Fused supracyclopentadienyl ligand precursors. synthesis, structure, and some reactions of 1,3-diphenylcyclopenta[l]phenanthrene-2-one, 1,2,3-Triphenylcyclopenta[l]phenanthrene-2-ol, 1-Chloro-1,2,3-triphenylcyclopenta[l]phenanthrene, 1-Bromo-1,2,3-triphenylcyclopenta[l]phenanthrene, and 1,2,3-Triphenyl-1H-cyclopenta[l]phenanthrene

Article abstract of DOI:10.1071/CH05172

The photochemical reaction of 1,3-diphenylcyclopenta[l]phenanthrene-2-one 5 (phencyclone) with oxygen in acetone leads to the formation of 1,2,3-trihydro-1,2,3-triphenylcyclo-penta[l]phenanthrene 7 (9,10-dibenzoylphenanthrene) along with a trace of the lactone 1,4-diphenylcyclo-3-pyran[l]phenanthrene-2-one 8. An independent synthesis of 8 was achieved by the reaction of 5 with FeCl₃ in CHCl₃. The treatment of 5 with phenyllithium yields 1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH in good yield. Subsequent reaction of 9-OH with SOCl₂ or SOBr₂ in pyridine leads to the formation of the halo-analogues 1-chloro-1,2,3-triphenylcyclopenta[l]phenanthrene 9-Cl and 1-bromo-1,2,3-triphenylcyclopenta[l]phenanthrene 9-Br, respectively. Treatment of 9-OH with HBr in acetic acid affords the rearranged product 1,1,3-triphenylcyclopenta[l]phenanthrene-2-one 10 with a trace of 9-Br. Treatment of 9-Cl or 9-Br with zinc in acetic acid affords 1,2,3-tri-phenyl-1H-cyclopenta[l]phenanthrene 9-H. 9,10-Phenanthrenediylbis(phenyl)methanone 7 is formed in good yield upon treatment of 9-OH with HI in acetic acid followed by heating with H ₂PO₄. Compounds 7, 8, 9-Cl, 9-Br, and 10 have been structurally characterized using X-ray crystallography. CSIRO 2006.

Full text of DOI:10.1071/CH05172

Full Paper
CSIRO PUBLISHING
www.publish.csiro.au/journals/ajc
Aust. J. Chem. 2006, 59, 135–146
Fused Supracyclopentadienyl Ligand Precursors. Synthesis, Structure,
and Some Reactions of 1,3-Diphenylcyclopenta[l]phenanthrene-2-one,
1,2,3-Triphenylcyclopenta[l]phenanthrene-2-ol,
1-Chloro-1,2,3-triphenylcyclopenta[l]phenanthrene,
1-Bromo-1,2,3-triphenylcyclopenta[l]phenanthrene, and
1,2,3-Triphenyl-1H-cyclopenta[l]phenanthrene
Glen D. Dennis,A David Edwards-Davis,A Leslie D. Field,A,B Anthony F. Masters,A,C
Thomas Maschmeyer,A Antony J. Ward,A Irmi E. Buys,A and Peter TurnerA
A Centre for Heavy Metals Research and School of Chemistry, University of Sydney,
Sydney NSW 2006, Australia.
B University of New South Wales, Kensington NSW 2052, Australia.
C Corresponding author. Email: a.masters@chem.usyd.edu.au
The photochemical reaction of 1,3-diphenylcyclopenta[l]phenanthrene-2-one 5 (phencyclone) with oxygen in
acetone leads to the formation of 1,2,3-trihydro-1,2,3-triphenylcyclo-penta[l]phenanthrene 7 (9,10-dibenzoyl-
phenanthrene) along with a trace of the lactone 1,4-diphenylcyclo-3-pyran[l]phenanthrene-2-one 8.An independent
synthesis of 8 was achieved by the reaction of 5 with FeCl3 in CHCl3. The treatment of 5 with phenyllithium yields
1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH in good yield. Subsequent reaction of 9-OH with SOCl2 or
SOBr2 in pyridine leads to the formation of the halo-analogues 1-chloro-1,2,3-triphenylcyclopenta[l]phenanthrene
9-Cl and 1-bromo-1,2,3-triphenylcyclopenta[l]phenanthrene 9-Br, respectively. Treatment of 9-OH with HBr in
acetic acid affords the rearranged product 1,1,3-triphenylcyclopenta[l]phenanthrene-2-one 10 with a trace of 9-Br.
Treatment of 9-Cl or 9-Br with zinc in acetic acid affords 1,2,3-tri-phenyl-1H-cyclopenta[l]phenanthrene 9-H.
9,10-Phenanthrenediylbis(phenyl)methanone 7 is formed in good yield upon treatment of 9-OH with HI in acetic
acid followed by heating with H2PO4. Compounds 7, 8, 9-Cl, 9-Br, and 10 have been structurally characterized
using X-ray crystallography.
Manuscript received: 12 July 2005.
Final version: 4 January 2006.
Introduction
difluorenylzirconium dichloride, was reported in 1965.[22]
However, in comparison with cyclopentadienyl ligands, the
ligand chemistry of the indenyl and fluorenyl anions has
received relatively little attention. There is some spectro-
scopic and structural evidence that the binding of a metal to
the η5-indenyl and η5-fluorenyl ligands is weaker than that to
a cyclopentadienyl ligand. However, the former compounds
appear to have enhanced reactivities, for example, several
metallotropic rearrangements of η5-indenyl and η5-fluorenyl
complexes have been reported.
Bulky substituents on the cyclopentadienyl ring often
confer greater kinetic stability on metal complexes than is
observed for analogues with less sterically demanding lig-
ands.Thus, for example, whereas many cyclopentadienyl and
pentamethylcyclopentadienyl complexes are air- and water-
sensitive, their decabenzyl and decaphenyl analogues can be
stored in air, sometimes indefinitely.
Pentaphenylcyclopentadiene was first reported in 1925,[1]
and the first metal complex of the pentaphenylcyclopenta-
dienyl anion was reported in 1964.[2] The ligand’s radical
chemistry received considerable early attention[3–16] and
there has been a steady increase in research into metal com-
plexes of the C5Ph−5 ligand since the mid-1970s.Almost 60%
of all research in this area has been published in the last
decade. Substituent variation of the ligand’s phenyl rings and
the investigation of related perbenzylated and other perary-
lated cyclopentadienyl ligand systems have been extensions
of this work.[17–20]
Substituent variation in cyclopentadienyl chemistry has
been extended to the study of cyclopentadienyl-related lig-
ands with extended π-systems, such as indenyl and fluorenyl
ligands. The first η5-indenyl complex, diindenyliron, was
reported in 1953,[21] and the first η5-fluorenyl complex,
© CSIRO 2006
10.1071/CH05172
0004-9425/06/020135

136
G. D. Dennis et al.
Ph
Ph
Ph
Ph
Ph
Ph
(a) ArMgBr
(b) Hϩ
Ph
Ph
Ph
O
HO
Ar
O
1
Ph
2
5
CH3CO2H
HBr
Fig. 1. Structure of 5.
Zn/Hϩ
or
HI/H3PO2
Ph
Ph
H
H
Ph
Ph
O
Ph
Ph
Ar
Br
3
6
Ph
Ph
Ph
Fig. 2. Structure of 6.
Zn/Hϩ
Ph
The ligand chemistry of condensed ring analogues of pen-
taphenylcyclopentadienyl complexes and the effects of the
altered electronic and steric demands of the ligands have been
examined. The most common route to pentaphenylcyclopen-
tadienyl complexes is either by the conversion of tetracyclone
1 to its hydroxy 2 and halogenated derivatives, which can
then be oxidatively added to a low-valent transition metal, or
converted to the pentaphenylcyclopentadienyl anion, either
directly or by conversion to pentaphenylcyclopentadiene
(Scheme 1).
