Binuclear half-sandwich cobalt(III) and rhodium(III) ortho- carboranedichalocogenolato complexes with ether chain-bridged bis(cyclopentadienyl) ligand

Article abstract of DOI:10.1039/b611266h

1, 1′-(3-Oxapentamethylene)dicyclopentadiene [O(CH₂CH ₂C₅H₅)₂] (1), containing a flexible chain-bridged group, was synthesized by the reaction of sodium cyclopentadienide with bis(2-chloroethyl) ether through a slightly modified literature procedure. Furthermore, the binuclear cobalt(iii) complex O[CH₂CH ₂(η⁵-C₅H₄)Co(CO)I ₂]₂ (3) and insoluble polynuclear rhodium(iii) complex {O[CH₂CH₂(η⁵-C₅H ₄)RhI₂]₂}_n (8) were obtained from reactions of 1 with the corresponding metal fragments and they react easily with PPh₃ to give binuclear metal complexes, O[CH₂CH ₂(η⁵-C₅H₄)Co(PPh ₃)I₂]₂ (4) and O[CH₂CH ₂(η⁵-C₅H₄)Rh(PPh ₃)I₂]₂ (9), respectively. Complexes 3, 4 and 9 react with bidentate dilithium dichalcogenolato ortho-carborane to give eight binuclear half-sandwich ortho-carboranedichalcogenolato cobalt(iii) and rhodium(iii) complexes O[CH₂CH₂(η⁵-C ₅H₄)Co(PPh₃)(E₂C₂B ₁₀H₁₀)]₂ (E = S (5a) and Se (5b)), O[CH ₂CH₂(η⁵-C₅H₄)] ₂Co₂(E₂C₂B₁₀H ₁₀) (E = S (6a) and Se (6b)), O[CH₂CH₂(η ⁵-C₅H₄)Co(E₂C₂B ₁₀H₁₀)]₂ (E = S (7a) and Se (7b)) and O[CH ₂CH₂(η⁵-C₅H₄) Rh(PPh₃)(E₂C₂B₁₀H ₁₀)]₂ (E = S (10a) and Se (10b)). All complexes have been characterized by elemental analyses, NMR spectra (¹H, ¹³C, ³¹P and ¹¹B NMR) and IR spectroscopy. The molecular structures of 3, 5a, 6a, 6b, 9 and 10b were determined by X-ray diffractometry. The Royal Society of Chemistry 2006.

Full text of DOI:10.1039/b611266h

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www.rsc.org/dalton | Dalton Transactions
Binuclear half-sandwich cobalt(III) and rhodium(III)
ortho-carboranedichalocogenolato complexes with ether chain-bridged
bis(cyclopentadienyl) ligand
Xiu-Feng Hou,* Shu Liu, Hui Wang, Yin-Qiang Chen and Guo-Xin Jin*
Received 3rd August 2006, Accepted 14th September 2006
First published as an Advance Article on the web 22nd September 2006
DOI: 10.1039/b611266h
1, 1ꢀ-(3-Oxapentamethylene)dicyclopentadiene [O(CH2CH2C5H5)2] (1), containing a flexible
chain-bridged group, was synthesized by the reaction of sodium cyclopentadienide with
bis(2-chloroethyl) ether through a slightly modified literature procedure. Furthermore, the binuclear
5
cobalt(III) complex O[CH2CH2(g -C5H4)Co(CO)I2]2 (3) and insoluble polynuclear rhodium(III) complex
5
{O[CH2CH2(g -C5H4)RhI2]2}n (8) were obtained from reactions of 1 with the corresponding metal
5
fragments and they react easily with PPh3 to give binuclear metal complexes, O[CH2CH2(g -
5
C5H4)Co(PPh3)I2]2 (4) and O[CH2CH2(g -C5H4)Rh(PPh3)I2]2 (9), respectively. Complexes 3, 4 and 9
react with bidentate dilithium dichalcogenolato ortho-carborane to give eight binuclear half-sandwich
5
ortho-carboranedichalcogenolato cobalt(III) and rhodium(III) complexes O[CH2CH2(g -
5
C5H4)Co(PPh3)(E2C2B10H10)]2 (E = S (5a) and Se (5b)), O[CH2CH2(g -C5H4)]2Co2(E2C2B10H10) (E = S
5
(6a) and Se (6b)), O[CH2CH2(g -C5H4)Co(E2C2B10H10)]2 (E = S (7a) and Se (7b)) and
5
O[CH2CH2(g -C5H4)Rh(PPh3)(E2C2B10H10)]2 (E = S (10a) and Se (10b)). All complexes have been
characterized by elemental analyses, NMR spectra (1H, 13C, 31P and 11B NMR) and IR spectroscopy.
The molecular structures of 3, 5a, 6a, 6b, 9 and 10b were determined by X-ray diffractometry.
Introduction
Half-sandwich transition metal complexes possessing an ancillary
dichalcogenolato-ortho-carboranyl ligand have received consid-
erable attentions, due to their unique molecular structures and
their wide-ranging potential applications.1 The rigid geometries
of the ortho, meta and para isomers of C2B10H12, together with the
relative ease of derivatisation at the carbon vertices make them
excellent candidates for crystal engineering.2 It is well-known that
the coordinatively unsaturated Co,3 Rh4 or Ir5 compounds (Fig. 1)
bearing both 1,2-E2-1,2-C2B10H10 and cyclopentadienyl units
could serve as excellent precursors to study the addition reactions
at the metal atom, even to form the heterometallic clusters6 or
discrete supramolecular assemblies.7
We are interested in using functionalized cyclopentadienyl lig-
ands to prepare half-sandwich ortho-carboranedichalocogenolato
Fig. 1 Half-sandwich complexes Cp*M(E2C2B10H10).
