Preparation, structure and coordination properties of 3,3-bis(diisopropylamino)-3-thioxo-1-(2,4,6-tri-tert-butylphenyl)-1,3-diphosphap ropene

Article abstract of DOI:10.1039/b305216h

(Z)-1-Chloro-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyllithium was allowed to react with bis(diisopropylamino)-phosphenium triflate to afford the corresponding 1,3-diphosphapropene which was converted to 3-thioxo-1,3-diphosphapropene [(Z)-Mes*P=C(Cl)-P(=S)(NⁱPr₂)₂]. The coordination properties of 3-thioxo-1,3-diphosphapropene were investigated with carbonyltungsten(0) and dichloroplatinum(II) reagents, and the molecular structure of the chelate dichloroplatinum(II) complex was unambiguously determined by X-ray crystallography together with the free ligand. The dichloroplatinum(II) complex underwent intramolecular cyclisation involving C-H activation to give a 5,7-di-tert-butyl-3,3-dimethyl-1-(phosphinomethyl)-1-phosphaindane derivative as well.

Full text of DOI:10.1039/b305216h

View Article Online / Journal Homepage / Table of Contents for this issue
Preparation, structure and coordination properties of
3,3-bis(diisopropylamino)-3-thioxo-1-(2,4,6-tri-tert-butylphenyl)-
1,3-diphosphapropene
Hongze Liang, Shigekazu Ito and Masaaki Yoshifuji*
Department of Chemistry, Graduate School of Science, Tohoku University, Aoba, Sendai,
980-8578, Japan. E-mail: yoshifj@mail.tains.tohoku.ac.jp
Received 9th May 2003, Accepted 24th July 2003
First published as an Advance Article on the web 6th August 2003
(Z)-1-Chloro-2-(2,4,6-tri-tert-butylphenyl)-2-phosphaethenyllithium was allowed to react with bis(diisopropylamino)-
phosphenium triflate to afford the corresponding 1,3-diphosphapropene which was converted to 3-thioxo-1,3-
diphosphapropene [(Z)-Mes*P᎐C(Cl)–P(᎐S)(NiPr ) ]. The coordination properties of 3-thioxo-1,3-diphosphapro-
᎐
᎐
2
2
pene were investigated with carbonyltungsten(0) and dichloroplatinum() reagents, and the molecular structure of the
chelate dichloroplatinum() complex was unambiguously determined by X-ray crystallography together with the free
ligand. The dichloroplatinum() complex underwent intramolecular cyclisation involving C–H activation to give a
5,7-di-tert-butyl-3,3-dimethyl-1-(phosphinomethyl)-1-phosphaindane derivative as well.
phosphaethenyllithium and was allowed to react with an equi-
Introduction
molar amount of (i-Pr2N)2PϩOTfϪ to afford 2-chloro-3,3-bis-
The chemistry of low-coordinated phosphorus compounds is
(diisopropylamino)-1-(2,4,6-tri-tert-butylphenyl)-1,3-diphos-
phapropene, (Z)-2, which was, however, contaminated with
some other unidentified species. As (Z)-2 was not so stable in
air, it was subsequently subjected, without purification, to a
sulfurisation reaction with one equivalent of sulfur in refluxing
toluene to give (Z)-3 (Scheme 1). Like the sulfurisation of
of current interest.1 At first, this interest most probably was
triggered by questions raised regarding the classical double
bond rule. Less was known about their catalytic properties in
organic synthesis compared with the well-studied trivalent
phosphines. Recently, increasing interest has been paid to the
catalytic properties of the complexes containing low-co-
2-chloro-3,3-diphenyl-(2,4,6-tri-tert-butylphenyl)-1,3-diphos-
ordinated phosphorus atoms.2,3 Some palladium and platinum
phapropene,5 this reaction proceeded regioselectively. The sp3-
complexes coordinated to bidentate 3,4-diphosphinylidene-
phosphorus atom was sulfurised, whereas the sp2-phosphorus
cyclobutenes show several promising properties in catalytic
atom remained unchanged. In contrast to the sulfurisation of
reactions.3 In the meantime, we are also interested in the
diphosphenes and other phosphaalkenes, no disulfurisation
molecular design and synthesis of new types of phosphaalkenes
product was obtained even if an excess of elemental sulfur was
and their derivatives. 1,3-Diphosphapropenes contain two dif-
employed.6 The results are understandable taking into account
ferent types of phosphorus atoms, one in a low-coordinated
the fact that the sp3-phosphorus atom is more basic than sp2-
state and the other in the normal state, and, therefore, they are
phosphorus. A higher temperature was preferable in the sulfuri-
potentially a new class of bidentate ligands. However, reports
sation, as separate experiments indicated that sulfurisation
on the synthesis and coordination properties of 1,3-diphos-
conducted at room temperature in toluene proceeded slug-
gishly. Photolysis of (Z)-3 was also explored, and a mixture of
(Z)-3 and (E)-3 with a ratio of 5 : 1 was observed when (Z)-3 in
THF was irradiated with a medium-pressure mercury lamp for
17 h.
phapropenes are limited.4 Very recently, we have reported some
results from our efforts to extend the P᎐C–P system to P᎐C–P᎐
᎐
᎐
᎐
S. Our preliminary studies show that this type of new ligand
system is a good chelating reagent towards transition metals
as depicted in Chart 1.5 Herein we report the synthesis and
coordination reactivities of an amino- and sulfur substituted
1,3-diphosphapropene.
