Palladium(II) Complexes of Homologated Ferrocene Phosphanylether and Thioether Ligands

Article abstract of DOI:10.1002/ejic.201701057

The reaction of [1′-(diphenylphosphanyl)ferrocenyl]methanol/borane (1:1) with in situ formed N,N,N′,N′,S-pentamethylisothiouronium iodide and sodium hydride, followed by removal of the borane protecting group with 1,4-diazabicyclo[2.2.2]octane, afforded 1-(diphenylphosphanyl)-1′-[(methylthio)methyl]ferrocene (3) as a new, homologated, hybrid phosphanylferrocene ligand. Compound 3 and the congeneric phosphanyl ether 2 were studied as ligands in Pd^II complexes. When treated with [PdCl₂(MeCN)₂] in a Pd/ligand ratio of 1:1, compound 3 furnished a mixture of two Pd complexes, including the ligand-bridged dimer [{μ(P,S)-3}PdCl₂]₂ (6), which was structurally characterized. Upon increasing the amount of ligand to 2 equiv., a similar reaction produced the bis(phosphane) complex [PdCl₂(3-κP)₂] (7). Bridge-cleavage reactions of the dipalladium complex [(L^NC)Pd(μ-Cl)]₂ {L^NC = 2-[(dimethylamino-κN)methyl]phenyl-κC¹} with donors 3 and 2 proceeded in a uniform manner to give the corresponding phosphane complexes [(L^NC)PdCl(3-κP)] (8) and [(L^NC)PdCl(2-κP)] (9). Conversely, removing the Pd-bonded chloride from these complexes with AgClO₄ generated the bis(chelate) complex [(L^NC)Pd(3-κ²P,S)] (10) and the aqua complex [(L^NC)Pd(H₂O)(2-κP)] (11), respectively, both of which could be converted back into their precursors by adding Bu₄NCl. The structures of the complexes 6–11 (some in solvated form) were determined by single-crystal X-ray diffraction analysis.

Full text of DOI:10.1002/ejic.201701057

DOI: 10.1002/ejic.201701057
Full Paper
Metallocenes
Palladium(II) Complexes of Homologated Ferrocene
Phosphanylether and Thioether Ligands
[a]
[b]
[a]
[a]
Martin Zábranský, Aleš Machara, Ivana Císařová, and Petr Štěpnička*
Abstract: The reaction of [1′-(diphenylphosphanyl)ferro- phane) complex [PdCl (3-κP) ] (7). Bridge-cleavage reactions of
2
2
NC
NC
cenyl]methanol/borane (1:1) with in situ formed N,N,N′,N′,S- the dipalladium complex [(L )Pd(μ-Cl)]2 {L = 2-[(dimethyl-
pentamethylisothiouronium iodide and sodium hydride, fol- amino-κN)methyl]phenyl-κC } with donors 3 and 2 proceeded
1
lowed by removal of the borane protecting group with 1,4- in a uniform manner to give the corresponding phosphane
NC
NC
diazabicyclo[2.2.2]octane, afforded 1-(diphenylphosphanyl)-1′- complexes [(L )PdCl(3-κP)] (8) and [(L )PdCl(2-κP)] (9). Con-
(methylthio)methyl]ferrocene (3) as a new, homologated, versely, removing the Pd-bonded chloride from these com-
hybrid phosphanylferrocene ligand. Compound 3 and the con- plexes with AgClO4 generated the bis(chelate) complex
[
II
NC
2
NC
generic phosphanyl ether 2 were studied as ligands in Pd com- [(L )Pd(3-κ P,S)] (10) and the aqua complex [(L )Pd(H O)-
2
plexes. When treated with [PdCl (MeCN) ] in a Pd/ligand ratio (2-κP)] (11), respectively, both of which could be converted
2
2
of 1:1, compound 3 furnished a mixture of two Pd complexes, back into their precursors by adding Bu NCl. The structures of
4
including the ligand-bridged dimer [{μ(P,S)-3}PdCl ] (6), which the complexes 6–11 (some in solvated form) were determined
2
2
was structurally characterized. Upon increasing the amount of by single-crystal X-ray diffraction analysis.
ligand to 2 equiv., a similar reaction produced the bis(phos-
Introduction
First reported in 1965,[1] 1,1′-bis(diphenylphosphanyl)ferrocene
(
dppf) has been extensively used as a versatile donor for coordi-
nation chemistry and as an efficient supporting ligand for a
plethora of transition-metal-catalyzed organic transforma-
[
2]
tions. The practical success of dppf has naturally led to the
search for analogues with different substituents on the phos-
[
3]
phorus atoms or with one of the two phosphane moieties
replaced by another functional group.[ Recently, we used an
alternative approach to modify the archetypal dppf structure
by inserting a spacer group between one of the functional sub-
stituents and the ferrocene unit, thereby preparing the semi-
4]
[
5]
homologous dppf congener 1 (see Scheme 1). More recently,
[
6]
we described the analogous O,P donor 2, related to the
[
7]
known phosphanyl ether A, and several other compounds of
this type.
[
8]
Scheme 1. Homologation route to new phosphanylferrocene ligands.
A recent serendipitous discovery led us to pursue the synthe-
been studied as ligands in coordination compounds and cata-
sis of phosphanyl thioether 3, which also has a directly func-
[
10]
[
9]
lysts.
In this contribution, we describe the synthesis and
tionalized ferrocene counterpart, namely compound
B
structural characterization of the new ferrocene-based phos-
(
Scheme 1), and is structurally related to planar-chiral phos-
II
phanyl thioether ligand 3 and its Pd complexes and compare
phanylferrocene donors with CH SR groups at the 2-position of
2
these with the complexes resulting from the analogous phos-
phanyl ether 2.
the ferrocene moiety. These phosphanylferrocene donors have
[
[
a] Department of Inorganic Chemistry, Faculty of Science, Charles University,
Hlavova 2030, 12840 Prague, Czech Republic
E-mail: petr.stepnicka@natur.cuni.cz
http://www.natur.cuni.cz
b] Department of Organic Chemistry, Faculty of Science, Charles University,
Hlavova 2030, 12840 Prague, Czech Republic
Results and Discussion
Synthesis of Ligand 3
The borane adduct of phosphanylferrocene thioether 3, com-
pound 4, was initially detected in varying minor amounts
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejic.201701057.
Eur. J. Inorg. Chem. 2017, 4850–4860
4850
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
among the products of the reactions of adduct [1′-(diphenyl- of 4 (63 %) was obtained when the reaction solvent was
[
6]
phosphanyl)ferrocenyl]methanol/borane (1:1; 5) with KOH changed to anhydrous tetrahydrofuran. In a subsequent step,
and 4-toluenesulfonyl (tosyl) chloride in dry dimethyl sulfoxide, the borane protecting group was removed by treatment with
[
15]
which were originally aimed at the synthesis of the tosyl deriva- 1,4-diazabicyclo[2.2.2]octane (dabco) in warm toluene, which
tive Ph PfcCH OTs·BH (fc = ferrocene-1,1′-diyl). The rather un- provided the target phosphanyl thioether 3 in virtually quanti-
2
2
3
expected formation of Ph PfcCH SMe·BH (4) suggested that tative yield after flash chromatography.
2
2
3
the methylthiolate anion derives from the solvent during the
reaction and also indicated intermediate formation of the men-
tioned tosylate. However, this tosylate could not be isolated.
A plausible mechanism for the formation of the methyl-
thiolate is formulated in Scheme 2 and involves a Pummerer
[
11]
rearrangement
activated with tosyl chloride
as its key step. Initially, dimethyl sulfoxide is
[
12]
and the species formed under-
goes elimination upon the action of a base (KOH) to afford
–
a thionium cation. Addition of OH to this cation provides an
intermediate hemithioacetal, which eventually degrades to
formaldehyde and the methylthiolate anion under basic condi-
tions.
Scheme 3. Synthesis of 1-(diphenylphosphanyl)-1′-[(methylthio)methyl]ferro-
cene (3). dabco = 1,4-diazabicyclo[2.2.2]octane.
Compounds 3 and 4 were characterized by NMR spectro-
scopy, electrospray ionization (ESI) mass spectrometry, and ele-
1
13
mental analysis. Their H and C NMR spectra show the charac-
teristic signals of the 1,1′-disubstituted ferrocene unit and its
diphenylphosphanyl substituent, which also gives rise to a char-
Scheme 2. Plausible mechanism for the conversion of dimethyl sulfoxide into
the MeS– anion upon the action of TsCl and KOH.
3
1
acteristic broad feature at δ = 16.4 ppm in the P NMR spec-
P
31
trum of 4 and a sharp singlet at δ = –16.3 ppm in the P NMR
P
spectrum of the free phosphane 3. The signals of the thioether
pendant in 3 are observed at δ = 1.97/δ = 15.47 ppm (SMe)
Because adduct 4 could be easily converted into phosphanyl
thioether Ph PfcCH SMe (3), which expands the family of do-
nors that are homologues of the known functional phosphanyl-
ferrocene ligands (see the Introduction section), we decided to
design a rational preparative route to this compound. Unfortu-
nately, repeated attempts to improve the yield of 4, either by
H
C
2
2
and δ = 3.18/δ = 33.25 ppm (SCH ).
