Inorganica Chimica Acta 350 (2003) 163 /174

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Synthesis and characterization of enolato-cobalt and -nickel

complexes bearing TpiPr2 ligand, [TpiPr2M(XCHY)]n
[TpiPr2
hydrotris(3,5-diisopropylpyrazolyl)borato; n
1, 2],
/ /

obtained from hydroxometal complexes, (m-OH)2(MTpiPr2)2,

and active methylene compounds, CH2XY
Masato Kujime, Shiro Hikichi 1, Munetaka Akita *
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan

Received 10 June 2002; accepted 12 September 2002

Dedicated to Prof. Pierre Braunstein in recognition of his important contribution to inorganic chemistry

Abstract

Reaction of hydroxo-cobalt and -nickel complexes, (TpiPr2M)2(m-OH)2 (1) [M
/Co (1Co), Ni (1Ni); TpiPr2: hydrotris(3,5-
diisopropylpyrazolyl)borato], with active methylene compounds, CH2XY (2) [X/Y
/CN/COPh (2a); CN/CN (2b); COCH2C-
Me2CH2CO (2d: dimedone); COMe/COOMe (2e); COOMe/COOMe (2f)], in the presence of a drying agent (e.g.
Na
 2SO4 ) results in
the dehydrative condensation to give N/O-bound enolato complexes with monomeric chelated structure TpiPr2/MXCHY (3e and
3f), or dimeric cyclic structure (TpiPr2M)2(m-XCHY)2 (3a, 3b, and 3d). In contrast, treatment of 1 with methyl cyanoacetate (2c) gives
the k2-carboxylato complex, TpiPr2M(k2-OOCCH2CN) (4c), via hydrolysis of the ester moiety by the action of the OH functional
group in 1. The reaction pathway (enolato formation vs. ester hydrolysis) is a combined result of various factors including the
acidity of the CH moiety in 2, rigidity of the enolato skeleton, and relative thermodynamic stability of possible structures. Molecular
structures of 3bCo-2py, 3eCo-MeCN, 3fNi and 4cNi determined by X-ray crystallography reveal the formation the N/O-bound
structure, where the negative charge is widely delocalized over the enolato functional group. No isomerization to C-bound enolate,
TpRM-CHXY, is observed, even when a less sterically hindered ligand, TpMe2, is employed. Reaction of 3aCo and 3aNi with
benzaldehyde carried out as a preliminary study of the reactivity of the obtained enolato complexes 3 affords the metallacyclic



products TpiPr2C/oO-C(Ph)-C(CN-CoTpiPr2)-CHPh-C(CN)-C(Ph)-O (5) (characterized by X-ray crystallography as a 2MeCN

 
adduct) and TpiPr2N/iO-C(Ph)-C(CN-H)-CHPh-C(CN)-C(Ph)-O (6), respectively, by way of double condensation of PhCHO with
two enolato functional groups.
# 2003 Elsevier Science B.V. All rights reserved.

Keywords: Enolato-cobalt complexes; Enolato-nickel complexes; Hydroxometal complexes; Methylene compounds

