Discovery and synthetic value of a novel, highly crowded cyclopentadienylphosphane Ph2P-CpH and its ferrocenyl-bisphosphane dppf

Article abstract of DOI:10.1002/ejic.200901266

Base-catalysed condensation of Ph₂P-C₅H₅ (1) with an excess of acetone leads to a fulvene-like diphenyl(4,4,6-trimethyl- 4,5-dihydropentalen-2-yl)phosphane Ph₂P-C₁₁H₁₃ (3) as a product of double condensation. Carbometallation of 3 with MeLi, followed by aqueous work-up, results in formation of a new cyclopentadienylphosphane bearing a highly sterically demanding, anellated 1,1,3,3-tetramethylcyclopentane moiety (4, Ph₂P-CpH). It reacts with chalcogene oxidants (H₂O₂, S₈, Se) to form the corresponding phosphane chalcogenides Ph₂P(=X)CpH, X = O (5), S (6), Se (7) in high yields. Quatemization of 4 with MeI gives the phosphonium salt 8 as a single isomer in high yield. Dehydrohalogenation of 8 by reaction with nBuLi gives Cp-phosphonium ylide Ph₂P(Cp )Me (9). An alternative protocol towards 9 that includes deprotonation of 8 with benzylpotassium followed by P-alkylation is superior and gives 9 in more than 95% yield. Staudinger reaction of 4 with tBuN₃ gives only P-arnino-cyclopentadienylidenephosphorane Ph₂P(Cp)-NHtBu (10), whereas with Me₃SiN₃ only the tautomeric P-imino-cyclopentadienylphosphane Ph₂P(NSiMe₃)CpH (11) was isolated. Hydrolysis of 11 with wet MeCN leads to the new parent P-arnino-cyclopentadienyhdenephosphorane Ph₂P-(Cp)NH ₂ (12). Treatment of 4 with benzylpotassium followed by transmetallation with FeCl₂ leads to the sterically most crowded ferrocenyl-bisphosphane [{Ph₂P-Cp}₂Fe] (13, dppf) in high yield. Its X-ray diffraction analysis reveals an anti-orientation of phosphane functionalities at both cyclopentadienyl rings. However, upon reaction of dppf with [PdCl₂(MeCN)₂], a constrained syn-orientation is achieved in the product [[dppf] PdCl₂] (14). Halogen exchange by reaction of 14 with NaI leads to the corresponding [{dppf}PdI₂] (15). Molecular structures of 4, 9, 13 and 15 have been confirmed by XRD studies.

Full text of DOI:10.1002/ejic.200901266

FULL PAPER
DOI: 10.1002/ejic.200901266
Discovery and Synthetic Value of a Novel, Highly Crowded
Cyclopentadienylphosphane Ph2P-CpTMH and Its Ferrocenyl-Bisphosphane
dppfTM
Alex R. Petrov,[a] Michael Elfferding,[a] Juri Möbus,[a] Klaus Harms,[a]
Konstantin A. Rufanov,[a,b] and Jörg Sundermeyer*[a]
Keywords: Phosphane ligands / Cyclopentadienyl ligands / Sandwich complexes / Phosphanes / Ferrocenes / Palladium
complexes
Base-catalysed condensation of Ph2P–C5H5 (1) with an ex- P-amino-cyclopentadienylidenephosphorane
Ph2P(CpTM)-
NHtBu (10), whereas with Me3SiN3 only the tautomeric P-
imino-cyclopentadienylphosphane
Ph2P(NSiMe3)CpTM
cess of acetone leads to a fulvene-like diphenyl(4,4,6-tri-
methyl-4,5-dihydropentalen-2-yl)phosphane Ph2P-C11H13 (3)
as a product of double condensation. Carbometallation of 3
with MeLi, followed by aqueous work-up, results in forma-
tion of a new cyclopentadienylphosphane bearing a highly
sterically demanding, anellated 1,1,3,3-tetramethylcyclo-
pentane moiety (4, Ph2P-CpTMH). It reacts with chalcogene
oxidants (H2O2, S8, Se) to form the corresponding phosphane
chalcogenides Ph2P(=X)CpTMH, X = O (5), S (6), Se (7) in
high yields. Quaternization of 4 with MeI gives the phospho-
nium salt 8 as a single isomer in high yield. Dehydrohaloge-
nation of 8 by reaction with nBuLi gives CpTM-phosphonium
ylide Ph2P(CpTM)Me (9). An alternative protocol towards 9
that includes deprotonation of 8 with benzylpotassium fol-
lowed by P-alkylation is superior and gives 9 in more than
95% yield. Staudinger reaction of 4 with tBuN3 gives only
H
(11) was isolated. Hydrolysis of 11 with wet MeCN leads to
the new parent P-amino-cyclopentadienylidenephosphorane
Ph2P-(CpTM)NH2 (12). Treatment of 4 with benzylpotassium
followed by transmetallation with FeCl2 leads to the steri-
cally most crowded ferrocenyl-bisphosphane [{Ph2P-
CpTM}2Fe] (13, dppfTM) in high yield. Its X-ray diffraction
analysis reveals an anti-orientation of phosphane functionali-
ties at both cyclopentadienyl rings. However, upon reaction
of dppfTM with [PdCl2(MeCN)2], a constrained syn-orienta-
tion is achieved in the product [{dppfTM}PdCl2] (14). Halogen
exchange by reaction of 14 with NaI leads to the correspond-
ing [{dppfTM}PdI2] (15). Molecular structures of 4, 9, 13 and
15 have been confirmed by XRD studies.
For our systematic investigation of chelating organo-
phosphorus(V) ligands of the general type [R2P(X)Z]– (X,
Z = S, NRЈ, CH2, CHRЈ, Cp, Ind, Flu; as for X = Z and
X ϶ Z)[8,9] it was necessary to synthesize Ph2P-{Cp} phos-
phanes, bearing sterically demanding substituents, e.g. a
tert-butyl group, at the C5 ring. Besides simple metathesis
of tBuCp anion with Ph2PCl, such ligand motive may be
achieved by carbometallation with MeLi of corresponding
6,6-dimethylfulvene that is easily accessible by a condensa-
tion of acetone with {Cp}H using 5–10 mol-% of pyrroli-
dine, as a catalyst, in methanol. The reaction is highly
chemoselective and, as a rule, high yields of fulvenes are
reported.[10] However, even minor changes of the reaction
conditions were found to be highly crucial to its further
transformation. Here we report our discovery of a new,
highly crowded cyclopentadienylphosphane, Ph2P-CpTMH,
its reactivity and synthetic potential.
Introduction
Cyclopentadienylphosphane ligands [R2P-{Cp}, {Cp} =
(non)-substituted Cp, Ind or Flu] are useful building blocks,
broadly applied in organometallic chemistry.[1] As struc-
tural motive they can be found in very useful ligands such
as dppf [{Ph2P-C5H4}2Fe] or CTC-Q-Phos [{Ph5C5}Fe-
{C5H4P(tBu)2}]. Most frequently R2P-{Cp} are represented
in the literature by phosphanes R2P-C5H5 (R = Me, Ph),[2]
R2P-C5Me4H (R = Me,[3] Ph[4]), (tBu)2P-C5H5,[5] 3-indenyl-
(Ph2P-C9H7)[6] and 9-fluorenyl- (Ph2P-C13H9),[7] that with
exception of 9-fluorenyl derivatives, show fluxional behav-
iour in solutions and appear as mixtures of isomers.
Commonly R2P-{Cp} are synthesized by nucleophilic
substitution of R2P–X (X = Hal, OAlk) with anionic forms
of appropriate cyclopentadienes. Nevertheless, their further
derivatization is very scarcely described in the literature.[2]
[a] Fachbereich Chemie, Philipps-Universität Marburg,
Hans-Meerwein-Str., 35032 Marburg, Germany
Tel: +49-6421-2825693
Results and Discussion
Synthesis and Molecular Structure of Ph2P-CpTM
H
E-mail: jsu@staff.uni-marburg.de
Condensation reaction of Ph2P-C5H5 (1)[2] with one
equivalent of acetone (MeOH, 10 mol-% pyrrolidine) leads
View this journal online at
[b] Chemical Diversity Research Institute,
Rabochaya 2a, Khimki, Moscow Region 141410, Russia
wileyonlinelibrary.com
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J. Sundermeyer et al.