Here, synthetic and structural studies on 1,3-diphenyl-
cyclopenta[l]phenanthrene-2-one 5 (phencyclone; Fig. 1),
and its derivatives are reported. Early work on the organic
and organometallic chemistry of the tetracyclones has been
comprehensively reviewed.[23]
H
Ar
ϩ isomers
4
Scheme 1. Preparation of 4.
Ph
Ph
O
OHϪ/⌬
ϩ
O
O
O
Ph
Ph
5
Scheme 2. Preparation of 5.
Results and Discussion
Ph
The synthesis of the fused ring polycyclic derivative,
1,3-diphenylcyclopenta[l]phenanthrene-2-one 5, was first
reported in 1935.[24] However, difficulties∗ in preparing
a pure product were subsequently noted.[25–27] Recently,
an alternative synthesis of substantially pure phencyclone
has been published.[26] The method involves the base-
catalyzed condensation of phenanthrenequinone with
1,3-diphenylacetone under conditions where the temperature
was carefully controlled (Scheme 2).
O
Ph
5
h␯/O2
Acetone
Yields of greater than 80% can be consistently obtained
by the procedure described herein. Similar yields have been
claimed previously, but the purity of the compound in many
of these reports was not well established, as phencyclone
was reported to have various colours and to have melt-
ing points in the range 245–258◦C.[25–28] In the present
study, the crystalline phencyclone is a black compound,
with a melting point of 238–240◦C after vacuum-drying.
The main impurity, found when the reaction was carried
out at temperatures above ∼70◦C or if the basic catalyst
Ph
Ph
O
O
O
Ph
Ph
ϩ
O
7
8
Scheme 3. Preparation of 7 and 8.
∗ A referee has commented (and we concur) that difficulties with the original synthesis can be caused by experimental technique — the phenanthrenequinone
purity and/or delays between synthesis steps.

Fused Supracyclopentadienyl Ligand Precursors
137
(a)
(b)
C(8)
C(9)
C(7)
C(6)
C(10)
C(13)
C(14)
C(12)
C(5)
C(15)
C(11)
C(1)
O(1)
C(2)
C(16)
C(17)
C(3)
O(2)
C(4)
C(18)
C(19)
C(22)
C(23)
C(21)
C(20)
C(24)
C(28)
C(25)
C(26)
C(27)
Fig. 3. ORTEP[44] plot (25% probability) of 9,10-dibenzoylphenanthrene (7) viewed (a) along and (b) perpendicular to the plane of the phenanthrene
backbone. Atomic numbering is illustrated in Fig. 3(b).
Table 2. Selected bond angles [◦] involving non-hydrogen atoms
Table 1. Selected bond distances [Å] involving non-hydrogen atoms
for 7
for 7
Atoms
Angle
Atoms
Angle
Atoms
Distance
Atoms
Distance
O(1)–C(1)–C(2)
O(1)–C(1)–C(5)
C(2)–C(1)–C(5)
C(1)–C(2)–C(3)
C(1)–C(2)–C(11)
C(3)–C(2)–C(11)
119.7(2)
121.5(2)
118.8(2)
119.5(2)
119.7(2)
120.6(2)
C(2)–C(3)–C(4)
C(2)–C(3)–C(22)
C(4)–C(3)–C(22)
O(2)–C(4)–C(3)
O(2)–C(4)–C(23)
C(3)–C(4)–C(23)
119.7(2)
121.4(2)
118.9(2)
120.5(2)
122.3(2)
117.2(2)
O(1)–C(1)
O(2)–C(4)
C(1)–C(2)
C(1)–C(5)
C(2)–C(3)
C(2)–C(11)
1.217(3)
1.219(3)
1.507(3)
1.490(3)
1.357(3)
1.441(3)
C(3)–C(4)
1.511(3)
1.440(3)
1.487(3)
1.413(3)
1.450(3)
1.414(3)
C(3)–C(22)
C(4)–C(23)
C(11)–C(16)
C(16)–C(17)
C(17)–C(22)
was added too rapidly,† has been assigned in the past as
1,3-dihydro-1,3-diphenylcyclopenta[l]phenanthrene-2-one 6
(dihydrophencyclone; Fig. 2).[24] The dihydrophencyclone
the photooxidation reaction. When the photooxidation reac-
tion was performed over a longer time, the lactone was not
observed, and this may be the result of photochemical decom-
position of the lactone. The products were characterized by
1
isomers 6 are readily detected by H NMR spectroscopy
1
mass spectrometry, vibrational and H and 13C{1H} NMR
due to the presence of a characteristic resonance at δH
5.2 ppm.[29]
spectroscopies, and X-ray crystallography.
The lactone 8 was made independently in near quantitative
yield by treating phencyclone 5 with FeCl3 in chloroform
in the presence of water. No mechanistic studies have been
undertaken to determine the course of the reaction.
Phencyclone 5 undergoes photooxidation to give 9,10-
phenanthrenediylbis(phenyl)methanone 7 (9,10-dibenzoyl-
phenanthrene).[30] The synthesis of 7 has also been achieved
by heating phencyclone at reflux in chlorobenzene or xylene
in the presence of oxygen, with the mechanism believed
Crystal Structures of 7 and 8
3
to be a stepwise 1,4-addition of O2 across the 1,3-diene
9,10-Dibenzoylphenanthrene 7 crystallized from acetone as
discrete molecules. The structure of the compound viewed
along, and perpendicular to, the phenanthrene plane is
illustrated in Fig. 3. Metric data are collected in Tables 1
and 2. Other crystallographic data have been deposited.
The crystal structure of 7 illustrates the non-planar nature
of the phenanthrene moiety, similar to the crystal structures of
system of the cyclopentadiene, followed by chelotropic extru-
sion of CO to form the diketone.[31] The diketone was
formed in the present work as large colourless crystals from
the reaction in wet acetone of phencyclone 5 and atmospheric
oxygen in direct sunlight.Also formed in this reaction was the
lactone 1,4-diphenylcyclo-3-pyran[l]phenanthrene-2-one 8
(Scheme 3). The lactone was formed in trace amounts during
† Impurities (including a hydrate) have been noted by several authors.[25–28] We find that reaction in refluxing propanol initially gives the cis isomer of 1,3-
dihydro-1,3-diphenylcyclopenta[l]phenanthrene-2-one 6 (dihydrophencyclone), which isomerizes to the trans isomer. Sonntag et al.[28] classify the reaction
as an ‘isomerization–cyclization’ rather than a reduction.

138
G. D. Dennis et al.
C(19)
C(15)
C(20)
C(16)
C(17)
C(14)
C(21)
C(18)
C(22)
C(25)
C(13)
C(23)
C(4)
C(12)
C(3)
C(2)
C(11)
C(10)
C(9)
C(5)
C(26)
C(6)
C(1B)
C(27)
C(24)
C(7)
O(1A)
O(1B)
C(28)
C(1A)
C(8)
C(29)
O(2A)
O(2B)
Fig. 4. ORTEP[44] plot (25% probability) of 1,4-diphenylcyclo-3-pyran[l]phenanthrene-2-one 8.
