Synthesis and structure of Os(η2-3,3-diphenylcyclopropene)Cl(NO)(PPh3)2 and the ring-opening reactions of the π-bound cyclopropene with acids

Article abstract of DOI:10.1016/j.ica.2006.02.012

Reaction between the zerovalent nitrosyl complex, OsCl(NO)(PPh₃)₃ and 3,3-diphenylcyclopropene yields the robust π-adduct, Os(η²-3,3-diphenylcyclopropene)Cl(NO)(PPh₃)₂ (1), the crystal structure of which reveals the chloride and nitrosyl ligands located mutually trans and the Os, the two PPh₃ ligands and the double bond of the cyclopropene, all lying in one plane. Treatment of 1 with the acids HX (X = Cl, O₂CCF₃) brings about a ring-opening of the cyclopropene ring (perhaps via an intermediate diphenylvinyl carbene complex) with the organic moiety remaining bound to osmium and with ultimate formation of the σ-diphenylallyl complexes, Os(CH₂CH{double bond, long}CPh₂)Cl₂(NO)(PPh₃)₂ (2) and Os(CH₂CH{double bond, long}CPh₂)Cl(O₂CCF₃)(NO)(PPh₃)₂ (3), respectively. A crystal structure determination for 2 has been obtained.

Full text of DOI:10.1016/j.ica.2006.02.012

Inorganica Chimica Acta 359 (2006) 3763–3768
www.elsevier.com/locate/ica
Synthesis and structure of
Os(g2-3,3-diphenylcyclopropene)Cl(NO)(PPh3)2 and the ring-opening
reactions of the p-bound cyclopropene with acids
*
George R. Clark, Laura G. Raymond, Warren R. Roper , Deborah M. Tonei,
*
L. James Wright
Department of Chemistry, The University of Auckland, Private Bag 92019, Auckland, New Zealand
Received 7 February 2006; accepted 7 February 2006
Available online 23 February 2006
Dedicated to Professor Michael Mingos, FRS, in recognition of his contributions to chemistry.
Abstract
Reaction between the zerovalent nitrosyl complex, OsCl(NO)(PPh3)3 and 3,3-diphenylcyclopropene yields the robust p-adduct,
Os(g2-3,3-diphenylcyclopropene)Cl(NO)(PPh3)2 (1), the crystal structure of which reveals the chloride and nitrosyl ligands located mutu-
ally trans and the Os, the two PPh3 ligands and the double bond of the cyclopropene, all lying in one plane. Treatment of 1 with the acids
HX (X = Cl, O2CCF3) brings about a ring-opening of the cyclopropene ring (perhaps via an intermediate diphenylvinyl carbene com-
plex) with the organic moiety remaining bound to osmium and with ultimate formation of the r-diphenylallyl complexes,
Os(CH2CH@CPh2)Cl2(NO)(PPh3)2 (2) and Os(CH2CH@CPh2)Cl(O2CCF3)(NO)(PPh3)2 (3), respectively. A crystal structure determina-
tion for 2 has been obtained.
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Nitrosyl complex; Osmium; 3,3-Diphenylcyclopropene complex; X-ray crystal structure
1. Introduction
ring-opening reactions (favoured at higher oxidation state
metal centres) that can give rise to various products includ-
ing vinyl alkylidene species (structure B in Chart 1) and
metallacyclobutenes (structure C in Chart 1). The nature
of the product formed depends on the transition metal,
the nature and size of accompanying ligands, and the sub-
stituents on the cyclopropene. Numerous examples of
structure type A have been reported and those for the fol-
lowing metals have been characterised by X-ray crystal
structure determinations, Mo [3], W [4], Ir [5], Ni [6], and
Pt [7]. Further well-characterised examples are provided
by the rhoda- and iridabenzvalene compounds described
by Haley [8], for which an alternative description of the
bonding is as tethered g2-cyclopropene complexes.
The interaction of cyclopropene and substituted cyclo-
propenes with transition metals has generated much inter-
est in organic and organometallic chemistry [1]. In
addition, transition metal complexes containing g2-bound
cyclopropenes have been studied in bioinorganic chemistry
in an endeavour to model nitrogenase reactivity [2].
In organometallic chemistry the reaction between cyclo-
propene and the metal substrate follows predominantly
two pathways [1], either to give g2-coordination of the
intact cyclopropene ligand (favoured at low oxidation state
metal centres) as represented by structure A in Chart 1, or
We have previously reported that OsCl(NO)(PPh3)3
forms stable complexes with tetrafluoroethylene and maleic
anhydride viz., Os(g2-C2F4)Cl(NO)(PPh3)2 and Os(g2-
*
Corresponding authors. Tel.: +64 9 373 7999x88320; fax: +64 9 373
7422.