1. Introduction

Transition metal hydroxo complexes have been re-

garded as versatile starting compounds for a variety of
inorganic compounds, because they are readily suscep-
* Corresponding author. Tel./fax: /81-45-924 5230. tible to dehydrative condensation with protic substrates
E-mail address: makita@res.titech.ac.jp (M. Akita).
1
Present address: Department of Applied Chemistry, School of
(M /OH/H/A 0/M /A/H2O). The reaction is pro-
Engineering, University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113- moted by the addition of a drying agent, which removes
8656, Japan. water and is afterwards readily separated by simple
0020-1693/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0020-1693(02)01547-5
164 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174
filtration together with adsorbed water, the only by-
product. Based on this synthetic method with these
advantages, we carried out systematic study of the
structure and reactivity of dioxygen complexes bearing
the TpR?M auxiliary2 [1,2] and, recently, we have shown
that organometallic species such as enolato-palladium
and alkynylcobalt complexes [3,4a] are also accessible
via this synthetic strategy. Herein, we wish to report the
results of synthesis and characterization of the enolato-
cobalt and -nickel complexes derived from the corre-
sponding hydroxo complexes and active methylene
compounds.
2. Experimental
2.1. General
All manipulations were carried out under Ar atmo-
sphere using standard Schlenk tube technique. Hexane
(Na /K/benzophenone) and CH2Cl2 and MeCN (P2O5)
were dried over appropriate drying agents under Ar and
distilled before use. IR (KBr pellets) and FD-MS spectra
were obtained on a JASCO FT/IR 5300 spectrometer
and a JEOL JMS-700 mass spectrometer, respectively.
The hydroxo complexes, (TpiPr2M)2(m-OH)2 (1), were
prepared according to the procedures reported by us [5].
Other chemicals were used as received without further
purification.
2.2. Preparation
As a typical example of the synthesis of enolato
complexes, the reaction of 1Co with benzoylacetonitrile
giving 3aCo is described. To a CH2Cl2 solution (15 ml) of
1Co (300 mg, 0.277 mmol) was added Na2SO4 (ca. 0.5 g)
and benzoylacetonitrile (83 mg, 0.59 mmol) and the
resultant mixture was stirred for 1 h at ambient
temperature. Filtration of the mixture through a Celite
plug, concentration of the filtrate and crystallization
from CH2Cl2 /hexane at /30 8C gave 3aCo (192 mg,
0.144 mmol, 52% yield) as purple crystals. IR 2536
cm 1 (nBH), 2187 cm1 (nCN), 1600, 1585 cm 1 (nCC).
Anal. Calc. for C72H104N14O2B2Co2: C, 64.67; H, 7.84;
N, 14.66. Found: C, 64.57; H, 7.94; N, 14.37%.
The other products were obtained following essen-
tially the same procedure. Yields and IR data of the
products are shown in Tables 1 and 2, respectively. 3aCo:
purple crystals. 3aNi: green crystals. IR 2536 cm 1
(nBH), 2187 cm 1 (nCN), 1602, 1585 cm 1 (nCC). Anal.
2 2.4. Reaction of 3aNi with PhCHO to give 6
Abbreviations used in this paper: TpR, hydrotris(pyrazolyl)borato
ligands; TpiPr2, 3,5-diisopropylpyrazolyl derivative; TpMe2, 3,5-
dimethylpyrazolyl derivative; pz, pyrazolyl ring. The central metal is
indicated as the superscript of the compound number.
Calc. for C72H104N14O2B2Ni2: C, 64.69; H, 7.84; N,
14.67. Found: C, 64.77; H, 7.95; N, 14.52%. 3bCo: purple
crystals. Anal. Calc. for C60.2H94.4N16B2Cl0.4Co2 (3bCo ×/
(CH2Cl2)0.2): C, 60.46; H, 7.96; N, 18.74. Found: C,
60.37; H, 8.10; N, 18.83%. 3bNi: green crystals. Anal.
Calc. for C60H94N16B2Ni2: C, 61.15; H, 8.04; N, 19.02.
Found: C, 60.90; H, 8.17; N, 19.20%. 3dCo: green
crystals. Anal. Calc. for C70H114N12O4B2Co2: C, 63.35;
H, 8.66; N, 12.66. Found: C, 63.56; H, 8.90; N, 12.40%.
3dNi: purple crystals. Anal. Calc. for
C70H114N12O4B2Ni2: C, 63.37; H, 8.66; N, 12.67.
Found: C, 62.82; H, 8.31; N, 12.38%. 3eCo: purple
crystals. Anal. Calc. for C32H53N6O3BCo: C, 60.10; H,
8.35; N, 13.14. Found: C, 60.29; H, 8.54; N, 13.25%.
3eNi: green crystals. Anal. Calc. for C32H53N6O3BNi: C,
60.12; H, 8.36; N, 13.15. Found: C, 59.91; H, 8.45; N,
12.98%. 3fCo: purple crystals. Anal. Calc. for
C32H53N6O4BCo: C, 58.63; H, 8.15; N, 12.82. Found:
C, 58.20; H, 8.24; N, 13.05%. 3fNi: green crystals. Anal.
Calc. for C32.1H53.2N6O4BCl0.2Ni (3fNi ×/(CH2Cl2)0.1): C,
58.08; H, 8.08; N, 12.66. Found: C, 57.78; H, 7.95; N,
12.76%. 4cCo: purple crystals. Anal. Calc. for
C30.6H49.4N7O2BCo (4cCo ×/hexane0.1): C, 59.56; H,
8.07; N, 15.89. Found: C, 59.89; H, 7.83; N, 15.76%.
4cNi: green crystals. Anal. Calc. for C30H48N7O2BNi: C,
59.24; H, 7.95; N, 16.12. Found: C, 59.44; H, 8.04; N,
15.70%.
The pyridine adduct of 3bNi (3bNi-2py) was obtained
by the dehydrative condensation (100 mg Na2SO4 in 15
ml CH2Cl2) between 1Ni (139 mg, 0.128 mmol) and
CH2(CN)2 (17 mg, 0.26 mmol) in the presence of
pyridine (25 ml, 0.31 mmol). 3bNi (63% yield): pale
blue crystals. IR 2534 cm 1 (nBH), 2204, 2153 cm 1
(nCN), 1602, 1577 cm1 (nCN(py)). 3dCo-2py was pre-
pared by similar procedure. 3bCo (70% yield): orange
crystals. IR 2535 cm 1 (nBH), 2201, 2147 cm 1 (nCN),
1600, 1576 cm1 (nCN(py)). Because the coordinated
pyridine molecules were lost upon drying under reduced
pressure as judged by the color change, analytically pure
samples of 3bNi,Co-2py could not be obtained.
2.3. Reaction of 3aCo with PhCHO to give 5
A THF solution (10 ml) of 3aCo (146 mg, 0.109 mmol)
and PhCHO (45 ml, 0.44 mmol) was stirred for 3 h at
ambient temperature. Concentration followed by crys-
tallization from THF /hexane gave 5 (115 mg, 0.081
mmol, 74% yield) as brown solid. IR 2534 cm 1 (nBH),
2188, 2150 cm 1 (nCN), 1583 cm 1 (nCC: Ph). Anal.
Calc. for C79H108N14O2B2Co2: C, 66.57; H, 7.64; N,
13.76. Found: C, 66.62; H, 7.63; N, 13.19%.
A THF solution (10 ml) of 3aCo (69 mg, 0.052 mmol)
and PhCHO (21 ml, 0.21 mmol) was stirred for 3 h at
 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174 165

