Synthesis and reaction chemistry of heterodi- and heterotrimetallic transition-metal complexes based on 1-(Diphenylphosphanyl)-1'- terpyridylferrocene

Article abstract of DOI:10.1002/ejic.201000365

The reaction of [Fe(η5-C₅H₄PPh ₂)(η⁵-C₅H₄terpy)] (5; terpy = 2,2':6',2''-terpyridin-4'-yl) with diverse transition-metal compounds including [PtCl₂(Et₂S)₂], [Pd(cod)X₂], [AuCl(tht)], [CuBr], [Mo(CO)₄(nbd)], and [{RhCl(cod)}₂] (X = Cl, Br; tht = tetrahydrothiophene; nbd = norbornadiene; cod = cyclooctadiene) to afford heterobi- and trimetallic complexes and a coordination polymer is reported. The following compounds were prepared: [Fe(η⁵-C ₅H₄PPh₂{PtCl₂(SEt ₂)})(η₅-C₅H₄terpy)] (7), trans-[PtCl₂{(Ph₂P-η⁵-C₅H ₄)(η⁵-C₅H₄terpy)-Fe} ₂] (9), [Fe(η⁵-C₅H₄PPh ₂PdCl₂)(η⁵-C₅H ₄terpy)] (12), [Fe{η⁵-C₅H ₄PPh₂(Cl₃Pd-)}(η⁵-C ₅H₄terpy{(dmso)₂ClNi⁺})] (14), trans-[PdX₂{(Ph₂P-η⁵-C₅H ₄)(η⁵-C₅H₄terpy)Fe} ₂] (16a, X = Cl; 16b, X = Br), [Mo(CO)₄{(η ⁵-C₅H₄PPh₂)(η⁵-C ₅H₄terpy)Fe}₂] (17), [Fe{η⁵- C₅H₄Ph₂P(CuBr)}(η⁵-C ₅H₄terpy)]n (19), [Fe{η⁵-C ₅H₄Ph₂P(AuCl)}(η⁵-C ₅H₄terpy)] (22), [Fe(η⁵-C₅H ₄Ph₂P-{Rh(cod)Cl})(η5-C₅H ₄terpy)] (23), [Ru({η⁵-C₅H ₄Ph₂P(AuCl)}-(η⁵-C₅H ₄terpy)Fe)₂]Cl₂ (25), and [Fe{η5-C ₅H₄PPh₂-(PdCl₂)}{η⁵- C₅H₄-CH=CHC(O)(py)}] (26). The molecular structures of 5, 9, 12, 14, 16b, 22, and 26 in the solid state are reported. They show typical features of related phosphanylferrocenes and terpyridylferrocenes. Characteristic of 12 is a C-H activation as a result of the close distance of palladium to the terpyridyl moiety. Complexes 12, 26, and [PdCl2(dppf)] [dppf = 1,1'-bis(diphenylphosphanyl)ferrocene], for comparison, were used in preliminary studies as catalysts in the carbon-carbon coupling of iodobenzene with tert-butyl acrylate to give (E)-tert-butyl cinnamate. The conversion amounts to 80% with a turnover number of 160 and turnover frequency of 48 h^-1.

Full text of DOI:10.1002/ejic.201000365

FULL PAPER
DOI: 10.1002/ejic.201000365
Synthesis and Reaction Chemistry of Heterodi- and Heterotrimetallic
Transition-Metal Complexes Based on 1-(Diphenylphosphanyl)-1Ј-
terpyridylferrocene
Alexander Hildebrandt,[a] Nora Wetzold,[a] Petra Ecorchard,[a] Bernhard Walfort,[a]
Tobias Rüffer,[a] and Heinrich Lang*[a]
Keywords: Heterometallic complexes / Metallocenes / Solid-state structures / Terpyridine / N,P ligands
The reaction of [Fe(η5-C5H4PPh2)(η5-C5H4terpy)] (5; terpy =
{Rh(cod)Cl})(η5-C5H4terpy)] (23), [Ru({η5-C5H4Ph2P(AuCl)}-
(25), and
[Fe{η5-C5H4PPh2-
2,2Ј:6Ј,2ЈЈ-terpyridin-4Ј-yl) with diverse transition-metal com- (η5-C5H4terpy)Fe)2]Cl2
pounds including [PtCl2(Et2S)2], [Pd(cod)X2], [AuCl(tht)],
[CuBr], [Mo(CO)4(nbd)], and [{RhCl(cod)}2] (X = Cl, Br; tht =
tetrahydrothiophene; nbd = norbornadiene; cod = cyclo-
octadiene) to afford heterobi- and trimetallic complexes and
(PdCl2)}{η5-C5H4-CH=CHC(O)(py)}] (26). The molecular
structures of 5, 9, 12, 14, 16b, 22, and 26 in the solid state are
reported. They show typical features of related phosphanyl-
ferrocenes and terpyridylferrocenes. Characteristic of 12 is a
a coordination polymer is reported. The following com- C–H activation as a result of the close distance of palladium
pounds were prepared: [Fe(η5-C5H4PPh2{PtCl2(SEt2)})(η5-
C5H4terpy)] (7), trans-[PtCl2{(Ph2P-η5-C5H4)(η5-C5H4terpy)-
Fe}2] (9), [Fe(η5-C5H4PPh2PdCl2)(η5-C5H4terpy)] (12), [Fe{η5-
C5H4PPh2(Cl3Pd–)}(η5-C5H4terpy{(dmso)2ClNi+})] (14), trans-
to the terpyridyl moiety. Complexes 12, 26, and [PdCl2(dppf)]
[dppf = 1,1Ј-bis(diphenylphosphanyl)ferrocene], for compari-
son, were used in preliminary studies as catalysts in the car-
bon–carbon coupling of iodobenzene with tert-butyl acrylate
to give (E)-tert-butyl cinnamate. The conversion amounts to
80% with a turnover number of 160 and turnover frequency
[PdX2{(Ph2P-η5-C5H4)(η5-C5H4terpy)Fe}2] (16a,
X
=
Cl;
16b, X = Br), [Mo(CO)4{(η5-C5H4PPh2)(η5-C5H4terpy)Fe}2]
(17), [Fe{η5-C5H4Ph2P(CuBr)}(η5-C5H4terpy)]n (19), [Fe{η5-
C5H4Ph2P(AuCl)}(η5-C5H4terpy)] (22), [Fe(η5-C5H4Ph2P-
of 48 h–1
.
and N/O hemilabile ligand systems. First reports about the
use of such asymmetric 1,1Ј-disubstituted ferrocenes in
homogeneous catalysis were reported as well.[7–9] One of the
reports implied a chiral thioether–phosphanylferrocene,
which was used in Pd-catalyzed allylic substitution of 1,3-
diphenylpropenyl acetate with malonate and nitrogen nu-
cleophiles.[13] The use of ferrocenes that contain unsymmet-
rical P/S or P/O ligands at the cyclopentadienyl rings as
catalytic active species in combination with palladium(0)
and palladium(II) reagents, respectively, were also tested
by Gibson and Long in the Suzuki–Miyaura carbon–
carbon cross-coupling reaction of 4-bromotoluene with
phenyl boronic acid to produce 4-methylbiphenyl.[8a]
Within this reaction the yield was doubled, when compared
with the symmetrical 1,1Ј-bis(diphenylphosphanyl)ferro-
cene.
These studies have prompted us to prepare 1-(diphenyl-
phosphanyl)-1Ј-terpyridylferrocene and to use this com-
pound for the synthesis of transition-metal complexes of
higher nuclearity. We chose this molecule as starting com-
pound because the diphenylphosphanyl group should pref-
erentially bind to soft and the terpyridyl unit to hard transi-
tion-metal-complex fragments.[14] The application of the ap-
propriate Fe–Pd-containing molecules in the Heck–Mizo-
roki reaction of iodobenzene with tert-butyl acrylate to give
Introduction
In recent years, ferrocene-based organometallics have re-
ceived remarkable attention because such molecules are in
general very robust and show a reversible redox character.[1]
They are of interest in many fields of chemistry including
organic synthesis, molecular recognition, material sciences,
and homogeneous catalysis.[2] Whereas symmetrically sub-
stituted ferrocenes with nitrogen,[3] phosphorus,[4] oxygen,[5]
or sulfur[6] donor groups at the cyclopentadienyl rings are
well studied, less is known about sandwich compounds that
bear two different coordination functionalities.[7] The latter
type of molecules, with their asymmetric 1,1Ј-substitution
pattern, are of great interest in, for example, homogeneous
catalysis due to their hemilabile coordination sites.[8] In this
respect, the work of Gibson et al.,[8a,9] Gimeno et al.,[10]
Keim et al.,[11] Long et al.,[7a,8a,9] and others[12] must be
mentioned, who recently reported about the systematic syn-
thesis, reaction behavior, and characterization of P/S, P/O,
[a] Technische Universität Chemnitz, Fakultät für
Naturwissenschaften,
Institut für Chemie, Lehrstuhl für Anorganische Chemie,
Straße der Nationen 62, 09111 Chemnitz, Germany
Fax: +49-371-531-21219
E-mail: heinrich.lang@chemie.tu-chemnitz.de
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H. Lang et al.
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(E)-tert-butyl cinnamate is reported as well. The molecular
structures of seven compounds in the solid state are dis-
cussed.
Results and Discussion
To synthesize asymmetric 1,1Ј-substituted ferrocene-
based heterodi- and heterotrimetallic FeM (M = Mo, Pd,
Pt, Rh, Cu, Au), Fe2M (M = Mo, Pd, Pt), Au2Fe2Ru, and
PdFeNi complexes, we chose [Fe(η5-C5H4PPh2)(η5-
C5H4terpy)] (5; terpy = 2,2Ј:6Ј,2ЈЈ-terpyridin-4Ј-yl) as the
key starting molecule, which is accessible by the reaction
sequence shown in Scheme 1 including an aldol condensa-
tion [reaction (i)] and a Michael addition with subsequent
ring closure [reaction (ii)]. Whereas molecules 1 and 5 are
orange-colored, complex 3 is purple, most probably re-
sulting from the α,β-unsaturated carbonyl pyridyl unit.