Table 4. Selected bond angles [◦] involving non-hydrogen atoms
for 8
Table 3. Selected bond distances [Å] involving non-hydrogen atoms
for 8
Atoms
Angle
Atoms
Angle
Atoms
Distance
Atoms
Distance
C(1A)–O(1A)–C(5)
O(2A)–C(1A)–O(1A) 119.6(3) C(3)–C(2)–C(6)
121.3(3) O(1B)–C(2)–C(6)
107.7(3)
O(1A)–C(1A)
O(2A)–C(1A)
O(1A)–C(2)
O(1B)–C(1B)
O(2B)–C(1B)
O(1B)–C(2)
C(1A)–C(5)
1.342(5)
1.215(4)
1.518(4)
1.340(11)
1.388(10)
1.272(5)
1.353(3)
C(1B)–C(5)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(2)–C(6)
C(5)–C(24)
1.486(10)
1.372(2)
1.456(2)
1.359(2)
1.485(2)
1.474(2)
128.21(15)
117.53(19)
114.2(2)
118.60(14)
118.79(14)
128.08(14)
O(2A)–C(1A)–C(2)
O(1A)–C(1A)–C(2)
C(2)–O(1B)–C(1B)
O(1B)–C(1B)–O(2B)
O(1B)–C(1B)–C(5)
O(2B)–C(1B)–C(5)
O(1B)–C(2)–C(3)
121.3(3) C(3)–C(2)–C(1A)
118.5(3) C(6)–C(2)–C(1A)
117.3(6) C(2)–C(3)–C(4)
117.2(8) C(3)–C(4)–C(5)
124.8(7) C(4)–C(5)–C(24)
116.5(7) C(24)–C(5)–C(1B) 118.2(4)
124.1(3) C(4)–C(5)–C(1B)
113.3(4)
theroomtemperaturephaseoftheparentphenanthrene.[32–35]
The distortion from planarity in phenanthrene has been
attributed to the close proximity of the hydrogen atoms at
C(15) and C(18). To relieve this steric pressure, the two
outer rings of phenanthrene are mutually inclined at an
angle of 2.4◦. Compound 7 exhibits a greater deviation
from planarity, with the two outer rings mutually inclined
at 7.3◦. The two free phenyl rings, C(5–10) and C(23–
28) are disposed on opposite sides of, and at angles of
74.50 and 88.64◦ to, the phenanthrene backbone. The pre-
viously reported structure of 7[31] shows no distortion of
the phenanthrene moiety and the trans phenyl rings reside
at dihedral angles of 79.1(2) and 80.8(2)◦, respectively, rela-
tive to the phenanthrene ring. All bond distances and angles
are otherwise unexceptional, suggesting that the twisting
in the phenanthrene backbone does not overly disrupt the
π-system.
The crystal structure of 1,4-diphenylcyclo-3-pyran[l]-
phenanthrene-2-one 8 (Fig. 4) shows disorder at the lactone
moiety with the carbonyl group showing occupancy of 65 and
35% over the two sites.The structure shows the phenanthrene
tobeplanar, withthelactonepuckeredout-of-plane.Thebond
lengths of the phenanthrene system show distinct alternating
single and double bonds indicating that it is not aromatic
(Tables 3 and 4).
Ph
Ph
OH
Ph
9-OH
Fig. 5. Structure of 9-OH.
described before this work. Experimental details for the
synthesis of this compound were limited,[36,37] and its char-
acterization was incomplete.
The only published method for the synthesis of 9-OH is
by the room temperature reaction of a suspension of phen-
cyclone 5 in ether with excess phenyllithium, followed by
hydrolysis.[37] The product was reported to be isolated in 42%
yield by this method, and was characterized by vibrational,
electronic, and 1H NMR spectroscopy. However, in this study,
the main product from these reactions was dihydrophency-
clone 6, identified by vibrational spectroscopy, melting point,
and H NMR spectra.[29] The NMR data for 6 show the
presence of both cis and trans isomers.
1
The carbinol 9-OH, prepared according to Scheme 4, is
highly soluble in a range of solvents and indefinitely air-
stable in the dark. Exposure to sunlight for extended periods
resulted in the formation of pale yellow products that were not
Synthesis of 9-OH
The synthetic routes to the carbinol, 1,2,3-triphenylcyclo-
penta[l]phenanthrene-2-ol 9-OH (Fig. 5) were not well

Fused Supracyclopentadienyl Ligand Precursors
139
Ph
Ph
H
H
Ph
Ph
Ph
(a) PhMgBr
(b) Hϩ
O
O
ϩ
OH
Ph
Ph
5
9-OH
6
Scheme 4. Preparation of 9-OH and 6.
Ph
Ph
H
Ph
Br
Ph
HBr/CH3CO2H/⌬
ϩ
O
Ph
OH
Ph
Ph
Ph
Ph
9-OH
10
Scheme 5. Preparation of 10 and 9-Br.
9-Br
in Tables 5 and 6. Crystals of 9-Br suitable for X-ray diffrac-
tion were obtained from chloroform. The structure of the
compound viewed along, and perpendicular to, the cyclopen-
tadienyl plane is illustrated in Fig. 7. Metric data are collected
in Tables 7 and 8.
Ph
X
Ph
Ph
Ph
SOX2/pyridine
Ph
OH
X ϭ Cl, Br
Ph
The preparation of 1-chloro-1,2,3-triphenylcyclopenta[l]-
phenanthrene 9-Cl has been briefly reported.[36] The com-
pound is prepared in good yield (72%) by the reaction
of 1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH with
thionyl chloride in dry pyridine (Scheme 6).
9-OH
9-Cl or 9-Br
Scheme 6. Preparation of 9-Cl and 9-Br.
characterized further but may be the 1-OH isomers, produced
Yields are mostly independent of temperature over the
range 0–50◦C, but the rigorous exclusion of water is essential.
The pale yellow crystals were characterized by vibrational
and 1H and 13C{1H} NMR spectroscopies, mass spectrome-
try, melting point, elemental analysis, and X-ray diffraction.
Crystals suitable for X-ray diffraction were obtained from
dichloromethane/hexane. The structure of 9-Cl is illustrated
in Fig. 8. Metric data are collected in Tables 9 and 10.
The crystal structures of 9-Cl and 9-Br are very similar.
Both compounds crystallize in the same space group. The
C–C bond lengths around the cyclopentadienyl moiety are
identical. However, the C(4)–C(24) bond length in 9-Br is
slightly shorter than the analogous bond length in 9-Cl, at
1.463(7) and 1.484(6) Å, respectively.
by the known photochemical rearrangement.[37]
1-Halo-1,2,3-triphenylcyclopenta[ l]phenanthrene
Derivatives
Theusefulsyntheticprecursor, 1-bromo-1,2,3,4,5-pentaphen-
ylcyclopentadiene 3, can be prepared in high yield by
the reaction of 1,2,3,4,5-pentaphenylcyclopentadiene-1-ol 2
with hydrobromic acid in glacial acetic acid (Scheme 1).[38]
However, themajorproductfromthecorrespondingsynthesis
using 1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH
was the 1,2-phenyl-shifted compound 1,1,3-triphenylcyclo-
penta[l]phenanthrene-2-one 10 in 70% yield (Scheme 5).
The desired product 1-bromo-1,2,3-triphenylcyclopenta[l]-
phenanthrene 9-Br was obtained in low yield (18%) as a yel-
low crystalline solid. Both compounds were characterized by
vibrational and 1H and 13C{1H} NMR spectroscopies, mass
spectrometry, melting point, elemental analysis, and X-ray
crystallography.
A higher yielding synthesis of 9-Br involved the reaction
of 1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH with
thionyl bromide (Scheme 6) in an identical fashion to the
synthesis of the analogous chloro compound 9-Cl, described
below. Using this method, the yield of 9-Br was 74%.
Diffraction-quality crystals of 10, prepared as illustrated
in Scheme 5, were obtained from chloroform.The structure of
the compound is illustrated in Fig. 6. Metric data are collected
Synthesis of 9-H
Two synthetic routes to 1,2,3-triphenyl-1H-cyclopenta[l]-
phenanthrene 9-H have been briefly reported.[36] The first
approachinvolvesthereactionof1,2,3,4,5-pentaphenylcyclo-
pentadiene-1-ol 2 with sulfuric acid and the second proceeds
by reduction of 1-chloro-1,2,3-triphenylcyclopenta[l]-
phenanthrene 9-Cl by the action of zinc in acetic acid. In this
study, reaction of 1,2,3,4,5-pentaphenylcyclopentadiene-1-ol
2 with concentrated sulfuric acid for two minutes afforded
1,2,3-triphenyl-1H-cyclopenta[l]phenanthrene 9-H in 36%
yield as one component of a mixture of about six products
(Scheme 7).