metal complexes and in studying the impact of flexible chains
(3-oxapentamethylene)dicyclopentadiene. Additionally, another
on the geometric structure of the complexes. Recently, we
efficient syntheses route for binuclear cobalt, iridium and ruthe-
have described the syntheses and characterization of several
nium complexes, by introducing pyridyl-based organic linkers, is
S- and O-functionalized cyclopentadienyl half-sandwich cobalt
presented concurrently in this issue (preceding paper).7
complexes containing dichalcogenolato ortho-carboranyl ligands.8
We find that the structures of these complexes are appar-
ently influenced by the functionalized side-arm of cyclopen-
tadienyl group. Herein, some binuclear half-sandwich ortho-
carboranedichalocogenolato cobalt and rhodium complexes with
ether chain-bridged bis(cyclopentadienyl) were obtained from 1,1ꢀ-
Results and discussion
Binuclear cobalt complexes
1,1ꢀ-(3-Oxapentamethylene)dicyclopentadiene 1 was prepared by
the reaction of sodium cyclopentadienide with bis(2-chloroethyl)
ether in THF through a slightly modified literature procedure.9
Shanghai Key Laboratory of Molecular Catalysis and Innovative Material,
Department of Chemistry, and Key Lab of Molecular Engineering of
1 reacted with Co2(CO)8 in refluxing CH2Cl2 solution to give an
Polymers of Chinese Ministry of Education, Department of Macromolecular
orange dicarbonyl complex 2 in moderate yield. The IR spectrum
of 2 showed two typical strong terminal carbonyl absorptions at
Science, Fudan University, 200433 Shanghai, China. E-mail: gxjin@
fudan.edu.cn; Fax: +86-21-65641740; Tel: +86-21-65643776
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2023 and 1960 cm−1, which was consistent with the previously
reported analogous complexes.10 Addition of elemental iodine
to a diethyl ether solution of 2 caused oxidative addition to the
cobalt center and gave the air-stable diiodocobalt(III) complex 3,11
Crystals of complex 3 was obtained by slow diffusion of hexane
into a concentrated solution of the complex in dichloromethane
at low temperature. As depicted in Fig. 2, the binuclear complex 3
possesses two three-legged half-sandwich CpM fragments, linked
by a five-atom chain with a cis-configuration. In each fragment,
5
according to the method of the preparation of [CH2(g -C5H4)2]-
12
5
[Co(CO)I2]2 (Scheme 1). Complex 3 showed a strong carbonyl
the Co atom is g -bound to the cyclopentadienyl ring and d-bound
absorption at 2062 cm−1 in the typical region for terminal carbonyl
groups, which was in agreement with the structure. In the 1H NMR
spectrum of 3 in CDCl3, the mono-substituted cyclopentadienyl
proton signals were observed at 5.65 and 5.42 ppm and the ether
chain protons (OCH2 and CH2) appear at 3.92 and 3.12 ppm.
to two terminal-iodine atoms and to one carbonyl group. The two
cyclopentadienyl rings lie in the same direction and the dihedral
angle between the two Cp planes is 176◦, indicating that the two
cyclopentadienyl rings are almost parallel. The distance of two
˚
iodine atoms in two adjacent molecules is 3.817 A, which is shorter
than the diameter of the iodine atom, suggesting that there is a
weak van der Waals attraction between different molecules.13
Fig. 2 Molecular structure of 3 with ellipsoids at the 30% probability
˚
level; H atoms are omitted for charity. Selected bond lengths (A)
and angles (◦): Co(1)–C(1) 1.795(13), Co(1)–I(1) 2.5722(15), Co(1)–I(2)
2.5754(15), C(1)–O(1) 1.080(12), Co(2)–C(2) 1.788(13), Co(2)–I(3)
2.5693(15), Co(2)–I(4) 2.5803(14), C(2)–O(2) 1.105(12), Co(1) · · · Co(2)
8.385; C(1)–Co(1)–I(1) 87.6(3), C(2)–Co(2)–I(3) 88.0(3), C(1)–Co(1)–I(2)
89.4(4), C(2)–Co(2)–I(4) 88.9(3), I(1)–Co(1)–I(2) 95.11(5), I(3)–Co(2)–I(4)
95.37(5), O(1)–C(1)–Co(1) 178.9(11), O(2)–C(2)–Co(2) 178.5(10).
The carbonyl groups of complex 3 could be easily displaced
by two PPh3 in CH2Cl2 and a CO-free binuclear derivative 4
was obtained. Treatment of binuclear complex 4 with dilithium
dichalcogenolato carborane gave binuclear dithiolate and dise-
lenolate carborane complexes (5a and 5b) as grass-green solids
(Scheme 2). Complexes 4, 5a and 5b have been characterized by
1H, 31P, 11B NMR and IR spectroscopy.
Scheme 1
Scheme 2
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Fig. 3 Molecular structure of 5a with ellipsoids at the 30% probability level; H atoms are omitted for charity.◦(a) Global view. (b) Side view (the
˚
phenyl groups and carboranyl groups have been omitted for clarity). Selected bond lengths (A) and angles ( ): Co(1)–P(1) 2.235(2), Co(1)–S(1)
2.241(2), Co(1)–S(2) 2.251(2), S(1)–C(1) 1.799(7), S(2)–C(2) 1.793(7), C(1)–C(2) 1.646(9), Co(1) · · · Co(1) 7.246, Co(2)–P(2) 2.236(2), Co(2)–S(3) 2.241(2),
Co(2)–S(4) 2.257(2), S(3)–C(3) 1.780(7), S(4)–C(4) 1.765(7), C(3)–C(4) 1.665(10); P(1)–Co(1)–S(1) 90.82(8), P(1)–Co(1)–S(2) 93.54(8), S(1)–Co(1)–S(2)
92.36(7), P(2)–Co(2)–S(3) 91.44(8), P(2)–Co(2)–S(4) 92.12(8), S(3)–Co(2)–S(4) 92.08(8).