Ferrocenes 3 and 5 could be isolated as solid materials that
dissolve in common polar organic solvents. The unsym-
metrical sandwich compound 5 is stable in the solid
state and in solution, whereas it rapidly decomposes on ex-
posure to light and hence should best be stored in the
dark.
Figure 1. ORTEP diagram of 5. Thermal ellipsoids are shown at
the 50% probability level. The hydrogen atoms are omitted for clar-
ity. Selected bond distances [Å] and angles [°]: Fe1–D1 1.647(3),
Fe1–D2 1.648(3), P1–C1 1.814(5), P1–C11 1.836(6), P1–C17
1.829(5), C6–C23 1.479(6); P1–C1–C2 130.6(4), P1–C1–C5
123.2(4), C11–P1–C17 102.3(2), C1–P1–C17 100.7(2); D1: centroid
of C1–C5, D2: centroid of C6–C10.
staggered by 9°. The geometry at P1 is distorted tetrahedral
with angles in the range of 100.7(2)–102.3(2)° (Figure 1).
The 2,2Ј:6Ј,2ЈЈ-terpyridyl group adopts, as expected, a
trans–trans conformation about the interannular C25–C28
and C26–C33 bonds.[15] In addition, the terpy group is
nearly planar [root mean-square deviation (RMSD) from
planarity = 0.068 Å]. The interplanar angle between the cy-
clopentadienyl ring C6–C10 and N1, C23–C27 is 11.1(3)°,
thereby showing that both groups are not coplanar to each
other (Figure 1). The bonds and angles about the ferrocene,
diphenylphosphanyl, and terpyridyl building blocks are
similar to those typically found for this type of frag-
ments.[16] As a guide to the coordination properties of 5, we
treated it with diverse transition-metal complexes including
[PtCl2(Et2S)2], [Pd(cod)X2], [Mo(CO)4(nbd)], [CuBr],
[AuCl(tht)], and [{RhCl(cod)}2] (X = Cl, Br; nbd = nor-
bornadiene; tht = tetrahydrothiophene; cod = cyclooctadi-
1,5-ene).
Scheme 1. Synthesis of 5 from 1: (i) dichloromethane/ethanol mix-
ture (1:5 v/v); NaOH, 25 °C, 2.5 h; (ii) ethanol, [H4N]OAc, 100 °C,
3 h.
The appropriate FePt compound [Fe(η5-C5H4PPh2-
{PtCl2(SEt2)})(η5-C5H4terpy)] (7) was formed by treatment
The molecular structure of 5 in the solid state was deter- of 5 with equimolar amounts of [PtCl2(SEt2)2] (6) in dichlo-
mined by single-crystal X-ray structure analysis, thus con- romethane as solvent at ambient temperature (Scheme 2).
firming the structural assignment made from spectroscopic Exclusive coordination of the diphenylphosphanyl group to
characterization (see Exp. Section). Single crystals of this platinum is observed. Since unsymmetrical substituted 7
compound were obtained by diffusion of n-pentane into a possesses with the Et2S donor group a labile ligand,[17] we
saturated solution of 5 in dichloromethane at room tem- treated it with a further equivalent of 5. After appropriate
perature. The molecular structure of 5 and selected bond workup, the expected trimetallic Fe2Pt complex
9
distances [Å] and angles [°] are presented in Figure 1. The (Scheme 2) could be isolated as an orange solid in 89%
crystal and structure refinement data are summarized in yield (see Exp. Section). The latter molecule was also
Table 3 (see Exp. Section).
formed when 7 was treated with triphenylphosphane. The
Ferrocene 5 represents a unsymmetrical 1,1Ј-disubsti- in situ formed unsymmetrical complex [{Pt(Cl)2(PPh3)}-
tuted sandwich molecule in which a diphenylphosphanyl {Fe(η5-C5H4PPh2)(η5-C5H4terpy)}] rapidly exchanges its li-
and a terpyridyl ligand are bonded to individual cyclopen- gands to give 9 and the respective [Pt(PPh3)2Cl2] species, a
tadienyl rings. They are rotated by 85.0(3)° to each other common feature of [Pt(L)(LЈ)Cl2] complexes (L, LЈ = 2-
(Figure 1). The C5H4 rings are inclined by 3.0(3)° and are electron donors).
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Heteromultimetallic Transition-Metal Complexes
Scheme 2. Synthesis of 7 and 9 from 5 and 6: (i) 25 °C, 10 min, dichloromethane; (ii) 25 °C, 30 min, tetrahydrofuran.
The identities of 7 and 9 have been confirmed by elemen- these two resonances disappear and the progress of the re-
1
1
tal analysis, H and 31P{1H} NMR spectroscopy, and ESI- action can therefore easily be controlled by H NMR spec-
TOF mass spectrometry (9). The molecular structure of 9 troscopy.
in the solid state was additionally measured by single-crys-
The formation of 9 is additionally evidenced from ESI-
tal X-ray structure determination (Figure 2).
TOF mass spectrometric investigations, which indicate the
The 31P{1H} NMR spectrum of 5 displays a resonance presence of the molecular ion [M + H]+ at a mass-to-charge
signal at δ = –18.3 ppm due to the presence of the nonco- ratio (m/z) of 1468.90 (see Exp. Section).
ordinating Ph2P unit. The P-coordination of the diphenyl-
Single crystals of 9 were obtained from slow diffusion of
phosphane moiety to a [PtCl2(SEt2)] fragment in 7 or a n-pentane into a saturated solution of 9 in dichloromethane
PtCl2 unit in 9 is best reflected by a significant shift to lower at 25 °C. The molecular structure of 9 is shown in Figure 2.
field (7, δ = 14.9 9, 10.0 ppm). The signals thereby show a The crystal and structural refinement data are summarized
characteristic coupling with 196Pt (I = ½, 25.3% abundance) in Table 3 (see Exp. Section). Compound 9, as the 2:1 ad-
1
31P,196Pt
giving doublets with typical J
coupling constants of duct of 5 and PtCl2, crystallized in the monoclinic centro-
3690 (7) and 2630 Hz (9). These values are in agreement symmetric space group P21/c with crystallographically im-
with the coupling data found in other square-planar plati- posed inversion symmetry at Pt1. The platinum atom is co-
num–diphosphanyl complexes with trans geometry.[18]
ordinated by two chlorido and two phosphorus atoms in a
1
The formation of 7 is also confirmed by H NMR spec- precisely planar geometry. For compound 9, an identical
troscopy since two new resonances for the [PtCl2(SEt2)] co- rotation of the Ph2P versus terpyridyl moieties, as discussed
ordination fragment can be observed at δ = 1.08 (CH3) and for 5, has been observed. The cyclopentadienyl rings are
3
2.50 ppm (CH2) with JH,H = 7.2 Hz. On replacement of inclined by 3.8(3)° and staggered by approximately 3–5°.
SEt2 by a second [Fe(η5-C5H4PPh2)(η5-C5H4terpy)] unit, Due to the Pt–P bond the angles around P1 are more open
Figure 2. ORTEP diagram (50% probability level) of the molecular structure of 9. The hydrogen atoms are omitted for clarity. Symmetry
transformations used to generate equivalent atoms labeled with A: –x, –y, –z + 1. Selected bond distances [Å] and angles [°]: Fe1–D1
1.650(2), Fe1–D2 1.653(2), P1–C1 1.827(3), P1–C13 1.803(4), P1–C7, C18–C23 1.473(5); Pt1–Cl1 2.301(1), Pt1–P1 2.322(1); C7–P1–C1
104.52(15), C13–P1–C1 102.14(16), Cl1–Pt1–P1 88.47(4) C1–P1–Pt1 112.15(11); D1: centroid of C13–C17, D2: centroid of C18–C22.
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H. Lang et al.
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relative to 5 and range from 104.5(2)–116.7(1)°. This is in sult of the paramagnetic character of 14 (octahedral-coordi-
a good agreement with the observations made in similar nated NiII), no standard NMR spectroscopic measurements
systems.[7a]
could be performed.
A further possibility to prepare heterodi- (FePd) and het-
As expected, 16 and 17 show different spectral features
erotrimetallic (Fe2M; M = Mo, Pd) transition-metal com- from 12 because in 12 the terpyridyl moiety asymmetrically
plexes based on 5 is given by the reactions depicted in coordinates with one of its pyridyl units to the PdII ion.
Scheme 3. In this respect, we treated 5 with the palladium That is why for the terpyridyl ligand two sets of signals are
1
source [PdCl2(cod)] in an equimolar amount, whereby dark found in the H and 13C{1H} NMR spectra (Exp. Section).
orange 12 was formed in good yield (see Exp. Section). In It is noteworthy that the hydrogen atom at C24 (see X-ray
12, the square-planar coordination geometry of the palladi- structure determination, Figure 3) is found at
δ =
um(II) ion is set up by two trans-oriented chlorido ligands, 10.46 ppm and is significantly shifted to lower field when
the diphenylphosphanyl group, and one pyridyl ligand of compared with the chemical shift of the hydrogen atom
the terpyridyl moiety. When molecule 12 was further treated bonded to C26 (δ = 8.61 ppm). An explanation for this be-
with a third transition-metal salt such as [NiCl2(dme)] (13; havior is the close proximity (2.55 Å) of the respective hy-
dme = dimethoxyethane) in tetrahydrofuran, a dark red drogen atom to palladium, which could be confirmed by X-
precipitate was formed. After appropriate workup, and ad- ray structure analysis (vide infra). For all other species, the
dition of dimethyl sulfoxide (dmso), zwitterionic heterotri- expected signal and coupling patterns are observed (Exp.
