Synthesis, structure and catalytic activity of thioether-phosphane complexes of Pd(II) and Pt(II)

Article abstract of DOI:10.1039/b502195b

New thioether-phosphanes 2-RSC₆H₄CH ₂PPh₂ (RS～PPh₂: R = Me, 'Bu, Ph) and the corresponding complexes [PdCl₂(MeS～PPh₂)], [PdCl ₂('BuS～PPh₂)], [PdCl₂

Full text of DOI:10.1039/b502195b

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F U L L P A P E R
Synthesis, structure and catalytic activity of thioether–phosphane
complexes of Pd(II) and Pt(II)
Jonathan R. Dilworth,*a Carlo A. Maresca von Beckh W.a and Sofia I. Pascub
a Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford,
UK OX1 3TA
b Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge,
UK CB2 1EW
Received 14th February 2005, Accepted 19th April 2005
First published as an Advance Article on the web 17th May 2005
New thioether–phosphanes 2-RSC6H4CH2PPh2 (RS∼PPh2: R = Me, tBu, Ph) and the corresponding complexes
[PdCl2(MeS∼PPh2)], [PdCl2(tBuS∼PPh2)], [PdCl2(PhS∼PPh2)], [PdClMe(MeS∼PPh2)] and [PtMe2(MeS∼PPh2)]
have been prepared, characterized and the X-ray crystal structures of all complexes determined. Whilst Pd(II)
complexes of RS∼PPh2 show low activity for CO/ethene copolymerisation, the complexes [PdCl2(RS∼PPh2)] have
been found to be very efficient for the Heck arylation of n-butylacrylate with bromobenzene under aerobic conditions.
Introduction
The use of transition metal complexes for homogeneous catalysis
has been established for a wide variety of phosphorus-, nitrogen-
and carbon-based ligands.1,2 In the quest for ever greater catalyst
activity and selectivity, these ligands continue to be the primary
focus of academic and industrial research, while other types of
ligands are rarely given much attention. Sulfur-based ligands
have been less explored in catalysis, possibly due to sulfur’s well-
known tendency to act as a “catalyst poison”,3–5 however recent
results have been very promising.6,7
We discovered that certain thioether ligands containing a
phosphane “pendant arm” (L1, L2, MeS∼PPh2 in Fig. 1) form
highly active catalysts for a number of homogeneous reac-
tions. Rhodium(I) thioether–phosphane complexes of the type
Fig. 2 Synthesis of ligands RS∼PPh2.
[RhX(CO)L1,2] (X = Cl, I) are three times more active than the
Monsanto catalyst [RhI2(CO)2]− for methanol carbonylation8
while the palladium(II) complex [PdCl2(MeS∼PPh2)] gives 1.2 ×
Christiaens et al.15 for Ia and although Ia–c, IIc and PhS∼PPh2
106 turnovers for the Heck arylation of styrene with various aryl
bromides and iodides under aerobic conditions.9
were contaminated with traces of starting material, purification
was not necessary for the subsequent steps of synthesis.
All RS∼PPh2 ligands were characterized by elemental anal-
1
1
ysis, mass spectroscopy (EI- or FI-MS), and H, 13C{ H} and
31P{ H} NMR spectroscopy (See Table 1). All 1H NMR spectra
1
show signals between d 6.79 and 8.02 ppm due to the aromatic
hydrogens. MeS∼PPh2 and tBuS∼PPh2 additionally show sharp
singlets at d 2.01 and 1.32 ppm corresponding to SCH3 and
SC(CH3)3, respectively. The CH2P signals appear as singlets
(d 3.66 ppm for R = Me, d 3.64 ppm for R = Ph) or finely-
Fig. 1 Thioether–phosphane ligands.
split doublets (d 3.64 ppm, 2JHP = 1.2 Hz for R = Bu). Simple
t
doublets are not observed due to free rotation about the CH2–P
bond, which averages the H–P scalar couplings to near-zero.16,17
This has been observed in other benzylphosphanes.18,19
We now wish to report the syntheses and structures of novel
Group 10 thioether–phosphane complexes and the catalysis test-
ing in C–C coupling reactions, i.e. CO/ethene copolymerisation
and Heck arylation. Pd(II) complexes of RS∼PPh2 show low
activity towards the copolymerisation of CO and ethene but
the complexes [PdCl2(RS∼PPh2)] are all highly active for Heck
arylation under aerobic conditions.
1
t
The 13C{ H} NMR spectra of BuS∼PPh2 and PhS∼PPh2
(MeS∼PPh2 has been described previously9) exhibit signals
between d 126.0 and 143.0 ppm due to aromatic car-
t
bons. BuS∼PPh2 additionally shows signals for SC(CH3)3 (d
31.4 ppm) and SC(CH3)3 (d 47.6 ppm), the latter with long-
range scalar coupling to phosphorus. The CH2P signals appear
as simple doublets (d 34.9 ppm, 1JCP = 15.6 Hz for R = Bu, d
t
Results and discussion
34.5 ppm, 1JCP = 16.4 Hz for R = Ph) since free rotation about
Ligands
CH2–P does not “average out” the C–P scalar coupling.
t
1
The ligands 2-RSC6H4CH2PPh2 (RS∼PPh2: R = Me, Bu, Ph)
Finally, all 31P{ H} NMR spectra exhibit sharp singlets at d
were synthesized by the three-step procedure of Kellner et al.10,11
as shown in Fig. 2 and described in the Experimental section.
Intermediates Ia–c12–14 were synthesized using the method of
−12.4 ppm (R = Me), d −7.4 ppm (R = Bu) and d −9.8 ppm
t
(R = Ph) which are typical for tertiary bis-aryl, mono-alkyl
phosphanes.20,21
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 5
D a l t o n T r a n s . , 2 0 0 5 , 2 1 5 1 – 2 1 6 1
2 1 5 1
©

