Triphenylstibine substituted manganese and rhenium carbonyls: Synthesis and multinuclear NMR spectroscopic studies. X-ray crystal structures of ax-[Mn2(CO)9(SbPh3)], [Mn(CO)5(SbPh3)][CF3SO3] and fac-[Re(CO)3Cl(SbPh3)2]

Article abstract of DOI:10.1016/S0022-328X(98)00763-3

The syntheses of [Mn₂(CO)_10-x(SbPh₃)_x] (x=1 or 2), [Re₂(CO)₉(SbPh₃)], [Mn(CO)₅(SbPh₃)][CF₃SO₃], [M(CO)₄Cl(SbPh₃)], fac-[M(CO)₃Cl(SbPh₃)₂] (M=Mn or Re) and mer,trans-[Mn(CO)₃Cl(SbPh₃)₂] are reported. The complexes have been characterised by chemical analysis, IR and multinuclear NMR (¹H, ¹³C{¹H} and ⁵⁵Mn) spectroscopies, and FAB mass spectrometry. The crystal structure of [Mn₂(CO)₉(SbPh₃)] established the axial position of the SbPh₃ ligand (Mn-Sb 2.525(1), Mn-Mn 2.909(1) A) and that of [Mn(CO)₅(SbPh₃)][CF₃SO₃] confirmed the cation structure (Mn-Sb 2.596(3) A). The crystal structure of fac-[Re(CO)₃Cl(SbPh₃)₂] establishes the stereochemistry (Re-Sb 2.726(1), 2.729(2) A). Differences in the products/isomers produced in reactions of [M₂(CO)₁₀] and [M(CO)₅Cl] with SbPh₃ and with the corresponding PR₃ and AsR₃ ligands are identified and discussed.

Full text of DOI:10.1016/S0022-328X(98)00763-3

Journal of Organometallic Chemistry 568 (1998) 213–223
Triphenylstibine substituted manganese and rhenium carbonyls:
synthesis and multinuclear NMR spectroscopic studies. X-ray crystal
structures of ax-[Mn2(CO)9(SbPh3)], [Mn(CO)5(SbPh3)][CF3SO3] and
fac-[Re(CO)3Cl(SbPh3)2]
Nicholas J. Holmes, William Levason *, Michael Webster
Department of Chemistry, Uni6ersity of Southampton, Southampton SO17 1BJ, UK
Received 1 May 1998
Abstract
The syntheses of [Mn2(CO)10−x(SbPh3)x] (x=1 or 2), [Re2(CO)9(SbPh3)], [Mn(CO)5(SbPh3)][CF3SO3], [M(CO)4Cl(SbPh3)],
fac-[M(CO)3Cl(SbPh3)2] (M=Mn or Re) and mer,trans-[Mn(CO)3Cl(SbPh3)2] are reported. The complexes have been character-
ised by chemical analysis, IR and multinuclear NMR (1H, 13C{1H} and 55Mn) spectroscopies, and FAB mass spectrometry. The
˚
crystal structure of [Mn2(CO)9(SbPh3)] established the axial position of the SbPh3 ligand (Mn–Sb 2.525(1), Mn–Mn 2.909(1) A)
˚
and that of [Mn(CO)5(SbPh3)][CF3SO3] confirmed the cation structure (Mn–Sb 2.596(3) A). The crystal structure of fac-
˚
[Re(CO)3Cl(SbPh3)2] establishes the stereochemistry (Re–Sb 2.726(1), 2.729(2) A). Differences in the products/isomers produced
in reactions of [M2(CO)10] and [M(CO)5Cl] with SbPh3 and with the corresponding PR3 and AsR3 ligands are identified and
discussed. © 1998 Elsevier Science S.A. All rights reserved.
Keywords: Manganese; Rhenium; Carbonyl; Stibine; X-ray structure
1. Introduction
between [Mn2(CO)10] and SbPh3 as the paramagnetic
[Mn(CO)4(SbPh3)] is thus open to considerable doubt.
Apart from an orange [Mn2(CO)8(SbPh3)2] mentioned
in a preliminary communication as a decomposition
product of [HMn(CO)4(SbPh3)] [8], the stibine com-
plexes have not been re-examined. Reports of tertiary
stibine complexes of rhenium carbonyls are even rarer,
and the only characterised complexes appear to be the
carbonyl iodides [Re(CO)nI(SbPh3)m] (n=4, m=1;
n=3, m=2) [1]. Our interest in these complexes arose
for two reasons: firstly in connection with our recent
studies of distibinomethane complexes of manganese
[9], and secondly as models for comparison with BiR3
complexes which we are currently investigating. We
report here the synthesis and structural characterisation
of some SbPh3 complexes with both manganese and
rhenium carbonyls.
Thermal or photochemical reaction of [Mn2(CO)10]
with phosphine or arsine ligands leads to [Mn2(CO)10−x
-
Lx] (L=PR3 or AsR3, x=1 or 2) [1]. Reports of
paramagnetic monomers [Mn(CO)4(PR3)] formed in the
thermal reactions [2] were not confirmed by subsequent
workers [3–6] who identified the products as
[Mn2(CO)10−x(PR3)x] or [HMn(CO)4(PR3)] and at-
tributed the paramagnetism of some samples to impuri-
ties. 17e radicals [Mn(CO)4(PR3)] which recombine very
rapidly, are formed by flash photolysis of the dinuclear
complexes in solution at low temperatures [7]. The brief
mention [2] of the product of the thermal reaction
* Corresponding author. Tel.: +44 1703 595000; fax: +44 1703
593782; e-mail: wxl@soton.ac.uk
0022-328X/98/$19.00 © 1998 Elsevier Science S.A. All rights reserved.
PII S0022-328X(98)00763-3

214
N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
2. Results and discussion
ax–eq or eq–eq substitution produces more complex
IR absorption patterns in the CO region [10]. The
13C{1H} NMR spectrum contains a single l(CO) reso-
nance consistent with the diaxial isomer, although due
to the line broadening caused by the 55Mn nuclei in
other systems, this result is not conclusive in isolation.
