Dioxygen oxidation of a carbonyl ligand to form a chelating peroxycarbonyl ligand: Synthesis, structure, and reactions of Os(C[O]OO)Cl(NO)](PPh 3)2

Article abstract of DOI:10.1016/j.ica.2003.11.043

Reaction between the carbonyl, nitrosyl complex, OsCl(CO)(NO)(PPh ₃)₂ (1) and dioxygen results in combination of CO and O₂, forming a chelating peroxycarbonyl ligand in the yellow complex, Cl(NO)(PPh₃)₂ (2). Confirmation of the unique peroxycarbonyl ligand arrangement in 2 is provided by crystal structure determination. When 2 is heated, as a suspension in heptane under reflux, there is a rearrangement to the regular chelating carbonate ligand in the orange complex, Cl(NO)(PPh₃)₂ (3). The structure of 3 has also been determined by X-ray crystallography. Compound 2 also undergoes the following reactions: with water, releasing CO₂ and forming Os(OH)₂Cl(NO)(PPh₃)₂ (4); with HCl releasing CO₂ and forming Os(OH)Cl₂(NO)(PPh₃) ₂ (5); and with excess triphenylphosphine releasing CO₂ and triphenylphosphine oxide forming OsCl(NO)(PPh₃)₃ (6).

Full text of DOI:10.1016/j.ica.2003.11.043

Inorganica Chimica Acta 357 (2004) 1767–1772
www.elsevier.com/locate/ica
Dioxygen oxidation of a carbonyl ligand to form a chelating
peroxycarbonyl ligand: synthesis, structure, and reactions
of
Cl(NO)(PPh )
Os(C[O]OO)
3 2
*
George R. Clark, Kerry R. Laing, Warren R. Roper , Anthony H. Wright
Department of Chemistry, The University of Auckland, Private Bag 92019, Auckland, New Zealand
Received 18 September 2003; accepted 3 November 2003
Dedicated to Professor Helmut Werner on the occasion of his 70th birthday, in recognition of his many major contributions
to inorganic and organometallic chemistry
Abstract
Reaction between the carbonyl, nitrosyl complex, OsCl(CO)(NO)(PPh3)2 (1) and dioxygen results in combination of CO and O2,
Os(C[O]OO)
peroxycarbonyl ligand arrangement in 2 is provided by crystal structure determination. When 2 is heated, as a suspension in heptane
forming a chelating peroxycarbonyl ligand in the yellow complex,
Cl(NO)(PPh3)2 (2). Confirmation of the unique
under reflux, there is a rearrangement to the regular chelating carbonate ligand in the orange complex, Os(OC[O]O)Cl(NO)(PPh3)2
(3). The structure of 3 has also been determined by X-ray crystallography. Compound 2 also undergoes the following reactions: with
water, releasing CO2 and forming Os(OH)2Cl(NO)(PPh3)2 (4); with HCl releasing CO2 and forming Os(OH)Cl2(NO)(PPh3)2 (5);
and with excess triphenylphosphine releasing CO2 and triphenylphosphine oxide forming OsCl(NO)(PPh3)3 (6).
Ó 2003 Elsevier B.V. All rights reserved.
Keywords: Peroxycarbonyl complex; Carbonate; Osmium; X-ray crystal structure
1. Introduction
observations are that the dioxygen complexes
Pt(O2)(PPh3)2 and Ir(O2)(CH3)(CO)(PR3)2 (R ¼ p-tolyl)
with CO form Pt(j2-O2CO)(PPh3)2 [3] and Ir(j2-
O2CO)(CH3)(CO)(PR3)2 [4], respectively. In the paper
describing the formation of IrCl(j2-O2CO)(TDPME)
from IrCl(CO)(TDPME) and O2 it is suggested that a
reasonable intermediate to the chelating carbonate li-
gand might be a peroxycarbonyl complex (I) (see Chart
1). The same peroxycarbonyl binding mode is also
drawn as a possible intermediate in [2].