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Table 1 Characterizing data of intermediates Ib–c and IIa–c, ligands RS∼PPh2 (R= Me, tBu, Ph) and complexes [MXY(RS∼PPh2)] (M = Pd, X =
Cl, Y = Cl or Me; M = Pt, X = Y = Me)
Compound
NMR data
Ib
C13H21NS
1H NMR (CDCl3, 300 MHz): 1.30 [9H, s, SC(CH3)3], 2.27 [6H, s, N(CH3)2], 3.77
[2H, s, CH2N], 7.20 [1H, td, 3JHH = 7.5, 4JHH = 1.6, H4 or H5], 7.34 [1H, td,
3JHH = 7.5, 4JHH = 1.4, H4 or H5], 7.54 [1H, d, 3JHH = 7.7, H3 or H6], 7.55 [1H, d,
3JHH = 7.7, H3 or H6]
RMM = 223.383
Light-yellow oil
Found: C, 69.25; H, 9.29; N, 5.27%
Calc.: C, 69.90; H, 9.48; N, 6.27%a
13C{ H} NMR (CDCl3, 75 MHz): 31.3 [s, SC(CH3)3], 45.7 [s, N(CH3)2], 47.3 [s,
1
EI-MS: 223.1 [M]+, 166.1 [M − Bu]+
SC(CH3)3], 61.9 [s, CH2N], 126.6 [s, C4 or C5], 128.9 [s, C4 or C5], 129.9 [s, C3 or
C6], 132.4 [s, C1 or C2], 138.7 [s, C3 or C6], 144.1 [s, C1 or C2]
t
Correct isotope pattern
Ic
C15H17NS
1H NMR (CDCl3, 300 MHz): 2.26 [6H, s, N(CH3)2], 3.56 [2H, s, CH2N]. Aromatic
RMM = 243.373
hydrogens: 7.07–7.54 [br m]b
1
Yellow oil
13C{ H} NMR (CDCl3, 75 MHz): 45.5 [s, N(CH3)2], 62.1 [s, CH2N]. Aromatic
EI-MS: 243.1 [M]+, 242.1 [M − H]+,
197.0 [M − 2H − NMe2]+
Correct isotope pattern
carbons: 126.9 [s], 127.9 [s], 129.2 [s], 130.2 [s], 130.6 [s], 131.1 [s], 132.1 [s], 135.9
[s], 136.3 [s], 139.7 [s]
IIa
C11H18INS
1H NMR (CDCl3, 300 MHz): 2.47 [3H, s, SCH3], 3.42 [9H, s, N(CH3)3], 4.97
[2H, s, CH2N], 7.24 [1H, td, 3JHH = 7.4, 4JHH = 1.3, H4 or H5], 7.36 [1H, dd,
3JHH = 8.0, 4JHH = 1.2, H3 or H6], 7.43 [1H, td, 3JHH = 7.6, 4JHH = 1.3, H4 or H5],
7.76 [1H, dd, 3JHH = 7.6, 4JHH = 0.9, H3 or H6]
RMM = 323.237
Off-white solid
Found: C, 41.16; H, 5.66; N, 4.37%
Calc.: C, 40.87; H, 5.61; N, 4.33%
ES-MS: 196.2 [M − I]+,
137.1 [M − I − NMe3]+
Correct isotope pattern
1
13C{ H} NMR (CDCl3, 75 MHz): 17.4 [s, SCH3], 53.5 [s, N(CH3)3], 66.4 [s,
CH2N]. Aromatic carbons: 125.8 [s], 126.1 [s], 128.3 [s], 131.6 [s], 134.9 [s], 141.4 [s]
IIb
C14H24INS
1H NMR (CDCl3, 300 MHz): 1.23 [9H, s, SC(CH3)3], 3.40 [9H, s, N(CH3)3], 5.18
[2H, s, CH2N], 7.47 [2H, m, H4 + H5], 7.69 [1H, dd, 3JHH = 7.1, 4JHH = 2.0, H3 or
H6], 7.97 [1H, dd, 3JHH = 7.1, 4JHH = 2.0, H3 or H6]
RMM = 365.318
Off-white solid
1
Found: C, 46.07; H, 6.91; N, 3.60%
Calc.: C, 46.03; H, 6.62; N, 3.83%
ES-MS: 238.2 [M − I]+,
179.2 [M − I − NMe3]+,
13C{ H} NMR (CDCl3, 75 MHz): 31.1 [s, SC(CH3)3], 49.3 [s, SC(CH3)3], 53.4 [s,
N(CH3)3], 66.6 [s, CH2N], 129.9 [s, C1 or C2], 130.9 [s, C4 or C5], 132.1 [s, C4 or
C5], 134.9 [s, C3 or C6], 135.9 [s, C1 or C2], 139.5 [s, C3 or C6]
123.1 [M − I − NMe3 − Bu]+
t
Correct isotope pattern
IIc
C16H20INS
1H NMR (CDCl3, 300 MHz): 3.50 [9H, s, N(CH3)3], 5.10 [2H, s, CH2N], 7.17 [2H,
m, H8/8ꢀ], 7.29 [br m, H9/9ꢀ + H10], 7.99 [1H, m, H6]. Other aromatic hydrogens:
7.54 [br m]b
RMM = 385.308
Off-white solid
1
Found: C, 50.11; H, 5.93; N, 3.65%
Calc.: C, 49.87; H, 5.23; N, 3.64%b
ES-MS: 258.1 [M − I]+,
227.1 [M − I − 2Me − H]+,
199.0 [M − I − NMe3]+
Correct isotope pattern
13C{ H} NMR (CDCl3, 75 MHz): 53.3 [s, N(CH3)3], 66.2 [s, CH2N], 127.8 [s, C10],
129.6 [s, C9/9ꢀ], 130.6 [s, C8/8ꢀ], 133.7 [s, C7], 135.3 [s, C6]. Other aromatic
carbons: 127.9 [s], 128.4 [s], 131.8 [s], 133.8 [s], 138.5 [s]
MeS∼PPh2
tBuS∼PPh2
C20H19PS
1H NMR (C6D6, 300 MHz): 2.01 [3H, s, SCH3], 3.66 [2H, s, CH2P], 6.79 [2H, m,
2H of H3–6], 6.94 [1H, m, 1H of H3–6]. Other aromatic hydrogens: 7.05 [7H, m],
7.45 [4H, m]
RMM = 322.411
White solid
1
31P{ H} NMR (C6D6, 122 MHz): −12.4 [s, CH2P]
C23H25PS
1H NMR (CDCl3, 300 MHz): 1.32 [9H, s, SC(CH3)3], 3.83 [2H, d, 2JHP = 1.2,
CH2P]. Aromatic hydrogens: 6.96 [1H, m], 7.10 [2H, m], 7.32 [5H, m], 7.41 [4H, m],
7.49–7.83 [2H, m]
RMM = 364.492
White solid
1
Found: C, 75.35; H, 7.28%
Calc.: C, 75.79; H, 6.91%
13C{ H} NMR (CDCl3, 75 MHz): 31.4 [s, SC(CH3)3], 34.9 [d, 1JCP = 15.6, CH2P],
47.6 [d, 5JCP = 1.1, SC(CH3)3]. Aromatic carbons: 126.0 [d, JCP = 2.6], 128.3 [d,
JCP = 6.4], 128.6 [s], 128.6 [s], 130.2 [d, JCP = 9.0], 132.5 [d, JCP = 4.3], 133.1 [d,
JCP = 18.4], 138.3 [d, JCP = 15.9], 138.8 [d, JCP = 1.4], 143.0 [d, JCP = 7.2]
FI-MS: 364.1 [M]+, 307.1 [M − Bu]+
t
Correct isotope pattern
1
31P{ H} NMR (CDCl3, 122 MHz): −7.4 [s, CH2P]
PhS∼PPh2
C25H21PS
1H NMR (CDCl3, 300 MHz): 3.64 [2H, s, CH2P], 6.91 [1H, m, 1H of H3–6]. Other
RMM = 384.452
aromatic hydrogens: 7.08 [3H, m], 7.15–8.02 [br m]b
1
Off-white solid
13C{ H} NMR (CDCl3, 75 MHz): 34.5 [d, 1JCP = 16.4, CH2P]. Aromatic carbons:
Found: C, 76.24; H, 5.41%
Calc.: C, 78.10; H, 5.51%b
EI-MS: 384.1 [M]+, 307.1 [M − Ph]+
Correct isotope pattern
126.5 [s], 127.2 [d, JCP = 3.0], 127.7 [d, JCP = 1.5], 128.5 [d, JCP = 6.5], 128.8 [s],
129.2 [s], 130.0 [s], 130.6 [d, JCP = 8.9], 133.2 [d, JCP = 18.8], 133.7 [d, JCP = 2.0],
134.4 [d, JCP = 4.0], 136.9 [d, JCP = 1.5], 138.2 [d, JCP = 15.9], 139.5 [d, JCP = 8.2]
1
31P{ H} NMR (CDCl3, 122 MHz): −9.9 [s, CH2P]
2 1 5 2
D a l t o n T r a n s . , 2 0 0 5 , 2 1 5 1 – 2 1 6 1

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Table 1 (Contd.)
