Reactivity of Planar-Chiral α-Ferrocenyl Carbocations towards Electron-Rich Aromatics

Article abstract of DOI:10.1002/ejic.201801430

The reaction of the enantiopure, planar-chiral α-ferrocenyl carbocation (S_p)-2-(P(=S)Ph₂)FcCH₂⁺ (Fc = Fe(η⁵-C₅H₅)(η⁵-C₅H₃)) towards electron-rich

Full text of DOI:10.1002/ejic.201801430

DOI: 10.1002/ejic.201801430
Full Paper
Thiophosphine Derivatives
Reactivity of Planar-Chiral α-Ferrocenyl Carbocations towards
Electron-Rich Aromatics
Marcus Korb,*[a][‡] Julia Mahrholdt,[a] Xianming Liu,[a] and Heinrich Lang*[a]
Abstract: The reaction of the enantiopure, planar-chiral biaryls, where sandwich compound (Sp)-1-(PPh2)-2-(o-NMe2-
α-ferrocenyl carbocation (Sp)-2-(P(=S)Ph2)FcCH2 (Fc = Fe(η5- C6H4)CH2-Fc gave an ee of 69 % (1 mol-% [Pd]), which is up to
+
C5H5)(η5-C5H3)) towards electron-rich arenes C6H5E (E = NH2, date the highest observed value for planar-chiral ferrocenes.
NMe2, NiPr2, NPh2, PPh2, P(=S)Ph2, OH, SH, SMe) regarding The absolute configuration of the chiral ferrocenes was con-
either a nucleophilic attack of the group E or an electrophilic firmed by single-crystal X-ray diffraction analysis. For seleno
+
aromatic substitution reaction of the arene at the CH2 unit is phosphane 1-(P(=Se)Ph2)-2-(CH2OH)-Fc a unique Se single-atom
reported. It was found that the amino, oxo or thio functionali- transfer occurred within its reaction with Sanger's reagent. The
ties gave the respective ferrocenes in various product distribu- presence of two chemically different Se atoms in 1-(P(=Se)Ph2)-
tions, while the P-based species didn't. Appropriate thiophos- 2-(((2,4-(NO2)2-C6H3)Se)CH2)-Fc was confirmed by 77Se{1H} NMR
phine derivatives could be reduced to their PIII species that spectroscopy and single-crystal X-ray diffraction analysis, re-
were applied as supporting ligands in atropselective C,C cross- spectively.
coupling reactions for the synthesis of sterically hindered
Introduction
We recently extended the scope of suitable hemilabile li-
gands to methoxy-substituted ferrocenyl phosphines of type 2-
OMe-1-PPh2-Fc (Fc = Fe(η5-C5H5)(η5-C5H3)), applying the anionic
phospho-Fries rearrangement for the synthesis of the diastereo-
pure (Rp) species.[10,11] However, due to the low steric demand
of the OMe group, a negligible ee was noticed within the cata-
lytically formed biaryls. Extension from a FcOMe to a FcCH2OR
structure increased the ee significantly, attributed to a more
flexible ligand backbone.[9,13] Within these studies, the forma-
tion of enantiopure α-ferrocenyl carbocations was observed as
rarely described species for 1,2-substituted ferrocenes,[14] which
allows for the introduction of various substitution patterns
(Scheme 1).[13] Under acidic conditions, the feasible removal of
the hydroxy group results in carbenium ions with a comparably
high electrophilicity value E of –2.57 according to Mayr,[15] due
Recently, planar-chiral ferrocenes gained great importance as
effective ligands within, for example, C,C cross-coupling cataly-
sis.[1] Although a phosphine group is essential for the formation
of stable, e.g. Pd complexes, additional substituents have been
introduced to further increase the stability of the active site
within the catalytic cycle.[2] It could be shown that ferrocenyl
phosphines, bearing an additional ortho-substituent, signifi-
cantly increase the catalytic activity of the respective Pd-cata-
lysts, due to the additional hemilabile donor functionality.[2]
A
variety of groups has been investigated, including, e.g. arenes,[3]
phosphonates,[4] C-stereogenic groups,[5] NHC ligands,[6] as well
as vinyl,[7,8] aryloxy[9,10] and alkyloxy[11,2b,12] fragments. Some
enantiopure examples were applied as ligands in order to inves-
tigate their ability to transfer planar-chirality within a catalytic
reaction. The Suzuki–Miyaura reaction for the synthesis of hin-
dered biaryls is a common test-reaction, whereby the ee of the
formed coupling products expresses the transferability.[7] So far,
a maximum ee of 54 % at catalyst loadings of low as 2 mol-%
[Pd] could be reached.[3]
+
to a stabilization by an intramolecular Fe···CH2 interac-
tion.[16,17]
Although, this approach is well-studied for the functionaliza-
tion of single- and 1,1′-substituted ferrocenyl methanols with
various arenes and nucleophiles,[17b,18] 1,2-substituted deriva-
tives had not been investigated. Therefore, we recently applied
the 2-(CH2OH)-1-(S=PPh2)-substituted ferrocene as a substrate
and studied its reaction with anisole, toluene and trimethyl-
phenol.[13] The obtained ferrocenyl phosphines possessed pla-
nar-chirality as the sole stereo element.[13] Such ferrocenes were
applied as supporting ligands for the synthesis of biaryls via
Pd-catalyzed Suzuki–Miyaura reactions of bromo arenes with
aryl boronic acids, which were obtained with up to 26 %
ee.[13,19,20]
[a] Technische Universität Chemnitz,
Faculty of Natural Sciences, Institute of Chemistry, Inorganic Chemistry,
09107 Chemnitz, Germany
E-mail: heinrich.lang@chemie.tu-chemnitz.de
marcus.korb@chemie.tu-chemnitz.de
Homepage:https://www.tu-chemnitz.de/chemie/anorg
[‡] Current address: M. Korb; University of Western Australia, School of
Molecular Sciences,
Crawley, Perth, WA 6009, Australia
Supporting information and ORCID(s) from the author(s) for this article are
available on the WWW under https://doi.org/10.1002/ejic.201801430.
Variation of the donor properties of E in (Sp)-1-(PPh2)-2-(o-E-
C6H4)CH2-Fc-type compounds from E = OMe to stronger func-
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lar amounts of pTsOH·H2O (Scheme 2, Scheme 3). In case of
aniline, an overall conversion of 75 % was observed, whereby a
mixture of SN- and SEAr-derived products was formed
(Scheme 2). Although, protonation of the amino functionality
occurred, a nucleophilic reaction of the N-atom towards the
carbocation gave (Sp)-2 in 22 %. The yield of (Sp)-2 could slightly
be increased by using 5 instead of 3 equiv of aniline and
6 equiv of pTsOH·H2O, respectively. The presence of a NH func-
tionality has inter alia been confirmed by single-crystal X-ray
diffraction analysis (Figure 1) and by IR spectroscopy (ν
=
˜
NH
3388 cm–1). Although the formation of an ammonium function-
ality lowers the electron density at the arene, SEAr-type reac-
tions occurred in overall 51 %, giving the ortho- and para-sub-
Scheme 1. Reaction strategy for the synthesis of ortho-substituted enantio-
pure ferrocenyl phosphines and their application as supporting ligands
within Pd-catalyzed Suzuki–Miyaura C,C cross-coupling reactions for the syn-
thesis of biaryls.[13] i) pTsOH·H2O, 1,4-dioxane, 90 °C, 24 h; a) obtained from
the respective bromo arenes (bold) and boronic acids.
tionalities should increase their bonding towards the Pd atom
and therefore result in a higher ee. Herein, we extend the sub-
strate scope of electron-rich arenes to E = amino, phosphino
and thio units and investigate their tendency to result in either
N- or Ar-type products within the reaction with enantiopure α-
ferrocenyl carbocations (Scheme 1). Their efficiency towards a
chirality transfer is evaluated within Suzuki–Miyaura C,C cross-
coupling studies for the atropselective synthesis of sterically
hindered biaryls.
Scheme 2. Reaction of the α-ferrocenyl carbocation (Sp)-1a+ with aniline. (Re-
action conditions: 3 equiv of aniline, 6 equiv of pTsOH·H2O, 1,4-dioxane, 90 °C;
a) 5 equiv of PhNH2 were used.)
We recently reported about the transfer of a single sulfur
atom from a P(=S)Ph2 moiety towards the CH2+ group, resulting
in a thiol functionality. This migration competed with the SEAr
of the substrate and therefore lowered the yield of the benzyl-
type product.[13] In order to prevent this reaction pathway, the
P···chalcogen bond strength was varied by using oxygen and
selenium instead. Hence, the occurrence of similar intermolec-
ular single-chalcogen-atom transfer is also reported herein.
Results and Discussion
The formation of the enantiopure α-ferrocenyl carbocation (Sp)-
1a+ is initiated by an acid-promoted release, respectively activa-
tion, of the OH functionality of (Sp)-1a by using a 3-fold excess
of pTsOH·H2O in dioxane at 90 °C, according to our recently
optimized reaction protocol (Scheme 1).[13] Alcohol (Sp)-1a was
synthesized according to a literature reported 7-step procedure
starting from ferrocene.[9,21] Formation of (Sp)-1a+ in the pres-
ence of amine functionalities required the addition of equimo-
Scheme 3. Reaction of the α-ferrocenyl carbocation (Sp)-1a+ with N-substi-
tuted anilines. (Reaction conditions: 6 equiv of pTsOH·H2O, 1,4-dioxane, 90 °C,
A: 3 equiv of the respective aniline; B: 5 equiv of PhNMe2 were used; a) 30 %
of (Sp,Sp)-12; b) 34 % of (Sp,Sp)-12; c) 60 % of (Sp,Sp)-12.)
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Figure 1. ORTEP drawing (50 % probability level) of the molecular structures of (Sp)-2 (left) and o-(Sp)-5 (right) with their atom-numbering schemes. All C-
bonded hydrogen atoms have been omitted for clarity. (Selected bond properties are summarized in Table 1).
stituted products of (Sp)-3 in a ratio of 3:2 (Scheme 2). The tions of (Sp)-1a with phenol (CH2Cl2 at 50 °C)[13] prompted us
preferred formation of the ortho-derivative is probably due a to re-investigate it under the reaction conditions reported
pre-coordination of the N atom towards the positively charged herein (1,4-dioxane at 90 °C), in order to compare the results
+
CH2 functionality, as observed for oxygen analogues,[13] and (Scheme 4). Although the overall conversion remained similar
two (o-) instead of one (p-) available position. In addition to (70 %), the formation of ortho- and para-substituted (Sp,Sp)-9
(Sp)-2,3, double substitution of aniline in N- and 4-position oc- (15 %) was observed. Most probably, o-(Sp)-8 underwent an ad-
curred, giving the diferrocenyl compound (Sp,Sp)-4 (Scheme 2). ditional SEAr reaction at 90 °C compared to 50 °C.
The occurrence as the 1,4- instead of the 1,2-isomer was evi-
denced by NMR spectroscopy (vide infra) and might be due to
steric effects.
The reaction of (Sp)-1a with N,N-dimethylaniline instead of
PhNH2 prevented the nucleophilic addition of the N atom at the
CH2+ moiety, solely resulting in the SEAr-derived compounds o-
and p-(Sp)-5 (Scheme 3). However, the higher basicity of the
dimethyl derivative (pKb = 8.93) compared to aniline itself (pKb =
9.13) resulted in the formation of more stable ammonium
ions.[22] The positively charged species acts as an electron defi-
cient arene, which explains the low yield of 13 % for o-(Sp)-5.
The respective para-isomer has just been observed in traces
together with o-(Sp)-5 and could not be separated by, e.g. chro-
matographic methods. Hence, applying the more electron-rich
Scheme 4. Reaction of the α-ferrocenyl carbocation (Sp)-1a+ with phenol.
and sterically more demanding NiPr2 aniline prevented a reac-
(Reaction conditions: A, 3 equiv of phenol, 3 equiv of pTsOH·H2O, 1,4-dioxane,
tion with the carbocation (Sp)-1a+ and did not result in the
90 °C; B: values derived from literature,[13] where CH2Cl2 and 50 °C were
formation of a type (Sp)-6 species (Scheme 3). In this case, the
absence of an appropriate and fast-reacting electrophile ena-
bled the slower conversion to thioether (Sp,Sp)-12 in up to 60 %,
requiring three molecules of (Sp)-1a or (Sp)-1a+. A proposed
mechanism for the formation of this unusual species has re-
cently been described and is additionally considered herein
(see below).[13]
applied instead.)
