Synthesis and Characterization of Diorganocobalt Chlorides by Aliphatic Vinylic C–Cl Bond Activation

Article abstract of DOI:10.1002/zaac.201600186

Three diorganocobalt chlorides [CoClMe(PMe₃)₂–{(C₅H₆)–CH=O}] (4), [CoClMe(PMe₃)₂–{(C₆H₈)–CH=O}] (5), and [CoClMe(PMe₃)₂–{(C₆H₇

Full text of DOI:10.1002/zaac.201600186

Journal of Inorganic and General Chemistry
www.zaac.wiley-vch.de
ARTICLE
Zeitschrift für anorganische und allgemeine Chemie
DOI: 10.1002/zaac.201600186
Synthesis and Characterization of Diorganocobalt Chlorides by Aliphatic
Vinylic C–Cl Bond Activation
Qingfen Niu,[a,b] Shumiao Zhang,[a] Xiaoyan Li,[a] Hongjian Sun,*[a] Olaf Fuhr,[c] and
Dieter Fenske[c]
Keywords: Cyclometalation; C–Cl activation; Aldehydes; Cobalt; Trimethylphosphine
Abstract. Three diorganocobalt chlorides [CoClMe(PMe3)2–{(C5H6)–
structures of complexes 4 and 5 were determined by single-crystal
CH=O}] (4), [CoClMe(PMe3)2–{(C6H8)–CH=O}] (5), and X-ray diffraction. Complexes 4–6 are stable in solution at room tem-
[CoClMe(PMe3)2–{(C6H7Memeta)–CH=O}] (6) were synthesized perature, but they decompose at above 30 °C affording C,C-couplings
through cyclometalation reactions with aldehyde as an anchoring group products with the formation of [Co(PMe3)3Cl]. The results of this work
involving aliphatic vinylic C–Cl bond activation. Complexes 4–6 were will be important for people to deepen the understanding of the C–Cl
characterized by IR and NMR spectroscopy. The crystal and molecular
bond activation mechanism.
plexes supported by trimethylphosphine ligands. A series of
organoiron, organonickel, and organocobalt complexes were
synthesized via C–Cl bond activation in the past years.[4–13]
Recently, the activation of vinylic C–Cl bonds in chloroalkenes
by nickel complexes was reported. Seven organo-
nickel(II) complexes were synthesized and characterized by
oxidative addition of the vinylic C–Cl bonds.[14] As the contin-
uation of the research on C–Cl bond activation, in this paper
the results on C–Cl bond activation with cobalt complex are
disclosed. Three novel organocobalt chlorides were synthe-
sized through cyclometalation reactions with aldehyde as an
anchoring group involving aliphatic vinylic C–Cl bond acti-
vation. These complexes are stable in solution at room tem-
perature and decompose at above 30 °C affording C,C-cou-
pling products with the formation of [Co(PMe3)3Cl]. The re-
sults of this work will be important for people to deepen the
understanding of the C–Cl bond activation mechanism.
1 Introduction
Organic chloride as one kind of important starting materials
can be widely used in many cross-coupling reactions, such as
the Heck reaction, Suzuki coupling, Kumada coupling, Sono-
gashira coupling, and Stille coupling. C–Cl bond activation is
the key step in these reactions. Therefore, the study on the C–
Cl bond activation and functionalization mediated by transition
metal complexes is always the research topic in organic syn-
thesis and organometallic chemistry. Density functional theory
calculations have been employed to model the double
C–Cl bond activation of CH2Cl2 at [CoCl(PR3)3] to give
[CoCl3(CH2PR3)(PR3)2].[1] The C–Cl bond activation of
CH2Cl2 with cobalt was studied by Pierre Braunstein and co-
workers.[2] A practical coupling between aryl chlorides and
arylmagnesium halides was developed with Co(acac) as pre-
catalyst in 2013.[3]
The research interest was focused on the C–Cl bond acti-
vation mediated by electron-rich cobalt, nickel, and iron com-
2 Results and Discussion
* Prof. Dr. H. Sun
Fax: + 86-531-88564464
[CoMe(PMe3)4] reacted with β-chlorinated vinylic alde-
hydes 1–3 to give rise to three cobalt(III) chlorides 4–6 by
oxidative addition of the C–Cl bond with aldehyde as an an-
choring group (Scheme 1). Crystallization in n-pentane at
–20 °C afforded complexes 4–6 as red crystals in yields of
74%, 76%, and 72%, respectively. Complexes 4–6 in solid
state are quite stable in air and they decompose at above 135–
146 °C.
