Fast propene dimerization using upper rim-diphosphinated calix[4]arenes as chelators

Article abstract of DOI:10.1002/adsc.200505410

The complexes [NiBr₂·1] and [NiBr₂· ₂], containing the upper rim-diphosphinated calixarenes 5,17-bis(diphenylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene (1) and 5,17-dibromo-11,23-bis(diphe-nylphosphino)-25,26,27,28-tetrapropoxycalix[4] arene (2) were assessed as propene dimerization catalysts. Combined with methylaluminoxane, both complexes result in highly efficient dimerization catalysts displaying C₆ selectivities in the range 80-97% and activities that compare with the best reported systems, the latter using PCy₃ as ligand. The origin of the remarkable activities of the calixarene derivatives may be the ability of the diphosphine to undergo a periodic bite angle increase that incidentally favors the insertion step. Calixarenes such as 1 or 2, which each incorporate two "stable" Ph₂PAr moieties, constitute interesting alternatives to the use PCy₃ in propene dimerization.

Full text of DOI:10.1002/adsc.200505410

FULL PAPERS
DOI: 10.1002/adsc.200505410
Fast Propene Dimerization Using Upper Rim-Diphosphinated
Calix[4]arenes as Chelators
a
a
a
a,
´
Manuel Lejeune, David Semeril, Catherine Jeunesse, Dominique Matt, *
Pierre Lutz,b Loïc Toupetc
Laboratoire de Chimie Inorganique Moleculaire, Universite Louis Pasteur, LC 3 CNRS-ULP, 1 rue Blaise Pascal,
F-67008 Strasbourg cedex, France
a
´
´
Fax: (þ33)-3-90-24-17-49, e-mail: dmatt@chimie.u-strasbg.fr
b
c
Institut Charles Sadron, UPR 22 CNRS, 6 rue Boussingault, F-67083 Strasbourg cedex, France
`
´
´
´
Groupe Matiere Condensee et Materiaux, UMR 6626, Universite de Rennes 1, Campus de Beaulieu,
F-35042, Rennes cedex, France
Received: October 18, 2005; Accepted: March 2, 2006
Abstract: The complexes [NiBr2 ·1] and [NiBr2 ·2], markable activities of the calixarene derivatives may
containing the upper rim-diphosphinated calixarenes be the ability of the diphosphine to undergo a period-
5,17-bis(diphenylphosphino)-25,26,27,28-tetrapropoxy- ic bite angle increase that incidentally favors the in-
calix[4]arene (1) and 5,17-dibromo-11,23-bis(diphe- sertion step. Calixarenes such as 1 or 2, which each in-
nylphosphino)-25,26,27,28-tetrapropoxycalix[4]arene
corporate two “stable” Ph2PAr moieties, constitute in-
(2) were assessed as propene dimerization catalysts. teresting alternatives to the use PCy3 in propene di-
Combined with methylaluminoxane, both complexes merization.
result in highly efficient dimerization catalysts dis-
playing C6 selectivities in the range 80–97% and ac-
tivities that compare with the best reported systems, Keywords: calixarenes; homogeneous catalysis; ligand
the latter using PCy3 as ligand. The origin of the re- design; nickel; P ligands; propene dimerization
Introduction
est activities. For example, on replacing PPh3 by PCy3,
the activity of Ni/AlEt2Cl systems is doubled, while
Propene dimerization is an industrial reaction produc- the 2,3-dimethylbutene/C6-olefins ratio increases from
ing valuable compounds which find applications as gas- 14.6% to 83.1%.