The molecular structure of 5a is depicted in Fig. 3. Complex
5a possesses basically two three-legged half-sandwich CpCo
structures, in which the two CpCo fragments are linked by an ether
bridge on the cyclopentadienyl rings. In each CpCo unit, the biden-
tate dichalcogenolate carborane group and PPh3 are, respectively,
coordinated to the cobalt atom. The two cyclopentadienyl rings of
complex 5a lie in an interesting position which is different from 3.
The two Cp rings face each other with their non-coordinated side
and the dihedral angle is 25.4◦, due to the repulsion of the bulky
ligands and the flexibility of the five-membered chain.
However, complex 3 reacted directly with dilithium di-
chalcogenolate carborane [Li2E2C2(B10H10), E = S, Se] to give com-
plexes 6a, 7a for dithiolate and complexes 6b, 7b for diselenolate.
As shown in Fig. 4, complexes 6a and 6b contain a pair
of cobalt atoms linked by a single metal–metal bond, one
chelated dichalcogenolato carborane ligand and the chain-bridged
cyclopentadienyl groups. The two molecules both contain a mirror
two-electron donor ligands such as PPh3, which gave the 18-
electron binuclear derivatives 5a or 5b, respectively.
Binuclear rhodium complexes
For comparison with binuclear cobalt complexes, a series
of binuclear rhodium complexes with an ether chain-bridged
bis(cyclopentadienyl) group have been synthesized. The 1,1ꢀ-(3-
oxapentamethylene)dicyclopentadiene 1 reacted with NaH and
then [Rh(COD)Cl]2 in THF solution to gave the cyclooctadiene
(COD) rhodium complex,14 which, without isolation, was easily
oxidized by elemental iodine in diethyl ether and gave the air-stable
diiodo rhodium(III) complex 8 in good yield.
Complex 8 is a black–red, air-stable solid, insoluble in all organic
solvents. The elemental analysis suggested that it should be an
organometallic polymer, perhaps linked by Rh–I–Rh bridges as
shown in Scheme 3.15 Occasionally, we found that complex 8
could react with PPh3 in CH2Cl2 and got a red soluble product.
It is possible that PPh3 could cleanly split the iodo-bridges to
form the 18e binuclear complex 9. Treatment of 9 with dilithium
dichalcogenolato carborane gave the dithiolate and diselenolate
carborane complexes 10a and 10b with similar structure to 5a
and 5b.
˚
˚
plane. The Co–Co distance is 2.4076(13) A for 6a and 2.4193(11) A
for 6b, which is a little longer than the bond length of the analogous
Cp complex (CpCo)2[S2C2(B10H10)],3a,b due to the tension of the
bridging bis(cyclopentadienyl) ligand. Thus complexes 6a and 6b
are formally 18-electron complexes.
The red products 7a and 7b were characterized by elemental
analyses and IR, NMR spectroscopy. The IR spectrum showed
an intense B–H stretching of carborane (2579 cm−1 for 7a and
2577 cm−1 for 7b). The 1H NMR spectrum indicated that both 7a
and 7b contain the 1,1ꢀ-(3-oxapentamethylene)dicyclopentadienyl
unit. We presumed that 7a or 7b were composed of two 16-electron
ortho-carboranedichalocogenolato cobalt units linked by the ether
chain. Their formulations have been confirmed by reaction with
The structures of 9 and 10b have been characterized by X-
ray analysis using single crystals grown from dichloromethane–
hexane. The crystal structure of 9 reveals that the RhI2(PPh3)
fragments are positioned on the C5H4 faces of the bridging ligand
so that inter-ring repulsions are minimized (Fig. 5). This results
˚
in a long interatomic separation of Rh(1) · · · Rh(2) (8.739 A),
which is a little longer than the similar cobalt complex 3
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Fig. 4 Molecular structures ◦of 6a (a) and 6b (b) with ellipsoids at the 30% probability level. All hydrogen atoms are omitted for charity. Selected
˚
bond lengths (A) and angles ( ): 6a: Co(1)–S(1) 2.2402(17), Co(1)–S(2) 2.2188(16), S(1)–C(15) 1.857(6), Co(2)–S(1) 2.2500(16), Co(2)–S(2) 2.2418(16),
S(2)–C(16) 1.862(6), Co(1)–Co(2) 2.4076(13); S(2)–Co(1)–S(1) 86.66(5), S(2)–Co(1)–Co(2) 57.79(4), S(1)–Co(1)–Co(2) 57.77(4). 6b: Se(1)–C(15)
1.978(5), Se(1)–Co(1) 2.3132(9), Se(1)–Co(2) 2.3175(9), Se(2)–C(16) 1.976(5), Se(2)–Co(2) 2.2982(9), Se(2)–Co(1) 2.3090(9), Co(1)–Co(2) 2.4193(11);
C(15)–Se(1)–Co(1) 100.13(13), C(15)–Se(1)–Co(2) 100.40(13), C(16)–Se(2)–Co(2) 101.02(13), C(16)–Se(2)–Co(1) 100.55(13), Co(1)–Se(1)–Co(2) 62.99(3),
Co(2)–Se(2)–Co(1) 63.35(3), Se(2)–Co(1)–Se(1) 87.32(3), Se(2)–Co(2)–Se(1) 87.48(3), Se(1)–Co(2)–Co(1) 58.42(2).