The peroxycarbonyl fragment can also be envisioned
as bridging between two metal centres as depicted in II
in Chart 1 or perhaps with additional carbonyl oxygen
coordination as in IIa or IIb. The binding mode IIa has
been proposed in the product from reaction between
Pt(O2)(PPh3)2 and [PtCl(CO)(PPh3)2]þ but this has not
been confirmed by crystal structure determination [5].
The binding mode II, spanning an Os–Os bond of the
The oxidation with dioxygen of a carbonyl ligand
bound in a low oxidation state complex, with the re-
sulting formation of a carbonate ligand, has been re-
ported on several occasions. A good example is the
iridium(I) carbonyl complex with the tripodal ligand
1,1,1-tris(diphenylphosphinomethyl)ethane (TDPME),
IrCl(CO)(TDPME), which undergoes a reaction with
dioxygen to form IrCl(j2-O2CO)(TDPME) [1]. The
iridium(I) carbonyl complex with the ligand o-diph-
enylphosphino-N,N-dimethylaniline (PN), IrCl(CO)PN
also reacts with dioxygen but here CO2 is formed along
with an hydroxy-bridged iridium complex [2]. Related
* Corresponding author. 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 Ó 2003 Elsevier B.V. All rights reserved.
doi:10.1016/j.ica.2003.11.043

1768
G.R. Clark et al. / Inorganica Chimica Acta 357 (2004) 1767–1772
O
C
O
O
O
O
M
M
M1
M
C
O
O
C
O
II
I
O
O
M1
M
M1
C
O
O
IIa
IIb
Chart 1. Possible binding modes for the fragment ‘‘O2CO’’ to one and
two metals.
Os3 triangle, has been proposed for the initial dioxygen
oxidation product of the anion [(l-H)Os3(CO)11]ꢀ [6].
In this paper, we report: (i) the formation of a stable
crystalline peroxycarbonyl complex, Os(C[O]OO)-
Cl(NO)(PPh3)2 (2) and define the chelating peroxycar-
bonyl binding mode I by crystal structure determination
of 2, (ii) the thermal rearrangement of 2 to the normal
Scheme 1. Synthesis and reactions of the peroxycarbonyl complex,
Os(OC[O]O)
chelating carbonate complex,
Cl(NO)-
Os(C[O]OO)Cl(NO)(PPh3)2 (2).
(PPh3)2 (3), (iii) the crystal structure of 3, (iv) reactions
of 2, with water and HCl which result in release of CO2,
and the formation of hydroxyl osmium(II) complexes,
and (v) the formation of a zero oxidation state complex,
OsCl(NO)(PPh3)3, in the presence of triphenylphos-
phine with formation of triphenylphosphineoxide.
dation product revealed a resonance at d, 169.4 ppm
which was a triplet (JCP ¼ 6:7 Hz) suggesting that the
‘‘CO3’’ ligand had a metal-bound carbon atom. Ac-
cordingly, the yellow 1:1 adduct of OsCl(CO)(NO)
(PPh3)2 and O2 was re-formulated as the peroxycar-
bonyl complex,
Cl(NO)(PPh ) (2). Con-
3 2
Os(C[O]OO)
2. Results and discussion
firmation that 2 did contain the unusual peroxycarbonyl
ligand bound as I in Chart 1 was sought through a
crystal structure determination of 2. Initially the struc-
ture solved well for everything except the electron den-
sity in the equatorial plane. The arrangement of the Cl,
NO, and peroxycarbonyl ligands appeared to be disor-
dered and made little chemical sense. Eventually, it was
appreciated that the structure was disordered by a 180°
rotation about the N(1)–Os–O(2) vector with the two
orientations present in a ratio of 2:1.
The molecular geometry of 2 is shown in Fig. 1.