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to the selective formation of the expected fulvenylphos- structure the bridging H2C-group of the aliphatic ring is
phane Ph2P-C8H9 (2) (Scheme 1). The product precipitates disordered with occupancies of 0.49/0.51; only one confor-
from the reaction mixture as a bright yellow, air-stable crys- mation is shown in Figure 1. As expected, the phosphorus
talline solid, 31P NMR (C6D6): δP = –16.8 ppm. Monitoring atom is threefold coordinated by two phenyl groups and a
of the reaction by 31P NMR spectroscopy indicated forma- CpTMH-moiety – all are twisted in a propeller-like arrange-
tion of ca. 10% of an unidentified impurity (δP
=
ment. The unsaturated Cp ring is essentially planar [∆max =
–13.9 ppm). By working in acetone as solvent, formation of 0.0002(2) Å for C8]. The C4 and C6 atoms of the aliphatic
2 was quantitative within minutes, however it was followed ring deviate only by values of 0.053 and 0.073(2) Å from
by conversion of 2 into this new compound 3 within 4 h as the CpTMH-ring plane.
monitored by 31P NMR spectroscopy. The structure and
composition of thus formed Ph2P-C10H13 (3) as annelated
phosphane (Scheme 1) have been confirmed by multinu-
clear and 2D NMR spectroscopic techniques, mass spectra
and elemental analysis.
Scheme 1.
Further carbometallation of 3 with MeLi in ether or hex-
ane as solvent followed by protonation of thus derived carb-
anion leads to a new annelated tetramethylpentalenyl-sub-
stituted phosphane (Ph2PCpTMH) 4, that, compared to its
3-tBu-substituted analogue, is higher both by its steric im-
pact and symmetry (Scheme 2). However, if the reaction
with MeLi is performed in THF a deprotonation of the
exocyclic fulvene methyl group of 3 rather than a carbomet-
allation took place. Phosphane Ph2P-CpTMH (4) was puri-
fied by preparative flash chromatography under anaerobic
conditions. This pale yellow needle-like crystalline material
with a faint phosphane-like odour is fairly air-stable and
can be handled and stored under aerobic conditions with-
out decomposition for months. The solubility of 4 is very
high in common organic solvents, but becomes moderate in
those ones of the higher polarity (CH3CN, MeOH) as well
as in cold lower alkanes (pentane, hexane). The molecular
structure of 4 was confirmed by multinuclear NMR spec-
troscopy, mass spectrometry, elemental and XRD single
crystal structure analysis.
Figure 1. Molecular structure of compound 4. All hydrogen atoms,
except of those at the Cp-ring, have been omitted for clarity. Se-
lected bond lengths [Å] and angles [°]: P1–C1 1.807(2), P1–C13
1.832(2), P1–C19 1.833(2), C1–C2 1.348(2), C2–C3 1.475(2), C3–
C7 1.334(2), C7–C8 1.487(2), C1–C8 1.517(2); C1–P1–C13
103.1(1), C13–P1–C19 102.3(1), C19–P1–C1 100.7(1), C1–C8–C7
102.7(1), C3–C2–C1–C8 0.2(2), C2–C3–C7–C8 0.2(2).
The average P–CPh bond length is of 1.832(3) Å and falls
in the typical range of other phosphanes Ar3P (1.82–
1.84 Å).[11] However, the P–C1 bond length is slightly
shorter [1.807(2) Å]. The olefinic bonds lengths are alter-
nating and are shorter at C1–C2 and C3–C7 with 1.348(2)
and 1.334(2) Å, respectively then other ones in the Cp ring
[C2–C3 1.475(2), C7–C8 1.487(2), C1–C8 1.517(2) Å]. All
C–P–C angles [100.7(1), 102.3(1) and 103.1(1) Å] lie in the
typical range reported for triarylphosphanes.[11] Although
several free indenyl- and fluorenylphosphanes are
known,[12] to the best of our knowledge, 4 is the first free
diorgano-cyclopentadienylphosphane characterized by X-
ray crystallography.
Reactivity of Ph2P-CpTMH as Phosphane
Scheme 2.
The phosphane 4 is readily oxidized by H2O2 (30% solu-
Crystals of the compound 4, suitable for X-ray diffrac- tion in water) in THF, elemental sulfur in toluene and red
tion analysis, were obtained by slow cooling of its hot con- selenium in CHCl3 to form corresponding chalcogenido
centrated ethanol solution. It crystallizes in the monoclinic phosphanes as air-stable, crystalline solids in high yields
space group P21/c with four molecules per cell unit. In the (Scheme 3).
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Novel, Highly Crowded Cyclopentadienylphosphane
Scheme 3.
As expected and confirmed by NMR spectroscopy, only Figure 2. Molecular structure of Ph2P(CpTM)Me (9). All hydrogen
atoms have been omitted for clarity. Only one independent mole-
one tautomeric form is observed for all these compounds.
cule is drawn. Selected bond lengths [Å] and angles [°]: P1–C1
Steric hindrance of the tetramethyltrimethylene backbone
1.714(2), P1–C13 1.803(2), P1–C19 1.802(3), P1–C25 1.795(3), C1–
prevents their dimerization by the Diels–Alder reaction typ-
C2 1.425(3), C2–C3 1.373(3), C3–C7 1.404(3), C7–C8 1.385(3), C1–
ically found for the parent C5-unsubstituted derivatives
C8 1.441(3), C1–P1–C13 107.37(12), C13–P1–C19 106.62(11),
C19–P–C1, 113.98(13), C1–P1–C25 113.72(13), C13–P1–C25
109.15(13), C19–P1–C25 105.74(13).
Ph2P(X)C5H5 (X = O, S).[2]
Quaternization of 4 with an excess of MeI leads to the
expected phosphonium salt [Ph2P(CpTMH)Me]+ I– (8)
(Scheme 4) as an air-stable, non-hygroscopic solid, that ap-
pears as a single isomer (δP = 12.2 ppm). It is worth to
mention, that sterically less hindered Ph2P-Cp and Ph2P-
Ind upon reaction with MeI lead to the mixtures of allylic
and vinylic isomers; for the Cp-derivative, Diels–Alder type
dimerization products were also obtained.[13,14] Dehydroha-
logenation of the salt 8 with nBuLi leads to the formation
of cyclopentadienyliden-phosphorane Ph2P(CpTM)Me (9)
as a pale yellow, crystalline solid in 67% yield. A superior
protocol towards 9 includes deprotonation of 4 with BnK
followed by in situ quaternization of thus obtained anionic
derivative with an excess of MeI that chemoselectively leads
to P-alkylation and gives 9 in almost quantitative yield.
the CpPN derivatives has been confirmed also for the enti-
tled ligand 4 (Scheme 5). Thus reaction of 4 with tBuN3
proceeds at ambient temperature yielding a yellow, micro-
crystalline solid as the single P-amino-cyclopentadienyl-
idenephosphorane tautomer Ph2P(CpTM)NH(tBu) (10).
The position of the NH-proton at δ = 2.04 ppm in 10 was
also established by the HMQC spectroscopy. The 31P NMR
resonance of 10 (δ =17.1 ppm) appears essentially at the
same δP as those ones of CpPN-ligands R2P(C5Me4)NHAd
(R = Me: 17.6 ppm,[8] and R = Ph: 17.8 ppm[16]). The reac-
tion of 4 with the less reactive Me3SiN3 was found to be
extremely slow and gave the desired product only if Me3-
SiN3 was used as a solvent at the reflux temperature (5 d,
ca. 100 °C). The 31P NMR monitoring the reaction mixture
after 14 h of heating reveals absence of both starting mate-
rial 4 and its Staudinger phosphazide adduct (δ = –27 ppm)
and two new resonances at ca. –5 (major) and 23 ppm
(minor). The major signal appears in the characteristic P-
iminophosphane region and belongs to the target 11,
whereas the minor signal is attributed to its tautomeric P-
aminophosphorane form similar to 10.[9] 11, the better solu-
ble tautomer was extracted from the reaction mixture into
hexane. It comprises a highly air-sensitive, crystalline solid,
that easily hydrolyzes, when in solution: first, by water
traces with release of (Me3Si)2O to P-amino-cyclopen-
tadienylidenephosphorane 12, and further by excess of
water with release of free CpTMH and precipitation of a
colorless, crystalline solid, identified as diphenylphosphinic
Scheme 4. Two alternative reaction sequences toward synthesis of
9.
Single crystals, suitable for X-ray diffraction analysis,
were obtained by storing of concentrated ether solution to
0 °C. Compound 9 crystallizes in the triclinic space group
¯
P1 with two independent molecules in the unit cell. The
molecular structure of one of these molecules is drawn in
Figure 2.
The P1–C1 bond length in 9 is significantly shorter
[1.714(2) Å] than in parent 4, this is in good agreement with
those in other cyclopentadienylidenephosphoranes.[15] An
alternating order of C–C bond lengths at the C5 ring was
observed: the short bonds are C2–C3 and C7–C8 [1.373(3)
and 1.385(3) Å], whereas C1–C2, C3–C7 and C1–C8,
respectively, are long [1.425(3), 1.404(3) and 1.441(3) Å].
