Co(III) and Cr(III) complexes of diphosphadithia ligands and the crystal structure of [CoCl2(L3)]PF6·CH2Cl 2 (L3=Ph2P(CH2)2S(o-C 6H4)S(CH2)2PPh2)

Article abstract of DOI:10.1016/S0277-5387(99)00285-5

[CrX₃(thf)₃] (X=Cl or Br) reacts with L (L=L¹-L³ or Ph₂[14]aneP₂S₂) (L¹=Ph₂P(CH₂)₂S(CH₂) ₂S(CH₂)₂PPh₂, L²=Ph₂P(CH₂)₂S(CH₂) ₃S(CH₂)₂PPh₂, L³=Ph₂P(CH₂)₂S(o-C₆H ₄)S(CH₂)₂PPh₂, Ph₂[14]aneP₂S ₂=4,8-diphenyl-1,11-dithia-4,8-diphosphacyclotetradecane) and TlPF₆ in MeNO₂ solution to yield the distorted octahedral complexes [CrX₂(L)]PF₆ as green coloured solids in high yield. UV/visible spectroscopy suggests that these are cis-dihalo species and they have also been characterised by IR spectroscopy, electrospray mass spectrometry and microanalyses. The Co(III) analogues [CoX₂(L)]⁺ are readily prepared in a two-stage reaction, involving treatment of CoX₂·6H₂O with L (L=L¹-L³) and NH₄PF₆ in EtOH solution to give a green/brown solid, followed by halogen oxidation of this product in CH₂Cl₂ solution using X₂/CCl₄, to give the final products as brown coloured solids. A mixture of PF₆^- and [CoX₄]^2- anions are present in the final Co(III) compounds in varying ratios. Crystal structures of [CoCl₂(L²)]₂[CoCl₄]·4H ₂O and [CoCl₂(L³)]PF₆·CH₂Cl ₂ confirm tetradentate P₂S₂ coordination of L in each case, with mutually cis halogens completing the distorted octahedral geometry. In both cases the complex cation adopts the cis-α form in the solid state and this is also consistent with the solution ³¹P{¹H} NMR spectroscopic data. ⁵⁹Co NMR spectroscopy reveals a very broad single resonance at ≈3200 ppm for these species. Elsevier Science Ltd.

Full text of DOI:10.1016/S0277-5387(99)00285-5

Polyhedron 18 (1999) 3553–3558
www.elsevier.nl/locate/poly
Co(III) and Cr(III) complexes of diphosphadithia ligands and the crystal
structure of [CoCl2(L3)]PF6?CH2Cl2
(L35Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2)
Julie Connolly, Robin J. Forder, Geoffrey W. Goodban, Simon J.A. Pope, Martin Predel,
*
Gillian Reid
Department of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK
Received 27 July 1999; accepted 9 September 1999
Abstract
[CrX3(thf)3] (X5Cl or Br) reacts with
L
(L5L1–L3 or Ph2[14]aneP2S2) (L15Ph2P(CH2)2S(CH2)2S(CH2)2PPh2, L25
Ph2P(CH2)2S(CH2)3S(CH2)2PPh2, L35Ph2P(CH2)2S(o-C6H4)S(CH2)2PPh2, Ph2[14]aneP2S254,8-diphenyl-1,11-dithia-4,8-diphos-
phacyclotetradecane) and TlPF6 in MeNO2 solution to yield the distorted octahedral complexes [CrX2(L)]PF6 as green coloured solids in
high yield. UV/visible spectroscopy suggests that these are cis-dihalo species and they have also been characterised by IR spectroscopy,
electrospray mass spectrometry and microanalyses. The Co(III) analogues [CoX2(L)]1 are readily prepared in a two-stage reaction,
involving treatment of CoX2?6H2O with L (L5L1–L3) and NH4PF6 in EtOH solution to give a green/brown solid, followed by halogen
oxidation of this product in CH2Cl2 solution using X2 /CCl4, to give the final products as brown coloured solids. A mixture of PF26 and
[CoX4]22 anions are present in the final Co(III) compounds in varying ratios. Crystal structures of [CoCl2(L2)]2[CoCl4]?4H2O and
[CoCl2(L3)]PF6?CH2Cl2 confirm tetradentate P2S2 coordination of L in each case, with mutually cis halogens completing the distorted
octahedral geometry. In both cases the complex cation adopts the cis-a form in the solid state and this is also consistent with the solution
31Ph1Hj NMR spectroscopic data. 59Co NMR spectroscopy reveals a very broad single resonance at ¯3200 ppm for these species.