Table 1
Crystallographic data

Compound 3bCo-2py×/ 3eCo-MeCN×/ 3fNi ×/hexane0.5 4cNi ×/(CH2Cl2)0.5 5-2MeCN (MeCN)4

(CH2Cl2)4 (MeCN)2

Empirical formula C74H112N18B2Cl8Co2 C38H62N9O3Bco C35H60N6O4BNi C30.25H49.5N7O2BC- C91H126N20O2B2Co2

l0.5Ni
Formula weight 1676.90 762.71 698.41 630.51 1671.60
Crystal system monoclinic monoclinic triclinic triclinic triclinic
Space group P 21/n P 21/n /P1 /P1 /P1

Unit cell dimensions

a (Å) 14.3298(4) 15.1255(5) 12.093(3) 16.6651(2) 20.748(2)
b (Å) 24.5282(7) 15.9014(5) 17.380(5) 18.7154(3) 20.890(1)
c (Å) 12.8399(4) 18.4613(4) 9.648(2) 13.3755(1) 11.6670(9)
a (8) 104.418(7) 95.518(1) 98.549(4)
b (8) 90.279(1) 92.046(1) 94.52(2) 110.333(2) 100.389(2)
g (8) 84.09(1) 110.830(1) 100.891(7)
V (Å3) 4513.0(2) 4437.4(2) 1950.4(8) 3539.35(8) 4796.1(6)
Z 2 4 2 4 2
Dcalc (g cm 3) 1.234 1.142 1.189 1.183 1.157
Absorption coefficient (mm1) 0.653 0.430 0.540 0.621 0.401
2umax (8) 54.96 54.96 54.96 54.94 54.96
Parameters 485 486 423 773 1076
R1 (for data with [I /2s (I )]) 0.0648 (for 5473 0.0443 (for 8116 0.0722 (for 4593 0.0770 (for 7478 0.0683 (for 12638 data)
data) data) data) data)
wR2 0.1806 (for all 0.1354 (for all 9874 0.2081 (for all 7174 0.2023 (for all 14497 0.1835 (for all 18296
10230 data) data) data) data) data)