oline additives and as precursors to various pharmaceut-
As part of a program aimed at assessing the catalytic
icals, agricultural chemicals, perfumes and polymers.[1] properties of the distally, upper rim-diphosphinated cal-
All current applications involve nickel catalysis. In, for ix[4]arenes 1 and 2, we now report a study on their use in
example, the Dimersol process, which is based on a Ni/ the nickel-catalyzed dimerization of propene. In two
Al system in the absence of any ligand, the non-regiose- previous reports we have shown that nickel(II) com-
lective propene dimerization affords C6-olefins with a plexes containing these ligands constitute readily acces-
À
composition of 22% n-hexenes, 72% 2-methylpentenes, sible precursors to highly active catalysts for some C C
and 6% 2,3-dimethylbutenes.[2,3] The dimer selectivity is coupling reactions.[6,7] A major advantage of these cata-
80%, some trimers (18%) and tetramers (2%) also being lysts, when compared with other active systems, is that
formed. In contrast, regioselective dimerization occurs the diphosphines are considerably less basic (and ac-
in the Sumitomo Chemical process, where a nickel salt cordingly less sensitive) than those usually employed
is combined with tricyclohexylphosphine.[4] In this for reaching the same activities. In the present study,
case, 2,3-dimethylbutenes represent 85% of the dimers we also report the solid state structure of one of the pre-
formed, the dimer selectivity being 59%. In fact, as al- catalysts tested, namely the tetrahedral complex [NiBr2 ·
ready established by several studies, the product distri- 1]. It is worth mentioning that to date chelating diphos-
bution in propene dimerizations catalyzed by Ni-phos- phines have been very rarely employed in propene di-
phine complexes is strongly dependent upon the nature merization, most studies having focused on monophos-
of the phosphine used.[4,5] Thus, employing monophos- phine ligands.[8–11]
phines that are both basic and bulky results in the high-
Adv. Synth. Catal. 2006, 348, 881 – 886
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Manuel Lejeune et al.
FULL PAPERS
Table 1. Selected bond lengths [Š] and angles [8] for 3.
Results and Discussion
Distances
The two paramagnetic nickel(II) complexes used in this
study, 3 and 4, were prepared according to a method de-
scribed previously (Scheme 1).[6] The molecular struc-
ture of 3 was determined by a single crystal X-ray dif-
fraction study. Important bond lengths and angles are
given in Table 1. In the solid state (Figure 1), the nickel
atom is positioned to one side, at adistance of1.1 Š from
the calixarene axis and, in keeping with the paramagnet-
ic nature of this complex, adopts a tetrahedral geometry,
with PNiP and BrNiBr angles of 110.4(1)8 and
126.15(7)8, respectively. The latter two values are very
close to those found in [NiBr2(PPh3)2].[12]
À
À
Ni(1) P(1)
2.339(3)
1.819(9)
Ni(1) P(2)
2.322(3)
1.815(11)
1.804(10)
1.817(10)
3.36(1)
À
À
P(1) C(23)
P(2) C(47)
À
À
P(1) C(35)
1.842(10) P(2) C(11)
À
À
P(1) C(29)
1.847(10) P(2) C(41)
À
À
O(1) O(2)
5.66(1)
O(3) O(4)
Angles
À
À
À
À
P(1) Ni(1) P(2) 110.43(10) Br(1) Ni(1) Br(2) 126.15(7)
À
À
À
À
C(35) P(1) C(23) 105.3(5)
C(47) P(2) C(11) 104.1(5)
À
À
À
À
C(29) P(1) C(23) 102.1(5)
C(41) P(2) C(11) 106.7(5)
À
À
À
À
C(41) P(2) Ni
109.7(3)
C(35) P(1) Ni
119.7(4)
The calixarene unit adopts a flattened cone conforma-
tion; the interplanar angle between the phosphorus-
bearing phenol rings is 18.58, while that between the oth- cavity entrance, and there is no symmetry to the struc-
er two facing phenol rings is À1088. Apparently as a re- ture. Its asymmetry is best seen by comparing the two
À
À
À
À
sult of steric interactions with the calixarene framework, angles C(41) P(2) Ni, 109.78, and C(35) P(1) Ni,
the two phosphino groups do not occupy equivalent po- 119.78. Similar distortions were observed in other che-
sitions in the structure. Thus, a single phenyl ring fills the late complexes obtained from 2. The present study,
which constitutes the first X-ray structural determina-
tion on a tetrahedral chelate complex obtained from 1,
firmly establishes that diphosphine 1 may undergo im-
portant bite angle variations. In the previously reported
diamagnetic, square planar complexes with this and re-
lated diphosphines, smaller bite angles were observed,
all lying in the range 99.78–103.38. It should be men-
tioned here that the latter complexes are dynamic in sol-
ution, the PMP plane undergoing a fast fanning motion
which shifts the metal from one side of the calixarene
axis to the other, the bite angle increasing by about 208
during this motion, as inferred from molecular mechan-
ics calculations. This motion is compatible with the in-
trinsic flexibility of the calix[4]arene core.[13,14] Given
the bite angle in the tetrahedral complex 3, 110.48, it ap -
Scheme 1.
pears very likely that a similar motion may occur for this
complex in solution, although we have no formal proof
for this assumption.