1999 Elsevier Science Ltd. All rights reserved.
Keywords: Mixed phosphathia ligands; Cr(III) and Co(III) complexes; Crystal structure
1. Introduction
[Cu(L)]1 and the helical dinuclear species [Au2(L1)2]Cl2,
which incorporates a Cl2 anion within the metallocyclic
cavity [1–6]. However, complexes involving these and
other phosphathia ligands with 3d metal ions such as
Co(III) and Cr(III) are rather less common. The prepar-
ation of the Co(II) species [CoXhPh2P(CH2)3S(CH2)3-
S(CH2)3PPh2j]BPh4(X5Cl, Br or I) [7] and Co(II) and
Co(III) complexes involving the bidentate o-
C6H4(PPh2)(SMe) [8] have been reported. Also, Ciam-
polini and co-workers have reported the preparation of
several Co(II) complexes involving the hexa-coordinated
P4S2-donor macrocycles [9–13]. A range of Cr(III) com-
plexes involving coordinated phosphine or thioether lig-
ands are known, including several macrocyclic thioether
derivatives, several of which have also been structurally
characterised [14–21].
Recently we have been interested in investigating the
binding characteristics of mixed phosphathia ligands such
as L1–L3 (L15Ph2P(CH2)2S(CH2)2S(CH2)2PPh2, L25
Ph2P(CH2)2S(CH2)3S(CH2)2PPh2, L35Ph2P(CH2)2S(o-
C6H4)S(CH2)2PPh2) and the macrocyclic analogue
Ph2[14]aneP2S2
(4,8-diphenyl-1,11-dithia-4,8-diphos-
phacyclotetradecane) with a variety of transition metal
centres. The majority of our work to-date has focused upon
the platinum group metals, e.g., the square planar [M(L)]21
and octahedral [PtX2(L)]21 (M5Pd, Pt; L5L1–L3 or
Ph2[14]aneP2S2; X5Cl or Br), [M9Cl2(L)]1 (M95Rh or
Ir) and RuCl2(L)], as well as complexes involving the
group 11 elements, including for example tetrahedral
We report herein the preparation and spectroscopic
characterisation of a range of distorted octahedral Cr(III)
and Co(III) complexes involving the phosphathia ligands
L1–L3 and the macrocycle Ph2[14]aneP2S2, of general
*Corresponding author. Tel.: 144-170-359-5000; fax: 144-170-359-
3781.
E-mail address: gr@soton.ac.uk (G. Reid)
0277-5387/99/$ – see front matter
PII: S0277-5387(99)00285-5
1999 Elsevier Science Ltd. All rights reserved.

3554
J. Connolly et al. / Polyhedron 18 (1999) 3553–3558
formula [MX2(L)]PF6, including the crystal structures of
tained. A solution of this species in CH2Cl2 was then
treated with excess X2 (X5Cl or Br) in CCl4 to give a
brown solution, which yielded a brown solid upon addition
of Et2O. The electrospray mass spectra for these final
products each show peaks with the correct isotopic dis-
tribution for [CoX2(L)]1. IR spectroscopy shows peaks
due to the coordinated L, and in some cases only weak
absorptions due to PF62 counter anion (840 and 558 cm21).
This suggests that while PF26 acts as the counterion in
some cases, in others an alternative anion is present,
probably [CoX4]22. The presence of this anion is clearly
identified in the crystal structure of [CoCl2(L2)]2[CoCl4]?
4H2O (see below). This type of partial decomposition to
produce some [CoX4]22 counterion has been observed
previously for other Co(III) complexes15 and, consequent-
ly, severely hinders attempts to obtain meaningful mi-
croanalytical data for these compounds.
[CoCl2(L3)]PF6?CH2Cl2 and [CoCl2(L2)]2[CoCl4]?4H2O.