H
C
2
II
Synthesis of Pd Complexes with Ligands 2 and 3
optimizing the original reaction conditions or by altering the To compare the coordination properties of the phosphanyl thio-
synthetic approach, were not successful. For instance, the reac- ether 3 with those of the previously studied ether analogue
[
6]
II
tions of the thiolate MeSNa with in situ generated sulfonates 2, we initially attempted to prepare simple Pd chloride com-
resulting from alcohol 5 and tosyl chloride/DMAP or, similarly, plexes by treating 3 with [PdCl (MeCN) ] at various Pd/ligand
[
2
2
from 5 and methanesulfonyl chloride/DMAP; DMAP = 4-(di- ratios (Scheme 4). The reaction performed first with equimolar
methylamino)pyridine] or acetates (generated in situ from 5 amounts of the starting materials and subsequent crystalliza-
and Ac O with and without added NaHCO , or by treatment of tion afforded a rusty-brown crystalline solid, which was struc-
2
3
5
with trifluoroacetic anhydride) failed to provide 4 according turally characterized as the ligand-bridged dipalladium(II) com-
to TLC analyses. Similarly, only traces of 4 were found in the plex [{μ(P,S)-3}PdCl ] (6) rather than the originally anticipated
2
2
2
crude reaction mixture resulting from the successive addition monopalladium chelate [PdCl (3-κ P,S)]. However, the analysis
2
[
13]
of the Vilsmeier–Haack–Arnold reagent ([ClCH=NMe ]Cl) and of the reaction mixture and even of the crystallized material
2
revealed the presence of two species characterized by 31P NMR
MeSNa to a solution of 5 in DMF.
1
Eventually, compound 4 was synthesized by using the resonances at δ = 24.5 and 29.9 ppm. Unfortunately, the H
P
method developed by Kajigaeshi and co-workers[ based on NMR spectra of both the reaction mixture and the crystallized
the reactions between the in situ formed S-alkylisothiouronium material provided little structural information about the species
salts and alcoholates. Thus, the reaction of [(Me N) SMe]I with formed because of extensive signal broadening. Nonetheless,
14]
2
2
5
4
/NaH (Scheme 3) afforded the protected phosphanyl thioether the splitting of the easily recognizable resonances due to the
in yields of 28 and 45 % when performed in N,N-dimethyl- SMe groups, attributed to interactions with phosphorus, and
formamide and acetonitrile, respectively. Finally, the best yield their shift to lower field suggest that these moieties are coordi-
Eur. J. Inorg. Chem. 2017, 4850–4860
www.eurjic.org
4851
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
nated in both cases [SMe: δ = 2.45 ppm (d, J = 4.6 Hz) and ether 2. The 31P NMR resonance of complex 7 can be observed
H
PH
δH = 2.66 ppm (d, JPH = 0.8 Hz)]. These facts and the NMR at δ = 15.7 ppm, similarly to the corresponding complex fea-
P
[
6]
spectroscopic
data
previously
reported
for
trans- turing ligand 2 (δ = 15.4 ppm ). The formulation of 7 was
led further confirmed by its C NMR spectrum, which shows the
us to tentatively formulate the products as the structurally char- signals of the P-coupled ferrocene and PPh carbon atoms as
P
2
[16]
13
[
PdCl (Ph PfcCONHCH CH SMe-κ S,P)] (δ = 23.6 ppm)
2
2
2
2
P
3
1
2
acterized dimer [{μ(P,S)-3}PdCl ] (6) and the plausible, but non- characteristic apparent triplets due to virtual coupling in the
2
2
2
13 31
31 12 [17]
isolated, chelate [PdCl (3-κ P,S)]. However, the two species ob- AA′X spin system C- P-Pd- P- C.
Finally, the presence of
2
served in solution could also be diastereoisomers of the same an uncoordinated thioether pendant was suggested by the
1
13
complex differing in the configuration of the two stereogenic practically negligible coordination shifts of its H and C NMR
sulfur atoms (i.e., meso form RS/SR and racemate RR/SS). Despite resonances [SMe: Δδ (SMe) = 0.04 ppm, Δδ (SMe) = 0.17 ppm].
H
C
this ambiguity, it is clear that compound 3 behaves differently
Structure determination indicated that compound 6 crystalli-
from the phosphanyl ether ligand 2, which afforded the chlor- zes in the form of stoichiometric solvate 6·3CHCl . Its structure
3
ide-bridged dimer [Pd(μ-Cl)Cl(2-κP)]2 (δP = 31.7 ppm) as the is shown in Figure 1, and the relevant structural parameters are
[
6]
sole product under similar conditions.
given in Table 1. Notably, the molecular structure of the com-
plex lacks any imposed symmetry and has the (S) configuration
at both sulfur atoms [the (R,R) enantiomeric molecules are also
present in the centrosymmetric crystal].
II
Scheme 4. Synthesis of Pd chloride complexes with ligand 3.
3
Figure 1. PLATON plot of the complex molecule in the structure of 6·3CHCl .
Upon increasing the amount of ligand 3 to 2 mol-equiv., the
complexation reaction with [PdCl (MeCN) ] took the expected
The coordination spheres around the structurally independ-
2
2
course, producing the bis(phosphane) complex 7 as the sole ent, but chemically equivalent, palladium atoms are similar in
product (Scheme 4), in analogy to the behavior of phosphanyl terms of both interligand distances and angles and are essen-
Table 1. Selected geometric parameters for complex 6·3CHCl
3
.[a]
Pd1–Cl1
Pd1–Cl2
Pd1–P1
Pd1–S2
Cl1–Pd1–P1
Cl1–Pd1–S2
Cl2–Pd1–P1
Cl2–Pd1–S2
Fe1–Cg1
2.3099(5)
2.2874(5)
2.2852(5)
2.3871(5)
94.30(2)
81.97(2)
89.70(2)
94.11(2)
1.6465(9)
1.6441(9)
3.0(1)
Pd2–Cl3
Pd2–Cl4
Pd2–P2
Pd2–S1
Cl3–Pd2–P2
Cl3–Pd2–S1
Cl4–Pd2–P2
Cl4–Pd2–S1
Fe2–Cg3
Fe2–Cg4
∠Cp3,Cp4
2.3057(5)
2.2892(5)
2.2708(5)
2.3754(5)
95.06(2)
82.55(2)
88.15(2)
94.19(2)
1.6492(9)
1.6522(9)
1.3(1)
Fe1–Cg2
∠Cp1,Cp2
τ
1
67.2(1)
τ
2
70.2(1)
P1–C1
C–P1–C
C11–S1
S1–C24
C6–C11–S1
C11–S1–C24
1.789(2)
102.45(9)–105.69(8)
1.821(2)
1.799(2)
109.3(1)
99.0(1)
P2–C51
C–P2–C
C61–S2
S2–C74
C56–C61–S2
C61–S2–C74
1.792(2)
103.89(8)–104.62(8)
1.824(2)
1.802(2)
108.9(1)
100.34(9)
[
a] Distances are given in Å and angles in °. The parameters are defined follows: Cp1 = C(1–5), Cp2 = C(6–10), Cp3 = C(51–55), Cp4 = C(56–60), Cgn (n =
1
–4) are the corresponding ring centroids. τ
1
= C1–Cg1–Cg2–C6, τ
2
= C51–Cg3–Cg3–C56.
Eur. J. Inorg. Chem. 2017, 4850–4860 www.eurjic.org
4852
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
II
tially planar, as indicated by the sums of the cis interligand an- open toward the Pd , and, in particular, for a displacement of
gles, which only marginally deviate from 360° (Table 1). Accord- the phosphorus atom from the plane of the parent cyclopenta-
[
18]
ing to a search in the Cambridge Structural Database,
com- dienyl ring C(1–5) and outward from the ferrocene core by
plex 6 represents a rare example of a structurally characterized 0.2387(6) Å. The 1,1′-disubstituted ferrocene moiety has an in-
II
Pd complex with a PSCl donor set having trans-P,S geometry termediate conformation characterized by the τ angle of
2
rather than the cis-P,S configuration exhibited by the majority 83.9(2)° (see Table 2). The CH SMe substituent is located on the
2
of similar, mostly chelate, complexes.[ In fact, the only related side of the phosphanylferrocenyl moiety and directed away
19]
example reported to date is the aforementioned complex from the palladium center.
2
[
PdCl (Ph PfcCONHCH CH SMe-κ S,P)], which shows similar Pd–
2
2
2
2
Table 2. Selected geometric parameters for 7.[a]
[
16]
donor bond lengths (within ±0.025 Å).
Cl–Pd–P[
b]
86.47(2)
93.53(2)
5.0(1)
Pd–Cl
Pd–P
Fe–Cg1
Fe–Cg2
P–C6
2.2897(7)
2.3400(6)
1.645(1)
1.647(1)
1.799(3)
1.822(2)
1.798(3)
The PdCl SP planes in the macrocyclic structure of 6·3CHCl
2
3
Cl′–Pd–P[
b]
are nearly parallel [dihedral angle: 4.07(2)°], but mutually offset
Pd1···Pd2 5.8544(5) Å]. The ferrocene moieties assume synclinal
eclipsed conformations (compare the τ angles in Table 1 with
∠Cp1,Cp2
[
τ
–83.9(2)
[c]
C–P–C
102.6(1)–103.9(1)
114.1(2)
99.5(1)
[
2b]
the ideal value of 72°, see ref. ). The cyclopentadienyl rings in
the ferrocene unit comprising atom Fe1 are mutually tilted by
approximately 3°, and the phosphane substituent is displaced
from its bonding plane toward atom Pd1 by as much as
C11–S
S–C24
C6–C11–S
C11–S–C24
[a] Distances are given in Å and angles in °. Definitions: Cp1 and Cp2 are the
cyclopentadienyl rings C(1–5) and C(6–10), respectively. Cg1 and Cg2 denote
their centroids. ∠Cp1,Cp2 is the dihedral angle of the least-squares cyclo-
pentadienyl planes (tilt angle), and τ is the torsion angle C1–Cg1–Cg2–Cg6.
b] The adjacent interligand angles sum up to 180° because of the imposed
symmetry. [c] Range of the C–P–C angles.