E-mail address: w.roper@auckland.ac.nz (W.R. Roper).
0020-1693/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2006.02.012

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G.R. Clark et al. / Inorganica Chimica Acta 359 (2006) 3763–3768
Complex 1 has a m(NO) band in the IR spectrum at
1768 cmꢀ1, greatly increased from the m(NO) observed for
OsCl(NO)(PPh3)3 at 1630 cmꢀ1 but similar to the value
observed for Os(g2-maleic anhydride)Cl(NO)(PPh3)2 at
1780 cmꢀ1 [9]. This observation is consistent with a strong
g2-interaction of the cyclopropene with the metal centre.
M
M
M
A
B
C
1
The H NMR spectrum of 1 shows the two cyclopropene
Chart 1. Three typical structure types from the interaction of cycloprop-
enes with metal centres.
protons as an apparent triplet (not a true triplet because
the two carbon atoms to which these protons are bound
have a more complex multiplicity, see below) at 4.07 ppm
with coupling to the two phosphorus nuclei of 5.1 Hz.
The 13C NMR spectrum of 1 shows the two metal-bound
carbon atoms as an apparent quintet at 53.5 ppm which
we interpret as being part of a second-order spectrum that
results because the two olefinic carbon atoms are not
exactly equivalent in solution. It is worth noting that the
closely related 3,3-diphenylcyclopropene complex of irid-
maleic anhydride)Cl(NO)(PPh3)2, respectively, and in both
complexes the triphenylphosphine ligands are located
mutually trans [9]. In this paper, we investigate the reaction
between OsCl(NO)(PPh3)3 and 3,3-diphenylcyclopropene,
and explore the reactivity of the resulting complex towards
acids.
We describe herein: (i) the formation and crystal struc-
ture of the g2-cyclopropene complex, Os(g2-3,3-diphenyl-
cyclopropene)Cl(NO)(PPh3)2 (1); (ii) the reaction of 1
with hydrochloric and trifluoroacetic acids to bring about
ring-opening of the cyclopropene and ultimate formation
of the r-diphenylallyl complexes, Os(CH2CH@CPh2)Cl2-
(NO)(PPh3)2 (2) and Os(CH2CH@CPh2)Cl(O2CCF3)-
(NO)(PPh3)2 (3), respectively; and (iii) the crystal structure
determination of 2.
ium(I),
Ir(g2-3,3-diphenylcyclopropene)Cl(CO)(PMe3)2,
which has the same structure as 1 (see below), has been
reported to show exactly the same multiplicity for the ole-
finic carbon atoms, and the resonance in this case was
described as a pseudoquintet at 37.1 ppm [5]. In the 31P
NMR spectrum of 1 the phosphorus resonance appears
as a singlet at ꢀ3.13 ppm. None of the above spectroscopic
information unambiguously defines the geometry of 1 and
therefore an X-ray crystal structure determination of 1 was
undertaken.
2. Results and discussion
The molecular geometry of 1 is depicted in Fig. 1.
Crystal data pertaining to this structure and the other
structure reported in this paper are presented in Table 1.
Selected bond lengths and angles for 1 are collected in
Table 2. The overall geometry about osmium can be
described as distorted octahedral with the two triphenyl-
phosphine ligands arranged mutually cis (P(1)–Os–P(2),
2.1. Reaction between OsCl(NO)(PPh3)3 and 3,3-
diphenylcyclopropene to form the p-complex, Os(g2-3,3-
diphenylcyclopropene)Cl(NO)(PPh3)2 (1) and the crystal
structure of complex 1
Treatment of a dark green solution of OsCl(NO)(PPh3)3
with 3,3-diphenylcyclopropene brings about an immediate
colour change to orange, and bright orange crystals of
Os(g2-3,3-diphenylcyclopropene)Cl(NO)(PPh3)2 (1) can
be isolated from the solution (see Scheme 1).
