Cationic species derived from the η1-amidosilyl-η5-cyclopentadienyl dimethyl titanium complex. Crystal structure of [Ti{η5-C5H4SiMe2[η 1-N(2,6-Me2C6H3)]}{CH 2B(C6F5)2}(C6F 5)]

Article abstract of DOI:10.1016/S0022-328X(99)00340-X

Reactions of the η⁵-cyclopentadienyl-η¹-amido dimethyl titanium derivative [Ti{η⁵-C₅H₄SiMe₂[η ¹-N(C₆H₃Me₂)]}Me₂] (1) with tris(pentafluorophenyl)borane B(C₆F₅)₃ in hexane at room temperature yield a thermally stable bright yellow microcrystaline solid identified by elemental analysis as [Ti{η⁵-C₅H₄SiMe₂[η ¹-N(C₆H₃Me₂)]}Me{MeB(C ₆F₅)₃}] (2). A solution of 1 in CD₂Cl₂ at -78°C affords the ion-pair complex 2, while in C₆D₆ it is slowly converted into the new neutral complex [Ti{η⁵-C₅H₄SiMe₂[η ¹-N(C₆H₃Me₂)]}{CH ₂B(C₆F₅)₂}(C₆F ₅)] (3). Complex 3 is the unique product obtained after stirring compound 2 or a mixture of complex 1 and B(C₆F₅)₃ in toluene or benzene for 12 h at room temperature. The molecular structure of complex 3 has been determined by diffraction methods.

Full text of DOI:10.1016/S0022-328X(99)00340-X

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 588 (1999) 22–27
Cationic species derived from the h1-amidosilyl-h5-cyclopentadienyl
dimethyl titanium complex.
Crystal structure of
[Ti{h5-C5H4SiMe2[h1-N(2,6-Me2C6H3)]}{CH2B(C6F5)2}(C6F5)]
Rafael Go´mez, Pilar Go´mez-Sal, Pedro A. del Real, Pascual Royo *
Departamento de Qu´ımica Inorga´nica, Uni6ersidad de Alcala´, Campus Uni6ersitario, E-28871 Alcala´ de Henares, Spain
Received 25 March 1999
Abstract
Reactions of the h5-cyclopentadienyl-h1-amido dimethyl titanium derivative [Ti{h5-C5H4SiMe2[h1-N(C6H3Me2)]}Me2] (1) with
tris(pentafluorophenyl)borane B(C6F5)3 in hexane at room temperature yield a thermally stable bright yellow microcrystaline solid
identified by elemental analysis as [Ti{h5-C5H4SiMe2[h1-N(C6H3Me2)]}Me{MeB(C6F5)3}] (2). A solution of 1 in CD2Cl2 at
−78°C affords the ion-pair complex 2, while in C6D6 it is slowly converted into the new neutral complex [Ti{h5-C5H4SiMe2-
[h1-N(C6H3Me2)]}{CH2B(C6F5)2}(C6F5)] (3). Complex 3 is the unique product obtained after stirring compound 2 or a mixture
of complex 1 and B(C6F5)3 in toluene or benzene for 12 h at room temperature. The molecular structure of complex 3 has been
determined by diffraction methods. © 1999 Elsevier Science S.A. All rights reserved.
Keywords: Amido-silylcyclopentadienyl; Cationic alkyltitanium complexes; Titanium
SiMe2NR%}(NR2%%)2}[3]. A less general synthetic route
restricted to titanium and non-substituted cyclopentadi-
1. Introduction
Currently there is interest in the synthesis of h5-cy-
enyl rings [4,5] uses the reaction of the suitable
chlorodimethylsilyl-substituted monocyclopentadienyl
titanium complex [Ti(C5H4SiMe2Cl)Cl3] [6] with pri-
mary alkyl or aryl amines to give the dichloro deriva-
clopentadienyl-h1-amido metal catalysts (CGC) derived
from the ansa-metallocene by replacement of one of the
cyclopentadienyl rings by a three-electron-donor amido
group. These compounds are alternatives to Kaminsky
and Brintzinger type catalysts, and provide highly ac-
tive systems that produce ethylene/a-olefin copolymeri-
sation with remarkable properties [1]. Two general
strategies are employed to develop efficient synthetic
tives.