Compound
NMR data
[PdCl2(MeS∼PPh2)]
C20H19Cl2PPdS
1H NMR (d6-DMSO, 300 MHz): 3.08 [3H, s, SCH3], 4.20 [2H, br d, 2JHP
=
RMM = 499.737
12.1, CH2P], 7.21 [1H, br d, 3JHH = 7.3, H3 or H6], 7.28 [1H, br td, 3JHH = 7.3,
J = 0.6, H4 or H5], 7.36 [1H, br tt, 3JHH = 7.7, J = 1.4, H4 or H5], 7.49 [4H, m,
Yellow–green solid
ES-MS: 961.4 [2M − Cl]+, 504.2 [M − (H12/12ꢀ + H16/16ꢀ) or (H13/13ꢀ + H17/17ꢀ)], 7.57 [2H, m, H14 + H18], 7.63
Cl + MeCN]+, 463.2 [M − Cl]+
[1H, br d, 3JHH = 7.7, H3 or H6], 7.81 [4H, br dd, J = 11.9, J = 7.6, (H12/12ꢀ +
H16/16ꢀ) or (H13/13ꢀ + H17/17ꢀ)]
Correct isotope pattern
1
31P{ H} NMR (d6-DMSO, 122 MHz): 60.9 [br s, CH2P]
1H NMR (CD2Cl2, 300 MHz): 3.13 [3H, s, SCH3], 3.80 [2H, d, 2JHP = 10.9,
CH2P], 6.80 [1H, d, 3JHH = 7.8, H6], 7.20 [1H, dd, 3JHH = 7.8, H5], 7.30 [6H, m,
H3 + H4 + H13/13ꢀ + H17/17ꢀ], 7.65 [2H, m, H14 + H18], 7.95 [4H, m,
H12/12ꢀ + H16/16ꢀ]
1
13C{ H} NMR (CD2Cl2, 75 MHz): 18.2 [br s, SCH3], 32.4 [br s, CH2P], 125.5
[br s, C5], 127.2 [br s, C4], 128.6 [s, C2], 128.8 [br s, C13/13ꢀ + C17/17ꢀ], 129.0
[s, C6], 131.4 [br s, C1], 132.3 [br s, C11 + C15], 132.4 [br s, C14 + C18], 133.4
[br s, C12/12ꢀ + C16/16ꢀ]
1
31P{ H} NMR (CD2Cl2, 122 MHz): 63.4 [s, CH2P]
[PdCl2(tBuS∼PPh2)]
C23H25Cl2PPdS
1H NMR (d6-DMSO, 500 MHz): 1.62 [9H, s, SC(CH3)3], 3.81 [1H, br dd,
2JHH = 14.9, 2JHP = 7.2, 1H of CH2P], 4.33 [1H, br t, 2JHH = 14.8, 2JHP = 16.7,
1H of CH2P], 7.37 [1H, br tt, 3JHH = 7.5, 4JHH = 1.7, 6JHP = 1.4, H4], 7.46 [4H,
m, H5 + H6 + H13/13ꢀ], 7.56 [3H, m, H14 + H17/17ꢀ], 7.63 [1H, m, H18], 7.71
[3H, m, H3 + H16/16ꢀ], 7.98 [2H, br t, 3JHH = 6.8, 3JHP = 8.3, H12/12ꢀ]
RMM = 541.818
Orange solid
Found: C, 51.05; H, 5.20%
Calc.: C, 50.98; H, 4.65%
ES-MS: 546.3 [M − Cl + MeCN]+,
505.3 [M − Cl]+
1
13C{ H} NMR (d6-DMSO, 126 MHz): 31.9 [d, 1JCP = 29.6, CH2P], 32.5 [s,
SC(CH3)3], 60.6 [s, SC(CH3)3], 125.0 [d, 1JCP = 53.1, C11 or C15], 129.0 [d,
5JCP = 2.9, C4], 130.9 [d, 1JCP = 58.4, C11 or C15], 131.5 [br s, C18], 134.8 [br d,
2JCP = 10.2, C12/12ꢀ], 136.1 [d, 4JCP = 1.8, C3]. Other aromatic carbons: 123.3
Correct isotope pattern
[d, JCP = 9.7], 128.6 [m], 132.3 [m], 132.5 [s], 133.1 [d, JCP = 6.2], 137.9 [d, JCP
=
3.2]
1
31P{ H} NMR (d6-DMSO, 202 MHz): 49.7 [s, CH2P]
[PdCl2(PhS∼PPh2)]
C25H21Cl2PPdS
1H NMR (d6-DMSO, 60 ◦C, 500 MHz): 3.63 [2H, d, 2JHP = 12.2, CH2P], 7.35
RMM = 561.808
[1H, br s, 1H of H3–6], 7.48 [6H, m, 2H of H3–6 + H13/13ꢀ + H17/17ꢀ], 7.57
Orange–green solid
[5H, m, H9/9ꢀ + H10 + H14 + H18], 7.71 [4H, br dd, 3JHH = 7.8, 3JHP = 12.0,
H12/12ꢀ + H16/16ꢀ], 7.82 [2H,◦m, H8/8ꢀ], 7.93 [1H, br s, 1H of H3–6]
Found: C, 52.77; H, 4.61%
Calc.: C, 53.45; H, 3.77%
ES-MS: 566.1 [M − Cl + MeCN]+,
533.1 [M − 2Cl + 2H + MeCN]+
Correct isotope pattern
1
13C{ H} NMR (d6-DMSO, 60 C, 126 MHz): 30.1 [d, 1JCP = 26.4, CH2P], 128.4
[d, 3JCP = 11.3, C13/13ꢀ + 17/17ꢀ], 129.3 [d, JCP = 3.3, 1C of C3–6], 129.5 [s,
C8/8ꢀ], 129.9 [s, C10], 130.1 [s, C9/9ꢀ], 131.8 [d, 4JCP = 2.9, C14 + C18], 132.6 [s,
1C of C3–6], 133.1 [m, 1C of C3–6 + C12/12ꢀ + C16/16ꢀ], 133.8 [s, 1C of C3–6].
Other aromatic carbon: 136.6 [d, JCP = 3.2]
31P{ H} NMR (d6-DMSO, 60 ◦C, 202 MHz): 56.2 [s, CH2P]
1
[PdClMe(MeS∼PPh2)] C21H22ClPPdS
RMM = 479.319
1H NMR (CD2Cl2, 300 MHz): 0.65 [3H, d, 3JHP = 3.7, PdCH3], 2.80 [3H, s,
SCH3], 3.58 [2H, d, 2JHP = 9.9, CH2P], 6.61 [1H, d, 3JHH = 7.5, H6], 6.90 [1H,
br d, 3JHH = 7.5, H5], 7.19 [1H, br m, H3], 7.29 [1H, br m, H4], 7.40 [6H, br m,
H13/13ꢀ + H14 + H17/17ꢀ + H18], 7.54 [4H, br m, H12/12ꢀ + H16/16ꢀ]
Air- and water-sensitive white solid
Found: C, 50.72; H, 3.16%
Calc.: C, 52.62; H, 4.63%
ES-MS: 921.4 [2M − Cl]+,
443.2 [M − Cl]+,
1
13C{ H} NMR (CD2Cl2, 75 MHz): 3.2 [br s, PdCH3], 14.9 [br s, SCH3], 34.5 [d,
1JCP = 22.7, CH2P], 123.4 [s, C3], 125.5 [s, C5], 127.5 [s, C4], 127.9 [d, 3JCP
=
10.6, C13/13ꢀ + C17/17ꢀ], 129.0 [s, C2] 130.8 [br s, C1], 131.2 [br d, 1JCP = 53.2,
475.2 [M − Cl + MeOH]+
Correct isotope pattern
C11 + C15], 131.5 [s, C6], 131.6 [d, 4JCP = 2.9, C14 + C18], 132.5 [d, 2JCP
=
11.6, C12/12ꢀ + C16/16ꢀ]
1
31P{ H} NMR (CD2Cl2, 122 MHz): 52.5 [s, CH2P]
[PtMe2(MeS∼PPh2)]
C22H25PPtS
1H NMR (CD2Cl2, 300 MHz): 0.39 [3H, d, 3JHP = 7.5, 2JHPt = 69.0, PtCH3 trans
to PPh2], 0.41 [3H, d, 3JHP = 8.1, 2JHPt = 87.6, PtCH3 cis to PPh2], 2.82 [3H, s,
3JHPt = 29.8, SCH3], 3.68 [2H, d, 2JHP = 8.4, 2JHPt = 25.8, CH2P], 6.70 [1H, d,
3JHH = 7.4, H6], 6.85 [1H, br d, 3JHH = 7.5, H5], 7.00 [1H, br m, H3], 7.10 [1H,
br m, H4], 7.25 [4H, br m, H12/12ꢀ + H16/16ꢀ], 7.50 [6H, br m, H13/13ꢀ +
H14 + H17/17ꢀ + H18]
RMM = 547.561
Air- and water-sensitive white solid
EI-MS: 553.4 [M + 6H]+
1
13C{ H} NMR (CD2Cl2, 75 MHz): 16.8 [br s, SCH3], 32.4 [br s, CH2P], 127.6
[br s, C13/13ꢀ + C17/17ꢀ], 130.7 [br s, C14 + C18], 132.0 [br s, C12/12ꢀ +
C16/16ꢀ], 139.6 [s, C2], 135.1 [br s, C1]. Other aromatic carbons: 130.3, 129.5,
128.9. 127.0, 125.2 [br s]
1
31P{ H} NMR (CD2Cl2, 122 MHz): 41.6 [s, CH2P, 1JPPt = 2072.0]
a Traces of C6H5CH2NMe2 and tBuSStBu present. b Traces of PhSSPh present.
Metal complexes
All complexes were characterized by elemental analysis, mass
1 1 31 1
spectrometry (ES- or EI-MS) and H, H{ P}, 13C{ H} and
t
1
31P{ H} NMR spectroscopy using COSY, HSQC, HMQC,
The metal complexes [PdCl2(RS∼PPh2)] (R = Me, Bu, Ph),
[PdClMe(MeS∼PPh2)] and [PtMe2(MeS∼PPh2)] were synthe-
sized from RS∼PPh2 and one equivalent of [MXY(COD)] (M =
Pd, X = Cl, Y = Cl or Me; M = Pt, X = Y = Me) as shown in
Fig. 3 and described in the Experimental section.
HMBC and NOE difference experiments (see Table 1). The
1
1
1H, 13C{ H} and 31P{ H} NMR spectra of all complexes are
downfield shifted with respect to the free RS∼PPh2 ligand,
indicative of bidentate coordination to the metal centre. The
D a l t o n T r a n s . , 2 0 0 5 , 2 1 5 1 – 2 1 6 1
2 1 5 3

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similarly between conformers II and IV) and for R = Ph there
is intermediate (coalescence-type) behaviour. The rate of r.i. is
1
temperature dependent, such that the H NMR spectrum of
◦
[PdCl2(PhS∼PPh2)] at 60 C shows an A2X doublet for CH2P
and one resolved set of multiplets for PPh2, consistent with faster
ring inversion (see Table 1).