Ph
Ph
(-PPh3)
H
Cl
Os
NO
Cl
Ph
H
Ph3P
Ph3P
C
C
Ph3P
Ph3P
Os
PPh3
C
NO
(1)
Ph
HX
*
+
PPh3
Os
PPh3
Os
Hydride
migration
Cl
X
Cl
H
C
-
X
H
ON
CH2
C
Ph
ON
Ph
Ph
PPh3
PPh3
C
C
C
(D)
H
Ph
H
(2) X = Cl
(3) X = O2CCF3
Scheme 1. Synthesis and reactions of Os(g2-3,3-diphenylcyclopro-
Fig. 1. Molecular geometry of Os(g2-3,3-diphenylcyclopropene)Cl(NO)-
(PPh3)2 (1) showing the atom labelling and atoms as 50% probability
displacement ellipsoids [22].
pene)Cl(NO)(PPh3)2 (1) with acids (compound labelled with
is a
*
postulated intermediate).

G.R. Clark et al. / Inorganica Chimica Acta 359 (2006) 3763–3768
3765
Table 1
Data collection and processing parameters for 1 and 2
Table 2
˚
Selected bond lengths (A) and angles (ꢁ) for 1
˚
Bond lengths (A)
Compound
1
2
Os–N
1.749(5)
Formula
C51H42ClNOOsP2
972.45
monoclinic
P21/c
13.6674(2)
11.1122(2)
27.9419(1)
90.0
101.305(1)
90.0
C51H43Cl2NOOsP2
1008.90
monoclinic
C2/c
31.6520(5)
10.6344(1)
26.3414(3)
90.0
106.249(1)
90.0
Os–C(1)
Os–C(2)
Os–Cl
Os–P(1)
Os–P(2)
O–N
C(1)–C(2)
C(2)–C(3)
C(1)–C(3)
C(3)–C(4)
C(3)–C(10)
2.081(6)
2.095(6)
2.4228(14)
2.4288(15)
2.4323(14)
1.171(6)
1.485(7)
1.542(8)
1.542(7)
1.502(8)
1.530(9)
Molecular weight
Crystal system
Space group
˚
a (A)
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
3
˚
V (A )
4161.3(1)
84
8512.3(2)
84
T (K)
Z
4
8
Bond angles (ꢁ)
N–Os–C(1)
N–Os–C(2)
C(1)–Os–C(2)
N–Os–Cl
C(1)–Os–Cl
Dcalc (g cmꢀ3
F(000)
)
1.552
1944
3.245
0.42 · 0.26 · 0.20
1.98–25.50
31373
1.574
4032
3.237
0.202 · 0.15 · 0.10
1.78–25.69
23306
105.4(2)
102.9(2)
41.6(2)
l (mmꢀ1
Crystal size (mm)
2h (minimum–maximum) (ꢁ)
Reflections collected
)
173.65(19)
80.93(14)
81.88(15)
87.32(18)
144.08(14)
103.23(16)
87.50(5)
93.80(15)
101.07(14)
141.91(16)
84.69(5)
111.62(5)
61.2(3)
C(2)–Os–Cl
Independent reflections (Rint
T (minimum–maximum)
Goodness-of-fit on F2
R (observed data)
)
7752 (0.0512)
0.4297–0.5521
0.991
R1 = 0.0428,
wR2 = 0.0907
R1 = 0.0648,
wR2 = 0.0982
P
8043 (0.0684)
0.5646–0.8249
1.027
R1 = 0.0416,
wR2 = 0.0846
R1 = 0.0651,
wR2 = 0.0935
N–Os–P(1)
C(1)–Os–P(1)
C(2)–Os–P(1)
Cl–Os–P(1)
N–Os–P(2)
R (all data)
C(1)–Os–P(2)
C(2)–Os–P(2)
Cl–Os–P(2)
P
P
P
2
2
1=2
R = iFo| ꢀ |Fci/ |Fo|; wR2 ¼ f ½wðF 2o ꢀ F c2Þ ꢁ= ½wðF o2Þ ꢁg
.