The selected IR and NMR spectroscopic data of complexes
4–6 are collected in Table 1. Compared with the (C=O) band
(1667–1679 cm–1) and the [C(=O)–H] band (3321–3352 cm–1)
of compounds 1–3, the related characteristic bands of com-
plexes 4–6 have a large red shift. These substantial red shifts
upon coordination of the C=O and O-donor atom acted as an-
E-Mail: hjsun@sdu.edu.cn
[a] School of Chemistry and Chemical Engineering
Key Laboratory of Special Functional Aggregated Materials,
Ministry of Education
Shandong University
Shanda Nanlu 27
Jinan, 250199, P. R. China
[b] Shandong Provincial Key Laboratory of Fine Chemicals
Qilu University of Technology
Jinan 250353, P. R. China
[c] Institut für Nanotechnologie (INT) und Karlsruher Nano-Micro-
Facility (KNMF)
Karlsruher Institut für Technologie (KIT)
Hermann-von-Helmholtz-Platz 1
76344 Eggenstein-Leopoldshafen, Germany
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/zaac.201600186 or from the au-
thor.
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Table 1. Selected spectroscopic data of complexes 4–6.
IR /cm–1
1H NMR /ppm
31P NMR /ppm
ν[C(O)–H]
ν(C=O)
ν(C=C)
ρ(PMe3)
PCH3
CoCH3
C(=O)H
PMe3
4
5
6
3220
3123
3239
1618
1594
1608
1540
1562
1561
941
944
931
0.99(t)
0.94(s)
1.04(m)
0.38(t)
0.22(s,br)
0.34(t)
8.61(s)
8.46(s)
8.58(s)
5.9(s, br)
5.2(s, br)
19.5(s, br)
Scheme 1. Synthesis of complexes 4, 5, and 6.
Figure 2. Molecular structure of 5, selected distances /Å and angles
/°: Co1–O1 2.020(2), Co1–Cl1 2.3470(9), Co1–C1 1.879(3), Co1–C8
1.996(3), Co1–P1 2.2250(9), Co1–P2 2.2197(9), O1–C7 1.249(4), C1–
C2 1.375(4); O1–Co1–Cl1 87.18(7), C1–Co1–C8 95.0(1), C8–Co1–
Cl1 94.8(1), C1–Co1–O1 83.1(1), P2–Co1–P1 175.06(4).
choring moiety indicate a weakening of these bonds. In the
13C NMR spectrum of complex 5, it was found that the PMe3
group gives rise to a virtual triplet signal between δ = 10.9 and
3
11.3 ppm with |1J(P,C) + J(P,C)| = 27.0 Hz. All the spectro-
scopic data of the three complexes are in agreement with an
octahedral configuration around the central cobalt(III) atom,
consisting of a P–Co–P axis and equatorial coordination of C,
C, Cl, and O donor atoms. The crystal and molecular structures
of complexes 4 and 5 were confirmed by single-crystal X-ray
diffraction analysis.
The molecular structures of complexes 4 and 5 are shown
in Figure 1 and Figure 2. The selected bond lengths and angles
are listed in the figure captions. The molecular structures of
the complexes 4 and 5 confirmed a hexa-coordinate octahedral
arrangement in the crystal.
