd. for
C27H28NO5P56Fe [M]+ 533.1055; found 533.1057.
[(η6-Cymene)RuCl2(2-κP)] (6b): Yield 143 mg (88%), light, orange
1
3
powder. H NMR (400.0 MHz, CDCl3, 25 °C): δ = 0.94 [d, JHH
General Procedure for the Preparation of (η6-Arene)RuII Complexes:
A solution of the ligand (0.2 mmol) in dichloromethane (10 mL)
was added to the solid ruthenium precursor {[(η6-C6Me6)RuCl2]2
or [(η6-cymene)RuCl2]2} or to its suspension in acetonitrile {[(η6-
C6H6)RuCl2]2 in 5 mL} (0.1 mmol). The resulting mixture was
stirred in the dark for 2 h, and the solvent was then evaporated
under reduced pressure. The crude product was purified by column
chromatography over silica gel by using dichloromethane/methanol
(50:1 or 20:1 v/v) as the eluent. A major reddish band was col-
lected, and the solvents were evaporated to dryness. The solid resi-
due was dissolved in a minimal amount of dichloromethane (1–
3 mL), and this solution was added dropwise to diethyl ether
(30 mL). The resulting precipitate was cooled to +4 °C overnight
and collected by suction. The obtained material was washed suc-
3
= 7.0 Hz, 6 H, CH(CH3)2], 1.87 (s, 3 H, CH3), 2.65 [sept, JHH
=
7.0 Hz, 1 H, CH(CH3)2], 3.17 (br. s, 2 H, CH of fc), 3.64 (br. s, 2
H, OH), 3.92 (d, J = 4.0 Hz, 2 H, CH2O), 4.14 (m, 1 H, CHNH),
4.48–4.49 (m, 4 H, CH of fc), 4.59 (vt, JЈ = 2.0 Hz, 2 H, CH of
fc), 5.11 (br. s, 4 H, C6H4), 7.42–7.50 (m, 6 H, PPh2), 7.51 (d, 3JHH
= 7.1 Hz, 1 H, NH), 7.78–7.83 (m, 4 H, PPh2) ppm. 31P{1H} NMR
(161.9 MHz, CDCl3, 25 °C): δ = 17.7 (s) ppm. MS (ESI+): m/z =
722 [M – H – HCl]+. C36H40Cl2FeNO3PRu·H2O (811.5): calcd. C
53.28, H 5.22, N 1.73; found C 53.08, H 5.24, N 1.73.
[(η6-C6Me6)RuCl2(2-κP)] (6c): Yield 152 mg (93%), light, orange
4
powder. 1H NMR (400.0 MHz, CDCl3, 50 °C): δ = 1.67 (d, JPH
=
0.7 Hz, 18 H, C6Me6), 3.93 (br. s, 4 H, CH2O), 4.06–4.13 (m, 1 H,
CHNH), 4.39–4.56 (m, 6 H, CH of fc), 7.27–7.42 (m, 7 H, PPh2
8
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Ru Complexes with Phosphanylferrocenecarboxamide Ligands
and NH), 7.76–7.90 (m, 4 H, PPh2) ppm. Resonances of two pro-
tons at the ferrocen-1,1Ј-diyl backbone and of the hydroxy groups
were not observed because of extensive signal broadening. 31P{1H}
equipped with a Cryostream Cooler (Oxford Cryosystems) at
150(2) K by using graphite monochromated Mo-Kα radiation (λ =
0.71073 Å) and were analyzed with the HKL program package.[46]
NMR (CDCl3, 50 °C): δ = 19.6 (bs) ppm. MS (ESI+): m/z = 750 The structures were solved by the direct methods (SIR97[47]) and
[M – Cl – HCl]+. C38H44Cl2FeNO3PRu (821.5): calcd. C 55.55, H refined to full convergence by full-matrix least-squares methods on
5.40, N 1.71; found C 55.32, H 5.26, N 1.63.
the basis of F2 (SHELXL97[48]). The non-hydrogen atoms were re-
fined with anisotropic displacement parameters. Hydrogen atoms
of the OH and NH groups were identified on the difference density
maps and refined as riding atoms with Uiso(H) assigned to a mul-
tiple of 1.2Ueq(O/N). Other hydrogen atoms were included in their
calculated positions and refined similarly. Relevant crystallographic
data and refinement parameters are presented in Table S3 (Sup-
porting Information). Particular details of the structure refinement
are discussed in the following paragraph.