Earlier, we reported the Staudinger reactions of a series
of R2P–{Cp} with organic azides.[8] Successful formation of Scheme 5. Reactions of 4 with organic azides.
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J. Sundermeyer et al.
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acid amide Ph2P(O)NH2 [δP(THF) = 25.0 ppm, m.p. 161–
162 °C].[17]
Further studies of thus obtained organophosphorus(V)
derivatives 5–12 of the title phopsphane Ph2P-CpTMH (4)
as chelating ligands in organometallic chemistry are the fo-
cus of our current investigations.
Reactivity of Ph2P-CpTMH as Bifunctional Ligand
We have studied a possibility to use 4 as a bifunctional
ligand in the synthesis of a bis-phosphanyl-substituted fer-
rocene and its further use as chelating, electron-rich and
sterically demanding ligand towards PdCl2.
Direct transmetallation of lithiated 4 by ferrous chloride
[FeCl2(THF)n] gave the desired ferrocene 13 in 28% isolated
yield (Scheme 6). A possible explanation for such a poor
yield might be a partial deprotonation of Ph2P-CpTMH due
to its low kinetic CH-acidity compared to unsubstituted
Ph2P-C5H5 (1) or the low nucleophilicity of the lithium salt.
Benzylpotassium [PhCH2K] is known as superior deproton-
ating reagent and its use instead of nBuLi gave rise to 13 in
83% isolated yield as a bright-orange, air-stable, non-vola-
tile solid. Being analogous to the prominent chelate ligand
[{Ph2P-C5H4}2Fe] (dppf),[18] we call this derivative 13
Figure 3. The molecular structure of [(CpTMPPh2)2Fe] (13). Hydro-
gen atoms have been omitted for clarity (Z = centroid of C5-ring).
Selected bond lengths [Å] and angles [°]: P1–C1 1.832(1), P1–C13
1.833(1), P1–C19 1.853(1), C1–C2 1.441(1), C2–C3 1.406(1), C3–
C7 1.400(1), C7–C8 1.427(1), C8–C1 1.437(1), Z···Fe1 1.682(1),
Fe1–C1 2.084(1), C1–P1–C13 101.2(2), C13–P1–C19 99.7(2), C19–
P1–C1 100.1(1), C8–C1–P1–C19 46.6(1), C2–C1–P1–C13 24.5(1),
P1–Z–ZЈ–P1Ј 180.00(2).
[1.682(1) Å] is slightly longer than those in [(C5H4PPh2)2Fe]
[1.646(5) Å],[20] [(Me4C5PPh2)2Fe] [1.653(1) Å].[21] Bond
lengths and angles involving the phosphorus atoms com-
pare well with the values in triphenylphosphane,
[(C5H4PPh2)2Fe] and 4 (vide supra). All Fe1–CC5 distances
lie in a narrow range varying from 2.064(1)–2.088(1) Å.
Reaction of 13 with [PdCl2(CH3CN)2] gives an light pur-
ple microcrystalline solid of composition [(dppfTM)PdCl2]
(14) in 66% yield. Further halogen exchange was achieved
by reaction of 14 with an excess of NaI in MeOH
(Scheme 7). Thus, [(dppfTM)PdI2] (15) was isolated as a
deep purple microcrystalline solid in 87% yield, higher than
in the analogous synthesis of the [(dppp)PdI2] reported re-
cently.[22] Identification of both compounds was completed
by microanalysis and multinuclear NMR spectroscopy.
dppfTM
.
Scheme 6. Yield dependence of 13 on deprotonation agent.
The 31P NMR spectroscopy reveals a single up-field
1
shifted resonance at –15.8 ppm. In the H NMR spectrum,
the geminal protons of the CH2-group and the methyl
groups are, as expected, diastereotopic. The high conforma-
tional rigidity in solution is presented in the 13C NMR
spectroscopy – the resonances to ortho- and ipso-Ph car-
bons, observed at δ = 134.6 and 141.2 ppm, resp., show
Scheme 7.
pseudo-triplet pattern (|2JCP
+ +
6JCPЈ| = 10.5 Hz, |1JCP
5JCPЈ| = 6.8 Hz, resp.). This coupling pattern is in contrast
NMR spectra of 14 and 15 are rather similar and spec-
to those reported for the unsubstituted ferrocene (dppf),[19] troscopic characteristics will be discussed for 14 as repre-
which shows for these resonances solely two doublets.
sentative. In its 1H NMR spectrum four resonances for
Orange crystals of 13, suitable for X-ray structure deter- methyl groups were observed whereas two diastereotopic
mination, were grown by slow cooling of its concentrated methyl groups are observed in dppfTM. Moreover, the pro-
alcohol solution. The molecular structure of ferrocene with tons at the C5 ring appear as two resonances at 3.64 (s) and
ellipsoids of 50% of probability is presented in Figure 3.
4.11 (d, 3JHP = 2.5 Hz) ppm. In the 13C NMR spectrum two
¯
Complex 13 crystallizes in the triclinic space group P1 diastereotopic para- and ipso-Ph carbon resonances were
with one molecule in the unit cell. The iron atom lies on the observed. These findings confirm the molecular rigidity in
crystallographic inversion center, the molecule as a whole is solution and a helical structure with low degree or absence
centrosymmetric. The molecule has a strictly anti-confor- of ∆-/Λ interconversion.
mation of substituents at both C5-rings. The distance be-
Single crystals of palladium complex 15, suitable for X-
tween the iron atom and centroid (Z) of the C5-ring ray diffraction analysis, were obtained by a slow evapora-
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Novel, Highly Crowded Cyclopentadienylphosphane
tion of its chloroform solution. The compound crystallizes zation of 4 with MeI proceeds smoothly to [Ph2P(CpTMH)-
in the orthorhombic space group Pca21 with four molecules Me]+ I– (8), its dehydrohalogenation by reaction with nBuLi
per unit cell (Figure 4).
gives P-methyl-cyclopentadienylidenephosphorane Ph2P-
(CpTM)Me (9). An alternative protocol towards 9, the de-
protonation of 8 with benzyl potassium followed by P-alk-
ylation is superior and gives 9 in more than 95% yield. The
NMR spectroscopy of the phosphane 4, its chalcogenides
5–7 as well as the phosphonium salt 8 shows the presence
of a single vinylic isomer in all cases. Compounds 4 and
9 have been structurally characterized by X-ray diffraction
analyses.
The Staudinger reaction of 4 with tBuN3 gives tautomer
Ph2P(CpTM)NHtBu (10) that exists exclusively in P-amino-
cyclopentadienylidenephosphorane form, whereas with
Me3SiN3 the major tautomer has the form of P-imino-cy-
clopentadienylphosphane Ph2P(NSiMe3)CpTMH (11). Hy-
drolysis of 11 with wet MeCN leads after tautomerization
to the novel P-amino-cyclopentadienylidenephosphorane
Ph2P(CpTM)NH2 (12).
Finally, ferrocene [(η5-CpTMPPh2)2Fe] (13) was synthe-
sized by metallation of Ph2P-CpTMH with [PhCH2K] and
transmetallation with FeCl2. In analogy to its known prede-
cessor dppf it is named dppfTM. Despite of its extreme steric
bulk and stereochemical rigidity, ferrocene 13 has been ap-
plied as a bidentate phosphane ligand for the synthesis of
palladium complexes [(dppfTM)PdCl2] (14) and [(dppfTM)-
PdI2] (15). Both 13 and 15 have also been characterized by
X-ray diffraction analysis. The reported high-yield chemical
transformation from cheap starting materials as well as
proof of ligand properties will stimulate further develop-
ment with respect to introducing other substituents at the
phosphorus atom or via carbometallation at the reactive
fulvene functionality.
Figure 4. The molecular structure of [(dppfTM)PdI2] (15). All H-
atoms have been omitted for clarity (Z = centroid of C5-ring). Se-
lected bond lengths [Å] and angles [°]: Pd1–I1 2.639(2), Pd1–I2
2.652(2), Pd1–P1 2.293(1), Pd1–P2 2.298(1), P1–C1 1.808(2), P2–
C13 1.801(2), Fe–Z 1.683(1), Fe–Z1 1.675(1), I1–Pd1–I2 90.2(1),
P1–Pd1–I1 86.3(1), P2–Pd1–I2 86.3(1), P1–Pd1–P2 99.3(1), Z–
Pd1–Z1 172.0(1).