ambient temperature. Concentration followed by crys-
tallization from THF/hexane gave 6 (37 mg, 0.041
mmol, 78% yield) as green solid. IR 3347 cm 1 (nNH),
2540 cm 1 (nBH), 2210 cm 1 (nCN), 1640, 1610 cm 1
(nCN(or O)), 1577 cm 1 (nCC: Ph). Anal. Calc. for
C52H63N8O2BNi: C, 69.27; H, 7.04; N, 12.43. Found: C,
69.23; H, 7.29; N, 12.27%.
2.5. X-ray crystallography
Crystallographic data and results of structure refine-
ments are summarized in Table 1. Single crystals of
3bCo-2py (CH2Cl2 /hexane), 3eCo-MeCN (MeCN), 3fNi
(CH2Cl2 /hexane), 4cNi (CH2Cl2 /hexane), and 5-
2MeCN (MeCN) were obtained by recrystallization
from the solvent systems shown in the parentheses and
mounted on glass fibers.
Diffraction measurements were made on an Rigaku
RAXIS IV imaging plate area detector with Mo Ka
radiation (l
/0.71069 Å) at /60 8C. The crystal to
detector distance was 110 mm (2umax
/558). Indexing
was performed from two oscillation images, which were
exposed for 5 min. The detector swing angle, the number
of oscillation images, and the exposed time were as
follows: 3bCo-2py: 3.08/60/12.5 min per degree; 3eCo-
MeCN: 4.08/45/7 min per degree; 3fNi: 5.08/36/13.7 min
per degree; 4cNi: 5.08/36/8 min per degree; 5-2MeCN:
5.08/36/11.5 min per degree. Readout was performed
with the pixel size of 100 mm /100 mm. In the reduction
of data, Lorentz and polarization corrections and
empirical absorption corrections were made [6].
The structural analysis was performed on an IRIS O2
computer using the TEXSAN structure solving program
system obtained from the Rigaku Corp., Tokyo, Japan
[7]. Neutral scattering factors were obtained from the
standard source [8].
The structures were solved by a combination of the
direct methods (SHELXS-86 [9] or SIR92 [10]) and Fourier
synthesis (DIRDIF94 [11]). Least-squares refinements
were carried out using SHELXL-97 [9] (refined on F2)
linked to TEXSAN. Unless otherwise stated, all the non-
hydrogen atoms were refined anisotropically, riding
refinements were applied to the methyl hydrogen atoms
[B(H)/B(C)], and the other hydrogen atoms were fixed
at the calculated positions. Details of the refinements
were as follows. 3fNi: The hexane solvate was refined
isotropically and hydrogen atoms attached to the
hexane molecule were not included in the refinement.
4cNi: During the refinement, a part of the nitrile groups
was found to be disordered and refined isotropically
taking into account two components (C3A /N3A:C3C /
N3C
/0.59:0.41) and hydrogen atoms attached to the
disordered atoms were not included in the refinement. 5-
2MeCN: One of the MeCN solvates was found to be
disordered and refined taking into account two compo-
nents (C77,78:C79,60
/0.5:0.5) with isotropic thermal
parameters. Hydrogen atoms attached to C78 and C80
were not included in the refinement.
166 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174
Table 2
Interaction of hydroxo complexes 1 with active methylene compounds
2
a
pKa values in DMSO [12].
b
Determined by X-ray crystallography.
3. Results and discussion
3.1. Dehydrative condensation of hydroxometal
complexes 1 with active methylene compounds 2 leading to
enolato complexes 3
Treatment of the hydroxo-cobalt and -nickel com-
plexes, (TpiPr2M)2(m-OH)2 (1) [M
/Co (1Co), Ni (1Ni)]
[5],2 with active methylene compounds, CH2XY (2a, 2b,
and 2d /2f) (X,Y
/CN, COR), in CH2Cl2 in the
presence of a drying agent (e.g. Na2SO4) readily
afforded the condensates (3a, 3b, and 3d/3f) as green
(3Ni) or purple crystals (3Co)2 after filtration of the
drying agent followed by crystallization from CH2Cl2 /
hexane. Reaction with methyl cyanoacetate (2c) did not
result in the condensation but ester hydrolysis to give
the k2-carboxylato complex 4c. The results are summar-
ized in Table 2. Although we also attempted reaction
with CH3COR (R
/CH3, Ph) and CH3CN, no con-
densation occurred indicating that the acidic C /H
functional group with pKa, at least, B/15.9 (for pKa
values, see [12]) is crucial for the condensation with 1.
IR data of products 3a, 3b and 3d /3f, and 4c are
summarized in Table 3 and compared with those of the
corresponding active methylene compounds 2. In every
case, the B /H vibration of the TpiPr2 ligand is observed
in the range above 2500 cm 1 suggesting its k3-
coordination to the metal center [13]. Judging from the
color of the products, they should be five-coordinate
square-pyramidal species rather than four-coordinate
tetrahedral species, which are usually pink (Ni) and blue
(Co). These data indicate that the enolato ligands
(CHXY) are coordinated as bidentate ligands.
Although the structure of the product is dependent on
the structure of the active methylene compound, lower
energy shift of the C /N and/or C /O vibrations clearly
indicates the formation of enolato complexes 3, where
the negative charge is delocalized over the five-mem-
bered linear or cyclic p-conjugated linkage. In contrast
to the substantial lower energy shift of the C /O
vibration (Dn /85 cm 1; nCO vibration for 3a and 3d
could not be located), the extent of the shift of the C /N
vibration is much smaller (Dn /60 cm 1). This is
because the electron density is localized more on the
more electronegative oxygen atom, causing an increase
of single-bond character of the C /O moiety. A couple of
structures as shown in Chart 1 are possible for the
enolato complexes derived from cyano compounds (3a
and 3b) and dimedone (3d), and these structures might
be discriminated by careful examination of the IR data.
The lower energy shift of the vibrations of the X and Y
functional groups discussed above eliminates the C-
bound structure (B), because significant delocalization
of the electrons of the M /C s-bond over the X and Y
moiety is not feasible for such a type of structures.
Discrimination of the other two structures (a mono-
meric structure containing the k1-enolato ligand (A) and
a dimeric cyclic structure containing the m-k1:k1-enolato
ligand (C)), however, is not always possible by the IR
data alone. For example, the monomeric N-bound
enolato-palladium complex, (TpiPr2)(py)Pd-(k1-
NCCHCN), previously reported by us [3] showed the
nCN vibrations (2189, 2110 cm 1) in the same region as
those for 3b (Table 3). Taking into account (1) the N- or
O-coordination (not C-coordination) of the CHXY
moiety, (2) the color of the complexes (solid sample3)
3
Thermochromism suggesting dissociation of the dimeric structure
was observed for 3a and 3d. The color of CH2Cl2 solutions of 3Ni
(green) and 3Co (purple) turned into orange (3?Ni) and blue (3?Co),
respectively, upon warming from a low temperature to room
temperature. The color of 3? is typical for monomeric tetrahedral
species with an A-type coordination mode.
 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174 167

Table 3
IR data for 2 /4 a

Complex X Y nBH nCN n C/O

2a CN COPh / 2254 1689

3aNi 2536 2187 n.d. b
3aCo 2537 2186 n.d.
2b CN CN / 2272 /
3bNi 2541 2212, 2152 /
3bCo 2540 2208, 2130 /
2c CN COOMe / 2260 1751
4cNi 2534 2285 1607
4cCo 2538 2282 1599
2d dimedone / / 1620 c
3dNi 2536 / n.d.
3dCo 2534 / n.d.
2e COOMe COMe / / 1748, 1718
3eNi 2534 / 1621
3eCo 2534 / 1618
2f COOMe COOMe / / 1740
3fNi 2535 / 1634
3fCo 2534 / 1655
a
Observed as KBr pellets (3, 4) and liquid films (2).
b
Not detected.
c
Intense broad signals were observed due to extensive enolization.