Crystal data pertaining to this structure and also to the
structure of 3 (see below) are presented in Table 1. Se-
lected bond lengths and angles for 2 are collected in
Table 2. The overall geometry about osmium is octa-
hedral with the two triphenylphosphine ligands ar-
ranged mutually trans. One of the peroxy oxygen atoms
(O(2)) is trans to the nitrosyl ligand. The Os–C(1) dis-
2.1. Reaction of OsCl(CO)(NO)(PPh3)2 with dioxygen
Os(C[O]OO)
and the structure of
Cl(NO)(PPh3)2 (2)
Treatment of a solution of OsCl(CO)(NO)(PPh3)2 in
dichloromethane/ethanol with dioxygen at atmospheric
pressure results in a rapid colour change from brown to
yellow and bright yellow crystals of a 1:1 adduct of
OsCl(CO)(NO)(PPh3)2 and O2 are formed (see Scheme
1). We first reported this observation in 1968 and de-
scribed the yellow product as a carbonate complex [7].
The IR spectrum of the yellow crystals shows m(NO) at
1780 cmꢀ1 and other bands at 1710, 1310, and 1025
cmꢀ1 which were associated with the carbonate ligand.
However, a later report [3] of the IR spectrum of the
related carbonate complex, Pt(j2-O2CO)(PPh3)2, gave
absorptions for the carbonate ligand at 1685, 1185, 980,
and 815 cmꢀ1. These values do not compare favourably
with those found for the yellow crystals. Further doubt
was cast on the original formulation when it was dis-
covered that the 13C NMR spectrum of the yellow oxi-
ꢀ
tance is short at 1.932(18) A and is in fact a typical Os–
ꢀ
CO distance. The O(2)–O(3) distance of 1.493(11) A is
normal for a peroxide linkage. All other bond lengths
and angles are as expected.

G.R. Clark et al. / Inorganica Chimica Acta 357 (2004) 1767–1772
1769
Table 2
ꢀ
Selected bond lengths (A) and angles (°) for 2
Os–Cl
2.454(5)
Os–P(1)
Os–P(2)
Os–O(2)
Os–N
2.4370(14)
2.4373(13)
2.022(5)
1.730(6)
Os–C(1)
O(1)–C(1)
O(3)–C(1)
O(2)–O(3)
1.932(18)
1.170(19)
1.409(17)
1.493(11)
C(1)–Os–O(2)
Os–C(1)–O(1)
Os–C(1)–O(3)
O(1)–C(1)–O(3)
C(1)–O(3)–O(2)
Os–O(2)–O(3)
P(1)–Os–P(2)
68.8(5)
138.9(14)
98.5(9)
Os(C[O]OO)
Fig. 1. Molecular geometry of
rings omitted from PPh3 ligands).
Cl(NO)(PPh3)2 (2) (phenyl
122.1(17)
100.7(9)
91.9(4)
175.99(6)
Table 1
Crystal data and structure refinement parametersa
Compound
2
3
We are aware of only one other stable peroxycar-
bonyl complex of the type exemplified by complex 2.
This is the 1:1 adduct of the carbyne complex,
Os(CAr)Cl(CO)(PPh3)2 (Ar ¼ p-dimethylaminophenyl)
Empirical formula
Molecular weight
Crystal system
Space group
C
840.21
37H30ClNO4OsP2 C37H30ClNO4OsP2
840.21
monoclinic
triclinic
ꢁ
P1
P21=c
and O2, which has IR bands at 1680 and 1058 cmꢀ1
,
ꢀ
a (A)
9.966(3)
9.9980(11)
17.098(2)
92.880(10)
96.570(15)
98.610(14)
1 669.4(5)
2
12.249(1)
16.404(1)
17.752(1)
90.0
ꢀ
b (A)
closely comparable with those found for complex 2 [8].