The palladium atom has a distorted square-planar geom-
etry. The similar distortion was reported for complexes
[(dppf)PdI2] (Hal = Br, I).[23]
The P1–Pd1–P2 bite angle is of 99.3(1)° and comparable
with those of in series [(dppf)PdHal2] (Hal = Cl – I: 98.9–
99.9°). The I1–Pd1–I2 angle is of 90.2(1)° and slightly larger
than those in dppf complexes (Hal = Cl – I: 87.2–
87.8°).[22,24] The most interesting feature is the dramatic dis-
tortion of both C5 rings in the molecule. The Z–Fe–Z1 an-
gle of 172.0(1)° is the lowest value in the whole series of the
[(dppf)PdHal2] [Hal = Cl: 179.5(1)°, Br 177.8(1), I:
178.3(1)°].[22,23]
Experimental Section
General Considerations: All manipulations were performed under
purified argon or nitrogen using standard high vacuum or Schlenk
or glovebox techniques. Solvent grade acetone, acetonitrile and
MeOH were used without purification. Hexane and THF were dis-
tilled under argon employing standard drying agents.[25] Ph2P-C5H5
(1)[2] and anhydrous metal salts FeCl2,[26] [PdCl2(MeCN)2][27] were
prepared according to the literature procedures. Ph2PCl (95%,
techn.) was used as supplied from Acros. NMR spectra were re-
corded at +25 °C on a Bruker ARX200 and Bruker AMX300. Ele-
mental analyses were performed at the Analytical Laboratory of
the Chemistry Department/Philipps-University of Marburg. EI
mass spectra were obtained on a Varian MAT CH7A (70 eV), ESI
mass spectra on a FINNIGAN TSQ 700 spectrometer. Melting
points were determined with a Büchi melting point B-540 appara-
tus.
Conclusions
Simple pyrrolidine catalyzed condensation of the known
phosphane Ph2P-C5H5 (1) with acetone leads to the forma-
tion of two different condensation products: either with
1 equiv. of acetone to yield diphenyl(6,6-dimethylfulven-2-
yl)phosphane (2) or with two equiv. of acetone when re-
acted in acetone as a solvent to yield diphenyl(4,4,6-tri-
methyl-4,5-dihydropentalen-2-yl)-phosphane (3). Subse-
quent carbometallation of 3 with MeLi resulted in the first
air-stable, sterically highly crowded tetramethypentalenyl-
phosphane 4. This cyclopentadienylphosphane (Ph2P-
CpTMH) appeared to be thermodynamically stable with re-
spect to its dimerisation and it is the first compound of this
class that has been crystallographically characterized. The
oxidation reactions of Ph2P-CpTMH with H2O2, S8 and Se
yield exclusively the corresponding chalcogenides Ph2P-
Fulvenylphosphane 2 (Ph2P-C8H9): To a stirred solution of phos-
phane 1 (745 mg, 2.98 mmol) in methanol (10 mL), acetone
(0.24 mL, 3.72 mmol, 1.1 equiv.) and pyrrolidine (0.1 mL, ca.
1.3 mmol, ca. 5 mol-%) were added at ambient temperature. The
reaction mixture progressively turns deep yellow. The solution was
stirred for 4 h whereupon a bright yellow, microcrystalline solid
forms. It was filtered off and dried in vacuo for 4 h; yield 59%
(X)CpTMH, X = O (5), X = S (6), X = Se (7). Quaterni- (510 mg); m.p. 83.0–83.5 °C. H NMR (300.1 MHz, C6D6, 25 °C):
1
Eur. J. Inorg. Chem. 2010, 4157–4165
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4161

J. Sundermeyer et al.
δ = 1.59, 1.67 (2ϫ s, 2 ϫ 3 H, 2ϫ Me), 6.52 (m, 1 H, CH), 6.56 (ca. 30%, ca. 1.6 mmol) was added in one portion at ambient tem-
FULL PAPER
(m, 1 H, CH), 6.71 (m, 1 H, CH), 7.07 (m, 6 H, Ph), 7.55–7.64 (m,
perature. An exothermic reaction takes place. The stirring was con-
tinued for 0.5 h after that the volatiles were completely removed in
high vacuum. The traces of water were removed by azeotropic dry-
ing with toluene (50 mL). The solid residue was washed with cold
hexane (2ϫ5 mL), crystallized from hot heptane and dried in
4 H, o-Ph) ppm. 13C{1H} NMR (75.5 MHz, C6D6, 25 °C): δ = 22.6
3
(s, Me), 122.4 (d, JC,P = 4.1 Hz, CC5), 128.7 (d, JC,P = 7.0 Hz, m-
Ph), 128.7 (s, p-Ph), 129.0 (d, JC,P = 22 Hz, P-CC5), 133.6 (d, JC,P
= 12.8 Hz, ipso-Ph), 134.0 (d, 2JP,C = 19.4 Hz, o-Ph), 138.5 (d, 1JC,P
= 11.1 Hz, CC5), 140.9 (d, JP,C = 10.3 Hz, CC5), 143.8, 149.6 (2ϫ vacuo; yield 71% (365 mg) of a colorless, microcrystalline solid;
d, JC,P = 7.8, JC,P = 2.5 Hz, C=CMe2) ppm. 31P{1H} NMR
(81.0 MHz, C6D6, 25 °C): δ = –16.8 ppm. EI-MS: m/z (%) = 290
(100) [M+], 275 (1) [M+ – Me], 213 (1) [M+ – Ph]. C20H19P (290.35):
calcd. C 82.73, H 6.60; found C 82.91, H 6.63.
m.p. 162.9–163.3 °C. 1H NMR (300.1 MHz, C6D6, 25 °C): δ = 0.97,
1.02 (2ϫ s, 2 ϫ 6 H, 2ϫ Me2C), 1.90 [s, 2 H, CH2(CMe2)2], 3.10
3
(s, 2 H, H2CC5), 6.95 (d, JC,P = 8.7 Hz, 1 H, HCC5), 7.05 (m, 6 H,
m-/p-Ph), 7.89 (m, 4 H, o-Ph) ppm. 13C{1H} NMR (75.5 MHz,
2
C6D6, 25 °C): δ = 29.8, 30.1 (2ϫ s, 2 ϫ Me2C), 36.8 (d, JC,P
=
Fulvenylphosphane 3 (Ph2P-C11H13): To a stirred solution of phos-
phane 1 (6.20 g, 24.8 mmol) in acetone (40 mL), pyrrolidine
(0.5 mL, 6.4 mmol, 25 mol-%) was added at ambient temperature.
The reaction mixture turns gradually deep orange. The proceeding
of the reaction was monitored by 31P{1H} NMR spectroscopy of
the reaction mixture sample. After the reaction completed (ca. 4 h),
all volatiles were removed in vacuo and resulting orange, viscous
oil was dried for 4 h at 60 °C under high vacuum. The obtained
crude product was crystallized twice from hexane (2ϫ20 mL) at
–30 °C to give a bright yellow, microcrystalline solid in 44% yield
(4.0 g); m.p. 93–94 °C. 1H NMR (300.1 MHz, C6D6, 25 °C): δ =
12.6 Hz, H2CC5), 40.1, 41.8 (2ϫ s, 2 ϫ Me2C), 61.4 [s, CH2-
(CMe2)2], 128.5, 128.7 (2ϫ s, m-/p-Ph), 131.1 (d, JC,P = 2.7 Hz,
CC5), 132.2 (d, J = 10.9 Hz, o-Ph), 141.6 (d, J = 9.8 Hz, HCC5),
155.0 (d, 3JC,P = 14.8 Hz, CC5CMe2), 164.2 (s, CC5, CC5CMe2) ppm.
31P{1H} NMR (81.0 MHz, C6D6, 25 °C): δ = +18.1 ppm. EI-MS:
m/z (%) = 362 (19) [M+], 347 (87) [M+ – Me]. C24H27OP (362.4):
calcd. C 79.53, H 7.51; found C 79.78, H 6.98.
Phosphane Sulfide 6 [Ph2P(S)CpTMH]: Sulfur powder (340 mg,
1.33 mmol, 1 equiv.) was added to a stirred solution of phosphane
4 (460 mg, 1.33 mmol) in toluene (12 mL) at ambient temperature.