[2].2 Although analytically pure samples could not be

Chart 1.
peculiar to five-coordination, and (3) a mononuclear
cyclic M(acac)-type structure being not feasible for the
cyano compounds with the linear C /C /N linkage (2a/
2c) and dimedone (2d), it is concluded that complexes
derived from the cyano compounds and dimedone (3a,
3b and 3d) adopt a C-type dimeric structure, which has
been confirmed for 3b and 3bCo-2py by X-ray crystal-
lography (see below). Monomeric chelated M(acac)-type
structure (3e and 3f) results from 1,3-diketone with a
flexible skeleton.
The reaction of methyl cyanoacetate 2c was the
exception, where ester hydrolysis was observed. The
nCN vibration (2285 cm1 (4cNi), 2282 cm 1 (4cCo)),
which appears in considerably higher energy region
compared with 3a and 3b (B/2212 cm 1) and is
comparable to (or even higher than) free nitrile (2260
cm 1), suggests the presence of non-deprotonated
nitrile, i.e. the NCCH2 moiety is retained in 4c. The
structure is finally determined for 4cNi by X-ray crystal-
lography (see below).
We also attempted reactions of the TpMe2 derivatives,
(TpMe2M)2(m-OH)2, bearing a less bulky TpMe2 ligand
obtained, IR data (e.g. 3aCo(TpMe2): 2507, 2155 cm 1;
3aNi(TpMe2): 2508, 2174 cm 1; 3bCo(TpMe2): 2510, 2210,
2150 cm 1; 3bNi(TpMe2): 2515, 2213, 2155 cm 1) were
very similar to those of the TpiPr2 derivatives 3a and 3b
(Table 3) suggesting formation of similar enolato
complexes with dimeric cyclic structures. It is notable
that no isomerization to the C-bound isomer, [TpMe2M /
CHXY]n , was observed. This behavior is in contrast to
that of enolato-palladium complexes with the TpMe2
ligand; the N/O-bound isomer of the TpMe2Pd com-
plexes is gradually converted to the C-bound isomer [3].
In both the Co/Ni and Pd systems, no N/O-to-C-
isomerization is observed for the TpiPr2 derivatives,
presumably because the C-bound isomer having an
M /C (secondary) bond suffers steric hindrance with
the TpiPr2M moiety more severely than the N/O-bound
isomer does.
Thus, dehydrative condensation between 1 and active
methylene compounds gives three types of products
irrespective of the central metals (Co/Ni): monomeric
(3e and 3f), dimeric N/O-bound enolato complexes (3a,
3b, and 3d), and carboxylato complex (4c).
3.2. X-ray structure determination of 3bNi,Co, 3bCo-2py,
3eCo-MeCN, 3fNi, and 4cNi
Molecular structures of 3bNi,Co, 3bCo-2py, 3eCo-
MeCN, 3fNi, and 4cNi were determined by X-ray
crystallography. Because structural analyses of 3bNi,Co
did not provide us with satisfactory results with a low
convergence,4 the pyridine adduct of 3bCo (3bCo-2py),
168 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174

MeCN, 3fNi) and Fig. 2 (4cNi), and selected structural

Scheme 1.
which was prepared via the dehydrative condensation in
the presence of pyridine (Scheme 1), was subjected to
crystallographic analysis. Crystallization of 3eCo from
acetonitrile afforded the MeCN-adduct (3eCo-MeCN).
Co Co
ORTEP drawings are shown in Fig. 1 (3b -2py, 3e -
parameters are shown in Table 4 and Chart 2.
In all complexes, the TpiPr2 ligand is coordinated to
the central metal in a symmetrical k3-fashion as was
suggested by the nBH signals (see above). The coordina-
tion geometries of the central metals are five- (3bNi,Co,
3fNi, 4cNi) and six-coordinate ones (3bCo-2py, 3eCo-
MeCN, 4c?Ni (see below)) depending on the absence/
presence of the additional donor (py, MeCN).
Complex 3bCo-2py derived from dicyanomethane 2b
contains a C-type 12-membered ring (Chart 1) resulting
from dimerization of the enolato skeleton. Coordination
of the pyridine ligand does not cause any significant
structural change when compared with the non-coordi-