2. Results and discussion
Reaction of [CrX3(thf)3] (X5Cl or Br) with one molar
equivalent of L (L5L1–L3 or Ph2[14]aneP2S2) in anhydr-
ous MeNO2 solution and in the presence of one molar
equivalent of TlPF6, gave a deep green or brown solution
and a white precipitate (TlX). After removal of the TlX
and concentration of the solution, dry Et2O was added to
afford green or brown powdered solids in high yield. These
compounds are stable in the solid state as long as they are
protected from a moist atmosphere. Similarly, they are
quite stable in anhydrous solvents and are soluble in
MeNO2, MeCN and acetone. Their electrospray mass
spectra (MeCN) show intense peaks, with the correct
isotope pattern corresponding to [CrX2(L)]1. IR spectra
were recorded as Nujol mulls and show peaks associated
31Ph1Hj NMR spectra were also recorded for the Co(III)
compounds (Table 1). In each case a singlet is observed
due to the coordinated ligand L (L5L1–L3) and the large,
positive coordination shift (dcomplex –dligand) is indicative of
the P donor atoms being part of a five-membered chelate
ring, thus confirming tetradentate P2S2 coordination in
solution [24]. The presence of a single resonance precludes
the existence of the cis-b isomer for these species,
although it does not distinguish between the trans and
cis-a forms. In some cases a septet at approximately 2145
ppm is also observed due to PF26 . Although, for the
reasons discussed above, the relative integrals of the L:PF62
resonances does not indicate a stoichiometric PF26 anion.
59Co NMR spectroscopy (I57/2, 100%) has previously
been shown to be a useful technique for the characterisa-
tion of cobalt(III) dihalogeno complexes of group 15 and
16 donor ligands, although the relatively high quadrupole
moment results in significant broadening of the resonances
[23,25–27]. For the complexes prepared in this work we
with the non-coordinating PF26 anion (840 and 558 cm21
)
as well as peaks associated with L and n(Cr–X)/n(Cr–S/
P) below 400 cm21. Together with microanalytical data,
these results indicate the successful formation of the
products [CrX2(L)]PF6, involving a distorted octahedral
P2S2X2 donor set at Cr(III). For an octahedral d3 metal
ion, theory predicts three spin allowed d–d transitions
although, in practice, usually only the two at lower energy
4
(4A2g→4T2g and A2g→4T1g(F)) are observed, the third
(4A2g→4T1g(P)) being obscured by more intense charge
transfer transitions [22]. For the Cr(III) compounds re-
ported here we observe two d–d transitions and their
energies are similar to those observed for other Cr(III)
phosphine and thioether complexes and are consistent with
the relatively soft P2S2X2 donor set at Cr(III) [14–21].
Furthermore, since no splittings of these bands are ob-
served, the compounds are assigned as cis isomers (trans
isomers usually exhibit marked splittings). For octahedral
complexes involving L1–L3, three gross geometric isomers
are possible, cis-a, cis-b and trans. The cis a arrangement
has been observed for several other octahedral complexes
involving L1, L2 and L3, e.g., cis-[RhCl2(L1)]1, cis-
[RuCl2(L1)]2, cis-[CoCl2(L2)]1 and [CoCl2(L3)]1 (see
below), thus it seems likely that the Cr(III) complexes
involving L1–L3 ligation also adopt the cis-a form. Since
these Cr(III) species are paramagnetic, NMR spectroscopy
cannot be used to confirm which isomer is adopted, and
attempts to obtain crystals of these rather unusual com-
plexes involving coordination of the soft phosphathia
ligands to hard Cr(III) ions were unsuccessful.