The compound differs from that mentioned [8] as a
We have previously found [9] that Ph2SbCH2SbPh2
does not react at all easily with [Mn2(CO)10] in high-
boiling solvents, and thus we sought alternative syn-
thetic routes. The reaction of [Mn2(CO)10] with SbPh3
and Me3NO (1:1.15:1 mol ratio) in toluene, followed by
removal of the solvent, and chromatography on silica
decomposition
product
of
[HMn(CO)4(SbPh3)]
eluting
with
n-hexane
produced
unchanged
(w(CO): 2062, 2010, 1980, 1953, 1825 cm−1), which
may have been an eq,eq isomer (full characterisation
was not provided). We note that [Mn2(CO)8(PR3)2]
(R3=Et3, PhMe2) are diaxial isomers, whereas
[Mn2(CO)8(AsR3)2] (R3=Et3, PhMe2, Me3) are diequa-
torial isomers, although [Mn2(CO)8(AsPh3)2] is again a
diaxial form [10]. Finally we re-examined the thermal
reaction of [Mn2(CO)10] with SbPh3 in boiling o-xylene
(12 h). Most of the starting materials were recovered
unchanged, along with some insoluble brown material,
and a very small amount of orange solid which had
w(CO) at 2013(m), 1998(m), 1968(s) cm−1. These fre-
[Mn2(CO)10] and moderate yields (10–15%) of orange-
brown [Mn2(CO)9(SbPh3)]. Use of a larger excess of
SbPh3 and Me3NO increased the proportion of the
monosubstituted complex, but did not produce the
expected disubstitution. Photolysis of a mixture of
[Mn2(CO)10] and SbPh3 (1:2 mol ratio) in toluene (12 h,
370 nm) produced a dark-red solution and some black
solid. Filtration, evaporation of the filtrate to dryness,
and chromatography on silica (n-hexane), gave three
main products, in addition to some dark orange mate-
rial which did not elute. The complexes were identified
in order of elution as [Mn2(CO)10], [Mn2(CO)9(SbPh3)],
and deep orange-yellow [Mn2(CO)8(SbPh3)2].
The identification of the [Mn2(CO)9(SbPh3)] complex
as the axial-substituted isomer (I) followed from the
presence of five CO stretching modes in its IR spectrum
[10], and this was confirmed by an X-ray study. The
13C{1H} NMR spectrum showed only two carbonyl
resonances, a weak one due to the unique axial CO
group and a much stronger one due to the eight equato-
rial CO’s. The failure to resolve two resonances corre-
sponding to the equatorial carbonyl groups in the
–Mn(CO)5 and the –Mn(CO)4(SbPh3) residues is at-
tributable to their very similar environments and the
line broadening produced by the 55Mn quadrupole mo-
ment [11]. The identification of the two manganese
centres by 55Mn NMR spectroscopy (Table 2) is nota-
ble and is discussed below.
quencies do not correspond to those of [Mn2(CO)10−x
-
(SbPh3)x] (x=1 or 2), nor those of [HMn(CO)4(SbPh3)]
[8], and due to the very poor yields the material was not
further characterised.
Photolysis of a mixture of [Re2(CO)10] and SbPh3
(1:2 mol ratio) in toluene was carried out in a similar
way to the reaction with [Mn2(CO)10]. Chromatography
using n-hexane–CH2Cl2 as elutant separated un-
changed [Re2(CO)10] and a yellow solid identified as
[Re2(CO)9(SbPh3)]. Under these conditions, and in con-
trast to the manganese chemistry, and to [Re2(CO)10]/
PR3 reactions [1], there was no evidence for
disubstitution. The [Re2(CO)9(SbPh3)] was identified as
the axial isomer [14] by IR spectroscopy (w(CO)
(CH2Cl2): 2086, 2008, 1994, 1978, 1925 cm−1), a very
The structure consists of discrete molecules based on
the [Mn2(CO)10] structure with an axially substituted
SbPh3 ligand (Fig. 1). The Mn–Mn distance (2.909(1)
˚
A) can be compared with the parent carbonyl
˚
(2.9038(6) ([12]a) and 2.8950(6) A ([12]b)) and a similar
axially substituted phosphine (PMe2Ph) derivative
˚
(2.904(−) A) [13]. Both of these compounds and the
present one show Mn–Mn–C angles less than 90° as
the equatorial CO’s bend towards the Mn–Mn bond,
and with the two Mn(CO)4 groups staggered (a typical
torsion angle C(1)–Mn(1)–Mn(2)–C(5) in the present
compound is 44.5(3)°). The axial CO on Mn(2) has a
significantly shorter Mn–C bond than the eight equato-
rial Mn–C distances (Table 1). Few Mn–Sb bonds
have been characterised crystallographically and none
with SbPh3.
The orange-yellow [Mn2(CO)8(SbPh3)2] was identified
as the diaxial isomer (II) since it shows only one broad
CO stretch in the IR spectrum (1977 cm−1) whereas
Fig. 1. Molecular structure of [Mn2(CO)9(SbPh3)] showing the atom
labeling scheme. Displacement ellipsoids are drawn at the 50% prob-
ability level.

N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
215
Table 1
˚
Selected bond lengths (A) and angles (°) for [Mn2(CO)9(SbPh3)], [Mn(CO)5(SbPh3)][CF3SO3] and [Re(CO)3Cl(SbPh3)2]
(a) [Mn2(CO)9(SbPh3)]
Mn(1)–Sb(1)
Mn(1)–Mn(2)
Mn(2)–C(9)
2.525(1)
2.909(1)
1.824(8)
Sb(1)–C(11)
Sb(1)–C(21)
Sb(1)–C(31)
2.164(7)
2.146(6)
2.146(6)
Mn–C (not C(9))
C–O
C–C
1.857(7)–1.884(8)
1.128(8)–1.166(8)
1.39(1)–1.42(1)
121.1(2)
117.2(2)
116.9(2)
Mn(1)–Sb(1)–C(11)
Mn(1)–Sb(1)–C(21)
Mn(1)–Sb(1)–C(31)
Mn(2)–Mn(1)–Sb(1)
Mn(1)–Mn(2)–C (ca. 90°)
Mn(2)–Mn(1)–C
Sb(1)–Mn(1)–C
Mn–C–O
C(11)–Sb(1)–C(21)
C(11)–Sb(1)–C(31)
C(21)–Sb(1)–C(31)
99.9(2)
98.6(2)
99.2(2)
178.06(4)
84.1(2)–88.2(2)
85.4(2)–89.2(2)
92.4(2)–94.7(2)
177.2(6)–179.9(7)
(b) [Mn(CO)5(SbPh3)][CF3SO3]
Mn(1)–Sb(1)
Sb(1)–C(21)
2.596(3)
2.129(7)
Sb(1)–C(11)
Mn(1)–C(5)
2.128(7)
1.824(8)
Sb(1)–C(31)
2.118(7)
Mn–C (not C(5))
C–O
C–C
Mn(1)–Sb(1)–C(11)
Mn(1)–Sb(1)–C(21)
Mn(1)–Sb(1)–C(31)
Sb(1)–Mn(1)–C(5)
Sb(1)–Mn(1)–C (ca. 90°)
Mn–C–O
1.874(8)–1.890(8)
1.119(9)–1.139(8)
1.36(1)–1.41(1)
117.9(2)
115.2(2)
112.6(2)
176.5(2)
85.1(2)–91.6(2), (88.6(av))
176.4(7)–178.5(6)
C(11)–Sb(1)–C(21)
C(11)–Sb(1)–C(31)
C(21)–Sb(1)–C(31)
101.0(3)
105.4(3)
102.9(3)
(c) [Re(CO)3Cl(SbPh3)2]
Re–Sb(1)
Re–Sb(2)
Re–Cl
Sb(1)–C(11)
2.729(2)
2.726(1)
2.504(3)
2.12(1)
2.12(1)
2.14(1)
Re–C(1)
Re–C(2)
Re–C(3)
Sb(2)–C(41)
Sb(2)–C(51)
Sb(2)–C(61)
1.95(1)
1.97(1)
1.92(1)
2.15(1)
2.12(1)
2.17(1)
Sb(1)–C(21)
Sb(1)–C(31)
C–O
C–C
Sb(1)–Re–Sb(2)
Sb(1)–Re–Cl
Sb(2)–Re–Cl
Sb(1)–Re–C(3)
Sb(2)–Re–C(1)
Re–Sb(1)–C(11)
Re–Sb(1)–C(21)
Re–Sb(1)–C(31)
C(11)–Sb(1)–C(21)
C(11)–Sb(1)–C(31)
C(21)–Sb(1)–C(31)
Re–C–O
1.06(1)–1.16(1)
1.34(2)–1.42(2)
95.73(3)
88.67(8)
84.24(7)
178.2(3)
173.8(3)
122.0(3)
113.3(3)
117.4(3)
97.8(5)
C(1)–Re–C(2)
C(1)–Re–C(3)
C(2)–Re–C(3)
Cl–Re–C(2)
92.3(4)
88.8(4)
89.1(4)
174.5(3)
Re–Sb(2)–C(41)
Re–Sb(2)–C(51)
Re–Sb(2)–C(61)
C(41)–Sb(2)–C(51)
C(41)–Sb(2)–C(61)
C(51)–Sb(2)–C(61)
114.1(3)
111.3(3)
125.9(3)
97.0(4)
105.7(4)
97.9(4)
104.2(4)
98.1(4)
176(1)–178(1)
similar pattern to that of ax-[Mn2(CO)9(SbPh3)]. The
complex is poorly soluble in n-hexane, but easily dis-
solves in chlorocarbons.
