Effect of anchoring group and valent of cobalt center on the competitive cleavage of C-F or C-H bond activation

Article abstract of DOI:10.1016/j.jorganchem.2010.04.031

Treatment of CoMe(PMe₃)₄ with 2,6- difluorobenzophenone imine and 2,6-difluorobenzophenone resulted in C-H bond activation complex, [Co(2-C₆H₄)-(CNH)-(2′,6″- F₂C₆H₃)(PMe₃

Full text of DOI:10.1016/j.jorganchem.2010.04.031

Journal of Organometallic Chemistry 695 (2010) 1873e1877
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Effect of anchoring group and valent of cobalt center on the competitive cleavage
of CeF or CeH bond activation
*
Tingting Zheng, Hongjian Sun, Jun Ding, Yanfeng Zhang, Xiaoyan Li
School of Chemistry and Chemical Engineering, Shandong University, Shanda Nanlu 27, 250100 Jinan, PR China
a r t i c l e i n f o
a b s t r a c t
Article history:
Treatment of CoMe(PMe3)4 with 2,6-difluorobenzophenone imine and 2,6-difluorobenzophenone
resulted in CeH bond activation complex, [Co(2-C6H4)-(C]NH)-(20,600-F2C6H3)(PMe3)3] (2), and CeF
bond activation complex [Co(Me)(F)(2-(6-FC6H3)-(C]O)-C6H5)(PMe3)2] (3) respectively. Using Co
(PMe3)4 instead of CoMe(PMe3)4 the CeF activation Co(_) complex [Co(2-(6-FC6H3)-(C]NH)-C6H5)
(PMe3)3] (1), was obtained by the reaction of Co(PMe3)4 with 2,6-difluorobenzophenone imine. In the
case of mono-fluorinated aromatic ketone, the reaction of CoMe(PMe3)4 with 2,40-difluorobenzophenone
afforded only CeH bond activation complex, [Co(2-(4-FC6H3)-(C]O)-(20-FC6H4)(PMe3)3] (4) in compar-
ison with the CeF activation in the di-fluorinated aromatic ketone 2,6-difluorobenzophenone system.
The crystal structures of complexes 1, 3 and 4 were determined by X-ray diffraction. The proposed
mechanisms were discussed.
Received 24 February 2010
Received in revised form
14 April 2010
Accepted 27 April 2010
Available online 2 June 2010
Keywords:
Cobalt complexes
CeF bond activation
CeH bond activation
Anchoring group
Ó 2010 Elsevier B.V. All rights reserved.
1. Introduction
three coordinate d8 metal complexes [20]. Hydrido osmium is
capable of producing the triple CeH bond activation of the
The intramolecular selective activation of CeF versus CeH bond
has attracted a great deal of attention in recent years because of
the requirements of “molecular surgery” in modern synthetic
chemistry. The priority of selective activation of CeF versus CeH
bond within one molecule is complicated and is related to many
factors [1e16]. It has not only thermodynamic but also kinetic
reason. A survey of competing CeF activation pathways in the
reaction of Pt(0) with fluoropyridines by Perutz was investigated
with both computational and experimental methods [17]. In 2008
Klein reported the first regioselective cyclometalation reactions of
cobalt in arylketone [18]. It was found that CoMe(PMe3)4 activates
ortho-(CeH) and ortho-(CeF) bonds of aromatic ketones and the
ortho-(CeF) activation is preferred over the ortho-(CeH) activation
in 2,3,4,5,6-pentafluorobenzophenone. Recently Johnson pub-
lished a combined experimental and computational study of
unexpected CeF bond activation intermediates and selectivity in
the reaction of pentafluorobenzene with a (PEt3)2Ni synthon [19].
Goldman reported addition at the aryl meta- and para-positions is
kinetically more favorable than at the ortho-position, although
thermodynamics favor the chelated ortho-(CeH) addition for
cyclohexyl group of cyclohexylmethyl ketone [21]. Esteruelas
found that the ortho-(CeH) bond activation is preferred over the
ortho-(CeF) bond activation in aromatic ketones with one
aromatic ring by phosphine-supported hexahydride osmium
complex [22]. Both CeF and CeH bond activations are favored by
an increase of the degree of fluorination of the substrates [23]. We
obtained the first organo cobalt(III) complex containing
a
[CeCoeF] fragment through
a
cyclometalation reaction
involving CeF bond activation at a cobalt(I) center with an alda-
zine-N atom as an anchoring group [24]. In this paper we present
competitive cleavage of CeF versus CeH bond in the cyclo-
metalation reaction at electron-rich cobalt center with ketone and
imine as anchoring group. Through the reaction of CoMe(PMe3)4
with 2,6-difluorobenzophenone, another example of organo
cobalt(III) complex, [Co(Me)(F)(2-(6-FC6H3)-(C]O)-C6H5)(PMe3)2]
(3), containing a [CeCoeF] fragment was obtained.