Scheme 3
Fig. 5 Molecular structure of 9 with ellipsoids at the 30% probability level; H atoms are omitted for charity. (a) Global view. (b) Side view (the
◦
˚
phenyl groups have been omitted for clarity). Selected bond lengths (A) and angles ( ): Rh(1)–P(1) 2.307(3), Rh(1)–I(1) 2.6872(14), Rh(1)–I(2)
2.6730(16), Rh(2)–P(2) 2.303(3), Rh(2)–I(3) 2.6672(16), Rh(2)–I(4) 2.6912(14), Rh(1)–Rh(2) 8.739; P(1)–Rh(1)–I(2) 90.46(8), P(1)–Rh(1)–I(1) 91.32(8),
I(2)–Rh(1)–I(1) 96.40(4), P(2)–Rh(2)–I(3) 91.86(8), P(2)–Rh(2)–I(4) 93.84(8), I(3)–Rh(2)–I(4) 93.26(4).
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Fig. 6 Molecular structure of 10b with ellipsoids at the 30% probability level. H atoms are omitted for charity. (a) Global view. (b) Side
◦
˚
view (the phenyl groups and carboranyl groups have been omitted for clarity). Selected bond lengths (A) and angles ( ): Rh(1)–P(1) 2.290(3),
Rh(2)–P(2) 2.286(3), Rh(1)–Se(2) 2.4520(13), Rh(1)–Se(1) 2.4557(13), Rh(2)–Se(3) 2.4569(13), Rh(2)–Se(4) 2.4514(14), Se(1)–C(1) 1.938(10), Se(2)–C(2)
1.949(10), C(1)–C(2) 1.641(13), C(53)–C(54) 1.586(12), Rh(1) · · · Rh(2) 7.403; P(1)–Rh(1)–Se(2) 90.04(8), P(1)–Rh(1)–Se(1) 91.05(8), P(2)–Rh(2)–Se(4)
93.03(8), P(2)–Rh(2)–Se(3) 88.50(8), Se(2)–Rh(1)–Se(1) 90.12(5), Se(4)–Rh(2)–Se(3) 91.13(5); the dihedral angles: Se1–Rh1–Se2/Se1–C1–C2–Se2 28.2,
Se3–Rh2–Se4/Se3–C53–C54–Se4 22.8.
˚
Conclusions
(8.385 A). The molecular structure is not symmetrical and the
two cyclopentadienyl rings are criss-crossed with each other at
a dihedral angle of 50.2◦. The bond length of Rh(1)–C(5) is the
longest among the bond lengths of rhodium and the five carbon
atom in the cyclopentadienyl group. This indicates that there is a
slight repulsion between the side-chain and the iodine atom. The
In this article, four binuclear half-sandwich cobalt or rhodium
halides with an ether chain-bridged bis(cyclopentadienyl)
group were synthesized. The obtained complexes have
been further converted to dinuclear half-sandwich ortho-
carboranedichalocogenolato cobalt and rhodium complexes to
examine the basic coordination properties of the ancillary biden-
tate dichalcogenolate-ortho-carboranyl ligand. Study of the crystal
structures of complexes 3, 5a, 6a, 6b, 9 and 10b indicates that the
presence of the flexible ether chain-bridge makes it possible for
the two Cp panels in each structure to have different dispositions,
which are shown in the structures of complexes 3, 5a and 9. On
the other hand, because of the twisted flexible ether chain-bridge,
channels were formed in the solid state and some solvent molecules
could be trapped.
˚
bond length of Rh(1)–P(1) is 2.307 A, which is a little shorter than
˚
˚
the bond length of Rh(1)–I(1) 2.6730 A and Rh–I(2) 2.6872 A,
due to the size difference between phosphorus and iodine.
The crystal structure of 10b shows that the O(CH2CH2-
C5H4)2 unit bridges a pair of [Rh(Se2C2B10H10)(PPh3)] fragments
to form a binuclear O[CH2CH2(g -C5H4)Rh(PPh3)(Se2C2B10H10)]2
complex and the distance of Rh(1)–Rh(2) is 7.403 A (Fig. 6). Both
5
˚
of the rhodium centers adopt a three-legged piano-stool confor-
mation and have a six-coordinated geometry, taking the Cp ligand
as a three-coordinated ligand. Angles between adjacent atoms
around the rhodium atoms are nearly 90◦. The five-membered
metallacycle RhSe2C2 has a distorted envelop conformation
similar to the RhSe2C2 ring found in Cp*Rh(PMe3)(Se2C2B10H10)4
and the RhS2C2 ring in CpttRh(CNtBu)(S2C2B10H10).4 The bond
angle Se(1)–Rh(1)–Se(2) in complex 10b is 90.12◦, which is typical
for half-sandwich rhodium complexes. The disposition of the two
Cp rings is similar to complex 3 with a relatively small dihedral
angle. Interestingly we find the presence of a hydrogen bond
between 10b and solvent molecule CH2Cl2 in the crystal. One
molecule of CH2Cl2 links two molecules of 10b with two H · · · Se
hydrogen bonds and channels are formed, seen from the stacking
of the molecules along the a-axis.