A slightly exothermic reaction with dissolution of sulfur was ob-
served. The reaction mixture was stirred for additional 2 h. The
solvent was removed in vacuo and the solid residue obtained was
triturated with hexane. The formed precipitate was filtered off and
washed with small amount of hexane. Yield 72% (360 mg) of yel-
low powder with the melting point of 133–134 °C. The sample of
analytical purity was obtained by crystallization from hot heptane
solution: yellow, crystalline solid; m.p. 134.4–134.7 °C. 1H NMR
4
1.12 (s, 6 H, Me2C), 1.59 (q, JH,H = 1.2 Hz, 3 H, MeC=C), 2.44
3
4
(s, 2 H, CH2), 5.97 (s, 1 H, CH), 6.27 (dd, JH,P = 3.0, JH,H
=
1.2 Hz, 1 H, CH), 7.09 (m, 6 H, m-/p-Ph), 7.65 (m, 4 H, o-Ph) ppm.
13C{1H} NMR (75.5 MHz, C6D6, 25 °C): δ = 16.4 (s, MeC=C),
2
29.2 (s, Me2C), 37.7 (Me2C), 61.3 (s, CH2), 115.7 (d, JC,P
=
2
17.6 Hz, HC), 117.3 (d, JC,P = 17.1 Hz, HC), 128.6 (s, Ph), 128.7
2
1
(s, Ph), 134.3 (d, JC,P = 19.8 Hz, o-Ph), 138.4 (d, JC,P = 11.3 Hz,
ipso-Ph), 148.7 (d, JC,P = 8.1 Hz, Flv), 151.3 (d, JC,P = 13.6 Hz,
Flv), 153.2 (d, JC,P = 3.0 Hz, Flv), 161.6 (d, JC,P = 5.8 Hz, Flv)
ppm. 31P{1H} NMR (81.0 MHz, C6D6, 25 °C): δ = –13.9 ppm. EI-
MS: m/z (%) = 331 (22.5) [M+ + H], 330 (100) [M+], 315 (18.6)
[M+ – CH3], 253 (8.3) [M+ – Ph]. C23H23P (330.41): calcd. C 83.61,
H 7.02; found C 83.31, H 6.64.
(300.1 MHz, C6D6, 25 °C): δ = 0.96, 1.00 (2ϫ s, 2 ϫ 6 H, Me2C),
3
1.87 [s, 2 H, CH2(CMe2)2], 3.20 (s, 2 H, H2CC5), 6.94 (d, JC,P
=
9.5 Hz, 1 H, HCC5), 7.01 (m, 6 H, m-/p-Ph), 7.97 (m, 4 H, o-Ph)
ppm. 13C{1H} NMR (75.5 MHz, C6D6): δ = 29.8, 30.1 (2ϫ s, 2 ϫ
2
Me2C), 36.8 (d, JCP = 12.6 Hz, H2CC5), 40.1, 41.8 (2ϫ s, 2 ϫ
Phosphane 4 (Ph2P-CpTMH): To a solution of fulvenylphosphane 3
(5.28 g, 16.0 mmol) in diethyl ether (50 mL), MeLi solution (1.6 
in ether, 15 mL, 24 mmol) was added at 0 °C during 15 min fol-
lowed by stirring at ambient temperature for 1 h. The reaction mix-
ture was quenched with methanol (3.5 mL). The clear, supernatant
solution was decanted from the sticky residue and all volatiles were
removed in vacuo. The residue was extracted into hexane (100 mL)
and the solution was filtered through a Celite® pad. Cooling the
solution to –80 °C overnight gives a pale yellow, crystalline mate-
rial, which was isolated by low temperature filtration and dried in
vacuo for 1 h. A pale yellow, crystalline solid was obtained in yield
of 91% (5.04 g); m.p. 108–109 °C. An almost colorless sample was
obtained by crystallization from SiMe4 at –30 °C; m.p. 109.0–
109.3 °C. 1H NMR (300.1 MHz, C6D6, 25 °C): δ = 1.02 (s, 6 H,
Me2C), 1.11 (s, 6 H, Me2C), 1.94 [s, 2 H, CH2(CMe2)2], 2.89 (t,
Me2C), 61.4 [s, CH2(CMe2)2], 128.5 (m, m-/p-Ph), 131.1 (d, JC,P
=
2.7 Hz, CC5), 132.2 (d, J = 10.9 Hz, o-Ph), 141.6 (d, J = 9.8 Hz,
3
HCC5), 155.0 (d, JC,P = 14.8 Hz, CC5CMe2), 164.2 (s, CC5CMe2)
ppm. 31P{1H} NMR (81.0 MHz, C6D6, 25 °C): δ = +31.4 ppm. EI-
MS: m/z (%) = 378 (55) [M+], 363 (65) [M+ – Me]. C24H27PS
(378.5): calcd. C 76.16, H 7.19; found C 76.46, H 7.13.
Phosphane Selenide 7 [Ph2P(Se)CpTMH]: Red selenium powder
(119 mg, 1.55 mol, 1.07 equiv.) was added to a solution of phos-
phane 4 (498 mg, 1.44 mmol) in chloroform (5 mL). The heterog-
enic reaction mixture was heated under reflux for 5 h. The excess
of red selenium was removed by filtration through a Celite® pad.
Removal of the solvent from the filtrate gives a brown, foamy solid;
yield 96% (588 mg) of brown solid. The sample of analytical purity
with the melting point of 143–144 °C was obtained by slow
crystallization from hot heptane. Colorless, crystalline solid; m.p.
147.7–148.0 °C. 1H NMR (300.1 MHz, C6D6, 25 °C): δ = 0.95, 1.00
(2ϫ s, 2 ϫ 6 H, 2ϫ Me2C), 1.86 [s, 2 H, CH2(CMe2)2], 3.25 (s, 2 H,
3
4
4JH,H = 1.5 Hz, 1 H, H2CC5), 7.76 (dt, JH,P = 5.4, JH,H = 1.5 Hz,
1 H, HCC5), 7.05 (m, 6 H, m-/p-Ph), 7.53 (m, 4 H, o-Ph) ppm.
13C{1H} NMR (75.5 MHz, C6D6, 25 °C): δ = 30.0, 30.4 (2ϫ s, 2 ϫ
3
H2CC5), 6.94 (d, JC,P = 9.8 Hz, 1 H, HCC5), 6.99 (m, 6 H, m-/p-
2
Ph), 7.97 (m, 4 H, o-Ph) ppm. 13C{1H} NMR (75.5 MHz, CDCl3,
CMe2) 37.6 (d, JC,P = 9.8 Hz, H2CC5), 40.2, 41.8 (2ϫ s, 2 ϫ
2
CMe2), 61.6 [s, CH2(CMe2)2], 128.6, 128.7 (2ϫ s, m-/p-Ph), 133.7
(d, 1JC,P = 19.7 Hz, ipso-Ph), 139.0 (d, 2JC,P = 24.1 Hz, o-Ph), 139.4
(d, JC,P = 10.9 Hz, CC5), 145.8 (d, JC,P = 14.8 Hz, CC5), 155.8 (d,
JC,P = 8.2 Hz, CC5), 160.6 (s, CC5) ppm. 31P{1H} NMR (81.0 MHz,
25 °C): δ = 30.0, 30.5 (2ϫ s, 2 ϫ Me2C), 36.8 (d, JC,P = 12.7 Hz,
H2CC5), 40.2, 42.1 (2ϫ s, 2 ϫ Me2C), 61.3 [s, CH2(CMe2)2], 128.6
3
4
(d, JC,P = 12.1 Hz, m-Ph), 131.5 (d, JC,P = 3.3 Hz, p-Ph), 132.4
2
1
(d, JC,P = 11.0 Hz, o-Ph), 132.5 (d, JC,P = 78 Hz, ipso-Ph), 138.3
C6D6, 25 °C): δ = –14.5 ppm. EI-MS: m/z (%) = 347 (1.4) [M+
+
1
2
(d, JC,P = 83 Hz, P-CC5), 143.2 (d, JC,P = 9.9 Hz, HCC5), 154.9
H], 346 (34.5) [M+], 331 (100) [M+ – Me], 269 (1) [M+ – Ph].
(d, 3JC,P = 15.4 Hz, CC5CMe2), 165.0 (d, 3JC,P = 7.2 Hz, CC5CMe2)
ppm. 31P{1H} NMR (81.0 MHz, C6D6, 25 °C): δ = 22.3 (1JP,Se
=
C24H27P (346.45): calcd. C 83.21, H 7.86; found C 83.38, H 7.79.
Phosphane Oxide 5 [Ph2P(O)CpTMH]: To a stirred solution of
phosphane 4 (490 mg, 1.42 mmol) in THF (10 mL), aq. H2O2
710 Hz) ppm. 77Se{1H} NMR (76 MHz, C6D6, 25 °C): δ = –260.8
1
(d, JSe,P = 741 Hz) ppm. EI-MS: m/z (%): 426 (32.8) [M+], 265
4162
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 4157–4165

Novel, Highly Crowded Cyclopentadienylphosphane
(84.5) [M+ – CpTM]. C24H27PSe (425.41): calcd. C 67.76, H 6.40;
found C 68.06, H 6.87.
reaction was monitored by 31P{1H} NMR spectroscopy. After the
reaction completed, all volatiles were removed in vacuo and the
solid residue was triturated with acetonitrile, whereupon a yellow
solid forms. The latter was filtered off and dried at high vacuum;
yield 41% (170 mg) of a yellow, microcrystalline solid; m.p. 165.5–
166.5 °C. The sample of the analytical purity was obtained by
crystallization from concd. hot acetonitrile solution (m.p. 166.3–
166.7 °C). The compound has high solubility in aromatic solvents,
THF; it is weakly soluble in acetonitrile, ether and aliphatic sol-
Phosphonium Salt 8 [Ph2P(CpTMH)Me]+I–: To a solution of phos-
phane 4 (350 mg, 1.00 mmol) in CH2Cl2 (5 mL), MeI (0.15 mL, ca.