At room temperature, the 1H NMR resonances of the R
group in all [PdCl2(RS∼PPh2)] complexes are very sharp. This
is indicative of very fast sulfur inversion (fast exchange between
conformers I and II and similarly between conformers III and
IV) taking place independently of ring inversion. Related pal-
ladium(II) thioether complexes show very fast sulfur inversion
at room temperature.24–26 Further studies of fluxionality by
variable-temperature NMR were hampered by the low solubility
of the metal complexes at lower temperatures.
We propose a mechanism to describe the fluxional behaviour
of the [PdCl2(RS∼PPh2)] complexes in solution (Fig. 4). At room
temperature, sulfur inversion (s.i.) is fast for all complexes whilst
ring inversion (r.i.) is dependent on the nature of R. When R =
Me or Ph, one equilibrium species of all four conformers can be
observed by 1H NMR as a result of the two fluxional processes.
t
When R = Bu, r.i. is much reduced and two equilibrium species
of conformers I and II (and separately conformers III and IV)
are present. These two equilibrium species are enantiomeric and
indistinguishable by 1H NMR.
The 1H NMR spectra of [PdClMe(MeS∼PPh2)] and
[PtMe2(MeS∼PPh2)] are similar to [PdCl2(MeS∼PPh2)], in-
dicating similar states of fluxionality. Additionally, for
[PdClMe(MeS∼PPh2)], the PdCH3 resonance was found at d
0.65 ppm as a doublet with coupling constant 3JHP = 3.7 Hz. The
strong PdCH3 to H(ortho) of PPh2 NOE indicates that themethyl
and phosphorus are coordinated cis on the palladium centre.
This geometry was further confirmed by X-ray crystallography
(vide infra). For [PtMe2(MeS∼PPh2)], a centred pair of doublets
was observed – assignable by NOE difference experiments to the
Pt(CH3)2 groups – at d 0.41 ppm (cis to PPh2, 3JHP = 8.1 Hz) and
d 0.39 ppm (trans to PPh2, 3JHP = 7.5 Hz). As expected, the H–Pt
Fig. 3 Synthesis of metal complexes.
chelate complexes are inert and show no hemilability22,23 or
tendency to dissociate in solution.
The most notable feature in the 1H NMR spectra of the
[PdCl2(RS∼PPh2)] complexes is the simultaneous variation of
t
the CH2P and PPh2 resonances as R changes from Me to Bu
to Ph. Room temperature d6-DMSO solutions of the complexes
show an A2X doubletfor CH2Pand oneresolved setofmultiplets
for PPh2 (R = Me), a broad singlet for CH2P and one broad set
of multiplets for PPh2 (R = Ph) or an ABX octet for CH2P
t
and two resolved sets of multiplets for PPh2 (R = Bu). This
coupling is somewhat larger for the PtCH3 cis to PPh2 (2JHPt
87.6 Hz) than for the PtCH3 trans to PPh2 (2JHPt = 69.0 Hz).
=
behaviour in solution is due to inversion of the six-membered
metal chelate ring which exchanges the chemically-inequivalent
AB hydrogens of CH2P at the same rate as the chemically-
inequivalent EF phenyl rings of PPh2 (Fig. 4). The rate of ring
X-Ray crystal structures
t
inversion (r.i.) increases with R = Me > Ph > Bu. Hence,
The solid-state structures of [PdCl2(MeS∼PPh2)], [PdCl2(tBuS∼
PPh2)], [PdCl2(PhS∼PPh2)], [PdClMe(MeS∼PPh2)] and [PtMe2-
(MeS∼PPh2)] were determined by single-crystal X-ray diffrac-
tion. Crystals suitable for structural determination were ob-
tained as described in the Experimental section.
for R = Me there is fast exchange between conformers I and
III (and similarly between conformers II and IV), for R =
tBu there is slow exchange between conformers I and III (and
We reported that when a mixture of dichloromethane and
methanol was used as crystallizing medium, the complex
[PdCl2(MeS∼PPh2)] crystallized at room temperature in the
monoclinic space group P21/n, with one molecule in the
asymmetric unit.9 We were recently surprised when we identified
a second polymorph particularly since, when crystals were
obtained from a mixture of dichloromethane and pentane
by slow cooling to −20 ◦C, the two polymorphs can be
crystallized concomitantly. We now report the structure of
the second polymorph (as a dichloromethane solvate) in the
¯
triclinic P1 space group, with two unique metal complex
molecules that have similar geometry and conformation in
the asymmetric unit. ORTEP representations for [PdCl2(MeS∼
PPh2)]·CH2Cl2, [PdCl2(tBuS∼PPh2)], [PdCl2(PhS∼PPh2)], [Pd-
ClMe(MeS∼PPh2)] and [PtMe2(MeS∼PPh2)] are presented in
Figs. 5–9 and their significant molecular parameters in Table 2.
Molecular structure determinations confirm that the stud-
ied Pd(II) and Pt(II) complexes are isostructural and their
structure is similar in solution and in the solid state. All
complexes exhibit pseudo-square-planar geometry at the metal
centre. For the MeS∼PPh2 ligand, the S–Pd–P bite angles are
88.51(4) and 88.34(4)◦ (molecules 1 and 2, respectively) in
[PdCl2(MeS∼PPh2)] and 92.09(4)◦ in [PdClMe(MeS∼PPh2)].
Fig.
4 Ring inversion (r.i.) and sulfur inversion (s.i.) in
[PdCl2(RS∼PPh2)] complexes (Cl ligands omitted for clarity).
2 1 5 4
D a l t o n T r a n s . , 2 0 0 5 , 2 1 5 1 – 2 1 6 1

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◦
t
˚
Table 2 Selected bond lengths (A) and angles ( ) for [PdCl2(MeS∼PPh2)], [PdCl2( BuS∼PPh2)], [PdCl2(PhS∼PPh2)], [PdClMe(MeS∼PPh2)] and
[PtMe2(MeS∼PPh2)]
[PdCl2(MeS∼PPh2)]
Molecule 1
Molecule 2
Pd1–P1
Pd1–S1
Pd1–Cl1
Pd1–Cl2
S1–C3
2.2475(10)
2.295(1)
2.3496(10)
2.3166(9)
1.771(4)
S1–C8
P1–C1
P1–C9
P1–C15
1.792(4)
1.840(4)
1.821(4)
1.814(4)
Pd2–P2
Pd2–S2
Pd2–Cl3
Pd2–Cl4
S2–C23
2.2540(10)
2.2873(10)
2.3549(10)
2.3195(9)
1.779(4)
S2–C28
P2–C21
P2–C29
P2–C35
1.792(4)
1.844(4)
1.801(4)
1.816(4)
P1–Pd1–S1
P1–Pd1–Cl1
S1–Pd1–Cl1
P1–Pd1–Cl2
S1–Pd1–Cl2
Cl1–Pd1–Cl2
88.51(4)
175.32(4)
93.46(4)
87.48(3)
172.54(4)
91.01(4)
Pd1–P1–C1
Pd1–P1–C15
Pd1–P1–C9
Pd1–S1–C3
Pd1–S1–C8
111.71(13)
114.17(12)
117.12(12)
105.38(12)
112.54(15)
P2–Pd2–S2
P2–Pd2–Cl3
S2–Pd2–Cl3
P2–Pd2–Cl4
S2–Pd2–Cl4
Cl3–Pd2–Cl4
88.34(4)
176.18(4)
93.57(4)
87.40(3)
173.09(4)
91.00(4)
Pd2–P2–C21
Pd2–P2–C29
Pd2–P2–C35
Pd2–S2–C23
Pd2–S2–C28
111.96(13)
113.18(13)
117.00(12)
106.08(12)
112.45(16)
[PdCl2(tBuS∼PPh2)]
[PdCl2(PhS∼PPh2)]
Pd1–Cl1
Pd1–Cl2
Pd1–S1
Pd1–P1
S1–C7
2.3686(9)
2.3157(9)
2.2979(9)
2.2247(9)
1.780(4)
S1–C8
1.879(3)
1.830(4)
1.812(4)
1.809(4)
Pd1–Cl2
Pd1–P1
Pd1–S1
Pd1–Cl1
P1–C1
2.3353(9)
2.2429(10)
2.2997(11)
2.3608(11)
1.840(4)
P1–C14
P1–C20
C7–S1
S1–C8
1.812(4)
1.805(4)
1.773(5)
1.798(5)
P1–C1
P1–C12
P1–C18
Cl1–Pd1–Cl2
Cl1–Pd1–S
Cl2–Pd1–S1
Cl1–Pd1–P1
Cl2–Pd1–P1
S1–Pd1–P1
91.64(3)
187.84(3)
173.81(3)
175.99(3)
84.54(3)
95.83(3)
Pd1–S1–C7
Pd1–S1–C8
Pd1–P1–C1
Pd1–P1–C12