0
.2510(4) Å, whereas the coordination of the other ferrocene
moiety (Fe2) does not cause a similar distortion [tilt angle: 1°,
distance of P2 from the C(51–55) plane: 0.0818(4) Å]. Both
[
(
methylthio)methyl substituents are directed below the ferro-
The reaction of 3 with di-μ-chlorobis{2-[(dimethylamino-
cene units (away from the iron atom) and coordinated in posi-
tions trans with respect to the phosphane moieties.
The molecular structure of compound 7 is shown in Figure 2,
and the representative geometric data are given in Table 2. Ap-
parently, the molecule of complex 7 adopts a geometry typical
1
NC
κN)methyl]phenyl-κC }dipalladium(II), [(L )Pd(μ-Cl)] , in a li-
2
gand/Pd ratio of 1:1 proceeded as expected through the cleav-
age of the chloride bridges to generate the phosphane com-
plex 8 (Scheme 5). The phosphanyl ether ligand 2 reacted simi-
1
13
[
8d,9b,20]
larly to furnish the analogous compound 9. The H and
C
of trans-[PdCl (Ph PfcX-κP) ] complexes.
The coordina-
2
2
2
NMR spectra of complexes 8 and 9 display signals due to the
auxiliary ortho-metalated ligand C H CH NMe and the P-coor-
tion environment of the central palladium atom in 7 is ideally
planar due to the imposed crystallographic symmetry (the Pd
atom resides on an inversion center). However, the pairs of adja-
cent interligand angles differ from 90° by ±3.5°, most likely for
steric reasons. Steric congestion may also account for a minor
tilting [5.0(1)°] of the ferrocene cyclopentadienyl rings, which
6
4
2
3
2
4
dinated ferrocenylphosphane, with the J and J coupling
PC
PC
constants of the phosphorus-coupled resonances of the
CH NMe moiety suggesting a trans-P,N arrangement in both
2
2
[
20d,20f,20j,20l,21]
cases.
The P-monodentate coordination of the
phosphanylferrocene donors could also be inferred from a shift
3
1
of the P NMR signals to a lower field (δ = 33.0 ppm for both
P
compounds; coordination shift: Δ ≈ 49 ppm) and from the fact
P
that the signals of the terminal EMe (E = S and O) groups re-
mained nearly unaffected by the coordination [cf. Δδ (EMe) =
H
0
.05 ppm for 8 and 9, Δδ (EMe) = 0.01 ppm for 8, and 0.09 ppm
C
1
for 9]. Notably, the H NMR signals of the SCH groups are con-
2
siderably more affected [Δδ (ECH ) = 0.32 and 0.25 ppm,
H
2
Δδ (ECH ) = 0.12 and 0.04 ppm for 8 for 9, respectively], being
C
2
influenced by the coordinated phosphanylferrocene moiety. Fi-
nally, the positive-ion ESI mass spectra of 8 and 9 show peaks
attributable to cations resulting from the loss of the chloride
+
ligand, [M – Cl] , at m/z = 670 and 654, respectively.
The structures of the solvated complexes 8·AcOEt and
9·1/2C6H14 were determined by single-crystal X-ray diffraction
analysis and are shown in Figure 3. Analysis of the geometric
data collected in Table 3 shows that the coordination geome-
tries of these complexes are very similar. In both cases, the coor-
II
dination environment of Pd is significantly distorted due to
varying Pd–donor bond lengths, different steric demands of
the Pd-bonded ligands, and the presence of a small and rigid
metallacycle. However, the geometric parameters are not signif-
icantly different from those reported for similar complexes
Figure 2. PLATON plot of the molecular structure of complex 7. For simplicity,
only one orientation of the disordered phenyl ring C(18–23) is shown. The
atoms labelled with primes are generated by crystallographic inversion.
NC
[20d,20f,20j,20l,21]
[(L )PdCl(Ph PfcX-κP)].
2
Eur. J. Inorg. Chem. 2017, 4850–4860
www.eurjic.org
4853
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
II
II
Scheme 5. Synthesis and mutual interconversion of Pd –2 and Pd –3 com-
1
NC
plexes with an auxiliary [2-(dimethylamino-κN)methyl]phenyl-κC (L ) li-
gand.
The distortion of the coordination planes can be illustrated
by the dihedral angles subtended by the half-planes {Pd,Cl,P}
and {Pd,N,C25}, being 14.1(1) and 16.96(8)° in 8·AcOEt and
Figure 3. PLATON plots of the molecular structures of 8·AcOEt (top) and
9
·1/2C H , respectively (please note: the sums of the inter-
6
9·1/2C H14 (bottom).
6
14
6 2 4 2
Table 3. Selected distances and angles for 8·AcOEt, 9·1/2C H14, 10·3/2C H Cl
, and 11.[a]
Parameter
X/E
8·AcOEt
Cl/S
9·1/2C
Cl/O1
6
H
14
10·3/2C
2
H
4
Cl
2
11
O1W/O1
S/S[
c]
Pd–X
Pd–P
Pd–N
Pd–C25
P–Pd–X
P–Pd–C25
N–Pd–X
N–Pd–C25
Fe1–Cg1
Fe1–Cg2
2.3972(7)
2.2531(7)
2.152(2)
2.010(2)
92.37(2)
96.24(7)
90.14(6)
82.50(9)
1.645(1)
1.645(1)
3.6(2)
2.3944(6)
2.2505(6)
2.158(2)
2.001(2)
92.96(2)
96.25(6)
90.77(5)
82.17(8)
1.646(1)
1.643(1)
3.1(1)
2.4103(7)
2.2552(6)
2.168(2)
2.035(2)
96.93(2)
95.34(5)
85.32(5)
82.30(7)
1.642(1)
1.654(1)
5.2(1)
2.169(1)
2.2546(6)
2.145(2)
1.977(2)
97.00(4)
93.20(6)
89.14(6)
81.17(7)
1.6439(8)
1.6452(9)
3.8(1)
∠Cp1,Cp2
τ
154.7(2)
1.808(2)
98.2(1)–105.0(1)
1.829(3)
1.799(4)
113.8(2)
97.0(2)
–147.4(2)
1.804(2)
98.66(9)–104.62(9)
1.435(3)
1.421(4)
112.4(2)
2.1(2)
1.795(2)
100.07(8)–111.02(9)
1.811(2)
1.804(2)
–144.1(1)
1.799(2)
102.64(8)–103.25(8)
1.426(2)
1.417(3)
113.3(2)
112.5(2)
P–C1
[
b]
C–P–C
C11–E
E–C24
C6–C11–E
C11–E–C24
114.0(1)
99.16(9)
112.4(2)
[
a] Distances are given in Å and angles in °. Definitions: Cp1 and Cp2 are the cyclopentadienyl rings C(1–5) and C(6–10), respectively, Cg1 and Cg2 denote
their respective centroids, ∠Cp1,Cp2 is the dihedral angle of the least-squares cyclopentadienyl planes (tilt angle), and τ is the torsion angle C1–Cg1–Cg2–
C6. [b] The range of C–P–C angles. [c] X is identical to E in this particular case.
Eur. J. Inorg. Chem. 2017, 4850–4860
www.eurjic.org
4854
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
ligand angles are 361.3 and 362.2°). The five-membered
The structure of solvate 10·3/2C H Cl is shown in Figure 4,
2
4
2
palladacycles have similar geometries and envelope conforma- and the pertinent geometric data are given in Table 3. Compari-
tions, with their nitrogen atoms located in endo positions [cf. son of the structural parameters determined for the parent
the ring-puckering parameters: ꢀ = 41.8(4) and 220.6(3)° for complex 8·AcOEt and the cationic bis(chelate) complex 10 re-
8
·AcOEt and 9·1/2C H , respectively; the ideal envelope re- vealed a slight but statistically significant elongation of the Pd–
6 14
[
22]
quires ꢀ to be an integer multiple of 36°, see ref. ]. The ferro- N and Pd–C25 bonds in the latter complex (naturally, the Pd–S
[
24]
cene moieties in both structures assume open conformations bond is also longer than the Pd–Cl bond in 8 ). Furthermore,
with τ angles of around 150°, and their uncoordinated CH EMe the formation of a second chelate ring in 10 results in an open-
2
(
E = O, S) substituents are diverted away from the center of the ing of the P–Pd–S/Cl angle and a closure of the adjacent N–Pd–
ferrocene unit and the palladium(II) atom.
S/Cl angle by approximately 5°, whereas the remaining interli-
gand angles remain practically unchanged. The dihedral angle
of the {Pd,P,S} and {Pd,N,C25} planes associated with the chelate
rings in 10 is 11.94(7)°, which is somewhat smaller than in the
parent chloride complex.
Preparation of complexes in which compounds 2 and 3
would possibly coordinate as P,E-chelate donors was attempted
by removing the Pd-bonded chloride ligands from 8 and 9
(Scheme 5). Upon treatment with silver(I) perchlorate, com-
pound 8 was, indeed, smoothly converted into the cationic
bis(chelate) complex 10. In contrast, a similar reaction with
complex 9 was complicated by a partial decomposition, which
resulted in the formation of green materials (most likely due to
oxidation of the ferrocene ligand), and the product isolated
after several crystallizations was characterized as the cationic
aqua complex 11 featuring ligand 2 as a P-monodentate donor.
After careful optimization, compound 11 was obtained in 30 %
yield by using reagent-grade chloroform as the solvent and an
excess of the silver salt (please refer to the Exp. Sect. for further
details). Notably, both cationic complexes could be converted
back into the neutral chloride complexes (i.e., their precursors)
by adding tetrabutylammonium chloride, whereas repeated at-
tempts to replace the coordinated water molecule in 11 with
another ligand failed. For instance, adding cyclohexyl isocyan-
ide, cyclohexyl cyanide, trimethylphosphane, or triphenylphos-
phane to 11 led, according to NMR analysis, to the formation of
complicated mixtures that typically deposited intractable black
materials during crystallization (a brown amorphous solid
formed in the case of cyclohexyl cyanide). The reactions of 11
with ammonia or sulfane also led to brown amorphous solids,
whereas the crystalline material isolated after adding benzyl
Figure 4. PLATON plot of the molecular structure of 10·3/2C
chlorate anion and the solvent have been omitted for clarity.