The structure consists of discrete octahedral cations
(Fig. 2, Table 1) with Mn–Sb 2.596(3) A longer (0.07
A) than in [Mn2(CO)9(SbPh3)]. The Mn–C trans to the
˚
˚
Reaction of [Mn(CO)5Br] with Ag[CF3SO3] and
SbPh3 in CH2Cl2 produced the carbonyl cation
[Mn(CO)5(SbPh3)][CF3SO3]. The [Mn(CO)5(SbPh3)]
ClO4 complex has been described previously [15]. The
pentacarbonyl cation (C4v) is easily identified by three
CO stretches at 2135(m), 2060(sh), 2050(s) cm−1, and
its structure was confirmed by an X-ray study.
Sb atom is shorter than the four remaining equatorial
distances but unlike the earlier dimetallic compound the
Sb–Mn–C(eq) angles do not show the same trend and
are close to 90°. It has been noted before in BiPh3
complexes that the C–Bi–C angle increases on coordi-
nation but with the effect less for lighter Group 15
ligands [16]. In the present examples the same trend can

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N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
be observed. In solid SbPh3 the C–Sb–C angle ranges
from 95.1(3)–98.0(3), 96.3° (av) [17], whereas in the
two manganese complexes reported here the values are
98.6(2)–99.9(2), 99.2° (av) and 101.0(3)–105.4(3),
103.1° (av) (Table 1) with the larger values being in the
cationic species.
mer,trans-[Mn(CO)3Cl(SbPh3)2] was grown from
CH2Cl2 solution by evaporation, but due to disorder
between the CO/Cl groups the structure was not satis-
factorily refined. Nonetheless the trans-SbPh3 groups
were clearly established [20]. An essentially identical
crystallographic
problem
was
found
in
Manganese carbonyl halides cis-[Mn(CO)4XL] and
mer, trans-[Mn(CO)3XL2] (X=Cl, Br or I; L=PR3,
AsR3, etc) are well known [1]. In the case of SbPh3 only
the bromides are at all well characterised [18,19]. We
have prepared three carbonyl chloride complexes. The
reaction of [Mn(CO)5Cl] with SbPh3 in CHCl3 at room
temperature produced orange cis-[Mn(CO)4Cl(SbPh3)],
the structure [III] following from the three w(CO)
modes in the IR spectrum (theory 4, the trans isomer
should have two, of which one will be of very low
intensity) [18]. Reacting [Mn(CO)5Cl] with two equiva-
lents of SbPh3 under reflux in CHCl3 produced the
orange-yellow fac-[Mn(CO)3Cl(SbPh3)2] which shows
three w(CO) stretches consistent with the Cs structure
[IV]. The isolation of fac isomers is unusual with
monodentate Group 15 ligands [1], although the corre-
sponding bromide is known [19]. On heating in solu-
tion, the fac isomer partially converts to the orange
mer,trans-[Mn(CO)3Cl(SbPh3)2] [V], which separates
first on concentrating the solution. The residual fac-
[Mn(CO)3Cl(SbPh3)2] can be recovered from the filtrate
after removal of the solid mer, trans isomer. No other
products were detected by IR spectroscopy of the solu-
tions. The mer,trans-[Mn(CO)3Cl(SbPh3)2] exhibits only
two w(CO) IR active modes (theory 3) [19]. A crystal of
[Re(NO)2Cl2(SbPh3)2] [21]; the cell dimensions were
very similar and again the unusual Z of three was
(
found in space group P1 with one molecule in a general
position and one positioned with the Re atom on a
centre of symmetry. The stereochemistry showed trans
Sb atoms and cis Cl atoms in the general position
molecule but NO/Cl disorder in the centrosymmetric
molecule. As noted above in the neutral carbonyl com-
plexes, the l(CO) resonances in the 13C{1H} NMR
spectra are less useful in determining stereochemistry in
these complexes due to the small chemical shift range
observed and the broadening caused by the 55Mn
quadrupole moment (Scheme 1).
The corresponding cis-[Re(CO)4Cl(SbPh3)] and fac-
[Re(CO)3Cl(SbPh3)2] were made by similar methods to
those used for the manganese analogues, although the
rates of substitution are very markedly slower. The
isomers present were identified from the carbonyl vibra-
tions in the IR spectra (Section 3). However fac-
[Re(CO)3Cl(SbPh3)2] showed no evidence for
isomerisation into the mer,trans form after 48 h. reflux
in CHCl3, as monitored via the IR spectrum of the
solution. Comparison of our IR data with Moedritzer’s
data [22] for the carbonyl iodide analogues shows only
very small differences in w(CO) on changing the halo-
gen. The structure of fac-[Re(CO)3Cl(SbPh3)2] was
confirmed by a crystal structure determination and the
molecule is shown in Fig. 3 with selected bond lengths
in Table 1. The octahedral Re geometry shows the
expected small angular distortions with Sb(1)–Re–
Sb(2) being the largest angle (95.73(3)°). There are very
few Re–Sb distances reported in the Cambridge struc-
tural database with [Re(NO)2Cl2(SbPh3)2] [21] being the
˚
closest chemical example (Re–Sb 2.711(8), 2.710(8) A)
and showing similar bond lengths to the present com-
pound. As commented on earlier for the Mn com-
pounds, the C–Sb–C angles (97.0(4)–105.7(4), 100.1°
(av)) are larger than in the free ligand.