Pd1–P1–C18
112.45(12)
115.45(12)
113.44(12)
111.38(12)
113.32(13)
Cl2–Pd1–P1
Cl2–Pd1–S1
P1–Pd1–S1
Cl2–Pd1–Cl1
P1–Pd1–Cl1
S1–Pd1–Cl1
88.49(4)
176.64(4)
94.74(4)
92.12(4)
176.50(4)
84.60(4)
Pd1–P1–C1
Pd1–P1–C14
Pd1–P1–C20
Pd1–S1–C8
C7–S1–Pd1
110.57(13)
116.89(14)
114.56(15)
106.27(15)
112.40(14)
[PdClMe(MeS∼PPh2)]
[PtMe2(MeS∼PPh2)]
Pd1–Cl1
Pd1–S1
Pd1–P1
Pd1–C1
S1–C2
2.3717(13)
S1–C3
1.781(4)
1.842(5)
1.806(5)
1.821(5)
Pt1–S1
Pt1–P1
Pt1–C1
Pt1–C2
S1–C3
2.3460(6)
S1–C4
1.786(2)
1.852(2)
1.821(2)
1.824(2)
2.4331(13)
2.2001(12)
2.069(6)
P1–C9
P1–C10
P1–C16
2.2603(6)
2.100(2)
2.062(2)
1.803(4)
P1–C10
P1–C11
P1–C17
1.797(5)
Cl1–Pd1–S1
Cl1–Pd1–P1
S1–Pd1–P1
Cl1–Pd1–C1
S1–Pd1–C1
P1–Pd1–C1
91.05(5)
174.74(5)
92.09(4)
89.51(16)
176.44(18)
87.10(16)
Pd1–S1–C2
Pd1–S1–C3
Pd1–P1–C9
Pd1–P1–C10
Pd1–P1–C16
112.37(19)
111.61(16)
110.48(15)
115.19(16)
116.29(17)
S1–Pt1–P1
S1–Pt1–C1
P1–Pt1–C1
S1–Pt1–C2
P1–Pt1–C2
C1–Pt1–C2
90.44(2)
91.25(8)
175.84(7)
178.30(8)
90.81(8)
87.43(11)
Pt1–S1–C3
Pt1–S1–C4
Pt1–P1–C10
Pt1–P1–C11
Pt1–P1–C17
111.88(11)
108.11(7)
111.11(9)
119.33(8)
114.76(8)
For the corresponding dichloro complexes of PhS∼PPh2 and
tBuS∼PPh2, the S–Pd–P bite angles are significantly larger:
94.74(4) and 95.83(3)◦ respectively, presumably as a result of
increased puckering of the chelate ring induced by bulkiness of
the S substituent. The palladium–halogen bond lengths are as
expected for Pd(II) complexes,27 with the longer metal–halogen
bond trans to the phosphorus atom. In [PdClMe(MeS∼PPh2)],
of the rings in terms of the dihedral angle between the
best-fit plane [M–P–S–X–Y], and that of the bridging 2-
C6H4CH2 unit. This angle decreases from 61.2 and 60.5◦
(molecule 1 and 2 respectively) in [PdCl2(MeS∼PPh2)] to 55.8◦
in [PtMe2(MeS∼PPh2)], 44.5◦ in [PdCl2(tBuS∼PPh2)], 43.8◦ in
[PdCl2(PhS∼PPh2)] and 43.6◦ in [PdMeCl(MeS∼PPh2)]. Note
that the same angle measures 42◦ in the earlier reported
polymorph of [PdCl2(MeS∼PPh2)].9 This data complements the
solution studies and indicates that complexes of MeS∼PPh2
prefer conformers II and III in the solid state whilst complexes
of tBuS∼PPh2 and PhS∼PPh2 prefer conformers I and IV in the
solid state (Fig. 4).
˚
the Pd–C bond length is 2.069(6) A with the methyl group
located cis to the phosphorus atom, as predicted by NMR for the
solution species. In general, little variation in the bond lengths
and angles of RS∼PPh2 is observed upon chelation to Pd(II).
In the case of [PtMe2(MeS∼PPh2)], the S–Pt–P bite angle is
90.44(2)◦. The Pt–C bond length for the methyl group situated
Finally, in [PdCl2(PhS∼PPh2)] the distance between Pd(1)
˚
˚
trans to phosphorus is 2.100(2) A. This is somewhat longer than
and H(91) is 2.80 A and that between Pd(1) and C(9) is
˚
˚
the Pd–C distance cis to PPh2 (2.062(2) A), which we attribute
3.36 A. The orientation of H(91) is almost perpendicular
to the greater trans-influence of PPh2 compared to the SMe
donor functionality. The remaining bond lengths and angles are
unexceptional and are within the expected limits.
All six-membered metal chelate rings have “boat” geometries,
with the methylene group deviated off the best-fit plane [M–P–
with respect to the Pd–P–S–Cl–Cl mean plane, i.e. the torsion
angle between the best-fit [Pd–P–S–Cl–Cl] plane and the [SPh]
plane is 87.8◦. Similar compounds have been characterized
in the solid state28–31 and the values found by us for ortho-
H · · · Pd and ortho-C · · · Pd distances are normal for chelated
palladium(II) phenylthioether complexes. The 1H NMR (d6-
DMSO, 60 ◦C) of [PdCl2(PhS∼PPh2)] shows no unexpected
features in the aromatic region indicative of a potential ortho-
H · · · Pd interaction.
˚
S–X–Y] at about 0.19 and 0.30 A (molecule 1 and 2, respectively)
t
˚
˚
in [PdCl2(MeS∼PPh2)], 0.40 A in [PdCl2( BuS∼PPh2)], 0.43 A
˚
in [PdCl2(PhS∼PPh2)], 0.49 A in [PdMeCl(MeS∼PPh2)] and
˚
0.29 A in [PtMe2(MeS∼PPh2)]. We defined the puckering
D a l t o n T r a n s . , 2 0 0 5 , 2 1 5 1 – 2 1 6 1
2 1 5 5

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Fig.
7
ORTEP representation of the molecular structure of
[PdCl2(PhS∼PPh2)].
Fig.
5
ORTEP representation of the molecular structure of
[PdCl2(MeS∼PPh2)]. Both complex molecules in the asymmetric unit
are shown. Solvent (CH2Cl2) excluded.
Fig.
8
ORTEP representation of the molecular structure of
[PdClMe(MeS∼PPh2)].
Fig.
6
ORTEP representation of the molecular structure of
[PdCl2(tBuS∼PPh2)].
CO/ethene copolymerisation testing
Bidentate phosphane ligands which form six-membered chelate
complexes with palladium(II) acetate have been shown to be
highly active for the copolymerisation of CO and ethene.32,33 We
were therefore interested in determining the catalytic activity of
in situ catalysts formed with the RS∼PPh2 ligands.
A mixture of palladium(II) acetate, p-toluenesulfonic acid
hydrate and RS∼PPh2 in methanol was heated at 80 ◦C for
2 h under a continuous pressure of 40 bar 1 : 1 CO–ethene.
The resultant grey insoluble copolymers were obtained in the
following yields: 0.0380 g (activity 1900 90 g mol Pd−1) for
Fig.
9
ORTEP representation of the molecular structure of
t
R = Me; 0.0003 g (activity 15 10 g mol Pd−1) for R = Bu;
[PtMe2(MeS∼PPh2)].
0.0014 g (activity 70 10 g mol Pd−1) for R = Ph. Furthermore,
a mixture of [PdClMe(MeS∼PPh2)], silver(I) tetrafluoroborate
and acetonitrile in dichloromethane under the same conditions
gave a grey insoluble copolymer in a yield of 0.0501 g (activity
2500 60 g mol Pd−1).
13C NMR analysis (1,1,1,3,3,3-hexafluoropropan-2-ol–C6D6
(9 : 1)) of the copolymers obtained from MeS∼PPh2 cat-
alysts shows that they consist of perfectly alternating CO
and C2H4 units.33 GC-MS analysis of the co-oligomers
2 1 5 6
D a l t o n T r a n s . , 2 0 0 5 , 2 1 5 1 – 2 1 6 1

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X(CH2CH2CO)nY (n = 1–4) shows a strong dependence on the
catalyst system used. For catalyses using palladium(II) acetate,
MeS∼PPh2 gives predominantly keto-esters (X = H, Y = OMe),
PhS∼PPh2 gives predominantly diesters (X = CO2Me, Y =
OMe) and tBuS∼PPh2 gives virtually no co-oligomers. Catalysis
using [PdClMe(MeS∼PPh2)] gives no co-oligomers either, which
is indicative of a “living” copolymerisation.34,35
Comparison to Ph2PCH2CH2CH2PPh2 (polymer yield
5.3560 g, activity 270000 10000 g mol Pd−1 under the same
conditions) shows that the RS∼PPh2 ligands give catalytic
systems that are over two orders of magnitude less active.