Experimental
General
All manipulations of the complexes were carried out using
standard Schlenk techniques under nitrogen atmosphere. Solvents
were dried by refluxing with appropriate drying agents and dis-
tilled under nitrogen prior to use. [(THF)3LiE2C2B10H10Li(THF)]2
(E = S (a), Se (b)),16 O(CH2CH2C5H5)2 (1),9 [Rh(COD)Cl]2
17
were synthesized according to the procedures described in the
literature. Separation of product mixtures and purification of
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the components was accomplished by column◦chromatography
over silica gel which had been activated at 200 C overnight and
kept under nitrogen before use. All other materials were obtained
commercially and were used as received, except as noted. The
elemental analyses were performed on a Rapid CHN-O 240C
Analyzer. Infrared spectra were recorded on a Nicolet-FT-IR-
Method B. To a solution of 4 (135 mg, 0.10 mmol) in
THF (10 mL) was added a diethyl ether solution (15 mL) of
Li2E2C2B10H10 (E = S or Se) (0.20 mmol) dropwise at 0 ◦C. After it
was stirred for 10 h, the solvent was removed under reduced pres-
sure. The main product was purified by column chromatography
on silica. Recrystallization of the product from CH2Cl2–hexane
afforded red crystals of 5a (68 mg, 45%) or 5b (68 mg, 47%).
1
50X spectrophotometer. H, 13C, 11B and 31P NMR spectra were
obtained using Bruker DMX-500 and DMX-300 spectrophotome-
ters in CDCl3, respectively. Chemical shifts (downfield from TMS
(1H and 13C), BF3·OEt2 (11B) and H3PO4 (31P)) and coupling
constants are reported in ppm and in Hz, respectively.
5a. Anal. Calc. for C54H66B20Co2OP2S4·3CH2Cl2: C 45.33; H
4.81; S 8.48. Found: C 45.20; H 4.79; S 8.45%. 1H NMR (500 MHz,
CDCl3, ppm): d 7.58–7.40 (m, 30H, Ph), 4.80 (t, 4H, Cp), 4.34
(t, 4H, Cp), 3.57 (t, 4H, OCH2), 2.49 (t, 4H, CH2). 13C NMR
(125 MHz, CDCl3, ppm): d 134.54, 132.37, 130.94, 128.35 (s, Ph),
117.22, 86.80, 85.83 (s, Cp), 68.63 (s, OCH2), 28.63 (s, CpCH2),
93.94 (s, C2-carborane). 11B NMR (160 MHz, CDCl3, ppm): d
−0.3, −5.96. −9.61. 31P NMR (202 MHz, CDCl3, ppm): d 34.33
(s). IR (KBr disk): m = 1093 cm−1 (mC–O–C, as), 2579 cm−1 (mB–H),
3055, 2922, 2858, 1630, 1480, 1433, 1356, 855, 739, 695, 526 cm−1.
Preparation of O[CH2CH2(g5-C5H4)Co(CO)I2]2 (3).
A
CH2Cl2 solution (40 ml) of 1 (536 mg, 2.65 mmol) and Co2(CO)8
(1.00 g, 2.92 mmol) was refluxed for 5 h and then solvent was
removed in vacuo. The residue was chromatographed on silica gel
column and eluted with diethyl ether–hexane (1 : 4). The orange
band was collected. The solvent was evaporated under vacuum
and afforded 2 (798 mg, 70%) as a red liquid. IR (film): m = 2023,
1960 cm−1 (mCO), 1114 cm−1 (mCOC), 1460, 1376, 1258, 800, 718 cm−1.
A solution containing iodine (508 mg, 2.0 mmol) in ether (20 ml)
was added dropwise to a solution of 2 (430 mg, 1.0 mmol) in
ether (20 ml) at 0 ◦C. The color of the solution changed from
orange to dark purple and a black–purple precipitate was formed.
The solution was allowed to warm to room temperature and
then stirred for 2 h. After filtration, the black–purple solid was
washed with ether (2 × 15 mL). Recrystallization of product from
CH2Cl2–hexane afforded black–purple crystals of 3 (475 mg,
54%). Anal. Calc. for C16H16Co2I4O3: C 21.79; H 1.83. Found: C
22.21; H 2.01%. 1H NMR (500 MHz, CDCl3, ppm): d 5.65 (t, 4H,
Cp), 5.42 (t, 4H, Cp), 3.92 (t, 4H, OCH2, JH–H = 11.4 Hz), 3.12 (t,
5b. Anal. Calc. for C54H66B20Co2OP2Se4: C 44.95; H 4.61.
1
Found: C 44.80; H 4.55. H NMR (500 MHz, CDCl3, ppm): d
7.75–7.41 (m, 30H, Ph), 4.75 (t, 4H, Cp), 4.41 (t, 4H, Cp), 3.55
(t, 4H, OCH2), 2.67 (t, 4H, CH2). 11B NMR (160 MHz, CDCl3,
ppm): d −4.23, −7.89, −8.79, −13.4, −14.5. 31P NMR (202 MHz,
CDCl3, ppm): d 37.48 (s). IR (KBr disk): m = 1096 cm−1 (mC–O–C
,
as), 2576 cm−1 (mB–H), 3054, 2922, 2857, 1629, 1478, 1433, 1383,
833, 693, 525 cm−1.
Preparation of O[CH2CH2(g5-C5H4)]2Co2(S2C2B10H10) (6a) and
O[CH2CH2(g5-C5H4) Co(Se2C2B10H10)]2 (7a). To a solution of
Li2S2C2B10H10 (0.360 mmol) in Et2O (10 ml) was added a THF
solution (20 ml) of 3 (156.0 mg, 0.177 mmol). The reaction mixture
was stirred overnight at room temperature and the solvent was
removed under reduced pressure. The residue was purified by
column chromatography on silica. The component in the first
band was eluted with CH2Cl2–hexane (1 : 1) and recrystallized
from CH2Cl2–hexane at −18 ◦C to give green crystals of 6a (5 mg,
5%). Anal. Calc. for C16H26B10Co2OS2: C 36.64; H 5.00; S 12.20.