1
metallic 14 could be isolated in which a [PdCl3(Ph2P)]– frag- Section). A representative H NMR spectrum of 12 is de-
1
ment and a [Ni(Cl)(dmso)2(terpy)]+ ion are connected by picted in Figure 3; for comparison the H NMR spectrum
the Fe(η5-C5H4)2 sandwich backbone (Scheme 3). A some- of 5 is presented as well.
what different reaction behavior was found when 5 was
From 31P{1H} NMR spectroscopic studies it is clear that
treated with [MLnLЈ] [11a, M = Pd, L = Cl, LЈ = cod, n = the diphenylphosphanyl groups in 12, 16, and 17 are
2; 11b, M = Pd, L = Br, LЈ = cod, n = 2; 15, M = Mo, L datively bonded to the transition metals palladium and mo-
= CO, LЈ = nbd, n = 4] in a 2:1 molar ratio (Scheme 3). lybdenum, respectively, since a distinct downfield shift is
Treatment of 5 with 11a or 11b exclusively gave trans- observed (δ = 14–26 ppm) relative to 5 (δ = –18.3 ppm; see
[PdL2{(η5-C5H4Ph2P)(η5-C5H4terpy)Fe}2] (16a, L = Cl; Exp. Section).
16b, L = Br), which could be isolated as an orange solid
Less information can be obtained from IR spectroscopic
material in 84% yield (Scheme 3, Exp. Section). Complex studies of 12, 14, 16a, and 16b, whereas the metal carbonyl
[Mo(CO)4{(η5-C5H4PPh2)(η5-C5H4terpy)Fe}2] (17) was building block in 17 shows the characteristic strong absorp-
prepared by combining 5 with 15, whereby nbd was con- tions typical for a [Mo(CO) ] fragment (ν = 2018, 1900,
˜
4
CO
comitantly eliminated from 15 (Scheme 3).
Complexes 16 and 17 are barely soluble in common or- the two bulky [Fe(η5-C5H4PPh2)(η5-C5H4terpy)] moieties.
ganic solvents (dichloromethane, tetrahydrofuran). Com- Figures 4, 5, and 6 highlight the solid-state structures
1867, 1812 cm–1), thereby indicating a cis coordination[19] of
pound 14 is, due to its zwitterionic nature, only moderately and selected bond lengths [Å] and angles [°] of 12 (Fig-
soluble in dmso. Due to the insufficient solubility of 16 and ure 4), 14 (Figure 5), and 16b (Figure 6). X-ray-quality sin-
17, no 13C{1H} NMR spectra could be obtained. As a re- gle crystals of these molecules could be grown by diffusion
Scheme 3. Synthesis of 12, 14, 16, and 17 from 5: (i) dichloromethane, 30 min, 25 °C; (ii) tetrahydrofuran, 1 min, 25 °C, recrystallization
from dmso; (iii) dichloromethane, 10 min, 25 °C.
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Heteromultimetallic Transition-Metal Complexes
1
Figure 3. H NMR spectra of 5 (top) and 12 (below) (in CDCl3, 25 °C, 250 MHz).
of n-hexane into solutions of 12 or 16b in chloroform, separation found in 12 [2.146(6) Å] is long compared to dis-
whereas crystals of 14 were obtained by diffusion of diethyl tances that involve Pd–N bonds that are trans oriented (i.e.,
ether into a mixture of dmso/dichloromethane in a ratio of 2.007 Å).[21] This can be explained by the trans influence.[22]
70:30 (v/v) at ambient temperature. The crystal and struc- The two noncoordinated pyridyl rings of the terpy unit are
ture refinement data of 12, 14, and 16b are summarized in found to be in-plane-bonded with the cyclopentadienyl ring
Table 3 (see Exp. Section).
C6–C10 (RMSD 0.070 Å) (Figure 4). The pyridyl ring co-
ordinated to Pd1 is twisted by about 36.9(9)° from this
plane. The unusual chemical shift of the hydrogen atom
bonded to C24 can be explained by the short Pd1–H24 dis-
tance, which is with 2.55 Å shorter than the sum of palla-
dium and hydrogen van der Waals radii (2.8 Å).[23]
The overall structural features of 14 are similar to those
of related structurally characterized molecules containing
(diphenylphosphanyl)ferrocene, terpyridylferrocene, palla-
dium chloride, and nickel chloride.[20,21,24] Complex 14 con-
sists of
a 1-(diphenylphosphanyl)-1Ј-terpyridylferrocene
centrality with a distorted square-planar Pd1, Cl1–Cl3, P1
fragment and a distorted octahedrally coordinated NiII ion
(Ni1, Cl4, O1, O2, N1–N3) (Figure 5). The Cl1–Pd1–Cl3
angle [170.78(8)°] is reduced from 180° as a result of the
steric demand of the organometallic [Fe(η5-C5H4PPh2)(η5-
C5H4terpy{NiCl(dmso)2})] building block. As expected, the
Pd1–Cl2 bond length of 2.399(3) Å is longer than the ap-
propriate Pd1–Cl1 [2.296(2) Å] and Pd1–Cl3 separations
[2.297(3) Å] that are trans-oriented to ligands with a trans
Figure 4. ORTEP diagram of 12. Thermal ellipsoids are shown at
the 50% probability level. All hydrogen atoms, except H24, and the influence weaker than phosphorus.[22] The cylopentadienyl
disordered tetrahydrofuran molecule as noncoordinating packing
rings of the ferrocenyl moiety are rotated by around 3°,
solvent have been omitted for clarity. Selected bond lengths [Å],
which verifies an almost eclipsed conformation. The Fe–D
angles [°], and torsion angles [°]: Fe1–D1 1.663(3), Fe1–D2
distances (D is the centroid of the respective cyclopen-
1.661(3), Pd1–P1 2.2413(16), Pd1–N2 2.146(6), Pd1–Cl1
2.3101(16), Pd1–Cl2 2.3128(16), P1–C1 1.803(6), C6–C25 1.468(9);
tadienyls) are characteristic[25] and indicate that the iron
C1–P1–Pd1 116.4(2), N2–Pd1–P1 175.44(17), Cl1–Pd1–Cl2
177.87(6), P1–Pd1–Cl1 94.97(6), Pd1–N2–C28 124.2(5); N1–C23–
C28–N2 –140.8(6), N1–C27–C33–N3 –177.3(6); D1: centroid of
C1–C5, D2: centroid of C6–C10.
atoms are almost equidistant from the cyclopentadienyl
rings and correspond to those bond lengths found for other
ferrocenes.[20b] The coordination sphere about Ni1 is set up
by a terpy (N1–N3) and one dmso (O2) ligand in equatorial
Crystallographic data of 12 reveal an almost square- positions, and Cl4 as well as the second dmso solvent mole-
planar geometry about the PdII center. The sum of the cule localized in axial positions (Figure 5). The Ni1–O2
angles around Pd1 is essentially 360° with trans-oriented bond [2.052(5) Å] is shorter than the Ni1–O1 distance
chlorido ligands. The Pd1–Cl1 and Pd1–Cl2 bond lengths [2.105(6) Å], thus indicating the trans influence of pyridyl
of 2.3101(16) and 2.3128(16) Å, respectively, are compar- and chloride ligands, respectively (Figure 5). The best
able with bond separations observed for other palladium planes of the terpy group and the cyclopentadienyl C6–C10
dichloride molecules that feature phosphane and/or pyridyl ring are rotated by 11.7(4)° to each other. The bond lengths
ligands.[20] As expected, the Pd1–P1 distance [2.2413(16) Å] and bond angles about the phosphanyl and terpy substitu-
is shorter than in trans-bis(phosphanyl)palladium(II) com- ents are close to those reported for analogous transition-
plexes (i.e., 2.325 Å),[20b] whereas the respective Pd1–N2 metal building blocks.[20,21,25]
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FULL PAPER
Figure 5. ORTEP diagram of 14. Thermal ellipsoids are shown at the 50% probability level. The hydrogen atoms and the disordered
dichloromethane molecule as noncoordinating packing solvent are omitted for clarity. Selected bond lengths [Å], angles [°], and torsion
angles [°]: Fe1–D1 1.6541(7), Fe1–D2 1.6552(8), Pd1–P1 2.252(3), Pd1–Cl1 2.296(2), Pd1–Cl3 2.297(3), Pd1–Cl2 2.399(3), P1–C1
1.803(10), C6–C23 1.457(11); Ni1–N1 1.987(6), Ni1–N2 2.124(6), Ni1–N3 2.106(6), Ni1–O1 2.105(6), Ni1–O2 2.052(5), Ni1–Cl4 2.390(2);
P1–Pd1–Cl1 89.68(10), Cl1–Pd1–Cl3 170.78(8), P1–Pd1–Cl2 176.08(8), N1–Ni1–O2 171.5(2), N3–Ni1–N2 156.8(2), O1–Ni1–Cl4
176.31(16), N3–Ni1–Cl4 90.31(19); N1–C26–C33–N3 –0.2(11), N1–C25–C28–N2 4.1(10), C7–C6–C23–C24 –8.1(13); D1: centroid of C1–
C5, D2: centroid of C6–C10.
Figure 6. ORTEP diagram of 16b. Thermal ellipsoids are shown at the 50% probability level (symmetry transformations used to generate
equivalent atoms: –x, –y, –z + 1; center of inversion on Pd1). The hydrogen atoms are omitted for clarity. Selected bond lengths [Å],
angles [°], and torsion angles [°]: Fe1–D1 1.646(3), Fe1–D2 1.643(3), Pd1–P1 2.3304(17), Pd1–Br1 2.3969(8), P1–C1 1.785(6), C6–C23
1.466(10); P1–Pd1–Br1 88.77(4), C1–P1–Pd1 115.7(2); C7–C6–C23–C24, N1–C25–C28–N3 175.5(5), N1–C26–C33–N2 –173.6(8); D1:
centroid of C1–C5, D2: centroid of C6–C10.