Very recently, we have shown that complex [Ti{h5-
C5H4SiMe2[h1-N(C6H3Me2)]}Cl2] can be readily con-
verted, at room temperature, into the dialkyl and
diamido complexes [Ti{h5-C5H4SiMe2[h1-N(C6H3-
Me2)]}X2] (X=alkyl or NMe2) or into the monoalkyl
procedures for these complexes. The metathetical reac-
derivative [Ti{h5-C5H4SiMe2[h1-N(C6H3Me2)]}MeCl]
tion of the dilithium salt of the [(C5R4)SiMe2NR%]2−
by salt metathesis using Grignard, organolithium or
dianions affords dichloro derivatives [M{(C5R4)-
SiMe2NR%}Cl2] (M=Ti, Zr, Hf) [2], and the reaction of
homoleptic metal amides M(NR%2%)4 with the bifunc-
tional [(C5R4H)SiMe2NHR%] ligand via amine elimina-
organoaluminium reagents [4b]. The dialkyl complexes
are precursors of the active cationic species when
treated with perfluoroaryl boranes and borates [7].
However, few studies have been reported for this type
of h5-cyclopentadienylsilyl-h1-amido titanium deriva-
tion produces diamido compounds [M{(C5R4)-
tive [8]. Here, we present the reactions of the dialkyl
titanium derivative [Ti{h5-C5H4SiMe2[h1-N(C6H3-
Me2)]}Me2] (1) with tris(pentafluorophenyl)borane
* Corresponding author. Fax: +34-1-8854683.
E-mail address: proyo@inorg.alcala.es (P. Royo)
B(C6F5)3 in different solvents.
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00340-X

R. Go´mez et al. / Journal of Organometallic Chemistry 588 (1999) 22–27
23
2. Results and discussion
behaviour has been observed in the reaction of either
the chelating diamido complex [Ti{(2,6-iPr2C6H3)-
N(CH2)3N(2,6-iPr2C6H3)}Me2] or o-arylphenoxide-cy-
clopentadienyl complexes [Ti(C5H5)(OAr)Me2] with
B(C6F5)3 to afford [Ti{(2,6-iPr2C6H3)N(CH2)3N(2,6-
iPr2C6H3)}{CH2B(C6F5)2}(C6F5)] [10] or [Ti(C5H5)-
The reaction of the dimethyl complex [Ti{h5-
C5H4SiMe2[h1-N(C6H3Me2)]}Me2] (1) with the strong
Lewis acid B(C6F5)3 has been studied using different
solvents. A mixture of compound 1 and B(C6F5)3 in
hexane at room temperature afforded a high yield of a
thermally stable bright yellow microcrystalline solid,
which was identified as [Ti{h5-C5H4SiMe2[h1-
N(C6H3Me2)]}Me {MeB(C6F5)3}] (2) by elemental anal-
ysis. Crystals of this compound were not suitable for
X-ray diffraction studies and therefore its structure
could only be investigated in solution.