observe a very broad resonance at ¯3200 ppm, w1 / 2
¯
10 000–20 000 Hz. These chemical shifts compare with
shifts
in
the
range
7062–7384
ppm
for
[CoX2([14]aneS4)]1 ([14]aneS451,4,8,11-tetrathiacyclo-
tetradecane) [25] and 8436–9590 ppm for [CoX2-
([16]aneSe4)]1 (X5Cl, Br or I; [16]aneSe451,5,9,13-
tetraselenacyclohexadecane) [26]. The previously re-
ported phosphathia ligand complexes trans-[CoCl2ho-
Table 1
31Ph1Hj and 59Co NMR spectroscopic dataa
d(31Ph1Hj)/ppm
d(59Co)/ppm
w1 / 2 /Hz
[CoCl2(L1)]1
[CoBr2(L1)]1
[CoCl2(L2)]1
[CoBr2(L2)]1
[CoCl2(L3)]1
[CoBr2(L3)]1
40.7
40.7
45.5
46.5
53.6
56.5
3410
3420
3390
3290
3210
3180
10 500
10 000
20 000
20 000
20 000
17 000
The Co(III) complexes were prepared in a two-step
procedure from CoX2. Thus, equimolar quantities of CoX2
(X5Cl or Br) and NH4PF6 were dissolved in degassed
EtOH. One molar equivalent of L (L5L1, L2 or L3) was
then added. After work-up, a dark green solid was ob-
a Spectra recorded in MeCN/CDCl3 at 145.8 and 85.6 MHz, respec-
tively, for 31Ph1Hj and 59Co.

J. Connolly et al. / Polyhedron 18 (1999) 3553–3558
3555
C6H4(PPh2)(SMe)j]BF4 show d(59Co)53475 (X5Cl) and
Table 2
Selected bond lengths and angles for [CoCl2(L3)]1
3430 (X5Br) ppm [28] and the line widths for these
species are comparable with the w1 / 2 values found for
[CoX2(L)]1. These are considerably larger than those
observed for the thioether and selenoether macrocyclic
complexes, reflecting the high dependence of the line-
widths upon subtle changes in the electric field gradient at
the metal centre. Cobalt-59 NMR data have been obtained
for a range of Co(III) phosphine complexes [27], e.g.,
[Co(Me2PCH2CH2PMe2)3]31 d(59Co) 22530 (w1 / 2
10 000 Hz) and trans-[CoCl2(Me2PCH2CH2PMe2)2]1
d(59Co) 11660 (14 000).
˚
Bond lengths (A)
Co(1)–Cl(1)
Co(1)–S(1)
Co(1)–P(1)
2.269(3)
2.202(3)
2.281(3)
Co(1)–Cl(2)
Co(1)–S(2)
Co(1)–P(2)
2.252(2)
2.207(3)
2.269(3)
Bond angles (8)
Cl(1)–Co(1)–Cl(2)
Cl(1)–Co(1)–S(2)
Cl(1)–Co(1)–P(2)
Cl(2)–Co(1)–S(2)
Cl(2)–Co(1)–P(2)
S(1)–Co(1)–P(1)
S(1)–Co(1)–P(1)
P(1)–Co(1)–P(2)
97.3(1)
86.5(1)
89.8(1)
175.4(1)
90.7(1)
89.0(1)
90.6(1)
176.4(1)
Cl(1)–Co(1)–S(1)
Cl(1)–Co(1)–P(1)
Cl(2)–Co(1)–S(1)
Cl(2)–Co(1)–P(1)
S(1)–Co(1)–S(2)
S(1)–Co(1)–P(2)
S(2)–Co(1)–P(2)
176.5(1)
87.7(1)
84.2(1)
92.2(1)
92.2(1)
93.4(1)
86.6(1)
In order to confirm the stereochemistry at Co(III), the
ligand conformation and the bond length and angle dis-
tributions, single crystal X-ray structure analyses were
undertaken on two samples, [CoCl2(L3)]PF6?CH2Cl2 and
[CoCl2(L2)]2[CoCl4]?4H2O. Crystals were grown by dif-
fusion of Et2O into a solution of the appropriate complex
in CH2Cl2. The structure of the former shows (Fig. 1,
Table 2) the Co(III) ion coordinated to a distorted octahed-
ral P2S2Cl2 donor set. The complex cation adopts the cis-a
form, with the P-donor atoms trans to one another and the
S-donor atoms trans to the Cl ligands, consistent with the
solution spectroscopic data. A PF26 anion maintains elec-
troneutrality. The bond lengths around the Co ion reveal
that d(Co–S),d(Co–Cl),d(Co–P), a similar trend is
The crystals of [CoCl2(L2)]2[CoCl4]?4H2O were rather
poor quality and hence the data were weak and the final
residuals higher than normal. However, the analysis1 was
sufficient to establish unambiguously the coordination
geometry at Co(III) and the nature of the anion present.