The single-crystal X-ray structure analysis of 16b shows the two isotopes of copper (63Cu, 65Cu).[27] Coordination
1
nearly the same structural features as discussed for 5 and 9 of the terpy group to copper(I) was proven by H NMR
(see Figures 1 and 2). Complex 16b crystallized in the mo- spectroscopy. The signals for the terpy ligand are shifted to
noclinic centrosymmetric space group P21/c with crystallo- a lower field than that of the starting material 5 [C5H2N: δ
graphically imposed inversion symmetry at Pd1. The plati- = 8.46 ppm (5); 8.53 ppm (19)] (see Exp. Section). Due to
num atom is coordinated in a planar geometry by two bro- this, we postulate that 19 is polymerically constructed. On
mides and two phosphorus atoms. The cyclopentadienyl addition of dmso, complex 19 was transformed to a species
rings are inclined by 3.7(5)° and staggered by 3–5°.
of
composition
[Fe(η5-C5H4Ph2P{CuBr(dmso)n})(η5-
Treatment of a solution of 5 in tetrahydrofuran with the C5H4terpy)], which affirms the postulation of a coordina-
copper(I) salt [CuBr] (18) resulted in the formation of co- tion polymer.
ordination polymer 19 in virtually quantitative yield
Organometallic 5 as a multitopic molecule with the
(Scheme 4, Exp. Section). Elemental analysis of 19 is in Lewis basic diphenylphosphanyl and terpyridyl units to al-
good agreement with the proposed composition. The low mono-, bi-, and/or tridentate coordination of different
31P{1H} NMR spectrum of 19 is indicative of the coordina- organometallic coordination fragments (vide supra) was
tion of the diphenylphosphanyl group to copper(I) because also treated with tetrahydrothiophene gold(I) chloride (20)
a typical chemical shift from δ = –18.3 (5) to –14.9 ppm (19) in tetrahydrofuran as solvent at 25 °C (Scheme 4). Within
is found.[26] A broad signal is observed that is attributed to this reaction the weakly bonded tht ligand is replaced by
3620
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Heteromultimetallic Transition-Metal Complexes
Scheme 4. Reaction chemistry of 5 towards [CuBr], [AuCl(tht)], and [{RhCl(cod)}2]: (i) tetrahydrofuran, 2 h, 25 °C; (ii) ethanol, 12 h,
reflux.
the stronger donor/acceptor group PPh2. After appropriate
workup,
pale
yellow
[Fe{η5-C5H4Ph2P(AuCl)}(η5-
C5H4terpy)] (22) was obtained in high yield (Exp. Section).
Heterobimetallic (FeRh) 23 could be prepared by treatment
of 5 with [{RhCl(cod)}2] (21) in a 1:1 molar ratio in tetra-
hydrofuran (Scheme 4).
Compounds 22 and 23 were characterized by elemental
analysis and IR and NMR spectroscopy. NMR spectro-
scopic properties of both complexes correlate with their for-
mulation as heterodimetallic FeM complexes (M = Au,
Rh). The identity of 22 was further confirmed by single-
crystal X-ray diffraction studies.
Figure 7. ORTEP diagram of 22. Thermal ellipsoids are shown at
the 50% probability level. The hydrogen atoms are omitted for clar-
ity. Selected bond lengths [Å], angles [°], and torsion angles [°]:
Fe1–D1 1.631(1), Fe1–D2 1.644(1), Au1–Cl1 2.2616(9), Au1–P1
2.2154(7), P1–C1 1.773(3), C6–C23 1.470; P1–Au1–Cl1 178.29(4),
Au1–P1–C1 113.78(9); N1–C26–C33–N3 172.2(2), N1–C25–C28–
N2 161.2(3), C7–C6–C23–C24 170.1(3); D1: centroid of C1–C5,
D2: centroid of C6–C10.
For compound 22, X-ray quality crystals could be ob-
tained by slow diffusion of n-pentane into a solution of 22
in dichloromethane at ambient temperature. The molecular
structure of 22 is presented in Figure 7 together with se-
lected bond lengths [Å] and angles [°]. The crystal and
structure refinement data are summarized in Table 4 (Exp.
Section).
¯
Molecule 22 crystallized in the triclinic space group P1.
The structure of 22 shows a linear geometry around Au1
set up by the Ph2P and Cl ligands, and Fe1 as part of a
sandwich structure. Geometrical parameters within the
Ph2PAuCl fragment and the ferrocenyl–terpy building block
are similar to those reported previously in comparable mo-
lecules.[16,28] As observed for 5, also in 22 the terpyridyl
moiety adopts a trans–trans conformation. In contrast to 5,
the terpyridyl moiety is not planar. Calculated interplanar
angels between the C5H4N groups range from 7.7(2) (N1,
C23–C27 vs. N3, C33–C37) to 20.6(2) ° (N1, C23–C27 vs.
N2, C28–C32).
For catalytic purposes, we treated 3 with equimolar
amounts of 11a [Reaction (1)]. The PdFe molecule 26
formed in this way was obtained as a deep purple solid.
Coordination of the terpyridyl donor group in 22 to ru-
thenium using [RuCl2(dmso)4] as the ruthenium source gave
pentametallic (Au2Fe2Ru) 25. In this molecule, two units of
22 are bridged through the coordination of their terpyridyl
(1)
Characterization of 26 is based on elemental analysis,
moieties to the centered ruthenium(II) ion, which was spectroscopy (NMR, IR) and mass spectrometry (ESI-
1
proven by H NMR spectroscopy [C5H2N: δ = 8.35 ppm TOF) (see Exp. Section) as well as single X-ray structure
(22), 9.67 ppm (25)].
analysis (Figure 8, Table 1).
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H. Lang et al.
FULL PAPER
Figure 8. ORTEP diagram (50% probability level) of the molecular structure of 26 forming a solvent-bridged centrosymmetric dimer in
the solid state, due to the formation of hydrogen bonds. All carbon-bonded hydrogen atoms have been omitted for clarity. Symmetry
operations used to generate equivalent atoms are labeled with A: –x + 2, –y + 2, –z. Selected bond lengths [Å] and angles [°]: Fe1–D1
1.634(4), Fe1–D2 1.648(4), Pd1–P1 2.2443(5), Pd1–N1 2.1337(13), Pd1–Cl1 2.2935(4), Pd1–Cl2 2.3073(4), C6–C23 1.453(2), C23–C24
1.341(2), P1–Pd1–N1 175.03(4), Cl1–Pd1–Cl2 175.379(15), Cl1–Pd1–P1 88.14(4), Cl2–Pd1–N1 87.85(4); D1: centroid of C1–C5, D2:
centroid of C6–C10.
Table 1. Bond lengths [Å] and angles [°] of the intermolecular hy- with the conventional [PdCl2(dppf)] system [dppf = 1,1Ј-
drogen bonds of 26 (D: donor, A: acceptor).
bis(diphenylphosphanyl)ferrocene] (30) were carried out so
that direct comparison might be achieved.
D–H···A
D–H [Å]
H···A [Å]
D···A [Å] D–H···A [°]
O2–H1O···O1
O2A–H2OA···O1 0.75(5)
0.82(5)
2.09(5)
2.21(5)
2.907(3) 176(4)
2.958(3) 175(6)
Crystallization of 26 was carried out in untreated sol-
vents; it resulted in the presence of water in the solid-state
structure. Compound 26 crystallized as a centrosymmetric
dimer in which two water molecules bridge two molecules
of 26 by the formation of intermolecular hydrogen bonds
by molecular recognition.
The PdCl2NP coordination setup is almost planar, as the
sum of all angles around Pd1 is 359.9(5)°, with trans-ori-
ented chlorido ligands. The Pd1–Cl1 and Pd1–Cl2 bond
lengths of 2.2935(4) and 2.3073(4) Å are comparable with
distances of related complexes.[20b]
In a preliminary study, heterobimetallic transition-metal
complexes 12 and 26 were screened for their catalytic activi-
ties in the Heck–Mizoroki reaction.[29] The results obtained
(rate of conversion, kinetic studies) are summarized in
Table 2 and Figure 9. To test the productivity of these two
organometallic species, we treated iodobenzene (27) with
tert-butyl acrylate (28) to give (E)-tert-butyl cinnamate (29)
in toluene and acetonitrile mixtures of ratio 1:1 (v/v) at
80 °C in presence of EtNiPr2 as a base and as reducing
agent with a catalyst loading of 0.5 mol-% [see reaction (2),
Table 2, Figure 9]. In addition to these studies, reactions
Figure 9. Kinetic investigations of 12, 26, and 30 (for comparison)
in the Heck–Mizoroki carbon–carbon cross-coupling of 27 with 28
(0.5 mol-% catalyst, 80 °C).
Table 2. Conditions of the Heck–Mizoroki carbon–carbon cross-
coupling reaction of 27 with 28 by complexes 12, 26, and 30 for
comparison (conc. 0.5 mol-%, 80 °C, 25 h).
(2)
Compound
Yield of 29 [%][a]
TON[b]
TOF [h–1 [b]
]
As summarized in Table 2 and Figure 9, the maximum
possible conversion amounts to 80%. As a consequence of
these data, it can be concluded that a higher productivity is
obtained with catalysts possessing hemilabile ligands as
given in complexes 12 and 26 when compared to an analo-
gous symmetrical diphosphane such as dppf.
12
26
30
79
81
50
158
162
100
48
42
23
[a] Yields have been measured by 1H NMR spectroscopy with ace-
tylferrocene as internal standard. [b] TON = turnover number.
Turnover frequencies (TOFs) are determined after one hour.
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Heteromultimetallic Transition-Metal Complexes
from tetramethylsilane (δ = 0.00 ppm) with the solvent as the refer-
Conclusion
1
ence signal (CDCl3: H NMR, δ = 7.26 ppm; 13C{1H} NMR, δ =
A new ligand system based on a ferrocenyl backbone 77.16 ppm).[19] 31P{1H} NMR spectra were recorded at
101.255 MHz in CDCl3 with P(OMe)3 as external standard [δ =
139.0 ppm, relative to H3PO4 (85%) with δ = 0.00 ppm]. ESI-TOF
mass spectra were recorded with a Mariner biospectrometry
workstation 4.0 (Applied Biosystems). Microanalyses were per-
formed with a C,H,N-analyzer FlashAE 1112 (Thermo Company).
