Gold and silver derivatives with the carborane-selenolate ligand [B10H11C2Se]-

Article abstract of DOI:10.1039/b310658f

The carborane-selenol [(B₁₀H₁₁C₂)SeH] has been isolated and its anion employed as a ligand. Reaction of the ligand with [AuClL] (L = PPh₃, AsPh₃) (1 : 1 molar ratio) or PPN[AuCl₂] (PPN = N(PPh₃)₂) (2 : 1 molar ratio) affords the mononuclear compounds [Au(SeC₂ B₁₀H₁₁)L] or PPN[Au(SeC₂B₁₀H₁₁)₂], respectively. Dinuclear derivatives [Au₂(SeC₂B₁₀ H₁₁)₂(μ-PP)] (PP = 1,1′-bis(diphenylphosphino) ferrocene (dppf), 1,2-bis(diphenylphosphino)ethane (dppe)) are synthesised by reaction of the ligand with [Au₂Cl₂(μ-PP)] or by reaction of [Au(SeC₂B₁₀H₁₁)-(AsPh₃)] with the bidentate ligand. The selenolate acts in a bridging mode in [M₂(μ-SeC₂B₁₀H₁₁) (PPh₃)₂]X₂ (M = Au, X = ClO₄; M = Ag, X = TfO), obtained by treatment of the ligand with [O{Au(PPh₃)}₃]ClO₄ or by reaction with [Ag(TfO)(PPh₃)] in 1 : 2 molar ratio, respectively. The crystal structure of [Au(SeC₂B₁₀H₁₁)(PPh₃)] has been determined by X-ray diffraction studies.

Full text of DOI:10.1039/b310658f

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Gold and silver derivatives with the carborane-selenolate ligand
[B10H11C2Se]؊
Silvia Canales,a Olga Crespo,a M. Concepción Gimeno,a Peter G. Jones,b Antonio Laguna*a
and Pilar Romeroc
a Departamento de Química Inorgánica, Instituto de Ciencia de Materiales de Aragón,
Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain. E-mail: alaguna@unizar.es
b Institut fur Anorganische und Analytische Chemie, Technischen Universität Braunschweig,
Postfach 3329, D-38023 Braunschweig, Germany
c Servicio de RMN, Instituto de Ciencia de Materiales de Aragón,
Universidad de Zaragoza-C.S.I.C, E-50009 Zaragoza, Spain
Received 2nd September 2003, Accepted 11th September 2003
First published as an Advance Article on the web 25th September 2003
The carborane-selenol [(B10H11C2)SeH] has been isolated and its anion employed as a ligand. Reaction of the
ligand with [AuClL] (L = PPh3, AsPh3) (1 : 1 molar ratio) or PPN[AuCl2] (PPN = N(PPh3)2) (2 : 1 molar ratio)
affords the mononuclear compounds [Au(SeC2B10H11)L] or PPN[Au(SeC2B10H11)2], respectively. Dinuclear
derivatives [Au2(SeC2B10H11)2(µ-PP)] (PP = 1,1Ј-bis(diphenylphosphino)ferrocene (dppf ), 1,2-bis(diphenylphosphino)-
ethane (dppe)) are synthesised by reaction of the ligand with [Au2Cl2(µ-PP)] or by reaction of [Au(SeC2B10H11)-
(AsPh3)] with the bidentate ligand. The selenolate acts in a bridging mode in [M2(µ-SeC2B10H11)(PPh3)2]X2 (M = Au,
X = ClO4; M = Ag, X = TfO), obtained by treatment of the ligand with [O{Au(PPh3)}3]ClO4 or by reaction with
[Ag(TfO)(PPh3)] in 1 : 2 molar ratio, respectively. The crystal structure of [Au(SeC2B10H11)(PPh3)] has been
determined by X-ray diffraction studies.