The complexes 3 and 4 were tested in propene dimeri-
zation under constant pressure using 400 equivs. methyl-
aluminoxane (MAO) as activator (Table 2 and Table 3).
Addition of MAO was accompanied by an instant color
change (green to pale yellow), and no induction period
was observed once MAO had been added. It turned
out that operating in chlorobenzene afforded signifi-
cantly higher activities than with toluene (Table 2, en-
tries 1 and 2). Therefore, the runs were carried out sys-
tematically in this polar solvent.
Activity of the Catalysts
For both complexes, the turnover frequency increased
with the propene pressure in the range 1–5 bar, the
C6-selectivity considerably surpassing 80% in most ex-
periments. In a typical example, applying a propene
Figure 1. Molecular structure of complex 3.
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Fast Propene Dimerization
FULL PAPERS
Table 2. Propene dimerization using 3.[a]
Run
P(C3H6) V(solv.) Time Tinit Ni
TOF[b]/10À5 C6
[wgt %]
Product distribution [mol %][c]
4M1P 4M2P 2M1P 2M2P hex TMEN
[bar]
[mL]
[h]
[8C] [mmol]
1[d]
2
3
4
5
6
7
8
5
30
30
30
30
30
30
30
50
50
50
50
50
50
0.25
0.25
0.5
25
25
25
25
5
25
25
25
25
25
25
25
25
4.5
4.5
4.5
4.5
4.5
4.5
4.5
0.848
0.848
0.225
0.090
0.090
0.090
0.57
2.19
1.61
1.08
1.56
1.13
0.46
0.20
7.62
12.11
19.28
14.98
14.01
89.2
79.9
86.6
81.2
87.7
87.3
93.9
97.1
90.6
93.8
95.1
93.7
94.3
18.1
2.7
1.7
5.3
2.8
3.1
10.8
30.5
6.0
8.8
9.9
6.1
6.6
29.7
31.0
31.3
28.1
31.0
32.6
36.1
28.0
35.0
36.7
38.1
38.2
39.4
30.9
21.7
23.9
19.2
24.7
26.2
19.8
21.1
15.2
9.3
12.5
33.9
34.5
36.2
31.9
28.9
18.7
11.0
36.6
40.0
35.5
42.5
41.0
8.3 0.5
8.1 2.4
6.6 2.2
8.1 3.2
8.3 1.3
7.7 1.5
14.0 0.6
9.0 0.5
6.2 0.9
4.8 0.5
7.0 0.4
3.1 0.4
4.3 0.5
5
5
5
5
3
1
5
5
5
5
5
5
1
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.50
1
9[e, f]
10[f, g]
11[f, h]
12[h]
13[f, h]
9.2
9.7
8.3
[a]
PhCl, MAO 400 equivs./Ni (MAO amount: 89 mg), yield determined by GC calibrated on heptane.
mol (C3H6) molÀ1 (Ni) hÀ1
[b]
[c]
.
4M1P¼4-methyl-1-pentene, 4M2P¼4-methyl-2-pentene, 2M1P¼2-methyl-1-pentene, 2M2P¼2-methyl-2-pentene, hex¼
hexenes, TMEN¼2,3-dimethyl-2-butene.
[d]
[e]
[f]
Toluene.
MAO 2100 equivs./Ni (MAO amount: 89 mg).
For these experiments the results were averaged.
MAO 7900 equivs./Ni (MAO amount 89 mg).
[g]
[h]
MAO 19800 equivs./Ni (MAO amount: 89 mg).