Melting points of analytical pure samples (sealed off in nitrogen-
that features a terpyridyl and a diphenylphosphanyl donor
group is described using consecutive synthesis methodo-
logies. A series of novel heterobi- and heterotrimetallic
complexes including [Fe(η5-C5H4Ph2{PtCl2(SEt2)})(η5-
C5H4terpy)], trans-[PtCl2{(η5-C5H4Ph2P)(η5-C5H4terpy)-
Fe}2], [Fe{η5-C5H4-PPh2(Cl2Pd)}(η5-C5H4terpy)], [Fe{η5-
C5H4PPh2(Cl3Pd–)}(η5-C5H4terpy{(dmso)2-ClNi+})], trans-
[PdX2{(η5-C5H4Ph2P)(η5-C5H4terpy)Fe}2] (X = Cl, Br),
purged capillaries) were determined with
MFB 595010 M melting point apparatus.
a
Gallenkamp
[Mo(CO)4{(η5-C5H4PPh2)(η5-C5H4terpy)Fe}2],
[Fe{η5-
Reagents: [PdCl2(cod)],[33] [PdBr2(cod)],[33] [PtCl2(SEt2)2],[34] [Mo-
(CO)4(nbd)],[35] [NiCl2(dme)],[36] [AuCl(tht)],[37] [{RhCl(cod)}2],[38]
pyridylacetylpyridinium iodide,[39] and 1-(diphenylphosphanyl)-1Ј-
formylferrocene[40] were prepared according to published pro-
cedures. All other chemicals were purchased from commercial sup-
pliers and were used as received.
C5H4Ph2P(CuBr)}(η5-C5H4terpy)]n,
[Fe{η5-C5H4Ph2P-
(AuCl)}(η5-C5H4terpy)], [Fe(η5-C5H4Ph2P{Rh(cod)Cl})-
(η5-C5H4terpy)], [Ru({η5-C5H4Ph2P(AuCl)}(η5-C5H4terpy)-
Fe)2]Cl2,
and
[Fe{η5-C5H4PPh2(PdCl2)}{η5-C5H4-
CH=CHC(O)(py)}] have been synthesized by treatment of
[PtCl2(Et2S)2], [Pd(cod)X2], [AuCl(tht)], [CuBr], [Mo(CO)4-
(nbd)], and [{Rh(cod)Cl}2] with [Fe(η5-C5H4PPh2)(η5-
C5H4terpy)] and [Fe(η5-C5H4PPh2){η5-C5H4-CH=CHC-
(O)(py)}], respectively. Seven compounds have been struc-
turally characterized by single-crystal X-ray diffraction
analysis. The appropriate molecules show typical features
known for related phosphanylferrocenes and terpyridylfer-
rocenes.[16] The phosphanyl and terpyridyl groups are oppo-
sitely oriented except for complex 12, due to the chelating
P/N coordination. A carbon–hydrogen bond activation
could be observed for 12 as a result of the close distance of
the palladium atom to the terpyridyl moiety. Complex 24 is
to the best of our knowledge the first zwitterionic hetero-
multimetallic system set up by organometallic and metal–
organic parts. For catalytic applications, two palladium
complexes with hemilabile P/N ligands of type [Fe(η5-
C5H4PPh2)(η5-C5H4terpy)] and [Fe(η5-C5H4PPh2){η5-
C5H4-CH=CHC(O)(py)}] were synthesized. They show
good activity (TON = 160, TOF = 48 h–1) as catalysts in the
Heck–Mizoroki reaction [see reaction (2), Table 2, Figure 9]
relative to [PdCl2(dppf)] [dppf = 1,1Ј-bis(diphenylphos-
phanyl)ferrocene]. However, catalysts reported by, for ex-
ample, Fu et al.,[30] Herrmann et al.,[31] and Reetz et al.,[32]
are more active than 12 and 26 and can even be used for
less-reactive aryl halides under mild conditions.
Synthesis of 3: Compound 1 (1.36 g, 3.34 mmol) was dissolved in
dichloromethane (30 mL) and ethanol (150 mL). Acetylpyridine (2)
(0.46 mL, 4.31 mmol) was added in a single portion to this mixture.
After 5 min of stirring, an NaOH solution (12 mL, 2 ) was slowly
dropped imto the reaction mixture. Stirring was continued for 2.5 h
at 25 °C. The solution changed from orange to purple. The reaction
mixture was evaporated to 50 mL and water (200 mL) was added.
This solution was extracted twice with dichloromethane (200 mL
potions). The organic phases were combined and dried with
MgSO4 and all volatile materials were removed in an oil-pump vac-
uum. The obtained crude material was purified by column
chromatography on silica gel (column size: 4ϫ15 cm, chloroform).
With chloroform the starting material 1 could be eluted (100 mg,
0.25 mmol), whereas with ethyl acetate the title compound 3 was
obtained. All volatiles were removed under reduced pressure. Com-
pound 3 was isolated as a dark purple solid; yield 1.2 g (2.4 mmol,
70% based on 1). C30H24FeNOP (501.34): calcd. C 71.87, H 4.83,
N 2.79; found C 71.60, H 5.05, N 2.71; m.p. 131 °C. IR (KBr): ν
˜
= 1433 (m, νPC), 1468 (m, νPC), 1577 (s, νC=C), 1594 (s, νC=C), 1663
(s, νCO) cm–1. 1H NMR (CDCl3): δ = 4.14 (m, 2 H, C5H4), 4.38
(pt, J = 1.9 Hz, 2 H, C5H4), 4.40 (pt, J = 1.8 Hz, 2 H, C5H4), 4.56
(pt, J = 1.9 Hz, 2 H C5H4), 7.27–7.4 (m, 10 H, C6H5), 7.47 (ddd,
4
3
3J = 7.6, 4.6 Hz, J = 1.0 Hz, 1 H, C5H4N), 7.72 (d, J = 15.8 Hz,
3
3
1 H, C5H4N), 7.77 (d, J = 15.8 Hz, 1 H, C5H4N), 7.86 (ddd, J =
7.6, 7.8 Hz, J = 1.8 Hz, 1 H, C5H4N), 8.17 (ddd, J = 7.8 Hz, J
4
3
4
5
3
4
= 1.0 Hz, J = 0.9 Hz, 1 H, C5H4N), 8.73 (ddd, J = 4.6 Hz, J =
1.8 Hz, J = 0.9 Hz, 1 H, C5H4N) ppm. 13C{1H} NMR (CDCl3):
5
3
δ = 70.4 (C5H4), 73.0 (C5H4), 73.3 (d, JCP = 4 Hz, C5H4), 74.4 (d,
2JCP = 14 Hz, Ci-C5H4), 77.9 (Ci-C5H4), 80.3 (C5H4), 118.8 (CO-
CH=CH-), 123.0 (C5H4N), 126.7 (C5H4N), 128.4 (3JCP = 7 Hz, m-
2
C6H5), 128.8 (p-C6H5), 133.6 (d, JCP = 20 Hz, o-C6H5), 137.0
(C5H4N), 138.8 (d, JCP = 10 Hz, Ci-C6H5), 146.4 (CO-CH=CH-),
1
Experimental Section
148.9 (C5H4N), 154.8 (C5H4N), 188.6 (CO-CH=CH-) ppm.
31P{1H} NMR (CDCl3): δ = –18.5 ppm. ESI-TOF-MS: m/z = [M
+ H]+ 502.17.
General Data: All reactions were carried out under an atmosphere
of nitrogen using standard Schlenk techniques. Tetrahydrofuran,
toluene, n-hexane, and n-pentane were purified by distillation from
sodium/benzophenone ketyl; dichloromethane and chloroform
were purified by distillation from calcium hydride. Diethylamine
and diisopropylamine were distilled from KOH; absolute methanol
was obtained by distillation from magnesium.
Synthesis of 5: Compound 3 (2.9 g, 5.78 mmol), ammonium acetate
(5.0 g, 64.87 mmol), and 4 (2.2 g, 6.93 mmol) were dissolved in de-
gassed ethanol (20 mL) and heated for 3 h to reflux. An orange
solid precipitated. The reaction mixture was allowed to cool to
25 °C. The orange solid was filtered off and washed twice with ice-
cooled ethanol (25 mL portions); the residue was dried in an oil-
pump vacuum; yield 1.67 g (2.77 mmol, 48% based on 3).
C37H28FeN3P (601.46): calcd. C 73.89, H 4.69, N 6.99; found C
Instruments: Infrared spectra were recorded with a Perkin–Elmer
FTIR spectrometer Spectrum 1000. NMR spectra were recorded
with a Bruker Avance 250 spectrometer [1H NMR at 250.12 MHz
and 13C(1H) NMR at 62.86 MHz] in the Fourier transform mode.
Chemical shifts are reported in δ units (parts per million) downfield
73.39, H 4.80, N 6.82; m.p. 186 °C. IR (KBr): ν = 1433 (m, νPC),
˜
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H. Lang et al.
FULL PAPER
1468 (m, νPC), 1576 (s, νC=C), 1584 (s, νC=C), 1602 (s, νC=C) cm–1.
1H NMR (CDCl): δ = 4.06 (pq, J = 1.9 Hz, 2 H, C5H4), 4.24 (pt,
J = 1.9 Hz, 2 H, C5H4), 4.34 (pt, J = 1.9 Hz, 2 H, C5H4), 4.88 (pt,
washed twice with n-hexane (20 mL), and dried in an oil-pump
vacuum; yield 485 mg (0.62 mmol, 74% based on 5).