a difficult problem, as well as a topic of interest. In the literature
three different methods have been developed with the aim of
Introduction
There is a growing interest in the study and synthesis of gold
selenolates because of their potential applications in the treat-
affording such species: (a) the use of a bulky ether as solvent
(dimethoxyethane, dme)22 which coordinates to the lithium
ment of rheumatoid arthritis, in photography, or electronic
atom and avoids the dilithiation of the carborane, (b) the pro-
microscope technology. The analyses of the gold complexes1
tection of one position (much work has been done based on
described thus far, show mononuclear [Au(SeR)(PPh3)] (R =
Ph, naphthyl),2,3 dinuclear [Au2(SeR)(PR3)2]ϩ (R = Ph, C6F4Cl,
CH2Ph, naphthyl, 4-NH2C6H4, 4-ClC6H4; PR3 = PPh3, PPh2Me,
C-substituted silyl carboranes),23 incorporation of the desired
substituent and deprotection of the original C-position, (c)
the reaction of B10H12(CH3CN)2 with the corresponding acetyl-
PPhMe2),2–5 [Au2(SePh)2(µ-PP)] (PP = dppm, dppe),3 or hetero-
᎐
ene derivative R–C᎐CH. In fact, this is the way in which
᎐
6
nuclear
[{Au(PPh3)}{WCp(CO)3}{µ-Se(CH2SiMe3)}]SbF6
o-carborane itself is prepared.24
complexes. The gold() compound with two [bispyrazine-2,3-
diselenolato]2Ϫ ligands,7 and the gold() derivative [Au2Cl-
(SePh){µ-Ph2P(CH2)2}2]8 have also been described. This brief
overview reveals that the most represented oxidation state is ϩ,
and also that this chemistry has been scarcely studied until now,
in comparison with the related thiolate gold chemistry. Silver
derivatives2 include stoichiometries [Ag{SeC(SiMe3)3}]4,9
(NMe4)2[Ag4(SePh)6],10 [Ag{Se(2,4,6-iPr3C6H2)}]8,11 [Ag6{µ3-Se-
(4-ClC6H4)}4(µ-dppm)](PF6)2,12 [Ag4(SeiPr)4(dppm)2],13 and
[Ag8(SeEt)8(dppm)]n.13 As commented above, the development
of this area can provide compounds with interesting properties.
These facts prompted us to introduce the properties of car-
borane clusters (derived both from the specific properties of the
deltahedral borane clusters and on those of elemental boron
itself ), to gold and silver selenolate chemistry. Some publi-
cations have reported interesting Rh, Ir and Fe compounds14–21
that incorporate the [B10H10C2Se2]2Ϫ unit, but the diselenol-
carborane ligand has not been isolated. Herein, we present the
synthesis and isolation of the moisture- and air-stable selenol
[(B10H11C2)SeH]. The reactivity of the corresponding selenolate
ligand towards gold and silver derivatives is also explored. The
crystal structure of [Au(SeC2B10H11)(PPh3)] has been deter-
mined by X-ray diffraction studies.
The synthesis of [(B10H11C2)SeH] (1) has been carried out
according to method (a) described above (Scheme 1), in a simi-
lar experiment to that from which [(B10H11C2)SH] is obtained.22
The reaction of 1,2-dicarba-closo-dodecaborane in dme,
with LinBu, followed by the addition of Se and HCl affords
[(B10H11C2)SeH] (1) and [(B10H11C2)Se]2 (2). Compound 2
separates from the mixture upon addition of light petroleum, in
which it is insoluble.
Scheme 1
Discussion
Because of the disproportionation of monolithio-o-carborane,
which leads to the undesired di-C-substituted product, the syn-
thesis of mono-C-substituted o-carborane derivatives has been
Compound 1 is isolated as a yellow solid. In its IR spectra
the ν(BH) vibrations appear as a broad band at about 2600
cmϪ1. These bands are observed in the same region for all the
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3
D a l t o n T r a n s . , 2 0 0 3 , 4 5 2 5 – 4 5 2 8
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Table 1 Bond lengths (Å) and angles (Њ) for compound 3
compounds described below. A broad signal, corresponding to
the hydrogen atoms of the carborane cage, between 1 and 3
ppm, is shown in its H NMR spectrum, the resonance due to
Au–P
Au–Se
Au–Au#1
Se–C(1)
2.2690(10)
2.4167(4)
3.3035(4)
1.940(4)
C(1)–C(2)
P–C(21)
P–C(11)
P–C(31)
1.682(6)
1.813(4)
1.821(4)
1.821(4)
1
the Se–H proton appears at 2.54 ppm, and that due to the C–H
hydrogen atom at 3.73 ppm. The 77Se NMR spectrum shows
one signal at 733 ppm. A phase-sensitive (1H–77Se) HMQC
experiment was recorded and the transfer delay was set for a
3J(1H–77Se) of 50 Hz. The positive Liquid Secondary Ion Mass
Spectrum (LSIMS(ϩ)) shows the molecular peak at m/z = 233
(40%). No signal corresponding to the Se–H hydrogen is pres-
P–Au–Se
175.08(3)
110.77(3)
73.740(10)
100.37(12)
106.57(17)
C(21)–P–C(31)
C(11)–P–C(31)
C(21)–P–Au
C(11)–P–Au
C(31)–P–Au
105.65(17)
107.04(18)
111.96(12)
112.89(14)
112.25(12)
P–Au–Au#1
Se–Au–Au#1
C(1)–Se–Au
C(21)–P–C(11)
1
ent in the H NMR spectrum of 2. The 77Se NMR spectrum
Symmetry transformations used to generate equivalent atoms: #1 Ϫx ϩ
1, Ϫy ϩ 1, z.
