Synthesis and structures of o-phenylene-bridged Cp/phosphinoamide titanium complexes

Article abstract of DOI:10.1016/j.jorganchem.2006.09.010

Addition of R′₂PCl to anilines substituted with di- or trimethylcyclopentadienyl unit at ortho-position affords ortho-phenylene-bridged Me₂Cp or Me₃Cp/phosophinoamide ligands, 2-(RMe₂C₅H₂)C

Full text of DOI:10.1016/j.jorganchem.2006.09.010

Journal of Organometallic Chemistry 691 (2006) 5626–5634
www.elsevier.com/locate/jorganchem
Synthesis and structures of o-phenylene-bridged
Cp/phosphinoamide titanium complexes
*
Chun Ji Wu, Sang Hoon Lee, Hoseop Yun, Bun Yeoul Lee
Department of Molecular Science and Technology, Ajou University, Suwon 443-749, Republic of Korea
Department of Chemistry, Ajou University, Suwon 443-749, Republic of Korea
Received 25 July 2006; received in revised form 25 August 2006; accepted 5 September 2006
Available online 19 September 2006
Abstract
Addition of R02PCl to anilines substituted with di- or trimethylcyclopentadienyl unit at ortho-position affords ortho-phenylene-
bridged Me2Cp or Me3Cp/phosophinoamide ligands, 2-(RMe2C5H2)C6H4NHPR02 (R = Me or H; R0 = Ph, iPr, or Cyclohexyl). Succes-
sive addition of Ti(NMe2)4 and Me2SiCl2 to the ligands affords the desired dichlorotitanium complexes, [2-(g5-RMe2C5H)C6H4NPR0 2ꢀ
j2N,P]TiCl2 (R = H, R0 = Ph, 9; R = Me, R0 = Ph, 10; R = H, R0 = iPr, 11; R = Me, R0 = iPr, 12; R = H, R0 = Cy, 13; R = Me,
R0 = Cy, 14). By using Zr(NMe2)4 instead of Ti(NMe2)4, a zirconium complex, [2-(g5-Me3C5H)C6H4NP(iPr)2ꢀj2N,P]ZrCl2 (15) is pre-
pared. Molecular structures of 10, 14 and [2-(g5-Me2C5H2)C6H4NPPh2ꢀ jN]Ti(NMe2)2 (16) were determined. The metric parameters
determined on the X-ray crystallographic studies and the chemical shifts of the 31P NMR signal indicate that the phosphorous atom
coordinates to the titanium in the dichloro-complexes 9–15. The titanium and zirconium complexes show negligible activity in ethylene
and ethylene/1-hexene (co)polymerization when activated with MAO or iBu3Al/[Ph3C][B(C6F5)4].
ꢀ 2006 Elsevier B.V. All rights reserved.
Keywords: Phosphinoamide; Constrained geometry catalyst; Titanium complexes; Cyclopentadienyl
1. Introduction
1-one is a key step in the route (Eq. (1)). Replacement of
the silylene-bridge with o-phenylene group leads to a struc-
tural change of narrower Cp(cent)–Ti–N angle, indicative
of more ‘‘constrained feature’’ in the o-phenylene bridged
complexes [6]. While the silicon atom in the CGC is severely
deviated from the cyclopentadienyl plane [7], the elements
constituting the chlelation in the o-phenylene bridged com-
plexes are not situated in a severely strained position. Some
complexes are superior to the CGC in ethylene/a-olefin
copolymerization in terms of activity, a-olefin incorpora-
tion, and molecular weight of the obtained polymer. Herein,
we report titanium complexes derived from o-phenylene-
bridged di- or trimethylcyclopentadienyl/phosphinoamide
ligands. Coordination chemistry utilizing phosphinoamide
ligand ([R2P–NR0]ꢀ) has drawn extensive attention recently
[8]. Bis(phosphinoamido)titanium and zirconium dichloride
[9] and unbridged Cp*/phosphinoamide titanium com-
plexes, Cp*TiCl2(g2-Ph2PNR) (R = tBu, nBu, and Ph)
[10] were prepared to be tested as a polymerization catalyst
The Constrained-Geometry Catalyst (CGC), [Me2Si(g5-
Me4C5)(NtBu)]TiCl2 [1] typically represents the homoge-
neous Ziegler–Natta catalysts [2]. Various modifications
have been successfully carried out either by replacement
of the Me4C5-unit with other p-donor ligands [3] or by
replacement of the NtBu-unit with other amides or phosp-
hides [4], but modification on the bridge has not been so
abundant and successful [5]. Recently, we disclosed a novel
preparation route for o-phenylene-bridged (dimethyl or
trimethylcyclopentadienyl)/(amide or sulfonamide) ligand
system [6]. Suzuki coupling reaction of 2-bromoaniline
compounds with 2-dihydroxyboryl-3,4-dimethyl-2-cyclop-
enten-1-one or 2-dihydroxyboryl-3-methyl-2-cyclopenten-
*
Corresponding author. Tel.: +82 31 219 1844; Fax: +82 31 219 2394.
E-mail address: bunyeoul@ajou.ac.kr (B. Yeoul Lee).
0022-328X/$ - see front matter ꢀ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.09.010

C. Ji Wu et al. / Journal of Organometallic Chemistry 691 (2006) 5626–5634
5627
but the bridged Cp/phosphinoamide analogues have not
been reported yet.
and the signals can be unambiguously assigned. Usually,
a mixture of isomers is obtained for substituted cyclopent-
adiene compounds by the facile 1,5-sigmatropic rearrange-
ment [11], but compounds 3–8 exist as a single isomer at
room temperature, showing only a set of signals in the
NMR spectra. The isomer where two hydrogens are
attached on the sp3-carbon is substantially thermodynami-
cally more stable and the isomer is predominant at room
temperature. Signal of the two protons attached on the
sp3-carbon of the cyclopentadiene unit are observed as an
AB spin system in the 1H NMR spectra, which implies that
the rotation around carbon–carbon bond between the
cyclopentadiene and phenylene is not free in the NMR time
scale. The proton attached at the 6-position of the pheny-
lene-unit is coupled with phosphorous with a coupling con-
stant of 4JPH = 3–4 Hz. In the 1H NMR spectra of 5 and 6,
four isopropyl CH3-signals are observed around 1 ppm as a
doublet of doublet coupled with the phosphorous and the
isopropyl-CH proton. Two signals show coupling con-
O
Me
R
B(OH)2
R"
Me
TiCl2
N
R
Me
R'
R = Me, H
R = Me, H
R' = Alkyl, CH3C6H4SO2-
2. Results and discussion
2.1. Synthesis and characterization
Aniline compounds substituted with dimethylcyclopen-
tadienyl or trimethylcyclopentadienyl-unit at ortho-posi-
tion, 2- (RMe2C5H2)R02C6H2NH2 are prepared through
the Suzuki-coupling reaction of 2-bromoanilines with 2-
dihydroxyboryl-3,4-dimethyl-2-cyclopenten-1-one or 2-
dihydroxyboryl-3-methyl-2-cyclopenten-1-one (Scheme 1).
Addition of R02PCl (R0 = phenyl, isopropyl, cyclohexyl)
to the aniline derivatives in the presence of pyridine affords
3–8 in 60–90% yields. In case of the diphenylphosphino
compounds, 3 and 4 addition of 1 equivalent of Ph2PCl
affords the desired compound and they are isolated as a
solid by recrystallization in pentane. In case of the reac-
tions of iPr2PCl and Cy2PCl, addition of slight excess of
chlorophosphine (1.3 equivalents) is required for complete
conversions. The remained iPr2PCl can be easily removed
by evacuation and spectroscopically pure 5 and 6 are affor-
ded as oil. The remaining Cy2PCl cannot be routinely
removed by the evacuation and 7and 8 are obtained, con-
taminated with some Cy2PCl, which is used for the next
reaction without further purification. The compounds are
3
3
stants of JHH = 6.8 and JPH = 10 Hz while the other
3
two exhibiting the coupling constants of JHH = 6.8 and
3JPH = 16 Hz. In the 13C NMR spectra, the 1, 2 and 6-car-
bons on the phenylene are coupled with phosphorus and
2
observed as a doublet with coupling constants of JPC
=
17,3JPC = 4, and JPC = 22 ppm at ꢁ146, ꢁ124, and
3
ꢁ114 ppm, respectively.