P(1)–Os–P(2)
C(1)–C(2)–C(3)
C(2)–C(1)–C(3)
C(2)–C(3)–C(1)
C(3)–C(1)–Os
C(1)–C(2)–Os
C(3)–C(2)–Os
C(4)–C(3)–C(10)
C(4)–C(3)–C(2)
C(10)–C(3)–C(2)
111.62(5)ꢁ) and the chloride and nitrosyl ligands mutually
trans (N–Os–Cl, 173.65(19)ꢁ). The two olefinic carbon
atoms of the cyclopropene occupy the remaining two sites
with the very small bite angle of 41.6(2)ꢁ. The two Os–C
distances are equivalent (Os–C(1), 2.081(6); Os–C(2),
61.2(4)
57.6(3)
108.7(4)
68.7(3)
108.1(3)
116.7(5)
123.2(5)
112.5(5)
˚
2.095(6) A) as are the two Os–P distances (Os–P(1),
˚
2.4288(15); Os–P(2), 2.4323(14) A). The Os–C distances
are short when compared with a regular Os–C r-bond such
as that in complex 2 (see below) where the Os–
opened alkenes. Nb(g2-C3H4)Cp2 for example, with HCl
gives only cyclopropane [10]. On the other hand, Leigh
et al., have made a detailed study of the reaction between
Pt(g2-3,3-diphenylcyclopropene)(PPh3)2 and HCl and
demonstrated that not only 1,1-diphenylcyclopropane but
3,3-diphenylpropene, 1,2-diphenylpropene, and 1,1-diphe-
nylpropene, are formed as well [1,11]. These organic prod-
ucts are all proposed to arise from a cyclopropyl–platinum
intermediate which may rearrange to a r-allyl platinum
complex before final cleavage from platinum.
˚
CH2CH@CPh2 distance is 2.196(5) A. The C(1)–C(2) dis-
˚
tance is 1.485(7) A, indicative of a C–C single bond and
reflecting the strong interaction of the cyclopropene with
osmium and justifying the depiction of the complex in
Scheme 1 as a metallabicyclobutane. The overall structure
is closely similar to that reported for the related compound
Ir(g2-3,3-diphenylcyclopropene)Cl(CO)(PMe3)2 [5] where
˚
the C–C distance is 1.445(9) A. It may be significant that
in both structures the cyclopropene ligand is buckled
towards the p-acid ligand (CO or NO).
It is frequently observed that the reaction of acids with
low oxidation state osmium complexes containing unsatu-
rated molecules bound as ligands give rise to isolable com-
plexes in which a reduced form of the ligand is retained in
the osmium coordination sphere [12]. An example is the g2-
ethylene complex of osmium, Os(g2-C2H4)(CO)2(PPh3)2
which reacts with HCl to give the isolable r-bound ethyl
complex Os(C2H5)Cl(CO)2(PPh3)2 [13]. It might therefore
have been expected that treatment of complex 1 with HCl
might generate the related r-bound 2,2-diphenylcyclopro-
pyl complex, ‘‘Os(C3H3Ph2)Cl2(NO)(PPh3)2’’. In fact, as
2.2. Reactions of Os(g2-3,3-diphenylcyclopropene)-
Cl(NO)(PPh3)2 (1) with HCl and trifluoroacetic acid to
form Os(CH2CH@CPh2)Cl2(NO)(PPh3)2 (2) and
Os(CH2CH@CPh2)Cl(O2CCF3)(NO)(PPh3)2 (3),
respectively, and the crystal structure of complex 2
Previous investigations of the protonation of g2-cyclo-
propene metal complexes have reported that the organic
fragment is lost from the metal and the isolated organic
products are the reduced cyclopropanes or derived ring-

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G.R. Clark et al. / Inorganica Chimica Acta 359 (2006) 3763–3768
Table 3
shown in Scheme 1 treatment of 1 with either HCl or triflu-
oroacetic acid generates, in high yield, the stable, yellow,
r-bound diphenylallyl complexes Os(CH2CH@CPh2)-
Cl2(NO)(PPh3)2 (2) or Os(CH2CH@CPh2)Cl(O2CCF3)-
(NO)(PPh3)2 (3), respectively. This surprising result can
be rationalized if it is supposed that initial protonation at
the osmium (oxidation) brings about a ring-opening of
the cyclopropene ring to form an intermediate diphenylvi-
nyl carbene complex, the proposed intermediate D in
Scheme 1. This is reasonable since ruthenium(II) and
osmium(II) substrates have been shown to react with
3,3-diphenylcyclopropene to form ring-opened diphenylvi-
nyl carbene complexes [4]. Since there is an adjacent
hydride ligand in this intermediate, migratory insertion
(hydride to carbene) would be expected to follow rapidly
and coordination of either chloride or trifluoracetate would
give the observed products. An alternative possibility is
that protonation of 1 occurs to give first a r-2,2-diphenyl-
cyclopropyl complex which might then rearrange to the
observed r-bound diphenylallyl complex [11].