In contrast to (Sp,Sp)-4, where a N,4-functionalization took
place, the formation of compound (Sp,Sp)-9, possessing a 2,4-
substitution pattern, is in accordance with the lower nucleophil-
icity of the oxygen compared to an amino moiety.[24] Most
likely, a consecutively mechanism initially gave o-(Sp)-8 followed
Applying NPh3 allows for a distribution of the positive charge by a subsequent SEAr reaction in para position to afford (Sp,Sp)-
over three instead of one arene. Hence, p-(Sp)-7 was formed 9. The OH groups of both species were identified by IR spectro-
within the reaction of NPh3 with (Sp)-1a. The absence of the scopy showing the characteristic νOH = band at 3377 cm–1.
˜
respective ortho-isomer of (Sp)-7, might be due to the steric
influence of the NPh2 moiety (Scheme 3).
With regard to the potential use of the ortho isomers of (Sp)-
3,5,8 as supporting ligands in Pd-catalyzed reactions, the intro-
First studies using phenols and anisole as arenes have re- duction of an additional phosphine moiety would change the
cently been investigated.[13,23] The lower nucleophilicity[24] of binding properties from hemilabile[7,12] to bidentate.[25] This
oxygen as compared to nitrogen increased the ability to un- would allow for a new access to such bis(phosphines), which
dergo SEAr reactions and hence o-(Sp)-8 was obtained in high are known to give a high ee within catalytic reactions.[26] Hence,
yield (74 %, Scheme 4). However, the different reaction condi- the reaction of (Sp)-1a with PPh3 was investigated in order to
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obtain (Sp)-11 (Scheme 5), or a product similar to the NPh3 spectroscopic data. IR spectroscopy is rather unsuitable, since
analogue (Sp)-7 (Scheme 3).
the CH2–S stretching frequency at 500–700 could not specifi-
cally be addressed.[28]
Scheme 5. Reaction of the α-ferrocenyl carbocation (Sp)-1a+ with phosphines.
(Reaction conditions: 3 equiv of the respective phosphine, 6 equiv of
pTsOH·H2O, 1,4-dioxane, 90 °C.)
Scheme 6. Reaction of the α-ferrocenyl carbocation (Sp)-1a+ with thiophenols.
(Reaction conditions: 3 equiv of the respective thio arene, 6 equiv of pTsOH,
1,4-dioxane, 90 °C.)
However, ferrocenyl-based species were absent after the
work-up, indicating that decomposition occurred during the re-
action progress. The presence of P(=S)Ph3 within the product
mixture supports our recent mechanistic proposal regarding
(Sp)-1a+ acting as a sulfur source and the subsequent decompo-
sition of the formed phosphine (Sp)-10+. Therefore, the latter
species could never be detected. We assume that the formation
of (Sp)-1a+ occurs rapidly under the reaction conditions applied,
whereby the positive charge lowers the bond strength of the
P=S bond. Hence, the higher σ donor ability of PPh3 causes a
sulfur transfer to form P(=S)Ph3. Although, an excess of PPh3
was used, no further reaction with the formed (Sp)-10+ species
occurred. The absence of (Sp,Sp)-12 also indicates that (Sp)-10+
is not suitable to form a similar desulfurized thioether.
In order to investigate if the formation of (Sp,Sp)-12[13] out of
(Sp)-1a could be suppressed by using different PV-chalco-
genides, rac-1b[29] (E = O) and selenide rac-1c (E = Se) were
synthesized (Experimental Section). In addition, the usage of
the racemic mixtures of 1a–c allows for the investigation of the
diastereoselectivity of the reaction to either produce the meso
(Rp,Sp) or a mixture of the racem isomers Rp,Rp and Sp,Sp, respec-
tively (Scheme 7).
The sulfur transfer was prevented by applying P(=S)Ph3 as
the starting material. However, the electron-withdrawing char-
acter of the P=S functionality reduced the ability of the phenyls
to undergo SEAr reactions, enabling the formation of (Sp,Sp)-12.
Interestingly, the comparably low yield of 62 % indicates that
the addition of a phosphine sulfide does not contribute within
the mechanism. This might be attributed to the higher electron
Scheme 7. Acid-catalyzed reaction of E=PV (E = O, S, Se) functionalized com-
pounds rac-1a–c to ethers 12, 15 and 16, respectively. (i) 3 equiv of
pTsOH·H2O, 1,4-dioxane, 90 °C.)
[27]
density in PPh3 compared to a cationic species, e.g. (Sp)-1a+,
and the therefore stronger P=S double bond in P(S)Ph3 as,
which is not able to act as a sulfur source.[8,13] Addition of ele-
mental sulfur does also not significantly enhance the yield of
(Sp,Sp)-12, as shown recently.[13]
Starting with rac-1a, thioether 12 was formed with a
1
meso/racem ratio of 1.37:1 (de = 0.16), as confirmed by H and
31P{1H} NMR spectroscopic studies (Scheme 7), whereby for the
In addition to N-,O- and P-containing arenes, also S-based yield of 36 %, three molecules of rac-1a were considered (ESI).
functionalities may support the chirality transfer of a planar- The assignment of each diastereomer was achieved by compari-
1
chiral ferrocene within a catalytically active species towards the son of the H and 31P{1H} NMR spectroscopic data of the mix-
substrate. Therefore, the behavior of thiophenol and thioanisole ture of 12 with a stereopure sample of (Sp,Sp)-12[13] (see
within the reaction with (Sp)-1a was investigated (Scheme 6). Schemes 5 and 6, and the ESI). In case of phosphine oxide 1b,
The SH species exclusively underwent a nucleophilic addition a column chromatographic work-up did neither give bis(ether)
to thioether (Sp)-13 according to reference[14], whereas thioani- 15 in significant amount, nor any further product (Scheme 7),
sol did not react with (Sp)-1a to (Sp)-14 and instead (Sp,Sp)-12 indicating that the α-ferrocenyl carbocation, formed upon treat-
was formed. This is contrary to the respective O-based sub- ment of rac-1b with acids, is less stable than its thio derivative
strates (Scheme 4),[13] but in accordance with reactions of non- 1a+. Similarly, seleno phosphine rac-1c resulted in the forma-
ortho-functionalized ferrocenyl carbenium ions with thiols.[18] tion of a small amount of a soluble material, which still consists
The identity of (Sp)-13 has inter alia been confirmed by single- of a complex mixture of isomers and products that could not
crystal X-ray diffraction analysis (Figure 3), in addition to NMR further be separated. Therefore, the migration of a chalcogene
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Scheme 8. Reaction of seleno phosphine (Sp)-1c with Sanger's reagent to afford selane rac-19. (i) Degassed DMF, 40 °C, 18 h; a) brsm = based on recovered
starting material; 43 % of rac-1c were recovered and two molecules of rac-1c were considered for the synthesis of rac-19.
+
from the respective phosphine towards a CH2 functionality ray diffraction analysis (Figure 4) and 77Se{1H} NMR spectro-
seems to be limited to sulfur for this type of reaction. It further- scopy. The latter studies revealed resonances at –261.3 ppm (d,
more implies that 1b,c are rather unsuitable for either SN or 1JSe,P = 727.4 Hz) and 438.0 ppm (s). For comparison, compound
SEAr reactions with electron-rich aromatics, due to a rapid de- rac-1c also showed a signal at –254.6 ppm (d, 1JSe,P = 709.0 Hz),
composition of the respective in situ formed carbo-cations.
To exclude, if the decomposition of 1b,c+ is due to the high
reaction temperature (90 °C) and the acidic media, exemplarily,
the reaction of 1c with Sangers reagent was investigated
(Scheme 8). It could recently be shown that a similar sulfur
which can therefore be ascribed to the P=Se functionality. The
singlet at lower field was assigned to the CH2–Se–arene func-
tionality, whereby appropriate 77Se NMR investigations of simi-
lar compounds are limited.[34b,37b]
The 31P{1H} chemical shifts of E=P ferrocenyl methanols 1a
transfer to a thioether species occurred, while using (Sp)-1a as (E = S), 1b (E = O) and 1c (E = Se) increase in the order Se (1c,
the starting material.[13] In similarity, a SNAr reaction occurred 30.0 ppm) < O (1b, 33.6 ppm[29]) < S (1a, 41.7 ppm[13]). The
to give rac-17, which in turn splits into α-ferrocenyl carbocation 31P77Se couplings of 709.0 (rac-1c) and 727.4 Hz (rac-19) are
rac-1c+ and a 2,4-dinitrophenolate anion, stabilized by a Fe···Cα similar to recently reported ferrocenyl phosphines,[8,13] reveal-
interaction[16,17] and a mesomeric push-pull system, respec- ing an increased donor strength for the latter species.
tively (Scheme 8). The latter species was identified as its proto-
Further properties and analytical data are discussed in the
ESI.
1
nated form by H and 13C{1H} NMR spectroscopy.
Consecutive intermolecular selenium transfer gave rac-18,
which underwent an additional SNAr reaction to give rac-19 in
a yield of 56 %, which already considers two molecules of rac-
1c (Scheme 8). Taking into account that 43 % of rac-1c were
recovered, the yield of rac-19 was amended to 98 %. The pro-
posed mechanism is supported by the isolation of rac-1b, de-
rived from de-selenated rac-1c. Hence, rac-1c and rac-19 were
formed in almost stoichiometric amounts. The recovering of the
starting material rac-1c indicates a rather low reaction rate to
rac-16, wherefore it can be considered as a selenium source.
Compound rac-1c+ in contrast, cannot be considered, since the
thio analogue 10+ has been shown to undergo rapid decompo-
sition (Scheme 5). Possible pathways for the formation of rac-
1b are proposed within Scheme S1. The proposed mechanism
for the formation of rac-19 also clarifies why the cationic spe-
cies 1a+ cannot be generated by conversion of the alcohols
1a,c into e.g. mesylates, due to their rapid fragmentation and
subsequent chalcogene migration.
Solid State Structure
The molecular structures of (Sp)-2, o-(Sp)-5, p-(Sp)-7, o-(Sp)-8,
(Sp)-13, rac-1b,c and rac-19 in the solid state have been deter-
mined by single-crystal X-ray diffraction analysis. Suitable crys-
tals were obtained by crystallization from saturated hexane so-
lutions. The ORTEP diagrams are shown in Figure 1 ((Sp)-2 and
o-(Sp)-5), Figure 2 (p-(Sp)-7 and o-(Sp)-8), Figure 3 ((Sp)-13) and
Figure 4 (rac-1c, rac-19). Selected bond lengths (Å), bond angles
(°) and torsion angles (°) are summarized in Table 1. The results
of a measurement of a single crystal of rac-1b (Figure S7), ob-
tained within the reaction of rac-1c to rac-19 (Scheme 8), are
in similarity with those reported in literature measured at
150 K.[29a] Herein, data from a measurement at 125 K are pro-
vided for comparison (Experimental Section, see the ESI).
Enantiopure phosphane sulfides (Sp)-2, o-5, p-7, o-8 and 13
crystallize in non-centrosymmetric monoclinic (o-5, P21) and in
the orthorhombic space group P212121 (2, p-7, o-8 and 13) with
one crystallographic independent molecule in the asymmetric
unit. The absolute structure parameters[38] below 0.034(5) con-
firm the (Sp) configuration. Selenophosphanes rac-1c and rac-
19, synthesized as a racemic mixture, crystallized in the centro-
Up to date, several mechanism,[30] e.g. SN reactions, radicalic
couplings or rearrangements[31] have been reported for the syn-
thesis of selanes, whereby SNAr reactions are limited to a few
examples.[32,33] The transfer of a single Se atom, as observed for
the synthesis of rac-19, is unique and the first example for this
type of selane formation at a sterically demanding ortho-substi-
tuted ferrocene. Usually SeCN–,[34] LiSeSiMe3,
H2Se[36] or dis-
[35]
symmetric space groups P1 (rac-19) and P2 /c (rac-1c).