Reaction of 3–8 with equimolar amount of Ti(NMe2)4in
benzene at 80 ꢁC for 15 h affords a bis(dimethylamido)tita-
nium complex. A single Me2N-signal is observed as a sin-
glet in the 1H NMR spectra of the symmetrically
substituted dimethylcyclopentadienyl complexes but two
Me2N-signals are observed for the trimethylcyclopentadie-
nyl complexes. The phosphorus signals in the 31P NMR
spectra are not severely shifted by the metallation, which
implies that the phosphorus atom does not coordinate with
the titanium in the (Me2N)2Ti-complexes. The coupling
constants between phosphorous and C–6 carbon on the
phenylene (3JPC) are significantly changed by metallation
(ꢁ21 Hz for 3–8 versus 6 Hz for the (Me2N)2Ti-com-
plexes). The dependence of the coupling constants on the
dihedral angle has been found empirically in many cases
[12]. The phosphorous atom is not situated on the pheny-
lene plane in the ligands 3–8 but it becomes coplanar with
the phenylene plane by the metallation which triggers
change of the P–N–C1–C6 dihedral angle, consequently
leading to the change of the coupling constant.
1
characterized by the H, 13C, and 31P NMR spectroscopy
Me
O
O
R
R
B(OH)2
i)
ii)
Me
Me
NH2
NH2
R
Me
1
2
R H Me
Me
Me
When Me2SiCl2 is employed as a chlorinating agent,
the 1H NMR spectra indicate that both Me2N-ligands
are replaced with the chloride ligands [13]. By the chlori-
nation, chemical shifts of the phosphorous signals are dra-
matically upfield-shifted from ꢁ45 ppm to ꢁ7 ppm for the
diphenylphosphino complexes. Similarly, large chemical-
shift change ((D(chemical shifts) = ꢁ36 ppm) is observed
in the diisopropylphosphino and the dicyclohexylphosph-
ino complexes. The dramatic chemical-shift change sug-
gests the coordination of the phosphorous atom to the
titanium. The coupling constants between phosphorous
R
R
iii)
iv)-v)
Me
Me
R'
TiCl2
NH
P
N
P
R'
5
H
R'
R'
3
4
6
7
8
9
10 11 12 13 14
R H Me Me H Me
R' Ph Ph iPr iPr Cy Cy
R H Me
R' Ph Ph iPr iPr Cy Cy
Me H Me
H
Scheme 1. (i) 2-BrC6H2(R0)2 NH2, Na2 CO3, Pd(PPh3)4 (1 mol%); (ii)
MeLi/CeCl3, then HCl (2 N); (iii) R02PCl, pyridine; (iv) Ti(NMe2)4 and (v)
Me2SiCl2.

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C. Ji Wu et al. / Journal of Organometallic Chemistry 691 (2006) 5626–5634
and C-6 carbon on the phenylene (3JPC) are not changed
significantly by the chlorination (3 Hz for 9–14).
A zirconium complex is prepared from 6 by using
Zr(NMe2)4 instead of Ti(NMe2)4 (equation 2). The phos-
phorus signal is observed at 44 and 34 ppm in the 13P
NMR spectra of the (Me2N)2Zr-complex and Cl2Zr-com-
plex, respectively. For the titanium complexes, slight
change of the 31P chemical shift is observed by metallation
to (NMe2)2-Ti complexes (D(chemical shifts) <5 ppm) but
significant
chemical-shift
change
((D(chemical
shifts) = 30–40 ppm) is observed by replacing the Me2N-
ligand with the chloride ligand. We attribute the large
change of the chemical shift to the coordination of the
phosphorus with the titanium. In the case of zirconium,
chemical-shift change (D(chemical shifts)) of 17 ppm is
observed in the first metallation to the (Me2N)2Zr-complex
and an additional 10 ppm change occurs in the second
chlorination step. We assume that phosphorus atom coor-
dinates with the zirconium in both (Me2N)2Zr- and Cl2Zr-
complexes with stronger interaction in the latter complex.
Fig. 1. Thermal ellipsoid plot (30% probability level) of 10. Hydrogen
atoms are omitted for clarity.
1
The signal pattern of the H and 13C NMR spectra is not
far from that observed for the corresponding titanium
complex.
˚
(ꢂ2.63 A) [14] indicating a chemical bonding between these
two atoms, but it is somewhat longer than those observed
for the unbridged analogues, Cp*TiCl2(g2-Ph2PNtBu)
Me
Me
2
10
(2.4928(9) A) and Cp*TiCl2(g -Ph2PNPh) (2.477(2) A).
˚
˚
i) Zr(NMe2)4
By the coordination, C(10)–N–P (129.9(2)ꢁ angle is
increased from the ideal 120ꢁ while Ti–N–P angle
Me
ZrCl2
6
ii) Me2SiCl2
N
P
˚
(95.93(15)ꢁ is contracted. The Ti–N distance (1.935(3) A)
is longer than those observed for [2-(g5-2,3,5-Me3C5H)-
15
6a
˚
C6H3NC6H11]TiCl2 (1.9003(13) A)
and the standard
7
˚
CGC (1.907(4) A) but substantially shorter than those
observed for the sulfonamide complex, [C6H4(g5-Me2-
6b
˚
2.2. X-ray crystallographic studies
H2C5)(NTs-jN,O)]TiCl2 (2.005(5) A) and the unbridged
2
complexes Cp*TiCl2(g -Ph2PNtBu) (2.004(2) A) and
˚
2
Cp*TiCl2(g -Ph2PNPh) (1.983(5) A). The P–N distance
˚
Single crystals of 10 suitable for X-ray crystallography
are obtained by vapor-phase addition of pentane to a ben-
zene solution. Fig. 1 shows the structure, and the selected
bond distances and angles are tabulated in Table 1. The
˚
(1.677(3) A) is slightly longer than those observed for the
2
unbridged analogues Cp*TiCl2(g -Ph2PNtBu) (1.638(2) A)
˚
2
*
˚
and Cp TiCl2(g -Ph2PNPh) (1.652(5) A). The Cp(cent)–
Ti–N angle has been used as a qualitative measure for
the ‘‘constrained geometry’’. The smaller the Cp(cent)–
˚
Ti–P distance (2.6881(19) A) is close to those observed
for titanium complexes coordinated with phosphine ligand
Table 1
˚
Selected bond distances (A) and angles (ꢁ)
10
14
16
Ti–P
Ti–NP
Ti–CpCentroid
2.6881(19)
1.935(3)
2.032
2.621(3)
1.919(6)
2.031
3.0343(12)
2.034(2)
2.042
Ti–Cl or Ti–NMe2
P–N
2.2934(19) 2.300(2)
1.677(3)
103.19
134.1(2)
95.93(15)
129.9(2)
108.01(9)
88.55
2.299(2) 2.293(2)
1.667(6)
102.19
135.6(6)
93.6(3)
130.8(5)
104.97(9)
89.00
1.907(3) 1.905(3)
1.697(3)
104.08
126.45(19)
108.49(13)
124.54(19)
101.72(14)
89.81
CpCentroid–Ti–NP
CBridge–N–P
Ti–N–P
Ti–N–CBridge
Cl–Ti–Cl (or Me2N-Ti-NMe2)
CBridgehead–CpCentroid–Ti
CpCentroid–CBridgehead–CBridge
CBridgehead–CBridge–CBridge
CBridge–CBridge–N
171.66
113.5(3)
112.7(3)
172.98
112.6(7)
112.3(8)
170.65
115.0(3)
115.5(2)

C. Ji Wu et al. / Journal of Organometallic Chemistry 691 (2006) 5626–5634
5629
Ti–N angle is, the more pronounced the ‘‘constrained
geometry’’ features should be. The Cp(cent)–Ti–N angle
(103.19ꢁ is larger than those observed for the o-pheny-
lene-bridged Cp/sulfonamido complex, [C6H4(g5-Me2-
H2C5)(NTs-jN,O)]TiCl2 (100.91ꢁ but it is smaller than
those observed for the standard CGC (107.6ꢁ and the
o-phenylene-bridged Cp/amido complex, [C6H4(g5-
Me2H2C5)(NC6H11-jN)]TiCl2 (104.8ꢁ. The iso-carbon on
the phenylene bridge (C(9)) is not severely deviated from
the cyclopentadienyl plane (Cp(cent)–C(1)–C(9) angle,
171.66ꢁ and the Cp(cent)–Ti vector is situated almost per-
pendicularly to the cyclopentadienyl plane (Ti-Cp(cent)–
C(1) angle, 88.55ꢁ. The nitrogen atom is trigonal and the
sum of bond angle around nitrogen is 360ꢁ. The cyclopen-
tadienyl plane is almost perpendicularly situated to the
phenylene plane (angle between the plane, 84.41(16)ꢁ and
all the Ti, N, and P atoms are situated on the phenylene
plane.