2. Results
2.1. Reaction of Co(PMe3)4 with 2,6-difluorobenzophenone imine
Co(PMe3)4 was combined with 2,6-difluorobenzophenone
imine affording the CeF bond activation complex 1 (eq. (1)).
* Corresponding author. Tel.: þ86 531 88361350; fax: þ 86 531 88564464.
E-mail address: xli63@sdu.edu.cn (X. Li).
0022-328X/$ e see front matter Ó 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2010.04.031

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T. Zheng et al. / Journal of Organometallic Chemistry 695 (2010) 1873e1877
The molecular structure of 1 (Fig. 1) shows a trigonal bipyra-
F
midal configuration around cobalt with C1 and P4 on axial
direction. The bite angle N1-Co1-C1 80.91(16)ꢀ is smaller than that
of complex 4. The sum of internal bond angles of the chelate ring
F
NH
F
PMe3
2
Co(PMe )
N
Co
2
2
+
F2PMe3 (1)
3
4
+
PMe3
PMe3
ꢀ
ꢀ
ꢀ
H
is (539.21 ). The distance of C7-N1 (1.336(5) A) is close to that
PMe3
(1.337(8) A) in the reported compound [25]. In comparison with
1
56%
the reaction of Co(PMe3)4 with 2,6-difluorobenzophenone [26],
the imine group is a better anchoring group than the keto group.
The CeF bond could be activated by the compensation of chelate
effect.
Complex
1 forms purple-blue crystals suitable for X-ray
diffraction which decompose above 140 ꢀC. In the IR spectra the
In the proposed mechanism (Scheme 1) the
p-coordination of
characteristic n
(C]N) band was found at 1603 cmꢁ1. The resonance
C]N double bond to the cobalt(0) center is the first step, which
makes closing of cobalt center to the ortho-(CeF) bond and the
formation of the intermediate A possible. Oxidative addition
between the CeF bond and the cobalt(0) center delivered cobalt(II)
intermediate B. B was reduced to cobalt(I) product 1.
of the NeH proton in the 1H NMR spectrum is registered at
8.36 ppm.
In our early work [27], the formation of F2PMe3 in the reaction of
perfluorotoluene with Co(PMe3)4 was confirmed via 31P NMR
spectroscopy. The fate of the fluorine atom in reaction (1) is not
experimentally identifiable.
2.2. Reaction of CoMe(PMe3)4 with 2,6-difluorobenzophenone
imine
Instead of cobalt(0) complex Co(PMe3)4, cobalt(I) complex CoMe
(PMe3)4 was combined with 2,6-difluorobenzophenone imine
affording deep-green crystals of complex 2 through CeH bond
activation (eq. (2)).
F
F
NH
F
PMe3
PMe3
CH4
CoMe(PMe )
(2)
+
Co
3
4
PMe3
N
PMe3
H
F
2
54%
ꢀ
ꢀ
Fig. 1. Molecular structure of 1 and selected bond distances (A) and angles ( ): Co1-N1
1.885(3), Co1-P2 2.1904(13), Co1-P3 2.2002(12), Co1-P4 2.2159(13), C1-Co1 1.936(4),
C7-N1 1.336(5); N1-Co1-C1 80.91(16), N1-Co1-P2 114.11(11), C1-Co1-P2 86.68(12), N1-
Co1-P3 133.89(11), C1-Co1-P3 93.66(13), P2-Co1-P3 111.18(5), P2-Co1-P4 97.46(5),
P3-Co1-P4 96.03(5), N1-Co1-P4 86.41(11), C1-Co1-P4 167.26(13), C7-N1-Co1 120.9(3),
N1-C7-C6 110.9(4), C6-C1-Co1 113.8(3), C1-C6-C7 112.7(3).