140
G. D. Dennis et al.
C(8)
C(9)
C(7)
C(10)
C(32)
C(30)
C(33)
C(31)
C(34)
C(11)
C(28)
C(29)
C(35)
C(5)
C(6)
C(27)
C(1)
O(1)
C(24)
C(4)
C(2)
C(17)
C(26)
C(25)
C(12)
C(3)
C(13)
C(14)
C(18)
C(16)
C(19)
C(23)
C(15)
C(20)
C(22)
C(21)
Fig. 6. ORTEP[44] plot (25% probability) of 1,1,3-triphenylcyclopenta[l]phenanthrene-2-one 10.
Table 6. Bond angles [◦] involving non-hydrogen atoms for 10
Table 5. Bond distances [Å] involving non-hydrogen atoms for 10
Atoms
Angle
Atoms
Angle
Atoms
Distance
Atoms
Distance
C(1)–C(2)–C(3)
C(1)–C(2)–O(1)
C(5)–C(1)–C(6)
C(5)–C(1)–C(12)
C(6)–C(1)–C(2)
C(6)–C(1)–C(12)
C(12)–C(1)–C(2)
O(1)–C(2)–C(3)
109.58(10)
125.54(11)
114.06(10)
112.78(10)
100.16(9)
113.82(10)
106.89(9)
124.87(11)
C(4)–C(3)–C(18)
C(4)–C(3)–C(2)
C(3)–C(4)–C(24)
C(3)–C(4)–C(5)
C(4)–C(5)–C(1)
C(1)–C(5)–C(35)
C(4)–C(5)–C(35)
C(5)–C(4)–C(24)
115.74(10)
101.64(9)
O(1)–C(2)
C(1)–C(2)
C(1)–C(5)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
C(1)–C(6)
1.2052(14)
1.5600(17)
1.5300(17)
1.5310(17)
1.5107(16)
1.3616(16)
1.5362(17)
C(1)–C(12)
C(3)–C(18)
C(4)–C(24)
C(24)–C(29)
C(29)–C(30)
C(30)–C(35)
C(5)–C(35)
1.5463(17)
1.5280(17)
1.4373(16)
1.4159(16)
1.4608(17)
1.4212(17)
1.4462(16)
125.16(11)
112.61(11)
112.40(10)
126.94(10)
120.65(11)
122.23(11)
The reduction of 1-chloro-1,2,3-triphenylcyclopenta[l]-
phenanthrene 9-Cl by zinc in acetic acid produced 1,2,3-
triphenyl-1H-cyclopenta[l]phenanthrene 9-H as a white crys-
talline solid in almost 80% yield (Scheme 8).
Conclusions
A series of derivatives of 1,3-diphenylcyclopenta[l]phenan-
threne-2-one 5 has been prepared and characterized by
elemental analyses, 1H and 13C{1H} NMR spectroscopy, and,
in some cases, single-crystal X-ray diffraction. The ambi-
guities in some earlier syntheses have been resolved, and
the pure compounds are available in good to high yields.
Several of these compounds are potential ligand precursors
for extremely bulky substituted cyclopentadienyl complexes.
Thus, for example, deprotonation of 1,2,3-triphenyl-1H-
cyclopenta[l]phenanthrene proceeds analogously to that of
pentaphenylcyclopentadiene. The chemistry of the metal
complexes will be reported separately.
1,2,3,4,5-Pentaphenylcyclopentadiene 4 is readily pre-
pared by reduction of 1,2,3,4,5-pentaphenylcyclopentadiene-
1-ol 2 or 1-bromo-1,2,3,4,5-pentaphenylcyclopentadiene 3
by zinc in acetic acid, or better, by the reaction of 1,2,3,4,5-
pentaphenylcyclopentadiene-1-ol 2 with hypophosphorus
andhydriodicacidsinaceticacid. However, hypophosphorus/
hydriodic acid reduction of 1,2,3-triphenylcyclopenta[l]-
phenanthrene-2-ol 9-OH produces 1,2,3-trihydro-1,2,3-
triphenylcyclopenta[l]phenanthrene 11 as a white crystalline
solidingoodyield(Scheme9).Theproductwascharacterized
1
by vibrational and H and 13C{1H} NMR spectroscopies,
mass spectrometry, melting point, and elemental analysis.
Salts of the pentaphenylcyclopentadienyl and penta-p-
tolylcyclopentadienyl anions are remarkably stable, decom-
posing only slowly in air.[19,39] Accordingly, the deproto-
nation of 1,2,3-triphenyl-1H-cyclopenta[l]phenanthrene 9-H
with butyllithium was attempted at room temperature. The
crude product was isolated as a beige powder in good yield
which decomposed rapidly on exposure to air.
Experimental
All reactions were carried out under an atmosphere of high purity argon
(CIG) or nitrogen (CIG) unless otherwise stated and manipulations were
performed using conventional Schlenk techniques.
Reagents
All solvents were distilled under an atmosphere of nitrogen before
use. Benzene (Merck), toluene (BDH), tetrahydrofuran (Merck or

Fused Supracyclopentadienyl Ligand Precursors
141
(a)
(b)
C(27)
C(28)
C(26)
C(25)
C(21)
C(22)
C(29)
C(24)
C(4)
C(20)
C(19)
C(23)
C(32)
C(31)
C(3)
C(2)
C(33)
C(34)
C(5)
C(30)
C(18)
C(17)
C(35)
C(1)
C(12)
C(13)
C(16)
Br(1)
C(6)
C(7)
C(11)
C(15)
C(14)
C(10)
C(9)
C(8)
Fig. 7. ORTEP[44] plot (25% probability) of 1-bromo-1,2,3-triphenylcyclopenta[l]phenanthrene 9-Br viewed (a) along and (b) perpendicular to
the plane of the phenanthrene backbone. Atomic numbering is illustrated in Fig. 7(b).
Table 8. Selected bond angles [◦] involving non-hydrogen atoms for
Table 7. Selected bond distances [Å] involving non-hydrogen atoms
9-Br
for 9-Br
Atoms
Angle
Atoms
Angle
Atoms
Distance
Atoms
Distance
Br(1)–C(1)–C(2)
Br(1)–C(1)–C(5)
Br(1)–C(1)–C(6)
C(2)–C(1)–C(5)
C(2)–C(1)–C(6)
C(5)–C(1)–C(6)
C(1)–C(2)–C(3)
C(1)–C(2)–C(12)
C(3)–C(2)–C(12)
110.2(4)
106.7(3)
111.5(4)
102.3(4)
114.2(5)
111.4(5)
109.8(5)
127.1(5)
123.0(5)
C(2)–C(3)–C(4)
C(2)–C(3)–C(23)
C(4)–C(3)–C(23)
C(3)–C(4)–C(5)
C(3)–C(4)–C(24)
C(5)–C(4)–C(24)
C(1)–C(5)–C(4)
C(1)–C(5)–C(30)
C(4)–C(5)–C(30)
108.1(5)
121.0(5)
130.8(5)
109.9(5)
126.3(5)
123.8(5)
109.5(5)
122.4(5)
127.9(5)
Br(1)–C(1)
C(1)–C(2)
C(1)–C(5)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(5)
1.985(5)
1.514(7)
1.536(7)
1.542(7)
1.364(7)
1.498(7)
1.333(7)
C(4)–C(24)
C(5)–C(30)
C(2)–C(12)
C(3)–C(23)
C(12)–C(17)
C(17)–C(18)
C(18)–C(23)
1.463(7)
1.465(7)
1.435(7)
1.435(8)
1.415(8)
1.426(8)
1.428(8)
Ph
Ph
H
Ph
Ph
Ph
Ph
Ph
(a) H2SO4
(b) H2O, 0ЊC
Ph
H
H
Ph
H
OH
Ph
(a) HI/CH3CO2H/⌬
(b) H2PO4/⌬
Ph
OH
Ph
Ph
Ph
2
9-H
9-OH
11
Scheme 7. Preparation of 9-H.
Scheme 9. Preparation of 11.
Cl
propanol (Merck), chloroform (Rhone–Poulenc), acetone (Merck), and
glacial acetic acid (BDH) were used as received.