2 4 2
H Cl . The per-
methyl sulfide to 11 in CDCl and crystallization from ethyl acet-
ate/hexane was identified as the starting Pd complex.
3
Because of a simultaneous coordination of both attached do-
nor moieties, the ferrocene unit in 10 adopts a synclinal
II
Although structure determination provided definitive proof eclipsed conformation (τ ≈ 2°) and is slightly tilted (by approxi-
of the formulation, the NMR spectra had already suggested that mately 5°). Additionally, the formation of the P,S-chelate ring
1
complexes 10 and 11 have different structures. The H NMR results in a displacement of the pivotal atom C11 by 0.208(2) Å
spectrum of 10 indicates coordination of the thioether moiety from the plane of its parent cyclopentadienyl ring and twisting
[
Δδ (SMe) = 0.46 ppm, Δδ (SCH ) = 0.08 ppm], whereas the of the CH SMe pendant arm, as shown by the angles between
H
H
2
2
spectrum of complex 11 suggests that the ether chain remains the plane of the cyclopentadienyl ring C(6–10) and the S–C11
free [Δδ (OMe) = 0.05 ppm, Δδ (OCH ) = 0.10 ppm]. A similar bond, which are 17.1(1)° in 10·3/2C H Cl and 65.1(1)° in
H
H
2
2
4
2
conclusion could be drawn from the 13C NMR spectroscopic 8·AcOEt.
data [10: Δδ (SMe) = 4.68 ppm; 11: Δδ (OMe) = 0.29 ppm], and
the P NMR spectra indicate coordination of the phosphane ture of complex 11 (Figure 5, parameters in Table 3) reduces
The presence of a coordinated water molecule in the struc-
C
C
3
1
moieties (δ = 33.3 ppm for 10 and δ = 30.4 ppm for 11). The the mutual tilting of the coordination half-planes {Pd,P,O1W}
P
P
IR spectra of the cationic complexes corroborate the presence and {Pd,N,C25} to 9.75(8)°. However, the range of the interligand
NC
II
of the perchlorate counter ions through strong composite angles in 11 is the largest in the entire set of (L )Pd com-
bands at approximately 1090 cm–1 [ν (ClO )] and, in the case plexes reported in this paper. The Pd–N and Pd–C bonds in 11
[23]
3
4
of 11, also indicated the presence of a water molecule (broad are shorter than those in its precursor 9 and the other cationic
–
1
band at 3185 cm ). Conversely, the ESI mass spectra only show complex 10, whereas the length of the Pd–OH bond is similar
2
NC
+
signals of the cations [(L )Pd(L)] (L = 2 and 3), which are to the Pd–OH distance determined for an analogous cationic
isobaric to the ions [M – Cl] resulting from the fragmentation complex with a PPh -substituted calix[4]arene ligand [2.171(2)
2
+
2
[
25,26]
of 8 and 9.
or 2.186(2) Å depending on solvation].
The 1,1′-disubsti-
Eur. J. Inorg. Chem. 2017, 4850–4860
www.eurjic.org
4855 © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
tuted ferrocene unit in 11 has an open conformation, similar to sion (O1W–H1W···O2 and O1W–H2W···O4). These interactions
that in compound 9, and its methoxymethyl substituent ex- result in the formation of closed centrosymmetric aggregates
NC
tends away from the ferrocene unit and the phosphane moiety. [(L )Pd(H O)(2-κP)] (ClO ) (Figure 6).
2
2
4 2
In the crystal, the coordinated water molecule forms O–H···O
hydrogen bonds with a pair of proximal perchlorate anions,
which are involved in similar interactions with the water mol-
ecule in a complex molecule related by crystallographic inver-
Conclusions
The preparation of phosphanylferrocene thioether 3 described
in this paper highlights the synthetic potential of the easily
[
6,27]
accessible adduct 5
as a stable, P-protected precursor of
new unsymmetric phosphanylferrocene donors. Furthermore,
the study of the coordination of the congeneric ligands 2 and
II
3
to Pd with various supporting ligands revealed a remarkable
difference in the coordination properties of these donors and
the impact of the introduced methylene spacer. Obviously, the
introduction of the methylene linking group considerably in-
creases the flexibility of the 1′-functionalized phosphanylferro-
cene ligands, which may, in turn, decrease their tendency to
form stable chelate complexes. For instance, compound A
(
Scheme 1) reacts with a PdCl precursor (in a Pd/P ratio of 1:1)
2
2
[7]
to afford the stable chelate complex [PdCl (A-κ O,P)], whereas
2
ligand 2 only provides the chloride-bridged dimer [Pd(μ-Cl)Cl-
[
6]
(
2-κP)]2. This trend is confirmed by the formation of the aqua
complex 11 rather than a bis(chelate) cation when removing
the Pd-bonded chloride from 9. The replacement of the hard
donor oxygen atom with the much softer sulfur atom appar-
II
ently circumvents this problem (in the case of soft Pd ), albeit
Figure 5. PLATON plot of the cation in the structure of 11.
only partly. As exemplified by the formation of a mixture of
products from the reaction of [PdCl (MeCN) ] and 3 (in a ratio
2
2
of 1:1), ligand 3 does not coordinate as a P,S-chelating donor
preferentially, although it may form stable chelate rings, for ex-
ample, in compound 10, under appropriate conditions.
Experimental Section
Materials and Methods: All manipulations were carried out under
[6]
argon using standard Schlenk techniques. Compounds 2, 5, and
NC
[28]
[
(L )Pd(μ-Cl)]2
All other chemicals were purchased from commercial suppliers
Sigma–Aldrich and Alfa-Aesar) and used without any additional pu-
were prepared according to literature methods.
(
rification. Toluene was dried with sodium metal and distilled under
argon. Unless stated otherwise, chloroform was dried with anhy-
drous potassium carbonate and distilled. Tetrahydrofuran was dried
by using a PureSolv MD5 solvent purification system (Innovative
Technology, USA). Solvents for crystallizations and chromatography
were used as received (analytical grade, Lach-Ner, Czech Republic).
NMR spectra were recorded at 25 °C with a Varian UNITY Inova 400
1
spectrometer operating at 399.95, 100.58, and 161.90 MHz for H,
1
3
31
C, and P, respectively. Chemical shifts (δ in ppm) are given rela-
1
13
tive to internal SiMe ( H and C) and external 85 % aqueous
H PO ( P), all set to 0 ppm. In addition to the standard notation
4
3
1
3
4
of the multiplicity of the NMR signals, vt and vq are used to denote
virtual triplets and quartets,which arise from the CH - and phos-
2
phane-substituted cyclopentadienyl rings, respectively. IR spectra
were measured with an FTIR Nicolet Magna 760 spectrometer in
the range 400–4000 cm . Electrospray ionization (ESI) mass spectra
were recorded with a Bruker Esquire 3000 spectrometer for samples
dissolved in HPLC-grade methanol. Elemental analyses were per-
formed by using a PE 2400 Series II CHNS/O Elemental Analyzer
Figure 6. Hydrogen-bonding interactions in the structure of complex 11. For
clarity, only the pivotal atoms of the phosphorus-bonded phenyl groups are
shown. The hydrogen bonds are indicated by dashed lines. Hydrogen-bond
parameters: O1W···O2 2.859(2) Å (angle at H1W 160°), O1W···O4 2.802(2) Å
–
1
(angle at H2W 168°). The atoms labeled with primes are generated by inver-
sion operation.
Eur. J. Inorg. Chem. 2017, 4850–4860
www.eurjic.org
4856
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
(
Perkin–Elmer). The amount of residual solvent (if present) was cor- (s) ppm. C H Cl Fe P Pd S (1215.3): calcd. C 47.44, H 3.82; found
48
46
4
2
2
2 2
roborated by NMR analysis.
C 47.31, H 3.84.