Found: C 36.55; H 4.93; S 12.10%. 1H NMR (500 MHz, CDCl3,
ppm): d 5.33 (t, 4H, Cp), 4.70 (t, 4H, Cp), 3.66 (t, 4H, OCH2,
JH–H = 13.8 Hz), 2.26 (t, 4H, CH2, JH–H = 11.5 Hz). 11B NMR
(160 MHz, CDCl3, ppm): d −3.72, −4.41, −5.31, −7.02, −8.23,
−9.16, −11.61, −12.55. IR (KBr disk): m = 1052 cm−1 (mC–O–C, as),
2576 cm−1 (mB–H), 3109, 2908, 1628, 1464, 1414, 1356, 857, 792,
725, 584 cm−1. The second band was collected and recrystallized
from CH2Cl2–hexane (3 : 1) to give yellow crystals of 7a (80.1 mg,
62%). Anal. Calc. for C18H36B20Co2OS4: C 29.58; H 4.97; S 17.51.
Found: C 29.45; H 4.87; S 17.35%. 1H NMR (500 MHz, CDCl3,
ppm): d 5.42 (t, 4H, Cp), 5.26 (t, 4H, Cp), 3.84 (t, 4H, OCH2), 2.22
(t, 4H, CH2). 11B NMR (160 MHz, CDCl3, ppm): d −6.76, −1.81,
−8.67, −9.63, −10.77, −11.87, −12.87. IR (KBr disk): m = 1103,
1061 cm−1 (mC–O–C), 2579 cm−1 (mB–H), 3110, 2961, 2860, 1628, 1474,
1410, 1357, 800, 722, 620 cm−1.
4H, CH2, JH–H = 11.4 Hz). IR (KBr disk): m = 3091 cm−1 (mC–H
,
Cp), 2062 cm−1 (mCO), 1107 cm−1 (mC–O–C) 2891, 1624, 1473, 1410,
1347, 845 cm−1.
Preparation of O[CH2CH2(g5-C5H4)Co(PPh3)I2]2 (4). To a
solution of 3 (197 mg, 0.22 mmol) in CH2Cl2 (5 mL) was added
a CH2Cl2 solution (5 mL) of PPh3 (140 mg, 0.27 mmol) dropwise
at room temperature. After it was stirred for 5 h, the solvent was
removed under reduced pressure. The product was purified by
column chromatography on silica. Recrystallization of the product
from CH2Cl2–hexane afforded dark-green crystals of 4 (261 mg,
88%). Anal. Calc. for C50H46Co2I4OP2: C 44.47; H 3.43. Found:
1
C 44.20; H 3.40%. H NMR (500 MHz, CDCl3, ppm): d 7.80–
7.45 (m, 30H, Ph), 5.28 (t, 4H, Cp), 4.06 (t, 4H, Cp), 3.86 (t, 4H,
OCH2), 3.26 (t, 4H, CH2). 13C NMR (125 MHz, CDCl3, ppm): d
133.79, 133.73, 130.28, 127.71 (s, Ph), 104.18, 91.10, 79.58 (s, Cp),
69.79 (s, OCH2), 29.44 (s, CpCH2). 31P NMR (202 MHz, CDCl3,
ppm): d 33.02 (s). IR (KBr disk): m = 1103 cm−1 (mC–O–C, as), 3053,
2925, 1618, 1482, 1435, 738 cm−1.
Preparation of O[CH2CH2(g5-C5H4)Co(PPh3) (E2C2B10H10)]2
(E = S (5a) and Se (5b)).
Method A. To a solution of 7a (73 mg, 0.1 mmol) or 7b (92 mg,
0.1 mmol) in CH2Cl2 (10 mL) was added a CH2Cl2 solution (5 mL)
of PPh3 (63 mg, 0.24 mmol) dropwise at 0 ◦C. After it was stirred
for 5 h, the reaction mixture was concentrated. Hexane was added
to the solution to cause separation of the crystals. The formed
dark-green crystals 5a·3CH2Cl2 (90.6 mg, 60%) or 5b (93.8 mg,
65%) were collected by filtration and washed with hexane.
Preparation of O[CH2CH2(g5-C5H4)]2Co2(Se2C2B10H10) (6b) and
O[CH2CH2(g5-C5H4)Co (Se2C2B10H10)]2 (7b). Reaction of com-
plex 3 (220 mg, 0.25 mmol) with Li2Se2C2B10H10 (0.5 mmol) in
THF solution (30 ml) by using a procedure similar to those used
in the synthesis of 6a and 7a, led to 6b as green crystals and 7b as a
red solid. 6b: Anal. Calc. for C16H26B10Co2OSe2: C 31.08; H 4.24.
5236 | Dalton Trans., 2006, 5231–5239
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1
Found: C 31.01; H 4.90%. H NMR (500 MHz, CDCl3, ppm):
d 5.17 (t, 4H, Cp), 4.65 (t, 4H, Cp), 3.66 (t, 4H, OCH2, JH–H
Preparation of O[CH2CH2(g5-C5H4)Rh(PPh3)I2]2 (9). To a
solution of 8 (190.8 mg, 0.2 mmol) in CH2Cl2 (15 mL) was
added a CH2Cl2 solution (10 mL) of PPh3 (105 mg, 0.4 mmol)
dropwise at 0 ◦C. After it was stirred for 3 h, the solvent was
removed under reduced pressure. The product was purified by
column chromatography on silica. Recrystallization of product
from CH2Cl2–hexane afforded dark-red crystals of 9 (262 mg,
91%). Anal. Calc. for C50H46I4OP2Rh2: C 41.75; H 3.22. Found:
=
13.8 Hz), 2.42 (t, 4H, CH2, JH–H = 11.5 Hz). 11B NMR (160 MHz,
CDCl3, ppm): d 3.72, −4.41, −5.31, −7.02, −8.23, −9.16, −11.61,
−12.55. IR (KBr disk): m = 1128, 1052 cm−1 (mC–O–C), 2577 cm−1
(mB–H), 3088, 2919, 2865, 1629, 1471, 1411, 1322, 809, 725, 626 cm−1.