Chart 1 A chelating tungsten(0) complex from the P᎐C–P᎐S system.
᎐
᎐
Results and discussion
Synthesis, E–Z photoisomerisation and molecular structure of
(Z )-3
Scheme 1 Sulfurisation of phosphinophosphaalkene. Reagents and
conditions: i, n-BuLi then (i-Pr2N)2PϩOTfϪ; ii) 1/8 S8; iii) hν; iv) n-BuLi
then Ph2P(S)Cl.
2,2-Dichloro-1-(2,4,6-tri-tert-butylphenyl)-1-phosphaethene
(1) was converted to 1-chloro-2-(2,4,6-tri-tert-butylphenyl)-1-
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 3 0 5 4 – 3 0 5 8
T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 3
3054

View Article Online
Table 1 Crystallographic data and collection parameters for (Z)-3, (Z)-3Pt and 5
(Z)-3
(Z)-3Pt
5ؒ½C7H8
Formula
Formula weight
Crystal system
Space group
a/Å
b/Å
c/Å
C31H57ClN2P2S
587.27
C31H57Cl3N2P2SPt
853.26
Monoclinic
P21/a (#14)
11.0215(6)
21.108(1)
16.2925(5)
90
92.524(2)
90
3786.6(3)
4
C34.5H61Cl3N2P2PtS
899.33
Triclinic
P-1 (#2)
14.2800(2)
25.481(2)
10.8300(3)
92.549(8)
111.862(2)
85.841(9)
3647.0(3)
4
Monoclinic
P21/n (#14)
20.7395(7)
16.5550(5)
11.8561(6)
90
90.060(2)
90
4070.7(3)
4
α/deg
β/deg
γ/deg
V/Å3
Z
Dcalcd/g cmϪ3
T/K
1.069
296
1.497
296
1.467
296
Scan method
2θ/deg
Reflections collected
Ind. reflections
R(int)
Multi-scan
55.0
25003
4876
0.057
Multi-scan
55.0
17979
6348
0.035
Multi-scan
55.0
31362
9148
0.060
Goodness-of-fit
R1
Rw
1.758
0.137
0.185
1.571
0.041
0.054
1.466
0.056
0.065
In contrast to its precursor (Z)-2, (Z)-3 was stable in air.
Finally, the structure of (Z)-3 was confirmed by X-ray crystal-
lography. Two independent molecules were observed in the unit
cell, and Fig. 1 shows one of them. The crystallographic data
and collection parameters of (Z)-3 are given in Table 1 and the
selected bond lengths and angles are listed in Table 2. The
P᎐C(Cl)–P᎐S system is similar in shape to that found in
᎐
᎐
2-chloro-3,3-diphenyl-3-thioxo-1,3-diphosphapropene (Z)-4.
The bond distances of P(1)–C(1) and P(2)–S(1) are within the
normal ranges of P᎐C and P᎐S bonds, respectively,1a,7 and are
᎐
᎐
comparable to those of (Z)-4.5
Scheme
2
Reactions of (Z)-3 with tungsten(0) carbonyls and
platinum() chloride. Reagents and conditions: i, W(CO)5(THF) or
W(CO)4(COD); ii, PtCl2(COD).
elemental analysis are in good agreement with the chelate-type
structure.8
Reaction of (Z )-3 with PtCl2(COD) and the crystal structure of
(Z )-3Pt and 5
The reaction of (Z)-3 with PtCl2(COD) also proceeded in a
mixture of THF and dichloromethane to afford the corre-
sponding platinum() complex (Z)-3Pt in 37% isolated yield.
This reaction proceeded slowly in THF alone. On the other
hand, no complex was obtained in the reaction of (Z)-4 with
PtCl2(COD), forming a sharp contrast to the present (Z)-3. The
Fig. 1 Molecular structure of (Z)-3. Hydrogen atoms are omitted for
clarity.
31P NMR spectrum indicated that the P᎐C phosphorus atom
᎐
coordinates to the platinum in an end-on form [the large JPPt
coupling constant (4562 Hz) together with the chemical shift (δP
234.0)].9 Additionally, another product 5 was also observed and
isolated in 14% yield as a compound indicating the same
molecular weight as that of (Z)-3Pt.
The structures of red (Z)-3Pt (37% yield) and yellow 5 (14%
yield) were characterised unambiguously by X-ray crystallo-
graphy. The crystallographic data and collection parameters of
(Z)-3Pt and 5 are given in Table 1. Selected bond lengths and
angles are listed in Table 2.