H
Ph
Ph
Zn/CH3CO2H/⌬
Ph
Phenanthrenequinone, 1,3-diphenylacteone, tetraphenylcyclopen-
tadienone, hypophosphorus acid, thionyl chloride, thionyl bromide,
hydrobromic acid, acetic anhydride, n-butyllithium (1.6 M in hexanes),
and tetramethylsilane (all Aldrich), were used as received. Bromoben-
zene, hydroiodic acid and zinc dust (all Merck) were used as received.
Flash silica (240–400 mesh) was obtained from Merck. 1,2,3,4,5-
Pentaphenylcyclopentadiene-1-ol was prepared following the procedure
described by Field et al.[38] The crude product, prepared in 93% yield,
was analyzed by vibrational spectroscopy and melting point and found
to be pure enough for use without further purification.
Ph
Ph
Ph
9-Cl
9-H
Scheme 8. Preparation of 9-H.
Rhone–Poulenc), hexane (Merck), and diethyl ether (Merck) were
distilled from sodium benzophenone ketyl. Dichloromethane (Rhone–
Poulenc) was pre-dried over calcium chloride and distilled from calcium
hydride. Chlorobenzene (Merck) was distilled from calcium hydride.
Pyridine (Merck) was pre-dried over potassium hydroxide and dis-
tilled from barium oxide. Methanol (Rhone–Poulenc), ethanol (CSR),
Instrumentation
1H NMR (300.13 MHz) and 13C{1H} NMR (75.48 MHz) spectra were
recorded on a Bruker DRX300 spectrometer. Spectra were referenced
internally to either residual solvent resonances or TMS. Diffuse

142
G. D. Dennis et al.
C(27)
C(28)
C(26)
C(25)
C(21)
C(20)
C(29)
C(22)
C(23)
C(24)
C(32)
C(31)
C(19)
C(4)
C(3)
C(2)
C(33)
C(34)
C(18)
C(30)
C(5)
C(17)
C(35)
C(1)
Cl(1)
C(16)
C(15)
C(12)
C(11)
C(6)
C(7)
C(13)
C(14)
C(10)
C(8)
C(9)
Fig. 8. ORTEP[44] plot(25%probability)of1-chloro-1,2,3-triphenylcyclopenta[l]phenanthrene
9-Cl viewed perpendicular to the plane of the phenanthrene backbone. The atomic numbering is
illustrated in Fig. 8(b).
Table 10. Selected bond angles [◦] involving non-hydrogen atoms
for 9-Cl
Table 9. Selected bond distances [Å] involving non-hydrogen atoms
for 9-Cl
Atoms
Angle
Atoms
Angle
Atoms
Distance
Atoms
Distance
C(2)–C(1)–C(5)
C(2)–C(1)–C(6)
C(5)–C(1)–C(6)
C(2)–C(1)–Cl(1)
C(5)–C(1)–Cl(1)
C(6)–C(1)–Cl(1)
C(3)–C(2)–C(12)
C(2)–C(3)–C(23)
102.8(3)
113.3(3)
111.1(3)
110.8(3)
107.7(3)
110.8(3)
122.5(4)
121.0(4)
C(2)–C(3)–C(4)
C(23)–C(3)–C(4)
C(5)–C(4)–C(24)
C(5)–C(4)–C(3)
C(24)–C(4)–C(3)
C(4)–C(5)–C(30)
C(4)–C(5)–C(1)
C(30)–C(5)–C(1)
108.2(4)
130.8(4)
124.9(4)
109.4(4)
125.7(4)
127.0(4)
109.8(3)
123.0(3)
Cl(1)–C(1)
C(1)–C(2)
C(1)–C(5)
C(1)–C(6)
C(2)–C(3)
C(3)–C(4)
C(4)–C(24)
1.824(4)
1.515(6)
1.520(6)
1.535(6)
1.370(6)
1.497(6)
1.484(6)
C(4)–C(5)
1.342(5)
1.471(6)
1.418(6)
1.435(6)
1.413(6)
1.451(6)
C(5)–C(30)
C(2)–C(12)
C(3)–C(23)
C(12)–C(17)
C(17)–C(18)
reflectance infrared spectra were recorded using a Digilab FTS-40
Fourier-transform spectrometer. Samples were analyzed as homoge-
neous suspensions in a potassium bromide matrix. The resolution used
was 4 cm−1 and, typically, 16 scans were averaged per spectrum. Mass
spectra were obtained either using a Kratos MS 902 double-focusing
spectrometer with a direct insertion probe and an electron-impact ion
source at 200◦C (variations as required), 70 eV ionization voltage, and
8 keV acceleration voltage, or by using a matrix assisted laser desorp-
tion ionization time-of-flight (MALDI-TOF) mass spectrometer with
18 keV acceleration voltage and 21 keV reflection voltage. In the lat-
ter case, samples were introduced on a direct insertion probe and data
were handled by OPUS software on a DECVAXstation 4000. Elemental
analyses were performed by the Australian Microanalytical Service and
melting points were recorded on a Reichert hot platform in air and are
uncorrected.
began to precipitate. The suspension was stirred for a further 15 min
at reflux, cooled in an ice bath for 20 min, and the solid separated by
filtration. The black crystalline solid was washed with methanol until
the washings were colourless, dried under high vacuum (33.4 g, 92%)
mp238–240◦C(lit. 245–255◦C,[25] 250–258◦C,[26] 248–250◦C[27])and
used without further purification. νmax (KBr)/cm−1 3084w, 3056w,
3027w, 1700vs, 1594m, 1494m, 1479m, 1449s, 1344s, 1303s, 1108m,
971w, 805s, 767s, 754vs, 729vs, 719s, 698vs, 637s. δH (CDC13)
7.80 (d, 2H, JHH 7.7, 2 × phenanthrene H), 7.53 (d, 2H, JHH 7.7,
2 × phenanthrene H), 7.40 (m, 10H,ArH), 7.27 (dd, 2H, 3JHH 8, 3JHH 8,
2×phenanthrene H), 6.94 (dd, 2H, 3JHH 8, 3JHH 8, 2×phenanthrene H).
δC (CDCl3) 148.6 (C=O), 134.5, 133.9, 132.6, 131.7, 130.3, 129.4,
128.9, 128.8, 128.6, 128.5, 126.8, 124.8. m/z 382 (100%, M+), 354
(90), 352 (37), 327 (18), 175 (28), 168 (13).
3
3
Syntheses
9,10-Dibenzoylphenanthrene 7
1,3-Diphenylcyclopenta[ l]phenanthrene-2-one 5 (Phencyclone)
Phencyclone 5 (0.50 g, 1.31 mmol) was dissolved in acetone and
left standing in an open vessel with access to direct sunlight for 48 h
until most of the solvent had evaporated. The crystalline material
(0.36 g, 71%) mp 202–204◦C (lit. 206◦C,[40] 208–209◦C,[41,42] 206.5–
207.5◦C[43]) was isolated and recrystallized from acetone. (Found:
Methanolic KOH (3.0 g, 53 mmol in 30 mL) was added dropwise
to a suspension of 1,3-diphenylacetone (20.0 g, 95 mmol) and 9,10-
phenanthrenequinone (19.8 g, 95 mmol) in boiling methanol (800 mL).