C37H28Cl2FeN3PPd (0.5 CH2Cl2) (821.25): calcd. C 55.17, H 3.53,
J = 1.9 Hz, 2 H, C5H4), 7.26–7.4 (m, 12 H, C6H5/5-C5H4N), 7.88 N 5.08; found C 55.47, H 3.62, N 4.97; m.p. 188 °C (dec.). IR
(ddd, 3J = 7.9, 8.0 Hz, 4J = 1.8 Hz, 2 H, C5H4N), 8.46 (s, 2 H,
C5H2N), 8.64 (ddd, 3J = 8 Hz, 4J = 1.0, 5J = 0.9 Hz, 2 H, C5H4N),
(KBr): ν = 1434 (m, νPC), 1471 (m, νPC), 1585 (s, νC=C), 1595 (s,
˜
νC=C) cm–1. 1H NMR (CDCl3): δ = 4.32 (br. s, 2 H, C5H4), 4.66
8.75 (ddd, 3J = 4.8 Hz, 4J = 1.8 Hz, 5J = 0.9 Hz, 2 H, C5H4N) (br. s, 2 H, C5H4), 4.7 (pt, J = 1.8 Hz, 2 H, C5H4), 5.30 (s, 1 H,
ppm. 13C{1H} NMR (CDCl3): δ = 68.4 (C5H4), 71.8 (C5H4), 73.8
CH2Cl2) 5.77 (br. s, 2 H, C5H4), 7.3–7.51 (m, 8 H, C6H5/C5H4N),
3
2
4
(d, JCP = 4 Hz, C5H4), 74.5 (d, JCP = 14 Hz, C5H4), 77.9 (Ci- 7.55–7.66 (m, 4 H, C6H5), 7.83 (ddd, 3J = 7.9, 7.8 Hz, J = 1.8 Hz,
C5H4), 82.4 (Ci-C5H4), 117.9 (3-C5H2N), 121.4 (C5H4N), 123.8 1 H, C5H4N), 7.95 (ddd, 3J = 7.9, 7.8 Hz, 4J = 2.0 Hz, 1 H, C5H4N-
3
3
4
5
(C5H4N), 128.4 (d, JCP = 7 Hz, m-C6H5), 128.8 (p-C6H5), 133.5
Pd), 8.37 (ddd, J = 7.8 Hz, J = 1 Hz, J = 0.8 Hz, 1 H, C5H4N-
2
4
3
4
(d, JCP = 20 Hz, o-C6H5), 138.9 (C5H4N), 139.2 (d, 1JCP = 10 Hz,
Pd), 8.61 (d, J = 1.3 Hz, 1 H, C5H2N), 8.63 (ddd, J = 7.8 Hz, J
Ci-C6H5), 149.1 (C5H4N), 150.1 (4-C5H2N), 156.5 (C5H4N), 158.1 = 1 Hz, 5J = 1 Hz, 1 H, C5H4N), 8.74 (ddd, 3J = 4.8 Hz, 4J =
(2-C5H2N) ppm. 31P{1H} NMR (CDCl3): δ = –18.3 ppm. ESI-MS:
m/z = [M + H]+ 602.24.
1.8 Hz, 5J = 0.8 Hz, 1 H, C5H4N), 9.04 (ddd, 3J = 3.7 Hz, 4J =
2 Hz, 5J = 1 Hz, 1 H, C5H4N-Pd), 10.46 (d, 4J = 1.3 Hz, 1 H,
C5H2N) ppm. 31P{1H} NMR (CDCl3): δ = 23.5 ppm. ESI-TOF-
MS: m/z = [M + H]+ 780.05.
Synthesis of 7: Compound 5 (200 mg, 0.33 mmol) dissolved in
dichloromethane (25 mL) was slowly dropped into a solution of
[PtCl2(SEt2)2] (6) (148.5 mg, 0.33 mmol) in dichloromethane
(20 mL). After 10 min of stirring, the solvent was evaporated to
5 mL and diethyl ether (30 mL) was added. Compound 7 crys-
tallized as orange needles at –30 °C. The crystals were washed with
diethyl ether (40 mL) and dried in an oil-pump vacuum; yield
172 mg (0.18 mmol, 55% based on 5). C41H38Cl2FeN3PPtS
(957.63): calcd. C 51.42, H 4.00, N 4.39; found C 51.50, H 3.82, N
Synthesis of 14: Compound 12 (100 mg, 0.13 mmol) was dissolved
in tetrahydrofuran (50 mL) and [NiCl2(dme)] (13) (28.3 mg,
0.13 mmol) was added in a single portion. After a few seconds, a
red solid started to precipitate. The solid was filtered off and
washed twice with diethyl ether. After drying the precipitate in an
oil-pump vacuum it was dissolved in dimethyl sulfoxide (10 mL).
Next, n-hexane (40 mL) was added, at which point 14 precipitated
in the form of red crystals that were washed twice with n-hexane
(30 mL); yield 112 mg (0.107 mmol, 81% based on 12).
C41H40Cl4FeN3NiO2PPdS2 (1064.65): calcd. C 46.25, H 3.79, N
3.96; found C 46.52, H 3.65, N 4.05. Mp. 215 °C (dec.). IR (KBr):
4.39; m.p. 189.3 °C (dec.). IR (KBr): ν = 1435 (m, νPC), 1468 (m,
˜
νPC), 1567 (s, νC=C), 1583 (s, νC=C), 1600 (s, νC=C), 2928 (w, νCH),
1
3
2966 (w, νCH) cm–1. H NMR (CDCl3): δ = 1.08 (t, J = 7.2 Hz 6
3
H, SCH2CH3), 2.50 (q, J = 7.2 Hz 4 H, SCH2CH3), 4.32 (pq, J =
ν = 1432 (m, νPC), 1472 (m, νPC), 1547 (s, νC=C), 1570 (s, νC=C),
˜
1.9 Hz, 2 H, C5H4), 4.35 (pt, J = 1.9 Hz, 2 H, C5H4), 4.70 (pt, J =
1602 (s, νC=C) cm–1.
1.8 Hz, 2 H, C5H4), 4.90 (pt, J = 1.8 Hz, 2 H, C5H4), 7.36 (ddd, 3J
4
Synthesis of 16a: Compound 16a was prepared as described for
the synthesis of 9. Instead of [PtCl2(SEt2)2] (6), [PdCl2(cod)] (11a)
(23 mg, 0.08 mmol) was used; yield 96 mg (0.07 mmol, 84% based
= 7.7, 1.2 Hz, J = 1.2 Hz, 2 H, C5H4N), 7.4–7.7 (m, 12 H, C6H5/
3
4
5-C5H4N), 7.88 (ddd, J = 7.7, 7.8 Hz, J = 1.8 Hz, 2 H, C5H4N),
8.46 (s, 2 H, C5H2N), 8.64 (ddd, 3J = 7.8 Hz, 4J = 1.2 Hz, 5J =
0.9 Hz, 2 H, C5H4N), 8.75 (ddd, 3J = 4.8 Hz, 4J = 1.8 Hz, 5J =
0.9 Hz, 2 H, C5H4N) ppm. 31P{1H} NMR (CDCl3): δ = 4.9 (JPPt
= 3690 Hz) ppm.
on 5); m.p. 140 °C (dec.). IR (KBr): ν = 1438 (m, νPC), 1467 (m),
˜
15767 (s, νC=C), 1584 (s, νC=C), 1602 (s, νC=C) cm–1. 1H NMR
(250 MHz, CDCl3): δ = 4.23 (m, 4 H, C5H4), 4.64 (m, 4 H, C5H4),
4.91 (m, 4 H, C5H4), 5.00 (m, 4 H, C5H4), 7.26–7.7 (m, 24 H, C6H5/
C5H4N), 7.86 (ddd, 3J = 7.9, 8.0 Hz, 4J = 1.8 Hz, 4 H, C5H4N),
8.47 (s, 4 H, C5H2N), 8.62 (ddd, 3J = 8 Hz, 4J = 1.0 Hz, 5J =
0.9 Hz, 4 H, C5H4N), 8.73 (ddd, 3J = 4.8 Hz, 4J = 1.8 Hz, 5J =
0.9 Hz, 4 H, C5H4N) ppm. 31P{1H} NMR (CDCl3): δ = 14.3 ppm.
ESI-MS: m/z = [M + H]+ 1379.24.
Synthesis of 9: Compound 5 (100 mg, 0.17 mmol) was dissolved in
dichloromethane (10 mL), and [PtCl2(SEt2)2] (6) (37 mg,
0.08 mmol) was added in a single portion. After 10 min of stirring,
the reaction solution was evaporated to 5 mL and n-hexane
(30 mL) was added. Molecule 9 crystallized as orange needles at
–30 °C. The crystals were washed with n-hexane (40 mL) and dried
in an oil-pump vacuum; yield 108 mg (0.073 mmol, 89% based on
5). C74H56Cl2Fe2N6P2Pt (0.5 C6H14) (1511.99): calcd. C 61.17, H
4.20, N 5.56; found C 61.07, H 4.43, N 5.18; m.p. 153 °C (dec.).
Synthesis of 16b: Compound 16b was prepared as described for
the synthesis of 9. Instead of [PtCl2(SEt2)2] (6), [PdBr2(cod)] (11b)
(30 mg, 0.08 mmol) was used; yield 103 mg (0.07 mmol, 84% based
on 5). C74H56Br2Fe2N6P2Pd (0.5 C6H14) (1509.07): calcd. C 61.16,
H 4.20, N 5.56; found C 61.10, H 4.39, N 5.35; m.p. 240 °C (dec.).
IR (KBr): ν = 1439 (m, νPC), 1468 (m, νPC), 1567 (s, νC=C), 1584
˜
(s, νC=C), 1602 (s, νC=C) cm–1. 1H NMR (CDCl3): δ = 4.22 (m, 4
H, C5H4), 4.61 (m, 4 H, C5H4), 4.91 (m, 4 H, C5H4), 5.08 (m, 4 H,
C5H4), 7.33 (ddd, 3J = 7.9, 4.8 Hz, 4J = 1.0 Hz, 4 H, C5H4N), 7.38–
7.7 (m, 24 H, C6H5/5-C5H4N), 7.86 (ddd, 3J = 7.9, 8.0 Hz, 4J =
IR (KBr): ν = 1467 (s, vPC), 1533 (m, vC=C) cm–1. 1H NMR
˜
(CDCl3): δ = 4.27 (pt, J = 1.8 Hz, 4 H, C5H4), 4.63 (pt, J = 1.8 Hz,
4 H, C5H4), 4.37 (pt, J = 1.8 Hz, 4 H, C5H4), 5.07 (pt, J = 1.8 Hz,
4 H, C5H4), 7.39–7.55 (m, 20 H, C6H5), 7.67–7.75 (m, 4 H,
C5H4N), 7.87 (dt, 3J = 7.5, 3.0 Hz, 4 H, C5H4N), 8.49 (s, 4 H,
3
1.8 Hz, 4 H, C5H4N), 8.47 (s, 4 H, C5H2N), 8.62 (ddd, J = 8 Hz,
4J = 1.0 Hz, 5J = 0.9 Hz, 4 H, C5H4N), 8.73 (ddd, 3J = 4.8 Hz,
4J = 1.8 Hz, 5J = 0.9 Hz, 4 H, C5H4N) ppm. 31P{1H} NMR
(CDCl3): δ = 10.0 (JPPt = 2629 Hz) ppm. ESI-MS: m/z =
[M + H]+ 1469.90.