˚
Selected bond lengths (A) and angles (ꢁ) for 2
˚
Bond lengths (A)
Os–N
1.763(6)
2.196(5)
Os–C(1)
Os–Cl(1)
Os–P(1)
Os–P(2)
Os–Cl(2)
O–N
C(1)–C(2)
C(2)–C(3)
C(3)–C(10)
C(3)–C(4)
2.3887(14)
2.4501(14)
2.4524(14)
2.4984(14)
1.127(6)
1.475(8)
1.349(8)
1.495(8)
1.509(8)
Bond angles (ꢁ)
N–Os–C(1)
N–Os–Cl(1)
C(1)–Os–Cl(1)
N–Os–P(1)
C(1)–Os–P(1)
Cl(1)–Os–P(1)
N–Os–P(2)
C(1)–Os–P(2)
Cl(1)–Os–P(2)
P(1)–Os–P(2)
N–Os–Cl(2)
C(1)–Os–Cl(2)
Cl(1)–Os–Cl(2)
P(1)–Os–Cl(2)
P(2)–Os–Cl(2)
O–N–Os
C(2)–C(1)–Os
C(3)–C(2)–C(1)
C(2)–C(3)–C(10)
C(2)–C(3)–C(4)
C(10)–C(3)–C(4)
92.5(2)
179.25(15)
87.12(14)
91.68(15)
89.78(15)
87.68(5)
89.96(15)
95.57(15)
90.71(5)
174.33(5)
89.65(15)
175.42(15)
90.71(5)
86.10(5)
88.49(5)
175.6(5)
119.3(4)
126.9(5)
122.2(5)
122.2(5)
115.5(5)
The IR spectra of 2 and 3 show m(NO) at 1825 and
1832 cmꢀ1, respectively, both values increased from the
1
value observed for 1 (1768 cmꢀ1). The H NMR spectrum
of 2 shows a doublet of triplets resonance at 4.10 ppm
3
(3JHP = 4.1 Hz, JHH = 8.4 Hz) for the osmium-bound
CH2 group, and a triplet resonance at 6.22 ppm (3JHH
=
8.5 Hz) for the –CH@ group of the diphenylallyl ligand.
Corresponding signals for 3 occur at 4.30 ppm (3JHP
=
3.9 Hz, JHH = 7.9 Hz), and 6.18 ppm (3JHH = 8.1 Hz).
The 13C NMR spectrum of 2 shows a broad signal at
13.1 ppm for the osmium-bound CH2 group, and a singlet
at 139.4 ppm for the –CH@ group of the diphenylallyl
ligand. Corresponding signals for 3 occur at 5.5 and
138.9 ppm. For both compounds there are virtual triplets
in the carbon resonances of the triphenylphosphine ligands
3
indicating a mutually trans arrangement of these ligands
and the 31P NMR spectra show singlets at ꢀ11.96 ppm
for 2 and ꢀ6.48 ppm for 3.
The molecular structure of 2 is depicted in Fig. 2.
Selected bond lengths and angles for 2 are collected in
Table 3.
The overall geometry about osmium can be described as
octahedral with the two triphenylphosphine ligands
arranged mutually trans and the two chloride ligands
mutually cis. The Os–Cl distance trans to the diphenylallyl
˚
ligand is 2.4984(14) A, while the corresponding distance
˚
trans to the nitrosyl ligand is 2.3887(14) A. This reflects
the strong structural trans influence of the diphenylallyl
ligand relative to the nitrosyl group. The Os–C distance
˚
is 2.196(5) A, typical for an Os–C single bond and can be
compared with the Os–Methyl distance in Os(Me)(Sn-
˚
Me2Cl)(CO)2(PPh3)2 which is 2.209(4) A [14]. The C–C dis-
tances within the diphenylallyl group are C(1)–C(2),
˚
˚
1.475(8) A, appropriate for a single bond and C(2)–C(3),
1.349(8) A, appropriate for a double bond.
3. Conclusions
Fig. 2. Molecular geometry of Os(C H2CH@CPh2)Cl2(NO)(PPh3)2 (2)
showing the atom labelling and atoms as 50% probability displacement
ellipsoids [22].
It has been demonstrated that the 3,3-diphenylcyclopro-
pene complex, Os(g2-3,3-diphenylcyclopropene)Cl(NO)-

G.R. Clark et al. / Inorganica Chimica Acta 359 (2006) 3763–3768
3767
(PPh3)2 (1) has a strong p-interaction with the C@C double
bond and the overall geometry has the chloride and nitro-
syl ligands located mutually trans and the Os, the two PPh3
ligands and the double bond of the cyclopropene, all lying
in one plane. Treatment of this compound with acids (HCl
and CF3CO2H) brings about a ring-opening of the cyclo-
propene ring with ultimate formation in high yield of the
stable r-diphenylallyl complexes, Os(CH2CH@CPh2)Cl2-
(NO)(PPh3)2 (2) and Os(CH2CH@CPh2)Cl(O2CCF3)(NO)-
(PPh3)2 (3), respectively. The structures of 2 and 3 are
established by spectroscopic data and a crystal structure
determination of 2.