ꢀ
c (A)
This complex, Os(C[O]OO)Cl(CAr)(PPh3)2, also re-
leases CO2 when treated with acids.
a (°)
b (°)
c (°)
111.00(1)
90.0
3
ꢀ
V (A)
3330.0(4)
4
1.676
Os(C[O]OO)
2.2. Thermal rearrangement of
Cl(NO)
Z
Dcalc (g cmꢀ3
)
1.671
1.67
(PPh3)2 (2) to Os(OC[O]O)Cl(NO)(PPh3)2 (3) and the
Dobs (g cmꢀ3
)
1.68
1 656
4.047
crystal structure of
Cl(NO) (PPh3)2 (3)
Os(OC[O]O)
F ð000Þ
828
4.036
l (mmꢀ1
Crystal size (mm)
)
0.34 ꢁ 0.23 ꢁ 0.14
1.20–27.01
7293
0.19 ꢁ 0.17 ꢁ 0.16
1.75–26.96
7804
Os(C[O]OO)
If a solution of
Cl(NO)(PPh3)2 (2) in
h (min–max) (°)
Reflections collected
benzene is heated under reflux the only identifiable
complex, formed in very low yield, is the dioxygen
Independent reflections 6948, Rint 0.019
T (min, max)
Goodness-of-fit on F 2
7000, Rint 0.030
0.522, 0.613
1.042
0.421, 0.636
1.034
complex,
Os(O2)Cl(NO)(PPh3)2.
However,
if
Os(C[O]OO)Cl(NO)(PPh3)2 (2) is suspended in heptane
and heated under reflux there is formed, in good yield,
R, wR2 (observed data) 0.0392, 0.0983
0.0229, 0.0519
P
P
P
P
2
2
1=2
a R ¼ jjFoj ꢀ jFcjj= jFoj. wR2 ¼ f ½wðFo2 ꢀ Fc2Þ ꢂ= ½wðFo2Þ ꢂg
.
the orange carbonate complex,
Cl(NO)
Os(OC[O]O)
(PPh3)2 (3) (see Scheme 1). In the IR spectrum of 3
m(NO) is at 1820, 1775 cmꢀ1 (solid state splitting, in
CH2Cl2 solution, 1800 cmꢀ1), which is higher than the
value found for complex 2. IR bands associated with the
chelated carbonate ligand are seen at 1705, 1168, 970,
and 790 cmꢀ1 which show a close correspondence with
those reported for Pt(j2-O2CO)(PPh3)2 (1685, 1185,
980, and 815 cmꢀ1). As expected, the 13C NMR spec-
trum reveals a carbon resonance for the carbonate car-
bon at d, 160.2 ppm which is a singlet.
Chemically, the carbonate ligand in complex 3 is ra-
ther inert and when 3 is heated with dilute HCl no re-
action ensues and 3 is recovered unchanged. In contrast,
the peroxycarbonyl ligand in complex 2 is much more
reactive (see below). For comparison with complex 2,
Following the usual convention that a linear NO li-
gand be regarded as formally NOþ, complex 2 can be
assigned
the
oxidation
state
+2.
Thus
Os(C[O]OO)
Cl(NO)(PPh3)2 (2) can be regarded as an
octahedral (d6) complex of osmium(II) and likewise
complexes 3–5, discussed below are all octahedral
complexes of osmium(II). As depicted in Scheme 1,
OsCl(CO)(NO)(PPh3)2 (1) may have a bent NO ligand
(formally NOꢀ) and would therefore be coordinatively
unsaturated thus permitting coordination of dioxygen
and the overall process forming the peroxycarbonyl
complex 2 could be thought of as an inter-ligand com-
bination reaction.

1770
G.R. Clark et al. / Inorganica Chimica Acta 357 (2004) 1767–1772
Os(C[O]OO)Cl(NO)(PPh3)2, reacts readily with water
releasing CO2 and forming the dihydroxy complex,
Os(OH)2Cl(NO)(PPh3)3 (4). The ease with which this
reaction occurs can be judged from the fact that even
solid samples of 2 stored in moist air are converted
quantitatively into 4. The IR spectrum of yellow com-
plex 4 has m(NO) at 1772 cmꢀ1, slightly lower than
m(NO) for 2 and 3. There is also an absorption at 3560
cmꢀ1 assigned to m(OH).