3
3
C5H2N), 8.62 (d, J = 3.0 Hz, 4 H, C5H4N), 8.75 (d, J = 4.79 Hz,
4 H, C5H4N) ppm. 31P{1H} NMR (CDCl3): δ = 13.4 ppm. ESI-
MS: m/z = [M + K]+ 1507.03.
Synthesis of 17: Compound 17 was prepared as described for 9.
Instead of [PtCl2(SEt2)2] (6), [Mo(CO)4(nbd)] (15) (24 mg,
0.08 mmol) was used; yield 68 mg (0.05 mmol, 59% based on 5);
Synthesis of 12: Compound 5 (500 mg, 0.83 mmol) was dissolved
in dichloromethane (25 mL) and [PdCl2(cod)] (11a) (237 mg,
0.83 mmol) was added in a single portion at 25 °C. After 30 min of
being stirred in the dark, the solution was filtered through Celite
and the filtrate was evaporated to 5 mL. The product precipitated
by addition of diethyl ether (30 mL). The solid was filtered off,
m.p. 153 °C (dec.). IR (KBr): ν = 1438 (m, νPC), 1468 (m, νPC),
˜
1567 (s, νC=C), 1584 (s, νC=C), 1602 (s, νC=C), 1812 (s, νCO), 1867 (s,
νCO), 1900 (s, νCO), 2018 (s, νCO) cm–1. 1H NMR (CDCl3): δ = 4.07
(m, 4 H, C5H4), 4.12 (m, 4 H, C5H4), 4.21 (pt, J = 1.8 Hz, 4 H,
3624
www.eurjic.org
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 3615–3627

Heteromultimetallic Transition-Metal Complexes
C5H4), 4.63 (pt, J = 1.8 Hz, 4 H, C5H4), 7.17–7.24 (m, 20 H, C6H5),
C5H4), 5.29 (pt, J = 1.9 Hz, 4 H, C5H4), 5.43 (pt, J = 1.9 Hz, 4 H,
3
4
3
7.34 (ddd, J = 7.5, 4.7 Hz, J = 1 Hz, 4 H, C5H4N), 7.86 (ddd, J C5H4), 7.06–7.43 (m, 20 H, C6H5), 7.54 (m, 4 H, C5H4N), 8.63 (dt,
= 7.5, 7.9 Hz, 4J = 1.8 Hz, 4 H, C5H4N), 8.33 (s, 4 H, C5H2N),
3J = 7.9 Hz, J = 3.0 Hz, 4 H, C5H4N), 9.46 (d, J = 3.0 Hz, 4 H,
3
3
3
4
5
3
8.61 (ddd, J = 7.9 Hz, J = 1 Hz, J = 0.8 Hz, 4 H, C5H4N), 8.73
C5H4N), 9.53 (dd, J = 4.30 Hz, 4J = 1.8 Hz, 4 H, C5H4N), 9.67
(ddd, 3J = 4.7 Hz, 4J = 1.8 Hz, 5J = 0.8 Hz, 4 H, C5H4N) ppm. (s, 4 H, C5H2N) ppm. 31P{1H} NMR (CDCl3): δ = 27.4 ppm.
31P{1H} NMR (CDCl3): δ = 25.9 ppm. ESI-MS: m/z = [M + H]+
Synthesis of 26: Compound 3 (500 mg, 1.0 mmol) was dissolved in
dichloromethane (25 mL) and [PdCl2(cod)] (11a) (285 mg,
1411.20.
Synthesis of [{CuBr(5)}n] (19): Compound 5 (100 mg, 0.17 mmol) 1.0 mmol) was added in a single portion. After 20 min of stirring,
was dissolved in tetrahydrofuran (20 mL) and [CuBr] (18) (24 mg,
0.17 mmol) was added in a single portion. After two hours of stir-
ring at 25 °C, the [CuBr] had been consumed and the solution was
evaporated to 5 mL. Next n-hexane (30 mL) was added, at which
point a red-orange material precipitated. The solid was filtered off
and washed twice with n-hexane (30 mL portions) and was then
dried in an oil-pump vacuum; yield 120 mg (0.16 mmol, 95% based
the reaction mixture was evaporated to 5 mL and diethyl ether
(30 mL) was added. A purple solid precipitated and was filtered
off. The solid was washed twice with n-hexane (10 mL) and dried
in an oil-pump vacuum; yield 612 mg (0.9 mmol, 90% based on 3).
C30H24Cl2FeNOPPd·(0.5 CH2Cl2·H2O) (730.14): calcd. C 50.17, H
3.59, N 1.92; found C 50.14, H 3.58, N 1.88; m.p. 215 °C (dec.).
IR (KBr): ν = 1435 (m, νPC), 1481 (m, νPC), 1586 (s, νC=C), 1602
˜
1
on 5). C37H28BrCuFeN3P (744.91): calcd. C 59.66, H 3.79, N 5.64; (s, νC=C), 1667 (s, νCO) cm–1. H NMR (CDCl3): δ = 4.63 (m, 2 H,
found C 59.16, H 4.02, N 5.49; m.p. 180 °C (dec.). IR (KBr): ν =
C5H4), 4.74 (m, 2 H, C5H4), 4.83 (m, 2 H, C5H4), 5.30 (s, 1 H,
˜
1473 (s, vPC), 1535 (m, vC=C) cm–1. 1H NMR (CDCl3): δ = 4.21 (pt, CH2Cl2), 5.38 (m, 2 H, C5H4), 7.3–7.68 (m, 10 H, C6H5), 7.63 (m,
3
J = 1.8 Hz, 2 H, C5H4), 4.37 (pt, J = 1.8 Hz, 2 H, C5H4), 4.43 (pt, 1 H, C5H4N), 7.94 (m, 1 H, C5H4N), 7.95 (d, J = 15.8 Hz, 1 H,
3
J = 1.9 Hz, 2 H, C5H4), 4.36 (pt, J = 1.9 Hz, 2 H, C5H4), 7.13–
CO-CH=CH), 8.01 (d, J = 15.8 Hz, 1 H, CO-CH=CH), 8.84 (m,
3
7.32 (m, 12 H, C6H5/C5H4N), 7.83 (pt, J = 7.9 Hz, 2 H, C5H4N), 1 H, C5H4N), 9.0 (m, 1 H, C5H4N) ppm. 13C{1H} NMR (CDCl3):
3
8.53 (s, 2 H, C5H4N), 8.64 (d, J = 7.9 Hz, 2 H, C5H4N), 8.32 (d, δ = 68.1 (C5H4), 69.7 (C5H4), 70.8 (d, 3JC,P = 4 Hz, C5H4), 72.8 (d,
3J = 4.33 Hz, 2 H, C5H4N) ppm. 31P{1H} NMR (CDCl3): δ =
–14.9 ppm. ESI-MS: m/z = [M – Br]+ 664.13.
2JC,P = 14 Hz, C5H4), 76.3 (Ci-C5H4), 81.5 (Ci-C5H4), 122.3 (CO-
3
CH=CH), 125.5 (C5H4N), 127.2 (C5H4N), 128.9 (d, JC,P = 7 Hz,
2
C6H5), 131.1 (C6H5), 134.0 (d, JC,P = 20 Hz, C6H5), 139.1
1
Synthesis of 22: Compound 22 was prepared as described for the
synthesis of 19. In this respect [AuCl(tht)] (20) (55 mg, 0.17 mmol)
was used; yield 131 mg (0.16 mmol, 93% based on 5.).
C37H28AuClFeN3P(C6H14) (920.05): calcd. C 56.13, H 4.60, N
4.57; found C 55.92, H 4.43, N 4.35; m.p. 135 °C (dec.). IR (KBr):
(C5H4N), 144.8 (CO-CH=CH), 151.2 (d, JC,P = 10 Hz, Ci-C6H5),
151.4 (C5H4N), 156.9 (C5H4N), 188.2 (CO-CH=CH) ppm.
31P{1H} NMR (CDCl3): δ = 22.1 ppm. ESI-MS: m/z = [M + H]+
678.08.
ν = 1471 (s, vPC), 1531 (m, vC=C) cm–1. 1H NMR (CDCl3): δ = 4.36
Heck–Mizoroki Reaction of Iodobenzene (27) with tert-Butyl Acryl-
˜
(pt, J = 1.8 Hz, 2 H, C5H4), 4.42 (pt, J = 1.8 Hz, 2 H, C5H4), 4.59 ate (28): Iodobenzene (654 mg, 5.1 mmol), tert-butyl acrylate
(pt, J = 1.9 Hz, 2 H, C5H4), 4.91 (pt, J = 1.9 Hz, 2 H, C5H4), 7.30– (672 mg, 5.2 mmol), EtNiPr2 (672 mg, 5.2 mmol), and acetylferro-
3
3
7.47 (m, 10 H, C6H5), 7.55 (ddd, J = 7.40 Hz, J = 4.9 Hz, 2 H,
cene (114 mg, 0.5 mmol) were dissolved in a toluene/acetonitrile
mixture [20 mL, ratio 1:1 (v/v)] and loaded with 0.5 mol-% of the
C5H4N), 7.87 (dt, 3J = 7.40, 3.0 Hz, 2 H, C5H4N), 8.35 (s, 2 H,
C5H2N), 9.62 (d, 3J = 7.9 Hz, 2 H, C5H4N), 9.75 (dd, J = 4.9 Hz, respective catalyst (12, 26, or 30). [CuI] (2 equiv.) was added in a
3
4J = 1.3 Hz, 2 H, C5H4N) ppm. 31P{1H} NMR (CDCl3): δ =
27.2 ppm. ESI-MS: m/z = [M – Cl]+ 798.14.
single portion. The reaction suspension was stirred at 80 °C. Sam-
ples (1 mL) were taken every hour over a period of 9 h. An ad-
ditional sample was taken after 25 h. The samples were subjected
to chromatography on silica gel with diethyl ether as eluent. All
volatiles were evaporated from the samples under reduced pressure.