Complex 4 shows an orthorhombic crystal structure. In the
distorted octahedral coordination, two trans-phosphine ligands
are in the axial direction, while the two coordination atoms
(C13, Cl1) and the chelate ring with [C1, O1] are in the equa-
torial plane. This is consistent with the observation in the 31P
NMR spectra. A five-membered metallacycle is formed
through cyclometalation with the coordination of the O atom
of the aldehyde group and the ortho-chelated C atom. The sum
of internal bond angles (539.88°) of this chelate ring indicates
ideal planarity. Typically, the Cl atom is trans-oriented to the
vinylic-C atom, which is well understood in terms of mutual
trans influence.[7–9] The bite angle of the chelating ligand [C1–
Co1–O1 = 81.98(13)°] is close to that in a related complex
[C1–Co–O1 = 80.27(10)°].[7] The two axial trimethylphos-
phine ligands are positioned [P1–Co1–P2 = 174.84(4)°] toward
the space between Co–Me and Co–Cl bonds for steric reasons.
However, both of the Co–C(13) [1.975(3) Å] and Co–Cl(1)
[2.312(1) Å] bond lengths are shorter than the related bond
lengths [Co1–C8 = 2.044(2), Co1–Cl1 = 2.3679(8) Å] in the
ortho-metalated cobalt(III) complex with the imine nitrogen
atom as anchoring group.[8] This can be explained by the
stronger coordination ability of N-donor atom than that of O-
donor atom.
In complex 5, the cobalt atom attains an octahedral coordi-
nation with one chloro ligand and a Me group [C8–Co1–Cl1
= 94.77(12)°], opposite to the planar [C:O]-chelate ring ligand
with a bite angle of [C1–Co1–O1 = 83.12(10)°]. The two axial
trimethylphosphine ligands are also slightly displaced [P2–
Co1–P1 = 175.06(4)°] toward the space between the Co–Me
and Co–Cl group for steric reasons. The sum (360.02°) of the
Figure 1. Molecular structure of 4, selected distances /Å and angles
/°: O1–C6 1.236(4), Co1–C1 1.825(3), Co1–C13 1.975(3), Co1–O1
2.039(2), Co1–P1 2.1937(9), Co1–P2 2.1947(9), Co1–Cl1 2.312(1),
C1–C5 1.352(5); C13–Co1–O1 175.3(1), P1–Co1–P2 174.84(4), C1–
Co1–Cl1 169.8(1), C5–C1–Co1 114.6(2), C1–Co1–O1 82.0(1), C6–
O1–Co1 109.5(2), C1–C5–C6 114.6(3), O1–C6–C5 119.2(4).
four angles [O1–Co1–Cl1
= 87.18(7), C1–Co1–C8 =
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94.95(14), C8–Co1–Cl1 = 94.77(12) and C1–Co1–O1 = give methylated cycloolefine aldehyde derivatives. The struc-
83.12(10)°] around the central cobalt atom in the equatorial tures of complexes 4 and 5 were determined by single-crystal
plane proves that the five atoms [Co1 O1 C1 C8 Cl1] are co- X-ray diffraction.
planar. The five-membered chelate ring and the cyclohexene
ring are almost in one plane. The C=O bond length [O1–C7
4 Experimental Section
= 1.249(4) Å], is longer than that of the uncoordinated C=O
(1.20 Å). This indicates a significant bond weakening upon co-
ordination of the O-donor atom. The formal C=C double bond
[C1–C2 (1.375(4) Å] of the cyclohexene ring in complex 5 is
longer than that of the related C1–C5 bond [1.352(5) Å] in
complex 4. This suggests that the cyclopentene ring in com-
plex 4 possesses stronger transannular strain than that of cyclo-
hexene in complex 5.
4.1 General Procedures and Materials
All reactions were carried out in an atmosphere of nitrogen using stan-
dard Schlenk and vacuum-line techniques. These standard vacuum
techniques were used in manipulations of volatile and air-sensitive ma-
terials. All the solvents were distilled from Na/benzophenone in a ni-
trogen atmosphere. [CoMe(PMe3)4][15] was prepared according to the
literature method. ortho-Chlorinated cycloalkenyl aldehydes (1–3)
were synthesized by published procedures.[16] All other chemicals
were purchased from Aldrich or Acros and used as received without
further purification. Infrared spectra, as obtained from Nujol mulls be-
tween KBr disks, were performed within the 4000–400 cm–1 region
with a Bruker ALPHA FT-IR Spectrometer. 1H, 13C, and 31P NMR
spectra (300, 75, and 121 MHz, respectively) were recorded with a
Complexes 4–6 are stable in solutions at room temperature.