Complex 2 reacts with one equivalent of dilute
aqueous HCl to form the mono-hydroxy complex,
Os(OH)Cl2(NO)(PPh3)3 (5). The IR spectrum of yellow
5 has m(NO) at 1790 cmꢀ1. The comparatively small
increase in m(NO) from the value of 1772 cmꢀ1 found for
4, suggests that the hydroxy group is positioned trans to
the nitrosyl ligand. Further support for this geometry,
with a mutually trans arrangement of Cl ligands, is
provided by the observation of only one m(OsCl) band at
Os(OC[O]O)
Fig. 2. Molecular geometry of
Cl(NO)(PPh3)2 (3) (phenyl
rings omitted from PPh3 ligands).
Table 3
ꢀ
Selected bond lengths (A) and angles (°) for 3
Os–Cl
2.3630(14)
2.4343(12)
2.4401(12)
2.045(3)
2.056(3)
1.818(5)
1.370(6)
1.351(6)
1.210(6)
Os–P(1)
Os–P(2)
Os–O(1)
Os–O(2)
Os–N
313 cmꢀ1
When a benzene solution of the peroxycarbonyl
complex, Cl(NO)(PPh ) , is heated the so-
.
Os(C[O]OO)
3 2
O(1)–C(1)
O(2)–C(1)
C(1)–O(3)
lution becomes very dark and the only identifiable
complex formed, in very low yield, is Os(O2)Cl(NO)
(PPh3)2. However, when three or more equivalents of
triphenylphosphine are added to the solution, and with
rigorous exclusion of dioxygen, a clean reaction ensues
forming CO2, triphenylphosphineoxide, and the green
zero oxidation state complex, OsCl(NO)(PPh3)3 (6). As
expected for a zero oxidation state complex the IR
spectrum of 6 has m(NO) at 1630 cmꢀ1 which is ca. 150
cmꢀ1 lower than the values found for the osmium(II)
nitrosyl complexes described in this paper. Complex 6
undergoes numerous oxidative addition reactions which
have been described elsewhere [9]. Two interesting ex-
amples are the formation of an osmium methylene
complex, Os(CH2)Cl(NO)(PPh3)2 [10], and a carbon
disulfide complex, Os(g2-CS2)Cl(NO)(PPh3)2 [11]. The
reactions of complex 6 are, in general, very similar to
those of the remarkable four coordinate, planar com-
plex, OsCl(NO)(PiPr3)2 described by Werner et al. [12].
Os–O(1)–C(1)
Os–O(2)–C(1)
O(1)–Os–O(2)
92.5(3)
92.6(3)
65.50(14)
O(1)–C(1)–O(2)
O(1)–C(1)–O(3)
O(2)–C(1)–O(3)
P(1)–Os–P(2)
109.3(4)
124.8(6)
125.9(5)
175.23(4)
Os(OC[O]O)
the crystal structure of
was determined.
Cl(NO)(PPh3)2 (3)
The molecular geometry of 3 is shown in Fig. 2. Se-
lected bond lengths and angles for 3 are collected in
Table 3. The overall geometry about osmium is again
octahedral with the two triphenylphosphine ligands ar-
ranged mutually trans. The carbonate ligand is re-
markably symmetrical with Os–O(1) (trans to NO) being
ꢀ
ꢀ
2.045(3) A and Os–O(2) (trans to Cl) being 2.056(3) A.
ꢀ
The Os–Cl distance of 2.3630(14) A is much shorter than
ꢀ
that found in 2 (2.454(5) A) but is close to the mean
3. Conclusions
value for previously determined Os–Cl distances
1
ꢀ
(mean ¼ 2.389 A, standard deviation ¼ 0.067 ). Clearly,
A stable intermediate in the oxidation of a carbonyl
ligand to a carbonate ligand is confirmed by a crystal
structure determination to contain the chelating per-
carbon has a greater trans influence than oxygen.