2.4 mmol) was added and resulting solution was stirred for 48 h.
Progress of the reaction was monitored by 31P{1H} NMR spec-
troscopy. After that all volatiles were removed in vacuo, ether
(10 mL) was added. Vigorous stirring results in formation of a pale
yellow, powdery solid that was filtered off and dried in high vac-
uum; yield 81% (395 mg); m.p. 195–200 °C 1H NMR (200.1 MHz,
CDCl3, 25 °C): δ = 1.23, 1.26 (2ϫ s, 2 ϫ6 H, 2ϫ Me2C), 2.12 [s,
1
vents. H NMR (300.1 MHz, C6D6 25 °C): δ = 0.90 (s, 9 H, tBu),
2
1.69 (s, 12 H, 2ϫ CMe2), 2.07 (d, JH,P = 5.1 Hz, 1 H, NH), 2.47
3
[s, 2 H, CH2(CMe2)2], 6.16 (d, JC,P = 4.0 Hz, 2 H, HCC5), 7.03
2
2 H, H2C(CMe2)2], 3.00 (d, JH,P = 13.5 Hz, MeP), 3.32 (br. d,
(m, 6 H, m-/p-Ph), 7.83–7.90 (m, 4 H, o-Ph) ppm. 13C{1H} NMR
3
4
4JH,H = 2.0 Hz, 2 H, H2CC5), 7.29 (dt, JH,P = 9.6, JH,H = 2.0 Hz,
1 H, HCC5), 7.69–7.83 (m, 10 H, Ph) ppm. 13C{1H} NMR
(50.1 MHz, CDCl3, 25 °C): δ = 12.2 (d, 2JC,P = 58 Hz, Me2P), 29.9,
3
(75.5 MHz, C6D6, 25 °C): δ = 31.4 (d, JC,P = 3.9 Hz, NCMe3),
4
33.3 (s, 2ϫ CMe2), 39.6 (d, JC,P = 1.7 Hz, 2ϫ CMe2), 53.1 (d,
1
2JC,P = 2.2 Hz, CMe3), 64.9 [s, CH2(CMe2)2], 80.5 (d, JC,P
=
=
=
2
30.3 (2ϫ s, 2 ϫ Me2C), 38.0 (d, JC,P = 13 Hz, H2CC5), 40.2, 42.5
2
3
118 Hz, P-CC5), 106.1 (d, JC,P = 16 Hz, HCC5) 128.5 (d, JC,P
1
(2ϫ s, 2 ϫ Me2C), 61.1 [s, H2C(CMe2)2], 120.5 (d, JC,P = 91 Hz,
1
4
12 Hz, m-Ph), 131.5 (d, JC,P = 105 Hz, ipso-Ph), 131.7 (d, JC,P
ipso-Ph), 122.2 (d, 1JC,P = 96 Hz, P-CC5), 130.5 (d, 3JC,P = 12.7 Hz,
2.8 Hz, p-Ph), 133.9 (d, 2JC,P = 9.9 Hz, o-Ph), 146 (3JC,P = 18.7 Hz,
Me2CCC5) ppm. 31P{1H} NMR (81.0 MHz, C6D6, 25 °C): δ =
+17.0 ppm. EI-MS: m/z (%): 417 (100) [M+], 340 (70) [M+ – Ph],
412 (25) [M+ – Me]. C28H36NP (417.56): calcd. C 80.54, H 8.69,
N 3.35; found C 80.25, H 8.57, N 3.38.
2
4
m-Ph), 132.8 (d, JC,P = 10.5 Hz, o-Ph), 134.9 (d, JC,P = 2.8 Hz,
2
3
p-Ph), 151.5 (d, JC,P = 10.7 Hz, HCC5), 156.3 (d, JC,P = 16.5 Hz,
3
P-C=CH-CC5CMe2), 171.0 (d, JC,P = 7.3 Hz, CH2-CC5CMe2)
ppm. 31P{1H} NMR (81.0 MHz, CDCl3, 25 °C): δ = +12.2 ppm.
ESI-MS: m/z (%) = 361 [Ph2P(CpTMH)Me]+. C25H30IP (488.39):
calcd. C 61.48, H 6.19; found C 61.31, H 6.35.
P-Iminophosphane 11 [Ph2P(NSiMe3)CpTMH]: A suspension of
phosphane
4 (334 mg, 0.96 mmol) in Me3SiN3 (1.0 mL, ca.
Methylenephosphorane 9 [Ph2P(CpTM)Me]. a) By Deprotonation of
8: To a suspension of phosphonium salt 8 (320 mg, 0.66 mmol) in
THF (20 mL), nBuLi (1.6 , 0.4 mL, 0.64 mmol) was added at
0 °C. The reaction mixture was stirred at same temperature for 1 h
and for further 14 h at ambient temperature. The pale yellow sus-
pension formed was filtered thought a Celite® pad and the filtrate
was concentrated in high vacuum to yield a waxy residue. Crystalli-
zation from ether gives a pale yellow microcrystalline solid; yield
67% (155 mg).
7.5 mmol) was stirred at 100 °C for 18 h, whereupon slow N2 evol-
ution takes place. The color of reaction mixture turns progressively
brown. The proceeding of the reaction was performed by 31P NMR
spectroscopy of the crude reaction mixture. After the reaction pro-
ceeded to 87%, it was terminated. Removal of all volatiles in vacuo
yields a light brown semisolid mass, which was extracted into hex-
ane (10 mL). Filtration from a small amount of amorphous, brown
solid followed by removal of the solvent results in the formation of
the light brown crystalline product (m.p. 94.0–94.5 °C) The moist-
ure and air-sensitive compound 11 shows very high solubility in all
common aprotic solvents at room temp. A sample of analytical
purity was obtained by crystallization from acetonitrile; m.p. 94.5–
94.7 °C. 1H NMR (300.1 MHz, C6D6, 25 °C): δ = 0.39 (s, 9 H,
SiMe3), 1.00, 1.04 (2ϫ s, 2 ϫ 6 H, 2ϫ Me2C), 1.91 [s, 2 H,
b) By Successive Reactions with [BnK] and MeI: To a solution of 4
(1.04 g, 3.00 mmol) in 20 mL of THF, solution of [BnK] (400 mg,
3.08 mmol) in THF (5 mL) was added drop-by-drop at 0 °C. After
addition was completed the orange reaction mixture was stirred for
15 min and MeI (0.3 mL, 1.6 equiv.) was added within 5 min at
room temp. After an exothermic reaction ceased, the pale yellow
suspension was filtered thought a Celite® pad, washed with THF
(5 mL) and the filtrate was completely evaporated under vacuum
yielding a yellow viscous oil. Addition of ether (20 mL) results in
crystallization with deposition of a pale yellow, microcrystalline so-
lid. An additional crop of product can be obtained by storing the
3
4
CH2(CMe2)2], 3.03 (dd, JH,P = 1.0, JH,H = 1.7 Hz, 2 H, H2CC5),
4
3
6.95 (dt, JH,H = 1.7, JH,P = 9.0 Hz, HCC5), 7.05 (m, 6 H, m-/p-
Ph), 7.80–7.90 (m, 4 H, o-Ph) ppm. 13C{1H} NMR (75.5 MHz,
2
C6D6 25 °C): δ = 4.5 (d, JC,P = 3.3 Hz, SiMe3), 29.9, 30.3 (2ϫ s,
2ϫ CMe2), 36.6 (d, JC,P = 12.7 Hz, H2CC5), 40.0, 41.7 (2ϫ s, 2 ϫ
2
3
CMe2), 61.6 [s, CH2(CMe2)2], 128.2 (d, JC,P = 10.6 Hz, m-Ph),
1
4
2
mother liquor at –30 °C; yield 95% (1.02 g); m.p. 203–204 °C. H
130.7 (d, JC,P = 2.8 Hz, p-Ph), 131.9 (d, JC,P = 10.5 Hz, o-Ph),
2
1
2
NMR (300.1 MHz, C6D6, 25 °C): δ = 1.56 (d, JC,H = 13.0 Hz,
136.8 (d, JC,P = 104 Hz, ipso-Ph), 140.3 (d, JC,P = 11 Hz, HCC5),
6
1
3
3 H, MeP), 1.72 (s, 12 H, 2ϫ Me2C), [d, JC,H = 0.6 Hz, 2 H,
144.6 (d, JC,P = 108 Hz, P-CC5) ppm. 155.5 (d, JC,P = 14.9 Hz,
3
CC5CMe2), 162.7 (d, JCP = 6.6 Hz, CC5CMe2) ppm. 31P{1H}
3
CH2(CMe2)2], 6.02 (d, JC,H = 3.6 Hz, 2 H, HCC5), 6.86 (m, 4 H,
m-Ph), 6.96 (m, 2 H, p-Ph), 7.24–7.31 (m, 4 H, o-Ph) ppm. 13C{1H}
NMR (81.0 MHz, C6D6): δ = –7.8 ppm. EI-MS: m/z (%): 433 (34)
[M+], 360 (100) [M+ – SiMe3]. C27H36NPSi (433.65): calcd. C 74.78,
H 8.37, N 3.23; found C 73.71, H 8.36, N 3.16.