Both naturally occuring rhenium isotopes (185Re and
187Re) have I=5/2 but these are associated with very
large quadrupole moments which make them unsuitable
for NMR investigation of rhenium complexes. In con-
trast, 55Mn is a very sensitive NMR nucleus (I=5/2,
100%, J=24.66, Dc=994), but probably due to the
moderate quadrupole moment (Q=0.55×10−28 m2),
has been relatively little used [11,23]. Table 2 lists the
55Mn chemical shifts for a range of stibine complexes
and Fig. 4 shows the spectrum of [Mn2(CO)9(SbPh3)].
The spectra are mostly obtainable in a few minutes,
although those containing very broad resonances need
Fig. 2. Structure of the cation in [Mn(CO)5(SbPh3)][CF3SO3] showing
the atom labeling scheme. Displacement ellipsoids are drawn at the
50% probability level and H atoms excluded for clarity.

N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
217
Scheme 1.
somewhat longer. As can be seen for the SbPh3 com-
plexes described above, the l(Mn) values span ca. 1700
ppm, and this wide chemical shift range coupled with
short acquisition times, makes the identification of the
components of mixtures straightforward, for example
the [Mn(CO)5−xCl(SbPh3)x]. As would be expected
from the size of the quadrupole, the line widths in the
55Mn spectra are very sensitive to the electric field
gradients at the manganese (Table 2), varying from a
few hundred Hz to ca. 20000 Hz. Overall 55Mn NMR
proves to be a very sensitive probe and merits more
widespread use.
usually mixtures of [Mn2(CO)10−x(L)x] (x=0, 1 or 2)
separable chromatographically [1]. In contrast, with
SbPh3 monosubstitution is favoured irrespective of the
SbPh3:M2(CO)10 ratio under both photochemical and
amine oxide promoted conditions, and we have not
observed any [Re2(CO)8(SbPh3)2] formation. Thermal
substitution of the decacarbonyls with SbPh3 is not a
satisfactory route, again contrasting with results in the
PR3 systems. These results largely parallel our previous
studies with Ph2SbCH2SbPh2 [9] which identified lower
levels of CO-substitution and poor yields compared
with the analogous diphosphine systems. In the car-
bonyl halide systems, the isolation of fac-
[Mn(CO)3Cl(SbPh3)2] which slowly isomerises on
heating, compared to the formation of only mer,trans-
isomers with most PR3 or AsR3 is also notable. These
results suggest that other stibine complexes merit a
detailed re-examination; in much of the earlier work,
the SbPh3 complexes received cursory mention and
often incomplete characterisation in papers focusing on
2.1. Some comparisons
The reactions of excess PR3 or AsR3 (L) with
[Mn2(CO)10] or [Re2(CO)10] either thermally or photo-
chemically result predominantly in the disubstituted
complexes [M2(CO)8L2], and even with stoichiometric
amounts of ligand and decacarbonyl, the products are

218
N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
3.1. Synthesis
[Mn2(CO)9(SbPh3)]·[Mn2(CO)10] (0.81 g, 2.1 mmol),
SbPh3 (2.1 g, 5.9 mmol) and Me3NO (0.31 g, 4.1 mmol)
were stirred together in toluene (30 ml) under nitrogen
at 40°C overnight in an attempt to produce
[Mn2(CO)8(SbPh3)2]. The solvent was then removed and
the residue adsorbed onto silica. The mixture was chro-
matographed on silica using n-hexane and the first two
bands collected, the first being unreacted [Mn2(CO)10]
and the second [Mn2(CO)9(SbPh3)]. The volume of
n-hexane in the second fraction was reduced to ca. 5 ml
and the solution placed in the freezer for 2 h to yield
orange-brown crystals. Yield 0.30 g, 22%. (Found: C,
45.2; H, 2.0. C27H15Mn2O9Sb requires C, 45.3; H,
2.1%). FAB MS (3-NOBA) M+ 686, 602, 519, 491,
462, 407. Anal. calc. for [Mn2(CO)8(121SbPh3)]+ 686,
[Mn2(CO)5(121SbPh3)]+ 602, [Mn(CO)4(121SbPh3)]+
519, [Mn(CO)3(121SbPh3)]+ 491, [Mn(CO)2(121SbPh3)]+
463, [Mn(121SbPh3)]+407. IR: Solution (hexane) 2089
(m), 2010 (m), 1995 (s), 1974 (m), 1937 (m); Nujol mull
Fig. 3. Molecular structure of [Re(CO)3Cl(SbPh3)2] showing the atom
labeling scheme. Displacement ellipsoids are drawn at the 50% prob-
ability level and H atoms are excluded for clarity.
2088 (m), 2008 (m), 1993 (s), 1980 (sh), 1936 (m) cm−1
.
1H NMR (CDCl3) 7.2–7.6 (m). 13C{1H} NMR (CDCl3)
224.2, 223.5, 135–129.
[Mn2(CO)8(SbPh3)2]. A solution of [Mn2(CO)10] (2.0
g, 5.13 mmol) and SbPh3 (4.0 g, 11.3 mmol) in toluene
(80 ml) was irradiated with UV light (370 nm) under
nitrogen with stirring for 12 h. The dark red solution
obtained was filtered, and the solvent removed to give a
red-brown oil, which was chromatographed in silica
using n-hexane to give firstly [Mn2(CO)10] followed by
[Mn2(CO)9(SbPh3)] and on switching to dichloro-
methane as the eluant [Mn2(CO)8(SbPh3)2]·CH2Cl2.
(Found: C, 47.6; H, 2.9. C45H32Cl2Mn2O8Sb2 requires
C, 48.0; H, 2.8%). IR: Solution (dichloromethane) 1977
phosphine and arsine analogues. It is becoming clear
that there are significant differences between SbR3 and
the lighter ligand analogues in many systems [24].
3. Experimental
Physical measurements were made as described else-
1
where [9]. H and 13C{1H} NMR chemical shifts are
quoted relative to TMS; 55Mn chemical shifts are rela-
tive to external aqueous KMnO4 solution (l=0).
1
(br); Nujol mull 1970 (br) cm−1. H NMR (CDCl3) 7.2
–7.6, 5.3 (CH2Cl2). 13C{1H} NMR (CDCl3/CH2Cl2)
216.6, 135–128.
Table 2
55Mn NMR spectroscopic dataa
[Mn(CO)5(SbPh3)][CF3SO3]·[Mn(CO)5Br] (0.337 g,
1.23 mmol) and AgCF3SO3 (0.47 g, 1.84 mmol) in
dichloromethane (50 ml) were stirred together under
nitrogen with the exclusion of light for 3 h. The mixture
was filtered (Schlenk) and the yellow filtrate stirred with
SbPh3 (1.3 g, 3.7 mmol) for a further 3 h. The volume
was reduced to ca. 10 ml and n-hexane (30 ml) added.