Os(C[O]OO)
2.3. Reactions of
water, HCl, and PPh3
Cl(NO)(PPh3)2 (2) with
oxycarbonyl ligand. This complex, Os(C[O]OO)
Cl(NO)(PPh3)2 (2), is shown to undergo a thermal re-
These reactions can be followed in Scheme 1. In
marked contrast to the lack of reactivity exhibited by the
carbonate complex 3, the peroxycarbonyl complex,
arrangement to a carbonate complex,
Os(OC[O]O)
Cl(NO)(PPh3)2 (3). The peroxycarbonyl ligand in com-
plex 2 is reactive and protic reagents release CO2 and
form hydroxyl osmium(II) complexes. In the absence of
protic reagents CO2 is still released but the remaining
oxygen atom is transferred to a triphenylphosphine li-
1
Cambridge Crystallographic Data Base.

G.R. Clark et al. / Inorganica Chimica Acta 357 (2004) 1767–1772
1771
3;5
gand forming triphenylphosphineoxide. When excess
triphenylphosphine is present the zero oxidation state
nitrosyl complex, OsCl(NO)(PPh3)3, can be isolated.
C6H5); 131.5 (s, p-C6H5); 134.4 (t0,
C6H5); 160.2 (s, CO3).
J
¼ 10:0 Hz, m-
CP
4.4. Preparation of Os(OH)2Cl(NO)(PPh3)2 (4)
Os(C[O]OO)
Cl(NO)(PPh3)2 stored
4. Experimental
Solid samples of
in a moist atmosphere for 1 week were found to be
converted quantitatively to Os(OH)2Cl(NO)(PPh3)2 as a
yellow solid. This material was recrystallised from
CH2Cl2/EtOH to give pure 4 as yellow crystals. Anal.
Calc. for C36H32ClNO3OsP2: C, 53.10; H, 3.96; N, 1.72;
Cl, 4.35. Found: C, 53.55; H, 4.20; N, 1.65; Cl 4.64%. IR
(cmꢀ1): 1772vs m(NO); 3560w m(OH); 313, 306 m(OsCl).
4.1. General procedures and instruments
Standard laboratory procedures were followed as
have been described previously [13]. The compound
OsCl(CO)(NO)(PPh3)2 (1) [7,14] was prepared accord-
ing to the literature method.
Infrared spectra (4000–400 cmꢀ1) were recorded as
Nujol mulls between KBr plates on a Perkin–Elmer 597
spectrometer. 13C NMR spectra were obtained on a Jeol
JNM FX-60 at 25 °C. Resonances are quoted in ppm
and 13C NMR spectra were referenced to CDCl3 (77.00
ppm). Elemental analyses were obtained from the Mi-
croanalytical Laboratory, University of Otago.
4.5. Preparation of Os(OH)Cl2(NO)(PPh3)2 (5)
Os(C[O]OO)
Cl(NO)(PPh3)2 (0.400 g, 0.476 mmol)
was dissolved in C6H6 (30 mL) and dilute aqueous HCl
(5 mL of 0.1 M, 0.5 mmol) was added. Sufficient ethanol
to make the mixture homogeneous was then added and
the solution heated under reflux for 20 min. The volume
of the solution was reduced using a rotary evaporator
until crystals appeared in the solution. On standing the
solution deposited further yellow crystals. These were
recrystallised from CH2Cl2/EtOH to give pure 5 as
bright yellow crystals (0.35 g, 88%). Anal. Calc. for
C36H31Cl2NO2OsP2: C, 51.92; H, 3.75; N, 1.68; Cl, 8.51.
Found: C, 52.17; H, 3.71; N, 1.57; Cl, 8.69%. IR (cmꢀ1):
1790vs m(NO); 313s m(OsCl); 628, 619, 607, 490, 444,
416.