The orange suspension slowly darkened and a black crystalline solid

Fused Supracyclopentadienyl Ligand Precursors
143
C 87.0, H 4.8. C28H18O2 requires C 87.0, H 4.7%). Characteriza-
tion showed the compound to be 9,10-dibenzoylphenanthrene 7. νmax
(KBr)/cm−1 3087w, 1667vs, 1586m, 1451m, 1304m, 1237vs, 1163m,
1011w, 829m, 764s, 712s, 689s, 613m. δH (CDCl3) 8.78 (d, 2H, 3JHH
1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH was obtained as a
fluorescent yellow solid after drying under high vacuum (4.2 g, 72%)
mp 222◦C (lit. 222–223◦C,[36] 275◦C[37]). νmax (KBr)/cm−1 3559vs,
3062w, 3028w, 1600w, 1494s, 1449s, 1166w, 1062w, 971w, 918m,
3
3
8.4, 2 × phenanthrene H), 7.79–7.64 (m, 8H), 7.50 (ddd, 4H, JHH 8,
756vs, 730vs, 720s, 703vs. δH (CDCl3) 8.01 (d, 2H, JHH 8, phenan-
3JHH 8, JHH 1), 7.32 (dd, 4H, 3JHH 8, 3JHH 8). δC (CDCl3) 198.3 (C=O),
137.8, 134.2, 134.0, 130.6, 130.3, 128.6, 128.1, 127.6, 127.3, 123.2. m/z
386 (35%, M+), 309 (32), 281 (32), 252 (45), 105 (100), 77 (88), 51 (11).
threne H), 7.60–7.10 (m, 17H,ArH and phenanthrene H), 6.94 (ddd, 2H,
3JHH 8, 3JHH 7, 4JHH 1, phenanthrene H), 6.56 (br s, 2H, phenanthrene
H), 2.12 (s, 1H, OH). δC (CDCl3) 147.2, 137.6, 136.4, 134.6, 133.4,
129.8, 129.3, 129.2, 129.0, 128.8, 128.7, 128.2, 127.8, 127.7, 127.6,
124.0. m/z 460 (100%, M+), 444 (12), 432 (12), 383 (15), 355 (25), 276
(15), 105 (8), 77 (10).
1,4-Diphenylcyclo-3-pyran[ l]phenanthrene-2-one 8
To a solution of phencyclone 5 (100 mg, 0.26 mmol) in undried
chloroform (100 mL) was added FeCl3 (127 mg, 0.78 mmol). An imme-
diate colour change occurred. The reaction mixture was stirred at
room temperature for 3 h. The solvent was removed under vacuum.
The residue was purified by flash chromatography on silica, with
dichloromethane as eluent. 1,4-Diphenylcyclo-3-pyran[l]phenanthrene-
2-one 8 was obtained as an orange crystalline solid upon recrystal-
lization from hot hexane (99 mg, 95%) mp 291–292◦C (dec.). (Found:
C 85.1, H 4.7. C29H18O2·3/11CH2Cl2 requires C 84.7, H 4.5%). νmax
(KBr)/cm−1 3067s, 3026m, 2925m, 2852m, 1706vs, 1520s, 1483m,
1446m, 1348m, 1174s, 1070s, 984s, 933m, 908m, 862w, 797s, 790s,
761s, 752m, 729vs, 705s, 695s. δH (CDCl3) 8.08 (dd, 2H, 3JHH 11, 3JHH
8, 2 × phenanthrene H), 7.79 (m, 2H), 7.52–7.32 (m, 12H), 7.01 (dddd,
2H, JHH 13, 3JHH 7, 3JHH 7, 3JHH 1). δH (CDCl3) 162.6 (C=O), 154.6,
145.8, 136.9, 135.0, 134.2, 131.4, 131.3, 131.1, 131.0, 130.6, 129.4,
129.2, 129.0, 128.6, 128.4, 128.0, 127.3, 126.9, 124.0, 124.0, 120.7,
113.1. m/z 398 (8%, M+), 370 (M+ − CO, 100), 341 (M+ − 2CO, 15),
265 (M+ − 2CO − Ph, 20).
1-Bromo-1,2,3-triphenylcyclopenta[ l]phenanthrene 9-Br
Method 1: A suspension of 1,2,3-triphenylcyclopenta[l]phenanthr-
ene-2-ol 9-OH (1.0 g, 2.17 mmol) in glacial acetic acid (75 mL) was
heated to 60◦C resulting in partial dissolution of the yellow carbinol.
A solution of hydrobromic acid (48%, 1.2 mL, 10.8 mmol) in glacial
acetic acid (4 mL) was added dropwise to the suspension, resulting in the
slow formation of a homogenous orange solution. After stirring at 70◦C
for 2 h, a flocculent white solid precipitated. Stirring was continued at
room temperature for 16 h. Water (30 mL) was added. Dichloromethane
(100 mL) was added and the resulting biphasic solution was separated.
The organic layer was washed with water (2 × 50 mL), 10% Na2CO3
(50 mL), dried over Na2SO4, and the solvent removed under vacuum to
afford a yellow powder. Recrystallization from dichloromethane/hexane
afforded the product 1,1,3-triphenylcyclopenta[l]phenanthrene-2-one
10 (695 mg, 70%) mp 271–273◦C (dec.) as a white microcrystalline
powder. (Found: C 90.3, H 5.5. C35H24O·0.1CH2Cl2 requires C 89.9, H
5.2%). νmax (KBr)/cm−1 3084w, 3059m, 3024w, 1748vs (CO), 1600w,
1494s, 1449m, 1034m, 782m, 757vs, 731s, 700s. δH (CDCl3) 8.79 (d,
2H, 3JHH 8), 8.70–7.55 (m, 4H), 7.50–7.40 (m, 3H), 7.35–7.17 (m, 9H),
7.13–7.07 (m, 5H), 5.32 (s, 1H, CH). δC (CDCl3) 212.9 (C=O), 142.0,
139.7, 139.0, 137.6, 135.3, 132.1, 131.7, 130.3, 129.8, 129.4, 129.0,
128.7, 128.6, 128.5, 128.0, 127.7, 127.6, 127.1, 127.0, 127.0, 70.1, 59.0.
m/z 460 (45%, M+), 432 (77, M − CO), 354 (M − C6H5 − CO), 276
(12), 254 (100), 176 (24).
Crystals suitable for X-ray diffraction were grown by the slow
evaporation of a toluene solution containing 8.
1,2,3-Triphenylcyclopenta[ l]phenanthrene-2-ol 9-OH
Method 1: Phenylmagnesium bromide, produced from magnesium
turnings (0.24 g, 10 mmol) and bromobenzene (1.2 mL, 10 mmol) in
ether (40 mL), was added slowly to a suspension of phencyclone 5
(2.5 g, 6.5 mmol) in benzene (150 mL). The resultant translucent red
solution was stirred at room temperature for 16 h. Upon exposure to air
the reaction mixture turned dark green. The organic phase was washed
with H2SO4 (1 M, 2 × 50 mL) and water (3 × 100 mL), dried over anhy-
drous calcium chloride, filtered, and the volume reduced under vacuum
until solid began to precipitate. Heptane was added until precipitation
was complete. The solid was separated by filtration and washed with
heptane until the washings were colourless.
The air-dried pale green solid was dissolved in benzene and loaded
onto a flash silica column. Using benzene as eluent three fractions were
collected. The first fraction was colourless. The solvent was removed
and the residue was recrystallized from dichloromethane/heptane,
to give a mixture of the cis and trans isomers of 1,3-dihydro-1,3-
diphenylcyclopenta[l]phenanthrene-2-one 6[24] (dihydrophencyclone)
as a pale yellow solid which was identified as comprising the known
isomers of 6 on the basis of melting point and infrared, mass, and
1H NMR spectra. The second fraction was dark green and spectro-
scopically identified as the starting material phencyclone 5. The third
fraction was an intense yellow, which, after removal of the solvent under
vacuum and recrystallization from dichloromethane/heptane, afforded
1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH as a fluorescent
yellow compound (0.30 g, 10%) mp 221–222◦C (lit. 222–223◦C, [36]
275◦C[37]).
X-Ray diffraction quality crystals were grown by the slow infusion
of hexane into a dichloromethane solution of the compound.
The yellow filtrate from the recrystallization was purified by
flash chromatography on silica (40% dichloromethane/60% hexane) to
afford 1-bromo-1,2,3-triphenylcyclopenta[l]phenanthrene 9-Br (0.1 g,
18%) mp 238–240◦C as a yellow powder. (Found: C 79.3, H 4.3.