[(η6-C6H6)RuCl2(3-κP)] (7a): Yield 137 mg (83%), orange, micro-
crystalline solid. 1H NMR (400.0 MHz, [D6]DMSO, 25 °C): δ =
3
3.64 (d, JHH = 5.8 Hz, 6 H, CH2O), 3.72 (vt, JЈ = 1.8 Hz, 2 H,
CH of fc), 4.48 (br. s, 2 H, CH of fc), 4.51–4.55 (m, 4 H, CH of
3
2
fc), 4.81 (t, JHH = 5.7 Hz, 3 H, OH), 5.40 (d, JPH = 0.7 Hz, 6 H,
C6H6), 6.55 (s, 1 H, NH), 7.42–7.52 (m, 6 H, PPh2), 7.70–7.77 (m,
4 H, PPh2) ppm. 31P{1H} NMR (161.9 MHz, [D6]DMSO, 25 °C):
δ = 20.2 (s) ppm. MS (ESI+): m/z = 696 [M – H – HCl]+.
C33H34Cl2FeNO4PRu·H2O·0.6Et2O (829.9): calcd. C 51.23, H 5.10,
N 1.69; found C 51.02, H 4.84, N 1.70.
The solvent present in the structure of 6c·Et2O was severely disor-
dered in structural voids, hence, its contribution to the overall scat-
tering was removed by the SQUEEZE[49] routine incorporated in
the PLATON program.[50] A total of 110 electrons were found in
566 Å3 of void space per unit cell (four molecules of diethyl ether
represent 136 electrons). It is also noteworthy that the largest elec-
tron density peak in the final difference density map (2.4 e·Å–3) for
compound 2 very likely corresponds to a lone electron pair at the
phosphorus atom (the second largest electron density maximum is
only ca. 0.35 e·Å–3). This assumption was confirmed by a refine-
ment of this “peak” as a helium atom (2 electrons), which led to a
decrease in the R value to 2.96% and gave a reasonable geometry
[P···He distance is 1.305(5) Å with a clear contact of He to H3O,
which is located in a proximal molecule: He···O3 ≈ 2.36 Å,
He···H3O–O3 ≈ 173°].
[(η6-Cymene)RuCl2(3-κP)] (7b): Yield 148 mg (90%), ruby-red,
1
microcrystalline solid. H NMR (400.0 MHz, [D6]DMSO, 25 °C):
3
δ = 0.83 [d, JHH = 7.0 Hz, 6 H, CH(CH3)2], 1.71 (s, 3 H, CH3),
2.31 [sept, 3JHH = 7.0 Hz, 1 H, CH(CH3)2], 3.61 (d, 3JHH = 5.8 Hz,
6 H, CH2O), 3.65 (vt, JЈ = 1.8 Hz, 2 H, CH of fc), 4.37–4.39 (m,
4 H, CH of fc), 4.50 (vq, JЈ = 1.7 Hz, 2 H, CH of fc), 4.81 (t, 3JHH
= 5.7 Hz, 3 H, OH), 5.23 (d, J = 6.3 Hz, 2 H, C6H4), 5.32 (dd, J
= 6.4, 1.2 Hz, 2 H, C6H4), 6.48 (s, 1 H, NH), 7.46–7.53 (m, 6 H,
PPh2), 7.79–7.86 (m, 4 H, PPh2) ppm. 31P{1H} NMR (161.9 MHz,
[D6]DMSO, 25 °C): δ = 20.3 (s) ppm. MS (ESI+): m/z = 752 [M –
H – HCl]+. C37H42Cl2FeNO4PRu (823.5): calcd. C 53.96, H 5.14,
N 1.70; found C 53.75, H 5.21, N 1.58.