Os(C[O]OO)
4.2. Preparation of
Cl(NO)(PPh3)2 (2)
OsCl(CO)(NO)(PPh3)2 (1.000 g) was dissolved in a
mixture of CH2Cl2 (100 mL) and ethanol (10 mL). The
solution was stirred for 10 min under O2 (1 atm) during
which time the colour changed from brown to yellow.
Reduction of the solvent to low volume using a rotary
evaporator gave pure 2 as bright yellow crystals (0.810
g, 78%). Anal. Calc. for C37H30ClNO4OsP2: C, 52.89; H,
3.60; N, 1.67. Found C, 52.92; H, 4.03; N, 1.57%. IR
(cmꢀ1): 1780vs m(NO); 1710s, 1310m, 1025m (peroxy-
carbonyl); 315s m(OsCl). 13C NMR (CDCl3, d): 126.9 (t0
4.6. Preparation of OsCl(NO)(PPh3)3 (6)
1;3
2;4
[13],
J
¼ 54:0 Hz, i-C6H5); 128.4 (t0,
J
J
¼ 12:0
Cl(NO)(PPh3)2 (1.00 g) was suspended
Os(C[O]OO)
CP
CP
Hz, o-C6H5); 131.3 (s, p-C6H5); 134.7 (t0,
Hz, m-C6H5); 169.4 (t, JCP ¼ 6:7 Hz, C[O]O2).
¼ 10:0
in freshly distilled, deoxygenated benzene (15 mL) with
triphenylphosphine (1.00 g) and the mixture heated
under reflux for 5 min. As the mixture was heated the
complex dissolved and the colour changed to dark
brown/black. Green crystalline material separated from
the reaction mixture as the mixture cooled. Additional
material could be obtained by adding freshly distilled n-
hexane (50 mL) (1.15 g, 93%) and this material was of
sufficient purity for further reactions. For the microan-
alytical sample, the original reaction mixture (benzene
only, no hexane) was cooled in an ice bath and filtered
rapidly under nitrogen to give pure 6 as green micro-
crystals (0.81 g, 65%). Anal. Calc. for C54H45ClNOOsP3:
C, 62.21; H, 4.35; N, 1.34; P, 8.91. Found: C, 62.85; H,
4.13; N, 1.45; P, 8.43%. IR (cmꢀ1): 1630vs m(NO).
3;5
CP
2
4.3. Preparation of
Cl(NO)(PPh ) (3)
3 2
Os(OC[O]O)
Os(C[O]OO)
Cl(NO)(PPh3)2 (0.500 g) was suspended
in distilled n-heptane (30 mL) and the mixture heated
under reflux for 10 min. During this time the suspended
solid changed colour from yellow to dark brown. After
cooling, the resultant solid was filtered, dissolved in a
minimum of CH2Cl2 and subjected to chromatography
on a 10 ꢁ 3 cm Florisil column with CH2Cl2 as eluant.
The bright orange band was collected and ethanol ad-
ded. Removal of solvent under reduced pressure yielded
orange crystals of the complex. The complex was re-
crystallised from CH2Cl2/EtOH to give pure 3 as orange
crystals
(0.400
g,
77%).
Anal.
Calc.