Fig. 1. Molecular structures of 3b-2py, 3eCo-MeCN and 3fNi drawn with thermal ellipsoids at the 30% probability level.
 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174
Fig. 2. Molecular structures of 4cNi and 4c?Ni drawn with thermal ellipsoids at the 30% probability level.
nated form 3bCo.4 The octahedral coordination geome-
try of 3bCo-2py is essentially mirror-symmetrical with
the Co /N distances within the very narrow range
(2.128/2.190 Å). The bridging CH(CN)2 moiety is also
symmetrical as indicated by the very similar C /N and
C /C distances (Chart 2), which are between the
corresponding single and double-bond lengths as is
consistent with the delocalized structure. Despite the
symmetrical structures of the components, the coordi-
4
Cell parameters: for 3bCo ×/CH2Cl2: a
/22.707(2) Å, b
/18.677(2)
Å, c
/9.4680(4), b
/90.007(4)8, V
/4015.3(5), monoclinic, space
group P 21/n ; for 3bNi ×/CH2Cl2: a
/22.682(2) Å, b
/18.642(2) Å, c
/
9.4863(8) Å, b
/89.632(4)8, V
/4011.1(5), monoclinic, space group
P 21/n . The present R values for the two complexes are approximately
0.20. Selected bond lengths (in Å) for 3bCo: Co1/N1: 2.11(2), Co1/
N2: 2.05(2), N1 /C1: 1.11(3), C1/C2: 1.38(3), C2/C3: 1.40(3), C3/N2:
1.12(3). Structural parameters for 3bNi are essentially the same as those
of 3bCo.
169
nation behavior of the two CN moieties is slightly
different. The C1 /N1 moiety is coordinated to the Co1
center in the virtually linear fashion with the Co /N /C
angle of 173.7(3)8, whereas the bent coordination is
observed for the other CN group (159.5(3)8). The
bending could be interpreted in terms of the contribu-
tion of the ketene-imine-type structure D, which involves
the sp2-hybridized imino nitrogen atom (Chart 2). The
presence of these two types of CN coordination modes is
also suggested by the two nCN vibrations (Table 2).
Analogous dinuclear LM(m-NC /C(R) /CN)2ML-type
complexes (e.g. ML/R
/(k4-triethylenetetramine)Ni/
CN) [14] are known and similar structural features are
noted.
The monomeric chelated species 3eCo-MeCN and 3fNi
adopt an octahedral six-coordinate structure and a
square-pyramidal five-coordinate structure, respectively.
The C /O and C /C lengths in the chelate rings (Plate 2)
are between the corresponding single- and double-bond
170 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174

Table 4
Selected structural parameters for the TpiPr2M parts of 3 and 4c a

Compound 3bCo-2py 3eCo-MeCN 3fNi 4cNi b

4c?Ni b

M/N11 2.154(3) 2.126(1) 2.101(4) 2.004(5) 2.028(4)

M/N21 2.156(3) 2.132(1) 2.112(3) 2.017(4) 2.028(5)
M/N31 2.151(3) 2.138(1) 2.069(3) 2.009(4) 2.088(4)
M/N41 (L) 2.190(3) (py) 2.204(2) (py) / / 2.232(5) (N1*)
N/M/N (TpiPr2) 85.7 /88.4(1) 86.12 /87.99(5) 85.0 /91.3(1) 90.4 /92.2(2) 87.8 /93.8(2)
X/M/Y 84.5(1) 87.32(5) 87.2(1) 61.2(2) 61.5(2)
(X, Y) (N1, N2) (O1, O2) (O1, O2) (O1, O2) (O1, O2)
X,Y/M/N(pz) cis 89.7 /95.7(1) 91.74 /94.47(5) 91.3 /104.1(1) 99.4 /112.1(2) 99.6 /103.2(2)
X/M/N(pz) trans 179.4(1) 179.63(5) 164.8(1) 151.3(1) 164.0(2)
Y/M/N(pz) trans 175.7(1) 177.73(5) 166.3(1) 160.7(1) 160.5(1)
a
See also Charts 2 and 3.
b
See text.

lengths as is usually observed for M(acac)-type com-
plexes. The dimethyl malonato complex 3fNi is virtually
mirror-symmetrical, whereas coordination of the methyl
acetoacetato ligand in 3eCo-MeCN is slightly unsymme-
trical owing to the E-type resonance contributor (Chart
2) resulting from electron donation from the ester
oxygen atom. The structural features of 3eCo-MeCN
and 3fNi are typical and very similar to the previous
examples [15].
A unit cell of the carboxylato complex obtained from
methyl cyanoacetate 2c contains two independent mo-
lecules (Fig. 2). It is notable that one of the two
molecules is the monomeric carboxylato species 4cNi
(A-series), where the cyano group is left uncoordinated,
but the other is the dimeric cyclic species 4c?Ni (B-series).
No significant difference is observed for the structural
parameters for the core parts of 4cNi and 4c?Ni as can be
seen from Chart 3. The bond lengths and angles
associated with C2 clearly indicate that the C2 atom is
sp3-hybridized; in other words, the methylene unit in 2c
is not deprotonated (cf. the enolato complexes 3
discussed above). Instead, the ester group is hydrolyzed
to form the k2-carboxylato functional group. The
association /dissociation process of 4c /4c? should be
such a low-energy process comparable to crystal packing
effects that the two isomeric forms should result in a
single crystal.
3.3. Factors determining the structures of the products
Reaction of the hydroxo complex 1 with active
methylene compounds 2 results in dehydrative conden-
sation leading to the monomeric or dimeric enolato
complexes 3b and 3d/3f or ester hydrolysis to give the
carboxylato complex 4c as discussed above. The reac-