In the IR spectra n .
(C]N) absorption was found at 1620 cmꢁ1
The signal of the (NH) group is registered at 8.33 ppm. In the 31P
NMR spectra there are three signals for PMe3 ligands at 43.9, 33.5
F
F
NH
F
PMe3
2
F2PMe3
+
N
Co
Co(PMe )
2
+
2
3
4
PMe3
PMe3
H
PMe3
1
56%
2 PMe3
F2PMe3
PMe
+
3
F
F
F
PMe3
PMe3
PMe3
Co
2
2
Co
PMe3
N
N
F
PMe3
PMe3
H
H
B
A
Scheme 1. Proposed mechanism for reaction (1).

T. Zheng et al. / Journal of Organometallic Chemistry 695 (2010) 1873e1877
1875
F
NH
F
F
CH4
PMe3
PMe3
CoMe(PMe )
+
Co
3 4
PMe3
N
F
PMe3
54%
H
2
PMe3
PMe
CH4
+
3
F
F
F
PMe3
PMe3
Me
PMe3
PMe3
Co
N
Co
PMe3
PMe3
N
H
H
F
Me
H
Scheme 2. Proposed mechanism for reaction (2).
and 22.1 ppm with the ratio of 1:1:1. All of the data confirm
a trigonal bipyramidal configuration around cobalt. A trial to obtain
the crystal and molecular structure information through X-ray
diffraction has failed.
F2C6H3-
h
2-(C]O)-C6H5)(PMe3)3] [26] in P ꢁ 1 space group. The
occurrence of complex [Co(2,6-F2C6H3-h
2-(C]O)-C6H5)(PMe3)3] in
the crystal of complex 3 could be attributed to the impurity of CoMe
(PMe3)4 with minor amount of Co(PMe3)4.
A proposed reaction mechanism is described in Scheme 2. The
imine-N coordination is the first step. With the cyclometalation
effect the ortho-(CeH) bond of the phenyl group in the imine ligand
is activated affording an active methyl hydrido cobalt(III) inter-
meadiate, which affords the product 2 through the escape of
methane with reductive elimination.
The molecular structure (Fig. 2) of complex 3 confirms the
octahedral coordination geometry around the Co1 atom with P1
and P2 on axial direction and F2-O1-C7 and C42 in an equatorial
plane. The bite angle of C7-Co1-O1 is 82.45(7)ꢀ which is a little
larger than that of the related compounds in early work by Klein
et al. [28]. The sum of the angles around the cobalt in metalacycle is
ꢀ
ꢀ
540 . The distance of Co1-O1 (2.0213(13) A) is longer than that of
complex [Co(2,6-F2C6H3-
distance of Co1-F2 (1.9316(14) A) is in the normal region for CoeF
h
2-(C]O)-C6H5)(PMe3)3] [26]. The
2.3. Reaction of CoMe(PMe3)4 with 2,6-difluorobenzophenone
ꢀ
bond lengths [24].
In the reaction of 2,6-difluorobenzophenone, an iso-electronic
compound of 2,6-difluorobenzophenone imine, with CoMe
(PMe3)4, gave rise to complex 3 (eq. (3)) through CeF bond acti-
vation. To the best of our knowledge, after the report of the prep-
aration of the first example of organo cobalt(III) complex containing
a [CeCoeF] fragment [24], complex 3 is the second example of
organo cobalt(III) complex with a [CeCoeF] fragment.
F
O
F
PMe
Co
3 F
O
(3)
CoMe(PMe )
+
3
4
Me
2 PMe3
F
PMe3
3
36%
Complex 3 was obtained as violet crystals from pentane at
ꢁ27 ꢀC. In the infrared spectra, there is a strong absorption at
1594 cmꢁ1 assigned to
n(C]O) bond, a large bathochromic shift
comparing with that (1677 cmꢁ1) of the free ligand. In the 1H NMR
spectra the proton resonance of two anisochrom trimethylphos-
phine ligands is regarded as a singlet at 0.79 ppm, while the signal
of CoeCH3 could be found at 0.30 ppm 31P NMR data clearly show
one signal at 20.4 ppm. Complex 3 crystallized with [Co(2,6-
ꢀ
ꢀ
Fig. 2. Molecular structure of 3 and selected bond distances (A) and angles ( ): Co1-C7
1.895(2), Co1-F2 1.9316(14), Co1-O1 2.0213(13), Co1-P1 2.2121(11), Co1-P2 2.2138(10),
Co1-C42 1.995(2), O1-C1 1.247(2); C7-Co1-F2 172.02(7), C7-Co1-C42 95.73(9), F2-Co1-
C42 92.14(8), C7-Co1-O1 82.45(7), F2-Co1-O1 89.71(5), F2-Co1-P1 89.01(5), C42-Co1-
O1 177.77(8), C7-Co1-P1 92.52(7), C42-Co1-P1 88.38(9), O1-Co1-P1 90.41(5), C7-Co1-
P2 94.16(7), F2-Co1-P2 84.83(5), O1-Co1-P2 93.77(5), P1-Co1-P2 172.53(2).