[(η6-C6Me6)RuCl2(3-κP)] (7c): Yield 154 mg (91%), ruby-red pow-
der. 1H NMR (400.0 MHz, CDCl3, 50 °C): δ = 1.67 (s, 18 H,
C6Me6), 3.83 (d, 3JHH = 4.8 Hz, 6 H, CH2O), 4.02 (br. s, 3 H, OH),
4.39 (d, JЈ = 1.7 Hz, 2 H, CH of fc), 4.44 (br. s, 2 H, CH of fc),
4.53 (br. s, 2 H, CH of fc), 7.02 (br. s, 1 H, NH), 7.32–7.42 (m, 6
H, PPh2), 7.77–7.91 (m, 4 H, PPh2) ppm. The resonance of two
protons at the ferrocen-1,1Ј-diyl backbone was not found because
of an extensive signal broadening. 31P{1H} NMR (161.9 MHz,
CDCl3, 50 °C): δ = 20.1 (bs) ppm. MS (ESI+): m/z = 780 [M – H –
HCl]+. C39H46Cl2FeNO4PRu (851.6): calcd. C 55.00, H 5.45, N
1.65; found C 54.66, H 5.64, N 1.61.
Geometric data and structural drawings were obtained with a re-
cent version of the PLATON program. All numerical values are
rounded with respect to their estimated deviations (ESDs) given in
one decimal. Parameters relating to atoms in constrained positions
(hydrogen atoms) are given without ESDs.
CCDC-889295 (for 2), -889296 (for 3), -889297 (for 3O), -889298
(for 5c·CH2Cl2) and -889299 (for 6c·Et2O) contain the supplemen-
tary crystallographic data for this paper. These data can be ob-
tained free of charge from The Cambridge Crystallographic Data
Centre via www.ccdc.cam.ac.uk/data_request/cif.
Catalytic Tests: A Schlenk tube was charged with the respective
allylic alcohol (1.0 mmol) and ruthenium catalyst, a base (in appro-
priate amounts), and 1-methoxy-2-(2-methoxyethoxy)ethane
(67 mg, 0.5 mmol) as an internal standard. The tube was flushed
with argon and sealed. The solvent (4 mL) was added, and the
resulting mixture was heated to 80 °C.
The conversions were determined by 1H NMR spectroscopy. The
identity of the products was confirmed by a comparison of the
NMR spectra with the literature (octan-3-one, trans-cinnamal-
dehyde and propiophenone;[39] 1,3-diphenylpropan-1-one,[40] 2-but-
anone,[41] 2-pentanone,[42] 3-phenylpropanal,[43] 2-butenal,[44] and
3-buten-2-one[45]) or with spectra of authentic samples (butyral-
dehyde, 2-methylpropanal, and 3-penten-2-one).
Supporting Information (see footnote on the first page of this arti-
cle): Crystal packing diagrams for 5c·CH2Cl2 (Figure S1) and
6c·Et2O (Figure S2), histograms showing the distribution of O···O
distances and O–H···O angles in P=O···H–O hydrogen bonds (Fig-
ures S3 and S4), results of catalytic tests, achieved in the model
redox isomerization reaction with 0.25 mol-% of 5–7 in 1,2-dichlor-
oethane at 80 °C (Table S1), results of catalytic tests for the isomer-
ization of various allylic alcohols with catalyst 5b in water
(Table S2), and a summary of crystallographic data (Table S3).
Acknowledgments
This work was financially supported by the Grant Agency of
Charles University in Prague (grant number 69309) and by the
Ministry of Education, Youth and Sports of the Czech Republic
(project number MSM0021620857).
X-ray Crystallography: Single crystals suitable for X-ray diffraction
measurements were obtained by liquid-phase diffusion from
ethyl acetate/hexane (2: orange plate, 0.20ϫ0.35ϫ0.45 mm3; 3:
orange plate, 0.03ϫ0.10ϫ0.25 mm3; 3O: orange prism,
0.23ϫ0.38ϫ0.55 mm3), dichloromethane/hexane (5c·CH2Cl2: red
plate, 0.20ϫ0.40ϫ0.50 mm3), or similarly from chloroform/meth-
anol/hexane (5c·Et2O: red bar, 0.08ϫ0.15ϫ0.30 mm3).