Chart 2.
 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174
Chart 3.
tion courses could be correlated with the structure and
physical properties of 2.
The action of 1 on methyl cyanoacetate 2c results in
ester hydrolysis rather than deprotonation from the CH2
moiety as observed for the other cyano compounds 2a
and 2b. The reason for the difference could be ascribed
to the least acidic nature of 2c of the three cyano
compounds 2a /2c examined, i.e., 2c is more resistant to
deprotonation than 2a and 2b and therefore undergoes
ester hydrolysis, although the difference in the pKa
values (Table 2 [12]) is not so large. On the other hand,
of the three ester compounds (X /CH2 /COOMe 2c, 2e
and 2f) only the cyano derivative 2c results in ester
hydrolysis, although the pKa value of the acidic hydro-
gen atom in 2c is the smallest of them, i.e., most acidic.
This dichotomy might be attributed to the structure of
the active methylene compounds. It is known that a part
of 1,3-diketone compounds like 2e and 2f adopts a cyclic
hydrogen-bonded enol form, which may be more acidic
than the corresponding keto form [16]. So, 1,3-diketones
2e and 2f could be susceptible to deprotonation more
readily than 2c. But this interpretation is not correct,
because the enol content increases in the following order
which cannot explain the unusual reactivity of 2c:2f
(7.7 /103%:the value for the ethyl ester) B/2c (2.5 /
101%) B/2e (8.4%) [16].
Thus, no direct relationship between different reactiv-
ity of the ester compounds (2c, 2e and 2f) and their
physical properties is established and then we conclude
that the reaction pathway may be determined by
thermodynamic stability of the reaction product. In
the case of the flexible substrates 2e and 2f, formation of
the six-membered 1,3-diketonato chelate should be
favorable in terms of energetics as well as entropy.
Meanwhile, as for the reaction with 2c, when the
carboxylato structure 4c and the enolato structure
171
resulting from deprotonation (like 3a) are compared,
the former structure should be favorable owing to the
following reasons. (1) In 4, the negative charge is
delocalized over the carboxylato group with the three-
atom system, whereas in the enolato structure the
negative charge is delocalized over the p-system spread-
ing over five atoms. The hard TpiPr2M fragment (M
/
Co, Ni) would prefer interaction with the former system,
where the negative charge is less widely delocalized, in
other words, a harder anion. (2) The positively charged
metal center and the anionic moiety are much closer in 4
than in the 3a-type enolato structure. The electrostatic
charge neutralization should be more effective in the
former system with a shorter separation of the cationic
and anionic charge. Deprotonation of 2c may occur as a
pre-equilibrium process in the case of 2c, too, but the
carboxylato complex 4c resulting from ester hydrolysis
should be a thermodynamic sink of the reaction system
owing to the reasons just mentioned above and, there-
fore, should be detected as the isolable species instead of
the deprotonated species. The ester hydrolysis should
follow nucleophilic addition of the OH group in 1 at the
ester carbon atom in 2c accompanied by the elimination
of methanol. Similar hydrolytic reactions by transition
metal hydroxo complexes (see, e.g., [17]) have been
studied as models for esterases.
3.4. Reaction of 3aCo with PhCHO
As a preliminary study on the reactivity of the
obtained enolato complexes, 3a was subjected to reac-
tion with benzaldehyde. Treatment of 3aCo with PhCHO
at ambient temperature in THF afforded the brown
product 5 (Scheme 2). An IR spectrum of 5 suggested
the presence of two types of CN groups and a phenyl
group, and an FD-MS spectrum revealed a dinuclear
structure (m /z 1425
/3aCo/PhCHO/H2O). The struc-
ture of the MeCN-adduct (5-2MeCN) obtained by
recrystallization from MeCN was determined unequi-
vocally by X-ray crystallography as shown in Fig. 3 and
Table 5.
The key structural features of 5-2MeCN are (1) the
eight-membered metallacyclic structure with the virtual
mirror-symmetry and puckered conformation and (2)
the zwitterionic structure with the negative charge on
the metallacycle and the positive charge on the CN-
coordinated cobalt center (Co2).
The nickel derivative 3aNi was also completely con-
sumed upon treatment with PhCHO to give the green
product (Scheme 2). An FD-MS analysis of 6 (m /z
/
901) reveals an ion peak corresponding to a protonated
form of the metallacyclic part (5(M
/Ni)/TpiPr2Co/
1(H)). Taking into account the NH vibration (3347
cm 1) and the single CN vibration, the green product
has been tentatively assigned to a metallacyclic structure
6 analogous to 5. Although the structure of 6 could not
172 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174

Scheme 2.