1876
T. Zheng et al. / Journal of Organometallic Chemistry 695 (2010) 1873e1877
2.4. Reaction of CoMe(PMe3)4 with 2,40-difluorobenzophenone
3. Conclusions
Under similar reaction conditions, the reaction of CoMe(PMe3)4
with 2,40-difluorobenzophenone afforded the CeH activation
complex 4 in the yield of 67.0% (eq. (4)).
The CeF or CeH bond of difluorobenzophenone can not be
activated by Co(PMe3)4 [26], while the CeF or CeH bond of the
difluorobenzophenone are activated by CoMe(PMe3)4. Both Co
(PMe3)4 and CoMe(PMe3)4 can activate the CeF or CeH bond with
the better anchoring group (C]NH) instead of the keto group. The
Co-methyl group is beneficial for the CeH activation because of the
thermodynamic contribution of evolution of methane. Increasing
the subsituted fluoroatoms in phenyl ring is advantageous to the
CeF bond activation.
PMe3
F
O
PMe3
F
O
Co
CH4
PMe3
CoMe(PMe )
+
(4)
3
4
PMe3
F
F
4. Experimental
4
67%
4.1. General procedures and materials
From the dark brown solution of diethyl ether complex 4 was
obtained as the black needle-shaped crystals. In the IR spectra of
complex 4 the absorption at 1596 cmꢁ1 belongs to (C]O) group. In
the 31P NMR spectra there are two sets of signals with the intensity
ratio of 1:2 at 43.9 and 17.5 ppm. The 19F NMR spectrum indicates
two signals at ꢁ113.2 and ꢁ118.8 ppm with the ratio of 1:1. All of
the spectroscopic data indicate that the activation of CeH bond is
performed instead of CeF bond activation.
The molecular structure of complex 4 was confirmed by X-ray
diffraction analysis (Fig. 3). A cobalt atom is centered in a trigonal
bipyramid with axial C1 and P2 and a five-membered metallacycle
occupying C-axial and O-equatorial position with a bite angle O1-
Co1-C1 ¼ 82.5(2)ꢀ, comparable with that (82.45(7)ꢀ) in complex 3.
The sum of the internal angles in the cobaltacycle is 539.7ꢀ, close to
Standard vacuum techniques were used in manipulations of
volatile and air-sensitive materials. Literature method was used in
the preparation of Co(PMe3)4 and CoMe(PMe3)4 [29]. 2,40-difluor-
obenzophenone were used as
purchased. 2,6-difluor-
obenzophenone and 2,6-difluorobenzophenone imine were
prepared by published procedures [30,31]. Melting points were
measured in capillaries sealed under argon and were uncorrected.
Elemental analyses were carried out on an Elementar Vario EL III.
Infrared spectra (4000 - 400 cmꢁ1), as obtained from Nujol mulls
between KBr disks, were recorded on a Nicolet 5700. 1H, 19F and 31
P
NMR (300, 282 and 121 MHz, respectively) spectra were recorded
on a Bruker Avance 300 spectrometer. 31P NMR resonances were
obtained with broadband proton decoupling. X-ray crystallography
was performed with a Bruker Smart 1000 diffractometer.