¯
1
elenides[37] are applied in Se transfer reactions. The identity of
All compounds exhibit similar tilt angles (Ct–Fe–Ct between
rac-19 with its two Se atoms was confirmed by single-crystal X- 175.89(5) and 178.24(3) °; Ct = centroid) and a rather eclipsed
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Figure 2. ORTEP drawing (50 % probability level) of the molecular structures of p-(Sp)-7 (left) and o-(Sp)-8 (right) with their atom-numbering schemes. All C-
bonded hydrogen atoms have been omitted for clarity. (Selected bond properties are summarized in Table 1.)
rotation of the cyclopentadienyls. The main difference is ob-
served for the torsion angles of the P=E functionalities (E = S,
Se), which are directed towards the ortho substituent and ro-
tated below the C5H3 plane. The smallest value of 29.1(8) °,
which is observed for rac-1c, may be caused by packing effects
instead of a steric interaction of the Se with the Fe atom, since
rac-19 reveals an increased value of 40.4(4) °. The C2–C1–P1–S
torsion angles increase to 35.5(3) and 35.8(3) ° for thio deriva-
tives (Sp)-2 and (Sp)-7. In both cases the ortho substituents are
rotated above the C5H3 fragment by 71.9(4) and 100.0(4) °, re-
spectively. An increased value is observed for o-5 (42.9(7) °),
due to an intermolecular non-classic S···H–C interaction with
the C9 atom of an adjacent molecule (Figure S5). The rotation
of the P=S moiety towards the Fe atom reaches a maximum
for ferrocenes o-8 (56.9(4) °) and 13 (48.7(3) °), due to a steric
interaction with the ortho-CH2 functionalities, exceptionally po-
sitioned below the C5H3 plane by 143.0(5) and 146.3(3) °. Conse-
quently, the CH2SPh moiety in 13, showing the highest bending
towards Fe1, results in an overlap of the van der Waals radii of
3.748 Å (ΣS,Fe-max = 3.94 Å),[39] indicating a weak intramolecular
Figure 3. ORTEP drawing (50 % probability level) of the molecular structure
of (Sp)-13 with the atom-numbering scheme. All hydrogen atoms and the
disordered C5H5 unit (occupancy ratio: 0.55/0.45) have been omitted for clar-
ity. (Selected bond properties are summarized in Table 1.)
Figure 4. ORTEP drawing (50 % probability level) of the molecular structures of rac-1c (left) and rac-19 (right) with the atom-numbering schemes Selected C-
bonded hydrogen atoms have been omitted for clarity. (Selected bond properties are summarized in Table 1.)
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Table 1. Selected bond properties (Å/°) of (Sp)-configured 2, o-5, p-7, o-8 and 13, rac-1c, and rac-19.[a]
(Sp)-2
NH, NH
o-(Sp)-5
p-(Sp)-7
o-(Sp)-8
(Sp)-13
S, S
rac-1b[b]
OH, –
rac-1c[c]
OH, –
rac-19c)
Se, Se
X, E
iC, NMe2
iC, NPh2
iC, OH
P=S
1.9640(11)
1.500(5)
1.458(5)
1.387(5)
–35.5(3)
–71.9(4)
1.952(3)
1.9599(14)
1.502(4)
1.512(4)
1.427(4)
–35.8(3)
–100.0(4)
1.9668(16)
1.493(6)
1.513(7)
1.375(6)
–56.9(4)
143.0(5)
1.9581(11)
1.494(5)
1.811(4)
1.768(4)
–48.7(3)
146.3(3)
1.4882(16)
1.498(3)
1.420(3)
–
–39.1(2)
161.7(2)
2.116(2)
1.520(12)
1.410(11)
–
–29.1(8)
–68.2(11)
2.1223(13)
1.493(6)
1.982(4)
1.891(4)
–40.4(4)
–85.9(5)
C2–C11
C11–X
1.491(10)
1.514(11)
1.446(11)
–42.9(7)
E–iC
C2–C1–P1–S
C1–C2–C11–X
–113.9(9)
[a] Negative values represent counter-clockwise torsion angles. [b] P=O instead of P=S; values are in accordance with those reported in ref.[29a]. [c] P=Se
instead of P=S.
stabilization. Contrary, the low rotation within (Sp)-2 (35.5(3) °) resulting in electrostatic N···O interactions between two adja-
shortens the S1···C11 distance to 3.476(3) Å, which is within the cent molecules. Together with parallel-displaced π···π contacts
sum of the van der Waals radii (ΣC,S-max = 3.50 Å).[39] However, between the C5H5 groups a one-dimensional network along
the different types of inter- and intramolecular weak interac- [210] is formed (Figure S6).
tions do not effect the P=S distance that remains within
1.952(3) and 1.9668(16) Å. For 1c the P=Se distance is increased
Catalysis
to 2.116(2) Å, which is within the range for ferrocenyl seleno
phosphines.[12,13,40]
The PIII species necessary for Pd-catalyzed C,C cross-coupling
reactions can be achieved by the reduction of the respective PV
compounds (Sp)-2,5,8 and 13 by desulfurization/reduction with
P(NMe2)3 according to our recent protocol. (Scheme 9).[13] The
successful PV/PIII reduction can be monitored by 31P{1H} NMR
spectroscopy, where a shift from 41 ppm to –23 ppm occurs,
similar to literature.[9,13]
The OH functionality in o-8 is stabilized by a weak interaction
within the sulfur atom (S1···O1, 3.449(4) Å; ΣO,S-max = 3.50 Å). In
contrast, compound 2 does not show any additional stabiliza-
tion of the NH moiety.
3
The difference of the JH,H coupling constants of the CH2
hydrogen atoms towards the OH group within phosphine sulf-
ide 1a and selenide 1c, may be caused by a fixed orientation
of the hydroxy moiety. Compounds 1a and 1c reveal almost
similar conformational properties of the P(E)Ph2 and CH2OH
substituents[29] and do not show any intra- or intermolecular
hydrogen bridge bonds. In contrast, the different rotation of
the CH2OH moiety (Table 1) of phosphine oxide 1b allows for
dimeric structures based on P=O···H–O hydrogen bridge bonds
in the crystal packing (Figure S7).[29] The therefore weakened
O–H bond does not allow for a coupling with the CH2 hydrogen
atoms. Furthermore, a preferred anti-conformation of one of
the CH2 hydrogen atoms towards the O–H group in 1a and 1c
can be assumed. Hence, the signal at 4.68 ppm (3JH,H = 12.9 Hz)
can be ascribed to H11B (Figure 4).
Recently, the crystal structure of racemic o-8 has been re-
ported.[23] Therein, the phenyl moiety is positioned above the
C5H3 plane (–108.9°; herein 143.0(5) °) and the OH group is
directed away from the P=S functionality, which results in the
formation of hydrogen bridge bonds with the sulfur atoms of
adjacent molecules, along the a-axis (Figure S8).
Scheme 9. Reduction of PV thiophosphines (Sp)-2,-5,-8,-12 and –13 to give
their respective PIII species. a) Literature value.[13]
The low yield of 15 % within the reduction of phenol-bearing
(Sp)-8 to (Sp)-8a is ascribed to a CH2–arene bond cleavage and
the formation of phenol within a retro-SEAr-type[41] reaction
(Scheme 10). This was observed by 1H and 13C{1H} NMR spectro-
scopy of the first (Sp)-8a-containing fraction (Figure S4). It also
confirms that the therein formed desulfurized α-carbon cation
10+ rapidly decomposes, which lowers the yield of (Sp)-8a (Fig-
The triaryl moiety of p-7 contains a sp2 hybridized nitrogen ure 5).
atom based of the surrounding C–N–C angle sum of 359.0(3) °.
The lowest value between the C6H5 groups (116.2(3) °) is due
to their rather perpendicular intersection with the C3N fragment
of 50.11(13)/61.20(12) °. Contrary, the almost co-planar
C3N···C6H4 intersection (15.4(2) °) results in a steric repulsion
and therefore increased C–N–C angles of 121.2(3)/121.6(3) °.
This also causes a deformation of the C6H4 arene and hence an
increased rms deviation of 0.0148, compared to 0.0039/0.0035
for C6H5. The nitrogen atom is positioned out of the surround-
ing C3 plane by solely 0.084(4) Å.
Enantiopure compounds (Sp)-2a, 5a, 8a and 13a were inves-
tigated as ligands within Suzuki-Miyaura C,C cross-coupling re-
actions for the synthesis of in ortho-position hindered biaryls.
The results are compared with those ones of structurally related
compounds to (Sp)-8a′ and (Sp,Sp)-12a, which resulted in 26 %
ee as recently reported by our group.[13] To ensure a compara-
bility of the results, the reaction conditions for the coupling
reactions have been adopted.[13] The yields of the obtained bi-
aryls at a catalyst loading of low as 1 mol-% [Pd] at 70 °C ap-
proaches up to 98 %. However, the presence of an OH-acidic
The NO2 functionalities in compound rac-19 are rotated group, as present in o-(Sp)-8a, decreased the yield of 22a to
away from the ferrocenyl backbone to prevent steric effects, 47 % (Figure 5).
Eur. J. Inorg. Chem. 2019, 973–987
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strates. It should be noted that the ee within the biaryls strongly
differs by the substrates applied, as shown on the example of
sterically less demanding 22b, where solely 3 % ee are charac-
teristic. The high discrepancies of the ee for different substrates
is in accordance with DFT calculations, where a complex inter-
play of all three catalytic steps was identified as enantio-deter-
mining, especially in case of the Suzuki-Miyaura reaction, and
therefore highly susceptible to substrate shapes.[44] Comparison
of the SPh functionalized species 13a with the recently re-
ported results of the OPh derivative reveals a similar ee of 8 %
(Table 1) and 12 %, respectively, whereby different substrates
were investigated.[9] The therein reported higher values of 37 %
ee, observed for a CH2–O–fenchyl ligand, are most likely due to
the C-stereogenic of the fenchyl group, instead of the planar-
chirality.[9]
Scheme 10. Attempted desulfurization of (Sp)-8 to (Sp)-8a and a subsequent
phenol formation.
Conclusions
The acid-catalyzed dehydration of ferrocene (Sp)-2-CH2OH-1-
(P(=S)Ph2)-Fc (Fc = Fe(η5-C5H5)(η5-C5H3)) to an α-ferrocenyl car-
bocation and its subsequent reaction with electron-rich arenes
PhX (X = NH2, NMe2, NiPr2, NPh2, PPh2, P(=S)Ph2, OH, SH, SMe)
is reported. They either underwent electrophilic aromatic sub-
stitution reactions (SEAr) in ortho and para position, or nucleo-
+
philically attacked the CH2 group (SN) with the hetero atom X,
resulting in new planar-chiral benzyl-, or ether-type products,
respectively. Phosphorus-based arenes (PPh3, P(=S)Ph3) did nei-
ther undergo SN, nor SEAr reactions with the carbocation. The
more nucleophilic SH group exclusively underwent nucleophilic
substitution to afford a CH2SPh functionality, contrary to the
respective phenol derivative, where ortho-functionalization
took place. It could be shown that the P(=S)Ph2 functionality
could act as a sulfur source, which transfers a single S atom
+
towards an in situ-formed 2-CH2 unit, by starting with 2-
CH2OH-1-P(=S)Ph2-Fc. This unique reaction pathway was ex-
tended to the isostructural selenium derivative 2-CH2OH-1-
P(=Se)Ph2-Fc to investigate the influence of the P=E bond
strength (E = S, Se). It was found that within these studies a
single selenium atom transfer was observed, when 2-CH2OH-1-
(P(=Se)Ph2)-Fc was treated with Sangers reagent, which is a
unique phenomenon for selenium compounds. 77Se{1H} NMR
spectroscopy and single-crystal X-ray diffraction analysis con-
firmed the presence of two chemically different selenium at-
oms. The SN- (CH2XPh; X = NH, S) and SEAr-derived (CH2–(2-
X-C6H4); X = NMe2, OH) ferrocenes, bearing an ortho-P(=S)Ph2
functionality, were reduced to their respective PIII species and
applied in Suzuki-Miyaura C,C cross-coupling reactions for the
synthesis of hindered biaryls. At catalyst loadings of 1 mol-%
[Pd], biaryls with an ee of up to 69 % were formed, which is
unique for planar-chiral ferrocenes. This confirms that the
herein reported 2-NMe2-C6H4-CH2-substituted planar-chiral fer-
rocenyl backbone is in principle sufficient for an efficient chiral-
ity transfer within a catalytic cycle.
Figure 5. Atropselective Pd-catalyzed Suzuki-Miyaura C,C cross-coupling reac-
tions for the synthesis of ortho-substituted biaryls 22a–c using o-(Sp)-5a,8a
and (Sp)-2a,13a as ligands L. Reaction conditions: i) aryl bromide (1 mmol),
boronic acid (1.5 mmol), [Pd2(dba)3] (0.5 mol-%), L (2 mol-%), K3PO4·H2O
(3 mmol), toluene (3 mL), 70 °C, 24 h. Reaction times have not been opti-
mized; a) taken from reference 13; b) 1 mol-% of the ligand; Fc* = Fe(η5-
C5H5)(η5-2-(PPh2)-C5H3).