No spontaneous elimination of chloromethane was observed at
room temperature. However, when the reactions were heated
at 30 °C for 2 h, violet crystals, [CoCl(PMe3)3], were found in
these three reactions. The C,C-coupling products, compounds
1
8 and 9, were isolated and characterized by H NMR spec-
Bruker Avance 300 spectrometer with C6D6 as the solvent. 13C and 31
P
troscopy. The isolation of compound 7 failed (Scheme 2). With
imine as anchoring group the similar C,C-coupling reaction
was also observed at the central cobalt atom in 2008.[8] It is
suggested that high temperatures could accelerate the reductive
elimination reaction. It seems that initial coordination of the
O-donor should be the key step in the formation of complexes
4–6. With aldehyde-O as an anchoring group the oxidative ad-
dition reactions proceed smoothly. The cyclometalated prod-
ucts 4–6 are quite air-stable at room temperature due to the
chelate effect.
NMR resonances were obtained with broadband proton decoupling.
Melting points were measured in capillaries sealed in a nitrogen atmo-
sphere and are uncorrected. X-ray crystallography was performed with
a Bruker Smart 1000 diffractometer. Elemental analyses were carried
out with an Elementar Vario EL III.
4.2 Synthesis of 4
[CoMe(PMe3)4] (0.60 g, 1.59 mmol) in pentane (30 mL) was com-
bined with 2-chlorocyclopent-1-enecarbaldehyde (1) (0.20 g,
1.53 mmol) in pentane (20 mL) at –80 °C. The reaction mixture was
allowed to warm to ambient temperature and stirred for 16 h. During
this period, the reaction mixture turned brown-red in color and a little
brown solid precipitated. After filtering in vacuo, the resulting solid
was extracted with Et2O (30 mL). Crystallization from pentane at
–20 °C afforded red crystals suitable for single-crystal X-ray diffrac-
tion analysis. Yield: 0.40 g, 74%. C13H28ClCoOP2, (356.67 g·mol–1):
calcd. C 43.78, H 7.91%; found: C: 44.18, H 8.11%. Dec Ͼ 135 °C.
IR (Nujol mull, 4000–400 cm–1): ν˜ = 3220 ν[C(=O)–H], 1618 ν(C=O),
1540 ν(C=C), 941 ρ(PMe3). 1H NMR (300 MHz, C6D6, 297 K, ppm):
3
4
δ = 0.38 [t, J(P,H) = 9.3 Hz, 3 H, CH3], 0.99 [tЈ, |2J(P,H) + J(P,H)|
= 8.1 Hz, 18 H, PCH3], 1.79–1.89 (m, 2 H, cyclopent-H), 2.44 [t,
2J(H,H) = 7.5, 3J(H,H) = 7.2 Hz, 4 H, Cyclopent-H], 8.61 [s, 1 H,
C(O)-H]. 31P NMR (121 MHz, C6D6, 297 K, ppm): δ = 5.9 (s, PCH3).
Scheme 2. The formation of methylation C,C-coupling products.