ˇ
[1] P. Steˇpnicˇka, Chem. Soc. Rev. 2012, 41, 4273–4305.
[2] a) Aqueous-Phase Organometallic Chemistry (Eds.: B. Cornils,
W. A. Herrmann), 2nd ed., Wiley-VCH, Weinheim, Germany,
2004; b) F. Joó, Aqueous Organometallic Catalysis, Kluwer,
Dordrecht, The Netherlands, 2001.
The diffraction data (ϮhϮkϮl, θmax = 26–27.5°, data completeness
Ն 99.3%) were collected with a Nonius KappaCCD diffractometer
Eur. J. Inorg. Chem. 0000, 0–0
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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Pages: 12
ˇ
J. Schulz, I. Císarˇová, P. Steˇpnicˇka
FULL PAPER
[3]
[16]
[17]
W. Zhang, Y. Yoneda, T. Kida, Y. Nakatsuji, I. Ikeda, Tetrahe-
dron: Asymmetry 1998, 9, 3371–3380.
a) Ferrocenes – Homogeneous Catalysis, Organic Synthesis, Ma-
terials Science (Eds.: A. Togni, T. Hayashi), Wiley-VCH,
Weinheim, Germany, 1995; b) Ferrocenes – Ligands, Materials
a) H. Jendralla, E. Paulus, Synlett 1997, 471–472; b) J.
ˇ
ˇ
and Biomolecules (Ed.: P. Steˇpnicˇka), Wiley, Chichester, UK,
Kühnert, M. Dusˇek, J. Demel, H. Lang, P. Steˇpnicˇka, Dalton
2008.
Trans. 2007, 2802–2811; c) J. Kühnert, I. Císarˇová, M. Lamacˇ,
ˇ
ˇ
P. S teˇpnicˇka, Dalton Trans. 2008, 2454–2464; d) P. Steˇpnicˇka,
H. Solarˇová, M. Lamacˇ, I. Císarˇová, J. Organomet. Chem.
[4]
For selected reviews, see: a) R. C. J. Atkinson, V. Gibson, N. J.
Long, Chem. Soc. Rev. 2004, 33, 313–328; b) P. Barbaro, C.
Bianchini, G. Giambastiani, S. L. Parisel, Coord. Chem. Rev.
2004, 248, 2131–2150; c) R. Goméz Arrayás, J. Adrio, J. C.
Carretero, Angew. Chem. 2006, 118, 7836; Angew. Chem. Int.
Ed. 2006, 45, 7674–7715.
a) X. Feng, B. Pugin, E. Küsters, G. Sedelmeier, H.-U. Blaser,
Adv. Synth. Catal. 2007, 349, 1803–1807; b) B. Pugin, Patent
WO 2001004131 A1 (2001).
a) J. Podlaha, P. Steˇpnicˇka, J. Ludvík, I. Císarˇová, Organome-
tallics 1996, 15, 543–550; b) P. Steˇpnicˇka, Eur. J. Inorg. Chem.
2005, 3787–3808.
J. Schulz, I. Císarˇová, P. Steˇpnicˇka, Organometallics 2012, 31,
729–738.
a) J. Tauchman, I. Císarˇová, P. Stepnicˇka, Organometallics
ˇ
2010, 695, 2423–2431; e) P. Steˇpnicˇka, H. Solarˇová, I. Císarˇová,
J. Organomet. Chem. 2011, 696, 3727–3740.
[18]
a) T. Gramstad, Acta Chim. Scand. 1961, 15, 1337–1346; b) J.
Mendel, A. Kolbe, Phosphorus Sulfur Relat. Elem. 1977, 3, 21–
26; c) E. V. RylЈtsev, A. K. Shurubura, Y. P. Egorov, V. Y. Se-
menii, Teoret. Eksperiment. Khim. 1980, 16, 497–503; d) For a
report concerning ferrocenylphosphanes and the correspond-
ing phosphane oxides, see: L. M. Ephstein, E. S. Shubina, A. I.