The enantiomeric excess (ee) of the resulting biaryls 22a–c
was determined with chiral HPLC (Figure S1). Most of the reac-
tions resulted in an ee of 10–20 %. Comparison with recent re-
sults, indicate that this is based on the steric effect of the ortho
CH2R group instead of an effective hemilabile bonding of donor
atoms. This is supported by the results of sterically most de-
manding biaryl 22c, showing an in general higher ee. Ligand
13a has been used within various catalytic reactions, with op-
posed stereoselectivities.[14,42] Its bidentate binding behavior is
reported for several transition metals, including Pd.[43]
Herein, the highest ee was observed for ortho NMe2-substi-
tuted o-(Sp)-5a, which gave 22a in 69 % and hence the highest
value for planar-chiral ferrocenes so far.
The absence of P and C stereocenters further verifies that
exclusively using the planar-chirality of a ferrocenyl backbone
Experimental Section
General. All reactions were carried out under an atmosphere of
can effectively be converted onto sterically demanding sub- argon using standard Schlenk techniques. Reaction flasks were
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Full Paper
heated at reduced pressure with a heat gun and flushed with argon.
General procedure for the reaction of (Sp)-1 with substituted
This procedure was repeated thrice. If necessary, solvents were de- benzenes (GP1)
oxygenated by standard procedures. For column chromatography
silica with a particle size of 40 – 60 μm (230 – 400 mesh (ASTM))
was used.
Compound (Sp)-1a (1 equiv) was dissolved in 50 mL of 1,4-dioxane
followed by the addition of pTsOH (3 or 6 equiv), the respective
arene (3 or 5 equiv) and MgSO4 (1.0 g). The reaction mixture was
heated for 24 h at 90 °C followed by concentration in vacuo. The
residue was collected in diethyl ether (50 mL) and washed with
water. The aqueous phase was extracted thrice with diethyl ether
(50 mL each). All organic phases were combined and dried with
MgSO4 followed by the removal of all volatiles in vacuo. Purification
was realized by column chromatography on silica (column size see
below) using various eluent mixtures followed by evaporation of all
volatiles in vacuo.
The assignment and labeling of the H and C atoms in the NMR
spectra follows the IUPAC recommendations.[45]
Reagents. Tetrahydrofuran was purified by distillation from sodium/
benzophenone ketyl. Dichloromethane, hexane and toluene were
dried and purified with an MBraun SPS–800 purification system and
stored over molecular sieve (4 Å). Aniline and N,N-dimethylaniline
were distilled prior to use. Compounds (Sp)-1a,[9] (Sp)-1b,[29] (Sp)-
2-CH2OH-1-PPh2-2-Fc (Sp)-10,[46] rac-10,[12] N,N-diisopropylaniline[47]
and 1-bromo-2-phenylnaphthaline[48] were synthesized according
to literature procedures reported elsewhere. All other chemicals
were purchased from commercial suppliers and were used without
further purification.
Reaction of (Sp)-1a with aniline
Compound (Sp)-1a (600 mg, 1.40 mmol), pTsOH (1.58 g, 8.4 mmol)
and aniline (0.38 mL, 4.2 mmol) were reacted according to GP1.
Purification was realized by column chromatography (silica,
4 × 16 cm) using a 5:1 hexane/ethyl acetate mixture (v/v) as the
eluent. As first fraction (Sp)-2 could be eluted, followed by a mixture
of o-(Sp)-3 and (Sp)-4 and finally p-(Sp)-3. A further column chromat-
ographic work-up (silica, 2.5 × 20 cm, CHCl3) separated the obtained
mixture into (Sp)-4, as the first fraction and o-(Sp)-3 as the second
one.
Instruments. FT-IR spectra were recorded as KBr pellets in the tran-
sition mode with a Nicolet IR 200 spectrometer (Thermo Comp).
NMR spectra were recorded with a Bruker Avance III 500 spectrome-
ter (500.3 MHz for 1H, 125.8 MHz for 13C, 202.5 MHz for 31P and
95.4 MHz for 77Se) are reported with chemical shifts in δ (ppm)
units downfield from tetramethylsilane with the solvent as the refer-
ence signal ([D1]chloroform1: 1H at 7.26 ppm and 13C{1H} at
77.00 ppm), by external standards (31P{1H} relative to 85 % H3PO4,
0.0 ppm and P(OMe)3, 139.0 ppm; 77Se{1H} relative to Ph2Se2,
463 ppm[49]) or by the 2H solvent lock signal.[50] Two decimal places
for 13C{1H} values are given to clarify the assignment of signals,
which are in close proximity to each other. The melting or decompo-
sition points were determined by using a Gallenkamp MFB 595
010 M melting point apparatus. Elemental analyses were performed
with a Thermo FlashAE 1112 instrument. High-resolution mass spec-
tra were recorded with a Bruker Daltonik micrOTOF-QII spectrome-
ter.
(Sp)-2-(N-Phenylaminomethyl)-1-(thiodiphenylphosphino)-
ferrocene (Sp)-2
Yield: 156 mg (0.308 mmol, 22 % based on (Sp)-1a). Orange solid.
Anal. Calcd for C29H26FeNPS·2 CH2Cl2 (507.39·2 116.99 g/mol): C,
54.98; H, 4.46; N, 2.07; found C, 54,96; H, 4.76; N, 1.90. Mp: 35 °C.
1H NMR (CDCl3, δ): 3.71–3.72 (m, 1H, C5H3), 4.07 (s/br, 1H, NH), 4.16
2
(d, JH,H = 14.8 Hz, 1H, CH2), 4.25–4.27 (m, 1H, C5H3), 4.32 (s, 5H,
2
C5H5), 4.62–4.62 (m, 1H, C5H3), 4.77 (d, JH,H = 14.8 Hz, 1H, CH2),
3
3
6.19 (d, JH,H = 7.7 Hz, 2H, 2,6-C6H5N), 6.56 (t, JH,H = 7.3 Hz, 1H, 4-
C6H5N), 6.98 (dd, 3JH,H = 8.3 Hz, 3JH,H = 7.5 Hz, 2H, 3,5-C6H5N), 7.25–
7.29 (m, 2H, C6H5), 7.39–7.43 (m, 1H, C6H5), 7.45–7.54 (m, 5H, C6H5),
7.78–7.83 (m, 2H, C6H5) ppm. 13C{1H} NMR (CDCl3, δ): 41.4 (1C, CH2),
68.7 (d, JC,P = 10.3 Hz, 1C, C5H3), 70.6 (s, 5C, C5H5), 74.0 (d, JC,P
HPLC measurements were performed with a Knauer system consist-
ing of a HPLC Pump K-500 and an UV detector K-2000 operating at
245 nm equipped with Chiralcel OD-H or OJ-H columns
(4.6 × 250 mm) using hexane/isopropanol mixtures as the eluents.
Retention times (t) are reported in minutes.
1
=
95.0 Hz, 1C, CC5H3–P), 74.56 (d, JC,P = 12.2 Hz, 1C, C5H3), 74.61 (d,
2
JC,P = 9.6 Hz, 1C, C5H3), 90.8 (d, JC,P = 10.2 Hz, 1C, CC5H3–C), 112.6
(2C, 2,6-C6H5N), 116.6 (1C, 4-C6H5N), 128.0 (d, JC,P = 12.4 Hz, 2C,
C6H5), 128.3 (d, JC,P = 12.4 Hz, 2C, C6H5), 128.8 (2C, 3,5-C6H5N), 131.1
4
4
Single crystal X-ray diffraction analysis. Data were collected with
an Oxford Gemini S diffractometer ((Sp)-2, o-(Sp)-5, o-(Sp)-8, rac-1b
and rac-19) and a Venture D8 diffractometer (p-(Sp)-7, (Sp)-13 and
rac-1c) with Cu K α radiation (λ = 1.54184 Å; (Sp)-2, o-(Sp)-5, p-(Sp)-
7, o-(Sp)-8, (Sp)-13 and rac-1c) and Mo Kα radiation (λ = 0.71073 Å,
rac-1b and rac-19) at 100 K (p-(Sp)-7, rac-1c), 120–125 K ((Sp)-2, o-
(Sp)-5, o-(Sp)-8, rac-1b and rac-19) and ambient conditions ((Sp)-13).
Measurements with Cu Kα radiation at the D8 Venture device were
performed with a fine-focus source. The molecular structures were
solved by direct methods using SHELXS-13[51] and refined by full-
matrix least-squares procedures on F2 using SHELXL-13.[52,53] All
non-hydrogen atoms were refined anisotropically and a riding
model was employed in the treatment of the hydrogen atom posi-
tions, except otherwise noted. Graphics of the molecular structures
have been created by using ORTEP.[54]
(d, JC,P = 2.9 Hz, 1C, 4-C6H5), 131.3 (d, JC,P = 3.0 Hz, 1C, 4-C6H5),
131.7 (d, JC,P = 10.7 Hz, 2C, C6H5), 132.0 (d, JC,P = 10.9 Hz, 2C, C6H5),
133.1 (d, JC,P = 86.1 Hz, 1C, qC6H5), 134.6 (d, JC,P = 86.8 Hz, 1C,
1
1
qC6H5), 147.2 (1C, qC–NH) ppm. 31P{1H} NMR (CDCl3, δ): 41.7 ppm.
IR data (KBr, ν = ): 3388 (NH), 3072, 3059, 3039, 2964, 2929, 2851,
˜
1598, 1503, 1479, 1436, 1309, 1207, 1165, 1043, 822, 756, 735 (P=
S), 612, 552, 533 cm–1
.
Crystal Data for (Sp)-2: C29H26FeNPS, M = 507.39 g mol–1, ortho-
rhombic, P212121, λ = 1.54184 Å, a = 8.8945(4) Å, b = 14.0045(8) Å,
c = 19.5825(10) Å, V = 2439.3(2) Å3, Z = 4, ρcalcd = 1.382 Mg m–3
,
μ = 6.502 mm–1, T = 119.95(10) K, θ range 3.881–64.493°, 10108
reflections collected, 4055 independent reflections (Rint = 0.0277),
R1 = 0.0293, wR2 = 0.0719 [I > 2σ(I)], absolute structure parameter[38]
–0.009(2).
(Sp)-2-((2-Aminophenyl)methyl)-1-(thiodiphenylphosphino)-
ferrocene o-(Sp)-3
CCDC 1868002 (for (Sp)-2), 1868003 (for o-(Sp)-5), 1868004 (for p-
(Sp)-7), 1868005 (for o-(Sp)-8), 1868006 (for (Sp)-13), 1868007 (for
rac-1b), 1868008 (for rac-1c), and 1868009 (for rac-19) contain the
supplementary crystallographic data for this paper. These data can
be obtained free of charge from The Cambridge Crystallographic
Data Centre.
Yield: 217 mg (0.427 mmol, 31 % based on (Sp)-1a). Orange solid.
Anal. Calcd for C29H26FeNPS·4 CH2Cl2 (507.41·4 84.93 g/mol): C,
46.79; H, 4.05; N, 1.65; found C, 46.69; H, 4.45; N, 1.52 (*best match).
Mp: 197–201 °C. 1H NMR (CDCl3, δ): 3.68 (dd, J = 3.8, 2.3 Hz, 1H,
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2
4
4
C5H3), 3.81 (br, 2H, NH2), 3.85 (d, JH,H = 15.9 Hz, 1H, CH2), 3.93 (d,
131.1 (d, JC,P = 3.0 Hz, 1C, C6H5), 131.2 (d, JC,P = 2.9 Hz, 1C, C6H5),
131.4 (d, 4JC,P = 2.8 Hz, 1C, C6H5), 131.7 (d, JC,P = 10.7 Hz, 2C, C6H5),
131.9 (d, JC,P = 10.6 Hz, 2C, C6H5), 132.0 (d, JC,P = 10.8 Hz, 4C, C6H5),
2JH,H = 15.9 Hz, 1H, CH2), 4.25 (dd, J = 4.1, 2.5 Hz, 1H, C5H3), 4.33 (s,
5H, C5H5), 4.45 (dd, J = 3.8, 1.9 Hz, 1H, C5H3), 6.43 (dd, 3JH,H = 7.9 Hz,
3
4
1
1
4JH,H = 1.1 Hz, 1H, C6H4), 6.57 (td, JH,H = 7.4 Hz, JH,H = 1.2 Hz, 1H,
133.2 (d, JC,P = 85.9 Hz, 1C, qC6H5), 133.7 (d, JC,P = 85.9 Hz, 1C,
3
4
C6H4), 6.88 (td, JH,H = 7.7 Hz, JH,H = 1.5 Hz, 1H, C6H4), 6.97 (dd,
qC6H5), 134.2 (d, 1JC,P = 86.7 Hz, 1C, qC6H5), 134.6 (d, 1JC,P = 86.8 Hz,
3JH,H = 7.6 Hz, JH,H = 1.4 Hz, 1H, C6H4), 7.22–7.26 (m, 2H, C6H5),
1C, C6H5), 145.3 (1C, CC6H4–NH) ppm. 31P{1H} NMR (CDCl3, δ): 41.7,
4
q
7.34–7.37 (m, 1H, C6H5), 7.45–7.53 (m, 5H, C6H5), 7.78–7.83 (m, 2H,
42.2 ppm.