Reactions of (Z )-3 with W(CO)5(THF) and W(CO)4(COD)
We investigated the coordination properties of (Z)-3 with tung-
sten(0) reagents as performed in the case of (Z)-4.6 Compound
(Z)-3 reacted with W(CO)5(THF) very slowly, even in refluxing
THF, to give (Z)-3W in 9% isolated yield after workup (Scheme
2). In contrast to the reaction of (Z)-4 with W(CO)5(THF),5 no
intermediary mono-coordinated complex via the sulfur atom
was observed in the case of (Z)-3. The reaction of (Z)-3 with
W(CO)4(COD) proceeded rather smoothly, and the yield of the
product greatly increased to 71%. The similarities in the spectra
between (Z)-3W and the corresponding complex of (Z)-45 and
Fig. 2 shows the molecular structure of (Z)-3Pt. The geom-
etry of the structure of (Z)-3Pt is almost the same as those
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 3 0 5 4 – 3 0 5 8
3055

View Article Online
Table 2 Selected bond lengths (Å) and angles (Њ) for (Z)-3, (Z)-3Pt
and 5
of 176.58(7)Њ and S(1)–Pt(1)–Cl(3) of 176.21(6)Њ, respectively.
The distance of P᎐C (1.666(5) Å) is smaller than that found in
᎐
the free ligand (1.68(1) Å), but is comparable to that found
in the reported 3,4-bis[(2,4,6-tri-tert-butylphenyl)phosphinyl-
idene]cyclobutene–platinum complex (1.669(3) Å).3d The bond
(Z)-3
P(1)–C(1)
P(2)–C(1)
P(1)–CMes*
P(2)–N(2)
1.68(1)
1.836(10)
1.84(1)
Cl(1)–C(1)
P(2)–S(1)
P(2)–N(1)
1.77(1)
1.969(5)
1.674(8)
distance of P᎐S in (Z)-3Pt (2.046(2) Å) is elongated due to the
᎐
coordination by the metal and, accordingly, the absorption of
P᎐S in the IR spectrum shifts to 597 cmϪ1, lower than 683 cmϪ1
1.651(8)
᎐
found in (Z)-3.
The 31P NMR signals of the complex 5 [δP 73.6, 25.9 (1JPPt
=
P(1)–C(1)–P(2)
C(1)–P(2)–S(1)
C(1)–P(1)–CMes*
117.7(6)
106.0(4)
101.8(5)
P(1)–C(1)–Cl(1)
P(2)–C(1)–Cl(1)
125.7(6)
116.6(6)
3550 Hz)] dramatically shifted to high field compared with
those of the free ligand (Z)-3 as well as the complex (Z)-3Pt.
X-Ray crystallography of 5 revealed that the Mes*P moiety
intramolecularly cyclises to construct the 1-phosphaindane
skeleton with a spiro structure as shown in Fig. 3. One of the
5-membered rings results from the intramolecular methyl
C–H activation of one of the o-tert-butyl groups and addition
(Z)-3Pt
Pt(1)–Cl(2)
Pt(1)–P(1)
P(1)–C(1)
P(2)–C(1)
P(1)–CMes*
P(2)–N(2)
2.328(2)
2.172(1)
1.666(5)
1.810(6)
1.816(5)
1.636(5)
Pt(1)–Cl(3)
Pt(1)–S(1)
Cl(1)–C(1)
P(2)–S(1)
P(2)–N(1)
2.318(2)
2.301(2)
1.726(5)
2.046(2)
1.638(5)
to the P᎐C bond. Accordingly, both P(1) and C(1) are now sp3-
᎐
hybridised, which is reflected in the elongation of the bond
distance of P(1)–C(1) from 1.666(5) Å in (Z)-3Pt to 1.869(8) Å
in 5, falling into the normal range of the P–C single bond
(1.82–1.87 Å).10 The corresponding distances of C(1)–P(2)
and C(1)–Cl(1) in 5 [1.836(8) Å and 1.778(7) Å] are also
longer than those in (Z)-3Pt [1.810(6) Å and 1.726(5) Å].
The sum of bond angles of C(1) (Σ 339.6Њ) also reflects the
sp3 character of C(1) in 5. The platinum centre coordinates to
the skeleton of 5 to form another 5-membered ring. The dis-
tances of two Pt–Cl bonds in 5 are comparable to those of
(Z)-3Pt, while the distance of the P(1)–Pt bond is 2.197(2) Å
in 5, slightly longer than that in (Z)-3Pt [2.172(1) Å]. Indeed,
the P(1) signal appeared at δ 25.9 (1JPPt = 3550 Hz) in the 31P
NMR spectrum, representing the sp3-hybridised character-
istics, and the resonance of sp3 C(1) appearing at δ 55.2 in
13C NMR spectroscopy showed a sharp contrast with that of
the sp2 C(1) in the free ligand (Z)-3. Interestingly, the 1,3-
diphosphapropane skeleton in 5 is found to be the meso iso-
mers (1R,2S) and (1S,2R), indicating that the C–H insertion
occurs in an anti fashion. The ( )-isomer was not formed in
this reaction as demonstrated by the NMR spectroscopy
showing the single diastereomer.