The structure shows (Fig. 2) a very similar coordination
geometry to that above, with the Co(III) centre coordinated
to a distorted octahedral P2S2Cl2 donor set with the ligand
in the cis-a form. A tetrahedral [CoCl4]22 anion on a
two-fold site maintains electroneutrality in this case,
despite the addition of PF26 during the reaction (see above).
The bond lengths around the metal ion in the Co(III)
cations are similar to those in cis-a-[CoCl2(L3)]1 above,
with d(Co–S),d(Co–P), however, more detailed com-
parisons of the geometric parameters are not justified for
this rather poor quality crystal.
2
observed in cis-a-[RhCl2(L1)]1 and in cis-a-[RuCl2(L1)],
and is attributed to the greater trans influence of
S(thioether) over Cl in these species. The angles involved
in the five-membered chelate rings are only marginally
smaller than the ideal 908, indicating that the ligand is well
suited to the ionic radius of Co(III).
These results confirm that the acyclic phosphathia
ligands L1–L3 and Ph2[14]aneP2S2 coordinate readily to
the 3d metal ions Cr(III) and Co(III) via both the P- and
S-donor atoms, giving tetradentate binding. The resultant
distorted octahedral complexes probably all exist as cis
isomers, with those involving L1–L3 adopting the cis-a
form and involving a P2S2X2 donor set. The new com-
pounds are relatively stable both in solution and in the
solid state.
1C62H76Co3Cl8O6P4S4 – blue-green crystal (0.2530.1530.10 mm), M5
1597.8, monoclinic, space group C2 / c, a531.495(3), b515.197(5), c5
3
˚
˚
˚
17.266(5) A, b5117.54(1)8, V57237(3) A , l50.71073 A, Z54, Dc 5
1.448 g cm23 m512.07 cm21
,
,
F(000)53284, T5150 K. Rigaku
AFC7S four-circle diffractometer, graphite monochromated Mo Ka radia-
tion, 6271 unique data. The structure was solved by heavy atom Patterson
methods [29] and expanded using Fourier techniques [30] to reveal one
[CoCl2(L2)]1 cation occupying a general position, one half [CoCl4]22
anion occupying a two-fold site and two solvent H2O molecules. At
isotropic convergence the data were corrected for absorption using
DIFABS [31]. All non-H atoms refined anisotropically, H atoms included
˚
in fixed, calculated positions [d(C–H)50.96 A] (the H atoms associated
with the H2O solvent molecules were not located and therefore were
omitted from the final structure factor calculation), 1740 observed
Fig. 1. View of the structure of [CoCl2(L3)]1 with the numbering
scheme adopted. Ellipsoids are drawn at the 40% probability level.
reflections with (I.2.0s(I)), 219 variables, R50.097, Rw 50.105, w21
s2(F).
5

3556
J. Connolly et al. / Polyhedron 18 (1999) 3553–3558
TlPF6 (0.085 g, 0.24 mmol) and L1 (0.12 g, 0.24 mmol).
Stirring for ¯2 h gave a white precipitate (TlCl) which
was removed by filtration, leaving a green solution. After
concentrating this solution in vacuo, Et2O was added to
afford a dark green solid (Yield 0.10 g, 54%). Required for
[C30H32Cl2CrF6P3S2] C, 45.8; H, 4.1; found: C, 45.4; H,
4.0%. Electrospray mass spectrum (MeCN): found m/z5
640; calculated for [52Cr35Cl2(L1)]1 m/z5640. IR spec-
trum (nujol): 834 s, 556 s, 353 br,w (cm21). UV-visible
spectrum (BaSO4 /cm21): 16 950, 21 370.
4.1.2. [CrBr2(L1)]PF6
Yield 51%. Required for [C30H32Br2CrF6P3S2] C, 41.1;
H, 3.7; found: C, 41.6; H, 3.9%. Electrospray mass
spectrum (MeCN): found m/z5730; calculated for
[52Cr79Br2(L1)]1 m/z5728. IR spectrum (nujol): 836 s,
556 s, 320 w (cm21). UV–visible spectrum (BaSO4 /
cm21): 16 470, 20 370.