C6H5) ppm. 13C{1H} NMR (CDCl3, δ): 28.9 (1C, CH2), 68.6 (d, JC,P
=
Reaction of (Sp)-1 with N,N-dimethylaniline
10.5 Hz, 1C, C5H3), 70.8 (s, 5C, C5H5), 73.67 (d, JC,P = 9.8 Hz, 1C,
C5H3), 73.73 (d, 1JC,P = 95.5 Hz, 1C, CC5H3–P), 74.28 (d, JC,P = 13.0 Hz,
Compound (Sp)-1a (600 mg, 1.40 mmol), pTsOH (1.58 g, 8.4 mmol)
and aniline (0.48 mL, 4.2 mmol) were reacted according to GP1.
Purification was realized by column chromatography (silica,
4 × 14 cm) using a 5:1 hexane/ethyl acetate mixture (v/v) as the
eluent. At first o-(Sp)-5 could be eluted, followed by (Sp,Sp)-12
(126 mg, 0.438 mmol, 31 % based on (Sp)-1a) containing traces
(< 5 %) of p-(Sp)-5 in a non-separable mixture.
2
1C, C5H3), 92.0 (d, JC,P = 12.6 Hz, 1C, CC5H3–C), 115.7 (1C, C6H4),
118.0 (1C, C6H4), 124.9 (1C, CC6H4–C), 126.9 (1C, C6H4), 127.97 (d,
JC,P = 12.5 Hz, 2C, C6H5), 128.01 (d, JC,P = 12.4 Hz, 2C, C6H5), 130.2
4
4
(1C, C6H4), 131.1 (d, JC,P = 2.9 Hz, 1C, 4-C6H5), 131.3 (d, JC,P
=
=
2.9 Hz, 1C, 4-C6H5), 131.8 (d, JC,P = 10.6 Hz, 2C, C6H5), 132.0 (d, JC,P
10.9 Hz, 2C, C6H5), 133.2 (d, JC,P = 86.2 Hz, 1C, qC6H5), 133.8 (d,
1JC,P = 86.4 Hz, 1C, qC6H5), 144.3 (1C, C–NH2) ppm. 31P{1H} NMR
(CDCl3, δ): 42.2 ppm.
1
(Sp)-2-((2-(N,N-Dimethylamino)phenyl)methyl)-1-(thiodiphenyl-
phosphino)-ferrocene o-(Sp)-5
(Sp)-2-((4-Aminophenyl)methyl)-1-(thiodiphenylphosphino)-
ferrocene p-(Sp)-3
Yield: 93 mg (0.18 mmol, 13 % based on (Sp)-1a). Orange solid. Anal.
Calcd for C31H30FeNPS·1/6 C6H14 (535.46·1/6 86.18 g/mol): C, 69.90;
H, 5.93; N, 2.55; found C, 69.82; H, 6.22; N, 2.33. Mp: 167–170 °C. H
NMR (CDCl3, δ): 2.56 (s, 6H, CH3), 3.73 (dd, J = 3.7, 2.2 Hz, 1H, C5H3),
4.14 (s, 2H, CH2), 4.18 (dd, J = 4.1, 2.4 Hz, 1H, C5H3), 4.24–4.25 (m,
1
Compound p-(Sp)-3 was obtained in a mixture with its ortho-deriva-
tive. NMR-Yield: 139 mg (0.247 mmol, 20 % based on (Sp)-1a).
Orange solid.
3
4
1H, C5H3), 4.34 (s, 5H, C5H5), 6.76 (td, JH,H = 7.4 Hz, JH,H = 1.3 Hz,
1H NMR (CDCl3, δ): 3.47 (br, 2H, NH2), 3.65 (dd, J = 3.7, 2.2 Hz, 1H,
C5H3), 3.83 (d, 2JH,H = 15.2 Hz, 1H, CH2), 4.06 (d, 2JH,H = 15.2 Hz, 1H,
CH2), 4.21 (dd, J = 4.0, 2.4 Hz, 1H, C5H3), 4.32 (s, 5H, C5H5), 4.36–
3
4
1H, C6H4), 6.99 (dd, JH,H = 7.6 Hz, JH,H = 1.4 Hz, 1H, C6H4), 7.01
3
4
3
(dd, JH,H = 8.0 Hz, JH,H = 1.2 Hz, 1H, C6H4), 7.07 (td, JH,H = 8.0 Hz,
4JH,H = 1.5 Hz, 1H, C6H4), 7.30–7.34 (m, 2H, C6H5), 7.39–7.42 (m, 1H,
C6H5), 7.44–7.52 (m, 3H, C6H5), 7.63–7.67 (m, 2H, C6H5), 7.82–7.87
(m, 2H, C6H5) ppm. 13C{1H} NMR (CDCl3, δ): 29.7 (1C, CH2), 45.0 (2C,
3
3
4.37 (m, 1H, C5H3), 6.36 (d, JH,H = 8.3 Hz, 2H, C6H4), 6.83 (d, JH,H
=
8.2 Hz, 2H, C6H4), 7.22–7.25 (m, 2H, C6H5), 7.35–7.39 (m, 1H, C6H5),
7.42–7.51 (m, 5H, C6H5), 7.77–7.81 (m, 2H, C6H5) ppm. 13C{1H} NMR
(CDCl3, δ): 33.1 (1C, CH2), 68.5 (d, JC,P = 10.6 Hz, 1C, C5H3), 70.7 (5C,
CH3), 68.2 (d, JC,P = 10.5 Hz, 1C, C5H3), 70.8 (5C, C5H5), 73.9 (d, JC,P
=
1
13.1 Hz, 1C, C5H3), 73.8 (d, JC,P = 95.6 Hz, 1C, CC5H3–P), 74.1 (d,
1
2
C5H5), 73.5 (d, JC,P = 9.8 Hz, 1C, C5H3), 73.4 (d, JC,P = 95.5 Hz, 1C,
JC,P = 9.9 Hz, 1C, C5H3), 93.4 (d, JC,P = 12.5 Hz, 1C, CC5H3–C), 119.2
2
CC5H3–P), 74.3 (d, JC,P = 13.0 Hz, 1C, C5H3), 93.5 (d, JC,P = 12.5 Hz,
(1C, C6H4), 122.8 (1C, C6H4), 126.6 (1C, C6H4), 127.9 (d, JC,P = 12.4 Hz,
2C, C6H5), 128.0 (d, JC,P = 12.5 Hz, 2C, C6H5), 130.6 (1C, C6H4), 130.9
1C, CC5H3–C), 114.7 (2C, C6H4), 127.91 (d, JC,P = 12.3 Hz, 2C, C6H5),
127.93 (d, 1JC,P = 12.5 Hz, 2C, C6H5), 129.8 (2C, C6H4), 130.6 (d, 4JC,P
2.9 Hz, 1C, 4-C6H5), 130.7 (1C, CC6H4–CH2), 131.1 (d, JC,P = 2.9 Hz,
=
4
4
(d, JC,P = 2.9 Hz, 1C, 4-C6H5), 131.0 (d, JC,P = 3.0 Hz, 1C, 4-C6H5),
131.9 (d, JC,P = 10.2 Hz, 2C, C6H5), 132.0 (d, JC,P = 10.0 Hz, 2C, C6H5),
133.8 (d, 1JC,P = 85.9 Hz, 1C, 1-C6H5), 134.1 (d, 1JC,P = 86.2 Hz, 1C, 1-
C6H5), 135.4 (1C, CC6H4–C), 152.6 (1C, C–N) ppm. 31P{1H} NMR (CDCl3,
4
1C, 4-C6H5), 131.9 (d, JC,P = 10.6 Hz, 2C, C6H5), 132.0 (d, JC,P
=
1
10.8 Hz, 2C, C6H5), 133.7 (d, JC,P = 85.9 Hz, 1C, qC6H5), 134.2 (d,
1JC,P = 86.7 Hz, 1C, qC6H5), 144.0 (1C, qC–NH2) ppm. 31P{1H} NMR
(CDCl3, δ): 42.1 ppm.
δ): 41.9 ppm. IR data (KBr, ν = ): 3091, 3068, 2924, 2855, 1591, 1461,
˜
1309, 1145, 1105, 1034, 945, 824, 765, 747, 692, 660, 545,
506 cm–1. HRMS (ESI-TOF, m/z): calcd. for C31H30FeNPS 536.1259,
found 536.1302 [M]+.
(Sp,Sp)-N,4-Bis((2-(thiodiphenylphosphino)ferrocene-1-yl)meth-
yl)aniline (Sp,Sp)-4
Crystal Data for o-(Sp)-5: C31H30FeNPS, M = 535.44 g mol–1, mono-
clinic, P21, λ = 1.54184 Å, a = 9.9736(12) Å, b = 12.5762(14) Å, c =
Yield: 20 mg (0.022 mmol, 2 % based on (Sp)-1a). Orange oil. 1H
NMR (CDCl3, δ): 3.62 (dd, J = 3.7, 2.3 Hz, 1H, C5H3), 3.70 (dd, J = 3.7,
2.3 Hz, 1H, C5H3), 3.78 (d, 2JH,H = 15.2 Hz, 1H, CH2), 3.86 (br, 1H, NH),
11.1041(12) Å, ꢀ = 107.584(13) °, V = 1327.7(3) Å3, Z = 2, ρcalcd
=
1.339 Mg m–3, μ = 6.000 mm–1, T = 120 K, θ range 4.177–64.490°,
4958 reflections collected, 3096 independent reflections (Rint
2
2
3.95 (d, JH,H = 15.2 Hz, 1H, CH2), 4.10 (d, JH,H = 14.7 Hz, 1H, CH2),
4.19 (dd, J = 4.1, 2.5 Hz, 1H, C5H3), 4.26 (dd, J = 4.0, 2.4 Hz, 1H,
C5H3), 4.30 (s, 5H, C5H5), 4.31 (s, 5H, C5H5), 4.34 (dd, J = 3.7, 1.8 Hz,
1H, C5H3), 4.58 (dd, J = 3.8, 1.7 Hz, 1H, C5H3), 4.63 (d, 2JH,H = 14.7 Hz,
=
0.0641), R1 = 0.0548, wR2 = 0.1211 [I > 2σ(I)], absolute structure pa-
rameter[38] 0.006(9).
3
3
1H, CH2), 5.91 (d, JH,H = 8.5 Hz, 2H, C6H4), 6.67 (d, JH,H = 8.5 Hz,
2H, C6H4), 7.16–7.20 (m, 2H, C6H5), 7.24–7.27 (m, 2H, C6H5), 7.28–
7.32 (m, 1H, C6H5), 7.38–7.54 (m, 11H, C6H5), 7.76–7.82 (m, 2H, C6H5)
ppm. 13C{1H} NMR (CDCl3, δ): 33.1 (1C, CH2), 41.6 (1C, CH2), 68.4 (d,
JC,P = 10.4 Hz, 1C, C5H3), 68.7 (d, JC,P = 10.3 Hz, 1C, C5H3), 70.6 (5C,
Synthesis of 2-((4-(diphenylamino)phenyl)methyl)-1-(thiodi-
phenyl-phosphino)-ferrocene p-(Sp)-7
Compound (Sp)-1a (600 mg, 1.40 mmol), pTsOH (1.58 g, 8.4 mmol)
and triphenylamine (1.72 g, 7.0 mmol) were reacted according to
GP1. Purification was realized by column chromatography (silica,
4 × 14 cm) using a 5:1 hexane/ethyl acetate mixture (v/v) as the
eluent, which gave o-(Sp)-5 followed by (Sp,Sp)-12 (126 mg,
0.438 mmol, 31 % based on (Sp)-1a) always containing traces
(< 5 %) of p-(Sp)-5 in a non-separable mixture. Removal of all vola-
tiles in vacuo gave (Sp)-6 as orange solid.