Cl(2)–Pt(1)–Cl(3)
Cl(2)–Pt(1)–P(1)
Cl(3)–Pt(1)–P(1)
Pt(1)–S(1)–P(2)
C(1)–P(2)–S(1)
C(1)–P(1)–CMes*
90.21(7)
176.58(7)
92.98(6)
105.60(7)
104.8(2)
110.5(2)
Cl(2)–Pt(1)–S(1)
Cl(3)–Pt(1)–S(1)
Pt(1)–P(1)–C(1)
P(1)–C(1)–P(2)
P(1)–Pt(1)–S(1)
Pt(1)–P(1)–CMes*
86.38(7)
176.21(6)
116.2(2)
117.0(3)
90.39(5)
133.2(2)
5
Pt(1)–Cl(2)
Pt(1)–S(1)
P(1)–C(1)
P(1)–C(19)
P(2)–C(1)
P(2)–N(1)
2.314(2)
2.288(2)
1.869(8)
1.823(7)
1.836(8)
1.653(6)
Pt(1)–Cl(3)
Pt(1)–P(1)
P(1)–C(2)
C(1)–Cl(1)
P(2)–S(1)
P(2)–N(2)
2.341(2)
2.197(2)
1.825(7)
1.778(7)
2.029(3)
1.645(6)
Cl(2)–Pt(1)–Cl(3)
Cl(2)–Pt(1)–P(1)
P(1)–Pt(1)–S(1)
Pt(1)–P(1)–C(1)
Pt(1)–P(1)–C(19)
C(1)–P(1)–C(19)
P(1)–C(1)–P(2)
P(2)–C(1)–Cl(1)
S(1)–P(2)–N(1)
90.67(8)
89.89(7)
93.72(7)
107.7(2)
114.1(2)
106.2(3)
111.5(4)
115.3(4)
112.7(2)
Cl(2)–Pt(1)–S(1)
Cl(3)–Pt(1)–P(1)
Pt(1)–S(1)–P(2)
Pt(1)–P(1)–C(2)
C(1)–P(1)–C(2)
C(2)–P(1)–C(19)
P(1)–C(1)–Cl(1)
C(1)–P(2)–S(1)
S(1)–P(2)–N(2)
176.38(7)
178.97(7)
107.41(10)
125.6(2)
106.1(3)
95.4(3)
112.8(4)
102.1(2)
111.8(2)
Thermal- or photo-induced intramolecular C–H activation
has been observed for phosphorus-containing compounds,11
observed for (Z)-3 and (Z)-4 except for the metal moiety. The
s-cis conformation remained unchanged, and the P᎐C(Cl)–P᎐S
᎐
᎐
skeleton and Pt formed a 5-membered ring with the torsion
angles of Pt–P(1)–C(1)–P(2) of 3.2(4)Њ and S–P(2)–C(1)–P(1)
of 18.6(4)Њ, respectively, taking an envelope form. The co-
ordination geometry around the platinum atom can be
described as square planar with angles P(1)–Pt(1)–Cl(2)
Fig. 2 Molecular structure of (Z)-3Pt. Hydrogen atoms are omitted
for clarity.
Fig. 3 Molecular structure of 5. Hydrogen atoms are omitted for
clarity.
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 3 0 5 4 – 3 0 5 8
3056

View Article Online
and some intermediary species involving phosphenium ions,11b
radicals,11c phosphinylidenes11d or phosphinylidene carbenes11e
were proposed for such activation and insertion reactions.
Although the reaction mechanism of the intramolecular
C–H activation and insertion is not clear, it seems likely that
platinum coordination to the ligand is a prerequisite. With-
out platinum, no product due to C–H activation and cyclis-
ation was formed, and only the normal complex (Z)-3Pt was
generated at the initial stage of the reaction. The yield of 5
almost doubled when the reaction was carried out for more
than 3 days. Future work will be focused on an investigation
into the effect of substitutions on such C–H activation and
cyclisation.
Reactions of (Z )-3 with W(CO)5(THF) and W(CO)4(COD)
A yellow THF (20 mL) solution of (Z)-3 (0.0855 g, 0.146
mmol) and W(CO)5(THF) (ca. 0.153 mmol, prepared from
W(CO)6 in THF by irradiation for 12 h with a medium-pressure
100 W Hg lamp at 0 ЊC) was refluxed overnight and the mixture
turned black. Purification by column chromatography (hexane :
toluene = 5 : 1) gave (Z)-3W (0.0118 g, 9%) together with the
recovery of (Z)-3 (0.044 g, 52%). (Z)-3W: Yellowish–black
solid, mp 158 ЊC (decomp.). Found: C, 47.49; H, 6.38; N, 3.14.