The yellow solid produced was filtered off, washed with
n-hexane (3×10 ml) and dried in vacuo. Yield 0.25 g,
29%. (Found: C, 41.5; H, 2.0. C24H15F3MnO8SSb re-
quires C, 41.3; H, 2.2%). ES MS (MeCN) M+ 547, 519,
491, 407, anal. calc. for [Mn(CO)5(121SbPh3)]+ 547,
[Mn(CO)4(121SbPh3)]+ 519, [Mn(CO)3(121SbPh3)]+ 491,
[Mn(121SbPh3)]+ 407. IR: Solution (dichloromethane)
2135 (m), 2060(sh), 2050 (s); Nujol mull 2135 (m), 2051
Complex
l(55Mn)
w12 (Hz)
Reference
Mn2(CO)10
[Mn2(CO)9(SbPh3)]
−2325
−2389, −2394
83
320,
650
14 000
20 000
3800
[11]
This work
[Mn2(CO)8(SbPh3)2]
−2070
This work
[9]
This work
[Mn2(CO)8(v-dpsm)]b −2195
[Mn(CO)5(SbPh3)]-
[CF3SO3]
[Mn(CO)5Cl]
−1825
−1004
−997
331
4000
5000
1000
[11]
This work
[9]
[Mn(CO)4Cl(SbPh3)]
[Mn(CO)4Cl(p1-dpsm)] −1277
fac-[Mn(CO)3Cl-
(SbPh3)2]
mer,trans-[Mn(CO)3-
Cl(SbPh3)2]
−730
−920
This work
15 000
This work
1
(m) cm−1. H NMR (CDCl3) 7.3–7.7. 13C{1H} NMR
a Chemical shifts relative to external aqueous KMnO4.
b dpsm, Ph2SbCH2SbPh2.
(CDCl3) 206.4(sh), 205.3, 137–126.

N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
219
Fig. 4. 55Mn NMR spectrum of [Mn2(CO)9(SbPh3)] in CHCl3/CDCl3.
[Mn(CO)4Cl(SbPh3)]·[Mn(CO)5Cl] (0.12 g, 0.52
mmol) and SbPh3 (0.18 g, 0.51 mmol) were stirred
together under nitrogen in chloroform (10 ml) for 24 h
to give an orange solution. The solution was filtered
and the solvent removed from the filtrate to give an
orange solid. Yield 0.27 g, 92%. (Found: C, 47.5; H,
2.7. C22H15ClMnO4Sb requires C, 47.5; H, 2.6%). FAB
MS (3-NOBA) M+519, 491, 444, 407, anal. calc. for
[Mn(CO)4(121SbPh3)]+ 519, [Mn(CO)3(121SbPh3)]+491,
[Mn35Cl(121SbPh3)]+ 442, [Mn(121SbPh3)]+, 407. IR:
Solution (chloroform) 2090 (m), 2012 (s), 1960 (m);
reduced in volume to ca. 2 ml. Hexane (40 ml) was
added and the yellow-orange solid produced was
filtered off, washed with hexane (2×10 ml) and dried
in vacuo. Yield 0.05 g, 13%. (Found: C, 53.3; H, 3.4.
C39H30ClMnO3Sb2 requires C, 53.2; H, 3.4%). FAB MS
(3-NOBA) M+ 845, 796, 761, 444, 407, anal. calc. for
[Mn(CO)3(121SbPh3)2]+ 845, [Mn35Cl(121SbPh3)2]+ 794,
[Mn(121SbPh3)2]+ 759, [Mn35Cl(121SbPh3)]+ 442,
[Mn(121SbPh3)]+ 407. IR: Solution (dichloromethane)
2024 (s), 1955 (m), 1912 (m); Nujol mull 2019 (s), 1954
(s), 1904 (m) cm−1
.
1H NMR (CDCl3) 7.2–7.7.
Nujol mull 2087 (s), 2002 (s), 1950 (s) cm−1. H NMR
13C{1H} NMR (CDCl3) 211.5, 206.0, 139–127.
1
(CDCl3) 7.3–7.7. 13C{1H} NMR (CDCl3) 215.5,
213.0(sh), 212.5, 136–130.
fac-[Mn(CO)3Cl(SbPh3)2]·[Mn(CO)5Cl] (0.10 g, 0.43
mmol) and SbPh3 (0.31 g, 0.88 mmol) in chloroform (30
ml) were refluxed together under nitrogen for 24 h. The
mixture was then cooled and filtered and the filtrate
mer, trans-[Mn(CO)3Cl(SbPh3)2]·[Mn(CO)5Cl] (0.10
g, 0.43 mmol) and SbPh3 (0.31 g, 0.88 mmol) in chloro-
form (30 ml) were refluxed together under nitrogen for
22 h. The mixture was then cooled and filtered and the
filtrate reduced in volume to ca. 2 ml. Hexane was
added and the orange solid produced was filtered off

220
N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
Table 3
Crystal data for [Mn2(CO)9(SbPh3)], [Mn(CO)5(SbPh3)][CF3SO3] and [Re(CO)3Cl(SbPh3)2]
Compound
[Mn2(CO)9(SbPh3)]
[Mn(CO)5(SbPh3)]-
[CF3SO3]
C24H15F3MnO8SSb
697.12
Monoclinic
P21/c (no. 14)
11.711(11)
14.705(16)
15.115(9)
90.0
93.45(6)
90.0
2598.3(3.7)
4
1.782
[Re(CO)3Cl(SbPh3)2]
Molecular formula
Mr
C27H15Mn2O9Sb
715.03
Triclinic
C39H30ClO3ReSb2
1011.82
Orthorhombic
Pbca (no. 61)
19.162(7)
20.765(10)
17.646(16)
90.0
90.0
90.0
7021.3(6.8)
8
1.914
Crystal system
Space group
(
P1 (no. 2)
˚
a (A)
10.143(2)
˚
b (A)
11.782(5)
13.266(2)
66.37(1)
75.20(1)
85.84(2)
1403.4(7)
2
˚
c (A)
h (°)
i (°)
k (°)
3
˚
V (A )
Z
Dcalc (g cm−3
)
1.692
2 Theta range for cell (°)
Temperature (K)
F(000) (e)
—
150
700
33.0–38.6
150
1368
44.2–49.1
150
3856
Crystal size (mm)
Scan mode
0.20×0.18×0.16
Area detector
0.40×0.20×0.07
ꢀ-2q
0.40×0.33×0.20
ꢀ-2q
Total no. of observations
No. of unique observations
hkl range
4931
5013
6801
6184
3803 (Rint=0.057)
−11 to 9,−13 to 13,−15 to
4769 (Rint=0.0197)
0−13, 0−17, −17 to 17 0−22, 0−24, 0−20
13
Absorption correction
None
None
Analytical
Max/min transmission
—,—
—,—
0.361,0.227
No. of data in refinement
No. of parameters/restraints
3803
3808 (F\4|(F))
6184
401/36
262/0
338/0
Weighting scheme (w−1
)
|2(Fo2)
|2(Fo2)
|2(Fo2)+(0.18P)2+(5.08P) P=(Fo2+2F2c)/3
˚
u (A) (Mo–Kh)
0.71073
18.9
0.71073
16.55
0.71073
50.8
v (cm−1
)
Max 2q (°)
S
49.5
0.47
50.0
3.15
50.0
1.09
Max shift (esd)
Residual electron density (eA
R (F\n|(F))
0.04
0.01
−0.10
−5.81 to +3.05
0.062 (n=4, 4942 refs.)