7b: Anal. Calc. for C18H36B20Co2OSe4: C 23.54; H 3.95. Found: C
23.49; H 3.90%. 1H NMR (500 MHz, CDCl3, ppm): d 5.25 (t, 4H,
Cp), 5.03 (t, 4H, Cp), 3.80 (t, 4H, OCH2), 2.60 (t, 4H, CH2). 11
B
C 41.65; H 3.20%. H NMR (500 MHz, CDCl3, ppm): d 7.65–
1
NMR (160 MHz, CDCl3, ppm): d −2.04, −3.00, −7.08, −7.89,
−8.89, −9.91, −12.06, −13.37, −14.40, −15.58 IR (KBr disk): m =
1125, 1050 cm−1 (mC–O–C, as), 2577 cm−1 (mB–H), 3090, 2920, 2860,
1630, 1474, 1410, 1322, 805, 725, 625 cm−1.
7.39 (m, 30H, Ph), 5.48 (t, 4H, Cp), 4.82 (t, 4H, Cp), 3.69 (t, 4H,
OCH2, JH–H = 11.6 Hz), 3.02 (t, 4H, CH2, JH–H = 14.9 Hz). 13C
NMR (125 MHz, CDCl3, ppm): d 134.45, 134.38, 130.84, 128.13
(s, Ph), 111.73, 91.97, 86.63 (s, Cp), 70.30 (s, OCH2), 29.28 (s,
CpCH2). 31P NMR (202 MHz, CDCl3, ppm): d 27.81 (d, JRh–P
=
142 Hz). IR (KBr disk): m = 1092 cm−1 (mC–O–C, as), 3049, 1618,
Preparation of [O[CH2CH2(g5-C5H4)RhI2]2]n (8). To a solution
of 1 (1.54 g, 7.62 mmol) in 15 ml THF was added an excess of
NaH at room temperature for about 5 h. The concentration of this
solution was 0.2304 M by titration with standard hydrochloric
acid. Then the THF solution (15 mL) of [O(CH2CH2C5H4Na)2]
(1.74 ml, 0.40 mmol) was added dropwise to a solution of
[Rh(COD)Cl]2 (400 mg, 0.81 mmol) in 15 ml THF at −78 ◦C. After
stirring for 5 h at room temperature, the solvent was removed
under vacuum. The residue was extracted in 20 ml diethyl ether
to remove NaCl salt. To this obtained orange solution was added
dropwise 15 ml diethyl ether containing I2 (0.41 g, 1.6 mmol) at
1479, 1433, 1391, 836, 745, 693, 524 cm−1.
Preparation of O[CH2CH2(g5-C5H4)Rh(PPh3)(E2C2B10H10)]2
(E = S (10a) and Se (10b)). To a solution of 9 (137 mg,
0.15 mmol) in THF (10 mL) was added a diethyl ether solution
(15 mL) of Li2E2C2B10H10 (E = S or Se) (0.30 mmol) dropwise
at −78 ◦C. After it was stirred for 10 h, the solvent was removed
under reduced pressure. The main product was purified by column
chromatography on silica. Recrystallization of product from
CH2Cl2–hexane afforded red crystals of 10a or 10b.
10a. (91.8 mg, 62%) Anal. Calc. for C54H66B20OP2Rh2S4: C
48.28; H 4.95; S 9.55. Found: C 47.98; H 4.85; S 9.32%. 1H NMR
(500 MHz, CDCl3, ppm): d 7.50–7.41 (m, 30H, Ph), 4.96 (t, 4H,
Cp), 4.82 (t, 4H, Cp), 3.68 (t, 4H, OCH2, JH–H = 11.9 Hz), 2.60 (t,
4H, CH2, JH–H = 10.5 Hz). 13C NMR (125 MHz, CDCl3, ppm):
d 134.56, 131.93, 131.06, 128.26 (s, Ph), 121.45, 90.55, 89.95
◦
−78 C. After 2 h stirring at room temperature, the upper clear
solution was removed, and after washing with diethyl ether twice,
afforded 8 (0.533 g, 72%) as a red insoluble solid. Anal. Calc. for
C14H16I4ORh2: C 18.4; H 1.77. Found: C 18.8; H 1.85%. IR (KBr
disk): m = 3079, 2862, 1623, 1467, 1394, 1359, 1104, 846 cm−1.