The low catalytic activity of thioether–phosphane ligands for
CO/ethene copolymerisation has been remarked before.32
catalysts therefore show high but not superior activity with
respect to this benchmark system. Further testing with a variety
of electron-rich and electron-poor aryl bromides and chlorides
is underway and will be reported elsewhere.
It is well known that under Heck arylation conditions many
palladium(II) catalysts decompose to some palladium(0) or
palladium(II) aggregate36,42–44 and this may well be the case
with the [PdCl2(RS∼PPh2)] catalysts also. Model studies in
d6-DMSO or d7-DMF at 130 ◦C (at concentrations several
orders of magnitude higher than those of catalysis) show that
[PdCl2(MeS∼PPh2)] and [PdCl2(tBuS∼PPh2)] dealkylate45,46 af-
ter only 2 h whilst [PdCl2(PhS∼PPh2)] slowly forms free
PhS∼P(O)Ph2. Addition of sodium carbonate and prolonged
heating gives black, insoluble solids that are slightly active for
Heck arylation. Whether discrete [PdCl2(RS∼PPh2)] species are
mainly responsible for the observed catalytic activity or not, it
is clear that sulfur-based ligands can be used in combination
with palladium to produce robust and effective Heck arylation
catalysis systems.
Heck arylation testing
We have recently shown that [PdCl2(MeS∼PPh2)] is an efficient
catalyst for the Heck arylation of styrene with various aryl
bromides and iodides under aerobic conditions, leading to
turnover numbers (TONs) of 106.9 We now report our latest
findings on the catalytic activity of [PdCl2(RS∼PPh2)] (R =
t
Conclusions
Me, Bu, Ph) for the Heck arylation of n-butylacrylate with
bromobenzene.
New Pd(II) and Pt(II) complexes of the thioether–phosphanes
A mixture of bromobenzene, 1.2 equivalents n-butylacrylate
and anhydrous sodium carbonate in 1-methyl-2-pyrrolidinone
(NMP) was heated at 130 ◦C for 72 hours in the presence
of [PdCl2(RS∼PPh2)] (Fig. 10). All three metal complexes
give quantitative yields of E-n-butylcinnamate with catalyst
loadings of 0.001 mol% (TON = 100000). At 0.0001 mol%
loading, maximum TONs are obtained for each complex (see
Table 3). The activities of [PdCl2(RS∼PPh2)] depend on R
t
2-RSC6H4CH2PPh2 (RS∼PPh2: R = Me, Bu, Ph) have been
prepared and fully characterized, showing the ability of the
ligand to coordinate in a chelating bidentate fashion. An initial
estimation of the catalytic activity of Pd(II) RS∼PPh2 complexes
is described: low activity is observed for the copolymerisation
of CO and ethene but high activity is observed for the Heck
arylation of n-butylacrylate with bromobenzene under aerobic
conditions.
t
(Me > Bu > Ph) although the differences are small. TONs
with n-butylacrylate are about one-eighth of those reported with
Experimental
styrene.9
General
All manipulations of air- and/or water-sensitive compounds
were performed under an inert atmosphere of pure Ar or
N2 using standard Schlenk line techniques or glove boxes.47
Inert gases were purified by passage through columns filled
with activated 4A molecular sieves and then either man-
ganese(II) oxide suspended on vermiculite (for Schlenk lines)
or BASF R-311 catalyst (for glove boxes). Where necessary,
solvents were pre-dried over activated 4A molecular sieves
and then refluxed and distilled under N2 from Na/K alloy
(light petroleum (bp 40–60 ◦C), pentane), sodium (toluene),
sodium/benzophenone (tetrahydrofuran, diethyl ether), cal-
cium hydride (dichloromethane, acetonitrile) or magnesium(II)
methoxide (methanol). CD2Cl2 and CDCl3 were stirred over
calcium hydride, distilled and degassed prior to use. d6-DMSO
was dried over activated 4A molecular sieves and degassed
prior to use. Elemental analyses (Oxidative Digestion/TCD)
were performed by the Microanalytical Service of the Inorganic
Chemistry Laboratory, University of Oxford. Electrospray (ES,
Fig. 10 Conditions of Heck arylation.
The great advantage of the [PdCl2(RS∼PPh2)] catalysts is that
they are stable to air and water both in solution and the solid
state. The Heck arylation with bromobenzene can be performed
under aerobic conditions with very high TONs (105) unlike
most reported high-activity catalysts which give only a few
hundred turnovers.36–41 For comparison, we tested Herrmann’s
palladacyclic catalyst [Pd2(l-OAc)2{2-CH2C6H4P(o-Tol)2}2]36,37
(o-Tol = 2-CH3C6H4) under aerobic conditions and were
surprised to find similar activity to the [PdCl2(RS∼PPh2)]
systems (See Table 3: [Pd2(l-OAc)2{2-CH2C6H4P(o-Tol)2}2] had
previously been reported to give only 96 turnovers with n-
butylacrylate and bromobenzene36). The [PdCl2(RS∼PPh2)]
Table 3 Heck arylation results
Catalyst
mol%
Yield (%)
TON
[PdCl2(MeS∼PPh2)]
0.001
0.0001
100.0
15.0
100000 8000
150000 10000
[PdCl2(tBuS∼PPh2)]
[PdCl2(PhS∼PPh2)]
0.001
0.0001
100.0
13.0
100000 7000
130000 10000
0.001
0.0001
100.0
4.5
100000 7000
45000 3000
[Pd2(l-OAc)2{2-CH2C6H4P(o-Tol)2}2]
0.001
0.0001
100.0
15.5
100000 4000
150000 7000
o-Tol = 2-CH3C6H4
D a l t o n T r a n s . , 2 0 0 5 , 2 1 5 1 – 2 1 6 1
2 1 5 7

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methanol–acetonitrile–water (1 : 1 : 1) eluent), electron ioniza-
tion (EI, 70 eV) and field ionization (FI) mass spectroscopy was
performed by the Mass Spectroscopy Service of the Inorganic
Chemistry Laboratory, University of Oxford. NMR spectra
were acquired on a Varian UNITYplus (1H 500 MHz, 13C
126 MHz, 31P 202 MHz) or a Varian Mercury VxWorks (1H
300 MHz, 13C 76 MHz, 31P 122 MHz) spectrometer and are
at room temperature unless otherwise stated. The spectra were
referenced internally to residual protio solvent (1H) or solvent
(13C) resonances relative to SiMe4 (1H, 13C, d = 0) or externally to
85% H3PO4 (31P, d = 0). Chemical shifts (d) are expressed in ppm
and coupling constants (J) in Hz. CO/ethene copolymerisations
were performed using a Parr 4561 (300 mL) stainless steel stirred
reactor fitted with a glass liner. GC-MS chromatographs and
spectra were acquired on an Agilent 6890 Plus instrument fitted
with a SGE 15 m × 0.25 mm (i.d.) BPX5 capillary column
coupled to a Micromass GCT instrument operating in chemical
ionization (CI, NH3) mode. GC chromatographs were acquired
on a Unicam ProGC instrument fitted with a 2 m × 4 mm (i.d.)
Carbowax 20 M packed column.
stirred for 1 h, filtered and the solvent evaporated off the filtrate
under reduced pressure. The resultant brown oil was extracted
with deionized water (3 × 75 mL) and filtered. To the vigorously
stirred filtrate was added K2CO3 (19.52 g) slowly at 0 ◦C and
the mixture then stirred for 2 h. Extraction with diethyl ether
(3 × 150 mL), drying over Na2SO4, filtration and evaporation
of solvent off the filtrate under reduced pressure gave purer Ic
(3.84 g).
2-MeSC6H4CH2NMe3I (IIa). To a vigorously stirred solu-
tion of crude Ia (1.21 g) in acetonitrile (7 mL) was added MeI
(8.61 mmol, 1.22 g, 0.54 mL) dropwise at room temperature.
The mixture was stirred overnight and the resultant off-white
suspension then filtered. The residue was washed with diethyl
ether (2 × 15 mL), filtered and dried under reduced pressure to
afford IIa (1.04 g, 3.22 mmol, 23% over two steps).
IIa is soluble in dichloromethane, chloroform, acetonitrile
and methanol. It is insoluble in tetrahydrofuran, diethyl ether,
toluene and hexane.
2-tBuSC6H4CH2NMe3I (IIb). To a vigorously stirred solu-
tion of crude Ib (1.51 g) in acetonitrile (8 mL) was added MeI
(10.1 mmol, 1.43 g, 0.63 mL) dropwise at room temperature. The
mixture was stirred overnight and the solvent then evaporated
under reduced pressure. The resultant off-white solid was
washed with diethyl ether (2 × 15 mL), filtered and dried under
reduced pressure to afford IIb (2.27 g, 6.20 mmol, 30% over two
steps).