ꢀ
ꢀ
planarity (540 ). The distance of P2-Co1 (2.227(2) A) is longer than
ꢀ
ꢀ
P3-Co1 (2.189(2) A) and P1-Co1 (2.184(2) A), owing to the stronger
trans-influence of carbon atom (C1). From reactions ((3) and (4)), in
the case of mono-fluorinated aromatic ketone, the reaction of CoMe
(PMe3)4 with 2,40-difluorobenzophenone afforded only CeH acti-
vation complex, [Co(2-(4-FC6H3)-(C]O)-(20-FC6H4)(PMe3)3] (4) in
comparison with the CeF activation in the double-fluorinated
aromatic ketone, 2,6-difluorobenzophenone system. Increasing the
substituted fluoroatoms in phenyl ring is beneficial for the CeF
bond activation.
4.2. Synthesis of 1
2,6-difluorobenzophenone imine 0.63 g (2.90 mmol) in pentane
(30 mL) was mixed at ꢁ80 ꢀC with Co(PMe3)4 1.06 g (2.92 mmol) in
30 mL of pentane. On warming, the reaction mixture turned blue
and was stirred for 18 h at 20 ꢀC. Crystallization in pentane at ꢁ27
afforded complex 1 as purple-blue crystals. Yield: 0.75 g (56.3%).
Dec >140 ꢀC. Analysis for 1 C22H36CoFNP3, [found (calculated)]: C,
54.11 (54.44); H, 7.13 (7.48). IR (Nujol): 1603
3195 (NeH), 946
(PMe3).1H NMR (300.1 MHz, C6D6, 300 K):
(s(br), 27H, PCH3), 6.63e7.77 (m, 8H, CHarom), 8.36 (s, H, NH). 31P
n(C]N), 1576
n
(C]C),
n
n
d
0.90
NMR (121.5 MHz, C6D6, 300 K):
d 45.3(s, P, PCH3), 14.1 (s, 2P, PCH3).
4.3. Synthesis of 2
A solution of 0.69 g (1.82 mmol) of CoMe(PMe3)4 in 30 mL of
pentane was combined with solution of 2,6-difluor-
a
obenzophenone imine 0.40 g (1.82 mmol) in pentane (30 ml) at
ꢁ80 ꢀC. The reaction mixture was allowed to warm to ambient
temperature and stirred for 18 h, turning green. Crystallization in
pentane at ꢁ27 ꢀC afforded complex 2 as deep-green crystals. Yield:
0.50 g (54.3.0%). Analysis for 2 C22H35CoF2NP3, [found (calculated)]:
C, 52.15 (52.49); H, 6.83 (7.01). IR (Nujol): 1620
n(C]N), 1589 n(C]
C), 3193 (NeH), 946
n
n
(PMe3). 1H NMR (300.1 MHz, C6D6, 300 K):
d
0.92 (s(br), 27H, PCH3), 6.65e7.73 (m, 7H, CHarom), 8.33 (s, H, NH).
31P NMR (121.5 MHz, C6D6, 300 K):
d 43.9 (s, 1P, PCH3), 33.5 (s, 1P,
PCH3), 22.1 (s, 1P, PCH3).
4.4. Synthesis of 3
ꢀ
ꢀ
Fig. 3. Molecular structure of 4 and selected bond distances (A) and angles ( ): P3-Co1
2.189(2), P2-Co1 2.227(2); P1-Co1 2.184(2), Co1-O1 1.905(4), Co1-C1 1.921(6), O1-Co1-
C1 82.5(2), O1-Co1-P1 115.91(15), C1-Co1-P1 92.2(2), O1-Co1-P3 131.80(15), C1-Co1-P3
90.78(19), P1-Co1-P3 111.99(8), O1-Co1-P2 80.45(14), C1-Co1-P2 162.7(2), P1-Co1-P2
97.76(9), P3-Co1-P2 98.48(8).
A solution of 0.83 g (3.81 mmol) 2,6-difluorobenzophenone in
30 mL pentane was combined with a solution of 1.44 g (3.81 mmol)
CoMe(PMe3)4 in 30 mL pentane at ꢁ80 ꢀC. This reaction mixture
was allowed to warm to ambient temperature and stirred for 18 h

T. Zheng et al. / Journal of Organometallic Chemistry 695 (2010) 1873e1877
1877
to form deep-red solution with green deposition in the bottom.
Crystallization from pentane at ꢁ30 ꢀC yielded violet single crystals
3 (0.61 g, yield 36.3%). Analysis for 3 C20H29CoF2OP2, [found
(calculated)]: C, 53.93 (54.06); H, 6.32 (6.58). Dec > 150 ꢀC. IR
were solved by direct methods and refined with full matrix least-
squares on all F2 (SHELXL-97) with non-hydrogen atoms
anisotropic.