Table 1 Crystallographic data for compounds 3, 6a and 6b
3
6a
6b
Empirical formula
Mr
C16H16Co2I4O3
881.75
Triclinic
¯
P1
C16H26B10Co2OS2
524.45
Monoclinic
C16H26B10Co2OSe2
618.25
Orthorhombic
Crystal system
Space group
P21/c
Pbca
˚
a/A
6.775(2)
12.239(4)
12.155(4)
18.230(5)
90
92.793(5)
90
2708.8(14)
4
1064
13.145(4)
15.462(5)
23.036(7)
90
90
90
4682(2)
8
1064
˚
b/A
12.876(4)
13.096(4)
86.583(5)
85.367(4)
82.294(4)
1127.1(6)
2
˚
c/A
a/◦
b/◦
c /◦
V/A
Z
3
˚
F(000)
804
Crystal size/mm
0.10 × 0.08 × 0.05
1.56–25.01
2.598
0.15 × 0.10 × 0.08
1.67–25.00
1.286
0.20 × 0.10 × 0.02
1.77–25.01
1.754
h Range/◦
Dc/Mg m−3
l/mm−1
6.961
1.386
4.535
No. reflns collected
No. ind. reflns
Rint
No. of data/restraints/params
Goodness-of-fit on F2
R Indices (I > 2rI)a
4756
3916
0.0337
3916/0/226
0.813
11212
4775
0.0485
4775/0/290
0.919
R1 = 0.0544
wR2 = 0.1520
R1 = 0.0850
wR2 = 0.1626
0.956, −0.615
18710
4130
0.0446
4130/0/290
0.891
R1 = 0.0372
wR2 = 0.0827
R1 = 0.0606
wR2 = 0.0880
1.975, −0.265
R1 = 0.0428
wR2 = 0.0881
R1 = 0.0754
wR2 = 0.0971
1.106, −0.824
R Indices (all data)
−3
˚
Dqmax, min/e A
ꢀ
ꢀ
ꢀ
ꢀ
a R1 = ꢁFo| − |Fcꢁ/ |Fo|; Rw = [ w(|Fo2| − |Fc2|)2/ w|Fo2|2]1/2
.
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Table 2 Crystallographic data for compounds 5a, 9 and 10b
5a
9
10b
Empirical formula
Mr
C54H66B20Co2OP2S4·3CH2Cl2
C50H46I4OP2Rh2
1438.23
Triclinic
¯
P1
C54H66B20OP2Rh2Se4·2CH2Cl2
1700.72
Monoclinic
1510.09
Crystal system
Space group
Monoclinic
P21/n
P21/n
˚
a/A
11.826(4)
18.124(6)
33.307(11)
90
90.714(6)
90
7138(4)
4
3088
8.080(3)
12.047(3)
18.278(5)
33.285(9)
90
90.573(5)
90
7329(3)
4
3352
˚
b/A
17.147(6)
17.467(6)
90.537(5)
94.058(5)
93.095(5)
2410.3(15)
2
˚
c/A
a/◦
b/◦
c /◦
V/A
Z
3
˚
F(000)
1372
Crystal size/mm
0.30 × 0.90 × 1.00
1.28–27.15
1.405
0.10 × 0.08 × 0.05
1.17–25.01
1.982
0.15 × 0.10 × 0.10
1.27–25.01
1.541
h Range/◦
Dc/Mg m−3
l/mm−1
0.891
3.349
2.664
No. reflns collected
No. ind. reflns
Rint
No. of data/restraints/params
Goodness-of-fit on F2
R Indices (I > 2rI)a
35152
15557
0.1111
15557/2/849
0.911
R1 = 0.0813
wR2 = 0.2005
R1 = 0.2023
wR2 = 0.2468
0.810, −0.986
10148
8386
0.0453
8386/0/532
0.908
R1 = 0.0566
wR2 = 0.1217
R1 = 0.1120
wR2 = 0.1521
1.195, −0.843
30475
12901
0.0783
12901/0/802
0.807
R1 = 0.0562
wR2 = 0.1252
R1 = 0.1553
wR2 = 0.1475
1.516, −0.574
R Indices (all data)
−3
˚
Dqmax, min/e A
ꢀ
ꢀ
ꢀ
ꢀ
a R1 = ꢁFo| − |Fcꢁ/ |Fo|; Rw = [ w(|Fo2| − |Fc2|)2/ w|Fo2|2]1/2
.
(s, Cp), 68.89 (s, OCH2), 27.78 (s, CpCH2), 92.15 (s, C2-carborane).
11B NMR (160 MHz, CDCl3, ppm): d −5.66, −9.94. 31P NMR
(202 MHz, CDCl3, ppm): d 38.46 (d, JRh–P = 148 Hz). IR (KBr
disk): m = 1093 cm−1 (mC–O–C, as), 2575 cm−1 (mB–H), 3055, 2922, 2861,
1624, 1480, 1434, 1357, 840, 744, 695530 cm−1.
with Siemens SHELXTL PLUS program.18 Details of crystal data
for complexes 3, 5a, 6a, 6b, 9 and 10b are summarized in Tables 1
and 2.
CCDC reference numbers 616733–616738.
For crystallographic data in CIF or other electronic format see
DOI: 10.1039/b611266h
10b. (140 mg, 55%) Anal. Calc. for C54H66B20OP2Rh2Se4·
1
2CH2Cl2: C 39.55; H 4.15. Found: C 38.89, H 4.09%. H NMR
(500 MHz, CDCl3, ppm): d 7.46–7.39 (m, 30H, Ph), 4.98 (t, 4H,
Cp), 4.94 (t, 4H, Cp), 3.68 (t, 4H, OCH2, JH–H = 11.9 Hz), 2.76
(t, 4H, CH2, JH–H = 10.5 Hz). 11B NMR (160 MHz, CDCl3, ppm):
d −5.09, −8.58, −11.12. 31P NMR (202 MHz, CDCl3, ppm): d
Acknowledgements
Financial support by the National Science Foundation of China
for Distinguished Young Scholars (20421303, 20531020), by the
National Basic Research Program of China (2005CB623800) and
by the Shanghai Science and Technology Committee (05JC14003,
05DZ22313) is gratefully acknowledged.
38.40 (d, JRh–P = 148 Hz). IR (KBr disk): m = 1093 cm−1 (mC–O–C
,
as), 2575 cm−1 (mB–H), 3053, 2922, 2857, 1577, 1478, 1433, 1384,
827, 743, 694, 529 cm−1.
Crystal structure determinations
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Dalton Trans., 2006, 5231–5239 | 5239
©