Table 3. Propene dimerization using 4.[a]
Run P(C3H6) V(solv.) Time Tinit Ni
TOF[b]/10À5 C6
[wgt %]
Product distribution [mol %][c]
[bar]
[mL]
[h]
[8C] [mmo])
4M1P 4M2P 2M1P 2M2P hex TMEN
1
2
3
4
5
5
5
5
5
5
3
1
5
5
5
30
30
30
30
30
30
30
50
50
50
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.25
0.50
1
25
15
5
-5
-15
5
4.5
4.5
4.5
4.5
4.5
4.5
4.5
0.09
0.09
0.09
2.37
2.63
2.59
0.98
0.36
1.20
0.80
25.99
17.82
13.49
86.5
84.8
90.7
94.8
96.8
91.5
92.2
94.9
95.0
94.3
1.8
2.6
1.4
10.8
24.2
5.6
2.7
6.8
8.1
9.2
31.7
30.1
32.6
32.4
29.0
33.1
30.1
36.8
39.7
37.0
19.3
21.9
20.1
23.6
20.2
22.7
30.5
12.3
7.4
31.6
35.9
27.7
24.2
16.5
30.4
30.0
39.2
40.1
39.9
13.9 1.8
7.4 2.1
17.2 1.1
8.6 0.5
9.7 0.3
7.3 0.8
5.7 1.0
4.6 0.4
4.2 0.4
3.8 0.5
6
7
5
8d
9d
10d
25
25
25
9.5
[a]
PhCl, MAO 400 equivs./Ni (MAO amount: 89 mg), yield determined by GC calibrated on heptane.
mol (C3H6) molÀ1 (Ni) hÀ1
[b]
[c]
.
4M1P¼4-methyl-1-pentene, 4M2P¼4-methyl-2-pentene, 2M1P¼2-methyl-1-pentene, 2M2P¼2-methyl-2-pentene, hex¼
hexenes, TMEN¼2,3-dimethyl-2-butene.
[d]
MAO 19800 equivs./Ni (MAO amount: 89 mg); for these experiments the results were averaged.
pressure of 5 bar for 15 min to a solution of 4.5 mmol 4 in the latter, the C6-selectivity drops to 29.5% under the
30 mL PhCl at 258C, resulted in an activity of 2.4Â105 conditions defined above (Table 4, entry 5). Note that
mol (C3H6) molÀ1 (Ni) hÀ1 with a C6-selectivity of the TOF of the reactions carried out with 3 or 4 can be
86% (!) (Table 3, entry 1). This activity is ca. 2–3 times drastically increased by lowering the catalyst concentra-
higher than that for other arylphosphine complexes, e.g., tion. This is not surprising, since operating at a lower Ni/
[NiBr2(PPh3)2] or [NiBr2(dppe)] (dppe¼Ph2PCH2CH2 propene ratio results in a lower concentration of pro-
PPh2), when used under similar conditions (Table 4, en- duced dimers, which may compete with propene for co-
tries 1–3). For comparison, the activity of the fastest di- ordination and so hinder the dimerization reaction. For
merization catalyst reported to date, [NiCl2(PCy3)2], is example, when the reaction described above for 4 was
2.8Â105 mol (C3H6) molÀ1 (Ni) hÀ1. However, with repeated with a catalyst concentration of 0.09 mmol/
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Table 4. Propene dimerization using conventional nickel-phosphine complexes.[a]
Entry
Ni complex
Tinit [8C]
TOF[b]/10À5
C6 [wgt %]
Product distribution [mol %][c]
4M1P
4M2P
2M1P
2M2P
hex
TMEN
1
2
3
4
5
(dppe)NiBr2
(PPh3)2NiBr2[d]
(PPh3)2NiBr2[e]
(PPh3)2NiBr2
(PCy3)2NiCl2
25
25
25
25
25
1.15
0.80
0.72
0.09
2.82
87.0
91.9
86.0
95.8
29.5
2.2
7.9
11.1
17.6
1.3
35.8
29.3
29.0
29.7
53.0
14.8
31.5
35.1
23.7
27.6
41.0
20.5
13.1
14.0
13.3
5.0
1.2
0.8
0.8
0.4
3.2
10.0
10.9
14.6
1.6
[a]
PhCl 30 mL, P(C3H6)¼5 bar, reaction time¼0.25 h, amount of Ni complex¼4.5 mmol except for entry 4 (0.848 mmol),
MAO 400 equivs./Ni, yield determined by GC calibrated on heptane.