1
C5H5), 70.7 (5C, C5H5), 73.29 (d, JC,P = 95.6 Hz, 1C, CC5H3–P), 73.5
(d, JC,P = 9.9 Hz, 1C, C5H3), 73.9 (d, 1JC,P = 95.0 Hz, 1C, CC5H3–P), 74.2
(d, JC,P = 12.9 Hz, 1C, C5H3), 74.50 (d, JC,P = 9.6 Hz, 1C, C5H3), 74.5
2
(d, JC,P = 12.6 Hz, 1C, C5H3), 91.0 (d, JC,P = 12.0 Hz, 1C, CC5H3–C),
94.4 (d, 2JC,P = 12.5 Hz, 1C, CC5H3–C), 112.4 (2C, C6H4), 127.9 (d, JC,P
=
12.3 Hz, 2C, C6H5), 127.97 (d, JC,P = 12.4 Hz, 2C, C6H5), 128.04 (d,
JC,P = 12.4 Hz, 2C, C6H5), 128.4 (d, JC,P = 12.5 Hz, 2C, C6H5), 128.9 Yield: 357 mg (0.54 mmol, 39 % based on (Sp)-1a). Anal. Calcd for
4
(1C, CC6H4–C), 129.4 (2C, C6H4), 130.9 (d, JC,P = 2.9 Hz, 1C, C6H5),
C41H34FeNPS ·[1]/2 EtOAc (659.60 ·1/2 88.11 g/mol): C, 73.40; H, 5.44;
Eur. J. Inorg. Chem. 2019, 973–987
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© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
1
N, 1.99; found C, 73.50; H, 5.38; N, 2.17. Mp: 215 °C. H NMR (CDCl3, (m, 2H, C6H5), 7.35–7.55 (m, 12H, C6H5), 7.75–7.80 (m, 4H, C6H5)
2
δ): 3.69 (dd, J = 2.2, 3.7 Hz, 1H, C5H3), 3.81 (d, JH,H = 15.1 Hz, 1H,
CH2), 4.26 (dd, J = 2.5, 4.1 Hz, 1H, C5H3), 4.33 (s, 5H, C5H5), 4.48 (d,
2JH,H = 15.1 Hz, 1H, CH2), 4.41 (m, JH,H = 1.8, 3.7 Hz, 1H, C5H3), 6.74
(d, 3JH,H = 8.5 Hz, 2H, H2-C6H4), 6.92 (d, 3JH,H = 8.5 Hz, 2H, H3-C6H4),
6.95–6.98 (m, 6H, C6H5), 7.19–7.25 (m, 6H, C6H5), 7.33–7.37 (m, 1H,
C6H5), 7.44–7.52 (m, 5H, C6H5), 7.77–7.82 (m, 2H, C6H5) ppm. 13C{1H}
NMR (CDCl3, δ): 33.5 (CH2), 68.9 (d, 3JP, C = 10.5 Hz, C5H3), 70.9 (C5H5),
ppm. 13C{1H} NMR (CDCl3, δ): 27.2 (o-CH2), 33.4 (p-CH2), 68.7 (d,
JC,P = 10.5 Hz, C5H3), 69.2 (d, JC,P = 10.6 Hz, C5H3), 70.8 (5C, C5H5),
70.9 (5C, C5H5), 73.20 (d, JC,P = 9.8 Hz, C5H3), 73.27 (d, 1JC,P = 96.0 Hz,
1
CC5H3–P), 73.29 (d, JC,P = 95.7 Hz, CC5H3–P), 73.6 (d, JC,P = 9.3 Hz,
C5H3), 73.8 (d, JC,P = 13.1 Hz, C5H3), 74.5 (d, JC,P = 13.0 Hz, C5H3),
92.7 (d, 2JC,P = 12.8 Hz, CC5H3–(o-)CH2), 94.2 (d, 2JC,P = 12.6 Hz, CC5H3
–
(p-)CH2), 116.5 (C6-C6H3), 125.5 (C2-C6H3), 128.06 (d, 3JC,P = 12.4 Hz,
1
3
3
3
73.7 (d, JP, C = 90.1 Hz, CC5H3–P), 74.1 (d, JP, C = 9.8 Hz, C5H3), 74.5
C3/5-C6H5), 128.11 (d, JC,P = 12.3 Hz, C3/5-C6H5), 128.21 (d, JC,P =
2
2
3
(d, JP, C = 12.9 Hz, C5H3), 93.0 (d, JP, C = 12.6 Hz, CC5H3–C), 122.4 (p- 12.3 Hz, C3/5-C6H5), 128.23 (C5-C6H3), 128.3 (d, JC,P = 12.1 Hz, C3/
C6H5N, 2C), 123.8 (o-C6H5N, 4C), 124.3 (C2-C6H4, 2C), 128.0 (d, 3JC,P
=
5-C6H5), 131.0 (d, JC,P = 2.8 Hz, C4-C6H5), 131.15 (C3-C6H3), 131.25
4
3
4
4
3.9 Hz, m-C6H5, 2C), 128.1 (d, JC,P = 3.7 Hz, m-C6H5, 2C), 129.2 (m- (d, JC,P = 2.8 Hz, C4-C6H5), 131.4 (d, JC,P = 2.8 Hz, C4-C6H5), 131.6
C6H5N, 4C), 129.7 (C3-C6H4, 2C), 131.1 (d, JC,P = 2.9 Hz, p-C6H5), (d, 4JC,P = 2.8 Hz, C4-C6H5), 131.84 (d, 4JC,P = 10.6 Hz, 2C, C2/6-C6H5),
4
131.3 (d, 4JC,P = 2.9 Hz, p-C6H5), 132.1 (d, 2JC,P = 8.5 Hz, o-C6H5, 2C),
132.2 (d, 2JC,P = 8.7 Hz, o-C6H5, 2C), 133.8 (d, 1JC,P = 79.8 Hz, qC6H5),
131.86 (d, JC,P = 10.7 Hz, 2C, C2/6-C6H5), 132.1 (d, JC,P = 9.9 Hz,
4
4
4
2C, C2/6-C6H5), 132.2 (d, JC,P = 10.4 Hz, 2C, C2/6-C6H5), 132.4 (d,
134.4 (d, JC,P = 80.4 Hz, qC6H5), 135.7 (qC6H4–C), 145.3 (qC6H4–N),
1JC,P = 86.9 Hz, C6H5), 133.68 (d, JC,P = 86.5 Hz, C6H5), 133.73 (d,
1
q
1
q
148.0 (qC6H5N, 2C) ppm. 31P{1H} NMR (CDCl3, δ): 41.8 ppm. IR data
1JC,P = 85.8 Hz, C6H5), 134.35 (d, JC,P = 86.6 Hz, qC6H5), 152.1 (C–
q
1
(KBr, ν = ): 3075, 3052, 3033, 2961, 2922, 2851, 1589, 1505, 1492,
OH) ppm. 31P{1H} NMR (CDCl3, δ): 42.3, 42.7 ppm. IR data (KBr, ν =
˜
˜
1435, 1326, 1269, 1176, 1142, 1100, 1074, 813, 766, 693, 658, 642, ): 3378 (OH), 3075, 3053, 2951, 2924, 2853, 1500, 1480, 1436, 1101,
614, 546 cm–1. HRMS (ESI-TOF, m/z): calcd. for C41H34FeNPS
1040, 999, 821, 749, 712 (νP=S), 692, 651, 541 cm–1
.
659.1494, found 659.1496 [M]+.
(Sp)-2-(Phenylthiomethyl)-1-(thiodiphenylphosphino)-ferrocene
(Sp)-13
Crystal Data for p-(Sp)-7: C41H34FeNPS, M = 659.57 g mol–1, ortho-
rhombic, P212121, λ = 1.54184 Å, a = 9.664(5) Å, b = 10.122(5) Å,
c = 32.681(5) Å, V = 3197(2) Å3, Z = 4, ρcalcd = 1.370 Mg m–3, μ =
5.096 mm–1, T = 100 K, θ range 2.704–65.438°, 10704 reflections
collected, 4882 independent reflections (Rint = 0.0396), R1 = 0.0321,
wR2 = 0.0720 [I > 2σ(I)], absolute structure parameter[38] 0.034(5).
Compound (Sp)-1a (600 mg, 1.40 mmol), pTsOH (792 mg, 4.2 mmol)
and thiophenol (0.43 mL, 4.2 mmol) were reacted according to GP1.
Purification was realized by column chromatography (silica,
4 × 16 cm) using a 6:1 hexane/ethyl acetate mixture (v/v) as the
eluent. Removal of all volatiles in vacuo gave (Sp)-6 as an orange
solid. The analytical data are in agreement with those reported in
literature.[14]
Reaction of (Sp)-1a with phenol
Compound (Sp)-1a (600 mg, 1.40 mmol), pTsOH (792 mg, 4.2 mmol)
and phenol (395 mg, 4.2 mmol) were reacted according to GP1.
Purification was realized by column chromatography (silica,
4 × 20 cm) using a 1:5 hexane/dichloromethane mixture (v/v) as the
eluent. The first fraction contained o-(Sp)-8[13] (391 mg, 0.768 mmol,
55 % based on (Sp)-1a), the second one (Sp,Sp)-9.
Yield: 605 mg (1.15 mmol, 83 % based on (Sp)-1a). Anal. Calcd for
C29H25FePS2 (524.46 g/mol): C, 66.41; H, 4.80; found C, 66.01; H,
1
4.79. Mp: 150–153 °C. H NMR (CDCl3, δ): 3.78 (dd, J = 3.8, 2.3 Hz,
1H, C5H3), 4.26 (dd, J = 4.1, 2.5 Hz, 1H, C5H3), 4.32 (s, 5H, C5H5), 4.32
(d, 2JH,H = 13.6 Hz, 1H, CH2), 4.39 (d, 2JH,H = 13.7 Hz, 1H, CH2), 4.48–
4.49 (m, 1H, C5H3), 7.12–7.16 (m, 1H, Ph), 7.20–7.24 (m, 4H, Ph),
7.37–7.41 (m, 2H, Ph), 7.45–7.50 (m, 3H, Ph), 7.50–7.54 (m, 1H, Ph),
7.64–7.68 (m, 2H, (P)Ph), 7.80–7.84 (m, 2H, (P)Ph) ppm. 13C{1H} NMR
(CDCl3, δ): 32.9 (1C, CH2), 69.1 (d, JC,P = 10.4 Hz, 1C, C5H3), 71.0 (s,
(Sp)-2-((2-Hydroxyphenyl)methyl)-1-(thiodiphenylphosphino)-
ferrocene o-(Sp)-8
Yield: 391 mg (0.768 mmol, 55 % based on (Sp)-1a). Spectroscopic
data are in agreement with those reported in reference 13.
1
5C, C5H5), 73.7 (d, JC,P = 9.1 Hz, 1C, C5H3), 74.1 (d, JC,P = 95.2 Hz,
1C, CC5H3–P), 74.6 (d, JC,P = 12.4 Hz, 1C, C5H3), 89.0 (d, 2JC,P = 11.9 Hz,
1C, CC5H3–C), 126.0 (1C, 4-(S)Ph), 128.1 (d, JC,P = 12.4 Hz, 2C, (P)Ph),
128.3 (d, JC,P = 12.5 Hz, 2C, (P)Ph), 128.7 (2C, (S)Ph), 129.7 (2C, (S)Ph),
131.31–131.35 (m, 2C, 4-(P)Ph), 132.12 (d, JC,P = 10.7 Hz, 2C, (P)Ph),
Crystal Data for o-(Sp)-8: C29H25FeOPS, M = 508.37 g mol–1
orthorhombic, P212121, λ = 1.54184 Å, a = 10.0767(9) Å, b =
,
11.2024(10) Å, c = 20.4504(19) Å, V = 2308.5(4) Å3, Z = 4, ρcalcd
=
1
132.13 (d, JC,P = 10.8 Hz, 2C, (P)Ph), 133.5 (d, JC,P = 86.2 Hz, 1C,
1.463 Mg m–3, μ = 6.892 mm–1, T = 119.95(10) K, θ range 4.324–
64.463°, 7582 reflections collected, 3611 independent reflections
(Rint = 0.0386), R1 = 0.0397, wR2 = 0.0989 [I > 2σ(I)], absolute struc-
ture parameter[38] –0.018(5).
q(P)Ph), 134.5 (d, 1JC,P = 87.2 Hz, 1C, q(P)Ph), 136.9 (1C, q(S)Ph) ppm.
31P{1H} NMR (CDCl3, δ): 41.5 ppm. IR data (KBr, ν = ): 3072, 3042,
˜
2922, 2854, 1479, 1434, 1237, 1099, 1044, 1026, 998, 822, 743, 715
(P=S), 694, 648, 546, 515 cm–1. HRMS (ESI-TOF, m/z): calcd. for
C29H25FePS2 524.0480, found 524.0491 [M]+.
(Sp,Sp)-2,4-Bis((2-(thiodiphenylphosphino)ferrocene-1-yl)meth-
yl)phenol (Sp,Sp)-9
Crystal Data for (Sp)-13: C29H25FePS2, M = 524.43 g mol–1, ortho-
rhombic, P212121, λ = 1.54184 Å, a = 9.5219(11) Å, b = 14.9476(17)
Yield: 101 mg (0.212 mmol, 15 % based on (Sp)-1a). Orange solid.