1
(OAr){CH2B(C6F5)2}(C6F5)] [11], respectively. The H-
and 13C-NMR spectra of 3 are consistent with C1
symmetry. The diastereotopic methylene protons
TiꢀCH2ꢀB appear as two broad resonances at l 3.92
and 3.14 in the 1H-NMR spectrum and one broad
signal at l 110.5 is observed in the corresponding
13C-NMR spectrum. The 19F-NMR spectrum at room
temperature shows the presence of two different pen-
tafluorophenyl groups, consistent with the migration of
one C6F5 group to the titanium atom. The TiꢀC6F5
resonances at l 115.3 (2F, ortho), 154.2 (1F, para) and
164.0 (2F, meta) and the CH2B(C6F5)3 resonances com-
pare well with those found in the [Ti{(2,6-iPr2C6H3)N-
1
The H-NMR spectrum of a CD2Cl2 solution of this
compound recorded at −78°C indicated that the
[MeB(C6F5)3]− anion was coordinated to the acidic
titanium centre, as evidenced by the broad signal due to
the TiꢀCH3B system observed at l 0.38 and the large
chemical shift difference of Dl=lm−lp=5.03 be-
tween the m- and p-resonances observed in the 19F-
NMR spectrum [9]. Moreover, exactly the same
spectral data were obtained from a CD2Cl2 solution
prepared by mixing compound 1 and B(C6F5)3 in a
molar ratio of 1:1 in a sealed NMR tube at −60°C.
This behaviour allows the species present in solution to
be formulated as the ion-pair complex [Ti{h5-
(CH2)3N(2,6-iPr2C6H3)}{CH2B(C6F5)2}(C6F5)]
[10]
complex discussed above and in other similar com-
plexes [12].
The structures proposed for the new complexes 2 and
3 are shown in Scheme 1 and their spectroscopic and
analytical data are collected in Section 4.
Orange crystals of 3, suitable for X-ray diffraction,
were obtained from its hexane solution after slow cool-
ing. The molecular structure of 3 is shown in Fig. 1 and
selected bond lengths and angles are listed in Table 1.
The titanium centre is in a pseudo-tetrahedral envi-
ronment defined by a chelate silylamido |-N coordi-
nated h5-cyclopentadienyl ligand, a pentafluorophenyl
group and a methylboron fragment. The TiꢀCpcent dis-
C5H4SiMe2[h1-N(C6H3Me2)]}Me{MeB(C6F5)3}]
(2).
This formulation is consistent with the other signals
1
observed in the H-NMR spectrum, which shows an
ABCD spin system for the cyclopentadienyl ring pro-
tons as well as two different methyl groups for the
SiMe2 bridging group and for the N(C6H3Me2) frag-
ment. These results indicate the presence of a chiral
metal center. One singlet was also observed for the
titanium bound terminal methyl group. The 13C{1H}-
NMR spectrum shows a resonance at l 72.0 due to the
TiꢀMe carbon, along with the rest of the signals at-
tributed to the ancillary dianionic ligand {h5-
C5H4SiMe2[h1-N(C6H3Me2)]}2− consistent with the
indicated symmetry. The chemical shift of the cyclopen-
tadienyl Cipso atom is typically shifted upfield from the
other ring carbon resonances and is therefore diagnos-
tic of chelation of the appended amido group in com-
plex (2) [6]. A similar ion-pair coordination has been
suggested for the more electron rich and sterically
encumbered complex [Ti{h5-C5Me4SiMe2(h1-NtBu)}-
Me{MeB(C6F5)3}] [8b].
,
tance of 2.033 A is slightly longer than the correspond-
ing distance in [Ti{h5-C5H4SiMe2[h1-N(C6H3Me2)]}Cl2]
,
(2.016 A), although the TiꢀN bond distance of 1.911(4)
,
A and the CpcentꢀTiꢀN angle of 105.3° are comparable
,
to those found in this complex (1.914(3) A and 105.1°,
respectively) [4b] and in other related h5-cyclopentadi-
enylsilyl-h1-amido metal derivatives [5,13]. However,
the CpcentꢀTiꢀN angle in 3 is considerably smaller than
in similar unlinked Cp-amido or Cp-arylphenoxide
complexes such as [Ti(C5H5)(NiPr2)Cl2] (116.2°) [14] or
[Ti(C5H5)(OAr)Cl2] (123.7°) [11], or than the NꢀTiꢀN
angle in diamido complexes such as [Ti{N-
(SiMe3)2}2(CH2Ph)2] (120.6°) [15], but larger than that
observed in bidentate diamide derivatives of the type
[Ti{h1 -N(2,6-iPr2C6H3)(CH2)3h1 -N(2,6-iPr2C6H3)}Cl2]
(99.2(2)°) [16]. The coordination geometry of both N
and B atoms is trigonal planar, consistent with sp2
hybridization. The TiꢀC6ꢀB angle of 114.9(4)° is close
to sp3 hybridization for the methylene carbon atom
but is smaller than that found in the analogous biden-
tate diamide [Ti{h1-N(2,6-iPr2C6H3)(CH2)3h1-N(2,6-
When the reaction of 1 with B(C6F5)3 was carried out
in an aromatic solvent (toluene or benzene), a mixture
of complex
2
and
a
new compound [Ti{h5-
C5H4SiMe2[h1-N(C6H3Me2)]}{CH2B(C6F5)2}(C6F5)] (3)
was formed in less than 5 min. When the mixture was
allowed to stir for longer periods only 3 was detected.