[b]
[c]
mol (C3H6) molÀ1 (Ni) hÀ1
.
4M1P¼4-methyl-1pentene, 4M2P¼4-methyl-2-pentene, 2M1P¼2-methyl-1-pentene, 2M2P¼2-methyl-2-pentene, hex¼
hexenes, TMEN¼2,3-dimethyl-2-butene.
[d]
[e]
Toluene 30 mL.
Using 0.848 mmol Ni and MAO 400 equivs./Ni, PhCl 50 mL.
50 mL, the activity increased to 26Â105 mol (C3H6)
molÀ1 (Ni) hÀ1 (Table 3, entry 8).
Interestingly, the activity of complex 4 is about 10–
20% higher than that of complex 3, whatever the catalyst
concentration (compare, e. g., Table 2, entry 11 and Ta-
ble 3, entry 8). This suggests that under the experimen-
tal conditions used the phenyl group Br atoms of ligand
2 may assist the catalytic process. The question whether
weak CH· · ·Br interactions may favor either the inser-
tion step in the [Ni(diphos)(propene)(propyl)]þ inter-
mediate or b-elimination at the end of the catalytic cycle
cannot be answered at this stage. Further investigations
such as, for example, substitution of the Br by F atoms,
are needed to fully understand this phenomenon.[15]
Finally, we observed that both catalysts remain active
after 1 h, whatever their concentration (Table 2 en-
tries 2–4 and 11–13, and Table 3, entries 8–10), the
C6-selectivity being practically the same as for short
time runs.
Product Distribution
The primary products as well as all isomerization prod-
ucts that were formed during propene dimerization are
shown in Scheme 2, together with the possible pathways
producing them.[16] The product distributions are shown
in the Tables 1 and 2. Both catalysts gave high methyl-
pentene (MP) selectivities, this feature being slightly
more pronounced at lower nickel concentrations. For
example, with catalyst 4 (P¼5 bar), MP selectivities
higher than 95% were reached using a catalyst concen-
tration of 0.09 mmol/50 mL PhCl (Table 3, entries 8–
10), vs. 85% at a nickel concentration of 4.5 mmol/
30 mL (Table 3, entry 1). As expected, higher tempera-
tures favor isomerization of the pentenes formed as pri-
mary products. This is best seen on examining the varia-
tion of the proportion of the 4M1P (Table 3, entries 1–
5). Isomerization also increases when raising the pro-
Scheme 2. Nickel-catalyzed propene dimerization. Organo-
metallic intermediates and products.
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Adv. Synth. Catal. 2006, 348, 881 – 886

Fast Propene Dimerization
FULL PAPERS
pene pressure. This is probably due to the exothermic other terms, the two reaction partners of the
nature of the reaction, so that with high reaction rates, [Ni(diphos)(propyl)(propene)]þ intermediate (in which
the temperature of the reaction medium increases. In- the metal center is assumed to adopt a planar geome-
terestingly, we found that with complex 3 the proportion try[15]) come closer together, hence favoring the inser-
of 4M1P, which is an a-olefin, may reach ca. 30% (Ta- tion step.
ble 2, entry 8), provided the temperature of the reaction
medium was maintained below 308C. Under similar
conditions [NiBr2(PPh3)]2 gave only 18% 4M1P (Ta-
ble 4, entry 4). The rather high proportion of 4M1P
Conclusion
could arise from a steric effect in the alkyl-Ni intermedi-
ate obtained according to path D (Scheme 2). Molecular
models indicate that there should be steric repulsions
between the calixarene backbone and the Ni-C6 chain
leading to preferential b-elimination at the b-CH3 rather
than the sec-butyl group.