(Nujol): 1594
(300.1 MHz, C6D6, 300 K):
6.33e7.75 (m, 8H, CHarom). 31P NMR (121.5 MHz, C6D6, 300 K):
20.4 (s, 2P).
n(C]O), 1541
n(C]C), 944 n
(PMe3). 1H NMR
Acknowledgment
d
0.30 (s, 3H, CH3), 0.79 (s(br),18H, PCH3),
We gratefully acknowledge the support by NSF China No.
20772072/20972087.
d
4.5. Synthesis of 4
Appendix A. Supplementary materials
A solution of 0.50 g (1.32 mmol) of CoMe(PMe3)4 in 30 mL of
solution of 2,40-difluor-
CCDC 742942, 742940 and 742943 contain the supplementary
crystallographic data for complexes 1, 3(þC22H35CoF2OP3[26]), and
4. These data can be obtained free of charge from the Cambridge
Crystallographic Data Center via www.ccdc.cam.ac.uk/data-
request/cif.
pentane was combined with
a
obenzophenone 0.28 g (1.32 mmol) in pentane (30 ml) at ꢁ80 ꢀC.
The reaction mixture was allowed to warm to ambient temperature
and stirred for 18 h, turning deep-brown. Crystallization in pentane
at ꢁ27 afforded complex 4 as red-brown crystals. Yield: 0.60 g
(67.0%). Analysis for 4 C22H34CoF2OP3, [found (calculated)]: C, 52.11
(52.39); H, 6.52 (6.79). IR (Nujol): 1596
(PMe3). 1H NMR (300.1 MHz, C6D6, 300 K):
PCH3), 6.50e8.18 (m, 7H, CHarom). 31P NMR (121.5 MHz, C6D6,
300 K):
43.9 (s, P, PCH3), 17.5 (s, 2P, PCH3). 19F NMR (282.4 MHz,
C6D6, 300 K):
ꢁ113.2(s, 1F), ꢁ118.8(s, 1F).
n
(C]O), 1572
n(C]C), 936 n
References
d
0.81e1.04 (s(br), 27H,
[1] T.G. Richmond, S. Murai, Topics in organometallic chemistry
3 (1999)
243e269.
d
[2] J.L. Kiplinger, T.G. Richmond, J. Am. Chem. Soc. 118 (1996) 1805e1806.
[3] J.L. Kiplinger, T.G. Richmond, C.E. Osterberg, Chem. Rev. 94 (1994) 373e431.
[4] T. Braun, R.N. Perutz, Chem. Commun. (2002) 2749e2757.
[5] J. Burdeniuc, B. Jedlicka, R.H. Crabtree, Chem. Ber. 130 (1997) 145e154.
[6] W.D. Jones, J. Chem. Soc. Dalton Trans. (2003) 3991e3995.
[7] E.F. Murphy, R. Murugavel, H.W. Roesky, Chem. Rev. 97 (1997) 3425e3468.
[8] M. Aizenberg, D. Milstein, Science 265 (1994) 359e361.
[9] M. Weydert, R.A. Andersen, R.G. Bergman, J. Am. Chem. Soc. 115 (1993)
8837e8838.
d
4.6. X-ray structure determinations
Intensity data were collected on a Bruker SMART diffractometer
ꢀ
with graphite-monochromated Mo K
Crystallographic data for complexes 1, 3DCo(2,6-C6H3F2-CO(
a
radiation (
l
¼ 0.71073 A).
h
2)-
[10] B.L. Edelbach, W.D. Jones, J. Am. Chem. Soc. 119 (1997) 7734e7742.
[11] J.L. Kiplinger, T.G. Richmond, J. Chem. Soc. Chem. Commun. (1996)
1115e1116.
C6H5)(PMe3)3 [26], and 4 are summarized in Table 1. The structures
[12] B.L. Edelbach, A.K.F. Rahman, R.J. Lachicotte, W.D. Jones, Organometallics 18
(1999) 3170e3177.
[13] B.M. Kraft, R.J. Lachicotte, W.D. Jones, J. Am. Chem. Soc. 123 (2001)
10973e10979.
Table 1
Crystallographic data for complexes 1, 3(þC22H35CoF2OP3[26]), and 4.