C6H5CH2NMe2, TMEDA (N,N,Nꢀ,Nꢀ-tetramethylethylene-
diamine), nBuLi in hexanes (1.6 M), MeSSMe, tBuSStBu,
PhSSPh, MeI, HOTs·H2O, AgBF4, 1-methyl-2-pyrrolidinone
(NMP), C6H5Br, nBuO2CCHCH2 (Aldrich), HPPh2 (Strem),
Pd(OAc)2 (Alfa-Aesar) and CO : C2H4 (1 : 1 by moles) (BOC)
were purchased and used as received.
15
2-MeSC6H4CH2NMe2
(Ia), [PdCl2(COD)],48 [PdClMe-
(COD)]49 and [PtMe2(COD)]50 were prepared according to the
literature methods.
IIb is soluble in dichloromethane, chloroform, acetonitrile
and methanol. It is insoluble in tetrahydrofuran, diethyl ether,
toluene and hexane.
2-tBuSC6H4CH2NMe2 (Ib). A solution of C6H5CH2NMe2
(0.05 mol, 6.76 g, 7.51 mL) and TMEDA (0.05 mol, 5.81 g,
7.55 mL) in tetrahydrofuran (50 mL) was transferred into a
500 mL three-necked round-bottomed flask equipped with two
dropping funnels and a magnetic stirrer. nBuLi in hexanes
(1.6 M, 0.075 mol, 46.88 mL) was added dropwise to the
vigorously stirred amine solution at room temperature and
the mixture stirred for 24 h. To the orange/red mixture was
2-PhSC6H4CH2NMe3I (IIc). To a vigorously stirred solu-
tion of crude Ic (5.13 g) in acetonitrile (10 mL) was added MeI
(21.7 mmol, 3.07 g, 1.35 mL) dropwise at room temperature. The
mixture became warm, was stirred overnight and the solvent was
then evaporated under reduced pressure. Under air, the resultant
off-white solid was washed with diethyl ether (4 × 60 mL),
filtered and dried under reduced pressure to afford crude IIc
(5.67 g).
t
added a solution of BuSStBu (0.055 mol, 9.81 g, 10.63 mL)
in tetrahydrofuran (50 mL) dropwise at 0 ◦C. The mixture was
stirred at room temperature overnight and was then quenched
with ice-water (ca. 150 mL). Under air, the tetrahydrofuran
phase was separated, the aqueous phase extracted with diethyl
ether (3 × 100 mL) and all ethereal solutions combined, dried
over Na2SO4, filtered and the solvent evaporated off the filtrate
under reduced pressure. Fractional distillation under reduced
pressure afforded crude Ib (73–83 ◦C/0.13 mbar, 3.64 g) as a
light-yellow oil.
Crude IIc is soluble in dichloromethane, chloroform, acetoni-
trile and methanol. It is insoluble in tetrahydrofuran, diethyl
ether, toluene and hexane.
2-MeSC6H4CH2PPh2 (MeS∼PPh2). To a vigorously stirred
suspension of small pieces of sodium (6.0 mmol, 0.138 g) in
tetrahydrofuran (20 mL) was added HPPh2 (5.0 mmol, 0.931 g,
0.87 mL) dropwise at room temperature. The red phosphide
solution was stirred overnight and then added dropwise to
a vigorously stirred suspension of IIa (4.0 mmol, 1.30 g) in
tetrahydrofuran (20 mL) at room temperature over the course
of 0.25 h. The mixture was stirred overnight and a light-
brown solution resulted. Evaporation of solvent under reduced
pressure gave a solid which was extracted with diethyl ether (3 ×
15 mL) and filtered. The light-yellow filtrate was evaporated
of solvent under reduced pressure and left to crystallize at
room temperature for 2 d. The white solid was washed with
methanol (8 mL), filtered and dried under reduced pressure to
give MeS∼PPh2 (0.670 g, 2.1 mmol, 52%).
2-PhSC6H4CH2NMe2 (Ic). A solution of C6H5CH2NMe2
(0.107 mol, 14.42 g, 16.02 mL) and TMEDA (0.107 mol,
12.39 g, 16.10 mL) in tetrahydrofuran (75 mL) was trans-
ferred into a 500 mL three-necked round-bottomed flask
equipped with two dropping funnels and a magnetic stir-
rer. nBuLi in hexanes (1.6 M, 0.16 mol, 100 mL) was
added dropwise to the vigorously stirred amine solution at
room temperature and the mixture stirred for 24 h. To
the orange/red mixture was added a solution of PhSSPh
(0.117 mol, 25.62 g) in tetrahydrofuran (80 mL) dropwise at
MeS∼PPh2 is soluble in dichloromethane, chloroform, ace-
tonitrile, tetrahydrofuran, diethyl ether and toluene. It is insol-
uble in methanol and light petroleum (bp 40–60 ◦C).
0
◦C. The mixture was stirred at room temperature overnight
and was then quenched with alkaline ice-water (NaOH,
pH 10, ca. 200 mL). Under air, the tetrahydrofuran phase
was separated, the aqueous phase extracted with diethyl ether
(3 × 175 mL) and all ethereal solutions combined, dried over
Na2SO4, filtered and the solvent evaporated off the filtrate under
reduced pressure. Fractional distillation under reduced pressure
afforded crude Ic (124–126 ◦C/0.13 mbar, 18.12 g) as a yellow
oil.
2-tBuSC6H4CH2PPh2 (tBuS∼PPh2). To a vigorously stirred
suspension of small pieces of sodium (8.4 mmol, 0.193 g) in
tetrahydrofuran (25 mL) was added HPPh2 (6.2 mmol, 1.15 g,
1.07 mL) dropwise at room temperature. The red phosphide
solution was stirred for 9 h and then added dropwise to a
vigorously stirred suspension of IIb (5.8 mmol, 2.12 g) in
tetrahydrofuran (30 mL) at room temperature over the course
of 1.5 h. The mixture was stirred overnight and an orange
solution resulted. Evaporation of solvent under reduced pressure
Ic can be purified as follows: To a vigorously stirred solution
of crude Ic (6.87 g) in methanol (35 mL) was added HCl(aq)
(12.9 M, 10.5 mL) dropwise at 0 ◦C. The brown suspension was
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gave an orange oil which was extracted with diethyl ether (3 ×
20 mL) and filtered. The orange–brown filtrate was evaporated
of solvent under reduced pressure, extracted with light petroleum
(bp 40–60 ◦C) (2 × 10 mL) and filtered. The yellow filtrate was
evaporated of solvent under reduced pressure and cooled to
for 20 h. The resultant orange–green suspension was filtered and
the residue washed with methanol (2 × 10 mL), filtered, washed
with diethyl ether (2 × 7.5 mL), filtered and dried under reduced
pressure to give [PdCl2(PhS∼PPh2)] (0.292 g, 0.52 mmol, 80%).
Crystals suitable for X-ray diffraction were grown from a super-
saturated d6-DMSO solution.
[PdCl2(PhS∼PPh2)] is soluble in dichloromethane, N,N-
dimethylformamide and hot dimethyl sulfoxide. It is sparingly
soluble in chloroform, acetonitrile, methanol, tetrahydrofuran,
benzene and toluene and insoluble in diethyl ether and hexane.
[PdClMe(MeS∼PPh2)]. A cold (−78 ◦C) solution of MeS∼
PPh2 (0.31 mmol, 0.100 g) in tetrahydrofuran (40 mL) was
added dropwise to a cold (−78 ◦C) tetrahydrofuran solu-
tion of [PdClMe(COD)] (0.31 mmol, 0.082 g). The complex
precipitated out of solution as a white powder after 1 h
of stirring. The reaction mixture was left to reach room
temperature and the filtrate was removed by filtration. The
filtrate was concentrated to 5 mL, layered with pentane and
stored at −20 ◦C to yield a second crop of pure complex
(total yield: 0.103 g, 0.21 mmol, 69%). Light-yellow crystals of
[PdClMe(MeS∼PPh2)] suitable for X-ray diffraction were grown
from a two-phase dichloromethane/pentane liquid diffusion
system.
◦
−78 C. Addition of methanol (3 × 5 mL) gave a white solid
which was filtered through a glass frit and dried under reduced
pressure to give tBuS∼PPh2 (0.839 g, 2.3 mmol, 37%).
tBuS∼PPh2 is soluble in dichloromethane, chloroform, ace-
tonitrile, tetrahydrofuran, diethyl ether and toluene. It is spar-
ingly soluble in methanol and pentane.