Overall, the present work demonstrates that, in catalytic
propene dimerization, sensitive basic monophosphines
may efficiently be replaced by robust bis(triarylphos-
phines) built on a calixarene backbone. It also consti-
tutes a further confirmation[17–21] that chelate complexes
containing diphosphines with unusual bite angles may
The results presented above show that the catalytic
systems based on 3 and 4 efficiently catalyze the dimeri-
zation of propene. The observed activities are 2–3 times
higher than those obtained with other arylphosphines
and approach those of the most active Ni-phosphine
precatalyst known, [NiCl2(PCy3)2]. The superiority of
the present catalysts over the [NiCl2(PCy3)2]/MAO sys-
tem is their considerable higher C6-selectivity, which
reaches 80–97%. The remarkable activity of the two
catalysts is consistent with the observations already
made in ethylene dimerization.[6] The origin of the effi-
ciency has already been discussed in our previous
work and its rationalization relies on the hypothesis
that in the active species the nickel atom moves from
one side of the calixarene axis to the other (Scheme 3).
Note, from studies carried out with the diamagnetic
complex [Ni(h5-C5H5)·2]þ, it was inferred that, at
158C, the frequency of the fanning motion is ca. 70 Hz.
As shown by molecular mechanics calculations, during
this motion the PMP bite angle increases, reaching a
maximum value when the metal crosses the calixarene
À
effectively modify the outcome of C C bond forming re-
actions. Further work is aimed at optimizing the systems
described in this study. In this respect, we will focus on
variants of 1 and 2 having bulky substituents tethered
at the lower rim that may induce larger bite angles.
Experimental Section
General Remarks
All reactions involving nickel complexes were performed un-
der dry argon. Solvents were dried by conventional methods
and distilled immediately prior to use. 5,17-Bis(diphenylphos-
phino)-25,26,27,28-tetrapropoxycalix[4]arene (1),[22] 5,17-di-
bromo-11,23-bis(diphenylphosphino)-25,26,27,28-tetrapro-
poxycalix[4]arene (2),[22] 3,[6] 4,[6] [NiBr2(PPh3)2] (5),[12]
[NiBr2(dppe)] (6),[23] and [NiCl2(PCy3)2] (7)[24] were prepared
according to methods reported in the literature. Gas chromato-
graphic analyses were performed on a Varian 3900 gas chroma-
tograph using a WCOT Fused Silica Column (25 m, 0.32 mm
inside diameter, 0.25 mm film thickness). MAO 10 wt % (Al-
drich) was used as the white powder which was obtained after
evaporation of the solvent (608C, 3 h). This treatment reduces
the amount of residual trimethylaluminium to ca. 3%. The re-
sulting solid residue was dried during 3 h at 608C under vac-
uum.
À
axis. While the angle between the two Ni P bonds in-
creases, that between the other two bonds shrinks. In
General Procedure for Propene Dimerization
A 200-mL Büchi glass autoclave was heated at 1008C under
vacuum for 2 h, cooled to room temperature and backfilled
with propene. A solution of the precatalyst in a given solvent
(20 mL) was introduced into the autoclave via a syringe under
low propene pressure and stirred for 15 min. The reactor was
vented, upon which a solution of MAO in the same solvent
was added (see Tables 2–4 for details). The reactor was then
pressurized. At the end of the run, the autoclave was cooled
down to 58C and depressurized over 1 h. At this stage, only
propene was evolved. 1 mL of heptane as internal standard
was added and a sample of the reaction mixture was taken
for GC analysis. The following GC conditions were applied: in-
jector temperature: 2508C; detector temperature: 2758C; oven
temperature program: 408C/10 min, 108C/min ramp, 2208C/
Scheme 3. Proposed dynamics of the Ni-calixarene com-
plexes.
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´
5 min, 158C/min ramp, 2508C/5 min. Retention times for the
dimers are as follows: 4-methyl-1pentene (4M1P), 1.65 min;
4-methyl-2-pentene (4M2P), 1.72 min; 2-methyl-1pentene
(2M1P), 1.81 min; 1-hexene, 1.82 min; 2-methyl-2-pentene
(2M2P), 1.91 min; hexene isomers, 1.95 min; 2,3-dimethyl-2-
butene (TMEN), 2.04 min. Peak identification was made
with GC-MS.