Synthesis of [PdCl (3-κP) ] (7): [PdCl (MeCN) ] (6.7 mg, 25 μmol)
Synthesis of 1-(Diphenylphosphanyl)-1′-[(methylthio)methyl]-
ferrocene–Borane (1:1) (4): Methyl iodide (71 mg, 0.50 mmol) was
added to a solution of N,N,N′,N′-tetramethylthiourea (100 mg,
2
2
2
2
and ligand 3 (21.5 mg, 50 μmol) were mixed in chloroform (1 mL),
and the resulting burgundy-red solution was stirred at room tem-
perature for 90 min. Then the reaction mixture was filtered through
a PTFE syringe filter (pore size 0.45 μm), and the filtrate was diluted
with chloroform (1 mL) and then layered with tert-butyl methyl
ether and hexane (5 mL each). Crystallization by liquid-phase diffu-
sion furnished complex 7 as deep-red crystals, which were filtered
0
.25 mmol) in dry THF (3 mL), and the resulting mixture was stirred
under argon for 1 h, which resulted in a white precipitate
{
presumably [(Me N) SMe]I}. The borane adduct 5 (100 mg,
2 2
0
.25 mmol) and sodium hydride (30 mg of a 60 % suspension in
mineral oil, 0.75 mmol) were added successively to the reaction
mixture, continuing stirring for another 1 h. Then the reaction was
terminated by adding water, and the resulting mixture was ex-
tracted with ethyl acetate (3 × 10 mL). The combined organic layers
off, washed with hexane and pentane, and, finally, dried under vac-
1
uum. Yield: 21.6 mg (83 %). H NMR (CDCl ): δ = 2.01 (s, 3 H, SMe),
3
3
.42 (s, 2 H, SCH ), 4.37 (m, 4 H, fc), 4.51 (vt, J′ = 1.8 Hz, 2 H, fc),
2
4
.53 (br. vt, J′ = 1.8 Hz, 2 H, fc), 7.35–7.45 (m, 6 H, PPh ), 7.61–7.67
were washed with brine, dried with anhydrous MgSO , and the sol-
2
4
13
1
(m, 4 H, PPh ) ppm. C{ H} NMR (CDCl ): δ = 15.64 (s, SCH ), 33.44
vents evaporated. Subsequent purification by column chromatogra-
2 3 3
(
s, SCH ), 70.36 (s, CH of fc), 71.11 (s, CH in fc), 71.67 (app. t, J′ =
phy (silica gel, toluene) afforded pure compound 4 as an orange
2
1
27 Hz, C-P of fc), 72.68 (app. t, J′ = 4 Hz, CH of fc), 76.05 (app. t, J′ =
Hz, CH of fc), 86.60 (s, C-CH of fc), 127.72 (app. t, J′ = 5 Hz, CH
solid. Yield: 70 mg (63 %). H NMR (CDCl ): δ = 0.75–1.75 (br. m, 3
3
5
H, BH ), 1.96 (s, 3 H, SMe), 3.11 (s, 2 H, SCH ), 4.04 (vt, J′ = 1.8 Hz,
2
3
2
of PPh ), 130.25 (s, CH
of PPh ), 131.34 (app. t, J′ = 25 Hz, C
2
4
7
3
7
1
H, fc), 4.16 (vt, J′ = 1.9 Hz, 2 H, fc), 4.36 (vq, J′ = 1.9 Hz, 2 H, fc),
2
para
2 ipso
31
1
of PPh ), 134.16 (app. t, J′ = 6 Hz, CH of PPh ) ppm. P{ H} NMR
.50 (d of vt, J′ = 1.1, 1.8 Hz, 2 H, fc), 7.38–7.50 (m, 6 H, PPh ), 7.55–
2
2
2
1
3
1
(CDCl ): δ = 15.7 (s) ppm. IR (Nujol): ν = 3056 (w), 2725 (w), 2672
.63 (m, 4 H, PPh ) ppm. C{ H} NMR (CDCl ): δ = 15.49 (s, SMe),
3.88 (s, SCH ), 69.09 (d, J = 6 Hz, C-P of fc), 69.80 (s, CH of fc),
3
˜
max
2
3
1
(w), 1668 (br., vw), 1327 (vw), 1305 (m), 1244 (m), 1223 (vw), 1194
w), 1185 (w), 1168 (m), 1131 (w), 1101 (m), 1093 (m), 1072 (w),
061 (w), 1042 (m), 1034 (m), 1024 (m), 999 (w), 978 (w), 964 (vw),
2
PC
(
1
0.45 (s, CH of fc), 72.58 (d, JPC = 7 Hz, CH of fc), 73.56 (d, JPC
=
0 Hz, CH of fc), 86.59 (s, C-CH of fc), 128.43 (d, J = 10 Hz, CH of
2
PC
4
1
927 (w), 917 (vw), 890 (w), 873 (w), 848 (w), 836 (w), 831 (w), 815
(s), 745 (s), 708 (m), 693 (vs), 624 (w), 544 (m), 517 (m), 506 (s), 496
PPh ), 130.90 (d, J = 2 Hz, CHpara of PPh ), 131.29 (d, J = 59 Hz,
Cipso of PPh ), 132.63 (d, J = 10 Hz, CH of PPh ) ppm. P{ H} NMR
2
PC
2
PC
1
3
1
2
PC
2
–
1
+
(s), 469 (m), 458 (w), 442 (w) cm . MS (ESI+): m/z = 571 [M – Cl –
(CDCl ): δ = 16.4 (br. d) ppm. MS (ESI+): m/z = 467 [M + H] , 430
3
+
+
+
3] , 1001 [M – Cl] . C H Cl Fe P PdS ·0.25CHCl (1067.8): calcd. C
[M – BH ] . C H BFeP (444.2): calcd. C 64.90, H 5.90; found C 64.97,
48 46 2 2 2 2 3
3
24 26
5
4.27, H 4.37; found C 54.21, H 4.33.
Synthesis of [(LNC)PdCl(3-κP)] (8): The dimer [(LNC)Pd(μ-Cl)]2
13.8 mg, 25 μmol) and compound 3 (21.5 mg, 50 μmol) were dis-
H 5.82.
Synthesis of 1-(Diphenylphosphanyl)-1′-[(methylthio)methyl]-
ferrocene (3): Adduct 4 (222 mg, 0.50 mmol) and 1,4-diazabi-
cyclo[2.2.2]octane (dabco; 60 mg, 0.53 mmol) were dissolved in an-
hydrous toluene (10 mL) in a reaction flask with a stirring bar. The
reaction vessel was flushed with argon, sealed with a rubber sep-
tum, and transferred into an oil bath maintained at 60 °C. The reac-
tion mixture was stirred at this temperature for 18 h and then
cooled to room temperature and concentrated under reduced pres-
sure, leaving a brown residue, which was purified by column chro-
matography (silica gel, diethyl ether/hexane, 1:1). A single orange
band was collected and concentrated to afford compound 3 as a
(
solved in chloroform (1 mL), and the resulting solution was stirred
at room temperature for 90 min and then concentrated under vac-
uum. The residue was dissolved in ethyl acetate (1 mL) and the
solution filtered through a PTFE syringe filter (pore size 0.45 μm).
The filtrate was diluted with ethyl acetate (1 mL) and layered with
hexane (10 mL). Crystallization by liquid-phase diffusion afforded
complex 8 in the form of orange crystals, which were filtered off,
washed with hexane and pentane, and dried under vacuum. Yield:
2
6.1 mg (74 %). 1H NMR (CDCl ): δ = 2.02 (s, 3 H, SMe), 2.84 (d,
3
4
4
JPH = 2.8 Hz, 6 H, NMe ), 3.50 (s, 2 H, SCH ), 4.12 (br. d, JPH
=
1
2
2
dark-amber oil that gradually solidified. Yield: 212 mg (quant.). H
2
.4 Hz, 2 H, NCH ), 4.32 (vtd, J′ = 1.9, 1.0 Hz, 2 H, fc), 4.36 (vq, J′ =
2
NMR (CDCl ): δ = 1.97 (s, 3 H, SMe), 3.18 (s, 2 H, SCH ), 4.02 (vt, J′ =
3
2
2.0 Hz, 2 H, fc), 4.43 (vt, J′ = 1.9 Hz, 2 H, fc), 4.54 (vt, J′ = 1.9 Hz, 2
1
.9 Hz, 2 H, fc), 4.06 (vq, J′ = 1.8 Hz, 2 H, fc), 4.10 (vt, J′ = 1.9 Hz, 2
H, fc), 6.29 (ddd, J = 7.8, 6.4, 1.3 Hz, 1 H, C H ), 6.41 (br. td, J = 7.6,
6
4
H, fc), 4.35 (vt, J′ = 1.8 Hz, 2 H, fc), 7.28–7.40 (m, 10 H, PPh ) ppm.
2
1
.5 Hz, 1 H, C H ), 6.84 (td, J = 7.3, 1.2 Hz, 1 H, C H ), 7.02 (dd, J =
13
1
6 4 6 4
C{ H} NMR (CDCl ): δ = 15.47 (s, SMe), 33.25 (s, SCH ), 69.19 (s, CH
3
2
7
.4, 1.6 Hz, 1 H, C H ), 7.30–7.35 (m, 4 H, PPh ), 7.38–7.44 (m, 2 H,
6
4
2
of fc), 69.77 (s, CH of fc), 71.55 (d, J = 4 Hz, CH of fc), 73.62 (d,
PC
13
1
PPh ), 7.53–7.59 (m, 4 H, PPh ) ppm. C{ H} NMR (CDCl ): δ = 15.48
1
2
2
3
JPC = 15 Hz, CH of fc), 76.12 (d, JPC = 6 Hz, C-P of fc), 85.65 (s, C-
3
(s, SMe), 33.37 (s, SCH ), 50.15 (d, J = 3 Hz, NMe ), 70.45 (s, CH
2 PC 2
CH of fc), 128.14 (d, J = 7 Hz, CHmeta of PPh ), 128.51 (s, CH
2
PC
2
para
of fc), 71.19 (s, CH of fc), 72.59 (d, J = 7 Hz, CH of fc), 73.53 (d,
1
PC
of PPh ), 133.50 (d, J = 19 Hz, CH
of PPh ), 139.06 (d, J
=
2
PC
ortho
2
PC
1
3
JPC = 60 Hz, C-P of fc), 73.62 (d, J = 3 Hz, NCH ), 76.02 (d, J =
3
1
1
PC
2
PC
9
Hz, Cipso of PPh ) ppm. P{ H} NMR (CDCl ): δ = –16.3 (s) ppm.
2
3
1
0 Hz, CH of fc), 86.42 (s, C-CH of fc), 122.49 (s, CH of C H ), 123.72
+
2 6 4
MS (ESI+): m/z = 431 [M + H] . C H FeP (430.3): calcd. C 66.99, H
2
4 23
(
1
s, CH of C H ), 124.82 (d, J = 5 Hz, CH of C H ), 127.84 (d, J
=
6
4
PC
6
4
PC
5
.39; found C 67.00, H 5.37.