−3
˚
)
−0.715 to +0.675
0.041 (n=4, 2669 refs.)
−1.99 to +1.53
0.048 (n=4, 3808 refs.)
R (all data)
wR2 (all data)
wR (F\n|(F))
0.049
0.130
—
—
—
0.081
0.225
—
0.057 (n=4, 3808 refs.)
1
1
[R=_ꢀꢀFoꢀ−ꢀFcꢀꢀ/SꢀFoꢀ; wR2=[Sw(Fo2−Fc2)2/SwFo4]2; wR=[Sw(Fo−Fc)2/SwFo2]2.
and by solution IR was shown to be a mixture of
fac-[Mn(CO)3Cl(SbPh3)2] and [Mn(CO)4Cl(SbPh3)].
The solid was refluxed with more SbPh3 (0.10 g, 0.28
mmol) in chloroform for a further 2 h. On cooling
hexane (20 ml) was added and the mixture reduced in
volume until an orange solid precipitated mer,trans-
[Mn(CO)3Cl(SbPh3)2]. This was filtered off and washed
with hexane. The yellow filtrate was reduced in volume
(s) cm−1
(CDCl3) 221.7, 219.8, 137–127.
.
1H NMR (CDCl3) 7.2–7.7. 13C{1} NMR
[Re2(CO)9(SbPh3)]·[Re2(CO)10] (0.50 g, 0.77 mmol)
and SbPh3 (0.54 g, 1.54 mmol) in degassed toluene (40
ml) were irradiated under nitrogen with stirring
overnight. The mixture was then adsorbed onto alu-
mina and eluted with dichloromethane-n-hexane (1:3)
to give [Re2(CO)10] (first band collected —colourless)
and [Re2(CO)9(SbPh3)] (second band collected—yel-
low). The solvent was removed from the collected frac-
tions and the residue recrystallised from CH2Cl2-hexane
to give a yellow solid. This was filtered, washed with
hexane (2×10 ml) and dried in vacuo. Yield 0.1 g,
13%. (Found: C, 32.9; H, 1.7. C27H15O9Re2Sb requires
C, 33.2; H, 1.5%). FAB MS (3-NOBA) 974, 948, 925,
893, 869, 623, 567, 539, anal. calc. for
further
to
yield
a
yellow-orange
solidfac-
[Mn(CO)3Cl(SbPh3)2] this was also filtered off and
washed with hexane. (Found: (mer,trans) C, 53.5; H,
3.3. C39H30ClMnO3Sb2 requires C, 53.2; H, 3.4%). FAB
MS (3-NOBA) 880, 845, 796, 761, 444, anal. calc. for
[Mn(CO)335Cl(121SbPh3)2]+ 878, [Mn(CO)3(121SbPh3)2]+
843, [Mn35Cl(121SbPh3)2]+ 794, [Mn(121SbPh3)2]+ 759,
[Mn35Cl(121SbPh3)]+ 442. IR: Solution (dichloro-
methane) 1950 (s), 1909 (m); Nujol mull 1942 (s), 1893
[
185Re2(CO)9(121SbPh3)]+ 974, [185Re2(CO)8(121SbPh3)]+

N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
221
Table 5
946,
[
185Re2(CO)7(121SbPh3)]+ 918,
[
185Re2(CO)6
2
˚
Atomic coordinates and equivalent displacement parameter (A ) for
[Mn(CO)5(SbPh3)][CF3SO3]
(
121SbPh3)]+ 890, [185Re2(CO)5(121SbPh3)]+ 862, [185Re2
(CO)9]+ 622,
[
185Re(CO)(121SbPh3)]+ 565,
[
185Re
1
(
121SbPh3)]+ 537. H NMR (CDCl3) 7.1–7.5. 13C{1H}
Atom
Sb(1)
Mn(1) −0.04881(9)
S(1)
F(1)
F(2)
F(3)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
C(1)
x
y
z
Beq
NMR (CDCl3) 193.0, 190.3, 188.2, 136–127. IR: Solu-
tion (dichloromethane) 2086 (w), 2009 (sh), 1996 (s),
1971 (s), 1925 (m); Nujol mull 2082 (m), 2008 (sh), 1994
0.17077(4)
0.16551(3)
0.18946(7)
0.2202(1)
0.1868(5)
0.3185(4)
0.2918(4)
0.0717(3)
0.3487(4)
0.3052(4)
0.0241(4)
0.2159(4)
0.1787(4)
0.3039(4)
0.1587(4)
0.1165(5)
0.2899(5)
0.2618(5)
0.0873(5)
0.2060(5)
0.0959(5)
0.1312(5)
0.0906(6)
0.0150(6)
0.88699(3)
0.88787(7)
0.6093(1)
0.6741(5)
0.7062(3)
0.5750(4)
1.0502(3)
1.0122(4)
0.7280(4)
0.7710(4)
0.8748(3)
0.6883(3)
0.5844(4)
0.5372(3)
0.9894(5)
0.9654(5)
0.7869(5)
0.8140(5)
0.8810(5)
0.9963(4)
1.0793(5)
1.1523(5)
1.1421(5)
1.0593(5)
0.9852(5)
0.8850(4)
0.8951(5)
0.8992(5)
0.8947(5)
0.8841(5)
0.8804(5)
0.7728(4)
0.7029(5)
0.6246(5)
0.6183(5)
0.6874(5)
0.7649(5)
0.6421(6)
1.42(1)
1.54(2)
1.84(4)
6.4(2)
4.6(1)
5.3(2)
2.3(1)
3.5(1)
2.9(1)
2.7(1)
2.2(1)
2.7(1)
3.1(1)
2.7(1)
1.9(2)
2.1(2)
1.9(2)
2.2(2)
1.8(2)
1.6(1)
2.3(2)
2.9(2)
2.7(2)
2.5(2)
2.1(2)
1.5(1)
2.2(2)
2.6(2)
2.3(2)
2.2(2)
1.9(2)
1.5(1)
2.1(2)
2.5(2)
2.5(2)
2.5(2)
2.4(2)
3.1(2)
0.7242(2)
0.5268(5)
0.5940(5)
0.5221(5)
−0.0492(4)
−0.0205(5)
−0.0147(5)
−0.0771(5)
−0.3034(4)
0.7755(5)
0.7766(5)
0.6970(5)
−0.0510(6)
−0.0294(6)
−0.0311(6)
−0.0677(6)
−0.2068(7)
0.2537(6)
0.2392(7)
0.2959(8)
0.3660(7)
0.3782(6)
0.3231(6)
0.2697(6)
0.3876(6)
0.4543(7)
0.4016(7)
0.2846(7)
0.2174(6)
0.2193(6)
0.2613(7)
0.2848(7)
0.2695(7)
0.2298(7)
0.2027(7)
0.5846(7)
(s), 1978 (s), 1925 (s) cm−1
.