Krylova, V. S. Tolkunova, V. D. Vil’chevskaya, D. N. Kravtsov,
Izv. Akad. Nauk SSR, Ser. Khim. 1987, 572–575.
[5]
[6]
ˇ
ˇ
ˇ
[19]
[20]
a) P. Steˇpnicˇka, I. Císarˇová, New J. Chem. 2002, 26, 1389–1396;
ˇ
[7]
[8]
b) B. F. M. Kimmich, C. R. Landis, D. R. Powell, Organome-
tallics 1996, 15, 4141–4146.
ˇ
A search for intermolecular P···H–O contacts in the Cam-
bridge Crystallographic Database (version 5.33 of November
2011 and updates of November 2011, February 2012, and May
2012) yielded eleven results (refcodes: BAXPUM, FEQKOC,
GOSLUV, KUYBOW, LAGMIR, MULXIA, NAPYIM, OK-
AZIJ, TOCHIC, TOCHOI, and TOXGAO). The shortest
(strongest) contacts were detected for phosphanylphenols hav-
ing acidic OH groups (P···O ca. 3.2–3.5 Å). For references, see:
a) J. Heinicke, R. Kadyrov, M. K. Kindermann, M. Koesling,
P. G. Jones, Chem. Ber. 1996, 129, 1547–1560; b) R. Kadyrov,
J. Heinicke, M. K. Kindermann, D. Heller, C. Fischer, R. Selke,
A. K. Fischer, P. G. Jones, Chem. Ber./Recueil 1997, 130, 1663–
1670; c) P. Schober, G. Huttner, A. Jacobi, J. Organomet. Chem.
1998, 571, 279–288.
ˇ
2009, 28, 3288–3302; b) J. Tauchman, I. Císarˇová, P. Steˇpnicˇka,
Eur. J. Org. Chem. 2010, 4276–4287; c) J. Tauchman, I. Císa-
ˇ
rˇová, P. Steˇpnicˇka, Dalton Trans. 2011, 40, 11748–11757; d) J.
ˇ
Tauchman, B. Therrien, G. Süss-Fink, P. Steˇpnicˇka, Organome-
tallics 2012, 31, 3985–3994.
a) J. Schulz, I. Císarˇová, P. Steˇpnicˇka, J. Organomet. Chem.
ˇ
[9]
2009, 694, 2519–2530; b) J. Schulz, A. K. Renfrew, I. Císarˇová,
ˇ
P. J. Dyson, P. Steˇpnicˇka, Appl. Organomet. Chem. 2010, 24,
392–397.
[10]
A prominent but rather solitary example of phosphanyl car-
boxamides with 2-hydroxyethyl groups is undoubtedly 2-(di-
phenylphosphanyl)-N-(2-hydroxyethyl)benzamide, which was
studied as a ligand in ReV complexes and because of its pro-
spective applications in nuclear medicine: a) J. D. G. Correia,
Â. Domingos, A. Paulo, I. Santos, J. Chem. Soc., Dalton Trans.
2000, 2477–2482; b) J. D. G. Correia, Â. Domingos, I. Santos,
Eur. J. Inorg. Chem. 2000, 1523–1529; c) J. D. G. Correia, Â.
Domingos, I. Santos, H. Spies, J. Chem. Soc., Dalton Trans.
2001, 2245–2250; d) J. D. G. Correia, Â. Domingos, I. Santos,
R. Alberto, K. Ortner, Inorg. Chem. 2001, 40, 5147–5151; e) T.
Kniess, J. D. G. Correia, Â. Domingos, E. Palma, I. Santos,
Inorg. Chem. 2003, 42, 6130–6135; f) C. Fernandes, J. D. G.
Correia, L. Gano, I. Santos, S. Seifert, R. Syhre, R. Bergmann,
H. Spies, Bioconjugate Chem. 2005, 16, 660–668.
[21]
[22]
The sum of the N–H···O and O···H···O angles around H1N is
346°.
π–π-Stacking interactions were detected for phenyl ring C(12–
17) and its inverted (parallel) image, and the distance between
the respective ring centroids is 4.140(2) Å.