4
1 Hz, CH of PPh ), 130.46 (d, J = 2 Hz, CHpara of PPh ), 131.77
2 PC 2
1
Reaction of [PdCl (MeCN) ] with 1 equiv. of 3 and Isolation of
(d, J = 49 Hz, Cipso of PPh ), 134.36 (d, J = 12 Hz, CH of PPh2),
2
2
PC
2
PC
Complex 6: Ligand 3 (22.0 mg, 0.05 mmol) and [PdCl (MeCN) ]
138.46 (d, JPC = 11 Hz, CH of C H ), 148.24 (d, J = 2 Hz, Cipso of
2
2
6 4 PC
31
1
(13.1 mg, 0.05 mmol) were dissolved in chloroform (2 mL). The mix- C H ), 152.13 (s, C
of C H ) ppm. P{ H} NMR (CDCl ): δ = 33.0
6
4
ipso 6 4 3
ture was stirred at room temperature for 30 min and then layered (s) ppm. IR (Nujol): ν˜max = 3042 (w), 2724 (w), 2669 (w), 1733 (vs),
successively with tert-butyl methyl ether (5 mL) and hexane (5 mL).
Crystallization by liquid-phase diffusion over several days afforded
a crystalline solid, which was isolated by suction, washed with pent-
ane, and dried under vacuum. Yield: 30.0 mg (quant). 1H NMR
1579 (m), 1407 (vw), 1396 (w), 1304 (m), 1270 (vw), 1248 (m), 1200
(vw), 1182 (w), 1166 (m), 1100 (m), 1072 (vw), 1060 (w), 1042 (m),
1026 (m), 993 (m), 969 (w), 930 (w), 890 (vw), 865 (w), 854 (m), 846
(m), 817 (m), 752 (m), 741 (s), 708 (m), 697 (s), 654 (vw), 627 (m),
617 (vw), 605 (vw), 546 (m), 526 (m), 510 (vs), 478 (m), 462 (m),
(
CDCl ), selected resonances: δ = 2.45 (d, J = 4.6 Hz, SMe), 2.66
3
P
H
3
1
1
–1
+
(
d, JPH = 0.8 Hz, SMe) ppm. P{ H} NMR (CDCl ): δ = 24.5 (s), 29.9
447 (w), 433 (w), 424 (w) cm . MS (ESI+): m/z = 670 [M – Cl] .
3
Eur. J. Inorg. Chem. 2017, 4850–4860
www.eurjic.org
4857 © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
C H ClFeNPPdS (706.4): calcd. C 56.11, H 4.99, N 1.98; found C
Cipso of PPh ), 133.33 (d, J = 12 Hz, CH of PPh ), 137.72 (d, J
=
33
35
2
PC
2
PC
5
5.76, H 5.03, N 1.84.
Synthesis of [(LNC)PdCl(2-κP)] (9): Compounds [(LNC)Pd(μ-Cl)]2
13.8 mg, 25 μmol) and 2 (20.7 mg, 50 μmol) were dissolved in
13 Hz, CH of C H ), 146.81 (d, J = 2 Hz, Cipso of C H ), 152.07 (br.
6 4 PC 6 4
31
1
s, Cipso of C
H
4
) ppm. P{ H} NMR (CDCl ): δ = 33.3 (s) ppm. IR
3
6
(
1
Nujol): ν˜
= 3049 (w), 2721 (w), 2671 (w), 1579 (m), 1406 (w),
301 (w), 1276 (w), 1235 (vw), 1200 (w), 1184 (w), 1165 (m), 1093
max
(
chloroform (1 mL) in an argon-flushed reaction flask, and the result-
ing solution was stirred for 90 min and then concentrated under
vacuum. The resulting orange residue was dissolved in ethyl acetate
(
9
br. vs), 1057 (m), 1043 (w), 1033 (m), 1023 (m), 995 (m), 977 (m),
34 (w), 923 (w), 888 (w), 865 (w), 848 (m), 823 (m), 756 (m), 746
s), 702 (s), 623 (m), 546 (w), 530 (s), 516 (m), 499 (m), 486 (m), 452
(
(
(
1.5 mL) and the solution filtered through a PTFE syringe filter (pore
size 0.45 μm) into a test tube. The filtrate was layered with hexane
10 mL) and set aside for crystallization. The orange crystals, which
–
1
NC
+
m), 436 (w) cm . MS (ESI+): m/z = 670 [(L )Pd(3)] . C H -
3
3 35
ClFeNO PPdS (770.4): calcd. C 51.45, H 4.58, N 1.82; found C 51.20,
4
(
H 4.57, N 1.65.
formed over several days, were filtered off, washed with hexane and
pentane, and dried under vacuum. Yield: 30.2 mg (86 %). H NMR
1
Synthesis of [(LNC)Pd(2-κP)(H O)]ClO (11): Complex 11 was pre-
4
2
4
(CDCl ): δ = 2.85 (d, J = 2.8 Hz, 6 H, NMe ), 3.29 (s, 3 H, OMe),
3
PH
2
pared in unpurified reagent-grade chloroform. The dimer
4
4
.12 (br. d, J = 2.3 Hz, 2 H, NCH ), 4.21 (s, 2 H, OCH ), 4.31 (vtd,
PH 2 2
NC
[
(L )Pd(μ-Cl)]2 (55.2 mg, 0.10 mmol) and compound 2 (82.8 mg,
J = 1.9, 1.0 Hz, 2 H, fc), 4.37 (vq, J′ = 2.0 Hz, 2 H, fc), 4.48 (vt, J′ =
0.20 mmol) were dissolved in chloroform (3 mL), and the solution
1
1
.9 Hz, 2 H, fc), 4.60 (vt, J′ = 1.9 Hz, 2 H, fc), 6.29 (ddd, J = 7.8, 6.5,
.2 Hz, 1 H, C H ), 6.41 (br. td, J = 7.5, 1.6 Hz, 1 H, C H ), 6.84 (td,
was stirred for 90 min. The thus formed solution of complex 9 was
added to solid silver(I) perchlorate (49.8 mg, 0.24 mmol; 2 mL of
chloroform was used to wash the reaction flask) and the resulting
mixture was stirred for another 30 min (a greyish precipitate sepa-
rated immediately after the addition). The reaction mixture was fil-
tered through a PTFE syringe filter (pore size 0.45 μm; an additional
6
4
6 4
J = 7.3, 1.1 Hz, 1 H, C H ), 7.02 (dd, J = 7.4, 1.6 Hz, 1 H, C H ), 7.30–
7
PPh ) ppm. C{ H} NMR (CDCl ): δ = 50.12 (d, J = 3 Hz, NMe2),
5
6
4
6 4
.35 (m, 4 H, PPh ), 7.37–7.43 (m, 2 H, PPh ), 7.55–7.57 (m, 4 H,
2
2
13
1
3
2
3
PC
7.77 (s, OMe), 70.35 (s, OCH ), 71.06 (s, CH of fc), 71.83 (s, CH of
2
3
fc), 72.12 (d, J = 7 Hz, CH of fc), 73.62 (d, J = 3 Hz, NCH ), 73.64
PC
PC
2
2
mL of chloroform was used to rinse the reaction flask), and the
1
(d, J = 60 Hz, C-P of fc), 75.80 (d, JPC = 10 Hz, CH of fc), 84.50 (s,
PC
filtrate was concentrated under vacuum, leaving a greenish residue,
which was taken up with ethyl acetate (5 + 2 mL) by sonication in
an ultrasound bath. The extract was filtered through the syringe
filter and carefully layered with a mixture of ethyl acetate/hexane
C-CH of fc), 122.49 (s, CH of C H ), 123.71 (s, CH of C H ), 124.84
2
6
4
6 4
(d, JPC = 6 Hz, CH of C H ), 127.85 (d, J = 11 Hz, CH of PPh ),
6 4 PC 2
30.48 (d, 4J = 2 Hz, CHpara of PPh ), 131.69 (d, J = 50 Hz, Cipso
1
1
PC 2 PC
of PPh ), 134.37 (d, J = 12 Hz, CH of PPh ), 138.46 (d, J = 11 Hz,
CH of C H ), 148.24 (d, J = 2 Hz, Cipso of C H ), 152.22 (s, C
2
PC
2
PC
(1:1; 3 mL) and then with pure hexane (10 mL). Crystallization by
of
=
6
4
PC
6
4
ipso
liquid-phase diffusion provided green-brown crystals of the prod-
uct, which were recrystallized once again as described above. The
resulting yellow crystals of 11 were filtered off, washed with hexane
31
1
C H ) ppm. P{ H} NMR (CDCl ): δ = 33.0 (s) ppm. IR (Nujol): ν˜
6
4
3
max
3
067 (w), 3044 (w), 1734 (m), 1580 (w), 1305 (w), 1248 (m), 1236
(w), 1201 (vw), 1184 (w), 1167 (m), 1097 (m), 1083 (s), 1058 (vw),
1
and pentane, and dried under vacuum. Yield: 40.4 mg (30 %). H
1
8
041 (m), 1028 (m), 993 (w), 970 (w), 931 (vw), 896 (w), 854 (m),
46 (m), 819 (m), 755 (m), 748 (m), 739 (s), 709 (m), 697 (m), 628
4
NMR (CDCl ): δ = 2.86 (d, J = 2.6 Hz, 6 H, NMe ), 3.29 (s, 3 H,
3
PH
2
OMe), 3.98 (br. s, 2 H, fc), 4.06 (br. s, 2 H, OCH ), 4.09 (br. d, J =
–
1
2
PH
(w), 545 (m), 527 (m), 516 (s), 479 (m), 435 (vw) cm . MS (ESI+):
1
.7 Hz, 2 H, NCH ), 4.36 (br. s, 2 H, fc), 4.42 (br. s, 2 H, fc), 4.49 (br.