4.1.3. [CrCl2(L2)]PF6
Yield 45%. Required for [C31H34Cl2CrF6P3S2] C, 48.1;
H, 4.5; found: C, 49.1; H, 4.8%. Electrospray mass
spectrum (MeCN): found m/z5654; calculated for
[52Cr35Cl2(L2)]1 m/z5654. IR spectrum (nujol): 840 s,
557 s, 348 br, w (cm21). UV–visible spectrum (BaSO4 /
cm21): 15 360, 20 880.
Fig. 2. View of the structure of [CoCl2(L2)]1 with the numbering
scheme adopted. Ellipsoids are drawn at the 40% probability level.
Co–Cl(1)52.25(1), Co–Cl(2)52.257(9), Co–S(1)52.22(1), Co–S(2)5
˚
2.27(1), Co–P(1)52.28(1), Co–P(2)52.26(1) A.
3. Experimental
4.1.4. [CrBr2(L2)]PF6
Infrared spectra were measured as KBr or CsI discs or
as Nujol mulls between CsI plates using a Perkin-Elmer
983G spectrometer over the range 200–4000 cm21. Mass
spectra were run by fast atom bombardment (FAB) using a
VG Analytical 70-250-SE normal-geometry double-focus-
ing spectrometer or by positive electrospray using a VG
Biotech Platform. 1H NMR spectra were recorded using a
Bruker AM300 spectrometer operating at 300 MHz.
31Ph1Hj and 59Co NMR spectra were recorded in 10 mm
O.D. tubes containing ¯10% deuterated solvent, using a
Bruker AM360 spectrometer operating at 145.8 and 85.6
MHz and are referenced to external 85% H3PO4 [d(31P)5
0] and external aqueous [Co(CN)6]32 respectively. Mi-
croanalyses were performed by the University of
Strathclyde microanalytical service, although, as discussed
in the text, facile rearrangement of the Co(III) complexes
resulted in some [CoX4]22 acting as counterion, and
precluded satisfactory microanalytical data. This behaviour
Yield 62%. Required for [C31H34Br2CrF6P3S2] C, 43.2;
H, 4.0; found: C, 43.0; H, 4.0%. Electrospray mass
spectrum (MeCN): found m/z5744; calculated for
[52Cr79Br2(L2)]1 m/z5742. IR spectrum (nujol): 837 s,
557 s, 283 br, w (cm21). UV–visible spectrum (BaSO4 /
cm21): 14 470, 19 120.
4.1.5. [CrCl2(L3)]PF6
Yield 60%. Required for [C34H32Cl2CrF6P3S2] C, 48.9;
H, 3.8; found: C, 48.9; H, 3.8%. Electrospray mass
spectrum (MeCN): found m/z5688; calculated for
[52Cr35Cl2(L3)]1 m/z5688. IR spectrum (nujol): 836 s,
556 s, 368 w, 348 w (cm21). UV/visible spectrum
(BaSO4 /cm21): 16 720, 21 280.
4.1.6. [CrBr2(L3)]PF6
Yield 40%. Required for [C34H32Br2CrF6P3S2] C, 44.2;
H, 3.5; found: C, 44.5; H, 3.6%. Electrospray mass
spectrum (MeCN): found m/z5778; calculated for
[52Cr79Br2(L3)]1 m/z5776. IR spectrum (nujol): 835 s,
556 s, 319 w (cm21). UV–visible spectrum (BaSO4 /
cm21): 16 260, 20 410.
15
is well known in cobalt coordination chemistry. L1–L3
and Ph2[14]aneP2S2 were prepared by the literature pro-
cedures.
4.1. Preparations
4.1.7. [CrCl2(Ph2 [14]aneP2S2 )]PF6
Yield 71%. Required for [C22H30Cl2CrF6P3S2] C, 38.4;
H, 4.4; found: C, 38.5; H, 4.2%. Electrospray mass
spectrum (MeCN): found m/z5542, 421; calculated for
[52Cr35Cl2(Ph2[14]aneP2S2)]1 m/z5542, [Ph2[14]ane-
4.1.1. [CrCl2(L1)]PF6
To a stirring solution of [CrCl3(thf)3] (0.09 g, 0.24
mmol) in dry, degassed MeNO2 (20 cm3) was added

J. Connolly et al. / Polyhedron 18 (1999) 3553–3558
3557
P2S2]1 m/z5420. IR spectrum (nujol): 840 s, 557 s, 348
4.1.13. [CoCl2(L3)]1
br,w (cm21). UV–visible spectrum (BaSO4 /cm21):
16 750, 23 100.