Calc. for C35H57ClN2P2SO4W: C, 47.60; H, 6.51; N, 3.17%. IR
(KBr, cmϪ1): 2019, 1913, 1874 (CO), 605 (P᎐S); 31P{1H} NMR
᎐
1
(162 MHz, CDCl , δ): 306.4 (P᎐C, JPW = 280 Hz), 77.3
᎐
3
(P(S)Ph2), 2JPP = 145 Hz; 1H NMR (400 MHz, CDCl3, δ): 7.51
4
3
(d, JPH = 2.4 Hz, 2H, Ph), 3.93 (sept, JHH = 7.2 Hz, 4H,
NCHMe2), 1.69 (s, 18H, o-tBu), 1.41 (s, 12H, NCHCMe2), 1.39
(s, 12H, NCHMe2), 1.38 (s, 9H, p-tBu); 13C{1H} NMR (101
MHz, CDCl3 δ): 209.8 (dd, 2JPC = 43.0 Hz, 3JPC = 6.6 Hz, COax),
Experimental
General
2
2
205.8 (d, JPC = 6.6 Hz, COeq), 202.7 (d, JPC = 9.3 Hz, COeq),
All manipulations were carried out under an argon atmosphere
by means of the standard Schlenk techniques or in a glove box.
155.6 (s, o-Mes*), 152.9 (s, p-Mes*), 145.5 (dd, 1JPC = 121.2 Hz,
1JPC = 14.7 Hz, P᎐C), 130.1 (dd, J = 8.0 Hz, JPC = 3.6 Hz,
1
3
᎐
PC
1
All solvents employed were dried by appropriate methods. H,
ipso-Mes*), 123.4 (d, 3JPC = 6.2 Hz, m-Mes*), 49.0 (s, d, 2JPC
=
13C{1H} and 31P{1H} NMR spectra were recorded on a Bruker
AVANCE 400 spectrometer in CDCl3 with Me4Si (1H, 13C) and
H3PO4 (31P), respectively, as internal or external standard. IR
spectra were measured on a Horiba FT-300 spectrometer as
KBr pellets. Melting points were measured on a Yanagimoto
MP-J3 apparatus without correction. Mass spectra were
recorded on a Bruker APEX3 spectrometer using fast atom
bombardment (FAB). X-Ray diffraction data were collected on
a Rigaku RAXIS-IV imaging plate diffractometer. Elemental
analyses were performed in the Instrumental Analysis Center
for Chemistry, Graduate School Science, Tohoku University.
5.6 Hz, NCHMe2), 39.3 (s, o-CMe3), 35.6 (s, p-CMe3), 34.4 (s,
3
o-CMe3), 31.6 (s, p-CMe3), 25.2 (d, JPC = 3.7 Hz, NCHMe2),
3
25.0 (d, JPC = 3.2 Hz, NCHMe2). The reaction of (Z)-3 with
W(CO)4(COD) proceeded faster than that with W(CO)5(THF).
31P NMR spectrum indicated that more than 60% of (Z)-3 was
converted to the corresponding tungsten(0) complex (Z)-3W
after the reaction mixture was stirred at room temperature for
4 h. The usual workup gave (Z)-3W in 71% yield.
Reaction of (Z )-3 with PtCl2(COD)