Complex 2 decomposes over a number of hours via
methane evolution to give 3 as orange crystals after
extraction into hexane and cooling at −40°C. Similar
iPr2C6H3)}{CH2B(C6F5)2}(C6F5)]
(125.1(3)°)
[10]

24
R. Go´mez et al. / Journal of Organometallic Chemistry 588 (1999) 22–27
Scheme 1.
where the deviation is due to steric interaction between
the B(C6F5)2 moiety and the C6F5 group bonded to
model HE-63 or MBraun. Solvents were purified by
distillation under argon from an appropriate drying
agent (sodium for toluene, sodium–potassium alloy
for hexane, sodium-benzophenone for THF and
CaH2 for acetonitrile). The tris(pentafluorophenyl)-
borane [17] and [Ti{h5-C5H4SiMe2[h1-N(2,6-Me2C6-
H3)]}Me2] (1) [4b] were prepared according to literature
procedures. C, H and N microanalyses were performed
on a Perkin–Elmer 240B and/or Heraeus CHN-O-
Rapid microanalyzer. NMR spectra were recorded on
a Varian Unity 300 (1H-NMR at 300 MHz, 19F-NMR
at 282 MHz and 13C-NMR at 75 MHz) spectrometer.
1H and 13C chemical shifts are reported in l units
relative to a TMS standard while 19F was referenced to
CFCl3.
,
titanium. The TiꢀCH2 bond distance in 3 (2.169(5) A) is
slightly larger than that observed in the latter com-
,
pound (2.111(4) A) and this is probably the reason for
an acute angle in 3.
3. Conclusions
The reaction of [Ti{h5-C5H4SiMe2[h1-N(C6H3Me2)]}-
Me2] (1) with B(C6F5)3 has been investigated in differ-
ent solvents. The ion-pair complex [Ti{h5-
C5H4SiMe2[h1-N(C6H3Me2)]}Me{MeB(C6F5)3}] (2) was
detected in the polar and poorly coordinating solvent
CD2Cl2 at low temperature, but decomposed to uniden-
tified complexes above −10°C. However, 2 was formed
at r.t. in aromatic solvents although it decomposed
slowly to give the neutral compound [Ti{h5-
C5H4SiMe2[h1-N(C6H3Me2)]}{CH2B(C6F5)2}(C6F5)] (3)
with evolution of methane. This behaviour is different
from that observed for the analogous cationic metallo-
cene complexes, but similar to the decomposition path-
way observed for analogous monocyclopentadi-
enyl-arylphenoxide [Ti(C5H5)(OAr)Me2], chelating di-
amido or [Ti{(2,6-iPr2C6H3)N(CH2)3N(2,6-iPr2C6H3)}-
Me2] complexes with B(C6F5)3.
4. Experimental
4.1. General considerations
All manipulations were performed under argon using
Schlenk and high-vacuum line techniques or a glovebox
Fig. 1. ORTEP view of the molecular structure of compound 3 with
atom-numbering scheme.