Electrospray mass spectrum (MeCN): found m/z5695;
calculated for [Co35Cl2(L3)]1 m/z5695. 1H NMR: d 7.1–
8.1 (br, m, aromatic CH, 24H), 2.4–3.5 (m, CH2, 8H). IR
spectrum (KBr disk): 3056 w, 2968 w, 2920 w, 2852 w,
1486 m, 1459 m, 1435 s, 1410 sh, 1359 s, 1263 w, 1194 w,
1094 m, 998 w, 839 s, 753 w, 742 m, 695 m, 668 m, 614
w, 558 m, 526 m, 497 w, 403 w (cm21).
4.1.8. [CrBr2(Ph2 [14]aneP2S2 )]PF6
Yield 62%. Required for [C33H40Br2CrF6P3S2] C, 34.0;
H, 3.9; found: C, 33.5; H, 3.5%. IR spectrum (nujol): 835
s, 557 s, 315 br, w (cm21). UV–visible spectrum (BaSO4 /
cm21): 16 290, 22 730.
4.1.14. [CoBr2(L3)]1
4.1.9. [CoCl2(L1)]1
Electrospray mass spectrum (MeCN): found m/z5785;
calculated for [Co79Br2(L3)]1 m/z5783. 1H NMR: d 7.2–
8.2 (br, m, aromatic CH, 24H), 2.6–3.5 (br m, CH2, 8H).
IR spectrum (KBr disk): 3056 w, 2964 w, 2924 w, 1569 w,
1433 m, 1404 m, 1359 s, 1264 w, 1092 m, 992 w, 850 m,
833 m, 808 m, 752 w, 745 m, 712 w, 695 m, 668 w, 613
w, 546 w, 524 m, 486 w (cm21).
CoCl2?6H2O (0.046 g, 0.19 mmol) and NH4PF6 (0.063
g, 0.39 mmol) were dissolved in degassed EtOH (10 cm3).
L1 (0.100 g, 0.19 mmol) was added and the resulting
mixture was stirred for 3 h to give a green solution.
Concentration of the solution in vacuo, followed by
addition of Et2O gave a green solid. This compound was
then dissolved in CH2Cl2 (4 cm3) and excess Cl2 in CCl4
was added. The mixture was stirred for 1 h, yielding a
brown solid which was filtered, washed with Et2O and
dried in vacuo. FAB mass spectrum (3-NOBA): found
m/z5647, 612, 577; calculated for [Co35Cl2(L1)]1 m/z5
4.2. X-ray crystallography
Details of the crystallographic data collection and
refinement parameters are given in Table 3. Crystals of
[CoCl2(L3)]PF6?CH2Cl2 were grown by vapour diffusion
of diethyl ether into solutions of the complexes in CH2Cl2.
Data collection used a Rigaku AFC7S four-circle diffrac-
tometer operating at 150 K, using graphite monochromated
1
647, [Co35Cl(L1)]1 m/z5612, [Co(L1)]1 m/z5577. H
NMR: d 7.0–8.0 (m, Ph, 20H), 2.0–3.5 (m, CH2, 12H). IR
spectrum (CsI disk): 3060 w, 2980 w, 2930 w, 1481 m,
1432 s, 1408 w, 1093 s, 998 w, 840 vs, 743 s, 697 s, 558 s,
521 s, 490 w, 312 w, 298 w (cm21).
Table 3
4.1.10. [CoBr2(L1)]1
Crystallographic data collection and refinement parameters
FAB mass spectrum (3-NOBA): found m/z5737, 658,
[CoCl2(L3)]PF6?CH2Cl2
577;
calculated
for
[Co79Br2(L1)]1
m/z5735,
[Co79Br(L1)]1 m/z5656, [Co(L1)]1 m/z5577. 1H NMR:
d 7.1–8.1 (m, Ph, 20H), 2.1–3.6 (m, CH2, 12H). IR
spectrum (CsI disk): 3050 w, 2980 w, 2920 w, 1481 m,
1431 s, 1093 m, 998 w, 840 vs, 744 s, 703 s, 558 s, 520 s,
490 w, 298 w (cm21).