[14] R.J. Young Jr., V.V. Grushin, Organometallics 18 (1999) 294e296.
[15] M.K. Whittlesey, R.N. Perutz, M.H. Moore, Chem. Commun. 6 (1996) 787e788.
[16] M. Aizenberg, D. Milstein, J. Am. Chem. Soc. 117 (1995) 8674e8675.
[17] A. Nova, S. Erhalt, N.A. Jasim, R.N. Perutz, S.A. Macgregor, J.E. McGrady,
A.C. Whitewood, J. Am. Chem. Soc. 130 (2008) 15499e15511.
[18] S. Camadanli, R. Beck, H.-F. Klein, Dalton Trans. (2008) 5701e5704.
[19] S.A. Johnson, E.T. Taylor, S.J. Cruise, Organometallics 28 (2009)
3842e3855.
[20] X. Zhang, M. Kanzelberger, T.J. Emge, A.S. Goldman, J. Am. Chem. Soc. 126
(2004) 13192e13193.
[21] P. Barrio, R. Castarlenas, M.A. Esteruelas, E. Onate, Organometallics 20 (2001)
2635e2638.
[22] P. Barrio, R. Castarlenas, M.A. Esteruelas, A. Lledos, F. Maseras, E. Onate,
J. Tomas, Organometallics 20 (2001) 442e452.
[23] M. Crespo, J. Granell, M. Font-Bardia, X. Solans, J. Organomet. Chem. 689
(2004) 3088e3092.
[24] X. Li, H. Sun, F. Yu, U. Flörke, H.-F. Klein, Organometallics 25 (2006)
4695e4697.
[25] H.-F. Klein, S. Camadanli, R. Reck, D. Leukel, Angew. Chem. Int. Ed. 44 (2005)
975e977.
1
3(DC22H35CoF2OP3[26])
4
Mol wt
FW
C
22H36CoFNP3 C42H64Co2F4O2P5
C22H34CoF2OP3
504.33
485.36
Triclinic
P ꢁ 1
949.64
Triclinic
P ꢁ 1
Crystal system
Space group
Monoclinic
P2 (1)/c
8.531 (3)
17.705 (5)
33.660 (10)
90
92.237 (6)
90
5081 (3)
2
ꢀ
a (A)
9.291 (2)
10.688 (3)
13.338 (3)
94.001 (4)
102.089 (4)
99.587 (4)
1269.4 (5)
2
9.0550 (18)
16.355 (3)
18.032 (4)
64.23 (3)
79.46 (3)
79.30 (3)
2347.2 (8)
2
ꢀ
b (A)
ꢀ
c (A)
a
b
g
(ꢀ)
(ꢀ)
(ꢀ)
3
ꢀ
V (A )
Z
T, K
273
273
273
Crystal size (mm)
0.25 ꢂ 0.20
0.34 ꢂ 0.25
0.32 ꢂ 0.36
ꢂ 0.20
ꢂ 0.27
ꢂ 0.28
Dc (g cmꢁ3
No. of rflns
)
1.270
1.344
1.319
7568
15,085
25,565
collections
No. of independent 5612
[26] J. Ding, X. Li, Acta Crystallogr. Sect. E. Struct. Rep. Online 65 (2009)
m495em496.
9113
9732
[27] T. Zheng, H. Sun, Y. Chen, X. Li, S. Durr, U. Radius, K. Harms, Organometallics
28 (2009) 5771e5776.
[28] H.-F. Klein, K. Ellrich, S. Lamac, G. Lull, L. Zsolnai, G. Huttner, Z. Naturforsch. B:
Anorg. Chem. Org. Chem. 40 (1985) 1377e1382.
[29] H.-F. Klein, H.H. Karsch, Chem. Ber. 108 (1975) 944e955.
[30] B. Zhao, X. Lu, Tetrahedron Lett. 47 (2006) 6765e6768.
[31] J.M. Birchall, R.N. Haszeldine, M.E. Jones, J. Chem. Soc. (C) (1971) 1343e1348.
rflns
Parameters
Rint
qmax (ꢀ)
R1 (I > 2
wR2 (all data)
262
587
523
0.0259
28.00
0.0661
0.2142
0.0774
26.81
0.0408
0.1244
0.0681
25.63
0.0797
0.2638
s(I))