R. Go´mez et al. / Journal of Organometallic Chemistry 588 (1999) 22–27
25
Table 1
tube. The NMR spectrum was recorded at −60°C to
give complex 2 as the sole spectroscopic compound.
1H-NMR (C6D6, 293 K): l 6.90 (m, 2Hmeta, C6H3Me2);
6.79 (m, 1Hpara, C6H3Me2); 6.47 (m, 1H, C5H4); 6.20
(m, 1H, C5H4); 6.02 (m, 1H, C5H4); 5.44 (m, 1H, C5H4);
1.54 (s, 3H, C6H3Me2); 1.26 (s, 3H, C6H3Me2); 0.94 (s,
3H, TiMe); 0.65 (br, 3H, MeB(C6F5)3); −0.16 (s, 3H,
,
Bond lengths (A) and angles (°) for 3
Bond lengths
Ti(1)ꢀN(1)
Ti(1)ꢀC(6)
Ti(1)ꢀC(31)
Ti(1)ꢀC(1)
Ti(1)ꢀC(5)
Ti(1)ꢀC(2)
Ti(1)ꢀC(3)
Ti(1)ꢀC(4)
Ti(1)ꢀSi(1)
Si(1)ꢀN(1)
Si(1)ꢀC(51)
Si(1)ꢀC(52)
Si(1)ꢀC(1)
N(1)ꢀC(41)
B(1)ꢀC(6)
B(1)ꢀC(11)
B(1)ꢀC(21)
Ti(1)ꢀCp
1.911(4)
2.169(5)
2.204(5)
2.304(5)
2.327(5)
2.336(5)
2.408(5)
2.418(5)
2.948(2)
1.749(4)
1.829(6)
1.845(6)
1.853(6)
1.439(5)
1.483(8)
1.602(8)
1.596(7)
2.033
1
SiMe2); −0.22 (s, 3H, SiMe2). H-NMR (CD2Cl2, 213
K): l 7.61 (m, 1H, C5H4); 7.19 (m, 1Hmeta, C6H3Me2,
JHꢀH=7.0 Hz); 7.05 (t, 1Hpara, C6H3Me2, JHꢀH=7.7
Hz); 6.87 (m, 1Hmeta, C6H3Me2, JHꢀH =7.3 Hz); 6.60
(m, 2H, C5H4); 6.30 (m, 1H, C5H4); 1.93 (s, 3H,
C6H3Me2); 1.37 (s, 3H, C6H3Me2); 1.29 (s, 3H, TiMe);
0.51 (s, 3H, SiMe2); 0.46 (s, 3H, SiMe2); 0.38 (br, 3H,
MeB(C6F5)3). 13C-NMR (CD2Cl2, 213 K): l 147.5 (d,
Cortho of C6F5, JCꢀF=232.6 Hz); 144.8 (Cipso of
C6H3Me2); 138.5 (d, Cpara of C6F5, JCꢀF=238.0 Hz);
136.1 (d, Cmeta of C6F5, JCꢀF=249.1 Hz); 130.6 (Cortho
of C6H3Me2); 129.2, 128.6, 128.1 (C6H3Me2 or C5H4);
127.7 (Cortho of C6H3Me2); 126.2, 124.6, 124.3, 120.5
(C6H3Me2 or C5H4); 111.1 (Cipso of C5H4); 72.0 (TiMe);
40.5 (MeB(C6F5)3); 19.0 (C6H3Me2); 18.5 (C6H3Me2);
−1.1 (SiMe2); 1.3 (SiMe2). 19F-NMR (CD2Cl2, 213 K):
Bond angles
N(1)ꢀTi(1)ꢀC(6)
N(1)ꢀTi(1)ꢀC(31)
C(6)ꢀTi(1)ꢀC(31)
N(1)ꢀSi(1)ꢀC(51)
N(1)ꢀSi(1)ꢀC(52)
C(51)ꢀSi(1)ꢀC(52)
N(1)ꢀSi(1)ꢀC(1)
C(41)ꢀN(1)ꢀSi(1)
C(41)ꢀN(1)ꢀTi(1)
Si(1)ꢀN(1)ꢀTi(1)
C(6)ꢀB(1)ꢀC(11)
C(6)ꢀB(1)ꢀC(21)
C(11)ꢀB(1)ꢀC(21)
B(1)ꢀC(6)ꢀTi(1)
N(1)ꢀTi(1)ꢀCp
C(31)ꢀTi(1)ꢀCp
C(6)ꢀTi(1)ꢀCp
107.35(18)
102.79(17)
107.66(19)
113.5(3)
115.7(2)
110.1(3)
89.6(2)
127.5(3)
125.3(3)
107.23(18)
125.6(5)
117.0(5)
117.3(5)
114.9(4)
105.3
l
−136.0 (6Fortho, C6F5); −161.1 (3Fpara, C6F5);
−166.15 (6Fmeta, C6F5); (Dl=lmeta−lpara=5.0).