Formula
M
C35H34Cl4CoF6P3S2
926.43
Deep red, column
0.5530.2030.10
Monoclinic
P21 /c
16.263(3)
12.632(3)
19.198(3)
103.39(1)
3836(1)
4
1880
1.604
10.16
50
7103
0.074
3109
Colour, morphology
Crystal dimensions (mm)
Crystal system
Space group
˚
a (A)
˚
b (A)
4.1.11. [CoCl2(L2)]1
Electrospray mass spectrum (MeCN): found m/z5661,
˚
c (A)
b (8)
U (A )
3
[Co35Cl2(L2)]1
m/z5661,
˚
626;
calculated
for
1
[Co35Cl(L2)]1 m/z5626. H NMR: d 7.1–8.0 (m, Ph,
20H), 2.0–3.3 (br m, CH2, 14H). IR spectrum (CsI disk):
3057 w, 2970 w, 2926 w, 1568 w, 1482 m, 1432 s, 1162 s,
1095 s, 1040 m, 998 w, 920 w, 894 w, 851 w, 820 m, 745
s, 690 s, 525 s, 483 w, 422 w, 406 w, 366 w, 336 w, 306
w, 297 w (cm21).
Z
F(000)
Dc (g cm23
)
m (Mo Ka, cm21
2umax (8)
)
Unique obs. reflections
Rint (based on F2)
Obs. reflections
with [I0 .2s(I0)]
No. of parameters
Goodness of fit
Ra
4.1.12. [CoBr2(L2)]1
455
2.14
0.057
0.061
0.01
Electrospray mass spectrum (MeCN): found m/z5751,
698;
calculated
for
[Co79Br2(L2)]1
m/z5749,
b
Rw
[Co79Br(L2)]1 m/z5695. 1H NMR: d 7.0–7.8 (br m, Ph,
20H), 1.8–3.2 (br m, CH2, 14H). IR spectrum (CsI disk):
3054 w, 2970 w, 298 w, 1481 m, 1431 s, 1408 s, 1261 w,
1092 s, 998 w, 907 w, 814 m, 743 s, 693 s, 522 s, 485 w,
297 w (cm21).
Final D (s)
Max. residual peak (e A
Max. residual trough (e A
23
˚
)
2.25
20.67
23
˚
)
a R 5 o(uFobsui 2 uFcalcui )/ouFobsui.
b Rw 5 œ[o wi(uFobsu 2 uFcalcui )2 /o wiuFobsu2i ].
i

3558
J. Connolly et al. / Polyhedron 18 (1999) 3553–3558
˚
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Mo Ka X-radiation (l50.71073 A). No significant crystal
decay or movement was observed. The structure was
solved by heavy atom Patterson methods [29] and de-
veloped by iterative cycles of full-matrix least-squares
refinement and difference Fourier syntheses which located
all non-H atoms [30]. A CH2Cl2 solvent molecule was also
identified in the asymmetric unit. All non-H atoms (except
the C atom in the CH2Cl2 molecule) were refined aniso-
tropically. H-atoms were placed in fixed, calculated posi-
tions with d(C–H)50.96 A. The weighting scheme w215
˚
s2(F) gave satisfactory agreement analyses. Selected bond
lengths and angles are presented in Table 2.
[15] L.R. Gray, A.L. Hale, W. Levason, F.P. McCullough, M. Webster, J.
Chem. Soc., Dalton Trans. (1983) 2573.
Supplementary data
[16] L.R. Gray, A.L. Hale, W. Levason, F.P. McCullough, M. Webster, J.
Chem. Soc., Dalton Trans. (1984) 47.
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Acta 234 (1995) 35.
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(1997) 1629.
Supplementary data are available from the Cambridge
Crystallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK on request, quoting the deposition number
132712.
[21] N.R. Champness, S.R. Jacob, G. Reid, C.S. Frampton, Inorg. Chem.
34 (1995) 396.
[22] A.P.B. Lever, Inorganic Electronic Spectroscopy, 2nd ed, Elsevier,
Amsterdam, 1984.
Acknowledgements
We thank the EPSRC and the University of South-
ampton for support.
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(1987) 2102.
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