shows a singlet at 750 ppm. The peak in the LSIMS(ϩ)
spectrum at m/z = 445 (30%) shows an experimental isotopic
distribution consistent with that calculated for the species {[(B10-
H11C)Se]2}ϩ. A peak corresponding to the species {(B10H11C)-
Se2}ϩ at m/z = 302 (20%) is also present. These data and the
behavior as a non-electrolyte in acetone solutions (ΛM = 1.6 ΩϪ1
cm2 molϪ1) are consistent with the structure shown in Scheme 1
for compound 2.
Reaction of 1 with chlorogold derivatives, in the presence of
Na2CO3, affords mono- or di-nuclear complexes (Scheme 2).
Thus, reaction with [AuClL] affords [Au(SeC2B10H11)L] (L =
PPh3 (3), AsPh3 (4)). The phosphorus atom of the PPh3 ligand
in 3 displays one signal at 36.8 ppm in the 31P(1H) NMR
spectrum. Both 1H NMR spectra are consistent with the
deprotonation of the ligand. The selenide atoms display reson-
ances in the 77Se NMR spectrum shifted about 300 ppm (δ 453
ppm (3), 440 ppm (4)), to high field from that corresponding
to the free ligand (1). The LSIMS(ϩ) mass spectra show
the molecular peak at m/z = 682 (10%, 3), and 727 (5%, 4),
respectively.
Fig. 1 Molecular structure of compound 3. Radii are arbitrary.
Hydrogen atoms have been omitted for clarity.
scopic data are consistent with the deprotonation of the
ligands. The LSIMS(–) spectrum shows the anionic molecular
peak at m/z = 641(60%).
The use of the dinuclear derivatives [Au2Cl2(µ-PP)] affords
the synthesis of [Au2(SeC2B10H11)2(µ-PP)] (PP = dppf (6), dppe
(7)). The compounds display only one signal in their 31P(1H)
NMR spectra at 30.5 (6) and 33.3 (7) ppm. For both derivatives
the LSIMS(ϩ) mass spectra show the peak arising from the loss
of one carborane ligand {M Ϫ SeC2B10H11}ϩ at m/z = 1171
(10%, 6) and 1015 (100%, 7). These compounds can be also
synthesized by reaction of 4 with the diphosphines in 2 : 1
molar ratio.
Scheme 2 i) [AuClL}, Na2CO3; ii) L = AsPh3, ½PP; iii) ½[Au2Cl2-
(µ-PP], Na2CO3; iv) ½PPN[AuCl2], Na2CO3; v) [O{Au(PPh3)}3]ClO4;
vi) 2[Ag(TfO)(PPh3)], Na2CO3.
The selenolate acts in a bridging mode in [M2(µ-SeC2B10-
H11)(PPh3)2]X (M = Au, X = ClO4 (8); M = Ag, X = TfO (9),
prepared by addition of 1 to [O{Au(PPh3)}3]ClO4 (molar ratio
1 : 1) or to [Ag(TfO)(PPh3)] (molar ratio 1 : 2). Compound 8
shows the vibrations corresponding to the perchlorate anion
(Td) at about 1100 and 619 cmϪ1, in 9 those corresponding
to the trifluoromethanesulfonate anion arise at about 1270
(νasym(SO3)), 1225 (νsym(SO3)), 1151 (νasym(CF3)) and 1033 cmϪ1
(νsym(SO3)). The coordination of two “AuPPh3” fragments in 8
is consistent with the 31P{1H} NMR data, the resonance due to
the two triphenylphosphine ligands (δ 35.8 ppm) is shifted 1
ppm to higher field from that in 3. The shift of these resonance
to higher field in the 31P{1H} NMR spectrum as the nuclearity
grows, has been observed in other gold selenide complexes.26
The 31P{1H} NMR of 9 shows a broad resonance centred at
12.7 ppm when the experiment is carried out at 25ЊC. This sig-
nal is split into two doublets, centred at 11.4 ppm at Ϫ55ЊC,
J(109AgP) 558, J(107AgP) 483 Hz. The cationic molecular peaks
The crystal structure of compound 3 has been determined by
X-ray diffraction studies. The gold atom (Fig. 1) displays a
slightly distorted linear geometry (P–Au–Se 175.08(3)Њ, Table
1). Close to ideal values are observed in [Au(SC2B10H11)L]25
(L = AsPh3, 178.34Њ, PPh3, 179.70Њ). In 3 the molecules associate
in pairs through gold ؒ ؒ ؒ gold interactions of 3.3035(4) Å,
but not in the [Au(SC2B10H11)L] derivatives mentioned above.