4.3. Synthesis of [Ti{p5-C5H4SiMe2[p1-N(2,6-
Me2C6H3)]}{CH2B(C6F5)2}(C6F5)] (3)
4.3.1. Method A
A solution of complex 2 (113 mg, 0.136 mmol) in
toluene (15 ml) was stirred at r.t. for 12 h in a glovebox.
After the solvent was completely removed under vac-
uum, the oily material was extracted into hexane (50
ml) and the solution filtered. The solution was concen-
trated and cooled to −40°C to give complex 3 (97 mg,
83%) as red–orange crystals.
116.6
115.9
151.3
Si(1)ꢀC(19ꢀCp
4.2. Synthesis of [Ti{p5-C5H4SiMe2[p1-N(2,6-
Me2C6H3)]}Me{MeB(C6F5)3}] (2)
4.3.2. Method B
A mixture of complex 1 (50 mg, 0.156 mmol) and
B(C6F5)3 (80 mg, 0.156 mmol) in toluene (15 ml) was
stirred at r.t. for 12 h. Following the procedure de-
scribed above, complex 3 was obtained (0.1 g, 85%).
Anal. Calc. for C34H21F15NBSiTi: C: 50.08; H: 2.59; N:
A
mixture
of
[Ti{h5-C5H4SiMe2[h1-N(2,6-
Me2C6H3)]}Me2] (1) (50 mg, 0.156 mmol) and B(C6F5)3
(80 mg, 0.156 mmol) in hexane (100 ml) was stirred at
r.t. for 12 h in a glovebox affording a bright yellow
precipitate slowly. After the solvent was completely
removed by filtration, the solid was washed with hexane
and dried in vacuo to give complex 2 (113 mg, 87%) as
1
1.72. Found: C: 49.76; H: 2.91; N: 2.03%. H-NMR
(C6D6, 298 K): l 7.35 (m, 1H, C5H4); 7.07 (m, 1H,
C5H4); 6.88–6.97 (m, 3H, C6H3Me2); 6.48 (m, 1H,
C5H4); 6.43 (m, 1H, C5H4); 4.15 (br, 1H, TiCH2B); 3.15
(br, 1H, TiCH2B); 1.92 (s, 3H, C6H3Me2); 1.24 (s, 3H,
C6H3Me2); −0.02 (s, 3H, SiMe2); −0.08 (s, 3H,
SiMe2). 1H-NMR (CD2Cl2, 298 K): l 7.53 (m, 1H,
C5H4); 7.30 (m, 1H, C5H4); 7.17 (m, 1H, C6H3Me2,
yellow
microcrystals.
Anal.
Calc.
for.
C35H25F15NBSiTi: C: 50.56; H: 3.03; N: 1.68. Found:
C: 50.94; H: 3.41; N: 2.12%.