A search for P=O···O–H contacts in the Cambridge Crystallo-
graphic Database (version as above) yielded 203 results with R
Ͻ 10% and free of a disorder. Histograms showing the distri-
bution of the O···O distances and the O–H···O angles (see Sup-
porting Information, Figures S3 and S4) clearly indicate the
directional nature of these interactions.
[23]
[11]
[12]
To the best of our knowledge, there is no report concerning
the preparation of phosphanylamides from H2NCH(CH2OH)2
(serinol).
[24]
The complexes often give rise to very broad and sometimes
multiple 31P{1H} NMR resonances, which is due to slow struc-
tural dynamics. Upon increasing the temperature of the mea-
surement, the signals become sharper and collapse into singlet
resonances.
a) 3-(Diphenylphosphanyl)-N-[2-hydroxy-1,1-bis(hydroxymeth-
yl)ethyl]propanamide, a hydrophilic phosphane prepared by
the addition of diphenylphosphane to CH2=CHCONHC-
(CH2OH)3, was studied as a ligand for Rh comlexes: L. Lav-
enot, M. H. Bortoletto, A. Roucoux, C. Larpent, H. Patin, J.
Organomet. Chem. 1996, 509, 9–14; b) Amides of the type
RC(O)NHCH2{CH2O(CH2)3NHC(O)CH2P(O)Y2}3, where Y
= RЈ or ORЈ, and some related compounds were evaluated in
extractions of metal ions: M. M. Reinoso-García, D. Janczew-
ski, D. N. Reinhoudt, W. Verboom, E. Malinowska, M. Pi-
etrzak, C. Hill, J. Bácˇa, B. Grüner, P. Selucky, C. Grüttner, New
J. Chem. 2006, 30, 1480–1492.
For related phosphanylferrocenecarboxamides, see: a) W.
Zhang, T. Shimanuki, T. Kida, Y. Nakatsuji, I. Ikeda, J. Org.
Chem. 1999, 64, 6247–6251; b) M. Lamacˇ, I. Císarˇová, P. Steˇp-
nicˇka, New J. Chem. 2009, 33, 1549–1562.
a) A. El-Faham, F. Albericio, Chem. Rev. 2011, 111, 6557–6602
(review article) b) B. Belleau, G. Malek, J. Am. Chem. Soc.
1968, 90, 1651–1652.
For an example of the application of EEDQ in the synthesis
of amides from HOC(CH2OH)3, see: I. Villanueva, B. Hernan-
dez, V. Chang, M. D. Heagy, Synthesis 2000, 1435–1438.
ˇ
ˇ
[25]
[26]
P. S teˇpnicˇka, J. Demel, J. Cejka, J. Mol. Catal. A 2004, 224,
161–169.
For 5c·CH2Cl2: Cg3–Ru–Cl1 125.83(4)°, Cg3–Ru–Cl2
123.22(4)°, Cg3–Ru–P 134.00(4)°; for 6c·Et2O2: Cg3–Ru–Cl1
126.27(4)°, Cg3–Ru–Cl2 123.27(4)°, Cg3–Ru–P 134.90(4)°; Cg3
denotes the centroid of the η6-benzene ring.
The dihedral angles subtended by these planes are 20.8(1)° and
19.9(1)° for 5c·CH2Cl2 and 6c·Et2O, respectively.
a) R. C. van der Drift, E. Bouwman, E. Drent, J. Organomet.
Chem. 2002, 650, 1–24; b) R. Uma, C. Crévisy, R. Grée, Chem.
Rev. 2003, 103, 27–51.
For recent reviews, see: a) V. Cadierno, P. Crochet, J. Gimeno,
Synlett 2008, 1105–1124; b) N. Ahlsten, A. Bartoszewicz, B.
Martín-Matute, Dalton Trans. 2012, 41, 1660–1670; c) P. Lo-
renzo-Luis, A. Romerosa, M. Serrano-Ruiz, ACS Catal. 2012,
2, 1079–1086.