This could explain the distortion from linear geometry. Inter-
molecular Au ؒ ؒ ؒ Au contacts of this type have been observed
for some of the gold complexes with selenido containing lig-
ands reported thus far, and the value found in 3 is among the
shortest. The Au–P (2.2690(10) Å) and Au–Se (2.417(4) Å)
bond distances are within the expected range, they resemble the
shortest found in other selenolate gold() complexes.
Compound PPN[Au(SeC2B10H11)2] (5) is afforded from the
reaction of 1 with PPN[AuCl2] in 2 : 1 molar ratio. The spectro-
D a l t o n T r a n s . , 2 0 0 3 , 4 5 2 5 – 4 5 2 8
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of compounds 8 and 9 are present in their LSIMS(ϩ) mass
spectra at m/z = 1141 (8, 5%), 962 (9, 1%).
addition of 1 mmol of LinBu (1.6 M, 0.625 mL). After 1 h of
reaction Se powder (1 mmol, 0.079 g) was added. The resulting
suspension was stirred for one day. The 1,2-dimethoxyethane
was evaporated and diethyl ether (30 mL) and HCl (20 ml, 1 M)
were then added. After 2 h of stirring the organic phase was
dried by adding anhydrous MgSO4, which was then filtered off.
The solution was dried in vacuo and a mixture of 1 and 2 was
obtained. Light petroleum (bp 40–60 ЊC) was added, and the
suspension filtered. The solid was identified as 2, compound 1
was isolated upon concentration of the filtrate. 1: Yellow solid.
Yield 40%. ΛM = 0.8 ΩϪ1 cm2 molϪ1 (Found: C, 10.9; H, 5.25.
C2H12B10Se requires C, 10.75; H, 5.4%). δH (CDCl3) 3.48–1.19
(10H, m, B10H10), 3.73 (1H, s, CH), 2.54 (1H, s, SeH). 2:
Orange–brown solid. Yield 28%. ΛM = 2 ΩϪ1 cm2 molϪ1 (Found:
C, 10.70; H, 4.75. C4H22B20Se2 requires C, 10.8; H, 5.0%).
δH (CDCl3) 3.60–1.15 (20H, m, B10H10), 3.69 (2H, s, CH).
Unfortunately no crystal suitable for X-ray studies has been
obtained. It is possible that compound 9, in the solid state,
shows the structure of its analogous sulfur derivative [Ag2(SC2-
B10H11)(PPh3)2]TfO27 (Fig. 2), in which two “Ag2(SC2B10H11)-
(PPh3)2” units are linked through two further Ag–S bonds. In
addition, triflate oxygen atoms chelate the silver atoms. The
centre of the molecule consists on a four-membered ring
formed by alternating sulfur and silver atoms. The other two
silver atoms are exocyclically bonded to the thiolate, which acts
in a triply bridging mode.
Synthesis of [Au(SeC2B10H11)L] [L ؍ PPh3 (3), AsPh3 (4)]. To
a solution of 1 (0.1 mmol, 0.0223 g) in dichloromethane (20
mL), Na2CO3 and [AuClL] [0.1 mmol, L = PPh3 0.0495 g; AsPh3
0.0538 g)] were added. The mixture was stirred for 30 min
and the excess of Na2CO3 filtered off. Removal of solvent to
ca. 5 mL and addition of n-hexane afforded a white solid. 3:
Yield 89%. ΛM = 2.5 ΩϪ1 cm2 molϪ1 (Found: C, 35.50; H, 3.82.