for
4.7. X-ray crystal structure determinations for complexes
2 and 3
C37H30ClNO4OsP2 ꢃ 1/3CH2Cl2: C, 51.63; H, 3.56; N,
1.61. Found: C, 51.93; H, 4.22; N, 1.41%. IR (cmꢀ1):
1820vs, 1775vs m(NO); 1705s, 1168m, 970m, 790m, 760m
(carbonate). 13C NMR (CDCl3, d): 125.0 (t0 [13],
Data were collected on an Enraf-Nonius CAD4 dif-
fractometer at 223 and 293 K, respectively, with
graphite-monochromated Mo Ka radiation (k 0.71073
1;3
2;4
J
¼ 54:0 Hz, i-C6H5); 128.5 (t0,
J
¼ 10:0 Hz, o-
CP
CP

1772
G.R. Clark et al. / Inorganica Chimica Acta 357 (2004) 1767–1772
ꢀ
A) using x=2h scans. Absorption corrections were ap-
plied using empirical w scan data [15]. Structures were
solved using SHELXS [16] and refined by full-matrix least
squares using SHELXL [17]. Hydrogen atoms were in-
cluded in calculated positions and allowed to ride on
their carrier atom. In the crystal structure of 2, the
equatorial ligands are disordered by a 180° rotation
about the N(1)–Os–O(2) vector. The arrangement
shown in Fig. 1 is present with occupancy 0.67, whereas
the alternative orientation (not shown) is present with
occupancy of 0.33. Data in Table 2 are for the model
with the larger occupancy. Crystal data and refinement
details for structures 2 and 3 are given in Table 1.
Irvine for valuable assistance with growing crystals of
Os(C[O]OO)
Cl(NO)(PPh3)2.
References
[1] W.O. Siegl, S.J. Lapporte, J.P. Collman, Inorg. Chem. 10 (1971)
2158.
[2] D.M. Roundhill, G.H. Allen, R.A. Bechtold, W.B. Beaulieu,
Inorg. Chim. Acta 54 (1981) L99.
[3] P.J. Hayward, D.M. Blake, G. Wilkinson, C.J. Nyman, J. Am.
Chem. Soc. 92 (1970) 5873.
[4] H.J. Lawson, J.D. Atwood, J. Am. Chem. Soc. 110 (1988) 3680.
[5] M. Kubota, F.S. Rosenberg, M.J. Sailor, J. Am. Chem. Soc. 107
(1985) 4558.
5. Supplementary material
[6] C.J. Cathey, B.F.G. Johnson, J. Lewis, P.R. Raithby, W.T. Wong,
J. Organomet. Chem. 450 (1993) C12.
[7] K.R. Laing, W.R. Roper, Chem. Commun. (1968) 1556.
[8] G.R. Clark, N.R. Edmonds, R.A. Pauptit, W.R. Roper, J.M.
Waters, A.H. Wright, J. Organomet. Chem. 244 (1983) C57.
[9] W.R. Roper, J. Organomet. Chem. 300 (1986) 167.
[10] 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 2 and 3 have been deposited with the Cambridge
Crystallographic Data Centre as supplementary publi-
cation nos. 216909 and 216910. Copies of this infor-
mation can be obtained free of charge from the
Director, CCDC, 12 Union Road, Cambridge CB2 1EZ,
UK (Fax: +44-1223-336-033; e-mail: deposit@ccdc.cam.
ac.uk or http://www.ccdc.cam.ac.uk).
[11] M. Herberhold, A.F. Hill, N. McAuley, W.R. Roper, J. Organo-
met. Chem. 310 (1986) 95.
[12] H. Werner, A. Michenfelder, M. Schulz, Angew. Chem., Int. Ed.
Engl. 30 (1991) 596.
[13] S.M. Maddock, C.E.F. Rickard, W.R. Roper, L.J. Wright,
Organometallics 15 (1996) 1793.
[14] R.D. Wilson, J.A. Ibers, Inorg. Chem. 18 (1979) 336.
[15] A.C.T. North, D.C. Phillips, F.S. Matthews, Acta Crystallogr.,
Sect. A 24 (1968) 351.
Acknowledgements
We thank the University of Auckland Research
Committee for partial support of this work through
grants-in-aid. We also thank Drs. Mabel Ng and Geoff
[16] G.M. Sheldrick, Acta Crystallogr., Sect. A 46 (1990) 467.
[17] G.M. Sheldrick, SHELXL, Program for Refinement of Crystal
€
Structures, University of Gottingen, Gottingen, Germany, 1997.
€