[7] D. Semeril, M. Lejeune, C. Jeunesse, D. Matt, J. Mol.
Catal. A: Chemical 2005, 239, 257–262.
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Crystallography
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A 1968, 1473–1486.
Single crystals of 3 were grown as green plates by slow diffusion
of heptane into a chloroform solution of the complex at room
temperature. Data were collected at 120 K on a Nonius Kappa
CCD diffractometer using an MoKa X-ray source (l¼
[13] E. Dahan, S. E. Biali, J. Org. Chem. 1991, 56, 7269–7274.
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[15] NMR measurements carried out on 3/MAO/hexene mix-
tures (in C6D6) revealed only the presence of diamagnet-
ic species. Hence, it appears likely that during catalysis
the nickel atom adopts a planar geometry. We assume
that in the catalytic intermediates obtained from 4, the
nickel centre has also this coordination geometry. Mo-
lecular models show that in the latter, the two Br atoms
of the calix platform do not sterically interact with the
metal plane.
[16] S. A. Svejda, M. Brookhart, Organometallics 1999, 18,
65–74.
[17] M. Kranenburg, P. C. J. Kamer, P. W. N. M. van Leeu-
wen, D. Vogt, W. Keim, Chem. Commun. 1995, 2177–
2178.
0.71073 Š) and
a graphite monochromator. Formula:
C64H66Br2NiO4P2; Mr ¼1179.64 g·molÀ1; monoclinic, space
group P21/c, a¼19.2276(4), b¼15.5620(4), c¼19.7108(5) Š,
b¼104.362(1)8, V¼5713.5(2) Š3; Z¼4; Dx ¼1.371 Mg·mÀ3
,
m¼18.41 cmÀ1
;
F(000)¼2440. Crystal dimensions 0.40Â
0.35Â0.22 mm. 10045 independent reflections, 8211 with I>
2s(I). Goodness of fit on F2 ¼1.198; R(I>2s(I))¼0.095;
wR2¼0.28, 659 parameters; maximum/minimum residual den-
sity 1.755/À0.991 e Š3. The crystal structure was solved with
SIR97[25] and refined with SHELXL97[26] by full matrix least-
squares using anisotropic thermal displacement parameters
for all non-hydrogen atoms. After anisotropic refinement,
many hydrogen atoms could be localized with a Fourier differ-
ence. CCDC-264585 contains the supplementary crystallo-
graphic data for this paper. These data can be obtained free
of charge via www.ccdc.cam.ac.uk/conts/retrieving.html [or
from Cambridge Crystallographic Data Centre, 12, Union
Road, Cambridge CB21EZ, UK; Fax: (þ44)-1223-336-033;
or deposit@ccdc.cam.ac.uk].
[18] M. Kranenburg, P. C. J. Kamer, P. W. N. M. van Leeu-
wen, Eur. J. Inorg. Chem. 1998, 155–157.
[19] P. C. J. Kamer, P. W. N. M. van Leeuwen, J. N. H. Reek,
Acc. Chem. Res. 2001, 34, 895–904.
[20] J. N. L. Dennett, A. L. Gillon, K. Heslop, D. J. Hyett, J. S.
Fleming, C. E. Lloyd-Jones, A. G. Orpen, P. G. Pringle,
D. F. Wass, J. N. Scutt, R. H. Weatherhead, Organometal-
lics 2004, 23, 6077–6079.
Acknowledgements
´
´
[21] I. Albers, E. Alvarez, J. Campora, C. M. Maya, P. Palma,
´
We are grateful to the Universite Louis Pasteur for support.
´
L. J. Sanchez, E. Passaglia, J. Organometal. Chem. 2004,
`
M. L. thanks the Ministere de lꢀEducation Nationale for a re-
689, 833–839.
search grant.
[22] M. Lejeune, C. Jeunesse, D. Matt, N. Kyritsakas, R. Wel-
ter, J.-P. Kintzinger, J. Chem. Soc. Dalton Trans. 2002,
1642–1650.
[23] C. A. McAuliffe, D. W. Meek, Inorg. Chem. 1969, 8, 904–
907.
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[26] G. M. Sheldrick, SHELXL-97, Program for Crystal
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886
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