Anal. Calcd for C54H48Fe2OP2S2 ·5/6 C6H14 (950.73 ·5/6 86.18 g/mol):
Å, c = 17.7190(19) Å, V = 2521.9(5) Å3, Z = 4, ρcalcd = 1.381 Mg m–3
,
μ = 7.049 mm–1, T = 300 K, θ range 3.869–65.465°, 43520 reflections
collected, 4203 independent reflections (Rint = 0.0437), R1 = 0.0275,
wR2 = 0.0687 [I > 2σ(I)], absolute structure parameter[38] 0.033(5).
1
C, 69.30; H, 5.88; found C, 69.04; H, 6.08. Mp: 138–141 °C. H NMR
2
(CDCl3, δ): 3.36 (d, JH,H = 15.4 Hz, 1H, o-CH2), 3.60–3.63 (m, 2H,
2
2
C5H3), 3.65 (d, JH,H = 15.4 Hz, 1H, o-CH2), 3.82 (d, JH,H = 15.1 Hz,
2
1H, p-CH2), 4.06 (d, JH,H = 15.1 Hz, 1H, p-CH2), 4.18 (s, 5H, C5H5),
rac-2-(Hydroxymethyl)-1-(selanyldiphenylphosphino)-ferrocene
rac-1c
4.20–4.21 (m, 1H, (o-)C5H3), 4.25–4.27 (m, 1H, (p-)C5H3), 4.32 (s, 5H,
C5H5), 4.35–4.37 (m, 1H, (o-)C5H3), 4.40–4.42 (m, 1H, (p-)C5H3), 6.42
3
3
4
(d, JH,H = 8.2 Hz, 1H, H6-C6H3), 6.67 (dd, JH,H = 8.2 Hz, JH,H
=
rac-1-(Diphenylphosphino)-2-(hydroxymethyl)ferrocene rac-10
(400 mg, 1 mmol) and selenium (240 mg, 3 mmol) were suspended
in 50 mL of degassed dichloromethane and stirred for 18 h at 25 °C.
4
2.1 Hz, 1H, H5-C6H3), 6.73 (s, 1H, OH), 6.76 (d, JH,H = 2.1 Hz, 1H,
H3-C6H3), 7.12 (td, JH,H = 7.8 Hz, J = 3.0 Hz, 2H, C6H5), 7.23–7.28
3
Eur. J. Inorg. Chem. 2019, 973–987
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1
The excess of Se was removed by filtration thru silica by using di- (d, JC,P = 9.5 Hz, 1C, C5H3), 71.6 (5C, C5H5), 73.3 (d, JC,P = 85.3 Hz,
chloromethane as the eluent. After removal of all volatiles, (Sp)-1c
was obtained as an orange solid.
1C, CC5H3–P), 74.6 (d, JC,P = 8.8 Hz, 1C, C5H3), 75.2 (d, JC,P = 10.6 Hz,
2
1C, C5H3), 86.6 (d, JC,P = 12.7 Hz, 1C, CC5H3–C), 121.5 (1C, C6H3),
4
126.8 (1C1, C6H3), 128.33 (d, JC,P = 12.5 Hz, 1C, o-C6H5), 128.35 (d,
Yield: 478 mg (1 mmol, 99 % based on rac-10). Anal. Calcd for
4JC,P = 12.5 Hz, 1C, o-C6H5), 130.9 (1C, C6H3), 131.7 (d, 1JC,P = 77.7 Hz,
1C, 1-C6H5), 131.74–131.78 (m, 4C, p-C6H5), 132.6 (d, 2JC,P = 10.7 Hz,
C23H21FeOPSe (479.18 g/mol): C, 57.65; H, 4.42; found C, 58.06; H,
2
4.34. Mp: 187–190 °C. 1H NMR (CDCl3, δ): 3.23 (dd, JH,H = 8.3 Hz,
2
1
2C, C6H5), 132.7 (d, JC,P = 11.0 Hz, 2C, C6H5), 133.0 (d, JC,P
=
3JH,H = 6.5 Hz, 1H, CH2), 3.74–3.76 (m, 1H, C5H3), 4.30–4.33 (m, 2H,
78.5 Hz, 1C, 1-C6H5), 144.7 (1C, C6H3–NO2), 144.8 (1C, C6H3–NO2),
C5H3, OH), 4.33 (s, 5H, C5H5), 4.60–4.61 (m, 1H, C5H3), 4.80 (dd,
145.4 (1C, CC6H3–Se) ppm. 31P{1H} NMR (CDCl3, δ): 29.8 (J31P,77Se
=
2
3JH,H = 12.9 Hz, JH,H = 8.3 Hz, 1H, CH2), 7.35–7.39 (m, 2H, C6H5),
727.4 Hz) ppm. 77Se{1H} NMR (CDCl3, δ): –261.3 (d, 1JSe,P = 727.4 Hz,
7.42–7.46 (m, 1H, C6H5), 7.47–7.51 (m, 2H, C6H5), 7.52–7.58 (m, 3H,
P=Se), 438.0 (Se–CH2) ppm. IR data (KBr, ν = ): 3104, 3072, 2932,
˜
C6H5), 7.82–7.86 (m, 2H, C6H5) ppm. 13C{1H} NMR (CDCl3, δ): 58.4
2851, 1590 (NO2), 1508, 1437, 1342 (NO2), 1298, 1098, 1040, 916,
1
(CH2), 69.0 (d, JC,P = 9.8 Hz, C5H3), 70.7 (5C, C5H5), 73.1 (d, JC,P
=
822, 695, 560, 538 cm–1
.
86.2 Hz, CC5H3–P), 74.8 (d, JC,P = 11.0 Hz, C5H3), 75.2 (d, JC,P = 9.8 Hz,
2
2
Crystal Data for rac-19: C29H23FeN2O4PSe2, M = 708.23 g mol–1, tri-
C5H3), 93.5 (d, JC,P = 13.1 Hz, CC5H3–C), 128.3 (d, JC,P = 12.5 Hz, o-
2
4
C6H5), 128.6 (d, JC,P = 12.6 Hz, o-C6H5), 131.56 (d, JC,P = 3.0 Hz, p-
C6H5), 131.65 (d, JC,P = 77.8 Hz, C6H5), 131.8 (d, JC,P = 3.1 Hz, p-
clinic, P1, λ = 0.71073 Å, a = 9.1387(9) Å, b = 10.7598(11) Å, c =
¯
1
q
4
13.8989(15) Å, α = 80.958(9), ꢀ = 83.840(8), γ = 77.922(9) °, V =
1315.9(2) Å3, Z = 2, ρcalcd = 1.787 Mg m–3, μ = 3.441 mm–1, T =
125(1) K, θ range 2.860–24.997°, 17128 reflections collected, 4623
independent reflections (Rint = 0.0813), R1 = 0.0439, wR2 = 0.0675
[I > 2σ(I)].
3
3
C6H5), 132.1 (d, JC,P = 10.9 Hz, m-C6H5), 132.8 (d, JC,P = 11.1 Hz,
m-C6H5), 134.2 (d, JC,P = 79.0 Hz, C6H5) ppm. 31P{1H} NMR (CDCl3,
1
q
δ): 30.0 (1J31P,77Se = 709.0 Hz) ppm. 77Se {1H} NMR (CDCl3, δ): –254.6
1
(d, JC,P = 709.0 Hz) ppm. IR data (KBr, ν = ): 3448 (OH), 3078, 3046,
˜
2942, 2922, 2861, 1478, 1435, 1356, 1308, 1242, 1182, 1099, 993,
General procedure for the reduction of phosphine sulfides into
phosphines (GP2)
932, 830, 755, 694, 629, 569, 542cm–1
.
Crystal Data for rac-1c: C23H21FeOPSe, M = 479.18 g mol–1, mono-
clinic, P21/c, λ = 1.54184 Å, a = 8.674(5) Å, b = 17.656(5) Å, c =
13.345(5) Å, ꢀ = 104.990(5) °, V = 1974.2(15) Å3, Z = 4, ρcalcd = 1.612
Mg m–3, μ = 9.070 mm–1, T = 100 K, θ range 4.246–65.997°, 13895
reflections collected, 3411 independent reflections (Rint = 0.1082),
R1 = 0.0849, wR2 = 0.1899 [I > 2σ(I)].
The respective thiodiphenylphospines (Sp)-2,5,8 and 12 were dis-
solved in 50 mL of chlorobenzene followed by the dropwise addi-
tion of P(NMe2)3 (10 equiv). The reaction mixture was heated for
18 h to 130 °C and was then cooled to ambient temperature. Water
(10 mL) was carefully added. This mixture was poured into water
(200 mL) and extracted with dichloromethane (3 × 50 mL). The
combined organic extracts were dried with MgSO4 followed by re-
moval of all volatiles in vacuo. Purification was realized by column
chromatography on silica (column size see below) using various
eluent mixtures followed by evaporation of all volatiles in vacuo for
each fraction.
rac-2-((2,4-Dinitrophenyl)selenylmethyl)-1-(selanyldiphenyl-
phos-phino)-ferrocene rac-19
Compound rac-1c (160 mg, 0.334 mmol), 1-fluoro-2,4-dinitrobenz-
ene (207 mg, 1.115 mmol) and K2CO3 (260 mg, 1.86 mmol) were
dissolved in 20 mL of DMF, whereby the color immediately dark-
ened from orange to black. The reaction mixture was heated to
40 °C and stirring was continued for 18 h at this temperature. After
cooling the reaction mixture to ambient temperature, it was diluted
with 50 mL of diethyl ether and washed with acidified (HCl) brine
(50 mL). After extraction with diethyl ether (3 × 50 mL) all organic
extracts were combined and dried with MgSO4 followed by removal
of all volatiles in vacuo. Purification was realized by column chroma-
tography (silica, 2.5 × 18 cm column size) using a 9:1 hexane/di-
chloromethane mixture (v/v) as the eluent for a first fraction, con-
taining rac-19, 1-fluoro-2,4-dinitrobenzene and 2,4-dinitrophenol.
The eluent was changed to a 4:1 dichloromethane/ethyl acetate
mixture for rac-1c (70 mg, 0.144 mmol, 43 % based on rac-1c) and
a 9:1 ethyl acetate/methanol mixture for eluting rac-1b (35 mg,
0.083 mmol, 44 % based on reacted rac-1c, ESI). After removal of
all volatiles of the first fraction a solid material was obtained, which
was treated with boiling hexane (3 × 50 mL) to remove the further
excess of both 2,4-dinitroarenes. After removal of the boiling hex-
ane layer, compound rac-19 was obtained as a purple solid.
(Sp)-2-(N-Phenylaminomethyl)-1-(diphenylphosphino)-ferro-
cene (Sp)-2a
Compound (Sp)-2 (155 mg, 0.30 mmol) and P(NMe2)3 (0.92 mL,
3.0 mmol) were reacted according to GP2. Purification was realized
by column chromatography (silica, 4 × 12 cm) using a 1:2 hexane/
dichloromethane (v/v) mixture as the eluent. Removal of all volatiles
in vacuo gave (Sp)-2a as an orange solid.