4.3 Synthesis of 5
A sample of [CoMe(PMe3)4] (0.65 g, 1.72 mmol) in pentane (30 mL)
was combined with 2-chlorocyclohex-1-enecarbaldehyde (2) (0.25 g,
1.72 mmol) in pentane (20 mL) at –80 °C. The reaction mixture was
allowed to warm to ambient temperature and stirred for 16 h. During
this period, the reaction mixture turned brown-red in color and a little
brown-red solid precipitated. After filtering in vacuo, the resulting so-
lid was extracted with Et2O (30 mL). Crystallization from pentane at
–20 °C afforded brown-red crystals suitable for single-crystal X-ray
diffraction analysis. Yield: 0.48 g, 76%. C14H30ClCoOP2
(370.70 g·mol–1): calcd. C: 45.36, H 8.16%; found: C: 45.74, H
8.31%. Dec Ͼ 138 °C. IR (Nujol mull, 4000–400 cm–1): ν˜ = 3123
ν[C(O)–H], 1594 ν(C=O), 1562 ν(C=C), 944 ρ(PMe3). 1H NMR
3 Conclusions
Three ortho-metalated diorgano cobalt(III) chlorides 4–6
were obtained via the reactions of [CoMe(PMe3)4] with β-
chlorinated vinylic aldehydes 1–3. These cyclometalated com-
plexes 4–6 formed via activation of the aliphatic vinylic C–Cl
bond have octahedral coordination arrangements. Complexes
4–6 were characterized by IR and NMR spectroscopy. Poten-
tial routes of formation of complexes 4–6 were discussed. In
solutions, complexes 4–6 showed a trend to undergo subse-
quent reductive elimination accompanied by C,C-coupling to (300 MHz, C6D6, 297 K, ppm): δ = 0.22 (br. s, 3 H, CH3), 0.94 (br. s,
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18 H, PCH3), 1.37 (br. s, 4 H, Cyclohex-H), 2.12 (br. s, 2 H, cyclohex-
A total of 24,491 reflections were collected, 7805 unique (Rint =
H), 2.30 (br. s, 2 H, cyclohex-H), 8.46 [s, 1 H, C(O)–H]. 13C NMR 0.0577), R1 = 0.0431 [for 7805 reflections with IϾ2 sigma(I)], wR2 =
(75 MHz, C6D6, 297 K, ppm): δ = 11.1 [tЈ, |1J(P,C)+ 3J(P,C)| = 0.1004 (all data). The structure was solved by direct methods and re-
27.0 Hz, PCH3], 23.2 (s, Ccyclohex), 24.4 (s, Ccyclohex), 24.8 (s, fined with full-matrix least-squares on all F2 (SHELXL-97) with non-
Ccyclohex), 38.3 (s, Ccyclohex), 100.0 (s, C=C), 139.4 (s, C=C), 192.8 (s,
C=O). 31P NMR (121 MHz, C6D6, 297 K, ppm): δ = 5.2 (s, PCH3).
hydrogen atoms anisotropic.
Complex 5: C14H30ClCoOP2, Mr = 370.70, orthorhombic, space group
Pbca, a = 15.936(3) Å, b = 18.579(3) Å, c = 25.264(4) Å, V =
7480(2) Å3, T = 273 K, Z = 16, Dc = 1.317 g·cm–3, μ = 1.224 mm–1.
4.4 Synthesis of 6
A total of 46,102 reflections were collected, 9433 unique (Rint
=
A sample of [CoMe(PMe3)4] (0.45 g, 1.19 mmol) in pentane (30 mL)
was combined with 2-chloro-5-methylcyclohex-1-enecarbaldehyde (3)
(0.19 g, 1.19 mmol) in pentane (20 mL) at –80 °C. The reaction mix-
ture was allowed to warm to ambient temperature and stirred for 16 h.
During this period, the reaction mixture turned dark brown-red in color
and a little brown-red solid precipitated. After filtering in vacuo, the
resulting solid was extracted with Et2O (30 mL). Crystallization from
pentane at –20 °C afforded red crystals. Yield: 0.33 g, 72%.
C15H32ClCoOP2 (384.71 g·mol–1): calcd. C: 46.83, H 8.38%; found:
C: 46.51, H 8.41%. Dec Ͼ 146 °C. IR (Nujol mull, 4000–400 cm–1):
0.0338), R1 = 0.0442 [for 9433 reflections with IϾ2 sigma(I)], wR2 =
0.1196 (all data). The structure was solved by direct methods and re-
fined with full-matrix least-squares on all F2 (SHELXL-97) with non-
hydrogen atoms anisotropic.