1
NMR (50.1 MHz, C6D6 25 °C): δ = 12.2 (d, JC,P = 62 Hz, MeP),
4
33.3 (s, 2ϫ Me2C), 39.6 (d, JC,P = 1.7 Hz, Me2C) 64.9 [s,
1
2
CH2(CMe2)2], 78.6 (d, JC,P = 108 Hz, P-CC5), 103.5 (d, JC,P
=
=
=
P-Aminophosphorane 12 [Ph2P(CpTM)NH2]: This compound was
isolated accidentally as a small amount of colorless precipitate by
crystallization attempt from solvent-grade acetonitrile. Therefore,
the synthesis of compound 12 was not optimized; m.p. 172.0–
173.0 °C. 1H NMR (300.1 MHz, C6D6 25 °C): δ = 1.66 (s, 12 H,
2ϫ Me2C), 2.10 (br. s, 2 H, NH2), 2.42 [s, 2 H, CH2(CCMe2)2],
16.5 Hz, HCC5), 128.6 (d, 3JC,P = 12.1 Hz, m-Ph), 129.5 (d, 1JC,P
86 Hz, ipso-Ph), 131.8 (d, JC,P = 2.8 Hz, p-Ph), 132.5 (d, JC,P
4
2
10.5 Hz, o-Ph), 145.7 (d, 3JC,P = 18.2 Hz, Me2CCC5) ppm. 31P{1H}
NMR (81.0 MHz, C6D6, 25 °C): δ = +4.2 ppm. ESI-MS: m/z (%)
= 361 [M+ + H]. C25H29P (360.48): calcd. C 83.30, H 7.98; found
C 82.97, H 8.21.
3
5.68 (d, JCP = 3.4 Hz, 2 H, HCC5), 6.87–7.03 (m, 6 H, m-/p-Ph),
P-Aminophosphorane 10 [Ph2P(CpTM)NHtBu]: To a solution of
7.48–7.56 (m, 4 H, o-Ph) ppm. 13C{1H} NMR (50.1 MHz, C6D6,
25 °C): δ = 33.2 (s, 2ϫ Me2C), 39.5 (s, 2ϫ CMe2), 64.8 [s,
phosphane
4 (360 mg, 1.04 mmol) in THF (10 mL), tBuN3
1
2
(500 mg, 5.0 mmol, 5.0 equiv.) was added at ambient temperature. CH2(CMe2)2], 82.0 (d, JC,P = 110 Hz, P-CC5), 104.8 (d, JC,P
=
=
The reaction mixture was stirred for 5 h. The proceeding of the
17.8 Hz, HCC5), 128.3 (d, 3JC,P = 12.6 Hz, m-Ph), 131.1 (d, 1JC,P
Eur. J. Inorg. Chem. 2010, 4157–4165
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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4163

J. Sundermeyer et al.
FULL PAPER
102 Hz, ipso-Ph), 131.7 (d, JC,P = 2.5 Hz, p-Ph), 132.4 (d, JC,P
4
2
=
orange, microcrystalline precipitate forms. It was filtered off and
10.7 Hz, o-Ph), 146.0 (d, 3JC,P = 19.3 Hz, Me2CCC5) ppm. 31P{1H} dried in high vacuum; yield 66% (395 mg). The compound is air-
NMR (81.0 MHz, C6D6, 25 °C): δ = +22.1 ppm. EI-MS: m/z (%): stable and shows high solubility in CH2Cl2 and low solubility in
361 (100) [M+], 284 (32) [M+ – Ph]. C24H28NP (361.47): calcd.
C 79.75, H 7.81, N 3.88; found C 80.30, H 8.18, N 3.98.
THF; not soluble in aromatic solvents, hexane, ether, acetone,
lower alcohols; m.p. Ͼ 250 °C. 1H NMR (300.1 MHz, C6D6,
25 °C): δ = 1.00, 1.03, 1.08, 1.39 (4ϫ s, 4 ϫ3 H, 4ϫ Me), 1.76,
Ferrocene Derivative 13 [(η5-CpTMPPh2)2Fe], (dppfTM): To a solu-
tion of phosphane 4 (690 mg, 2.05 mmol) in THF (25 mL), a solu-
tion of [PhCH2K] (255 mg, 1.98 mmol) in THF (10 mL) at 0 °C
was added followed by addition of solid FeCl2 (64 mg, 0.50 mmol).
A dark brown suspension forms. The reaction mixture was stirred
for 2 h at room temp., after that all volatiles were removed in vacuo
and residue was extracted with hexane; solvent was stripped off
yielding a brown-orange, foamy residue. This was dissolved in ace-
tonitrile, treated with ultrasound whereupon an orange-pink solid
forms. It was filtered off and dried in high vacuum; yield 83%
(620 mg). Ferrocene 13 is highly soluble in hydrocarbons, aromatic
solvents, ethers, ethanol and virtually insoluble in methanol and
2
2.30 (2ϫ d of AB system, JH,H = 13.4 Hz, 2ϫ 1 H, exo-/endo-
3
CH2), 3.64 (s, 1 H, HCC5), 4.11 (d, JH,P = 2.5 Hz, 1 H, HCC5),
7.33–7.65 (m, 8 H, Ph), 8.11 (m, 2 H, Ph) ppm. 13C{1H} NMR
(75.5 MHz, C6D6, 25 °C): δ = 29.4, 30.4, 31.7, 32.7 (4ϫ s, 4 ϫ Me),
36.3, 38.1 (2ϫ s, 2 ϫ CMe2), 58.1 [s, CH2(CMe2)2], 62.2 (s, HCC5),
1
66.5 (pst, |2JC,P
+
4JC,P| = 20.2 Hz, HCC5), 71.1 (dd, JC,P = 56,
3JC,P
CC5CMe2), 127.2, 128.1 (2ϫ pst, |3JC,P
5JC,P| = 11.6 Hz, 2ϫ m-Ph), 130.0, 131.6 (2ϫ s, 2 ϫ p-Ph), 133.7
=
4 Hz, P-CC5), 112.6 (pst, |3JC,P
+ | = 5.4 Hz,
5JC,P
+
5JC,P| = 11.0, |3JC,P
+
4
1
(pst, |2JC,P + JC,P| = 9.2 Hz, o-Ph), 134.6 (d, JC,P = 60 Hz, ipso-
Ph), 135.6 (pst, |2JC,P 4JC,P| = 12.4 Hz, o-Ph) ppm. 31P{1H}
+
NMR (121.0 MHz, CD2Cl2, 25 °C): δ = +30.3 ppm. ESI-MS:
m/z (%): 924.2 [M+]. C48H52Cl2FeP2Pd (924.07): calcd. C 62.39,
H 5.67; found C 62.05, H 5.81.
1
acetonitrile; m.p. 180.5 °C (dec. Ͼ 188 °C). H NMR (300.1 MHz,
C6D6, 25 °C): δ = 1.16 (s, 6 H, 2ϫ Me), 1.25 (s, 6 H, 2ϫ Me), 1.68,
2.42 [2ϫ d of AB system, 2JH,H = 12.8 Hz, 2ϫ 1 H, diastereotopic
H2C(CMe2)], 4.00 (s, 2 H, HCC5), 7.06 (m, 6 H, p-/m-Ph), 7.60 (m,
4 H, o-Ph) ppm. 13C{1H} NMR (75.5 MHz, C6D6, 25 °C): δ = 31.3
(s, Me), 32.7 (s, Me), 37.9 (s, CMe2), 59.2 (s, CH2), 63.7
Palladium Complex 15 [(dppfTM)PdI2]: A stirred suspension of com-
plex 14 (166 mg, 0.18 mmol) and NaI (660 mg, 4.4 mmol, ca.