C35H23Br·0.1CH2Cl2 requires C 79.2, H 4.4%). νmax (KBr)/cm−1
3065m, 3042m, 1568w, 1493s, 1445s, 1034w, 831m, 758vs, 727s,
702vs. δH (CDCl3) 8.80 (dd, 2H, 3JHH 7, 4JHH 1), 7.81 (dd, 1H, 3JHH
4
8, JHH 1), 7.66–7.59 (m, 3H), 7.52–7.05 (m, 15H), 6.80 (m, 2H). δC
(CDCl3) 152.8, 142.6, 140.1, 137.1, 136.7, 133.8, 132.3, 131.3, 130.9,
130.0, 129.8, 128.5, 128.4, 128.3, 128.2, 127.8, 127.7, 127.4, 127.2,
126.8, 126.7, 126.5, 126.4, 126.2, 126.1, 125.9, 123.6, 123.3, 72.2. m/z
524 (3%, M+), 443 (100), 363 (98), 340 (30), 301 (18), 289 (27), 165
(30), 206 (28), 182 (45), 80 (23).
Method 2: Thionyl bromide (0.08 mL, 1.09 mmol) was added to
a suspension of 1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol (9-OH)
(0.50 g, 1.09 mmol) in pyridine (20 mL). The resulting deep red solution
was stirred at room temperature overnight. The solvent was removed
under vacuum. The resulting residue was dissolved in dichloromethane
(50 mL) and washed with water (2 × 50 mL), 10% Na2CO3 solution
(50 mL), and dried over MgSO4. The solvent was removed under vac-
uum to afford an orange powder. The residue was purified by flash
chromatography on silica (eluting with 40% dichloromethane/60%
hexane) to afford 1-bromo-1,2,3-triphenyl-cyclopenta[l]phenanthrene
(9-Br, 0.42 g, 74%).
Method 2: A phenyllithium solution (produced from finely
chopped lithium wire (1.55 g, 0.223 mol) and bromobenzene (11.4 mL,
0.112 mol) in ether (70 mL) was added slowly to a stirred suspen-
sion of phencyclone 5 (4.83 g, 13 mmol) in benzene (300 mL). The
resultant translucent red solution was stirred for 1 h. A methano-
lic KOH solution (3.0 g, 53 mmol in 60 mL) was added dropwise. A
bright yellow solid precipitated and the suspension was stirred for
16 h. The volume of the solvent was reduced by approximately half
under vacuum. The bright yellow solid was separated by filtration.
The crude product was recrystallized from dichloromethane/hexane and
1-Chloro-1,2,3-triphenylcyclopenta[ l]phenanthrene 9-Cl
1,2,3-Triphenylcyclopenta[l]phenanthrene-2-ol 9-OH (0.17 g,
0.37 mmol) was dissolved in pyridine (10 mL) to give a bright yellow/
orange solution. Thionyl chloride (0.03 mL, 0.40 mmol) was added
and gradually the solution colour faded. The solution was stirred at

144
G. D. Dennis et al.
Table 11. X-ray crystallographic data for compounds 7, 8, 9-Br, 9-Cl, and 10
7
8
9-Br
9-Cl
10
Crystal habit
Diffractometer
Temperature [K]
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
Colourless prism
Rigaku
Orange prism
Brüker
Yellow needle
Rigaku
Yellow crystal
Enraf-Nonius
Colourless plate
Brüker
294
2
150
2
294
2
294
2
150
2
C28H18O2
386.45
C29H18O2
398.43
Triclinic
C35H23Br
523.47
C35H23Cl
479.02
C35H24
460.54
O
Monoclinic
P21/n (#14)
10.038(2)
15.211(2)
13.417(1)
90.00
92.324(9)
90.00
2047.0(4)
1.254
Orthorhombic
P212121 (#19)
14.473(2)
19.323(2)
8.732(3)
90.00
90.00
90.00
2442.0(7)
1.424
Orthorhombic
P212121 (#19)
8.743(1)
14.459(1)
19.084(2)
90.00
90.00
90.00
2412.5(3)
1.32
Monoclinic
P21/c (#14)
16.241(5)
9.821(3)
14.979(5)
90.00
101.479(5)
90.00
2341.5(13)
1.306
¯
P1 (#2)
10.4184(19)
10.5625(19)
10.624(2)
64.396(3)
72.359(3)
74.150(3)
990.9(3)
1.335
b [Å]
c [Å]
α [◦]
β [◦]
γ [◦]
V [Å3]
Dcalc [g cm−3
]
Z
4
2
4
4
4
µ [mm−1
]
0.614 (CuKα
3382
3181 (0.02704)
2617 (3.0)
0.0437
)
0.083 (MoKα
41660
4577 (0.0343)
3059 (2.0)
0.0490
0.1143 (F2o, all)
)
2.452 (CuKα
2106
1762
1762 (2.5)
0.0331
0.0320 (Fo)
)
0.182 (MoKα
1644
1327
1341 (2.0)
0.029
0.030 (Fo)
)
0.077 (MoKα
22525
5547 (0.0502)
3860 (2.0)
0.040
0.1143 (F2o, all)
)
No. reflections
Nind (Rmerge
Obs. reflections (I > Xσ(I))
R (Fo)
Rw
)
0.0480 (Fo)
room temperature for 16 h, yielding a pale yellow solid and a pale
yellow/green supernatant. The solvent was removed under vacuum.
The residue was dissolved in dichloromethane (50 mL) and washed
with water (2 × 50 mL), 10% Na2CO3 solution (50 mL), and dried
over MgSO4. The solvent was reduced in volume under vacuum
and hexane was added resulting in the precipitation of the desired
product. Filtration and washing with hexane afforded 1-chloro-1,2,3-
triphenylcyclopenta[l]phenanthrene9-Clasapaleyellowpowder, which
was dried under high vacuum (0.41 g, 77%) mp 257–259◦C (lit. 253–
123.5, 123.4, 58.6. m/z 444 (100%, M+), 365 (11), 289 (16), 265 (6),
183 (8), 165 (4).
Method 2: 1,2,3,4,5-Pentaphenylcyclopentadiene-1-ol 2 (2.0 g,
4.3 mmol) was added to rapidly stirring concentrated sulfuric acid
(50 mL), immediately producing an intense purple solution. After 2 min
of stirring, the acidic solution was quenched with ice-water yielding a
lightbrownsuspension.Thesolubleorganicproductswereextractedinto
dichloromethane (100 mL) and the orange/brown extract was washed
with saturated sodium hydrogen carbonate solution (2 × 100 mL), water
(2 × 100 mL) and saturated sodium chloride solution (100 mL). Analy-
sis of the reaction mixture byTLC with a hexane/dichloromethane (2/1)
solvent system showed the presence of at least six different species.
The solvent was removed under vacuum. The brown residue was redis-
solved in hexane and dichloromethane (2/1) and loaded onto a flash
silica column. The separation on the column was not as well defined
as that on the TLC plate and only two distinct bands were collected.
The first fraction, when analyzed by TLC, showed the presence of three
compounds. The solvent was removed under vacuum. Fractional crys-
tallization from a dichloromethane/hexane mixture yielded two white
compounds, the more insoluble of which was found to be 1,2,3,4,5-
pentaphenylcyclopentadiene 2 (∼0.5 g, 26%). The other compound was
the desired product, 1,2,3-triphenyl-1H-cyclopenta[l]phenanthrene 9-H
(0.7 g, 36%).
3
254◦C[36]). δH (CDCl3) 8.78 (dd, 2H, JHH 8, JHH 11), 7.80 (dd, 1H,
3JHH 8, 4JHH 1), 7.61 (m, 3H), 7.48–7.01 (m, 15H), 6.78 (m, 2H). δC
(CDCl3) 152.5, 142.4, 141.0, 137.5, 136.7, 133.5, 132.3, 130.9, 130.8,
130.1, 129.8, 128.6, 128.4, 128.1, 127.8, 127.7, 127.4, 127.3, 126.9,
126.8, 126.7, 126.7, 126.3, 126.2, 125.9, 125.7, 123.6, 123.3, 78.5. νmax
(KBr)/cm−1 3087w, 3062w, 1594w, 1488s, 1444s, 1069w, 1031w, 875s,
754vs, 740m, 725s, 701vs, 560s. m/z 478 [79%, M − H], 444 (M − Cl,
100), 365 (M − Cl − C6H5, 56), 352 (11), 289 (M − Cl − 2C6H5, 21),
265 (24), 212 (7), 182 (42).