vivid orange microcrystals (0.329 g, 50%). Anal. Calc. for
C51H42ClNOOsP2: C, 62.99; H, 4.35; N, 1.44. Found: C,
62.89; H, 4.50; N, 1.50%. IR (cmꢀ1): 1768 m(NO). 1H
3
NMR (CDCl3, d): 4.07 (apparent t, 2H, JHP = 5.1 Hz,
HC@CH), 7.01–7.88 (m, 40H, PPh3 and C3H2Ph2). 13C
NMR (CDCl3, d): 53.5 (apparent quintet, 2JCP = ca.18 Hz,
HC@CH), 69.2 (s, CPh2), 126.3, 127.4, 132.2, 147.1, 151.9
(s, CPh2), 127.9, 130.0, 132.7, 134.4 (s/m, PPh3). 31P{1H}
NMR (CDCl3, d): ꢀ3.13 (s, PPh3).
4.3. Preparation of Os(CH2CH@CPh2)Cl2(NO)(PPh3)2
(2)
4. Experimental
Os(g2-3,3-diphenylcyclopropene)Cl(NO)(PPh3)2
(1)
(0.256 g) was dissolved in a solvent mixture of dry dichloro-
methane (30 mL) and ethanol (3 mL). HCl (36%, 30 lL)
was added via syringe to this stirred orange solution and
after 15 min the dichloromethane was removed under
reduced pressure. Pale orange microcrystals of pure 2 were
4.1. General procedures and instruments
Standard laboratory procedures were followed as have
been described previously [15]. The compounds OsCl(NO)-
(PPh3)3 (and its precursor Os(peroxycarbonyl)Cl(NO)-
(PPh3)2) [16] and 3,3-diphenylcyclopropene [17] were
prepared according to the literature methods.
1
collected (0.218 g, 81%). These micro crystals retained a
4
mole equivalent of CH2Cl2 as evidenced by the NMR spec-
trum and the elemental analysis. However, the single crystal
grown slowly by layering ethanol over a CH2Cl2 solution of
2 was unsolvated. Anal. Calc. for C51H43Cl2NOOsP2 Æ
1/4CH2Cl2: C, 59.70; H, 4.22; N, 1.36. Found: C, 59.91;
H, 4.33; N, 1.58%. IR (cmꢀ1): 1825 m(NO). 1H NMR
Infrared spectra (4000–400 cmꢀ1) were recorded as
Nujol mulls between KBr plates on a Perkin–Elmer Para-
gon 1000 spectrometer. NMR spectra were obtained on
either a Bruker DRX 400 or a Bruker Avance 300 at
1
3
3
25 ꢁC. For the Bruker DRX 400, H, 13C, and 31P NMR
(CDCl3, d): 4.10 (dt, 2H, JHP = 4.1 Hz, JHH = 8.4 Hz,
3
spectra were obtained operating at 400.1 (1H), 100.6
(13C), and 162.0 (31P) MHz, respectively. For the Bruker
CH2), 6.22 (t, 1H, JHH = 8.5 Hz, CH@), 6.53–7.94 (m,
40H, PPh3 and C3H2Ph2). 13C NMR (CDCl3, d): 13.1
1
Avance 300, H, 13C, and 31P NMR spectra were obtained
(broad s, CH2), 126.9, 127.7, 130.8, 135.7, 139.9, 142.9 (s,
2,4
operating at 300.13 (1H), 75.48 (13C), and 121.50 (31P)
MHz, respectively. Resonances are quoted in ppm and
1H NMR spectra referenced to either tetramethylsilane
(0.00 ppm) or the proteo-impurity in the solvent
(7.25 ppm for CHCl3). 13C NMR spectra were referenced
to CDCl3 (77.00 ppm), and 31P NMR spectra to 85%
orthophosphoric acid (0.00 ppm) as an external standard.
Elemental analyses were obtained from the Microanalytical
Laboratory, University of Otago.
CPh2), 128.1 (t0 [15],
J
= 10.2 Hz, o-PPh3), 129.4 (t0,
CP
1,3
J
J
= 52.6 Hz, i-PPh3), 130.5 (s, p-PPh3), 134.5 (t0,
CP
CP
= 9.8 Hz, m-PPh3), 139.4 (s, @CH). 31P{1H} NMR
3,5
(CDCl3, d): ꢀ11.96 (s, PPh3).