[Re(CO)4Cl(SbPh3)]·[Re(CO)5Cl] (0.066 g, 0.18
mmol) and SbPh3 (0.064 g, 0.18 mmol) were refluxed in
chloroform (30 ml) for 2 h. On cooling n-hexane (25
ml) was added and on reducing the volume a white
solid obtained. This was filtered off, washed with hex-
ane (2×10 ml) and dried in vacuo. Yield 0.080 g, 65%.
(Found: C, 38.6; H, 2.3. C22H15ClO4ReSb requires C,
C(2)
C(3)
C(4)
C(5)
Table 4
2
3
˚
Atomic coordinates and equivalent displacement parameter (A ×10 )
for [Mn2(CO)9(SbPh3)]
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(40)
Atom
x
y
z
Ueq
Sb(1)
Mn(1)
Mn(2)
O(1)
O(2)
O(3)
O(4)
O(5)
O(6)
O(7)
O(8)
O(9)
C(1)
C(2)
C(3)
C(4)
C(5)
C(6)
0.24203(4)
0.42107(10) 0.72969(8)
0.62891(11) 0.59879(8)
0.83866(3)
0.83696(3)
0.74050(7)
0.63684(8)
0.5825(4)
0.9016(4)
0.8860(4)
0.5679(5)
0.6570(5)
0.8772(4)
0.6294(4)
0.4158(4)
0.5320(4)
0.6428(5)
0.8406(5)
0.8308(6)
0.6338(6)
0.6482(6)
0.7855(6)
0.6337(5)
0.4988(6)
0.5724(6)
0.7707(5)
0.6549(6)
0.6151(6)
0.6910(6)
0.8063(6)
0.8461(6)
1.0118(5)
1.0949(6)
1.2094(6)
1.2423(6)
1.1598(6)
1.0441(6)
0.8510(5)
0.8541(6)
0.8656(6)
0.8718(6)
0.8660(5)
0.8565(5)
16(1)
16(1)
20(1)
34(1)
31(1)
31(1)
43(1)
43(1)
32(1)
36(1)
47(2)
41(1)
22(2)
19(2)
22(2)
25(2)
28(2)
21(2)
25(2)
30(2)
28(2)
20(1)
27(2)
30(2)
32(2)
34(2)
25(2)
20(1)
24(2)
30(2)
33(2)
29(2)
26(2)
18(1)
30(2)
38(2)
27(2)
23(2)
22(2)
−0.0195(5)
0.0206(5)
0.2868(5)
0.2808(5)
0.3585(5)
0.4438(5)
0.4502(5)
0.3727(5)
0.0953(5)
0.1428(5)
0.0991(5)
0.0057(5)
−0.0421(5)
0.0006(5)
0.2558(6)
0.5923(5)
0.5985(5)
0.2877(5)
0.2625(6)
0.8453(6)
0.6191(5)
0.3883(6)
0.6065(6)
0.8305(6)
0.5250(7)
0.5300(7)
0.3379(7)
0.3249(8)
0.7618(8)
0.6210(7)
0.4804(8)
0.6137(8
0.7530(8)
0.0667(7)
0.0827(7)
−0.0287(8)
−0.1598(8)
−0.1764(8)
−0.0637(7)
0.1419(7)
0.1361(7)
0.0754(8)
0.0215(8)
0.0257(8)
0.0858(7)
0.3087(7)
0.4455(8)
0.4896(8)
0.3963(7)
0.2615(7)
0.2177(7)
0.9611(4)
0.6930(4)
0.4774(4)
0.7580(5)
0.7473(5)
0.4225(4)
0.4673(4)
0.8037(5)
0.4575(5)
0.8731(6)
0.7059(5)
0.5741(6)
0.7462(6)
0.6938(6)
0.4895(6)
0.5174(6)
0.7264(6)
0.5119(6)
0.9154(5)
0.9924(6)
1.0520(6)
1.0331(6)
0.9547(6)
0.8955(6)
0.7353(5)
0.7818(6)
0.7103(6)
0.5893(6)
0.5425(6)
0.6147(6)
0.9993(5)
1.0085(6)
1.1149(6)
1.2070(6)
1.1980(6)
1.0930(5)
C(7)
C(8)
C(9)
38.5; H,2.2%). FAB MS (3-NOBA) 687, 651, 623. Anal.
calc. for [185Re35Cl(CO)4(121SbPh3)]+ 684, [185Re(CO)4
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
(
121SbPh3)]+ 649, [185Re(CO)3(121SbPh3)]+ 621. 1H
NMR (CDCl3) 7.3–7.6. 13C{1H} NMR (CDCl3) 186.0,
182.7, 182.4, 136–129. IR: Solution (chloroform) 2107
(m), 2013 (s), 1947 (m); Nujol mull 2103 (m), 1997 (s),
1936 (s) cm−1
.
fac-[Re(CO)3Cl(SbPh3)2]·[Re(CO)5Cl] (0.10 g, 0.28
mmol) and SbPh3 (0.21 g, 0.59 mmol) were refluxed in
chloroform (30 ml) for 45 h. On cooling the volume
was reduced to ca. 5 ml and diethyl ether (20 ml) added
to give a light fawn solid. This was filtered off, washed
with diethyl ether (2×10 ml) and dried in vacuo. Yield
0.15 g, 53%. (Found: C, 46.7; H, 3.1. C39H30ClO3ReSb2
requires C, 46.3; H, 3.0%). FAB MS (3-NOBA) 1011,
983, 623, 539. Anal. calc. for
[
185Re35Cl(CO)3
(
121SbPh3)2]+ 1008, [185Re35Cl(CO)2(121SbPh3)2]+ 980,

222
N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
[
185Re35Cl(CO)3(121SbPh3)]+ 621,
[
185Re(121SbPh3)]+
(freezer, −20°C)
a
hexane solution overnight
537. 1H NMR (CDCl3) 7.2–7.5. 13C{1H} NMR
(CDCl3) 191–186(br), 136–130. IR: Solution (dichloro-
methane) 2032 (s), 1952 (m), 1906 (m); Nujol mull 2021
([Mn2(CO)9(SbPh3)]) and by liquid diffusion of diethyl
ether into a dichloromethane solution for the other two
compounds. Crystals were mounted on glass fibres us-
ing the oil-film technique and held at 150 K using an
Oxford Cryosystems low temperature device. Data were
recorded using an Enraf-Nonius FAST system
([Mn2(CO)9(SbPh3)] only) and a Rigaku AFC7S both
diffractometers being fitted with graphite monochroma-
tor and Mo–Kh radiation. For all structures, the heavy
atoms were located using SHELXS-86 direct methods
[25] and lighter atoms added by repeated structure
factor and electron density calculations. No significant
decay was noted and no absorption correction was
applied to the manganese data. No evidence for the H
atom positions appeared in later maps for
[Mn2(CO)9(SbPh3)] and they were not included in the
model. Full-matrix least-squares refinement on F2 was
carried out using SHELXL-97 [26] with anisotropic
(Sb, Mn, O, C (of CO’s)) and isotropic (C (phenyl))
thermal displacement parameters. For [Mn(CO)5
(SbPh3)][CF3SO3], all the H atoms appeared in the later
electron-density maps and they were added to the
model but not refined. For this compound, refinement
on F was carried out using the teXsan package [27] with
anisotropic thermal displacement parameters for all
atoms types (except H). For the rhenium compound, an
analytical absorption correction was applied and refine-
ment carried out using SHELXL-97 [26]. Some C atom
anisotropic displacement parameters became non-posi-
tive definite and the rigid bond approximation was
introduced for the phenyl rings (DELU instruction for
adjacent atoms). A number of plausible H atoms ap-
peared in later electron density maps and all the H’s
were introduced into the model in calculated positions
(s), 1954 (s), 1926 (s) cm−1
.