Synthesis of 23: Compound 23 was prepared as described for the
synthesis of 19. In this case, [{RhCl(cod)}2] (21) (42 mg,
0.09 mmol) was used; yield 137 mg, 0.16 mmol, 95% based on 5;
1
The conversions were determined by H NMR spectroscopy with
m.p. 194 °C (dec.). IR (KBr): ν = 1473 (s, vPC), 1535 (m, vC=C
)
˜
acetylferrocene as an internal standard.
cm–1. 1H NMR (CDCl3): δ = 2.40 (m, 8 H, cod), 4.28 (pt, J =
1.8 Hz, 2 H, C5H4), 4.69 (pt, J = 1.8 Hz, 2 H, C5H4), 4.74 (pt, J = Crystal data for 5, 9, 12, 14, 16b, 22, and 26 are presented in Table 3
1.9 Hz, 2 H, C5H4), 5.15 (pt, J = 1.9 Hz, 2 H, C5H4), 5.60 (s, 4 H, (5, 9, 12, 14) and Table 4 (16b, 22, 26). The data for 12, 14, and 26
cod), 7.25-7.31 (m, 10 H, C6H5), 7.54 (dpt, 3J = 8.00 Hz, 4J =
were collected with an Oxford Gemini S diffractometer, whereas
3
4
2.0 Hz, 2 H, C5H4N), 7.83 (ddd, J = 7.90 Hz, J = 1.9 Hz, 2 H, the data for 5, 9, 16b, and 22 were collected with a Bruker Smart
3
C5H4N), 8.55 (s, 2 H, C5H2N), 8.66 (d, J = 3.0 Hz, 2 H, C5H4N), 1K CCD diffractometer with graphite-monochromatized Mo-Kα (λ
8.73 (dd, 3J = 4.30 Hz, 4J = 1.8 Hz, 2 H, C5H4N) ppm. 31P{1H}
= 0.71073 Å) for 5, 9, 12, 16b, 22, and 26 or Cu-Kα radiation (λ =
NMR (CDCl3): δ = 22.1 (d, JRh,P = 151 Hz) ppm. ESI-MS: m/z = 1.54184 Å) for molecule 14 using oil-coated shock-cooled crystals.
[M – cod]+ 739.07, [M]+ 847.21.
The structures were solved by direct methods using SHELXS-97[41]
or SIR-92[42] and refined by full-matrix least-squares procedures
on F2 using SHELXL-97.[43] All non-hydrogen atoms were refined
anisotropically and a riding model was employed in the refinement
of the hydrogen atom positions.
Synthesis of 25: Compound 22 (300 mg, 0.36 mmol) was dissolved
in ethanol (50 mL) and [RuCl2(dmso)4] (24) (87 mg, 0.18 mmol)
was added in a single portion. The reaction mixture was heated to
reflux for 12 h. After removing all volatiles in an oil-pump vacuum,
the remaining solid was washed five times with n-hexane (10 mL
portions) and dried in vacuo; yield 315 mg (0.17 mmol, 95% based
CCDC-775761 (for 5), -775762 (for 9), -775763 (for 12), -775764
(for 14), -775765 (for 16b), -775766 (for 22), and -775767 (for 26)
on 22). C74H56Au2Cl4Fe2N6P2Ru (1839.73): calcd. C 48.31, H 3.07, contain the supplementary crystallographic data for this paper.
N 4.57; found C 48.66, H 3.21, N 4.38%; m.p. 245 °C (dec.). IR These data can be obtained free of charge from The Cambridge
(KBr): ν = 1431 (m, νPC), 1609 (s, νC=C) cm–1. H NMR (CDCl3): Crystallographic Data Centre via http://www.ccdc.cam.ac.uk/
1
˜
δ = 4.21 (pt, J = 1.8 Hz, 4 H, C5H4), 4.43 (pt, J = 1.8 Hz, 4 H,
data_request/cif.
Eur. J. Inorg. Chem. 2010, 3615–3627
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3625

H. Lang et al.
FULL PAPER
Table 3. Crystal and intensity collection data for 5, 9, 12, and 14.
5
9
12
14
Formula weight
Chemical formula
Crystal system
Space group
a [Å]
b [Å]
c [Å]
601.44
1468.88
850.85
1234.46
C37H28FeN3P
tetragonalic
P42/n
27.667(10)
27.667(10)
7.751(5)
90
C74H56Cl2Fe2N6P2Pt
monoclinic
P21/c
13.113(4)
17.246(4)
14.707(5)
90
C41H36Cl2FeN3OPPd
monoclinic
P21/c
14.5568(7)
20.0956(6)
14.6087(6)
90
C43H44Cl8FeN3NiOPPdS2
monoclinic
P21/c
15.6337(7)
12.9595(3)
25.0932(2)
90
α [°]
β [°]
90
90
5933(5)
1.347
2496
110.954(10)
90
3106.0(15)
1.571
116.427(5)
90
3826.9(3)
1.477
95.5010(10)
90
5060.59(14)
1.620
γ [°]
V [Å3]
ρcalcd. [gcm–3]
F(000)
1472
1728
2488
Crystal size [mm]
Z
Index ranges
0.3ϫ0.03ϫ0.02
8
–23 Յ h Յ 23
0 Յ k Յ 33
0 Յ l Յ 9
0.594
0.2ϫ0.2ϫ0.1
2
–16 Յ h Յ 15
0 Յ k Յ 21
0 Յ l Յ 18
2.895
0.6ϫ0.5ϫ0.3
4
–17 Յ h Յ 17
–24 Յ k Յ 24
–18 Յ l Յ 18
1.066
0.3ϫ0.1ϫ0.1
4
–17 Յ h Յ 17
–14 Յ k Յ 13
–28 Յ l Յ 28
10.807
µ [mm–1]
T [K]
θ [°]
Total reflections
Unique reflections
Rint [%][a]
298
1.47 to 25.35
25251
6524
7.04
298
1.66 to 26.38
34416
6598
4.45
100
2.97 to 26.00
34308
7352
2.55
100
3.20 to 60.69
35666
7547
3.83
Data/restraints/parameters 5441/0/380
6359/0/394
0.0279, 0.0521
0.0427, 0.0589
1.148
7352/122/497
0.0663, 0.1762
0.0778, 0.1831
1.193
7547/66/615
0.0670, 0.1931
0.0962, 0.2201
1.157
[a]
R1,[a] wR2[a] [IՆσ(I)]
R1,[a] wR2 (all data)
Godness-of-fit on F2[b]
∆ρ [eÅ–3]
0.0664, 0.1719
0.1393, 0.2299
1.040
0.405, –0.434
0.859, –0.811
3.103, –1.414
2.446, –1.902
[a] R = [Σ(||Fo| – |Fc||)/Σ|Fo|]/Σ|Fo|; wR2 = {Σ[w(F2o – Fc2)2]/Σ(wF4o)} . w = 1/[σ2(F2o) + (0.0835P)2 + 4.1728P], P = (F2o + 2F2c)/3. [b] S =
½
½
[Σw(F2o – F2c)2]/(n – p) (n = number of reflections, p = parameters used).
Table 4. Crystal and intensity collection data for 16b, 22, and 26.
16b
22
26
Formula weight
Chemical formula
Crystal system
Space group
a [Å]
b [Å]
c [Å]
1469.11
833.85
689.43
C74H56Br2Fe2N6P2Pd
monoclinic
P21/c
12.879(3)
17.208(5)
14.573(4)
90
110.185(4)
14.573(4)
3031.5(14)
1.609
C37H28AuClFeN3P
triclinic
C30H25.20Cl2FeNO1.60PPd
triclinic
¯
¯
P1
P1
9.9416(14)
12.6191(18)
13.860(2)
112.005(2)
101.591(2)
91.244(2)
1570.2(4)
1.764
10.1183(9)
11.1906(8)
13.5351(10)
90.340(6)
99.045(7)
113.162(7)
1387.64(19)
1.650
α [°]
β [°]
γ [°]
V [Å3]
ρcalcd. [gcm–3]
F(000)
1480
816
692
Crystal size [mm]
Z
Index ranges
0.3ϫ0.1ϫ0.1
2
–16 Յ h Յ 15
0 Յ k Յ 21
0 Յ l Յ 188
2.188
0.3ϫ0.2ϫ0.2
2
–12 Յ h Յ 12
–15 Յ k Յ 15
–17 Յ l Յ 17
5.296
0.4ϫ0.3ϫ0.2
2
–12 Յ h Յ 12
–13 Յ k Յ 13
–16 Յ l Յ 16
1.448
µ [mm–1]
T [K]
θ [°]
Total reflections
Unique reflections
Rint [%](a)
298
1.68 to 26.46
21852
6505
7.72
298
1.63 to 26.41
17961
6400
2.81
100
2.91 to 26.05
13913
5483
1.11
Data/restraints/parameters
6171/0/394
0.0826, 0.2113
0.1081, 0.2393
1.054
6400/0/397
0.0217, 0.0519
0.0282, 0.0544
1.020
5483/0/351
0.0165, 0.0408
0.0196, 0.0429
1.063
[a]
R1,[a] wR2[a] [IՆσ(I)]
R1,[a] wR2 (all data)
Godness-of-fit on F2[b]
∆ρ [eÅ–3]
2.771, –3.241
0.543, –0.597
0.442, –0.309
½
[a] R = [Σ(||Fo| – |Fc||)/Σ|Fo|]/Σ|Fo|; wR2 = {Σ[w(F2o – Fc2)2]/Σ(wF4o)} . w = 1/[σ2(F2o) + (0.0835P)2 + 4.1728P], P = (F2o + 2F2c)/3. [b] S =
½
[Σw(F2o – F2c)2]/(n – p) (n = number of reflections, p = parameters used).
3626
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Eur. J. Inorg. Chem. 2010, 3615–3627

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Acknowledgments
We gratefully acknowledge the generous financial support by the
Deutsche Forschungsgemeinschaft (DFG) and the Fonds der
Chemischen Industrie.
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Received: April 1, 2010
Published Online: July 7, 2010
Eur. J. Inorg. Chem. 2010, 3615–3627
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
3627