A pale yellow suspension of (Z)-3 (0.1 g, 0.17 mmol) and
PtCl2(COD) (0.0637 g, 0.17 mmol) in THF (6 mL) was refluxed
for 2 h. 31P NMR spectrum indicated that a new species
Synthesis of (Z )-2-chloro-3,3-bis(diisopropylamino)-3-thioxo-1-
(2,4,6-tri-tert-butylphenyl)-1,3-diphosphapropene (Z-3) and
photo-isomerisation
2
(δP 234.0, 67.0, JPP = 131 Hz) in a trace amount was formed
together with the starting material. After addition of CH2Cl2
(12 mL) to this suspension, it became a clear yellowish–orange
solution. This solution was then heated at 50 ЊC and monitored
Compound
1 was prepared according to the literature
method.12 To a stirred THF solution (15 mL) of 1 (1.712 g, 4.76
mmol) was added n-BuLi (1.56 M in hexane, 5.24 mmol) at Ϫ78
ЊC. This reaction mixture immediately turned yellowish–orange
and was stirred at Ϫ78 ЊC for 10 min. Then, (i-Pr2N)2PϩOTfϪ
(1.994 g, 5.24 mmol)13 was added to the above solution at
Ϫ78 ЊC and stirred for 30 min at the same temperature and
then at room temperature for 1 h. THF was removed and the
residue was extracted with hexane (50 mL) to give a brown oil
by 31P NMR spectrum. The intensity of the first new species
2
increased and the second new species (δP 74.2, 26.0, JPP
=
52 Hz) then appeared after the solution was refluxed for 6 h.
The reaction mixture gradually turned orange after refluxing
overnight. Evaporation of the solvents afforded an orange–
yellow residue and the residue was purified by column chrom-
atography (toluene : hexane : THF = 3 : 3 :1) to yield (Z)-
3Pt (0.054 g, 37%) and 5 (0.023 g, 14%) together with the
recovered (Z)-3 (0.04 g, 40%). (Z)-3Pt: Red crystals, mp 255 ЊC
(decomp.). Found: C, 43.28; H, 6.56; N, 3.20. Calc. for
C31H57Cl3N2P2SPt: C, 43.64; H, 6.73; N, 3.28%; IR (KBr, cmϪ1):
597 (P᎐S); 31P{1H} NMR (162 MHz, CDCl , δ): 230.9 (P᎐C,
2
of crude (Z)-2 (δP 269.3, 71.0, JPP = 98 Hz). Without purifi-
cation, crude (Z)-2 was treated with sulfur (0.165 g, 5 mmol) in
toluene (10 mL) and the mixture was refluxed overnight. The
solvent was removed in vacuo to give a brown residue which was
purified on silica gel (hexane : toluene = 3 : 1 to toluene), giving
(Z)-3 (0.934 g, 33% from 1), pale yellow crystals, mp 144–146
ЊC. Found: C, 63.20; H, 9.68; N, 4.58. Calc. for C31H57ClN2P2S:
᎐
᎐
3
1JPPt = 4562 Hz), 65.6 (P(S)Ph2, 2JPPt = 57 Hz), 2JPP = 128 Hz; 1H
4
NMR (400 MHz, CDCl3, δ): 7.61 (d, JPH = 4.8 Hz, 2H, Ph),
C, 63.40; H, 9.80; N, 4.77%. IR (KBr, cmϪ1): 683 (P᎐S); 31P{1H}
3.91 (sept, 3JHH = 7.2 Hz, 4JHH = 6.8 Hz, 4H, NCHMe2), 1.76 (s,
᎐
NMR (162 MHz, CDCl , δ): 314.5 (P᎐C), 70.9 (P(S)Ph ), 2J
=
18H, o-tBu), 1.52 (d, JHH = 7.2 Hz, 12H, NCHMe2), 1.47 (d,
3
᎐
3
2
PP
106 Hz; 1H NMR (400 MHz; CDCl3, δ): 7.44 (s, 2H, Ph), 3.93
3JHH = 6.8 Hz, 12H, NCHMe2), 1.35 (s, 9H, p-tBu); 13C{1H}
3
1
(sept, JHH = 6.8 Hz, 4H, NCHMe2), 1.50 (s, 18H, o-tBu), 1.45
NMR (101 MHz, CDCl3): δ 156.1 (d, JPC = 4.2 Hz, o-Mes*),
4
1
(dd, 3JHH = 6.8 Hz, 3JPH = 2.4 Hz, 24H, NCHCMe2), 1.36 (s, 9H,
155.2 (d, JPC = 2.6 Hz, p-Mes*), 129.5 (dd, JPC = 110.2 Hz,
1
p-tBu); 13C{1H} (101 MHz, CDCl3, δ): 164.3 (dd, JPC = 100.0
1JPC = 60.0 Hz, P᎐C), 125.7 (d, 3JPC = 10.6 Hz, m-Mes*), 114.8
᎐
Hz, 1JPC = 85.1 Hz, P᎐C), 153.9 (s, o-Mes*), 150.9 (s, p-Mes*),
(dd, JPC = 28.2 Hz, JPC = 9.2 Hz, ipso-Mes*), 49.6 (s,
1
3
᎐
1
3
135.8 (dd, JPC = 67 Hz, JPC = 14 Hz, ipso-Mes*), 122.9 (s,
m-Mes*), 48.7 (d, JPC = 5.6 Hz, NCHMe2), 38.4 (s, o-CMe3),
NCHMe2), 49.5 (s, NCHMe2), 39.9 (s, o-CMe3), 35.6 (s,
2
3
p-CMe3), 35.0 (s, o-CMe3), 31.4 (s, p-CMe3), 24.8 (d, JPC
=
4
35.3 (s, p-CMe3), 33.6 (d, JPC = 7.2 Hz, o-CMe3), 31.7 (s,
3.4 Hz, NCHMe2), 24.7 (d, 3JPC = 2.9 Hz, NCHMe2). 5: Yellow
crystals, mp 178 ЊC (decomp.); Found: C, 49.81; H, 7.38; N,
2.75. Calc. for C31H57Cl3N2P2SPtؒ1.5C7H8: C, 50.19; H, 7.00; N,
p-CMe3), 25.0 (s, NCHMe2), 24.7 (d, 3JPC = 3.1 Hz, NCHMe2).
A THF (0.3 mL) solution of (Z)-3 (0.01g) in an NMR tube
was irradiated with a medium-pressure Hg lamp (100 W) at
0 ЊC for 17 h. 31P NMR spectrum indicated the formation of the
(E)-3 isomer (δP 329.2, 65.4, 2Jpp = 60 Hz). The ratio of (Z)-3 to
(E)-3 was 5 : 1, but no further attempt was made to separate
them.