Fig. 2 shows the structure of 14. The phosphorus atom
in 14 is a better donor than that in 10, hence either stronger
Ti–P or stronger Ti–N bonding interaction is expected. As
expected, the distances of Ti–P and Ti–N are shorter than
the corresponding distances observed for 10, respectively
(Table 1). The Cp(cent)–Ti–N angle (102.19ꢁ is slightly
smaller than that observed for 10 (103.19ꢁ. Other metrical
parameters and molecular shape are close to those
observed for 10.
Single crystals of the bis(dimethylamido)titanium com-
plex 16 were obtained by recrystallization in pentane
ꢀ30 ꢁC. Fig. 3 shows its structure. The Ti–P separation
˚
(3.0343(12) A) is significantly longer than those observed
˚
˚
for 10 (2.6881(19) A) and 14 (2.621(3) A), and it is too
large to be considered as a chemical bonding between these
two atoms. Similar binding mode change by replacing the
dimethylamide ligand with chloride was observed in dim-
ethylsilylene bridged Me4C5/hydrazide ((g5–C5Me4)Si-
Me2(NNMe2)) titanium complex [15]. Due to the absence
of chemical bonding between the P and the Ti, the Ti–
N–P angle increases to 108.49(13)ꢁ from those observed
for the P-coordinated complexes 10 and 14 (95.93(15)ꢁ
and 93.6(3)ꢁ, respectively) and inversely the C(13)–N–P
angle decreases from 134.1(2)ꢁ and 135.6(6)ꢁ to
126.45(19)ꢁ. The Cp(cent)–Ti–N angle in 16 (104.08ꢁ is
slightly larger than those in 10 and 14. The nitrogen atom
is trigonal and the sum of bond angle around the nitrogen
is 359.5ꢁ. All the Ti, N, and P atoms are situated on the
phenylene plane.
2.3. Polymerization studies
The newly prepared complexes are tested for ethylene
and ethylene/1-hexene (co)copolymerization after activa-
tion with (Ph3C)[B(C6F5)4] and iBu3Al (polymerization
conditions: 30 mL toluene solution of 1-hexene (0.3 M),
0.50 lmol Ti, 2.0 lmol of [Ph3C][B(C6F5)4], 0.200 mmol
of Al(iBu)3, 60 psig ethylene, 90 ꢁC, 10 min) or after activa-
tion with MMAO (polymerization conditions: 30 mL tolu-
ene solution of 1-hexene (0.3 M), 0.50 lmol Ti, Al/Ti,
5000, 60 psig ethylene, 90 ꢁC, 10 min). All the complexes
show negligible activity (<200 kg/molTiÆh). Additional
coordination of phosphorous might be attributed to the
low activity [16]. Very low activities compared with the
standard CGC were observed with the dimethylsilylene
Me
Me
Me
Ti(NMe2)2
N
P
Ph
Ph
16
Fig. 2. Thermal ellipsoid plot (30% probability level) of 14. Hydrogen
Fig. 3. Thermal ellipsoid plot (30% probability level) of 16. Hydrogen
atoms are omitted for clarity.
atoms are omitted for clarity.

5630
C. Ji Wu et al. / Journal of Organometallic Chemistry 691 (2006) 5626–5634
bridged Me4C5/hydrazide titanium complex [(g5-
C5Me4)SiMe2(NNMe2)]TiCl2, where both nitrogens coor-
dinate to the titanium. Activity of the unbridged Cp/phos-
phinoamide titanium complexes, Cp*TiCl2(g2–Ph2PNR) is
also low while the similar complexes constructed with
monodentate ligand instead of the bidentate phosphinoa-
mide ligand, Cp*TiCl2(N = CNR2) or Cp*TiCl2(OAr),
show high activity [17].
1.64 (s, 3H, CH3), 1.74 (s, 3H, CH3), 1.76 (s, 3H, CH3),
2.53 and 2.60 (AB, J = 22 Hz, 2H, Cp-CH2), 4.87 (d,
J = 7.2 Hz, 1H, NH), 6.86 (td, J = 1.2, 7.6 Hz, 1H,
C6H4), 6.98–7.08 (m, 6H, Ph), 7.11 (d, J = 7.2 Hz, 1 H,
C6H4), 7.16 (td, J = 1.6, 7.6 Hz, 1H, C6H4), 7.38–7.48 (m,
4H, Ph), 7.70 (dd,J = 3.6, 8.0 Hz, 1H, C6H4) ppm.
13C{1H} NMR(C6D6): d 12.09 (CH3), 13.75 (CH3), 14.60
3
(CH3), 48.91 (Cp-CH2), 115.26 (d, JCP = 21 Hz, C6H4-
3
C6), 119.48 (C6H4-C4), 125.55 (d, JCP = 4.0 Hz, C6H4-
3
3. Experimental section
C2), 128.68 (d, JCP = 7 Hz, Ph-meta), 128.68 (C6H4-
C5 or 3), 128.71 (d, 3JCP = 6 Hz, Ph-meta), 129.03 (Ph-para)
2
3.1. General remarks
130.27 (C6H4-C5 or 3), 131.21 (d, JCP = 21 Hz, Ph-ortho),
2
131.30 (d, JCP = 21 Hz, Ph-ortho), 133.75 (Cp), 135 87
1
All manipulations were performed under an inert
atmosphere using standard glovebox and Schlenk tech-
niques. Toluene, pentane, and C6D6 were distilled from
benzophenone ketyl. NMR spectra were recorded on a
Varian Mercury plus 400. Elemental analyses were carried
out on a Perkin-Elmer 2400 CHN microanalyzer. Prepa-
ration of the starting materials 1 and 2 was previously
reported [6b].
(Cp), 137.62 (Cp), 140.23 (Cp), 141.25 (d, JCP = 14 Hz),
1
2
141.64 (d, JCP = 13 Hz), 145.09 (d, JCP = 17 Hz, C6H4-
C1) ppm. 31P NMR (C6D6): d 45.78 ppm. Anal. Calc.
(C26H26NP): C, 81.44; H, 6.86; N, 3.65. Found: C, 81.33;
H, 7.01; N, 3.54%.
3.4. Compound 5
The compound was synthesized by the reaction of 1 and
chlorodiisopropylphosphine using almost same conditions
and procedures as for 3. Excess chlorodiisopropylphos-
phine (1.3 equivalents) should be added to convert 1 com-
pletely to the desired product. The remained
chlorodiisopropylphosphine could be removed by evacua-
tion. Colorless oil was isolated in 75% yield. 1H NMR
3.2. Compound 3
To a flask containing 2-(Me2C5H3)C6H4NH2 (0.113 g,
0.61 mmol) in benzene (0.6 mL) was added pyridine
(0.240 g, 3.04 mmol) and chlorodiphenylphosphine
(0.134 g, 0.61 mmol). After the solution was stirred for 3
hours at room temperature, the generated white solid was
filtered. All volatiles were removed to give a residue which
was purified by recrystallization in pentane at -30 ꢁC.
White solid was isolated (0.144 g, 64%). 1H NMR
(C6D6): d 1.68 (s, 3H, CH3), 1.74 (d, J = 1.6 Hz, 3H,
3
3
(C6D6): d 0.89 (dd, JHH = 6.8 Hz, JPH = 10 Hz, 3H,
3
3
CH-CH3), 0.91 (dd, JHH = 6.8 Hz, JPH = 10 Hz, 3H,
3
3
CH-CH3), 0.93 (dd, JHH = 6.8 Hz, JPH = 16 Hz, 3H,
3
3
CH-CH3), 0.95 (dd, JHH = 6.8 Hz, JPH = 16 Hz, 3H,
CH-CH3), 1.38–1.49 (m, 2H, CH), 1.82 (s, 3H, CH3),
1.83 (q, J = 2.0 Hz, 3H, CH3), 2.74–2.89 (m, 2H, Cp-
CH2), 4.01 (d, J = 10.8 Hz, 1H, NH), 5.93 (dd, J = 1.6,
3.2 Hz, 1H, Cp-CH), 6.76 (td, J = 1.2, 7.6 Hz, 1H,
C6H4), 7.00 (dd, J = 1.6, 7.2 Hz, 1H, C6H4), 7.16 (td,
J = 1.6, 7.6 Hz, 1H, C6H4), 7.73 (ddd,J = 1.2, 4.0, 8.4 Hz,
1H, C6H4) ppm. 13C{1H} NMR(C6D6): d 14.93 (CH3),
15.01 (CH3), 17.04 (d, 1JCP = 8 Hz), 17.13 (d, 1JCP = 8 Hz),
2
CH3), 2.58 and 2.67 (AB, J = 22 Hz, 2H, Cp–CH2), 4.75
(d, J = 7.2 Hz, 1H, NH), 5.81 (d, J = 1.2 Hz, 1H, Cp–H),
6.79 (td, J = 1.2, 7.2 Hz, 1H, C6H4), 6.94–7.06 (m, 7H,
C6H4, Ph), 7.09 (td, J = 1.2, 8.0 Hz, 1 H, C6H4), 7.34–
7.42 (m, 4H, Ph), 7.65 (dd,J = 3.2, 8.0 Hz, 1H, C6H4)
ppm. 13C{1H} NMR(C6D6): d 14.89 (CH3), 15.00 (CH3),
3
44.55 (Cp–CH2), 115.21 (d,
JCP = 22 Hz, C6H4–C6),
3
2
2
119.48 (C6H4-C4), 124.82 (d, JCP = 4.0 Hz, C6H4-C2),
19.17 (d, JCP = 20 Hz, PCHCH3), 27.11 (d, JCP = 13 Hz,
3
2
125.27 (Cp–CH), 128.74 (d, JCP = 7 Hz, Ph-meta),
PCHCH3), 27.26 (d, JCP = 13 Hz, PCHCH3), 44.64 (Cp-
128.80 (C6H4-C5 or 3), 129.10 (d, JCP = 6 Hz, Ph-meta),
CH2), 114.69 (d, JCP = 22 Hz, C6H4-C6), 118.14 (C6H4-
3
3
129.12 (Ph-para) 130.29 (C6H4-C5 or 3), 131.14 (d, 2J
C4), 123.61 (d,presup3JCP = 3.0 Hz, C6H4-C2), 125.06
(Cp-CH), 128.71 (C6H4-C5 or 3), 130.02 (C6H4-C5 or 3),
140.40 (Cp), 141.68 (Cp), 143.87 (Cp), 147.12 (d,
2
CP = 21 Hz, Ph-ortho), 131.30 (d, JCP = 21 Hz, Ph-ortho),
1
139.77 (Cp), 141.13 (d, JCP = 13 Hz), 141.52 (d,
1JCP = 13 Hz), 142.12 (Cp), 143.60 (Cp), 145.00 (d,
2JCP = 16 Hz, C6H4-C1) ppm. 31P NMR (C6D6):
d
2JCP = 17 Hz, C6H4-C1) ppm. 31P NMR (C6D6):
d
61.93 ppm. HRMS-EI m/z = M+ Calcd. (C19H28NP):
301.1959. Found: 301.1958.
45.56 ppm. Anal. Calc. (C25H24NP): C, 81.28; H, 6.55; N,
3.79. Found: C, 81.66; H, 6.31; N, 3.91%.
3.5. Compound 6
3.3. Compound 4
The compound was synthesized by the reaction of 2 and
The compound was synthesized by the reaction of 2 and
chlorodiphenylphosphine using same conditions and pro-
cedures as for 3. White solid was isolated by recrystalliza-
tion in pentane at ꢀ30 ꢁC (58%). 1H NMR (C6D6): d
chlorodiisopropylphosphine using almost same conditions
and procedures as for 5. Colorless oil was isolated in 52%
3
yield. 1H NMR (C6D6): d 0.92 (dd, JHH
= 6.8 Hz,
3JPH = 10 Hz, 3H, CH-CH3), 0.94 (dd, JHH = 6.8 Hz,
3

C. Ji Wu et al. / Journal of Organometallic Chemistry 691 (2006) 5626–5634
5631
3
3JPH = 16 Hz, 3H, CH-CH3), 0.95 (dd, JHH = 6.8 Hz,
1.74 (s, 3H, CH3), 1.86 (s, 3H, CH3), 1.87 (s, 3H, CH3),
2.71 and 2.80 (AB, J = 22.4 Hz, 2H, Cp-CH2), 4.16 (d,
J = 10.8 Hz, 1H, NH), 6.81 (td, J = 0.8, 7.6 Hz, 1 H,
C6H4), 7.06 (d, J = 6.4 Hz, 1H, C6H4), 7.21 (td,J = 1.6,
8.0 Hz, 1H, C6H4), 7.75 (dd, J = 4.0, 8.0 Hz, 1H, C6H4)
ppm. 13C{1H} NMR(C6D6): d 12.19 (CH3), 13.83 (CH3),
3
3JPH = 10 Hz, 3H, CH-CH3), 0.98 (dd, JHH = 6.8 Hz,
3JPH = 16 Hz, 3H, CH-CH3), 1.38–1.52 (m, 2H, CH),
1.74 (s, 3H, CH3), 1.85 (s, 6H, CH3), 2.69 and 2.79 (AB,
J = 22.4 Hz, 2H, Cp-CH2), 4.12 (d, J = 10.8 Hz, 1H,
NH), 6.81 (t, J = 7.2 Hz, 1H, C6H4), 7.07 (d, J = 7.2 Hz,
1 H, C6H4), 7.20 (t, J = 7.6 Hz, 1H, C6H4), 7.80
(dd,J = 4.0, 8.0 Hz, 1H, C6H4) ppm. 13C{1H}
NMR(C6D6): d 12.15 (CH3), 13.85 (CH3), 14.67 (CH3),
2
14.72 (CH3), 26.8–27.8 (m, P-Cy), 29.54 (d, JCP = 18 Hz,
2
PCHCH2), 29.57 (d, JCP = 18 Hz, PCHCH2), 36.97 (d,
1
1JCP = 13 Hz), 37.16 (d, JCP = 13 Hz), 49.07 (Cp-CH2),
1
1
3
17.07 (d, JCP = 7 Hz), 17.13 (d, JCP = 7 Hz), 19.13 (d,
114.90 (d, JCP = 22 Hz, C6H4-C6), 118.07 (C6H4-C4),
2JCP = 20 Hz, PCHCH3), 19.20 (d, 2JCP = 20 Hz,
124.38 (C6H4-C2), 128.54 (C6H4-C5 or 3), 129.97 (C6H4-
C5 or 3), 133.60 (Cp), 136.15 (Cp), 137.12 (Cp), 141.04
2
PCHCH3), 27.10 (d, JCP = 13 Hz, PCHCH3), 27.20 (d,
2JCP = 13 Hz, PCHCH3), 49.00 (Cp-CH2), 114.64 (d,
3JCP = 21 Hz, C6H4-C6), 118.12 (C6H4-C4), 124.26 (d,
3JCP = 3.0 Hz, C6H4-C2), 128.58 (C6H4-C5 or 3), 130.06
(C6H4-C5 or 3), 133.57 (Cp), 136.04 (Cp), 137.21 (Cp),
(Cp), 147.41 (d, JCP = 17 Hz, C6H4-C1) ppm. 31P NMR
2
(C6D6):
d
56.77 ppm. HRMS-EI m/z = M+ Calcd.
(C26H38NP): 395.2742. Found: 395.2741.
140.81 (Cp), 147.14 (d, JCP = 16 Hz, C6H4-C1) ppm. 31P
3.8. Compound 9
2
NMR (C6D6): d 61.77 ppm. HRMS-EI m/z = M+ Calcd.
(C20H30NP): 315.2116. Found: 315.2118.
Compound3 (0.144 g, 0.39 mmol), Ti(NMe2)4(0.092 g,
0.041 mmol) and benzene (1.5 mL) were added into a seal-
able tube. The solution was stirred overnight at 80 ꢁC.
Removal of solvent gave red solid which was pure by the
NMR analysis. Single crystals of the bis(dimethylam-
ido)titanium complex were obtained by recrystallization
3.6. Compound 7
The compound was synthesized by the reaction of 1 and
chlorodicyclohexylphosphine using almost same conditions
and procedures as for 3. Excess chlorodicyclohexylphos-
phine (1.3 equivalents) should be added to convert 1 com-
pletely to the desired product. The remained
chlorodicyclohexylphosphine could not be removed from
the product by evacuation, The product was obtained con-
taminated with some chlorodicyclohexylphosphine in 82%
yield, which is used for the next reaction without further
1
in pentane at ꢀ30 ꢁC. H NMR (C6D6): d 1.97 (s, 6H,
CH3), 3.19 (s, 6H, NCH3), 3.20 (s, 6H, NCH3), 5.81 (s,
2H, Cp-CH ), 6.70–6.82 (m, 3H), 7.02–7.08 (m, 2H),
7.09–7.18 (m, 5H, ph-H), 7.62–7.72 (m, 4H) ppm.13C{1H}
NMR(C6D6): d 13.37 (CH3), 50.21 (NCH3), 50.26 (NCH3),
3
110.24 (C6H4-C4), 119.57 (d, JCP = 6 Hz, C6H4-C6),
119.79 (Cp-CH), 127.26 (Cp-CCH3), 127.71 (C6H4-
1
3
purification. H NMR (C6D6): d 1.06–1.78 (m, 22H, Cy),
C5 or 3), 127.71 (C6H4-C5 or 3), 128.11 (d, JCP = 7 Hz, Ph-
3
1.88 (s, 3H, CH3), 1.90 (q, J = 2.0 Hz, 3H, CH3), 2.79–
2.90 (m, 2H, Cp-CH2), 4.11 (d, J = 10.4 Hz, 1H, NH),
5.96 (t, J = 2.0 Hz, 1H, Cp-H), 6.81 (td, J = 1.2, 7.6 Hz,
1H, C6H4), 7.06 (dd, J = 1.2, 7.6 Hz, 1H, C6H4), 7.22
(td,J = 1.6, 7.6 Hz, 1H, C6H4), 7.80 (ddd, J = 0.8, 4.0,
8.0 Hz, 1H, C6H4) ppm. 13C{1H} NMR (C6D6): d 15.02
(CH3), 15.07 (CH3), 27.1–27.7 (m, P-Cy), 29.54 (d,
2JCP = 18 Hz, PCHCH2), 29.59 (d, 2JCP = 18 Hz,
PCHCH2), 37.00 (d, 1JCP = 13 Hz), 37.13 (d,
meta), 128.55 (Ph-para), 129.08 (d, JCP = 6 Hz, C6H4-C2),
2
131.07 (d, JCP = 18 Hz, Ph-ortho), 137.13 (Cp-Cbridgehead),
1
2
140.19 (d, JCP = 33 Hz), 161.38 (d, JCP = 10 Hz, C6H4-
C1) ppm. 31P NMR (C6D6): d 40.67 ppm. To a flask con-
taining the resulting bis(dimethylamido)titanium complex
in benzene (1.5 mL) was added Me2SiCl2(0.14 mL,
1.2 mmol). After the solution was stirred for 3 hours at
room temperature, all volatiles were removed under vac-
uum to give a yellow residue. The residue was dissolved
in CHCl3 and filtered over Celite. After removing solvent,
the residue was triturated in pentane to give brownish red
solid (0.14 g, 72%). 1H NMR (CDCl3): d 2.03 (s, 6H,
CH3), 6.46 (d, J = 8.0 Hz, 1H, C6H4), 6.83 (s, 2H, Cp-
CH), 7.15 (t, J = 7.2 Hz, 1H, C6H4), 7.20 (t, J = 7.6 Hz,
1H, C6H4), 7.36–7.48 (m, 7H, C6H4and Ph), 7.57–7.63
(m, 4H, ph-CH) ppm. 13C{1H} NMR(CDCl3): d 14.96
1JCP = 13 Hz), 44.71 (Cp-CH2), 114.83 (d, JCP = 21 Hz,
3
C6H4-C6), 118.04 (C6H4-C4), 123.62 (d, JCP = 3.0 Hz,
3
C6H4-C2), 125.07 (Cp-CH), 128.63 (C6H4-C5 or 3), 129.96
(C6H4-C5 or 3), 140.58 (Cp), 141.61 (Cp), 143.90 (Cp),
2
147.39 (d, JCP = 16 Hz, C6H4-C1) ppm. 31P NMR
(C6D6):
d
56.32 ppm. HRMS-EI m/z = M+ Calcd.
(C25H36NP): 381.2585. Found: 381.2585.
3
(CH3), 114.69 (C6H4-C4), 121.01 (d, JCP = 3 Hz, C6H4-
3.7. Compound 8
C6), 124.44 (Cp-CH), 128.44 (C6H4-C5 or 3), 128.54 (d,
3JCP = 8 Hz, Ph-meta), 129.96 (Ph-para), 130.29 (d,
1JCP = 6 Hz), 130.61 (d, 3J CP = 7 Hz, C6H4-C2), 132.11
The compound was synthesized by the reaction of 2 and
chlorodicyclohexylphosphine using almost same conditions
and procedures as for 7. The product was obtained con-
taminated with some chlorodicyclohexylphosphine in 75%
yield, which is used for the next reaction without further
2
(d, JCP = 14 Hz, Ph-ortho), 139.98 (Cp-CCH3), 142.34
2
(Cp-Cbridgehead), 161.25 (d, JCP = 8 Hz, C6H4-C1) ppm.
31P NMR (CDCl3):
d
7.73 ppm. Anal. Calc.
(C25H22Cl2NPTi): C, 61.76; H, 4.56; N, 2.88. Found: C,
61.97; H, 4.43; N, 3.21%.
1
purification. H NMR (C6D6): d 1.02–1.72 (m, 22H, Cy),

5632
C. Ji Wu et al. / Journal of Organometallic Chemistry 691 (2006) 5626–5634
3.9. Compound 10
3JCP = 5 Hz, C6H4-C6), 119.39 (Cp-CH), 127.49 (Cp-
3
CCH3), 128.05 (C6H4-C5 or 3), 128.60 (d, JCP = 8 Hz,
The complex was synthesized from 4 using same condi-
tions and procedures as for 9. Overall yield from 4 was
86%. The NMR data for the bis(dimethylamido)titanium
C6H4-C2), 128.96 (C6H4-C5 or 3), 137.22 (Cp-Cbridgehead),
2
164.30 (d, JCP = 9 Hz, C6H4-C1) ppm. 31P NMR (C6D6):
d 63.21 ppm. The analytical data for 11: 1H NMR
1
3
3
complex: H NMR (C6D6): d 1.82 (s, 3H, CH3), 1.93 (s,
(CDCl3): d 0.96 (dd, JHH = 6.8 Hz, JPH = 14 Hz, 6H,
3
3
6H,CH3), 2.90 (s, 6H, NCH3), 3.42 (s, 6H, NCH3), 5.90
(s, 1H, Cp-CH), 6.62–6.74 (m, 2H), 7.02–7.14 (m, 8 H),
7.52–7.58 (m, 2H), 7.66–7.72 (m, 2H) ppm. 13C{1H}
NMR(C6D6): d 11.90 (CH3), 12.68 (CH3), 12.92 (CH3),
48.07 (NCH3), 52.08 (NCH3), 52.18 (NCH3), 114.60
(C6H4-C4), 119.61 (Cp-CCH3), 119.71 (Cp-CCH3), 119.72
CH-CH3), 1.22 (dd, JHH = 6.8 Hz, JPH = 20 Hz, 6H,
CH-CH3), 1.81 (s, 6H, CH3), 2.28 (septet, J = 6.8 Hz,
2H, CH), 6.34 (d, J = 8.0 Hz, 1H, C6H4), 6.51 (s, 2H,
Cp-H), 6.94 (t, J = 7.2 Hz,
1 H, C6H4), 7.03 (d,
J = 7.6 Hz, 1H, C6H4), 7.08 (td, J = 1.6, 8.0 Hz, 1H,
C6H4) ppm. 13C{1H} NMR(CDCl3): d 14.69 (CH3), 19.26
(Cp-CH), 120.06 (d, JCP = 3 Hz, C6H4-C6), 124.40 (Cp-
(d, JCP = 3 Hz), 21.03 (d, JCP = 20 Hz, PCHCH3),
3
1
2
CCH3), 127.31 (C6H4-C5 or 3), 127.47 (C6H4-C5 or 3),
30.46 (d, JCP = 14 Hz, PCHCH3), 113.81 (C6H4-C4),
2
3
3
3
128.30 (d, JCP = 8 Hz, Ph-meta), 128.34 (d, JCP = 8 Hz,
121.90 (d, JCP = 3 Hz, C6H4-C6), 124.34 (Cp-CH),
3
Ph-meta), 128.72 (Ph-para), 129.65 (d, JCP = 6 Hz,
128.96 (C6H4-C5 or 3), 128.99 (C6H4-C5 or 3), 130.87 (d,
C6H4-C2), 130.55 (d, JCP = 17 Hz, Ph-ortho), 131.27 (d,
3JCP = 6 Hz, C6H4-C2), 137.78 (Cp-CCH3), 141.14 (Cp-
2
2JCP = 19 Hz, Ph-ortho), 136.92 (Cp-Cbridgehead), 140.47
Cbridgehead), 163.31 (d, JCP = 8 Hz, C6H4-C1) ppm. 31P
2
1
1
(d, JCP = 34 Hz), 141.40 (d, JCP = 34 Hz), 161.84 (d,
2JCP = 10 Hz, C6H4-C1) ppm. 31P NMR (C6D6):
NMR
(CDCl3):
d
28.53 ppm.
Anal.
Calc.
d
(C19H26Cl2NPTi): C, 54.57; H, 6.27; N, 3.35. Found: C,
54.72; H, 6.43; N, 3.12%.
42.21 ppm. Single crystals of 10 were obtained by vapor-
phase addition of pentane to a benzene solution. The ana-
1
lytical data for 10: H NMR (C6D6): d 1.75 (s, 3H, CH3),
3.11. Compound 12
1.92 (s, 3H, CH3), 2.27 (s, 3H, CH3), 6.32 (s, 1H, Cp-H),
6.53 (d, J = 7.6 Hz, 1H, C6H4), 6.82 (td,J = 1.6, 7.6 Hz,
1H, C6H4), 6.86 (t, J = 7.2 Hz, 1H, C6H4), 6.92–7.04 (m,
4H, Ph), 7.09 (d, J = 6.8 Hz, 1H, C6H4), 7.47–7.66 (m,
6H, Ph) ppm. 13C{1H} NMR(C6D6): d 12.69 (CH3),
14.40 (CH3), 15.23 (CH3), 115.15 (C6H4-C4), 121.58 (d,
3JCP = 6 Hz, C6H4-C6), 124.39 (Cp-CH), 128.73 (C6H4-
The complex was synthesized from 6 using same condi-
tions and procedures as for 9. Overall yield from 6 was
67%. The NMR data for the bis(dimethylamido)titanium
3
complex: 1H NMR (C6D6): d 0.81 (dd, JHH = 6.8 Hz,
3
3JPH = 10 Hz, 3H, CH-CH3), 1.19 (dd, JHH = 6.8 Hz,
3
3JPH = 10 Hz, 3H, CH-CH3), 1.19 (dd, JHH = 6.8 Hz,
3
3
C5 or 3), 128.83 (d, JCP = 8 Hz, Ph-meta), 128.87 (d,
3JPH = 18 Hz, 3H, CH-CH3), 1.24 (dd, JHH = 6.8 Hz,
3JCP = 8 Hz, Ph-meta), 128.93 (C6H4-C5 or 3), 129.98 (Ph-
3JPH = 18 Hz, 3H, CH-CH3), 1.79 (s, 3H, CH3), 1.82 (s,
3H, CH3), 1.88 (s, 3H, CH3), 2.50 (septet, J = 6.8 Hz,
2H, CH), 2.94 (s, 6H, NCH3), 3.43 (s, 6H, NCH3), 5.91
(s, 1H, Cp-H), 6.89 (d, J = 8.4 Hz, 1H, C6H4), 6.90 (t,
J = 7.6 Hz, 1H, C6H4), 7.17 (d, J = 8.4 Hz, 1 H, C6H4),
7.20 (t, J = 8.0 Hz, 1H, C6H4) ppm. 13C{1H} NMR(C6D6):
d 11.59 (CH3), 12.67 (CH3), 12.71 (CH3), 19.84 (d,
1JCP = 9 Hz), 21.02 (d, 1JCP = 9 Hz), 21.29 (d,
2JCP = 33 Hz, PCHCH3), 23.14 (d, 2JCP = 37 Hz,
1
para), 130.11 (Ph-para), 131.51 (d, JCP = 8 Hz), 131.51
1
3
(d, JCP = 8 Hz), 131.58 (d, JCP = 6 Hz, C6H4-C2),
2
131.81 (Cp-CCH3), 132.42 (d, JCP = 15 Hz, Ph-ortho),
2
132.65 (d, JCP = 15 Hz, Ph-ortho), 139.13 (Cp-CCH3),
139.40 (Cp-CCH3), 142.24 (Cp-Cbridgehead), 162.19 (d,
2JCP = 8 Hz, C6H4-C1) ppm. 31P NMR (C6D6):
d
6.33 ppm. Anal. Calc. (C26H24Cl2NPTi): C, 62.43 ; H,
4.84; N, 2.80. Found: C, 62.11; H, 5.11; N, 2.88%.
2
PCHCH3), 27.50(d, JCP = 26 Hz, PCHCH3), 29.60 (d,
3.10. Compound 11
2JCP = 30 Hz, PCHCH3), 44.24 (NCH3), 48.16 (NCH3),
53.50 (NCH3), 53.62 (NCH3), 114.76 (C6H4-C4), 117.00
3
The complex was synthesized from 5 using same condi-
tions and procedures as for 9. Overall yield from 5 was
75%. The NMR data for the bis(dimethylamido)titanium
(d, JCP = 6 Hz, C6H4-C6), 119.13 (Cp-CH), 119.68 (Cp-
CCH3), 122.95 (Cp-CCH3), 127.04 (Cp-CCH3), 128.96
(C6H4-C5 or 3), 136.93 (Cp-Cbridgehead), 164.80 (d,
3
complex:1H NMR (C6D6): d 0.99 (dd, JHH = 6.8 Hz,
2JCP = 9 Hz, C6H4-C1) ppm. 31P NMR (C6D6):
d
3
1
3JPH = 10 Hz, 6H, CH-CH3), 1.21 (dd, JHH = 6.8 Hz,
65.77 ppm. The analytical data for 12: H NMR (C6D6):
3JPH = 18 Hz, 6H, CH-CH3), 1.84 (s, 6H, CH3), 2.48 (sep-
tet, J = 6.8 Hz, 2H, CH), 3.15 (s, 6H, N-CH3), 3.16 (s, 6H,
N-CH3), 5.67 (s, 2H, Cp-H), 6.84 (d, J = 8.4 Hz, 1H,
C6H4), 6.88 (td, J = 1.2, 7.6 Hz, 1H, C6H4), 7.14 (dd,
J = 2.0, 7.2 Hz, 1 H, C6H4), 7.18 (ddd, J = 1.6, 7.2,
8.0 Hz, 1H, C6H4) ppm. 13C{1H} NMR(C6D6): d 13.38
d 0.94 (dd, JHH = 6.8 Hz, JPH = 14 Hz, 3H, CHCH3),
3
3
3
3
0.98 (dd, JHH = 6.8 Hz, JPH = 14 Hz, 3H, CHCH3),
1.23 (dd, J = 6.8, 20 Hz, 6H, CHCH3), 1.62 (s, 3H, CH3),
1.85 (s, 3H, CH3), 2.26 (s, 3H, CH3), 2.34 (septet,
J = 6.8 Hz, 2H, CH), 6.30 (s, 1H, Cp-H), 6.40 (d,
J = 7.6 Hz, 1H, C6H4), 7.02 (t, J = 7.2 Hz, 1 H, C6H4),
7.13 (d, J = 6.8 Hz, 1H, C6H4), 7.18 (t, J = 7.6 Hz, 1H,
C6H4) ppm.13C{1H} NMR(C6D6): d 12.29 (CH3), 14.13
1
2
(CH3), 20.57 (d, JCP = 9 Hz), 22.15 (d, JCP = 33 Hz,
2
PCHCH3), 28.48 (d, JCP = 27 Hz, PCHCH3), 51.00
(NCH3), 51.07 (NCH3), 110.42 (C6H4-C4), 116.90 (d,
(CH3), 14.92 (CH3), 19.27 (d, JCP = 5 Hz), 19.31 (d,
1

C. Ji Wu et al. / Journal of Organometallic Chemistry 691 (2006) 5626–5634
5633
2
1JCP = 3 Hz), 21.10 (d, JCP = 20 Hz, PCHCH3), 30.30 (d,
9. Overall yield from 4 was 83%. The NMR data for the
2JCP = 15 Hz, PCHCH3), 30.39 (d, 2JCP = 14 Hz,
bis(dimethylamido)zirconium complex: H NMR (C6D6):
1
PCHCH3), 113.84 (C6H4-C4), 122.27 (d, JCP = 3 Hz,
d 0.80 (dd, JHH = 6.8 Hz, JPH = 12 Hz, 3H, CH-CH3),
3
3
3
C6H4-C6), 124.30 (Cp-CH), 129.00 (C6H4-C5 or 3), 129.09
1.07 (dd, JHH = 6.8 Hz, JPH = 12 Hz, 3H, CH-CH3),
1.09 (dd, JHH = 6.8 Hz, JPH = 18 Hz, 3H, CH-CH3),
3
3
(C6H4-C5 or 3), 131.01 (Cp-CCH3), 131.43 (d, JCP = 7 Hz,
3
3
3
C6H4-C2), 137.47 (Cp-CCH3), 137.81 (Cp-CCH3), 141.20
1.14 (dd, JHH = 6.8 Hz, JPH = 18 Hz, 3H, CH-CH3),
1.82 (s, 3H, CH3), 1.90 (s, 3H, CH3), 1.98 (s, 3H, CH3),
2.34–2.48 (m, 2H, CH), 2.87 (6H, NCH3), 3.14 (6H,
NCH3), 5.87 (s, 1H, Cp-H), 6.72 (d, J = 8.0 Hz, 1H,
C6H4), 6.89 (td, J = 1.2, 7.2 Hz, 1H, C6H4), 7.16 (td,
J = 1.6, 7.6 Hz, 1H, C6H4), 7.21 (dd, J = 1.2, 7.2 Hz, 1H,
C6H4) ppm.31P NMR (C6D6): d 44.47 ppm. The analytical
3
3
(Cp-Cbridgehead), 163.56 (d, JCP = 9 Hz, C6H4-C1) ppm.
2
31P NMR (C6D6): d 26.04 ppm. Anal. Calc. (C20H28Cl2-
NPTi): C, 55.58; H, 6.53; N, 3.24. Found: C, 55.82; H,
6.39; N, 3.37%.
3.12. Compound 13
1
3
data for 15: H NMR (C6D6): d 0.94 (dd, JHH = 7.2 Hz,
3
The complex was synthesized from 7 using same condi-
tions and procedures as for 9. Overall yield from 7 was
56%. The analytical data for 13: 1H NMR (CDCl3): d
1.1–2.6 (m, 22H, Cy), 1.88 (s, 6H, CH3), 6.67 (d,
J = 8.0 Hz, 1H, C6H4), 6.70 (s, 2H, Cp-H), 7.23 (t,
J = 7.2 Hz, 1H, C6H4), 7.39 (td, J = 1.6, 7.6 Hz, 1H,
C6H4), 7.42 (d, J = 7.2 Hz, 1H, C6H4) ppm. 13C{1H}
NMR(CDCl3): d 14.64 (CH3), 25.82 (Cy), 27.04 (Cy),
3JPH = 14 Hz, 3H, CHCH3), 0.97 (dd, JHH = 7.2 Hz,
3JPH = 14 Hz, 3H, CHCH3), 1.10 (dd, JHH = 7.2 Hz,
3
3JPH = 20 Hz, 3H, CHCH3), 1.11 (dd, JHH = 7.2 Hz,
3
3JPH = 20 Hz, 3H, CHCH3), 1.68 (s, 3H, CH3), 1.89 (s,
3H, CH3), 2.18 (s, 3H, CH3), 2.20–2.32 (m, 2H, CH),
6.08 (s, 1H, Cp-H), 6.44 (d, J = 8.0 Hz, 1H, C6H4), 6.94
(td, J = 0.8, 7.2 Hz, 1 H, C6H4), 7.08–7.14 (m, 2H, C6H4)
ppm.13C{1H} NMR(C6D6): d 11.26 (CH3), 13.24 (CH3),
13.63 (CH3), 19.15 (d, 1JCP = 3 Hz), 19.20 (d, 1JCP = 3 Hz),
1
27.15 (d, JCP = 7 Hz, Cy), 27.92 (Cy), 31.17 (d,
2JCP = 15 Hz, Cy), 40.17 (d, JCP = 14 Hz, Cy), 113.42
20.53 (d, JCP = 19 Hz, PCHCH3), 28.25 (d, JCP = 11 Hz,
2
2
2
(C6H4-C4), 121.70 (d, JCP = 3 Hz, C6H4-C6), 124.22 (Cp-
PCHCH3), 28.32 (d, JCP = 11 Hz, PCHCH3), 115.90
3
2
CH), 128.66 (C6H4-C5 or 3), 128.83 (C6H4-C5 or 3), 130.27
(C6H4-C4), 116.56 (d, JCP = 3 Hz, C6H4-C6), 122.93 (Cp-
3
(d, JCP = 7 Hz, C6H4-C2), 138.14 (Cp-CCH3), 141.15
CH), 126.12 (Cp-CCH3), 129.02 (C6H4-C5 or 3), 129.81
3
(Cp-Cbridgehead), 163.29 (d, 2JCP = 8 Hz, C6H4-C1) ppm.31P
NMR (CDCl3): d 19.49 ppm. Anal. Calc. (C25H34Cl2-
NPTi): C, 60.26; H, 6.88; N, 2.81. Found: C, 60.44; H,
6.63; N, 2.95%.
(C6H4-C5 or 3), 130.41 (d, JCP = 7 Hz, C6H4-C2), 131.03
3
(Cp-CCH3), 131.20 (Cp-CCH3), 136.73 (Cp-Cbridgehead),
160.31 (d, JCP = 10 Hz, C6H4-C1) ppm.31P NMR
2
(C6D6): d 34.12 ppm. Anal. Calc. (C20H28Cl2NPZr): C,
Table 2
3.13. Compound 14
Crystallographic Parameters of 10, 14 and 16
10
14
16
The complex was synthesized from 8 using same condi-
tions and procedures as for 9. Overall yield from 8 was
78%. Single crystals of 14 were obtained by vapor-phase
addition of pentane to a benzene solution. The analytical
Formula
Fw
C26H24Cl2NPTi C26H36Cl2NPTi C29H34N3PTi
500.23
0.1 · 0.1 · 0.3
10.777(8)
13.924(16)
16.261(17)
90
512.33
503.46
Size (mm3)
0.15 · 0.15 · 0.5 0.2 · 0.15 · 0.05
˚
a (A)
10.205(3)
17.172(6)
14.795(5)
90
103.857(11)
90
2517.3(15)
Monoclinic
P21/n
1.352
4
0.630
23058
9.655(3)
15.373(7)
17.746(7)
90
98.110(14)
90
2607.6(18)
Monoclinic
P21/n
1.282
4
0.412
23913
1
˚
data for 14: H NMR (C6D6): d 1.1–2.6 (m, 22H, Cy),
b (A)
˚
c (A)
1.67 (s, 3H, CH3), 1.90 (s, 3H, CH3), 2.29 (s, 3H, CH3),
6.32 (s, 1H, Cp-H), 6.49 (d, J = 7.6 Hz, 1H, C6H4), 6.96
(t, J = 7.6 Hz, 1H, C6H4), 7.08–7.20 (m, 2H, C6H4)
ppm.13C{1H} NMR(C6D6): d 12.35 (CH3), 14.10 (CH3),
14.99 (CH3), 26.26 (Cy), 27.41 (Cy), 27.53 (d, 1JCP = 5 Hz,
a (ꢁ)
b (ꢁ)
c (ꢁ)
90
90
3
˚
V (A )
2440(4)
Orthorhombic
P212121
1.362
Crystal system
Space group
D (calc), gcmꢀ1
Z
2
Cy), 28.36 (Cy), 31.53 (d, JCP = 17 Hz, Cy), 40.42 (d,
2
2JCP = 15 Hz, Cy), 40.48 (d, JCP = 15 Hz, Cy), 113.68
4
3
(C6H4-C4), 122.40 (d, JCP = 3 Hz, C6H4-C6), 124.12 (Cp-
l, mmꢀ1
0.649
22465
CH), 128.93 (C6H4-C5 or 3), 129.09 (C6H4-C5 or 3), 131.00
Number of
data collected
Number of
unique data
Number of
variables
R (%)
Rw (%)
Goodness of fit
3
(Cp-CCH3), 131.45 (d, JCP = 7 Hz, C6H4-C2), 137.20
(Cp-CCH3), 137.54 (Cp-CCH3), 141.01 (Cp-Cbridgehead),
5523
377
5633
425
5858
447
2
164.22 (d, JCP = 8 Hz, C6H4-C1) ppm. 31P NMR (C6D6):
d 17.26 ppm. Anal. Calc. (C26H36Cl2NPTi): C, 60.95; H,
7.08; N, 2.73. Found: C, 60.78; H, 7.17; N, 2.99%.
0.0510
0.1302
1.002
0.0952
0.2580
1.019
0.0641
0.1746
1.083
3.14. Compound 15
˚
Data collected at 150(2) K with Mo Ka radiation (k(Ka) = 0.7107 A),
P
P
P
2
R(F) = iFoj ꢀ Fci/ jFoj with Fo > 2.0r(I), Rw = [ [wðF 2o ꢀ F c2Þ ]/
The complex was synthesized by the reaction 4 and
Zr(NMe2)4 using same conditions and procedures as for
P
[w(Fo)2]2]1/2 with Fo > 2.0r(I).

5634
C. Ji Wu et al. / Journal of Organometallic Chemistry 691 (2006) 5626–5634
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A. Fait, E. Ciaccia, I. Camurati, J. Am. Chem. Soc. 125 (2003)
10913;
50.51 ; H, 5.93; N, 2.95%. Found: C, 50.33 ; H, 5.69 ; N,
3.29%.
(d) J. Klosin, W.J. Kruper Jr., P.N. Nickias, G.R. Roof, P. De
Waele, K.A. Abboud, Organometallics 20 (2001) 2663.
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3.15. X-ray crystallography
Crystals of 10 , 14, and 16 coated with grease (Apiezon
N) were mounted onto a thin glass fiber with epoxy glue
and placed in a cold nitrogen stream at 150(2) K on Rigaku
single crystal X-ray diffractometer. The structures were
solved by direct methods (SHELXL-97) and refined against
all F2 data (SHELXL-97). All non-hydrogen atoms were
refined with anisotropic thermal parameters. The hydrogen
atoms were treated as idealized contributions. The crystal
data and refinement results are summarized in Table 2.
(b) C. Wang, G. Erker, G. Kehr, K. Wedeking, R. Frohlich,
Organometallics 24 (2005) 4760;
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Organometallics 15 (1996) 1572.
4. Supplementary material
CCDC 615699, 615700 and 615701 contain the supple-
mentary crystallographic data for 10, 14 and 16. These data
can be obtained free of charge via http://www.ccdc.cam.
ac.uk/conts/retrieving.html, or from the Cambridge Crys-
tallographic Data Centre, 12 Union Road, Cambridge
CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail: deposit@
ccdc.cam.ac.uk.
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Acknowledgement
[9] O. Kuhl, T. Koch, F.B. Somoza Jr., P.C. Junk, E. Hey-Hawkins, D.
¨
This work was supported by grant No. R01-2006-000-
10271-0 from the Basic Research Program of the Korea
Science & Engineering Foundation.
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