Crystallographic data (excluding structure factors) for the structures in
this paper have been deposited with the Cambridge Crystallographic
Data Centre, CCDC, 12 Union Road, Cambridge CB21EZ, UK.
Copies of the data can be obtained free of charge on quoting the
depository numbers CCDC-910939 (4) and CCDC-918121 (5)
(Fax: +44-1223-336-033; E-Mail: deposit@ccdc.cam.ac.uk, http://
www.ccdc.cam.ac.uk).
1
ν˜ = 3239 ν[C(O)–H], 1608 ν(C=O), 1561 ν(C=C), 931 ρ(PMe3). H
3
NMR (300 MHz, C6D6, 297 K, ppm): δ = 0.34 [t, J(P,H) = 9.0 Hz, 3
2
H, CoCH3], 0.98 [d, J(H,H) = 9.0 Hz, 3 H, Cyclohex-CH3], 1.04 (m,
18 H, PCH3), 1.57 (m, 1 H, Cyclohex-H), 1.78 (m, 3 H, Cyclohex-H),
2.29 [d, 2J(H,H) = 12.0 Hz, 2 H, Cyclohex-H], 2.63 [d, 2J(H,H) =
15.0 Hz, 1 H, Cyclohex-H], 8.58 [s, 1 H, C(O)–H]. 31P NMR
(121 MHz, C6D6, 297 K, ppm): δ = 19.5 (s, PCH3).
Acknowledgements
The authors gratefully acknowledge the financial support by National
Natural Science Foundation of China no. 21572119/21272138.
4.5 Isolation of Compounds 8 and 9
References
Compound 8: A sample of [CoMe(PMe3)4] (0.65 g, 1.72 mmol) in
pentane (30 mL) was combined with 2-chlorocyclohex-1-enecarbal-
dehyde (2) (0.25 g, 1.72 mmol) in pentane (20 mL) at –80 °C. The
reaction mixture turned to brown red immediately. After the tempera-
ture was raised to 30 °C the reaction solution was stirred for 2 h and
the solution became to brown yellow. During this process, a lot of
bluish-violet crystals of CoCl(PMe3)4 precipitated. After filtration the
filtrate was treated with diluted HCl and extracted with diethyl ether.
The organic layer was dried with MgSO4. After remove of the solvents
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1
compound 8 was isolated as pale yellow oil. Yield: 0.10 g, 48%. H
NMR (300 MHz, C6D6, 297 K, ppm): δ = 2.10 (s, 3 H, vinylic-CH3),
1.57 (m, 4 H, cyclohex-H), 2.16 (m, 4 H, cyclohex-H), 10.11 [s, 1 H,
C(O)–H].
Compound 9: Compound 9 was isolated with the same method as
compound 8. Yield: 52%. 1H NMR (300 MHz, C6D6, 297 K, ppm):
δ = 1.00 [d, 2J(H,H) = 9.0 Hz, 3 H, cyclohex-CH3], 1.20 (m, 1 H,
cyclohex-H), 1.59 (m, 4 H, cyclohex-H), 2.14 (s, 3 H, vinylic-CH3),
2.26 (m, 2 H, Cyclohex-H), 10,14 [s, 1 H, C(O)–H].
[14] Q. Niu, X. Zhang, S. Zhang, X. Li, H. Sun, Inorg. Chim. Acta
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4.6 Crystallographic Data
Complex 4: C13H28ClCoOP2, Mr = 356.67, orthorhombic, space group
Pbca, a = 15.739(3) Å, b = 17.609(4) Å, c = 24.675(5) Å, V =
6839(2) Å3, T = 293 K, Z = 16, Dc = 1.386 g·cm–3, μ = 1.335 mm–1.
Received: May 25, 2016
Published Online: ᭿
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Q. Niu, S. Zhang, X. Li, H. Sun,* O. Fuhr,
D. Fenske .......................................................................... 1–5
Synthesis and Characterization of Diorganocobalt Chlorides by
Aliphatic Vinylic C–Cl Bond Activation
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