C20H26AuB10PSe requires C, 35.24; H, 3.82%). δH (CDCl3)
3.60–1.20 (10H, m, B10H10), 3.83 (1H, s, CH), 7.56–7.47 (15H,
m, Ph). 4: Yield 82%. ΛM = 99Ϫ1 cm2 molϪ1 (Found: C, 33.20;
H, 3.68. C20H26AuAsB10Se requires C, 33.10; H, 3.58%).
δH (CDCl3) 3.40–1.40 (10H, m, B10H10), 3.83 (1H, s, CH), 7.54–
7.44 (15H, m, Ph).
Fig. 2 Scheme of the molecular structure of [Ag2(SC2B10H11)(PPh3)2]-
TfO; TfO = trifluoromethanesulfonate.
Conclusions
The first carborane selenol [(B10H11C2)SeH] has been isolated as
an stable solid by a conventional method, in which it is easily
separated from undesired products. Its reactivity towards gold
complexes has been studied and has led to the synthesis of
the first gold carborane-selenolate complexes with different
structural patterns.
Unlike the analogous [Au(SC2B10H11)L] (AsPh3, PPh3), the
structure of [Au(SeC2B10H11)(PPh3)] displays gold ؒ ؒ ؒ gold
interactions in the solid state. This interactions are probably
responsible of a more distorted linear geometry towards the
gold centre.
Synthesis of PPN[Au(SeC2B10H11)2] (5). To a solution of 1
(0.2 mmol, 0.0446 g) in dichloromethane (20 mL), PPN[AuCl2]
(0.1 mmol, 0.0805 g) and Na2CO3 were added. The mixture was
stirred for 30 min and the excess of Na2CO3 filtered off.
Removal of solvent to ca. 5 mL and addition of n-heptane
afforded a white solid. Yield 78%. ΛM = 99 ΩϪ1 cm2 molϪ1
(Found: C, 40.89; H, 4.36; N, 1.40. C40H52AuB20NP2Se2 requires
C, 40.71; H, 4.41; N, 1.19%). δH (CDCl3) 3.30–1.35 (20H, m,
B10H10), 3.85 (2H, s, CH), 7.50–7.20 (30H, m, Ph).
Experimental
Reagents
Synthesis of [Au2(SeC2B10H11)2(ꢀ-PP)] [PP ؍ dppf (6), dppe
(7)]. Method a. To a solution of 1 (0.2 mmol, 0.0446 g) in
dichloromethane (20 mL), Na2CO3 and [Au2Cl2(µ-PP)] (0.1
mmol, PP = dppf 0.1019 g; dppe 0.087 g) were added. The
mixture was stirred for 30 min and the excess of Na2CO3 filtered
off. Removing of solvent to ca. 5 mL and addition of diethyl
ether afforded an orange solid.
o-Carborane was purchased from Katchem Ltd., dppe and
dppf from Aldrich. All were used as received. [AuClL] (L =
PPh3, AsPh3),28 [Au2Cl2(µ-PP)] (PP = dppe,29 dppf30), [O{Au-
(PPh3)}3]ClO4,28b PPN[AuCl2]31 and [Ag(TfO)(PPh3)]32 were
synthesized according to literature methods.
Method b. To a solution of 4 (0.2 mmol, 0.1448 g) in di-
chloromethane (20 mL) PP (0.1 mmol, PP = dppf 0.0554 g;
dppe 0.0398 g) was added. The mixture was stirred for 30 min.
Removal of solvent to ca. 5 mL and addition of n-hexane
afforded a white solid.
General procedure
Infrared spectra were recorded on a Perkin-Elmer FT-IR Spec-
trum 1000 spectrophotometer, in the range 4000–400 cmϪ1
,
using Nujol mulls between polyethylene sheets. Conductivities
were measured in ca. 5 × 10Ϫ4 M acetone solutions with a
Jenway 4010 conductimeter. C, H, N and S analysis were
carried out with a Perkin-Elmer 240C microanalyser. Mass
spectra were recorded on a VG Autospec using the LSIMS
(ϩ, Ϫ) techniques and nitrobenzyl alcohol as matrix and on
6: Yield 87%. ΛM = 2.1 ΩϪ1 cm2 molϪ1 (Found: C, 32.94;
H, 3.01. C38H50Au2B20FeP2Se2 requires C, 32.76; H, 3.59%).