2.82%; IR (KBr, cmϪ1): 606 (P᎐S); 31P{1H} NMR (162 MHz,
᎐
CDCl , δ): 73.6 (P᎐S), 2JPPt = 52 Hz, 25.9 (PCHCl, 1JPPt = 3550
᎐
3
2
1
Hz), JPP = 50 Hz; H NMR (400 MHz, CDCl3, δ): 7.57 (d,
4JHP = 6.0 Hz, 1H, Ph), 7.13 (s, 1H, Ph), 4.51 (sept, JHH = 6.8
3
3
Hz, 2H, NCHMe2), 3.89 (sept, JHH = 7.2 Hz, 2H, NCHMe2),
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 3 0 5 4 – 3 0 5 8
3057

View Article Online
3.76 (pseudo-t, (2JPH ϩ 2JHH)/2 = 6.5 Hz, 1H, PCHCl), 3.10 (d,
2JHH = 15.0 Hz, 1H, PCH2), 2.77 (dd, 2JHH = 15.0 Hz, 2JHP = 11.6
Hz, 1H, PCH2), 1.85 (s, 9H, o-tBu), 1.62 (d, 3JHH = 6.8 Hz, 6H,
3 (a) F. Ozawa, H. Okamoto, S. Kawagishi, S. Yamamoto, T. Minami
and M. Yoshifuji, J. Am. Chem. Soc., 2002, 124, 10968–10969;
(b) T. Minami, H. Okamoto, S. Ikeda, R. Tanaka, F. Ozawa and
M. Yoshifuji, Angew. Chem., Int. Ed., 2001, 40, 4501–4503;
(c) F. Ozawa, S. Yamamoto, S. Kawagishi, M. Hiraoka, S. Ikeda,
T. Minami, S. Ito and M. Yoshifuji, Chem. Lett., 2001, 972–973;
(d ) S. Ikeda, F. Ohhata, M. Miyoshi, R. Tanaka, T. Minami,
F. Ozawa and M. Yoshifuji, Angew. Chem., Int. Ed., 2000, 39, 4512–
4513; (e) K. Toyota, K. Masaki, T. Abe and M. Yoshifuji,
Chem. Lett., 1995, 221–222.
4 (a) S. Ito and M. Yoshifuji, Chem. Commun., 2001, 1208–1209;
(b) R. Appel and W. Schuhn, J. Organomet. Chem., 1987, 329, 179–
185; (c) R. Appel, W. Schuhn and F. Knoch, Angew. Chem., Int. Ed.
Engl., 1985, 24, 420–421.
5 S. Ito, H. Liang and M. Yoshifuji, Chem. Commun., 2003, 398–399.
6 (a) K. Toyota, H. Takahashi, K. Shimura and M. Yoshifuji,
Bull. Chem. Soc. Jpn., 1996, 69, 141–145; (b) M. Yoshifuji,
K. Shibayama and N. Inamoto, Heterocycles, 1984, 22, 681–686;
(c) M. Yoshifuji, K. Ando, K. Shibayama, N. Inamoto, K. Hirotsu
and T. Higushi, Angew. Chem., Int. Ed. Engl., 1983, 22, 418–419;
(d ) M. Yoshifuji, K. Shibayama, N. Inamoto, K. Hirotsu and
T. Higuchi, J. Chem. Soc., Chem. Commun., 1983, 862–863.
7 K. M. Pietrusiewicz, M. Kuznikowski, W. Wieczorek and A. Brandi,
Heteroat. Chem., 1992, 3, 37–40.
3
NCHMe2), 1.60 (s, 3H, CMe2), 1.56 (d, JHH = 7.2 Hz, 6H,
3
NCHMe2), 1.52 (s, 3H, CMe2), 1.48 (d, JHH = 6.8 Hz,
6H, NCHMe2), 1.43 (d, 3JHH = 7.2 Hz, 6H, NCHMe2), 1.35 (s,
9H, p-tBu); 13C{1H} NMR (101 MHz, CDCl3, δ): 161.8 (d,
2JPC = 23.6 Hz, o-Mes*), 157.0 (d, 4JPC = 2.4 Hz, p-Mes*), 154.1
2
3
(d, JPC = 10.3 Hz, o-Mes*), 125.7 (d, JPC = 9.1 Hz, m-Mes*),
3
1
119.5 (d, JPC = 12.3 Hz, m-Mes*), 116.4 (dd, JPC = 57.2 Hz,
3JPC = 8.1 Hz, ipso-Mes*), 55.2 (dd, JPC = 76.9 Hz, JPC
=
1
1
2
12.6 Hz, PCHCl), 50.8 (d, JPC = 4.1 Hz, NCHMe2), 49.8 (d,
2JPC = 3.9 Hz, NCHMe2), 44.4 (s, PCH2CMe2), 39.1 (s,
o-CMe3), 35.8 (d, 2JPC = 3.9 Hz, PCH2CMe2), 35.6 (s, p-CMe3),
34.4 (s, o-CMe3), 31.5 (s, PCH2CMe2), 30.7 (s, p-CMe3), 26.2 (d,
3JPC = 2.4 Hz, NCHMe2), 24.7 (d, JPC = 2.9 Hz, NCHMe2),
3
3
3
24.5 (d, JPC = 5.7 Hz, NCHMe2), 24.0 (d, JPC = 2.4 Hz,
NCHMe2); m/z (FAB) 852 (M Ϫ H, relative intensity 20%), 782
(M Ϫ H Ϫ 2Cl, 100%).