3.2. Crystallography
Air-stable crystals were obtained from cooling
Table 6
2
3
˚
Atomic coordinates and equivalent displacement parameter (A ×10 )
for [Re(CO)3Cl(SbPh3)2]
Atom
x
y
z
Ueq
Re
0.09677(2)
0.11545(4)
0.23520(4)
0.59561(2)
0.64721(3)
0.58573(3)
0.96568(3)
0.82490(4)
0.99927(4)
1.02015(18)
0.9456(6)
0.8977(5)
1.1202(5)
0.9535(5)
0.9213(6)
1.0633(6)
0.7757(7)
0.7636(10)
0.7333(10)
0.7181(11)
0.7304(14)
0.7588(13)
0.7372(7)
0.6623(8)
0.6065(7)
0.6229(7)
0.6966(7)
0.7535(7)
0.8012(7)
0.7281(7)
0.7088(7)
0.7627(9)
0.8354(8)
0.8544(7)
0.9796(6)
0.9239(6)
0.9149(8)
0.9604(8)
1.0130(8)
1.0231(7)
1.1179(7)
1.1485(7)
1.2264(7)
1.2748(8)
1.2440(7)
1.1665(7)
0.9665(6)
0.9692(8)
0.9558(7)
0.9401(10)
0.9375(12)
0.9504(11)
21(1)
23(1)
23(1)
30(1)
39(2)
38(2)
38(2)
14(2)
20(2)
24(2)
29(2)
43(3)
57(4)
66(5)
86(7)
72(6)
24(2)
30(3)
36(3)
36(3)
33(3)
30(2)
27(2)
30(2)
35(3)
41(3)
43(3)
35(3)
24(2)
29(2)
39(3)
37(3)
37(3)
34(3)
27(2)
31(2)
34(3)
33(3)
30(2)
29(2)
27(2)
43(3)
36(3)
52(4)
71(5)
61(5)
Sb(1)
Sb(2)
Cl
O(1)
O(2)
O(3)
C(1)
C(2)
C(3)
0.10833(15) 0.70647(14)
−0.0622(4)
0.0954(4)
0.0697(5)
−0.0038(5)
0.0974(5)
0.0811(6)
0.2159(6)
0.2556(7)
0.3229(8)
0.3503(8)
0.3114(10)
0.2446(9)
0.0689(6)
0.0926(6)
0.0617(6)
0.0074(6)
−0.0172(6)
0.0137(6)
0.0650(6)
0.0692(6)
0.0291(7)
−0.0119(7)
−0.0163(8)
0.0232(7)
0.2784(6)
0.3297(6)
0.3533(7)
0.3296(7)
0.2771(7)
0.2533(7)
0.2523(6)
0.3115(6)
0.3229(6)
0.2747(7)
0.2163(6)
0.2056(6)
0.3158(6)
0.3834(8)
0.4344(6)
0.4174(7)
0.3474(8)
0.2950(8)
0.6106(5)
0.4615(4)
0.5316(4)
0.6035(4)
0.5087(5)
0.5579(5)
0.6572(5)
0.6027(6)
0.6065(8)
0.6672(9)
0.7220(8)
0.7149(7)
0.5917(4)
0.5954(5)
0.5585(7)
0.5181(6)
0.5135(6)
0.5505(5)
0.7371(5)
0.7618(5)
0.8159(6)
0.8458(6)
0.8196(7)
0.7657(6)
0.4918(6)
0.4795(5)
0.4185(6)
0.3675(6)
0.3795(6)
0.4424(6)
0.5883(5)
0.5603(5)
0.5613(6)
0.5899(5)
0.6179(5)
0.6177(5)
0.6534(6)
0.6366(7)
0.6830(7)
0.7451(7)
0.7605(7)
0.7134(7)
C(11)
C(12)
C(13)
C(14)
C(15)
C(16)
C(21)
C(22)
C(23)
C(24)
C(25)
C(26)
C(31)
C(32)
C(33)
C(34)
C(35)
C(36)
C(41)
C(42)
C(43)
C(44)
C(45)
C(46)
C(51)
C(52)
C(53)
C(54)
C(55)
C(56)
C(61)
C(62)
C(63)
C(64)
C(65)
C(66)
˚
(d(C–H)=0.95 A) with a common refined displace-
ment parameter. The large peak and trough in the
difference electron-density map is close to the rhenium
˚
(ca. 1 A) and an alternative c-scan absorption correc-
tion failed to change matters. These features pre-
sumably reflect an inadequate absorption correction.
Crystallographic data are summarised in Table 3 and
atomic coordinates are given in Tables 4–6. Figs. 1–3
were produced using ORTEP [28].
4. Supplementary material available
Displacement parameters, atomic coordinates, hydro-
gen atom coordinates, full bond length, angle data and
crystallographic data for [Mn2(CO)9(SbPh3)], [Mn(CO)5-
(SbPh3)][CF3SO3] and [Re(CO)3Cl(SbPh3)2] have been
deposited at the Cambridge Crystallographic Data
Centre.

N.J. Holmes et al. / Journal of Organometallic Chemistry 568 (1998) 213–223
223
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Acknowledgements
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We thank the EPSRC for support (NJH) and for
funds to purchase the X-ray diffractometer and for
access to the Chemical Database Service at the Dares-
bury Laboratory. We also thank Professor M.B. Hurst-
house for data collection on the EPSRC X-ray service
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˚
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3
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(
(
groups were located by direct methods in space groups P1 and
(
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.