δH (CDCl3) 3.40–1.40 (20H, m, B10H10), 4.51 (4H, m, C5H4),
4.41 (4H, m, C5H4), 3.73 (2H, s, CH), 7.59–7.46 (20H, m, Ph). 7:
Yield 69%. ΛM = 2.3 ΩϪ1 cm2 molϪ1 (Found: C, 28.45; H, 3.36.
C26H46Au2B20P2Se2 requires C, 28.15; H, 3.56%). δH (CDCl3)
3.40–1.20 (20H, m, B10H10), 3.85 (2H, s, CH), 2.67 (4H, s, CH2),
7.68–7.41 (20H, m, Ph).
a HP59987 A ELECTROSPRAY. H, 19F, 77Se and 31P NMR
1
spectra were recorded on a Bruker ARX 300 or Varian Unity
300 in CDCl3 solutions. Chemical shifts are quoted relative
to SiMe4 (1H, external), CFCl3 (19F, external), H3PO4 (85%)
(31P, external) and Me2Se2 (77Se, external).
Synthesis of [Au2(ꢀ-SeC2B10H11)(PPh3)2]ClO4 (8). To a solu-
tion of 1 (0.1 mmol, 0.0223 g) in dichloromethane (20 mL),
[O{Au(PPh3)}3]ClO4 (0.1 mmol, 0.1492 g) was added. The
mixture was stirred for 1 h. Removing of solvent to ca. 5 mL
and addition of diethyl ether afforded a white solid. Yield 75%.
ΛM = 100 ΩϪ1 cm2 molϪ1 (Found: C, 36.95; H, 3.35. C38H41Au2-
B10ClO4PSe requires C, 36.80; H, 3.31%). δH (CDCl3) 3.40–1.20
(10H, m, B10H10), 3.92 (1H, s, CH), 7.60–7.38 (30H, m, Ph).
Synthesis of the complexes
Synthesis of [(B10H11C2)SeH] (1). In a three-necked round-
bottomed flask (100 mL) with a dinitrogen inlet/outlet and
a dropping funnel was prepared a solution of 1,2-dicarba-
closo-dodecaborane (1 mmol, 0.144 g) in 25 mL of 1,2-di-
methoxyethane. The flask was cooled at 0 ЊC during the
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A single crystal of 3 was mounted in inert oil on a glass fibre
and transferred to the cold gas stream of a Bruker SMART
1000 CCD system diffractometer. Crystal data: C20H26AuB10-
PSe, M = 681.40, orthorhombic, space group Fdd2, a =
22.810(2), b = 41.698(4), c = 10.4693(11) Å, U = 9957.9(17) Å3,
T = 143 K, Z = 16, µ(Mo-Kα) = 7.445 mmϪ1, 29202 reflections
measured (2θmax = 60Њ, ω-scans), 7236 unique (Rint = 0.0428),
absorption correction based on multiple scans (program
SADABS33). The structures were refined on F 2 using the
program SHELXL-97.34 All non-hydrogen atoms were refined
anisotropically. The structure was refined as an enantiomeric
twin. Final R = 0.0252, Rw = 0.0585, for 299 parameters, 211
restraints; max. ∆ρ = 1.99 e ÅϪ3
.
CCDC reference number 218880.
See http://www.rsc.org/suppdata/dt/b3/b310658f/ for crystal-
lographic data in CIF or other electronic format.
Acknowledgements
We thank the Dirección General de Investigación nЊ BQU2001–
2409-C02–01 for financial support.
27 M. M. Artigas, O. Crespo, M. C. Gimeno, P. G. Jones, A. Laguna
and M. D. Villacampa, Inorg. Chem., 1997, 36, 6454.
28 (a) R. Usón and A. Laguna, Inorg. Synth., 1982, 21, 71; (b) M. I.
Bruce, B. K. Nicholson and O. B. Shawkataly, Inorg. Synth., 1989,
26, 324.
29 S. J. Berners-Price and P. J. Sadler, Inorg. Chem., 1986, 25, 3822.
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P. D. Stupik, J. H. Zhang, W. M. Reifj and D. S. Eggleston,
Inorg. Chem., 1989, 28, 3529; (b) M. C. Gimeno, A. Laguna,
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31 J. Vicente, M.-T. Chicote, R. M. Dávila, M. S. Adrian and J. P.
Fackler, Jr., Inorg. Synth., 1998, 32, 172.
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D a l t o n T r a n s . , 2 0 0 3 , 4 5 2 5 – 4 5 2 8
4528