X-Ray crystal data
8 X-Ray analysis for (Z)-3W was performed. Although the data were
not good due to the poor quality of the single crystal, the chelating
coordination pattern was observed.
9 (a) H. W. Kroto, J. F. Nixon, M. J. Taylor, A. A. Frew and K. W.
Muir, Polyhedron, 1982, 1, 89–95; (b) T. A. van der Knaap,
F. Bickelhaupt, J. G. Kraaykamp, G. van Koten, J. P. Bernards,
H. T. Edzes, W. S. Veeman, E. de Boer and E. J. Baerends,
Organometallics, 1984, 3, 1804–1811.
Selected crystallographic data and collection parameters for
(Z)-3, (Z)-3Pt, and 5 are listed in Table 1. CCDC reference
numbers 206703–206705. See http://www.rsc.org/suppdata/ob/
b3/b305216h/ for crystallographic data in .cif or other electro-
nic format.
10 G. Becker, W. A. Herrman, W. Kalcher, G. W. Kriecbaum, C. Pahl,
C. T. Wagner and M. L. Ziegler, Angew. Chem., Int. Ed. Engl., 1983,
22, 413.
Acknowledgements
11 (a) A. J. Termaten, T. Nijbacker, M. Schakel, M. Lutz, A. L.
Spek and K. Lammertsma, Chem. Eur. J., 2003, 9, 2200;
(b) K. Lammertsma and M. J. M. Vlaar, Eur. J. Org. Chem., 2002, 7,
1127–1138; (c) M. E. García, V. Riera, M. A. Ruiz, D. Sáez,
J. Vaissemann and J. C. Jeffery, J. Am. Chem. Soc., 2002, 124, 14304–
14305; (d ) C.-H. Tsang, C. A. Rohrick, T. S. Saini, B. O. Patrick
and D. P. Gates, Organometallics, 2002, 21, 1008–1010; (e) S. Shah,
M. C. Simpson, R. C. Smith and J. D. Protasiewicz, J. Am. Chem.
Soc., 2001, 123, 6925–6926; ( f ) K. Tsuji, S. Sasaki and M. Yoshifuji,
Heteroat. Chem., 1998, 9, 607–613; (g) S. Ito, K. Toyota and
M. Yoshifuji, Chem. Commun., 1997, 1637–1638; (h) M. Yoshifuji,
T. Sato and N. Inamoto, Chem. Lett., 1988, 1735–1738; (i) A. H.
Cowley and M. Pakulski, Tetrahedron Lett., 1984, 25, 2125–2126;
(j) M. Yoshifuji, I. Shima, K. Ando and N. Inamoto, Tetrahedron
Lett., 1983, 24, 933–936; (k) M. Freytag, P. J. Dyson, L. Ernst,
P. G. Jones and R. Schmutzler, Inorg. Chem. Commun., 2002, 5,
808–810.
This work was supported in part by Grants-in-Aid for Scientific
Research (No. 13303039 and 14044012) from the Ministry of
Education, Culture, Sports, Science and Technology, Japan.
H. Liang is grateful to the Japan Society for the Promotion
of Science for the Postdoctoral Fellowships for Foreign
Researchers.
References and Notes
1 (a) M. Regitz and O. J. Scherer, Multiple Bonds and Low
Coordination in Phosphorus Chemistry, Georg Thieme Verlag,
Stuttgart, 1990; (b) K. B. Dillon, F. Mathey and J. F. Nixon,
Phosphorus: The Carbon Copy, John Wiley & Sons, Chichester,
1998; (c) M. Yoshifuji, J. Chem. Soc., Dalton Trans., 1998, 3343–
3349.
2 L. Weber, Agnew. Chem., Int. Ed., 2002, 41, 563–572 . See also
M. Doux, N. Mézailles, M. Melaimi, L. Ricard and P. Le Floch,
Chem. Commun., 2002, 1566–1567; O. Daugulis, M. Brookhart
and P. S. White, Organometallics, 2002, 21, 5935–5943; A. Ionkin
and W. Marshall, Chem. Commun., 2003, 710–711.
12 (a) S. J. Goede and F. Bickelhaupt, Chem. Ber., 1991, 124, 2677–
2684; (b) S. J. Goede, M. A. Dam and F. Bickelhaupt, Recl. Trav.
Chim. Pays-Bas, 1994, 113, 278–282; (c) R. Appel, C. Cassser and
M. Immenkeppel, Tetrahedron Lett., 1985, 26, 3551–3554.
13 M. R. Maziéres, C. Roques, M. Sanchez and J. P. Majoral,
Tetrahedron, 1987, 43, 2109–2118.
O r g . B i o m o l . C h e m . , 2 0 0 3 , 1, 3 0 5 4 – 3 0 5 8
3058