be verified owing to the failure in getting a single crystal,
the FD-MS data clearly indicates the formation of a
mononuclear metallacycle resulting from double con-
densation of PhCHO with two enolato groups.
A possible formation mechanism of 5 and 6 is
delineated in Scheme 3. Nucleophilic addition of the
enolato moiety in 3a at benzaldehyde should form the
aldolate intermediate F as usually observed for aldol
condensation [18] (see also [16]). Subsequent proton
migration is promoted by the formation of a new
enolate structure G. Formation of the delocalized
system G should be the driving force of the proton
migration. Migration of the OH group to the cobalt
center leads to H, which contains the enone structure as
well as the hydroxometal moiety. The coordinated
enone in H should be susceptible to Michael addition
by the remaining enolate moiety to give the adduct I,
which is converted to 5 via dehydration followed by
switching of coordination of the resulting polyfunctional
ligand. Complex 6 should be formed by protonolysis of
intermediate I.
4. Conclusions
Reaction between the hydroxo complex 1 and active
methylene compounds 2 affords the monomeric (3e and
3f) and dimeric N/O-bound enolato complexes (3a, 3b,
and 3d) except for methyl cyanoacetate 2c, which is
converted to the k2-carboxylato complex 4c via hydro-
lysis of the ester functional group. It is notable that no
C-bound enolato complex, TpRM-CHXY, analogous to

Fig. 3. Molecular structure of 5-2MeCN drawn with thermal ellipsoids at the 30% probability level.
 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174 173

Table 5 the tetrahedral hydrocarbyl complexes, TpRM-hydro-

Selected structural parameters for 5-2MeCN a carbyl [4], has been detected at all; the hard TpRM
Bond lengths
moiety (M
/Co, Ni) prefers interaction at the hard N/
Co1/O1 1.982(3) N1 /C6 1.148(6) O-atom rather than with the C-atom. Although the
Co1/O2 2.033(2) N2 /C7 1.149(5) direct relationship between the reaction pathways (en-
Co1/N11 2.084(3) N3 /C26 1.133(5) olato formation (3) vs. ester hydrolysis (4)) and the
Co1/N21 2.201(2) N4 /C28 1.133(5) structure and physicochemical properties of 2 cannot be
Co1/N31 2.064(3) C1/C2 1.371(5)
Co2/N2 2.092(3) C1/C8 1.508(5)
established, it is revealed that the reaction pathway is a
Co2/N3 2.159(3) C2/C3 1.532(5) combined result of a variety of factors including the
Co2/N4 2.200(3) C2/C6 1.427(5) acidity (pKa value) of the CH moiety in 2, rigidity of the
Co2/N41 2.131(3) C3/C4 1.518(4) enolato skeleton, and relative thermodynamic stability
Co2/N51 2.142(3) C3/C14 1.535(5) of the structures of possible products.
Co2/N61 2.135(3) C4/C5 1.397(5)
O1/C1 1.297(4) C4/C7 1.407(5)
Thus this work provides an additional example which
O2/C5 1.285(4) C5/C20 1.501(4) displays the effectiveness of the synthetic approach via
Bond angles
the dehydrative condensation with hydroxo complexes
O1/Co1/O2 96.93(9) C3/C4/C5 121.1(3) [1,3,4a]. The obtained enolato-Co/Ni complexes 3a are
O/Co1/N b 89.7 / C3/C4/C7 117.2(3) found to be nucleophilic enough toward benzaldehyde
102.6(1) to give the metallacyclic adducts 5 and 6 resulting from
O1/Co1/N11 162.6(1) C5/C4/C7 120.9(2) double condensation. Reactivity of the enolato com-
O2/Co1/N21 171.0(1) O2/C5/C4 122.5(2)
N/Co1/ 81.7 /92.3(1) O2/C5/C20 114.6(3)
plexes 3 toward various electrophiles is now under study
N(TpiPr2) b and results will be reported in due course.
Co1/O1/C1 140.1(2) C4/C5/C20 122.9(3)
Co1/O2/C5 143.4(2) N1 /C6/C2 177.6(4)
O1/C1/C2 125.1(3) N2 /C7/C4 176.9(3)
O1/C1/C8 113.5(3) C1/C8/C9 120.0(3) 5. Supplementary materials
C2/C1/C8 121.4(3) C1/C8/C13 121.6(3)
C1/C2/C3 121.9(3) C9/C8/C13 118.3(4)
C1/C2/C6 120.5(3) N/Co2/N b 83.7 /
Crystallographic data (positional, thermal and struc-
94.1(1) tural parameters) are available from the authors upon
C3/C2/C6 117.6(3) N/Co2/ 86.6 / request.
N(TpiPr2) b 88.4(1)
C2/C3/C4 111.1(3) Co2/N2/C7 167.0(2)
C2/C3/C14 113.7(3) Co2/N3/C26 168.8(3)
C4/C3/C14 115.2(3) Co2/N4/C28 169.0(3) Acknowledgements
a
Bond lengths in Å and bond angles in 8.
b
Values for cis -arranged ligands. We are grateful to the Ministry of Education, Culture,
Sports Science and Technology of the Japanese Govern-

Scheme 3.
174 M. Kujime et al. / Inorganica Chimica Acta 350 (2003) 163 /174
ment for financial support of this research (Grant-in-Aid
for Scientific Research No. 11228201).
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