2-PhSC6H4CH2PPh2 (PhS∼PPh2). A solution of HPPh2
(5.2 mmol, 0.966 g, 0.90 mL) in tetrahydrofuran (11 mL) was
n
added dropwise into a vigorously stirred solution of BuLi in
hexanes (1.6 M, 5.2 mmol, 3.24 mL) at −40 ◦C. The orange
solution was stirred at −40 ◦C for 2 h and then added dropwise
into a vigorously stirred suspension of crude IIc (2.000 g) in
tetrahydrofuran (88 mL) at −78 ◦C over the course of 0.5 h.
The mixture was stirred overnight and an orange solution
resulted. Evaporation of solvent under reduced pressure gave
an orange oil which was extracted with diethyl ether (3 ×
10 mL) and filtered. The light-yellow filtrate was evaporated
of solvent under reduced pressure and triturated with methanol
(15 mL). The resultant off-white solid was washed with methanol
(20 mL), filtered and dried under reduced pressure to give crude
PhS∼PPh2 (1.84 g).
[PdClMe(MeS∼PPh2)] is soluble in dichloromethane, chloro-
form and tetrahydrofuran. It is sparingly soluble in toluene and
insoluble in pentane and hexane.
PhS∼PPh2 is soluble in dichloromethane, chloroform,
tetrahydrofuran and toluene. It is sparingly soluble in acetoni-
trile and diethyl ether and insoluble in methanol and pentane.
[PtMe2(MeS∼PPh2)].
A
cold (−78 ◦C) solution of
MeS∼PPh2 (0.31 mmol, 0.100 g) in tetrahydrofuran (40 mL) was
added dropwise to a cold (−78 ◦C) tetrahydrofuran solution of
[PtMe2(COD)] (0.31 mmol, 0.103 g). The reaction mixture was
left to reach room temperature under stirring in darkness for
10 h. The volatiles were removed under reduced pressure to give a
white powder, which was washed with pentane and recrystallized
from a two-phase tetrahydrofuran/pentane liquid diffusion
system. Yellow crystals of [PtMe2(MeS∼PPh2)] suitable for X-
ray diffraction were thus formed and isolated by filtration. Yield:
0.087 g, 0.16 mmol, 51%.
[PdCl2(MeS∼PPh2)]. [PdCl2(COD)] (0.62 mmol, 0.177 g)
and MeS∼PPh2 (0.62 mmol, 0.200 g) were suspended in
methanol (20 mL) and vigorously stirred at room temperature
for 23 h. The resultant yellow-green suspension was filtered and
the residue washed with methanol (2 × 7.5 mL), filtered, washed
with diethyl ether (7.5 mL), filtered and dried under reduced
pressure to give [PdCl2(MeS∼PPh2)] (0.253 g, 0.51 mmol, 82%).
Alternatively, the solids [PdCl2(COD)] (0.31 mmol, 0.089 g)
and MeS∼PPh2 (0.31 mmol, 0.100 g) were mixed in a Schlenk
tube and cold (−78 ◦C) tetrahydrofuran was added (50 mL). The
reaction mixture was left stirring for 10 h and the solids then
removed by filtration. The filtrate was concentrated to 5 mL,
layered with pentane and stored at −20 ◦C. Light-yellow crystals
of [PdCl2(MeS∼PPh2)] formed, were isolated by filtration and
dried under reduced pressure (0.120 g, 0.24 mmol, 77%). Crystals
suitable for X-ray diffraction were grown from a two-phase
dichloromethane/pentane liquid diffusion system at −20 ◦C. X-
ray diffraction shows that this is a different polymorph than that
reported by us earlier.9
[PtMe2(MeS∼PPh2)] is soluble in CH2Cl2, CHCl3 and THF. It
is sparingly soluble in toluene and insoluble in pentane and
hexane.
CO/ethene copolymerisation testing. Pd(OAc)2 (0.02 mmol,
4.5 mg), RS∼PPh2 (0.022 mmol) and HOTs·H2O (0.04 mmol,
7.6 mg) were placed into a stirred reactor. The reactor was
thoroughly purged with N2 and methanol (55 mL) was added.
The solution was degassed, all reactor valves closed and
the solution then heated up to 80 ◦C with vigorous stirring
(1400 rpm) for 1 h. The reactor was pressurized to 40 bar with
CO : C2H4 (1 : 1 by moles) and left for another 2 h. It was
then cooled to room temperature, vented and opened. Under
air, the grey suspension was filtered and the filtrate immediately
analyzed by GC-MS. The residue was washed with methanol
(3 × 12 mL), filtered and dried under reduced pressure at 80 ◦C.
To a solution of [PdClMe(MeS∼PPh2)] (0.02 mmol, 9.6 mg)
in dichloromethane : acetonitrile (9 mL : 0.05 mL) was added
AgBF4 (0.024 mmol, 4.7 mg) and the mixture stirred for 2 min.
The suspension was filtered into a thoroughly N2-purged stirred
reactor and dichloromethane (46 mL) was added. The solution
was degassed, all reactor valves closed and the solution then
heated up to 80 ◦C with vigorous stirring (1400 rpm) for 0.5 h.
The reactor was pressurized to 40 bar with CO : C2H4 (1 : 1
by moles) and left for another 2 h. It was then cooled to
room temperature, vented and opened. Under air, the grey
suspension was filtered and the filtrate immediately analyzed
by GC-MS. The residue was washed with dichloromethane (3 ×
15 mL), filtered and dried under reduced pressure at 80 ◦C.
[PdCl2(MeS∼PPh2)] is soluble in dichloromethane and hot
dimethyl sulfoxide. It is sparingly soluble in chloroform,
methanol, tetrahydrofuran and toluene and insoluble in ace-
tonitrile, diethyl ether and hexane.
[PdCl2(tBuS∼PPh2)]. [PdCl2(COD)] (0.53 mmol, 0.150 g)
and tBuS∼PPh2 (0.53 mmol, 0.191 g) were suspended in
methanol (20 mL) and vigorously stirred at room temperature
for 18 h. The resultant orange suspension was filtered and the
residue washed with methanol (2 × 7.5 mL), filtered, washed
with diethyl ether (10 mL), filtered and dried under reduced
pressure to give [PdCl2(tBuS∼PPh2)] (0.184 g, 0.34 mmol, 65%).
Crystals suitable for X-ray diffraction were grown from a two-
phase dichloromethane/methanol liquid diffusion system.
[PdCl2(tBuS∼PPh2)] is soluble in dichloromethane, acetoni-
trile, N,N-dimethylformamide and warm dimethyl sulfoxide. It
is sparingly soluble in chloroform, tetrahydrofuran, benzene and
toluene and insoluble in methanol, diethyl ether and hexane.
[PdCl2(PhS∼PPh2)]. [PdCl2(COD)] (0.65 mmol, 0.186 g)
and PhS∼PPh2 (0.65 mmol, 0.250 g) were suspended in
methanol (20 mL) and vigorously stirred at room temperature
Heck arylation testing. Under air, a stock solution of
[PdCl2(RS∼PPh2)] in 1-methyl-2-pyrrolidinone (NMP) was pre-
pared and 5 mL thereof transferred into a 100 mL ampoule
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equipped with a Young’s TapTM and a magnetic stirrer. C6H5Br
(5 mmol, 0.785 g, 0.527 mL), nBuO2CCHCH2 (6 mmol, 0.769 g,
0.860 mL) and anhydrous Na2CO3 (6 mmol, 0.636 g) were added
and ◦the ampoule closed. The mixture was vigorously stirred at
130 C for 72 h, cooled to room temperature and immediately
analyzed by GC.
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X-Ray crystallography
In each case, a single crystal was selected under an inert
atmosphere, encased in perfluoro-polyether oil and mounted
on the end of a glass fibre. The fibre, secured in a goniometer
head, was placed under a cold stream of N2 maintained at 150 K
and diffraction data then collected on a Nonius KappaCCD
diffractometer with graphite monochromated Mo-Ka radiation
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ˇ
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atoms were refined with anisotropic displacement parameters.
All hydrogen atoms were generated and allowed to ride on their
corresponding carbon atoms with fixed thermal parameters after
each cycle of refinement. Three-term Chebychev polynomial
weighting schemes were applied. All solution, refinement, and
graphical calculations were performed using the CRYSTALS52
and CAMERON53 programs. The crystallographic data are
summarised in Table 4.
ˇ
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CCDC reference numbers 257327–257331.
See http://www.rsc.org/suppdata/dt/b5/b502195b/ for cry-
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Acknowledgements
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¨
36 W. A. Herrmann, C. Brossmer, K. Ofele, C.-P. Reisinger, T. Prier-
We would like to thank Dr Andrew R. Cowley for assistance with
crystallography, the Inorganic Chemistry Laboratory, Oxford
for technical support and the EPSRC for funding.
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