4.4. Preparation of
Os(CH2CH@CPh2)Cl(O2CCF3)(NO)(PPh3)2 (3)
Os(g2-3,3-diphenylcyclopropene)Cl(NO)(PPh3)2
(1)
(0.182 g) was dissolved in a solvent mixture of dichloro-
methane (25 mL) and ethanol (2.5 mL). CF3COOH
(16 lL) was added via syringe to this stirred orange solu-
tion and after 15 min the dichloromethane was removed
under reduced pressure. Yellow microcrystals of pure 3
were collected (0.157 g, 77%). Anal. Calc. for C53H43-
ClF3NO3OsP2: C, 58.59; H, 3.99; N, 1.29. Found: C,
58.70; H, 4.08; N, 1.30%. IR (cmꢀ1): 1832 m(NO), 1676
4.2. Preparation of Os(g2-3,3-
diphenylcyclopropene)Cl(NO)(PPh3)2 (1)
Os(peroxycarbonyl)Cl(NO)(PPh3)2 (see Ref. [16])
(0.569 g) and PPh3 (0.564 g) were placed in freshly distilled
benzene (35 mL) contained in a Schlenk tube. The mixture
was then deoxygenated by several ‘‘freeze–pump–thaw’’
cycles, and then heated under reflux under a nitrogen atmo-
sphere for 5 min. After cooling to room temperature,
3,3-diphenylcyclopropene (260 lL) was added via syringe
to the dark green reaction mixture (now containing OsCl-
(NO)(PPh3)3), immediately turning the colour of the solu-
tion orange. After 10 min the benzene was removed in
vacuo, leaving a dark orange oil. Dry hexane was added
to this oil and the mixture was stirred for several hours,
causing precipitation of a pale orange powder. Recrystalli-
sation of this powder from CH2Cl2/EtOH yielded pure 1 as
1
3
m(CO). H NMR (CDCl3, d): 4.30 (dt, 2H, JHP = 3.9 Hz,
3
3JHH = 7.9 Hz, CH2), 6.18 (t, 1H, JHH = 8.1 Hz, CH@),
6.86–7.74 (m, 40H, PPh3 and C3H2Ph2). 13C NMR
1
(CDCl3, d): 5.5 (broad s, CH2), 114.7 (q, JCF
=
291.4 Hz, CF3), 127.2, 127.8, 136.6, 137.9, 140.2, 143.3 (s,
2,4
CPh2), 128.4 (t0,
J
= 9.8 Hz, o-PPh3), 129.4 (t0,
CP
1,3
J
J
= 53.0 Hz, i-PPh3), 130.8 (s, p-PPh3), 134.4 (t0,
= 9.8 Hz, m-PPh3), 138.9 (s, @CH), 160.8 (q,
CP
3,5
CP
2JCF = 36.8 Hz, O2CCF3). 31P{1H} NMR (CDCl3, d):
ꢀ6.48 (s, PPh3).

3768
G.R. Clark et al. / Inorganica Chimica Acta 359 (2006) 3763–3768
[3] R.P. Hughes, J.W. Reisch, A.L. Rheingold, Organometallics 4 (1985)
241.
[4] (a) L.K. Johnson, R.H. Grubbs, J.W. Ziller, J. Am. Chem. Soc. 115
(1993) 8130;
4.5. X-ray crystal structure determinations for complexes 1
and 2
X-ray intensities were recorded on a Siemens SMART
diffractometer with a CCD area detector using graphite
monochromated Mo Ka radiation (k = 0.71073 A) at
(b) S.T. Nguyen, L.K. Johnson, R.H. Grubbs, J.W. Ziller, J. Am.
Chem. Soc. 114 (1992) 3974.
[5] R.T. Li, S.T. Nguyen, R.H. Grubbs, J.W. Ziller, J. Am. Chem. Soc.
116 (1994) 10032.
˚
84 K. Data were integrated and corrected for Lorentz
and polarisation effects using SAINT [18]. Semi-empirical
absorption corrections were applied based on equivalent
reflections using SADABS [19]. The structures were solved
by direct methods and refined by full-matrix least-squares
on F2 using programs SHELXS-97 [20] and SHELXL-97 [21].
All non-hydrogen atoms were refined anisotropically.
Hydrogen atoms were located geometrically and refined
using a riding model. Diagrams were produced using
ORTEP-3 [22]. Crystals of compounds 1 and 2 contain
no solvent molecules of crystallization. There are no hydro-
gen bonds. Crystal data and refinement details for both
structures are given in Table 1.