4.2.1. In situ generation of 2
JHꢀH=6.6 Hz); 7.02 (m, 2H, C6H3Me2, JHꢀH=6.6 Hz);
[Ti{h5-C5H4SiMe2[h1-N(2,6-Me2C6H3)]}Me2] (1) (50
mg, 0.156 mmol) and B(C6F5)3 (80 mg, 0.156 mmol)
was dissolved in CD2Cl2 at −78°C in a sealed NMR
6.88 (m, 1H, C5H4); 6.79 (m, 1H, C5H4); 3.92 (br, 1H,
TiCH2B); 3.14 (br, 1H, TiCH2B); 2.08 (s, 3H,
C6H3Me2); 1.41 (s, 3H, C6H3Me2); 0.52 (s, 3H, SiMe2);

26
R. Go´mez et al. / Journal of Organometallic Chemistry 588 (1999) 22–27
0.45 (s 3H, SiMe2). 13C-NMR (CD2Cl2, 298 K): l
150–134 (C6F5); 148.5 (Cipso of C6H3Me2); 131.3
(C6H3Me2 or C5H4); 130.1 (Cortho of C6H3Me2); 129.3,
128.8 (C6H3Me2 or C5H4); 128.6 (Cortho of C6H3Me2);
128.4, 125.9, 125.4, 120.8 (C6H3Me2 or C5H4); 110.8
(Cipso of C5H4); 110.5 (C of TiCH2B); 19.6 (C6H3Me2);
19.5 (C6H3Me2); −0.6 (SiMe2); −1.3 (SiMe2). 19F-
NMR (CD2Cl2, 298°K): l −115.3 (d, 2Fortho, TiC6F5);
were collected at r.t. Intensities were corrected for
Lorenz and polarisation effects in the usual manner.
No absorptions or extinctions were made. The structure
was solved by direct methods (SHELXL90) [18] and
refined by least squares against F2 (SHELXL93) [19]. All
non-hydrogen atoms were refined anisotropically, and
the hydrogen atoms were introduced from geometrical
calculations and refined using a riding model with fixed
thermal parameters. Calculations were carried out on
an ALPHA AXP (Digital) workstation.
−132.0 (br, 4Fortho, B(C6F5)2); −151.0 (br, 2Fpara
,
B(C6F5)2); −154.2 (t, 1Fpara, TiC6F5); −164.0 (t,
2Fmeta, TiC6F5); −164.3 (br, 4Fmeta, B(C6F5)2).
5. Supplementary material
4.4. X-ray structure determination of 3
The supplementary material includes a list of the
positional parameters and their standard deviations, a
complete list of bond lengths and angles, anisotropic
displacement parameters, the calculated fractional coor-
dinates of the hydrogen atoms and a list of observed
and calculated structure factors. This is available on
request from the authors. Crystallographic data for the
structure reported in this paper have been deposited in
the Cambridge Crystallographic Data Centre, CCDC
no. 116437. Copies of this information may be obtained
free of charge from the Director, CCDC, 12 Union
Road, Cambridge, CB2 1EZ, UK (Fax: +44-1223-336-
033; e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
Crystals of compound 3 were obtained by crystallisa-
tion from hexane and a suitable sized crystal was
mounted in a Lindemann tube, which was then
mounted in an Enraf–Nonius CAD 4 automatic four-
circle diffractometer with graphite monochromated
,
MoꢀKa radiation (u=0.71073 A). Crystallographic and
experimental details are summarised in Table 2. Data
Table 2
Crystal, experimental data and structure refinement procedures for
compound 3
Formula
Mw
C34,H21,F15,B,N,Si,Ti
815.32
Crystal habit
Colour
Prismatic
Red–orange
Crystal size (mm)
Symmetry
0.25×0.28×0.30
Monoclinic P21/n
Acknowledgements
Unit cell dimensions
We are grateful to the DGICYT (Project PB-97-
0776) for financial support of this research.
,
a (A)
11.292(3), 17.166(4), 18.057(5)
,
b (A)
,
c (A)
i (°)
105.54(1)
3372(1)
4
1.606
1632
4.00
3
,
V (A )
References
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