Yield: 110 mg (0.23 mmol, 76 % based on (Sp)-2). Anal. Calcd for
C29H26FeNP (475.35 g/mol): C, 73.28; H, 5.51; N, 2.95; found C, 73.30;
H, 6.40; N, 2.51 (best match). Mp: 140 °C. 1H NMR (CDCl3, δ): 3.47
(s, 1H, NH), 3.72–3.74 (m, 1H, C5H3), 4.10–4.12 (s, 6H, C5H5, CH2),
4.17 (dd, 2JH,H = 13.3, J = 1.7 Hz, 1H, CH2), 4.26–4.27 (m, 1H, C5H3),
4.51–4.52 (m, 1H, C5H3), 6.35–6.37 (m, 2H, H2-C6H5N), 6.64–6.67 (m,
1H, H4-C6H5N), 7.08–7.12 (m, 2H, H3-C6H5N), 7.19–7.22 (m, 2H,
C6H5), 7.27–7.30 (m, 3H, C6H5), 7.38–7.40 (m, 3H, C6H5), 7.51–7.55
3
(m, 2H, C6H5) ppm. 13C{1H} NMR (CDCl3, δ): 42.6 (d, JC,P = 10.0 Hz,
CH2), 69.3 (C5H3), 69.8 (5C, C5H5), 71.5 (d, JP, C = 3.8 Hz, C5H3), 72.0
Yield: 67 mg (0.093 mmol, 56 % based on used rac-1c and 98 % (d, JP, C = 3.6 Hz, C5H3), 76.6 (d, 1JP, C = 7.2 Hz, CC5H3–P), 90.9 (d, 2JP, C
=
based on reacted rac-1c). Anal. Calcd for C29H23FeN2O4PSe2
23.6 Hz, CC5H3–C), 113.1 (2C, C2-C6H5N), 117.4 (C4-C6H5N), 128.3 (d,
(708.23 g/mol): C, 49.18; H, 3.27; N, 3.96; found C, 48.96; H, 3.20; N,
3JP, C = 7.6 Hz, 2C, C3/5-C6H5), 128.5 (d, 3JP, C = 6.3 Hz, 2C, C3/5-C6H5),
1
4.00. Mp: 245 °C (rapid decomp.). H NMR (CDCl3, δ): 3.80–3.82 (m,
128.6 (C4-C6H5), 129.1 (2C, C3-C6H5N), 129.3 (C4-C6H5), 132.8 (d,
2
1H, C5H3), 4.37 (d, 2JH,H = 11.3 Hz, 1H, CH2), 4.37–4.39 (m, 1H, C5H3),
2JP, C = 18.8 Hz, C2/4-C6H5 ), 134.8 (d, JP, C = 20.62 Hz, C2/4-C6H5),
4.42 (s, 5H, C5H5), 4.64–4.65 (m, 1H, C5H3), 5.19 (d, JH,H = 11.3 Hz,
137.0 (d, 1JP, C = 9.0 Hz,qC6H5 ), 139.6 (d, 1JP, C = 10.3 Hz, qC6H5), 147.9
2
1H, CH2), 7.27–7.31 (m, 2H, C6H5), 7.38–7.42 (m, 1H, C6H5), 7.46–7.58 (C1-C6H5N) ppm. 31P{1H} NMR (CDCl3, δ): –23.7 ppm. IR data (KBr,
3
(m, 5H, C6H5), 7.79 (d, JH,H 8.9 Hz, 1H, C6H3), 7.79–7.84 (m, 2H,
ν = ): 3390 (NH), 3068, 3046, 3020, 2955, 2925, 2854, 1602, 1505,
˜
C6H5), 8.22 (dd, JH,H = 8.9, JH,H = 2.5 Hz, 1H, C6H3), 8.22 (d, JH,H
=
1431, 1310, 1106, 997, 818, 748, 703, 690 cm–1. HRMS (ESI-TOF, m/z):
3
4
4
2.5 Hz, 1H, C6H3) ppm. 13C{1H} NMR (CDCl3, δ): 26.2 (1C, CH2), 69.7
calcd. for C29H26FeNP 474.1069, found 474.1082 [M]+.
Eur. J. Inorg. Chem. 2019, 973–987
www.eurjic.org
984
© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Full Paper
(Sp)-2-((2-(N,N-Dimethylamino)phenyl)methyl)-1-(diphenyl- dichloromethane (v/v) mixture as the eluent. Removal of all volatiles
phosphino)-ferrocene o-(Sp)-5a
in vacuo gave (Sp)-13a as an orange solid.
Yield: 187 mg (0.37 mmol, 98 % based on (Sp)-13). Anal. Calcd for
C29H25FePS (492.39 g/mol): C, 70.74; H, 5.12; found C, 70.92; H, 5.17.
Mp: 78–81 °C. 1H NMR (CDCl3, δ): 3.78–3.79 (m, 1H, C5H3), 4.02 (s,
Compound o-(Sp)-5 (171 mg, 0.32 mmol) and P(NMe2)3 (0.98 mL,
3.2 mmol) were reacted according to GP2. Purification was realized
by column chromatography (silica, 2.5 × 16 cm) using dichloro-
methane as the eluent. Removal of all volatiles in vacuo gave o-
(Sp)-5a as a yellow solid.
2
4
5H, C5H5), 4.06 (dd, JH,H = 13.1 Hz, JH,P = 2.2 Hz, 1H, CH2), 4.14 (d,
2JH,H = 13.1 Hz, 1H, CH2), 4.26 (t, J = 2.4 Hz, 1H, C5H3), 4.42 (dd, J =
3.7, 1.9 Hz, 1H, C5H3), 7.13–7.16 (m, 1H, C6H5), 7.17–7.26 (m, 9H,
C6H5), 7.38–7.40 (m, 3H, C6H5), 7.55–7.58 (m, 2H, C6H5) ppm. 13C{1H}
Yield: 110 mg (0.22 mmol, 68 % based on o-(Sp)-5). Anal. Calcd for
C31H30FeNP·C5H10 (503.40·70.13 g/mol): C, 75.13; H, 7.36; N, 2.43;
3
NMR (CDCl3, δ): 33.7 (d, JC,P = 12.3 Hz, 1C, CH2), 69.5 (1C, C5H3),
1
found C, 74.87; H, 7.79; N, 2.16. Mp: 79 °C. H NMR (CDCl3, δ): 2.60
69.8 (5C, C5H5), 71.3 (d, JC,P = 3.7 Hz, 1C, C5H3), 71.5 (d, JC,P = 3.6 Hz,
1C, C5H3), 75.9 (d, 1JC,P = 7.8 Hz, 1C, CC5H3–P), 89.8 (d, 2JC,P = 25.5 Hz,
1C, CC5H3–C), 126.0 (1C, 4-Ph), 127.7 (1C, 4-Ph), 127.9 (d, JC,P = 5.9 Hz,
2C, (P)Ph), 128.1 (d, JC,P = 8.0 Hz, 2C, (P)Ph), 128.7 (2C, (S)C6H5),
2
(s, 6H, CH3), 3.72–3.73 (m, 1H, C5H3), 3.90 (d, JH,H = 15.6 Hz, 1H,
2
4
CH2), 4.07 (s, 5H, C5H5), 3.09 (d, JH,H = 15.6 Hz, JH,P = 2.1 Hz, 1H,
CH2), 4.23 (dd, J = 2.4, 2.4 Hz, 1H, C5H3), 4.37 (dd, J = 3.5, 2.0 Hz,
1H, C5H3), 6.76 (td, 3JH,H = 7.5 Hz, 4JH,H = 1.2 Hz, 1H, C6H4), 6.91 (dd,
129.1 (1C, 4-Ph), 129.6 (2C, (S)Ph), 132.3 (d, JC,P = 17.7 Hz, 2C, (P)Ph),
4
3JH,H = 7.9 Hz, JH,H = 1.0 Hz, 1H, C6H4), 6.98–7.01 (m, 2H, C6H4),
1
135.0 (d, JC,P = 21.2 Hz, (P)Ph), 137.4 (1C, qPh-S), 137.4 (d, JC,P
=
7.03–7.15 (m, 5H, C6H5), 7.38–7.39 (m, 3H, C6H5), 7.56–7.60 (m, 2H,
C6H5) ppm. 13C{1H} NMR (CDCl3, δ): 29.4 (d, 3JC,P = 10.3 Hz, 1C, CH2),
44.9 (2C, CH3), 68.7 (1C, C5H3), 69.8 (5C, C5H5), 70.8 (d, JC,P = 4.0 Hz,
8.2 Hz, 1C, qPh-P), 139.7 (d, JC,P = 8.9 Hz, 1C, qPh-P) ppm. 31P{1H}
1
NMR (CDCl3, δ): –24.0 ppm. IR data (KBr, ν = ): 3068, 3048, 2925,
˜
2854, 1478, 1434, 1236, 1106, 1024, 1002, 826, 750, 741, 702, 688,
627 cm–1. HRMS (ESI-TOF, m/z): calcd. for C29H25FePS 492.0759,
found 492.0787 [M]+.
1C, C5H3), 72.4 (d, JC,P = 4.0 Hz, 1C, C5H3), 75.5 (d, 1JC,P = 6.4 Hz, 1C,
1
C
C5H3–P), 94.1 (d, JC,P = 26.0 Hz, 1C, CC5H3–C), 118.8 (1C, C6H4),
122.7 (1C, C6H4), 126.4 (1C, C6H4), 127.4 (1C, C6H5), 127.7 (d, JC,P
6.2 Hz, 2C, C6H5), 128.0 (d, JC,P = 7.7 Hz, 2C, C6H5), 128.9 (1C, C6H5),
130.0 (1C, C6H4), 132.4 (d, JC,P = 18.4 Hz, 2C, C6H5), 135.0 (d, JC,P
=
=
20.9 Hz, 2C, C6H5), 135.6 (1C, CC6H4–C), 137.9 (d, JC,P = 8.8 Hz, 1C, 1-
C6H5), 139.3 (d, JC,P = 9.8 Hz, 1C, 1-C6H5), 152.2 (1C, C–N) ppm.
Acknowledgments
M. K. thanks the Forrest Research Foundation for a postdoctoral
fellowship.
31P{1H} NMR (CDCl3, δ): –22.8 ppm. IR data (KBr, ν = ): 3068, 3053,
˜
2955, 2925, 2854, 2818, 2780, 1452, 1307, 1262, 1182, 1095, 1049,
1001, 947, 816, 742, 697, 570 cm–1. HRMS: C31H30FeNP+H calcd:
504.1544, found 504.1537 [M + H]+.
Keywords: Ferrocene · Planar chirality · C,C Cross-
coupling · Phosphine · Chiral biaryls · Selenium atom
transfer
(Sp)-2-((2-Hydroxyphenyl)methyl)-1-(diphenylphosphino)-ferro-
cene o-(Sp)-8a
Compound o-(Sp)-8 (155 mg, 0.33 mmol) and P(NMe2)3 (0.98 mL,
3.2 mmol) were reacted according to GP2. Purification was realized
by column chromatography (silica, 2.5 × 16 cm) using a 1:9 hexane/
dichloromethane mixture (v/v) as the eluent. Removal of all volatiles
in vacuo gave o-(Sp)-8a as a yellow solid in a non-separable
2:1 mixture together with phenol. (The resonances of phenol are
omitted from the data given below but can be found in the SI).
Crystallization of the mixture from hexane further purified o-(Sp)-
8a.
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2011, 33, 139–175.
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E. Manoury, R. Poli, B. Çetinkaya, A. Labande, New J. Chem. 2014, 38,
338–347.
Yield: 25 mg (0.05 mmol, 15 % based on o-(Sp)-8). Anal. Calcd for
C29H25FeOP (476.33 g/mol): C, 73.12; H, 5.29; found C, 71.57; H, 6.96
(best match). Mp: 300 °C. 1H NMR (CDCl3, δ): 3.75–3.77 (m, 2H, CH2),
3.79–3.80 (m, 1H, C5H3), 3.88 (s, 5H, C5H5) 4.26–4.27 (m, 1H, C5H3),
4.43–4.44 (m, 1H, C5H3), 5.64 (d, J = 2.8 Hz, 1H, OH), 6.69–6.72 (m,
2H, C6H4), 6.97–7.05 (m, 4H, C6H4, C6H5), 7.11–7.18 (m, 3H, C6H5),
7.39–7.42 (m, 3H, C6H5), 7.60–7.63 (m, 2H, C6H5). 13C{1H} NMR
3
(CDCl3, δ): 29.8 (d, JC,P = 1.8 Hz, CH2), 69.3 (C5H3), 69.9 (5C, C5H5),
2
70.7 (d, JC,P = 4.1 Hz, C5H3), 71.7 (d, JC,P = 4.5 Hz, C5H3), 74.8 (d,
1JC,P = 2.8 Hz, CC5H3–P), 94.2 (d, 2JC,P = 27.9 Hz, CC5H3–C), 116.3 (H3/
6-C6H4), 120.6 (H3/6-C6H4), 127.8 (H4/5-C6H4), 127.84 (H4/5-C6H4),
3
3
127.85 (CC6H4–C), 128.1 (d, JC,P = 6.2 Hz, m-C6H5), 128.3 (d, JC,P
=
=
=
4
8.3 Hz, m-C6H5), 129.6 (p-C6H5), 130.7 (p-C6H4), 132.1 (d, JC,P
4
1
17.3 Hz, p-C6H5), 135.3 (d, JC,P = 20.8 Hz, p-C6H5), 136.9 (d, JC,P
1
4.3 Hz, qC6H5), 139.1 (d, JC,P = 5.8 Hz, qC6H5), 153.5 (CC6H4-O).
31P{1H} NMR (CDCl3, δ): –22.9.
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2014, 2014, 6676–6685.
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dier, J. Organomet. Chem. 2014, 772–773, 258–264; b) A. Karpus, O. Yesy-
(Sp)-2-(Phenylthiomethyl)-1-(diphenylphosphino)-ferrocene
(Sp)-13a
Compound (Sp)-13 (200 mg, 0.381 mmol) and P(NMe2)3 (0.92 mL,
3.0 mmol) were reacted according to GP2. Purification was realized
by column chromatography (silica, 4 × 12 cm) using a 1:2 hexane/
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