[6] H. Weiss, F. Hampel, W. Donabauer, M.A. Grundl, J.W. Bats,
A.S.K. Hashmi, S. Schindler, Organometallics 20 (2001) 1713.
[7] (a) J.P. Visser, A.J. Schipperijn, J. Lukas, D. Bright, J.J. de Boer, J.
Chem. Soc., Chem. Commun. (1971) 1266;
(b) D.L. Hughes, G.J. Leigh, C.N. McMahon, J. Chem. Soc., Dalton
Trans. (1997) 1301.
[8] (a) H.-P. Wu, T.J.R. Weakley, M.M. Haley, Organometallics 21
(2002) 4320;
(b) R.D. Gilbertson, T.J.R. Weakley, M.M. Haley, J. Am. Chem.
Soc. 121 (1999) 2597;
(c) R.D. Gilbertson, T.J.R. Weakley, M.M. Haley, Chem.-Eur. J. 6
(2000) 437;
(d) R.D. Gilbertson, T.L.S. Lau, S. Lanza, H.-P. Wu, T.J.R.
Weakley, M.M. Haley, Organometallics 22 (2003) 3279;
(e) H.-P. Wu, T.J.R. Weakley, M.M. Haley, Chem.-Eur. J. 11 (2005)
1191.
[9] A.K. Burrell, G.R. Clark, C.E.F. Rickard, W.R. Roper, D.C. Ware,
J. Organomet. Chem. 398 (1990) 133.
5. Supplementary material
[10] S. Fredericks, J.L. Thomas, J. Am. Chem. Soc. 100 (1978) 350.
[11] G.J. Leigh, C.E. McKenna, C.N. McMahon, Inorg. Chim. Acta 280
(1998) 193.
[12] W.R. Roper, J. Organomet. Chem. 300 (1986) 167.
[13] K.R. Grundy, W.R. Roper, J. Organomet. Chem. 216 (1981) 255.
[14] G.-L. Lu, C.E.F. Rickard, W.R. Roper, L.J. Wright, J. Organomet.
Chem. 690 (2005) 4114.
[15] S.M. Maddock, C.E.F. Rickard, W.R. Roper, L.J. Wright, Organo-
metallics 15 (1996) 1793.
[16] (a) A.F. Hill, W.R. Roper, J.M. Waters, A.H. Wright, J. Am. Chem.
Soc. 105 (1983) 5939;
Crystallographic data (excluding structure factors) for
the structures reported have been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary
publication Nos. CCDC 283171 and 283172 for 1 and 2.
Copies of this information can be obtained free of charge
from the Director, CCDC, 12 Union Road, Cambridge
CB2 1EZ, UK (fax: +44 1223 336 033; e-mail: depos-
it@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk).
(b) G.R. Clark, K.R. Laing, W.R. Roper, A.H. Wright, Inorg.
Chim. Acta 357 (2004) 1767.
Acknowledgements
[17] J.-H. Huang, T.-Y. Lee, D.C. Swenson, L. Messerle, Inorg. Chim.
Acta 345 (2003) 209.
[18] SAINT: Area Detector Integration Software, Siemens Analytical
Instruments Inc., Madison, WI, USA, 1995.
[19] G.M. Sheldrick, SADABS: Program for Semi-empirical Absorption
Correction, University of Go¨ttingen, Go¨ttingen, Germany, 1997.
[20] G.M. Sheldrick, SHELXS-97: Program for Crystal Structure Determi-
nation, University of Go¨ttingen, Go¨ttingen, Germany, 1977.
[21] G.M. Sheldrick, SHELXL-97: Program for Crystal Structure Refine-
ment, University of Go¨ttingen, Go¨ttingen, Germany, 1997.
[22] M.N. Burnett, C.K. Johnson, ORTEP-III: Oak Ridge Thermal
Ellipsoid Plot Program for Crystal Structure Illustrations, Oak Ridge
National Laboratory Report ORNL-6895, 1996.
We thank Associate Professor Peter Boyd for assisting
with the crystal structure of 2, and the Foundation for
Research, Science and Technology for granting a Post-
doctoral Fellowship to D.M.T. We also thank The Univer-
sity of Auckland for partial support of this work through
grants-in-aid.
References
[1] G.J. Leigh, C.N. McMahon, J. Organomet. Chem. 500 (1995) 219.
[2] G.J. Leigh, J. Organomet. Chem. 689 (2004) 3999.