+
2
m/z = 654 [M – Cl] . C H ClFeNOPPd·0.1C H (698.9): calcd. C
5
3
3
35
6 14
s, 2 H, fc), 6.34 (br. t, J = 7.0 Hz, 1 H, C H ), 6.48 (br. t, J = 7.4 Hz, 1
6
4
7.74, H 5.25, N 2.00; found C 57.75, H 5.52, N 1.84.
H, C H ), 6.92 (br. t, J = 7.2 Hz, 1 H, C H ), 7.03 (br. dd, J = 7.4,
6
4
6 4
NC
2
Synthesis of [(L )Pd(3-κ P,S)]ClO4 (10): The dimeric precursor
1.5 Hz, 1 H, C H ), 7.39–7.45 (m, 4 H, PPh ), 7.47–7.53 (m, 2 H,
6
4
2
NC
[(L )Pd(μ-Cl)] (13.8 mg, 25 μmol) and ligand 3 (21.5 mg, 50 μmol)
2
PPh ), 7.59–7.66 (m, 4 H, PPh ) ppm; please note: the signal due to
2
2
were allowed to react in chloroform (1 mL) for 90 min, as described
above. Then, the reaction solution was poured onto solid AgClO4
13
1
coordinated water could not be identified. C{ H} NMR (CDCl ): δ =
3
3
49.75 (d, J
= 2 Hz, NMe ), 57.97 (s, OMe), 70.06 (s, OCH ), 70.72
PC
2
2
(10.4 mg, 50 μmol), whereupon a greyish precipitate (AgCl) sepa-
(
s, CH of fc), 71.29 (s, CH of fc), 71.99 (s, NCH ), 72.60 (d, J = 7 Hz,
2 PC
rated. After stirring for another 30 min, the reaction mixture was
filtered through a PTFE syringe filter (pore size 0.45 μm), and the
filtrate was concentrated. The residue was dissolved in 1,2-dichloro-
ethane (2 mL), and the solution was layered with 1,2-dichloro-
ethane/tert-butyl methyl ether (1:1; 2 mL) and pure tert-butyl
methyl ether (11 mL). The mixture was set aside for crystallization
by liquid-phase diffusion. The yellow crystals that formed after sev-
CH of fc), 74.80 (d, JPC = 10 Hz, CH of fc), 85.05 (s, C-CH2 of fc),
23.53 (s, CH of C H ), 125.08 (s, CH of C H ), 125.50 (d, J = 6 Hz,
1
6
4
6
4
PC
1
CH of C H ), 128.39 (d, J = 11 Hz, CH of PPh ), 129.34 (d, J
=
=
6
4
PC
2
PC
5
0 Hz, Cipso of PPh ), 131.26 (s, CH
of PPh ), 134.36 (d, J
2
para
2
PC
1
2 Hz, CH of PPh ), 137.83 (d, J = 12 Hz, CH of C H ), 141.71 (br.
2
PC
6 4
s, Cipso of C H ), 147.78 (d, J = 2 Hz, Cipso of C H ) ppm; the signal
6
4
PC
6 4
of C-P of fc was not found, presumably due to overlapping signals.
eral days were filtered off, washed with tert-butyl methyl ether, and
31
1
P{ H} NMR (CDCl ): δ = 30.4 (s) ppm. IR (Nujol): ν˜
= 3374 (br.,
3
max
1
dried under vacuum. Yield: 21.7 mg (56 %). H NMR (CDCl ): δ =
3
m), 3185 (br., w), 1582 (w), 1305 (w), 1234 (w), 1167 (m), 1129 (s),
1117 (s), 1097 (vs), 1085 (vs), 1064 (s), 1054 (s), 1041 (m), 1027 (m),
996 (m), 970 (m), 926 (w), 899 (w), 874 (vw), 842 (m), 820 (w), 756
4
2
.43 (s, 3 H, SMe), 2.89 (d, J = 2.9 Hz, 6 H, NMe ), 3.26 (s, 2 H,
SCH ), 4.31 (br. d, J = 1.8 Hz, 2 H, NCH ), 4.37 (vt, J′ = 1.9 Hz, 2
PH
2
4
2
PH
2
H, fc), 4.51 (vt, J′ = 1.8 Hz, 2 H, fc), 4.65 (br. m, 2 H, fc), 4.69 (br. m,
H, fc), 6.24 (ddd, J = J = 7.5, J = 1.1 Hz, 1 H, C H ), 6.31 (br. t,
(
m), 747 (m), 710 (w), 695 (m), 660 (vw), 625 (m), 549 (m), 527 (m),
2
–1
1
2
3
6
4
513 (s), 488 (m), 481 (m), 450 (w), 438 (w) cm . MS (ESI+): m/z =
654 [(L )Pd(2)] . C H ClFeNO PPd (772.3): calcd. C 51.32, H 4.83,
J = 7.5 Hz, 1 H, C H ), 6.81 (br. t, J = 7.3 Hz, 1 H, C H ), 7.02 (dd, J =
NC
+
6
4
6
4
33 37 6
7
4
.4, 1.5 Hz, 1 H, C H ), 7.36–7.44 (br. m, 6 H, PPh ), 7.70–7.78 (br. m,
6 4 2
N 1.81; found C 51.43, H 4.64, N 1.83.
13
1
H, PPh ) ppm. C{ H} NMR (CDCl ): δ = 20.15 (s, SMe), 34.48 (s,
2
3
3
1
SCH ), 50.47 (d, J = 2 Hz, NMe ), 69.69 (d, J = 59 Hz, C-P of
Reactions of 10 and 11 with Bu NCl: Complex 10 (10 μmol) was
2
PC
2
PC
4
fc), 69.73 (s, CH of fc), 70.36 (s, CH of fc), 73.01 (d, J = 8 Hz, CH of
dissolved in CDCl3 (0.5 mL) by sonication in an ultrasound bath.
Solid tetrabutylammonium chloride (3.0 mg, 10 μmol) was added,
PC
3
fc), 73.61 (d, J = 3 Hz, NCH ), 76.55 (d, J = 12 Hz, CH of fc),
PC
2
PC
8
1
2.77 (s, C-CH of fc), 123.19 (s, CH of C H ), 125.17 (s, CH of C H ), and the mixture was stirred for 30 min. After filtration through a
2 6 4 6 4
25.51 (d, JPC = 6 Hz, CH of C H ), 128.80 (d, J = 11 Hz, CH of
syringe filter (PTFE, pore size: 0.45 μm), the mixture was analyzed
6
4
PC
4
1
PPh ), 131.23 (d, J = 2 Hz, CHpara of PPh ), 131.25 (d, J = 52 Hz, by NMR spectroscopy, which confirmed the clean formation of com-
2
PC
2
PC
Eur. J. Inorg. Chem. 2017, 4850–4860
www.eurjic.org
4858
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
pound 8. Under similar conditions, complex 11 was converted back
into the chloride complex 9.
[8] a) P. Štěpnička, J. Schulz, T. Klemann, U. Siemeling, I. Císařová, Organome-
tallics 2010, 29, 3187–3200; b) U. Siemeling, T. Klemann, C. Bruhn, J.
Schulz, P. Štěpnička, Dalton Trans. 2011, 40, 4722–4740; c) P. Štěpnička,
M. Zábranský, I. Císařová, ChemistryOpen 2012, 1, 71–79; d) M. Zábranský,
I. Císařová, P. Štěpnička, Dalton Trans. 2015, 44, 14494–14506; e) M. Záb-
ranský, I. Císařová, P. Štěpnička, Eur. J. Inorg. Chem. 2017, 2557–2572.
[9] a) N. J. Long, J. Martin, G. Opromolla, A. J. P. White, D. J. Williams, P.
Zanello, J. Chem. Soc., Dalton Trans. 1999, 1981–1986; b) V. C. Gibson,
N. J. Long, A. J. P. White, C. K. Williams, D. J. Williams, M. Fontani, P.
Zanello, J. Chem. Soc., Dalton Trans. 2002, 3280–3289.
[10] For examples, see: a) L. Routaboul, S. Vincendeau, J.-C. Daran, E. Man-
oury, Tetrahedron: Asymmetry 2005, 16, 2685–2690; b) R. Malacea, E.
Manoury, L. Routaboul, J.-C. Daran, R. Poli, J. P. Dunne, A. C. Withwood,
C. Godard, S. B. Duckett, Eur. J. Inorg. Chem. 2006, 1803–1816; c) E.
Le Roux, R. Malacea, E. Manoury, R. Poli, L. Gonsalvi, M. Peruzzini, Adv.
Synth. Catal. 2007, 349, 309–313; d) R. Malacea, L. Routaboul, E. Manoury,
J.-C. Daran, R. Poli, J. Organomet. Chem. 2008, 693, 1469–1477; e) M.
Biosca, M. Coll, F. Lagarde, E. Brémond, L. Routaboul, E. Manoury, O.
Pàmies, R. Poli, M. Diéguez, Tetrahedron 2016, 72, 2623–2631.
11] a) S. K. Bur, A. Padwa, Chem. Rev. 2004, 104, 2401–2432; b) C. R. Johnson,
W. G. Phillips, J. Am. Chem. Soc. 1969, 91, 682–687; c) K. S. Feldman,
Tetrahedron 2006, 62, 5003–5034.
[12] The addition of a dimethyl sulfoxide solution of 5 and tosyl chloride to
KOH dissolved in the same solvent during the experiment resulted in an
exothermic reaction, presumably between the tosyl chloride and the
solvent: a) F. Saadati, K. Yousefi, Synth. Commun. 2014, 44, 2818–2825;
b) J. D. Albright, J. Org. Chem. 1974, 39, 1977–1979.