[27]
[28]
[13]
[29]
[30]
ˇ
[14]
[15]
a) C. Slugovc, E. Rüba, R. Schmid, K. Kirchner, Organometal-
lics 1999, 18, 4230–4233; b) I. E. Markó, A. Gautier, M. Tsuka-
zaki, A. Llobet, E. Plantalech-Mir, C. J. Urch, S. M. Brown,
Angew. Chem. 1999, 111, 2126; Angew. Chem. Int. Ed. 1999,
10
www.eurjic.org
© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 0000, 0–0

Job/Unit: I20733
/KAP1
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Pages: 12
Ru Complexes with Phosphanylferrocenecarboxamide Ligands
38, 1960–1962; c) C. Bianchini, A. Meli, W. Oberhauser, New
J. Chem. 2001, 25, 11–12; d) R. C. van der Drift, J. W. Spreng-
ers, E. Bouwman, W. P. Mul, H. Kooijman, A. L. Spek, E.
Drent, Eur. J. Inorg. Chem. 2002, 2147–2155; e) B. Martín-Ma-
tute, K. Bogár, M. Edin, F. B. Kaynak, J.-E. Bäckvall, Chem.
Eur. J. 2005, 11, 5832–5842; f) P. Crochet, M. A. Fernández-
Zúmel, J. Gimeno, M. Scheele, Organometallics 2006, 25, 4846–
4849; g) N. Ahlsten, H. Lundberg, B. Martín-Matute, Green
Chem. 2010, 12, 1628–1633; h) M. Batuecas, M. A. Esteruelas,
C. García-Yebra, E. Oñate, Organometallics 2010, 29, 2166–
2175; i) A. P. da Costa, J. A. Mata, B. Royo, E. Peris, Organo-
metallics 2010, 29, 1832–1838; j) V. Bizet, X. Pannecoucke, J.-
L. Renaud, D. Cahard, Angew. Chem. Int. Ed. 2012, 51, 6467–
6470.
Fernández-Zúmel, J. Gimeno, Adv. Synth. Catal. 2006, 348, 93–
100; c) A. E. Díaz-Álvarez, P. Crochet, M. Zablocka, C. Du-
hayon, V. Cadierno, J. Gimeno, J.-P. Majoral, Adv. Synth. Ca-
tal. 2006, 348, 1671–1679; d) M. Fekete, F. Joó, Catal. Com-
mun. 2006, 7, 783–786; e) B. Lastra-Barreira, J. Díez, P. Cro-
chet, Green Chem. 2009, 11, 1681–1686; f) A. Azua, S. Sanz,
E. Peris, Organometallics 2010, 29, 3661–3664.
[36]
[37]
A. Chanda, V. V. Fokin, Chem. Rev. 2009, 109, 725–74.
R. A. Zelonka, M. C. Baird, Can. J. Chem. 1972, 50, 3063–
3072.
M. A. Bennett, T.-N. Huang, T. W. Matheson, A. K. Smith,
Inorg. Synth. 1982, 21, 74–78.
X. Wang, R. Liu, Y. Jin, X. Liang, Chem. Eur. J. 2008, 14,
2679–2685.
D. J. Fox, D. S. Pedersen, S. Warren, Org. Biomol. Chem. 2006,
4, 3102–3107.
S. Pääkkönen, J. Pursiainen, M. Lajunen, Tetrahedron Lett.
2010, 51, 6695–6699.
[38]
[39]
[40]
[41]
[42]
[43]
[31] For a review on asymmetric isomerizations of allylic alcohols,
see: L. Mantilli, C. Mazet, Chem. Lett. 2011, 40, 341–344.
[32] K. Tanaka, G. C. Fu, J. Org. Chem. 2001, 66, 8177–8186.
[33] Selected reviews: a) S. Ribe, P. Wipf, Chem. Commun. 2001,
299–307; b) J. B. F. N. Engberts, M. J. Blandamer, Chem. Com-
mun. 2001, 1701–1708; c) C. J. Li, Chem. Rev. 2005, 105, 3095–
3165; d) M. C. Pirrung, Chem. Eur. J. 2006, 12, 1312–1317; e)
R. N. Butler, A. G. Coyne, Chem. Rev. 2010, 110, 6302–6337;
f) M. O. Simon, C.-J. Li, Chem. Soc. Rev. 2012, 41, 1415–1427.