24 equiv.) in MeOH (30 mL) was refluxed for 10 min. After that
the reaction mixture was cooled to room temperature and major
amount of inorganic salts was removed by centrifugation. The fil-
trate was collected by decantation and the solid was extracted in
the same way three times. The solvent from combined organic
phases was removed in vacuo and the brown residue was extracted
with CH2Cl2. The subsequent filtration and removal of the solvent
yield a deep purple, microcrystalline solid; yield 87% (173 mg). The
compound shows very high solubility in CH2Cl2; marginally solu-
(pst, |2JC,P
+
3JC,P| = 7.6 Hz, HCC5), 109.6 (s, CC5CMe2), 128.4,
128.7 (2ϫ s, m-/p-Ph), 134.6 (pst, |2JC,P + JC,P| = 10.5 Hz, o-Ph),
6
141.2 (pst, |1JC,P
+
5JC,P| = 6.8 Hz, ipso-Ph) ppm. 31P{1H} NMR
(81.0 MHz, C6D6, 25 °C): δ = –16.7 ppm. ESI-MS: m/z (%) = 747.2
[M+ + H]. C48H52FeP2 (746.7): calcd. C 77.21, H 7.02; found
C 76.62, H 7.13.
Palladium Complex 14 [(dppfTM)PdCl2]: To a solution of ferrocene
13 (500 mg, 0.67 mmol, 1.07 equiv.) in THF (10 mL),
[PdCl2(MeCN)2] (160 mg, 0.63 mmol) was added and reaction mix-
ture was stirred for 24 h. During that period a lustrous, purple-
1
ble in THF and insoluble in MeCN and Et2O; m.p. Ͼ 250 °C. H
NMR (300.1 MHz, CDCl3, 25 °C): δ = 1.01, 1.06, 1.039 (3ϫ s,
Table 1. Details of the crystal data, structural resolution and refinement procedure for compounds 4, 9, 13 and 15.
4
9
13
15
Empirical formula
C24H27P
346.43
colorless, prism
0.30ϫ0.18ϫ0.12
monoclinic
P 21/c
C25H29P
360.45
C48H52FeP2
746.69
C48H52FeI2P2Pd
1106.89
light red, plate
0.21ϫ0.06ϫ0.03
orthorhombic
Pca21
Fw /gmol–1
Crystal color, habit
Crystal size /mm
Crystal system
Space group
colorless, needle
0.36ϫ0.08ϫ0.04
triclinic
dark red, prism
0.08ϫ0.05ϫ0.03
triclinic
¯
P1
¯
P1
Z
a /Å
b /Å
c /Å
α /°
β /°
4
4
1
4
6.4001(3)
37.8489(13)
8.4024(4)
90
96.017(6)
90
2024.16(15)
1.137
0.139
10.5140(11)
13.1131(13)
15.7793(17)
89.722(8)
72.761(8)
86.898(8)
2074.6(4)
1.154
8.8276(18)
11.002(3)
11.123(3)
80.50(2)
71.261(17)
84.658(19)
1008.0(4)
1.230
26.3109(17)
11.4236(7)
14.8667(7)
90
90
90
4468.4(5)
1.645
2.212
γ /°
Volume /Å3
dcalcd. /gcm–3
µ /mm–1
0.138
0.486
F(000)
744
IPDS1
173(2)
12322
776
IPDS2
100(2)
23974
396
IPDS2
130(2)
8283
3532
2192
IPDS2
100(2)
20064
Diffractometer type
Temperature /K
Number of reflections collected
Number of independent reflec-
tions
3874
23794
7797
Absorption correction
R(int)
semi-empirical
0.0510
none
integration
semi-empirical
0.0745
“HKLF 5” refinement, no 0.1276
merging, BASF = 0.157
GOF
R1 [IϾ2σ(I)]
wR2 (all data)
0.956
0.0379
0.0953
0.690
0.00583
0.1313
0.763
0.0551
0.0980
0.898
0.0439
0.0767
4164
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© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2010, 4157–4165

Novel, Highly Crowded Cyclopentadienylphosphane
3 H, 6 H, 3 H, 4ϫ Me), 1.75, 2.30 (2ϫ d of AB system, JH,H
12.6 Hz, 2ϫ 1 H, exo-/endo-CH2), 3.55 (s, 1 H, HCC5), 3.94 (d,
2JH,P = 3.3 Hz, 1 H, HCC5), 7.30–7.44 (m, 5 H, Ph), 7.51–7.63 (m,
3 H, Ph), 8.00–8.06 (m, 2 H, Ph) ppm. 13C{1H} NMR (75.5 MHz,
CDCl3, 25 °C): δ = 30.0, 31.2, 32.4, 33.5 (4ϫ s, 4 ϫ Me), 36.8,
38.5 (2ϫ s, 2 ϫ CMe2), 58.7 [s, CH2(CMe2)2], 62.7 (s, HCC5), 67.0
2
[7] a) S. P. Mesyats, E. N. Tsvetkov, E. S. Petrov, M. I. Terekhova,
A. I. Shatenshein, M. I. Kabachnik, Izv. Akad. Nauk SSSR,
Ser. Khim. 1974, 2489–2496; b) L. Baiget, M. Bouslikhane, J.
Escudie, G. C. Nemes, I. Silaghi-Dumitrescu, L. Silaghi-Dumi-
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1961.
=
[8] K. A. Rufanov, A. Spannenberg, Mendeleev Commun. 2008,
1
3
(pst, |2JC,P
6 Hz, P-CC5), 112.4 (d, JC,P
+
4JC,P| = 21 Hz, HCC5), 73.9 (dd, JC,P = 47, JC,P
=
18, 32–34.
3
= 6.6 Hz, CC5CMe2), 112.5
[9] A. R. Petrov, K. A. Rufanov, B. Ziemer, P. Neubauer, V. V. Ko-
tov, J. Sundermeyer, Dalton Trans. 2008, 909–915.
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b) I. Erden, F.-P. Xu, A. Sadoun, W. Smith, G. Sheff, M. Os-
sun, J. Org. Chem. 1995, 60, 813–820.
(pst, |3JC,P + JC,P| = 2.2 Hz, CC5CMe2), 127.4, 128.2 (2ϫ pst, 2ϫ
5
|3JC,P
+
5JC,P| = 11.6 Hz, m-Ph), 130.3, 131.6 (2ϫ s, 2 ϫ p-Ph),
132.2 (d, JC,P = 54 Hz, ipso-Ph), 134.8, 135.9 (2ϫ pst, |2JC,P
+
1
4JC,P| = 9.4 Hz, |2JC,P + JC,P| = 12.5 Hz, 2ϫ o-Ph), 136.6 (d, JC,P
= 55 Hz, ipso-Ph) ppm. 31P{1H} NMR (81.0 MHz, CDCl3, 25 °C):
δ = +19.9 ppm. ESI-MS: m/z (%): 1106.4 [M+]. C48H52FeI2P2Pd
(1106.97): calcd. C 52.08, H 4.74; found C 52.53, H 4.65.
4
1
[11]
The av. C–P bond length for Ph3P (1.83 Å): J. J. Daly, J. Chem.
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+25 °C), 9 (Et2O, 0 °C) and 15 (CH2Cl2, 0 °C). Diffraction data
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diffractometers using graphite monochromated Mo-Kα radiation (λ
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azzo, 2004) and refined by the full-matrix least-squares procedure
based on F2, using the SHELXL-97 (Sheldrick, 1997) computer
program. ORTEP plots of all molecular structures were generated
with Diamond 3.1, Crystal Impact software.
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For diphenyl(inden-1-yl)phosphane, see: K. A. Fallis, G. K.
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J. H. Brownie, M. C. Baird, H. Schmider, Organometallics
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CCDC-746654 (for 4), -746655 (for 9), -746656 (for 13), -746657
(for 15) contain the supplementary crystallographic data for this
paper. These data can be obtained free of charge from The Cam-
bridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/
data_request/cif.
[15]
1.718(2) Å for Ph3PC5H4: H. L. Ammon, G. L. Wheeler, P. H.
Watts Jr., J. Am. Chem. Soc. 1973, 95, 6158–6163; av. 1.727 Å
for Ph2P(C5H4)Me: see ref.[13] for a substituted indenylidene
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Rufanov, B. Ziemer, M. Hummert, S. Schutte, Eur. J. Inorg.
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Acknowledgments
K. A. R. thanks Deutsche Akademischer Austausch Dienst
(DAAD) for funding of a research fellowship at Philipps-Uni-
versität Marburg within the Ostpartnerschaftsprogramm. Financial
support of Deutsche Forschungsgemeinschaft (DFG) (SPP-1166)
is gratefully acknowledged.
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Received: December 31, 2009
Published Online: July 28, 2010
Eur. J. Inorg. Chem. 2010, 4157–4165
© 2010 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
4165