X-ray Crystallography: The diffraction data (completeness
≥
99.8 %, θmax = 27.5°) were collected by using a Nonius-KappaCCD
diffractometer equipped with a Bruker Apex-II image plate detector
6·3CHCl ) or a Bruker D8 VENTURE Duo diffractometer equipped
(
3
with a PHOTON100 detector and an IμS micro-focus X-ray tube (all
other structures), both equipped with a Cryostream Cooler (Oxford
Cryosystems). Mo-K radiation (λ = 0.71073 Å) was used in all cases.
α
[
29]
The structures were solved by direct methods (SHELXS-97 ) and
refined by a full-matrix least-squares procedure based on F using
2
SHELXL-2014.[ The non-hydrogen atoms were refined by using
anisotropic displacement parameters. All hydrogen atoms were in-
cluded in their theoretical positions and refined by using the “riding
model” with Uiso(H) set to a multiple of Ueq of their bonding atom.
One of the P-phenyl substituents in the structure of 7 was disor-
dered, and three of its carbon atoms had to be refined with two
positions. Occupancies of the contributing orientations were refined
to 31:69. In the case of 8·AcOEt, the solvent molecules were heavily
30]
[
disordered around the inversion centers (two molecules of ethyl
acetate per unit cell), and hence PLATON SQUEEZE[
31]
was used to
compensate for this spread of electron density. Relevant crystallo-
graphic data, data collection details, and structure refinement pa-
rameters are presented in Table S1 in the Supporting Information.
All geometric calculations were performed by using a recent version
of the PLATON program,[ which was also used to prepare the
[
13] C. Reichardt, J. Prakt. Chem. 1999, 341, 609–615, and references cited
32]
therein.
structural diagrams. CCDC 1569126 (for 6·3CHCl ), 1569127 (for 7),
[14]
3
S. Fujisaki, I. Fujiwara, Y. Norisue, S. Kajigaeshi, Bull. Chem. Soc. Jpn. 1985,
58, 2429–2430.
1
569128 (for 8·AcOEt), 1569129 (for 9·1/2C H ), 1569130 (for
6 14
1
0·3/2C H Cl ), and 1569131 (for 11) contain the supplementary
[15] J. M. Brunel, B. Faure, M. Maffei, Coord. Chem. Rev. 1998, 178–180, 665–
2
4
2
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre.
698.
[16] J. Tauchman, I. Císařová, P. Štěpnička, Dalton Trans. 2014, 43, 1599–1608.
[
17] W. H. Hersh, J. Chem. Educ. 1997, 74, 1485–1488.
Supporting Information (see footnote on the first page of this
article): NMR spectra and a summary of the crystallographic data.
[
18] Cambridge Structural Database, version 5.38 of November 2016 with
updates of November 2016, February 2017 and May 27 (accessed August
1
4, 2017).
5
5
[
[
19] “Isomeric” ligands of the type [Fe(η -C H PPh -1-CH SR-2)(η -C H )] (R =
5
3
2
2
5 5
Acknowledgments
2
Et, tBu, and Ph) also form cis chelate complexes [LPdCl ]. For structurally
characterized examples, see ref.[
10d]
This study was funded by the Czech Science Foundation
20] a) R. J. Coyle, Y. L. Slovokhotov, M. Y. Antipin, V. V. Grushin, Polyhedron
998, 17, 3059–3070; b) P. Štěpnička, J. Podlaha, R. Gyepes, M. Polášek,
(
project no. 15-11571S).
1
J. Organomet. Chem. 1998, 552, 293–301; c) P. Štěpnička, I. Císařová, R.
Gyepes, Eur. J. Inorg. Chem. 2006, 926–938; d) P. Štěpnička, I. Císařová,
Collect. Czech. Chem. Commun. 2006, 71, 215–236; e) J. Kühnert, M.
Dušek, J. Demel, H. Lang, P. Štěpnička, Dalton Trans. 2007, 2802–2811; f)
J. Tauchman, I. Císařová, P. Štěpnička, Organometallics 2009, 28, 3288–
Keywords: Metallocenes · Phosphane ligands · Hybrid
ligands · Palladium · Structure elucidation · X-ray diffraction
3
302; g) J. Schulz, I. Císařová, P. Štěpnička, J. Organomet. Chem. 2009,
[
1] G. P. Sollot, J. L. Snead, S. Portnoy, W. R. Peterson, H. E. Mertwoy, U. S.
Dept. Com., Office Tech. Serv., PB Rep. 1965, vol. II, pp. 441–452; Chem.
Abstr. 1965, 63, 18174.
2] a) S. W. Chien, T. S. A. Hor in Ferrocenes: Ligands, Materials and Bio-
molecules (Ed.: P. Štěpnička), Wiley, Chichester, 2008, chapter 2, pp. 33–
6
94, 2519–2530; h) P. Štěpnička, J. Schulz, T. Klemann, U. Siemeling, I.
Císařová, Organometallics 2010, 29, 3187–3200; i) P. Štěpnička, H. Solař-
ová, M. Lamač, I. Císařová, J. Organomet. Chem. 2010, 695, 2423–2431; j)
P. Štěpnička, H. Solařová, I. Císařová, J. Organomet. Chem. 2011, 696,
[
3
727–3740; k) J. Schulz, I. Císařová, P. Štěpnička, Organometallics 2012,
116; b) K.-S. Gan, T. S. A. Hor in Ferrocenes: Homogeneous Catalysis, Or-
3
1, 729–738; l) H. Charvátová, I. Císařová, P. Štěpnička, J. Organomet.
ganic Synthesis Materials Science (Eds.: A. Togni, T. Hayashi), Wiley-VCH,
Weinheim, 1995, chapter 1, pp. 3–104; c) G. Bandoli, A. Dolmella, Coord.
Chem. Rev. 2000, 209, 161–196.
Chem. 2016, 821, 25–39.
[
21] a) J.-F. Ma, Y. Yamamoto, Inorg. Chim. Acta 2000, 299, 164–171; b) P.
Štěpnička, I. Císařová, Organometallics 2003, 22, 1728–1740; c) H. Solař-
ová, I. Císařová, P. Štěpnička, Organometallics 2014, 33, 4131–4147; d) K.
Škoch, I. Císařová, P. Štěpnička, Organometallics 2015, 34, 1942–1956.
22] D. Cremer, J. A. Pople, J. Am. Chem. Soc. 1975, 97, 1354–1358.
23] K. Nakamoto, Infrared and Raman Spectra of Inorganic and Coordination
Compounds, 6th ed., Part A (“Theory and Applications in Inorganic
Chemistry”), Wiley, Hoboken, NJ, 2009, pp. 192–204.
[
[
3] T. J. Colacot, S. Parisel in Ferrocenes: Ligands, Materials and Biomolecules
(
Ed.: P. Štěpnička), Wiley, Chichester, 2008, chapter 3, pp. 117–140.
4] a) P. Štěpnička in Ferrocenes: Ligands, Materials and Biomolecules (Ed.: P.
Štěpnička), Wiley, Chichester, 2008, chapter 5, pp. 177–204; b) P. Štěp-
nička in The Chemistry of Organoiron Compounds (Eds.: I. Marek, Z. Rap-
poport), Wiley, Chichester, 2013, chapter 4, pp. 103–154.
[
[
[
5] a) P. Štěpnička, I. Císařová, J. Schulz, Organometallics 2011, 30, 4393–
[24] The Pd–S bond length is similar to that in [(LNC*)Pd(Ph
4
1
403; b) P. Štěpnička, I. Císařová, J. Organomet. Chem. 2012, 716, 110–
19.
2
2 2
PCH CH SMe-
2
NC
κ P,S)][PF ], in which L * = (R)-1-[1-(dimethylamino)ethyl]-2-naphthyl-
6
2
2
[
[
6] P. Štěpnička, I. Císařová, Dalton Trans. 2013, 42, 3373–3389.
7] R. C. J. Atkinson, V. C. Gibson, N. J. Long, A. J. P. White, D. J. Williams,
Organometallics 2004, 23, 2744–2751.
(κ C ,N) [2.396(3)–2.421(3) Å for four independent cations]: S. Y. M.
Chooi, T. S. A. Hor, P. H. Leung, K. F. Mok, Inorg. Chem. 1992, 31, 1494–
1500.
Eur. J. Inorg. Chem. 2017, 4850–4860
www.eurjic.org
4859
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
[
25] L. Monnereau, D. Sémeril, D. Matt, L. Toupet, Chem. Eur. J. 2010, 16,
237–9247.
26] Somewhat for
[28] A. C. Cope, E. C. Friedrich, J. Am. Chem. Soc. 1968, 90, 909–913.
[29] G. M. Sheldrick, Acta Crystallogr., Sect. A: Found. Crystallogr. 2008, 64,
112–122.
[30] G. M. Sheldrick, Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 3–8.
[31] A. L. Spek, Acta Crystallogr., Sect. C: Struct. Chem. 2015, 71, 9–18.
[32] A. L. Spek, Acta Crystallogr., Sect. D: Biol. Crystallogr. 2009, 65, 148–155.
9
[
longer
)(H O)][PF
phenyl-10H-9-thia-10-phosphaanthracene 9,9-dioxide [2.221(7)
Pd–O
distances
were
determined
], in which L = 10-
at
NC
NC
[
(L )Pd(PPh
3
2
6
] and [(L )Pd(L-κP)(H
2
O)][SbF
6
Å
room temperature and 2.203(1) Å at 150 K, respectively]: a) J.-F. Ma, Y.
Kojima, Y. Yamamoto, J. Organomet. Chem. 2000, 616, 149–156; b) C. J.
Chapman, C. G. Frost, M. F. Mahon, Dalton Trans. 2006, 2251–2262.
27] M. Zábranský, L. Kolářová, I. Císařová, P. Štěpnička, J. Organomet. Chem.
[
2017, 846, 217–222.
Received: September 3, 2017
Eur. J. Inorg. Chem. 2017, 4850–4860
www.eurjic.org
4860
© 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim