Synthesis, structure, and properties of 9-phospha-10-silatriptycenes and their derivatives

Article abstract of DOI:10.1021/om060681s

A variety of 9-phospha-10-silatriptycenes (PSiT) and some derivatives, such as the phosphine selenides and cis-platinum complexes, have been prepared in order to study their structures and characteristics as a phosphine ligand. The ¹J(P-Se) NMR coupling constant of the phosphine selenides demonstrate the large s character of the lone pair orbital on the phosphorus atom, attributable to the small C-P-C bond angles of the PSiT framework, as confirmed by X-ray crystallography. The strong trans influence of PSiT has been determined from the ¹J(Pt-C) coupling constant measurements of the cis-[PtMe₂(psit)₂], which is due to the increase in the P-Pt-P angle in the complexes derived from the steric repulsion between the two bulky PSiT ligands. Both the substituent on the silicon and the bridging benzene rings affect the electronic character. Electron-withdrawing substituents on the silicon atom slightly increase the s character of the phosphorus lone pair orbital, and the isopropoxy groups on the bridging benzene rings increase the trans influence.

Full text of DOI:10.1021/om060681s

6142
Organometallics 2006, 25, 6142-6148
Synthesis, Structure, and Properties of 9-Phospha-10-silatriptycenes
and their Derivatives
Hayato Tsuji,*,†,‡ Tomoyuki Inoue,† Yasuhiro Kaneta,† Shohei Sase,† Atsushi Kawachi,† and
Kohei Tamao*,†,§
International Research Center for Elements Science (IRCELS), Institute for Chemical Research,
Kyoto UniVersity, Uji, Kyoto, 611-0011, Japan
ReceiVed July 30, 2006
A variety of 9-phospha-10-silatriptycenes (PSiT) and some derivatives, such as the phosphine selenides
and cis-platinum complexes, have been prepared in order to study their structures and characteristics as
1
a phosphine ligand. The J(P-Se) NMR coupling constant of the phosphine selenides demonstrate the
large s character of the lone pair orbital on the phosphorus atom, attributable to the small C-P-C bond
angles of the PSiT framework, as confirmed by X-ray crystallography. The strong trans influence of
PSiT has been determined from the 1J(Pt-C) coupling constant measurements of the cis-[PtMe2(psit)2],
which is due to the increase in the P-Pt-P angle in the complexes derived from the steric repulsion
between the two bulky PSiT ligands. Both the substituent on the silicon and the bridging benzene rings
affect the electronic character. Electron-withdrawing substituents on the silicon atom slightly increase
the s character of the phosphorus lone pair orbital, and the isopropoxy groups on the bridging benzene
rings increase the trans influence.
the other bridgehead position have been extensively studied
(Figure 1a). Focused on the former series, the molecular
structure and the electronic character of the phosphorus lone
pair are expected to be modified by changing the other
bridgehead atom and the substituent on it. While phosphatrip-
tycene (E ) C, Figure 1a)2 and phosphagermatriptycene (E )
Ge)3a have already been reported, phosphasilatriptycene (E )
Si) is unprecedented, to the best of our knowledge. It would be
important to prepare the “missing link” compound for the
systematic study of the group 14 element-containing phospha-
triptycenes as well as exploring the application of the phos-
phatriptycene family as a new series of coordinating ligands.
We now report the synthesis of the 9-phospha-10-silatriptycenes
(PSiT) (Figure 1b) and some derivatives, such as the phosphine
selenides and cis-dimethylplatinum complexes, in order to study
their structures and characteristics as a phosphine ligand.
Introduction
Organophosphorus compounds with the phosphorus atom
fixed at the bicyclic bridgehead positions constitute a unique
class of ligands in organometallic chemistry. For example,
phosphabarrelenes,1 phosphatriptycenes,2,3 the silicon-con-
strained monodentate alkylphosphine (SMAP),4 and bicyclic
phosphites5 have been already reported. Some transition metal
complex-catalyzed reactions are known to easily proceed using
such a structurally fixed phosphorus ligand.1,2c,6 Besides the
catalytic activity, applications in functional materials science
are also envisioned based on their structural features. That is,
the phosphorus lone pair and the substituent on the other
bridgehead position are directed opposite on the same straight
line, which can be leveraged for molecular assembly, such as a
one-dimensional metal-coordinating polymer7 and a monolayer
on a metal surface.
Among these constrained phosphorus compounds, a series
of phosphatriptycenes with a group 14 or 152d,8-11 element on
Results and Discussion
* To whom correspondence should be sent. E-mail: tsuji@chem.s.u-
tokyo.ac.jp.
1. Synthesis and Structure. 1.1 Preparation of PSiT
Frameworks. Several synthetic routes to the unsymmetrical
heteroatom-substituted triptycenes have been already reported.
Bickelhaupt and co-workers employed o-phenylenemagnesium
derived from o-phenylenemercury12 to prepare symmetrical and
unsymmetrical 9,10-dimetallatriptycenes, such as the 9-germa-
10-phosphatriptycene derivative.3a Takahashi13 and Kawashima2b,d
prepared a 9,10-disilatriptycene derivative and a 9-phospha-
† Kyoto University.
‡ Present address: Department of Chemistry, Graduate School of Science,
The University of Tokyo, Hongo, Bunkyo-ku, Tokyo 113-0033, Japan.
§ Present address: RIKEN Frontier Research System, 2-1 Hirosawa,
Wako, Saitama 351-0198, Japan.
(1) (a) Breit, B.; Fuchs, E. Chem. Commun. 2004, 694. (b) Piechaczyk,
O.; Doux, M.; Ricard, L.; le Floch, P. Organometallics 2005, 24, 1204.
(2) (a) Jongsma, C.; Kleijn, J. P.; Bickelhaupt, F. Tetrahedron 1974,
30, 3465. (b) Kobayashi, J.; Agou, T.; Kawashima, T. Chem. Lett. 2003,
32, 1144. (c) Agou, T.; Kobayashi, J.; Kawashima, T. Chem. Lett. 2004,
33, 1028. (d) Agou, T.; Kobayashi, J.; Kawashima, T. Heteroat. Chem.
2004, 15, 437.
(3) (a) Rot, N.; de Wijs, W.-J.; de Kanter, F. J. J.; Dam, M. A.;
Bickelhaupt, F.; Lutz, M.; Spek, A. L. Phosphorus, Main Group Met. Chem.
1999, 22, 519. (b) Bickelhaupt, F Chem. Soc. ReV. 1999, 28, 17.
(4) Ochida, A.; Hara, K.; Ito, H.; Sawamura, M. Org. Lett. 2003, 5, 2671.
(5) Wadsworth, W. S.; Emmons, W. D. J. Am. Chem. Soc. 1962, 84,
610.
(6) Yamashita, H.; Catellani, M.; Tanaka, M. Chem. Lett. 1991, 241.
(7) Ishii, A.; Yoshioka, R.; Nakayama, J.; Hoshino, M. Tetrahedron Lett.
1993, 34, 8259.
(8) Azaphospha: (a) Hellwinkel, D.; Schenk, W. Angew. Chem., Int.
Ed. Engl. 1969, 8, 987. (b) Schomburg, D.; Sheldrick, W. S. Acta
Crystallogr. 1976, B32, 1021.
(9) Diphospha: (a) Weinberg, K. G.; Whipple, E. B. J. Am. Chem. Soc.
1971, 93, 1801. (b) Weinberg, K. G. J. Org. Chem. 1975, 40, 3586. (c)
Schomburg, D.; Sheldrick, W. S. Acta Crystallogr. 1975, B31, 2427. (d)
van der Putten, N.; Stam, C. H. Acta Crystallogr. 1980, B36, 1250.
(10) Arsaphospha and phosphastiba: Al-Jabar, N. A. A.; Massey, A. G.
J. Organomet. Chem. 1985, 287, 57.
(11) Diphosphathiophenetriptycenes: (a) Ishii, A.; Tsuchiya, T.; Na-
kayama, J.; Hoshino, M. Tetrahedron Lett. 1993, 34, 2347.
10.1021/om060681s CCC: $33.50 © 2006 American Chemical Society
Publication on Web 11/16/2006

9-Phospha-10-silatriptycenes and their DeriVatiVes
Organometallics, Vol. 25, No. 26, 2006 6143
Scheme 2
Figure 1. Structures of (a) phosphatriptycenes with a group 14
element on the other bridgehead and (b) 9-phospha-10-silatrip-
tycenes with substituents R1 and R2.
Scheme 1
Scheme 3
triptycene using tri(o-lithiophenyl)silane and tri(o-lithiophenyl)-
phosphine derivatives as the key intermediate, respectively. We
employed halogen-metal exchange reactions using o-dibro-
mobenzene 1 as the starting material14 for the preparation of
PSiT.
The synthetic procedure of H-PSiT-R2 5 is shown in
Scheme 1. The halogen-lithium exchange reaction of one of
the two bromine atoms of the o-dibromobenzene 1 was
performed in an Et2O/THF mixed solvent at -110 °C, followed
by the reaction with phosphorus trichloride to give tris(2-
bromophenyl)phosphine 2. The trilithio species, generated from
2 and tert-butyllithium, was treated with silicon tetrachloride
to give the desired phosphasilatriptycene derivative H-PSiT-
Cl 3. After the exchange of the chlorine atom on the silicon
center of 3 to a fluorine atom using aqueous hydrofluoric acid,
the resulting fluorosilane 4 was treated with methylmagnesium
bromide and n-dodecylmagnesium bromide to afford the cor-
responding H-PSiT-Me 5a and H-PSiT-n-C12H25 5b in 54%
and 32% yields from 2, respectively, as moisture- and air-stable
solids. The 31P and 29Si NMR chemical shifts of the phosphorus
and the silicon nuclei of 5 (in THF-d8) were significantly upfield
shifted (δP -44.4, δSi -27.9 for 5a; δP -42.5, δSi -29.9 for
5b) as compared with those of the triphenylphosphine (δP -3.1
in C6D6) and methyltriphenylsilane (δSi -10.4 in C6D6), similar
to the other phospha- and silatriptycenes.10-13 These observa-
tions are reasonably understood by the narrowed C-P-C and
C-Si-C angles of the PSiT framework, as observed in the
palladium complex trans-[PdCl2(psit-Me)2], which we recently
reported.15
Similarly, a series of i-PrO-PSiT-R2 10a-f and their
derivatives with various substituents on the bridgehead silicon
atom and two isopropoxy groups on the benzene rings have
been synthesized using 1,2-dibromo-4,5-diisopropoxybenzene
6 as the starting material (Scheme 2) to investigate the
substituent effect on the phosphorus lone pair orbital of PSiT.
The isopropoxy groups were introduced to enhance the solubility
of the PSiT derivatives.
1.2. Preparation of PSiT Derivatives. To clarify the
structures and properties of the PSiT framework, some deriva-
tives were synthesized (Scheme 3). The phosphine selenides
11 and 12 were prepared by the reaction of 5a and 10 with
selenium powder, respectively.16 The ligand exchange reaction
of cis-[PtMe2(cod)]17 or [PtMe2(µ-SMe2)]218 with PSiT deriva-
tives 5b and 10 afforded the soluble transition metal complexes
cis-[PtMe2(psit)2] 13 and 14, respectively.
(12) (a) Dam, M. A.; Akkerman, O. S.; de Kanter, F. J. J.; Bickelhaupt,
F.; Veldman, N.; Spek, A. L. Chem.-Eur. J. 1996, 2, 1139. (b) Dam, M.
A.; de Kanter, F. J. J.; Bickelhaupt, F.; Smeets, W. J. J.; Spek, A. L.; Fornies-
Camer J.; Cardin, C. J. Organomet. Chem. 1998, 550, 347. (b) Dam, M.
A.; Hoogervorst, W. J.; de Kanter, F. J. J.; Bickelhaupt, F.; Spek, A. L.
Organometallics 1998, 17, 1762.
(13) Takahashi, M.; Hatano, K.; Kawada, Y.; Koga, G.; Tokitoh, N.;
Okazaki, R. J. Chem. Soc., Chem. Commun. 1993, 1850.
(14) (a) Kyushin, S.; Shinnai, T.; Kubota, T.; Matsumoto, H. Organo-
metallics 1997, 16, 3800. (b) Chen, L. S.; Chen, G. J.; Tamborski, C. J.
Organomet. Chem. 1980, 193, 283.
(15) Tsuji, H.; Inoue, T.; Sase, S.; Tamao, K. Acta Crystallogr. E 2006,
E62, m535.
(16) Allen, D. W.; Taylor, B. F. J. Chem. Soc., Dalton Trans. 1982, 51.
(17) Haar, C. H.; Nolan, S. P.; Marshall, W. J.; Moloy, K. G.; Prock,
A.; Giering, W. P Organometallics 1999, 18, 474.
(18) Scott, J. D.; Puddephatt, R. J. Organometallics 1983, 2, 1643.

6144 Organometallics, Vol. 25, No. 26, 2006
Tsuji et al.
Table 2. 1J(P-Se) Values for Phosphine Selenides Derived
from PSiT, Ph3P, (2-furyl)3P, and Phosphatriptycene
entry
Ar3PdSe
1J(P-Se)/Hz
1
2
3
4
5
6
7
8
9
11
12a
12b
12c
12d
12e
12f
Ph3PdSe
(2-furyl)3PdSe
15b
795
786
786
786
786
794
794
732a
793a
828
Figure 2. ORTEP drawing of the platinum complex 14b with
thermal ellipsoid plot (50% probability). Hydrogen atoms and
isopropoxy groups are omitted for clarity. Selected bond lengths
(Å) and angles (deg): Pt(1)-C(1) 2.110(5), Pt(1)-C(2) 2.141(5),
Pt(1)-P(1) 2.2865(13), Pt(1)-P(2) 2.2964(13), P(1)‚‚‚Si(1) 3.1012-
(19), C(1)-Pt(1)-C(2) 81.31(19), P(1)-Pt(1)-P(2) 106.32(5).
10
b
a Ref 16. Structure is shown below. See ref 2.
Table 1. Crystal Data and Details of the Structure
Determination for 14b
Table 3. 1J(Pt-C) Values for cis-[PtMe2L2]
cis-[PtMe2L2]
1J(Pt-C)/Hz
13
14b‚AcOEt
entry
empirical formula
fw
C94H130N2O14P2PtSi2
1825.21
1
2
3
4
5
6
7
8
9
607
601
602
602
602
602
603
616
594
temperature
wavelength
cryst syst
173(2) K
0.71070 Å
triclinic
14a
14b
14c
14d
14e
14f
space group
unit cell dimens
P1h
a ) 15.139(4) Å, R ) 80.194(11)°
b ) 16.748(4) Å, â ) 69.414(10)°
c ) 20.323(5) Å, γ ) 78.327(11)°
4696.4(19) Å3
[PtMe2(PPh3)2]
[PtMe2(PPhMe2)2]
volume
Z
2
density (calcd)
absorp coeff
F(000)
cryst size
θ range for data collection
index ranges
1.291 Mg/m3
measured.16 Table 2 lists the data together with those of some
other phosphine selenides, including 15 derived from a 9-phos-
phatriptycene derivative2b for comparison. The 1J(P-Se) value
of 11 (795 Hz) is comparable to that of the tri(2-furyl)phosphine
selenide (793 Hz)16 and between those of Ph3PdSe (732 Hz)
and the selenide of phosphatriptycene 15 (828 Hz). This trend
1.614 mm-1
1912
0.20 × 0.15 × 0.15 mm3
3.22° to 25.50°
-18 e h e 18,
-20 e k e 17,
-23 e l e 24
1
no. of reflns collected
no. of indep reflns
33 086
17 045
in the J(P-Se) values (Ph3PdSe < 11 < 15) agrees with the
descending order of the C-P-C angles: Ph3P > PSiT15
>
completeness
97.5%
9-phosphatriptycene.2,19 These results demonstrate that the PSiT
derivatives possess a larger s character and thus work as weaker
σ-donating ligands, as compared to the ordinary triarylphos-
phines such as Ph3P.
max. and min. transmn
refinement method
no. of data/restraints/params
goodness-of-fit on F2
final R indices [I > 2σ(I)]
R indices (all data)
0.7938 and 0.7385
full-matrix least-squares on F2
17 045/0/1067
1.064
R1 ) 0.0516, wR2 ) 0.1079
R1 ) 0.0673, wR2 ) 0.1161
1.086 and -0.811 e‚Å-3
The data for 12a-f in Table 2 represent the influence of the
silicon substituents. Although the substituent effect on the 1J(P-
Se) values is not as drastic as the structural effect, the following
trends have been observed. The electron-donating groups on
the silicon atom, such as 4-Me2N-C6H4 and 4-MeO-C6H4, do
largest diff peak and hole
1.3. Structure of the cis-Dimethylplatinum Complex. The
structure of the platinum complex 14b determined by X-ray
crystallography is shown in Figure 2, and the details are
summarized in Table 1. The platinum complex 14b possesses
a distorted square-planar geometry about the platinum center
with a large P-Pt-P angle (106.32(5)°) and a small C-Pt-C
angle (81.31(19)°), which is due to the steric congestion of the
bulky PSiT ligands located at the cis positions. Such a severe
steric hindrance distorts even the PSiT structure as compared
to the trans-[PdCl2(psit)2].15 Thus, one of the three C-P-C
bond angles of PSiT in 14b is exceptionally smaller (94.9(2)°
for P(1); 94.4(2)° for P(2)) than the others (102.2(2)° and 103.1-
(2)° for P(1); 102.6(2)° and 103.1(2)° for P(2)). The P‚‚‚Si
distances (3.1012(19) and 3.0983(18) Å) are smaller than the
sum (3.90 Å) of the van der Waals radii of each atom and are
almost the same as that in the palladium complex.15
1
not cause any change in the J(P-Se) values as compared to
the parent C6H5 group (entries 3-5). In contrast, the electron-
withdrawing groups, such as 4-CF3-C6H4 and 3,5-(CF3)2-
1
C6H3, slightly increase the J(P-Se) value (entries 5-7). Not
only the substituents on the silicon atom but also the isopropoxy
groups on the bridging benzene rings affect the 1J(P-Se) values;
the 1J(P-Se) of 12a is smaller than that of 11 (entries 1 and 2)
by 9 Hz.
2.2. Trans Influence of PSiT as a Ligand. The trans
influence20 of the PSiT ligand in cis-[PtMe2(psit)2] was evaluated
1
on the basis of the coupling constant J(Pt-C) measurements
as listed in Table 3. The 1J(Pt-C) values of 13 and 14a-f are
between those of cis-[PtMe2(PPh3)2] and cis-[PtMe2(PMe2-
(19) The estimated C-P-C angles of the optimized structure at the
B3LYP/6-311G* level are as follows: Ph3P (102.4°) > 9-phospha-10-
silatriptycene (98.7°) > 9-phosphatriptycene (94.1°).
(20) Appleton, T. G.; Clark, H. C.; Manzer, L. E. Coord. Chem. ReV.
1973, 10, 335.
2. Properties of PSiT as a Ligand. 2.1. The s Character
of the Phosphorus Lone Pair Orbital. To estimate the s
character of the lone pair orbital of PSiT, the NMR coupling
1
constant J(P-Se) of the phosphine selenides 11 and 12 was

9-Phospha-10-silatriptycenes and their DeriVatiVes
Organometallics, Vol. 25, No. 26, 2006 6145
Ph)2],21 demonstrating that the trans influence of PSiT is greater
than that of PPh3 and smaller than that of PMe2Ph. Although
the aryl groups on the silicon atom exhibit a negligible effect,
the substituents on the bridging benzene rings affect the
electronic nature of the PSiT. Thus, the 1J(Pt-C) value of cis-
[PtMe2(iPrO-PSiT-Me)2] 14a is smaller than that of cis-
[PtMe2(H-PSiT-n-C12H25)2] 13. The enhancement of the trans
influence in 14a as compared to 13 is attributable to the greater
electron-donating ability of the isopropoxy groups on the
bridging benzene rings.
mixture was stirred for an additional 2 h, the mixture was allowed
to warm gradually to room temperature. The solvents were
evaporated, and the residue was dissolved in toluene and passed
through a pad of silica gel. The filtrate was concentrated to give
the crude product. The crude product was recrystallized from
toluene/EtOH to give 2 (10.9 g, 21.8 mmol, 62%) as colorless
1
crystals. H NMR (C6D6): δ 6.69-6.82 (m, 6H), 6.90-6.94 (m,
3H), 7.36-7.40 (m, 3H). 13C NMR (CDCl3): δ 127.7, 130.2, (d,
J(C-P) ) 34 Hz), 130.6, 133.1, 134.6, 136.6 (d, J(C-P) ) 11
Hz). 31P NMR (CDCl3): δ -3.00.
Preparation of H-PSiT-Cl (3). A solution of t-BuLi in pentane
(1.56 M, 55 mL, 86 mmol) was added dropwise to a solution of 2
(7.00 g, 14.0 mmol) in Et2O (140 mL) and THF (30 mL) at -78
°C. After the addition was completed, the mixture was stirred for
an additional 2 h and a solution of silicon tetrachloride (1.52 g,
14.0 mmol) in Et2O (30 mL) was added dropwise to the mixture at
-78 °C. After the mixture was stirred for an additional 2 h,
chlorotrimethylsilane (9.77 g, 90.0 mmol) was added and the
mixture was allowed to warm to room temperature. The solvents
were evaporated, and the residue was dissolved in toluene and
filtered. The filtrate was concentrated to give the crude product 3.
The crude product was used in the preparation of 4 without further
The greater trans influence of PSiT than that of PPh3 seems
to contradict the fact that the lone pair orbital of PSiT has a
high degree of s character as estimated using the phosphine
selenides. This discrepancy can be understood to be due to steric
effects. In general, the greater trans influence is observed for
complexes having a larger bite angle (P-M-P),22 which is also
the case with these cis-[PtMe2(psit)2] complexes, as observed
by the X-ray structure of 14b (Figure 2).
Conclusion
In summary, we have synthesized phosphasilatriptycenes
(PSiT) and their derivatives, such as phosphine selenide and
the cis-[PtMe2(psit)2] complexes, in order to study the ability
of PSiT as a ligand. The NMR coupling constant measurements
of the phosphine selenides demonstrate the large s character of
the lone pair orbital due to the small C-P-C bond angles, and
the strong trans influence as a ligand in cis-[PtMe2(psit)2]
compared to PPh3 due to the steric bulkiness. Regarding the
substituent effect, the isopropoxy groups on the bridging benzene
rings intensify the trans influence of PSiT. However, at least in
the cis bis(phosphine) complexes, the trans influence is domi-
nated by the steric bulkiness rather than the electronic effect.
1
purification. H NMR (C6D6): δ 6.88-6.99 (m, 6H), 7.81-7.92
(m, 6H). 13C NMR (THF-d8): δ 128.1, 129.2, (d, J(C-P) ) 27
Hz), 132.2, 135.2 (d, J(C-P) ) 46 Hz), 140.1, 146.3. 29Si NMR
(THF-d8): δ -18.4 (d, J(Si-P) ) 9.5 Hz). 31P NMR (THF-d8): δ
-55.4.
Preparation of H-PSiT-F (4). A 47% aqueous solution of
hydrofluoric acid (50 mL) was added to a solution of 3 (7.78 g,
24.1 mmol) in toluene (300 mL) at room temperature. The mixture
was stirred for 2 h. After removal of the aqueous layer, the organic
layer was washed with water, dried over MgSO4, and filtered. The
filtrate was concentrated to give the crude product 4. The crude
1
product was used in the next step without further purification. H
NMR (C6D6): δ 6.90-6.95 (m, 6H), 7.75-7.78 (m, 3H), 7.84-
7.90 (m, 3H). 13C NMR (CDCl3): δ 128.2 (d, J ) 27 Hz), 128.6,
131.7, 134.7 (dd, J ) 46 and 2.2 Hz), 138.6 (d, J ) 15 Hz), 145.6
(dd, J ) 10 and 6.7 Hz). 19F NMR (C6D6): δ -195.7. 29Si NMR
(CDCl3): δ -22.6 (dd, J ) 308 and 9.4 Hz). 31P NMR (C6D6): δ
-54.8. HRMS (EI): calcd for C18H12FPSi 306.0430, found
306.0443.
Experimental Section
General Procedures. All manipulations were carried out under
an argon atmosphere using standard Schlenk techniques. 1H NMR
spectra were measured with a Varian Mercury-300 (300 MHz)
spectrometer. 13C, 19F, 29Si, and 31P NMR were measured with a
JEOL EX-270 (67.8 MHz for 13C, 254 MHz for 19F, 53.5 MHz for
29Si, and 109 MHz for 31P). Chemical shifts are reported in δ (ppm),
Preparation of H-PSiT-R (5a,b). A typical procedure is
reported for 5b. A solution of n-C12H25MgBr in THF (0.736 M,
2.70 mL, 3.67 mmol) was added dropwise to a solution of the crude
product 4 (3.00 g, 9.80 mmol) in THF at 0 °C. The mixture was
allowed to warm to room temperature and stirred for 3 h. The
reaction was quenched with 5% aqueous NH4Cl. The aqueous layer
was extracted with Et2O, and the combined organic layer was
washed with water, dried over MgSO4, and filtered. The filtrate
was concentrated to give the crude product 5b. The crude product
was purified by silica gel column chromatography (eluent: hexane/
ethyl acetate ) 100/1) to give 5b (46.4 mg, 0.102 mmol, 32% yield
based on 2) as colorless crystals.
referenced to H of residual protons and 13C signals of deuterated
1
solvents as internal standards or to 19F, 29Si, and 31P of CFCl3, Me4-
Si, and 85% H3PO4 as external standards, respectively. Melting
points were determined with a Yanaco MP-S3 instrument. Mass
spectra and elemental analysis were performed at the Mass
Spectrum and Microanalysis Division of Institute for Chemical
24
Research, Kyoto University. [PtMe2(cod)]23 and [PtMe2(µ-SMe2)]2
were prepared according to the reported procedures. Benzene was
distilled over sodium. Other chemicals and solvents (Wako Pure
Chemical Industries, anhydrous products) were used without further
purification.
Preparation of Tris(2-bromophenyl)phosphine (2). A solution
of n-BuLi in hexane (1.60 M, 80.0 mL, 128 mmol) was added
dropwise to a solution of 1,2-dibromobenzene 1 (30.2 g, 128 mmol)
in Et2O (256 mL) and THF (200 mL) at -110 °C. After the addition
was completed, the mixture was stirred for an additional 2 h, and
a solution of phosphorus trichloride (4.88 g, 35.5 mmol) in Et2O
(20 mL) was added dropwise to the mixture at -110 °C. After the
1
5a: colorless crystals. Mp: 278-279 °C. H NMR (C6D6): δ
0.83 (s, 3H), 6.96-7.06 (m, 6H), 7.51-7.54 (m, 3H), 8.00-8.06
(m, 3H). 13C NMR (THF-d8): δ -14.0, 128.2 (d, J(C-P) ) 16
Hz), 132.3, 134.5, 135.2, 143.4, 147.5 (d, J(C-P) ) 9.0 Hz). 29Si
NMR (THF-d8): δ -27.9 (d, J(Si-P) ) 6.8 Hz). 31P NMR (THF-
d8): δ -44.4. Anal. Calcd for C19H15PSi: C, 75.47; H, 5.00.
Found: C, 75.37; H, 5.14.
5b: colorless crystals. Mp: 89-90 °C. 1H NMR (C6D6): δ 0.98
(m, 3H), 1.37-1.44 (m, 16H), 1.60-1.68 (m, 4H), 2.02-2.07 (m,
2H), 6.97-7.10 (m, 6H), 7.71-7.73 (m, 3H), 8.04-8.09 (m, 3H).
13C NMR (C6D6): δ 6.45, 14.5, 23.3, 24.3, 29.8, 30.0, 30.26, 30.31,
30.34, 30.4, 32.5, 34.7, 128.0 (d, J ) 30 Hz), 132.7, 134.9, 135.6,
143.2 (d, J ) 2.2 Hz), 147.7 (d, J ) 8.9 Hz). 29Si NMR (C6D6):
(21) 13C NMR data for Organometallic Compounds; Mann, B. E., Taylor,
B. F., Eds.; Academic Press: London, 1981.
(22) (a) Appleton, T. G.; Bennett, M. A.; Tomkins, I. B. J. Chem. Soc.,
Dalton Trans. 1976, 439. (b) Hietkamp, S.; Stufkens, D. J.; Vrieze, K. J.
Organomet. Chem. 1979, 169, 107.
(23) Clark, H. C.; Manzer, L. E. J. Organomet. Chem. 1973, 59, 411.
(24) Scott, J. D.; Puddephatt, R. J. Organometallics 1983, 2, 1643.

6146 Organometallics, Vol. 25, No. 26, 2006
Tsuji et al.
δ -29.9 (d, J ) 6.7 Hz). 31P NMR (C6D6): δ -42.5. HRMS (EI):
calcd for C30H37PSi 456.2402, found 456.2422.
-42.9. MS(EI): 742 (M+). Anal. Calcd for C43H55O7PSi: C, 69.51;
H, 7.46. Found: C, 69.21; H, 7.53.
10d: colorless crystals. Mp: 195-197 °C. 1H NMR (C6D6): δ
1.13 (d, J ) 6.0 Hz, 18H), 1.14 (d, J ) 6.0 Hz, 18H), 4.29 (sept,
J ) 6.0 Hz, 3H), 4.34 (sept, J ) 6.0 Hz, 3H), 7.37 (m, 2H), 7.69
(s, 3H), 7.96 (d, J(H-P) ) 12.3 Hz,3H), 8.38 (m, 2H). 13C NMR
(C6D6): δ 22.5, 22.5, 71.4, 72.1, 123.6 (d, J(C-P) ) 2.2 Hz), 124.1
(d, J(C-P) ) 53.2 Hz), 129.1, 131.0, 135.7, 136.6, 142.2 (d, J(C-
P) ) 5.6 Hz), 148.7, 149.1, 149.3. 29Si NMR (C6D6): δ -36.3 (d,
J(Si-P) ) 5.4 Hz). 31P NMR (C6D6): δ -42.8. MS(EI): 712 (M+).
Anal. Calcd for C42H53O6PSi: C, 70.76; H, 7.49. Found: C, 70.49;
H, 7.61.
Preparation of Tris(2-bromo-4,5-diisopropoxyphenyl)phos-
phine (7). The preparative procedure is the same as that of 2.
Yield: 45%, colorless solid. Mp: 149-150 °C. 1H NMR
(CDCl3): δ 1.13 (d, J ) 6.0 Hz, 18H), 1.34 (d, J ) 6.0 Hz, 18H),
4.05 (sept, J ) 6.0 Hz, 3H), 4.49 (sept, J ) 6.0 Hz, 3H), 6.28 (d,
J ) 2.4 Hz,3H), 7.13 (d, J ) 3.6 Hz,3H). 13C NMR (CDCl3): δ
22.1, 22.3, 72.4, 72.5, 121.3 (d, J(C-P) ) 3.3 Hz), 121.4 (d, J(C-
P) ) 35 Hz), 123.7, 128.8 (d, J(C-P) ) 11 Hz), 148.3, 150.7. 31
P
NMR (CDCl3): δ -1.31. MS(EI): 848 (M+). Anal. Calcd for
C36H48Br3O6P: C, 51.02; H, 5.71. Found: C, 51.13; H, 5.59.
10e: colorless crystals. Mp: 220-221 °C. 1H NMR (C6D6): δ
1.13 (d, J ) 6.0 Hz, 18H), 1.16 (d, J ) 6.0 Hz, 18H), 4.28 (sept,
J ) 6.0 Hz, 3H), 4.38 (sept, J ) 6.0 Hz, 3H), 7.47 (d, J ) 8.1 Hz,
2H), 7.58 (s, 3H), 7.95 (d, J(H-P) ) 12.3 Hz,3H), 8.23 (d, 7.5
Hz, 2H). 13C NMR (C6D6): δ 22.4, 22.6, 71.4, 72.5, 123.7, 123.9,
124.4, 125.6 (d, J ) 3.3 Hz), 134.8, 136.8, 142.28 (d, J ) 5.6 Hz),
148.7, 149.4, 149.7. 19F NMR (C6D6): δ -62.6. 29Si NMR
(C6D6): δ -36.7 (d, J(Si-P) ) 6.7 Hz). 31P NMR (C6D6): δ
-42.7. MS(EI): 780 (M+). Anal. Calcd for C43H52F3O6PSi: C,
66.13; H, 6.71. Found: C, 66.34; H, 6.84.
10f: colorless crystals. Mp: 208-209 °C. 1H NMR (C6D6): δ
1.13 (d, J ) 6.0 Hz, 18H), 1.17 (d, J ) 6.0 Hz, 18H), 4.29 (sept,
J ) 6.0 Hz, 3H), 4.34 (sept, J ) 6.0 Hz, 3H), 7.45 (s, 3H), 7.94
(d, J(H-P) ) 12.0 Hz,3H), 8.02 (m, 1H), 8.83 (m, 2H). 13C NMR
(C6D6): δ 22.42, 71.62, 72.12, 122.1, 124.0, 124.7, 132.0, 132.5,
133.7, 133.8 (d, J ) 2.2 Hz), 136.2, 141.7 (d, J ) 5.6 Hz), 149.0,
149.2, 149.5. 19F NMR (C6D6): δ -62.5. 29Si NMR (C6D6): δ
-36.7 (d, J(Si-P) ) 5.4 Hz). 31P NMR (C6D6): δ -43.2. MS-
(EI): 848 (M+). Anal. Calcd for C43H52F3O6PSi: C, 62.25; H, 6.06.
Found: C, 62.08; H, 6.21.
Preparation of i-PrO-PSiT-Cl (8). A solution of t-BuLi (1.56
M, 46.0 mL, 71.8 mmol) in pentane was added dropwise to a
solution of 7 (10.0 g, 11.8 mmol) in Et2O (120 mL) and THF (24
mL) at -78 °C. After the addition was completed, the mixture was
stirred for an additional 1 h and a solution of silicon tetrachloride
(2.00 g, 11.8 mmol) in Et2O (25 mL) was added dropwise to the
mixture at -78 °C. After the mixture was stirred for an additional
2 h, the mixture was allowed to warm to room temperature. The
solvents were evaporated, and the residue was dissolved in hexane
and filtered. The filtrate was concentrated to give the crude product
8. The crude product was used in the next reaction without further
1
purification. H NMR (C6D6): δ 1.12 (d, J ) 6.3 Hz, 18H), 1.16
(d, J ) 6.6 Hz), 4.24 (sept, J ) 6.0 Hz, 3H), 4.34 (sept, J ) 6.0
Hz, 3H), 7.76 (s, 3H), 7.81 (d, J ) 11.7 Hz, 3H). 31P NMR
(C6D6): δ -52.6. HRMS (EI): calcd for C36H48O635ClPSi 670.2646,
found 670.2637.
Preparation of i-PrO-PSiT-F (9). The procedure is the same
as that of 4. The obtained crude product 9 was used in the next
1
reaction without further purification. H NMR (C6D6): δ 1.12 (d,
J ) 4.2 Hz, 18H), 1.16 (d, J ) 9.9 Hz), 4.20-4.30 (m, 6H), 7.69
(s, 3H), 7.80 (dd, J ) 1.5, 11.9 Hz, 3H). 13C NMR (C6D6): δ 22.4,
71.6, 71.7, 120.6, 124.1 (d, J ) 47 Hz), 129.3, 132.4, 141.0 (dd, J
) 6.6, 6.6 Hz), 149.4 (d, J ) 15 Hz). 19F NMR (C6D6): δ -193.2
(d, J ) 5.1 Hz). 31P NMR (C6D6): δ -55.9. HRMS (EI): calcd
for C36H48O6FPSi 654.2942, found 654.2954.
Preparation of i-PrO-PSiT-R (10a-f). PSiT 10a-f were
prepared similarly to 5a in 28, 63, 45, 42, 55, and 37% yields based
on 7, respectively.
10a: colorless crystals. Mp: 175-176 °C. 1H NMR (C6D6): δ
0.99 (s, 3H), 1.13 (d, J ) 6.3 Hz, 18H), 1.22 (d, J ) 6.3 Hz, 18H),
4.26 (sept, J ) 6.0 Hz, 3H), 4.45 (sept, J ) 6.0 Hz, 3H), 7.50 (s,
3H), 7.88 (d, J(H-P) ) 12.0 Hz, 3H). 13C NMR (C6D6): δ -14.3,
21.2, 21.4, 70.1, 71.1, 121.5 (d, J(C-P) ) 2.2 Hz), 122.7 (d, J(C-
P) ) 50 Hz), 135.2 (d, J(C-P) ) 2.2 Hz), 140.8 (d, J(C-P) ) 6.7
Hz), 147.4, 148.0 (d, J(C-P) ) 18 Hz). 29Si NMR (C6D6): δ -27.0
(d, J(Si-P) ) 5.4 Hz). 31P NMR (C6D6): δ -48.6. HRMS (EI):
calcd for C37H51O6PSi 650.3193, found 650.3195.
10b: colorless crystals. Mp: >300 °C. 1H NMR (C6D6): δ 1.14
(s, 18H), 1.16 (s, 18H), 2.54 (s, 6H), 4.31 (sept, J ) 6.0 Hz, 3H),
4.40 (sept, J ) 6.0 Hz, 3H), 6.77 (d, J ) 8.7 Hz, 2H), 7.83 (s,
3H), 7.98 (d, J(H-P) ) 12.6 Hz, 3H), 8.35 (d, 8.7 Hz, 2H). 13C
NMR (C6D6): δ 22.5, 22.6, 39.6, 71.4, 72.1, 113.0, 123.9, 124.6,
136.9 (d, J(C-P) ) 2.2 Hz), 137.7, 142.4 (d, J(C-P) ) 5.6 Hz),
148.7, 148.9, 149.2, 152.1. 29Si NMR (C6D6): δ -36.3 (d, J(Si-
P) ) 5.4 Hz). 31P NMR (C6D6): δ -43.0. MS(EI): 755 (M+).
Anal. Calcd for C42H53O6PSi: C, 69.90; H, 7.73. Found: C, 69.74;
H, 7.84.
Preparation of Phosphine Selenide of H-PSiT-Me (11). A
mixture of 5a (31.5 mg, 0.0417 mmol) and selenium (27.6 mg,
0.349 mmol) in CHCl3 (2.5 mL) was stirred for 3.5 h under reflux.
The excess of selenium in the reaction mixture was removed by
filtration, and the filtrate was evaporated to give the crude product,
which was recrystallized from toluene/EtOH to give pure 11 (246
mg, 0.645 mmol, 65% yield) as colorless crystals. Mp: >300 °C.
1H NMR (CD2Cl2): δ 1.30 (s, 3H), 7.36-7.46 (m, 6H), 7.74-
7.79 (m, 3H), 8.36-8.45 (m, 3H). 13C NMR (CDCl3): δ -14.3,
128.2 (d, J(C-P) ) 13 Hz), 128.8 (d, J(C-P) ) 2.2 Hz), 130.8
(d, J(C-P) ) 10 Hz), 131.2 (d, J(C-P) ) 13 Hz), 138.3 (d, J(C-
P) ) 71 Hz), 140.3 (d, J(C-P) ) 7.8 Hz). 29Si NMR (CDCl3): δ
-30.9 (d, J(Si-P) ) 29.6 Hz). 31P NMR (CDCl3): δ 11.9 (satellite,
J(P-Se) ) 795 Hz). Anal. Calcd for C19H15PSiSe: C, 59.84; H,
3.96. Found: C, 59.61; H, 4.12.
Preparation of Phosphine Selenide of i-PrO-PSiT-R (12a-
f) and Their Spectral Data. Phosphine selenides PSiT 12a-f were
prepared similarly to 11 in 87, 86, 85, 89, 83, and 79% yields,
respectively.
12a: colorless crystals. Mp: >300 °C. 1H NMR (C6D6): δ 0.86
(s, 3H), 1.13 (d, J ) 6.3 Hz, 18H), 1.19 (d, J ) 6.0 Hz), 4.39-
4.55 (m, 6H), 7.37 (d, J(H-P) ) 4.2 Hz, 3H), 8.65 (d, J(H-P) )
15.9 Hz, 3H). 13C NMR (C6D6): δ -14.1, 22.2, 22.6, 71.3, 72.6,
120.0 (d, J(C-P) ) 17 Hz), 121.7 (d, J(C-P) ) 12 Hz), 134.0 (d,
J(C-P) ) 5.6 Hz), 134.5 (d, J(C-P) ) 92 Hz), 149.2 (d, J(C-P)
) 2.2 Hz), 149.8 (d, J(C-P) ) 17 Hz). 29Si NMR (C6D6): δ -30.6
(d, J(Si-P) ) 29.5 Hz). 31P NMR (C6D6): δ 15.9 (satellite, J(P-
Se) ) 786 Hz). HRMS (EI): calcd for C37H51O6PSeSi 730.2358,
found 730.2319.
12b: colorless crystals. Mp: >300 °C. 1H NMR (C6D6): δ 1.11
(d, J ) 6.3 Hz, 18H), 1.13 (d, J ) 6.3 Hz), 2.52 (s, 6H), 4.34 (m,
6H), 6.72 (d, J ) 8.4 Hz, 2H), 7.75 (d, J(H-P) ) 4.2 Hz, 3H),
8.23 (d, J ) 8.7 Hz, 2H), 8.37 (d, J(H-P) ) 12.6 Hz, 3H). 29Si
NMR (C6D6): δ -40.5 (d, J(Si-P) ) 29.5 Hz). 31P NMR (C6D6):
10c: colorless crystals. Mp: 168-169 °C. 1H NMR (C6D6): δ
1.14 (d, J ) 6.0 Hz, 18H), 1.15 (d, J ) 6.0 Hz, 18H), 3.35 (s, 3H),
4.30 (sept, J ) 6.0 Hz, 3H), 4.38 (sept, J ) 6.0 Hz, 3H), 7.00 (d,
J ) 8.7 Hz, 2H), 7.74 (s, 3H), 7.97 (d, J(H-P) ) 12.3 Hz,3H),
8.32 (d, 8.7 Hz, 2H). 13C NMR (C6D6): δ 22.5, 22.6, 54.8, 71.4,
72.2, 115.2, 123.8, 124.5, 136.2 (d, J(C-P) ) 2.2 Hz), 138.1, 142.3
(d, J(C-P) ) 5.6 Hz), 148.7, 149.1, 149.3, 162.2. 29Si NMR
(C6D6): δ -36.3 (d, J(Si-P) ) 5.4 Hz). 31P NMR (C6D6): δ

9-Phospha-10-silatriptycenes and their DeriVatiVes
Organometallics, Vol. 25, No. 26, 2006 6147
δ 16.2 (satellite, J(P-Se) ) 786 Hz). HRMS (FAB): calcd for
C44H59NO6PSeSi [M + H]+ 836.3014, found 836.3022.
12c: colorless crystals. Mp: 263-264 °C. 1H NMR (C6D6): δ
1.12 (d, J ) 6.0 Hz, 18H), 1.15 (d, J ) 6.0 Hz), 3.33 (s, 3H), 4.36
(sept, J ) 6.0 Hz, 3H), 4.56 (sept, J ) 6.0 Hz, 3H), 6.96 (d, J )
8.7 Hz, 2H), 7.63 (d, J(H-P) ) 4.2 Hz, 3H), 8.19 (d, J ) 8.7 Hz,
2H), 8.76 (d, J(H-P) ) 15.9 Hz, 3H). 31P NMR (C6D6): δ 16.4
(satellite, J(P-Se) ) 786 Hz). EI-MS: 823 ([M + H]+). Anal.
Calcd for C43H55O7PSeSi: C, 62.84; H, 6.74. Found: C, 62.72; H,
7.02.
12d: colorless crystals. Mp: 271-272 °C. 1H NMR (C6D6): δ
1.10 (d, J ) 6.3 Hz, 18H), 1.15 (d, J ) 6.0 Hz), 4.32 (sept, J )
6.3 Hz, 3H), 4.55 (sept, J ) 6.0 Hz, 3H), 7.33 (m, 3H), 7.58 (d,
J(H-P) ) 4.2 Hz, 3H), 8.24 (m, 2H), 8.75 (d, J(H-P) ) 16.5 Hz,
3H). 31P NMR (C6D6): δ 16.5 (satellite, J(P-Se) ) 786 Hz).
HRMS (EI): calcd for C42H53O6PSeSi 792.2514, found 792.2514.
12e: colorless crystals. Mp: 284-286 °C. 1H NMR (C6D6): δ
1.13 (d, J ) 6.0 Hz, 18H), 1.14 (d, J ) 6.3 Hz), 4.37 (sept, J )
6.0 Hz, 6H), 4.54 (sept, J ) 6.3 Hz, 3H), 7.46 (s, 3H), 7.47 (s,
3H), 8.10 (d, J(H-P) ) 7.8 Hz, 2H), 8.74 (d, J(H-P) ) 16.2 Hz,
3H). 31P NMR (C6D6): δ 16.6 (satellite, J(P-Se) ) 794 Hz).
HRMS (FAB): calcd for C43H52F3O6PSeSi 860.2388, found
860.2421.
Hz), 136.3 (virtual triplet, J ) 6.7 Hz), 138.1 (virtual dt, J ) 46
and 8.9 Hz), 138.7, 148.4 (virtual triplet, J ) 7.8 Hz), 148.8, 163.2.
31P NMR (109 MHz, C6D6): δ 10.3 (satellite, J ) 2005 Hz). MS
(FAB): 1711 ([M + H]+). Anal. Calcd for C76H106O14P2PtSi2: C,
61.77; H, 6.83. Found: C, 61.76; H, 6.89.
14d: colorless crystals. Mp: 171-172 °C (dec). 1H NMR
(C6D6): δ 1.14 (d, J ) 6.0 Hz, 36H), 1.21 (d, J ) 6.0 Hz, 36H),
1.80 (A3A3′XX′ satellite, J(H-Pt) ) 70.8 Hz, 6H), 4.22-4.35 (m,
12H), 7.35-7.39 (m, 6H), 7.60 (d, J ) 1.2 Hz, 6H), 8.36-8.39
(m, 4H), 8.46 (d, J ) 12.6 Hz, 6H). 13C NMR (acetone-d6): δ
10.4 (dd satellite, J ) 98, 10, and 604 Hz), 22.6, 22.7, 71.3, 72.9,
122.8 (virtual triplet, J ) 3.3 Hz), 125.3 (virtual quintet, J ) 15
Hz), 127.4, 130.0, 132.4, 136.0 (virtual triplet, J ) 7.8 Hz), 137.1,
138.1 (virtual dt, J ) 45 and 8.9 Hz), 148.5 (virtual quintet, J )
7.8 Hz), 148.9. 31P NMR (C6D6): δ 10.0 (satellite, J ) 2005 Hz).
HRMS (FAB): calcd for C86H112O12P2195PtSi2 1649.6815, found
1649.6833.
14e: colorless crystals. Mp: 278-279 °C (dec). 1H NMR
(C6D6): δ 1.17 (d, J ) 5.7 Hz, 36H), 1.20 (d, J ) 5.9 Hz, 36H),
1.80 (A3A3′XX′ satellite, J(H-Pt) ) 69.9 Hz, 6H), 4.23-4.38 (m,
12H), 7.47 (d, J ) 7.8 Hz, 4H), 7.50 (s, 6H), 8.25 (d, J ) 7.8 Hz,
4H), 8.45 (d, J ) 12.4 Hz, 6H). 13C NMR (acetone-d6): δ 10.5
(dd satellite, J ) 98, 10, and 604 Hz), 22.6, 22.7, 71.4, 72.9, 122.7,
125.2 (q, J ) 270 Hz), 125.3 (virtual quintet, J ) 13 Hz), 126.5
(q, J ) 3.4 Hz), 133.1, 133.3 (q, J ) 32 Hz), 135.1 (virtual triplet,
J ) 6.6 Hz), 137.9, 138.0 (virtual dt, J ) 45 and 8.9 Hz), 148.6
(virtual quintet, J ) 8.9 Hz), 149.0. 19F NMR (acetone-d6): δ
-62.5. 31P NMR (C6D6): δ 10.5 (satellite, J ) 2005 Hz). MS
(FAB): 1787 ([M + H]+). Anal. Calcd for C88H110F6O12P2PtSi2:
C, 59.15; H, 6.20. Found: C, 58.97; H, 6.18.
12f: colorless crystals. Mp: 283-285 °C. 1H NMR (C6D6): δ
1.10 (d, J ) 6.0 Hz, 18H), 1.16 (d, J ) 6.0 Hz), 4.31 (m, 3H),
7.37 (d, J(H-P) ) 4.2 Hz, 3H), 8.00 (s, 1H), 8.35 (d, J(H-P) )
12.3 Hz, 3H), 8.72 (s, 2H). 31P NMR (C6D6): δ 16.2 (satellite,
J(P-Se) ) 794 Hz). HRMS (FAB): calcd for C44H52F6O6PSeSi
[M + H]+ 929.2340, found 929.2327.
Preparation of cis-[PtMe2(H-PSiT-n-C12H25)2] (13). A solu-
tion of [PtMe2(cod)] (14.6 mg, 0.0438 mmol) and 5b (40.0 mg,
0.0876 mmol) in THF (3.0 mL) was stirred for 38 h at 40 °C. The
solvents were evaporated, and the residue was washed with hexane
to remove COD. The crude product was recrystallized from CH2-
Cl2/hexane to give 7 as colorless crystals (27.0 mg, 54% yield).
cis-PtMe2(psit)2 14b and 14f were prepared according to the
following procedure: A solution of [PtMe2(µ-SMe2)]2 (28.4 mg,
0.0495mmol) and 10b (150 mg, 0.198 mmol) in Et2O (3.0 mL)
was stirred for 5 h. The solvents were removed, and the residue
was recrystallized from CH2Cl2/hexane to give 14b (133 mg, 83%
yield) as colorless crystals. cis-PtMe2(psit)2 14f was similarly
prepared in 60% yield.