1,2,3-Triphenyl-1H-cyclopenta[ l]phenanthrene 9-H
Method 1: A suspension of 1-chloro-1,2,3-triphenylcyclopenta[l]-
phenanthrene 9-Cl (0.20 g, 0.42 mmol) and zinc dust (0.11 g, 1.7 mmol)
was stirred in acetic acid (20 mL) at 100◦C for 2 h. The result-
ing suspension was cooled to room temperature. Water (50 mL) was
added and the resulting solution was extracted with dichloromethane
(3 × 50 mL). The organic phase was washed with water (2 × 50 mL),
10% Na2CO3 solution (1 × 50 mL), and dried over MgSO4. The
solvent was removed under vacuum. The residue was recrystal-
lized from dichloromethane/hexane to afford 1,2,3-triphenyl-1H-
cyclopenta[l]phenanthrene 9-H as an off-white microcrystalline powder
(0.14 g, 76%) mp 224–225◦C (lit. 220–221◦C[36]). (Found: C 94.8, H
5.6. Calc. forC35H24 C94.6, H5.4%). νmax (KBr)/cm−1 3057m, 3025m,
2926w, 1600w, 1493s, 1443s, 1073w, 1029m, 836w, 755vs, 724s, 714s,
696vs, 559m. δH (CDCl3) 8.71 (dd, 2H, JHH 19, 3JHH 8), 7.85 (d, 1H,
3JHH 8), 7.65–7.49 (m, 5H), 7.46–7.23 (m, 5H), 7.17–7.00 (m, 10H),
5.45 (s, 1H, CpH). δC (CDCl3) 150.2, 142.9, 141.3, 139.6, 138.5, 135.7,
131.5, 130.9, 129.7, 129.6, 129.1, 128.8, 128.7, 128.6, 128.5, 128.4,
127.7, 127.6, 126.8, 126.8, 126.6, 126.0, 125.8, 125.6, 125.3, 124.6,
The second fraction did not contain any of the desired product and
was not analyzed further.
1,2,3-Trihydro-1,2,3-triphenylcyclopenta[l]phenanthrene 11
Hydriodic acid (57%, 0.29 mL, 2.16 mmol) was added dropwise to
a suspension of 1,2,3-triphenylcyclopenta[l]phenanthrene-2-ol 9-OH
(0.25 g, 0.54 mmol) in glacial acetic acid (20 mL) at 50◦C.After 10 min,
hypophosphorous acid (50%, 0.29 mL, 2.70 mmol) was added drop-
wise and the solution was refluxed for a further 2 h. The orange colour
faded over this period and the colourless solution was cooled and stirred
at room temperature for 15 h. The solvent was removed under vac-
uum. The residue was dissolved in dichloromethane (50 mL), and the
organic phase was washed with water (2 × 50 mL), 10% Na2CO3 solu-
tion (50 mL), and dried over MgSO4. The solvent was removed under
vacuum to afford the product as an-off white powder. Recrystalliza-
tion from dichloromethane/methanol yielded the product as an off-white

Fused Supracyclopentadienyl Ligand Precursors
145
crystalline powder 11 (169 mg, 70%) mp 196–198◦C. (Found: C 90.06,
H 5.16. C35H26·0.3CH2Cl2 requires C 89.80, H 5.69%). δH (CDCl3)
8.73 (dd, 2H, JHH 20, 3JHH 8), 7.88 (d, 1H, JHH 8), 7.69–7.25 (m, 12H),
7.18–7.06(m, 10H), 5.48(s, 1H). δC (CDCl3)150.2, 142.9, 141.3, 139.6,
138.5, 135.7, 131.5, 130.9, 129.7, 129.1, 128.8, 128.7, 128.6, 128.5,
128.4, 127.7, 127.6, 126.8, 126.6, 126.0, 125.8, 125.6, 125.3, 124.6,
123.4, 123.4, 58.6. νmax (KBr)/cm−1 3060w, 3026m, 2902w, 1601m,
1494s, 1451s, 1156w, 1036w, 780m, 758vs, 727vs, 702vs, 534m. m/z
446 (100%, M+), 368 (33), 355 (30), 289 (14), 279 (22), 165 (6), 145
(18), 91 (8), 58 (11), 43 (42).
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Single Crystal X-ray Diffraction
Crystals were mounted on thin fibres and all measurements were made
using either (a) a Rigaku AFC7R 12 kW rotating anode diffractome-
ter and CuKα radiation (λ 1.5418 Å), (b) an Enraf-Nonius CAD4 and
MoKα radiation (λ 0.7107 Å), or (c) a Bruker SMART 1000 CCD and
MoKα radiation. Radiation was graphite monochromated. Crystallo-
graphic data are summarized in Table 11, and ORTEP[44] depictions
are provided in Figs 3, 4, 6, 7, and 8. A Gaussian[45] correction was
applied to data from 8, empirical absorption corrections based on the
azimuthal scans of several reflections[46] were applied to 7 and 9-Br,
and no correction was applied for 9-Cl and 10.
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2002, 58, 8875. doi:10.1016/S0040-4020(02)01054-2
[30] J.-J. Basselier, F. Caumartin, J.-C. Cherton, J.-P. L. Roux, Bull.
Soc. Chim. Fr. 1974, 12, 2950.
[31] A. P. Marchand, G. Srinivas, W. H. Watson, Arkivoc 2003, 6, 8.
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0X63001626
[34] M. I. Kay, Y. Okaya, D. E. Cox, Acta Crystallogr. B 1971, 27, 26.
doi:10.1107/S0567740871001663
[35] B. Benzina, L. Cisarova, L. Hummel, J. Kroupa, V. Petricek, Acta
Crystallogr. B 1990, 46, 830.
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doi:10.1021/JA01478A046
[37] J.-J. Basselier, F. Caumartin, J.-P. L. Roux, J.-C. Cherton, Bull.
Soc. Chim. Fr. 1974, 12, 2935.
[38] L. D. Field, K. M. Ho, C. M. Lindall, A. F. Masters, A. G. Webb,
Aust. J. Chem. 1990, 43, 281. doi:10.1071/CH9900281
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1982, 229, 109. doi:10.1016/S0022-328X(00)90273-0
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97. doi:10.1002/PRAC.19381510401
[41] H. E. Zimmerman, G. D. Heinz, R. S. Givens, R. G. Lewis, J. Am.
Chem. Soc. 1967, 89, 1863. doi:10.1021/JA00984A019
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1972, 758, 16.
The structures were solved by direct methods (SHELXS-86[47] for
7, 9-Br, 9-Cl, SHELX-97[48] for 10, and SIR97[49] for 8), and expanded
using Fourier techniques using either DIRDIF[50] (7, 9-Br, 9-Cl) or
SHELX [48] (8 and 10) and the teXsan,[51] WinGX [52] and Xtal[53] graph-
ical interfaces. Non-hydrogen atoms were refined anisotropically and
hydrogen atoms were included at calculated positions. The ester unit
in 8 is disordered about two orientations, with complementary occu-
pancies refined and then fixed at 0.65 and 0.35. The partial-occupancy
non-hydrogen sites were modelled with isotropic displacement param-
eters. The absolute structure of 9-Cl was determined but not reliably
established with the Flack[54–57] parameter refining to 0.0(1) for the
unique dataset; the absolute structure of 9-Br was established with the
Flack parameter refining to 0.00(3).
Crystal structure data have been deposited at the Cambridge Crystal-
lographicDataCentrewithdepositionnumbersCCDC263929–263933.
Acknowledgement
We thank the Australian Research Council for financial
support.
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