[34] a) V. Cadierno, S. E. García-Garrido, J. Gimeno, Chem. Com-
mun. 2004, 232–233; b) V. Cadierno, S. E. García-Garrido, J.
Gimeno, A. Varela-Álvarez, J. A. Sordo, J. Am. Chem. Soc.
2006, 128, 1360–1370; c) T. Campos-Malpartida, M. Fekete,
F. Joó, Á. Kathó, A. Romerosa, M. Saoud, W. Wojtków, J.
Organomet. Chem. 2008, 693, 468–474; d) P. Servin, R. Laur-
ent, L. Gonsalvi, M. Tristany, M. Peruzzini, J.-P. Majoral, A.-
M. Caminade, Dalton Trans. 2009, 4432–4434; e) J. García-
Álvarez, J. Gimeno, F. J. Suárez, Organometallics 2011, 30,
2893–2896; f) L. Bellarosa, J. Díez, J. Gimeno, A. Lledós, F. J.
Suárez, G. Ujaque, C. Vicent, Chem. Eur. J. 2012, 18, 7749–
7765.
M. Puchberger, W. Rupp, U. Bauer, U. Schubert, New J. Chem.
2004, 28, 1289–1294.
S. A. Van Arman, Tetrahedron Lett. 2009, 50, 4693–4695.
[44] M. R. Rohman, M. Rajbangshi, B. M. Laloo, P. R. Sahu, B.
Myrboh, Tetrahedron Lett. 2010, 51, 2862–2864.
[45] R. J. Abraham, M. Mobli, J. Ratti, F. Sancassan, T. A. D.
Smith, J. Phys. Org. Chem. 2006, 19, 384–392.
[46] Z. Otwinowski, W. Minor, Methods Enzymol. 1997, 276, 307–
326.
[47] A. Altomare, M. C. Burla, M. Camalli, G. L. Cascarano, C.
Giacovazzo, A. Guagliardi, A. G. G. Moliterni, G. Polidori, R.
Spagna, J. Appl. Crystallogr. 1999, 32, 115–119.
[48] G. M. Sheldrick, Acta Crystallogr., Sect. A 2008, 64, 112–122.
[49] P. van der Sluis, A. L. Spek, Acta Crystallogr., Sect. A 1990,
46, 194–201.
[50] A. L. Spek, J. Appl. Crystallogr. 2003, 36, 7–13.
[35] a) V. Cadierno, P. Crochet, S. E. García-Garrido, J. Gimeno,
Dalton Trans. 2004, 3635–3641; b) P. Crochet, J. Díez, M. A.
Received: July 2, 2012
Published Online: ᭿
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11

Job/Unit: I20733
/KAP1
Date: 10-09-12 16:04:22
Pages: 12
ˇ
J. Schulz, I. Císarˇová, P. Steˇpnicˇka
FULL PAPER
Polar Phosphanyl Carboxamides
Ruthenium(II) complexes of the type [(η6-
arene)RuCl2(L)], obtained from phosphan-
ylferrocenecarboxamides bearing polar
hydroxyalkyl pendants and the respective
dimers [(η6-arene)RuCl2]2 (arene = C6H6,
p-cymene, C6Me6), were evaluated as cata-
lysts for redox isomerizations of allylic al-
cohols to the corresponding carbonyl com-
pounds.
J. Schulz, I. Císarová,
ˇ
ˇ
P. S teˇpnicˇka* .................................. 1–12
Arene–Ruthenium Complexes with Phos-
phanylferrocenecarboxamides Bearing Po-
lar Hydroxyalkyl Groups – Synthesis, Mo-
lecular Structure, and Catalytic Use in Re-
dox Isomerizations of Allylic Alcohols to
Carbonyl Compounds
Keywords: Metallocenes / Structure eluci-
dation / Isomerization / Phosphane li-
gands / Ruthenium
12
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