1
Mp: 157-158 °C (dec). H NMR (C6D6): δ 0.90-1.05 (m, 6H),
1.21-1.54 (m, 36H), 1.54-1.70 (m, 4H), 1.88 (A3A3′XX′ satellite,
J(H-Pt) ) 70.2 Hz, 6H), 1.96-2.12 (m, 4H), 6.74-6.98 (m, 12H),
7.61-7.70 (m, 6H), 8.67-8.79 (m, 6H). 13C NMR (THF-d8): δ
1.09, 5.98, 8.76 (dd satellite, J ) 99, 10, and 607 Hz), 14.1, 23.3,
24.4, 29.9, 30.0, 30.3, 30.36, 30.41, 32.6, 34.9, 127.1 (virtual
quintet, J ) 5.6 Hz), 127.7, 131.9, 136.5 (virtual quintet, J ) 15
Hz), 143.2 (virtual triplet, J ) 7.8 Hz), 143.7 (virtual dt, J ) 41
and 10 Hz). 31P NMR (C6D6): δ 9.85 (satellite, J ) 1972 Hz).
HRMS (FAB): calcd for C62H80P2195PtSi2 1137.4922, found
1137.4956.
1
14b: colorless crystals. Mp: >300 °C (dec). H NMR (C6D6):
δ 1.17 (d, J ) 6.2 Hz, 36H), 1.24 (d, J ) 5.9 Hz, 36H), 1.83
(A3A3′XX′ satellite, J(H-Pt) ) 69.9 Hz, 6H), 2.53 (s, 12H), 4.26-
4.42 (m, 12H), 6.76 (d, J ) 8.6 Hz, 4H), 7.76 (s, 6H), 8.35 (d, J
) 8.6 Hz, 4H), 8.51 (d, J ) 12.4 Hz, 6H). 13C NMR (acetone-d6):
δ 10.9 (dd satellite, J ) 99, 8.9, and 603 Hz), 22.6, 22.8, 40.2,
71.2, 72.8, 110.1, 113.4, 123.0, 125.2 (virtual quintet, J ) 16 Hz),
137.0 (virtual triplet, J ) 6.7 Hz), 138.0, 138.2 (virtual dt, J ) 45
and 8.9 Hz), 148.3 (virtual triplet, J ) 7.8 Hz), 148.7, 153.3. 31P
NMR (C6D6): δ 10.5 (satellite, J ) 2005 Hz). HRMS (FAB): calcd
for C90H122N2O12P2195PtSi2 1735.7659, found 1735.7683.
Preparation of cis-PtMe2(psit)2 (14a-f). cis-PtMe2(psit)2 14a
and 14c-e were prepared in a manner similar to 13 in 72, 59, 74,
and 62% yields, respectively.
14f: colorless crystals. Mp: 240-241 °C (dec). 1H NMR
(C6D6): δ 1.18 (d, J ) 6.5 Hz, 36H), 1.21 (d, J ) 6.2 Hz, 36H),
1.82 (A3A3′XX′ satellite, J(H-Pt) ) 70.8 Hz, 6H), 4.21-4.36 (m,
12H), 7.39 (s, 6H), 8.00 (s, 2H), 8.43 (d, J(H-P) ) 12.4 Hz, 6H),
8.86 (s, 4H). 13C NMR (acetone-d6): δ 10.4 (dd satellite, J ) 98,
10, and 605 Hz), 22.56, 22.60, 71.4, 72.8, 122.0 (virtual triplet, J
) 3.3 Hz), 124.5 (q, J ) 271 Hz), 125.4 (virtual quintet, J ) 15
Hz), 126.1 (virtual triplet, J ) 3.3 Hz), 132.0, 132.5 (q, J ) 33
Hz), 134.4 (virtual triplet, J ) 7.8 Hz), 137.2, 137.8 (virtual dt, J
) 45 and 8.9 Hz), 148.6 (virtual quintet, J ) 8.9 Hz), 149.1. 19F
NMR (acetone-d6): δ -62.3. 31P NMR (C6D6): δ 10.1 (satellite,
J ) 1993 Hz). MS (FAB): 1923 ([M + H]+). Anal. Calcd for
C90H108F12O12P2PtSi2: C, 56.21; H, 5.66. Found: C, 56.05; H, 5.70.
X-ray Crystallographic Analysis of 14b. A colorless crystal
(0.20 × 0.15 × 0.15 mm) was mounted using a cryoloop. The
intensity data were collected using a Rigaku single-crystal CCD
X-ray diffractometer (Saturn 70) with Mo KR radiation (λ )
0.71070 Å) and a graphite monochromator. The structure was solved
by direct methods (SIR-97) and refined by full-matrix least-squares
14a: colorless crystals. Mp: 226-227 °C (dec). 1H NMR
(C6D6): δ 0.90 (s, 6H), 1.16 (d, J ) 6.2 Hz, 36H), 1.23 (d, J ) 5.9
Hz, 36H), 1.71 (A3A3′XX′ satellite, J(H-Pt) ) 69.9 Hz, 6H), 4.17
(sept, J ) 6.2 Hz, 6H), 4.40 (sept, J ) 5.9 Hz, 6H), 7.37 (s, 6H),
8.32 (d, J ) 12.4 Hz, 6H). 13C NMR (acetone-d6): δ -13.4, 10.1
(dd satellite, J ) 98, 10, and 602 Hz), 22.6, 22.8, 71.2, 72.7, 121.8,
125.1 (virtual quintet, J ) 15 Hz), 137.1 (virtual triplet, J ) 7.8
Hz), 137.9 (virtual dt, J ) 46 and 7.8 Hz), 148.3 (virtual triplet, J
) 7.9 Hz), 148.9. 31P NMR (C6D6): δ 9.55 (satellite, J ) 1993
Hz). HRMS (FAB): calcd for C76H108O12P2195PtSi2 1525.6502,
found 1525.6527.
14c: colorless crystals. Mp: 258-259 °C (dec). 1H NMR
(C6D6): δ 1.17 (d, J ) 6.0 Hz, 36H), 1.22 (d, J ) 6.0 Hz, 36H),
1.82 (A3A3′XX′ satellite, J(H-Pt) ) 69.9 Hz, 6H), 3.35 (s, 6H),
4.24-4.41 (m, 12H), 7.00 (d, J ) 8.4 Hz, 4H), 7.66 (s, 6H), 8.32
(d, J ) 8.4 Hz, 4H), 8.48 (d, J ) 12.9 Hz, 6H). 13C NMR (acetone-
d6): δ 10.4 (dd satellite, J ) 98, 8.9, and 602 Hz), 22.6, 22.8,
55.8, 1.3, 72.8, 116.0, 117.4, 122.8, 125.3 (virtual quintet, J ) 13

6148 Organometallics, Vol. 25, No. 26, 2006
Tsuji et al.
on F2 (SHELXL-97). All the non-hydrogen atoms were anisotro-
pically refined, and all the hydrogen atoms were placed using the
AFIX instructions and refined isotopically. The crystal data and
analytical conditions are summarized in Table 1.
Science and Technology, Japan. We also thank Prof. F. Ozawa
and Prof. M. Okazaki for their valuable discussions.
Supporting Information Available: CIF files of 14b. NMR
chart of 3, 4, 5b, 8, 9, 10a, 12a,b, 12d-f, 13, 14a,b, and 14d.
Cartesian coordinates of PPh3, PSiT, and 9-phosphatriptycene
optimized at the B3LYP/6-311G* level. This material is available
free of charge via the Internet at http://pubs.acs.org.
Acknowledgment. This work was supported by the “Joint
Project of Chemical Synthesis Core Research Institutions” and
a Grant-in-Aid for COE Research on “Elements Science”, No.
12CE2005, from the Ministry of Education, Culture, Sports,
OM060681S