Tungsten complexes of aromatic and aliphatic thioaldehydes

Inorganica Chimica Acta 357 (2004) 1886–1896

www.elsevier.com/locate/ica

Tungsten complexes of aromatic and aliphatic thioaldehydes ^q

*

Wolfdieter A. Schenk , Birgit Vedder, Christian Eichhorn

Institut f€ur Anorganische Chemie, Universit€at W€urzburg, Am Hubland, W€urzburg D-97074, Germany

Received 10 November 2003; accepted 29 November 2003

Dedicated to Professor Helmut Werner on the occasion of his 70th birthday, in grateful recognition

of his outstanding contributions to organometallic chemistry

Abstract

Reaction of PPN[W(CO)₃(R₂PC₂H₄PR₂)(SH)] (PPN ¼ Ph₃PNPPh₃; R ¼ Me, 1; R ¼ Ph, 2) with aromatic aldehydes in the

presence of triﬂuoroacetic acid gave tungsten complexes of thiobenzaldehydes mer-[W(CO)₃(R₂PC₂H₄PR₂)(g²-S@CHR⁰)] (R ¼ Me,

3a–3f; R ¼ Ph, 4a–4e) in high yields. Analogous complexes of aliphatic thioaldehydes mer-[W(CO)₃(Me₂PC₂H₄PMe₂)(g²-

S@CHR⁰)] (3g–3l) could only be obtained from the highly electron-rich thiolate complex 1. The structure of 3i (R⁰¼ i-Bu) was

determined by X-ray crystallography. In solution the complexes 3 and 4 are in equilibrium with small quantities of their isomers fac-

[W(CO)₃(R₂PC₂H₄PR₂)(g²-S@CHR⁰)]. Reaction of complexes 3 with dimethylsulfate followed by salt metathesis with NH₄PF₆

gave the alkylation products mer-[W(CO)₃(Me₂PC₂H₄PMe₂)(g²-MeS@CHR⁰)]PF₆(5a–5l) as mixtures of E and Z isomers. The

methylated thioformaldehyde complex mer-[W(CO)₃(Me₂PC₂H₄PMe₂)(g²-MeS@CH₂)]PF₆(5m) was prepared similarly. Nucleo-

philic addition of hydride (from LiAlH₄) to 5 initially gave thioether complexes mer-[W(CO)₃(Me₂PC₂H₄PMe₂)(MeSCH₂R⁰)] (mer-

6) which rapidly isomerized to fac-[W(CO)₃(Me₂PC₂H₄PMe₂)(MeSCH₂R⁰)] (fac-6).

Keywords: Thioaldehyde; Tungsten; Structure; Electrophilic addition

R

1. Introduction

R

C

H

SH

W

C O

S

Shortly after the ﬁrst synthesis of a thioformaldehyde

complex of osmium by hydride transfer Eq. (1) [1],

Gingerich and Angelici published a seemingly straight-

forward route to thiobenzaldehyde complexes of tung-

sten Eq. (2). Surprisingly, this reaction was limited to a

few benzaldehydes carrying electron-releasing substitu-

ents in the para position [2]. Lateron, a somewhat wider

range of W(CO)₅complexes of aromatic thioaldehydes

was obtained by using imines instead of aldehydes [3]

OC

CO

OC

H

CO

W

ð2Þ

H

C

O

C

O

R = 4-C₆H₄Me, 4-C₆H₄OMe, 4-C₆H₄NMe₂

Fischer et al. [4] developed a general access to tung-

sten complexes of thiobenzaldehydes as well as the

corresponding seleno and telluro analogs, namely, the

insertion of sulfur (selenium, tellurium) into the tung-

sten–carbon double bond of the corresponding phenyl-

carbene complexes Eq. (3) [4]

H

PPh₃

Os

PPh₃

-

C

H

OC

BH₄OC

Cl

CO

H

Os

ð1Þ

H

OC

C

S

C

S

PPh₃

PPh

³S

R

C

R

H

^qThe coordination chemistry of the C@S function, part 18. For part

17 see [11a].

^*Corresponding author. Tel.: +49-931-8885259; fax: +49-931-

8884605.

E-mail address: wolfdieter.schenk@mail.uni-wuerzburg.de (W.A.

C

E

[ E ]

OC

CO

ð3Þ

W

C

O

C

O

E = S, Se, Te

Schenk).

doi:10.1016/j.ica.2003.11.032

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

1887

In fact, most of our knowledge about structure,

H

dynamics and reactivity of thioaldehyde complexes

originates from a systematic investigation of these pro-

totypical compounds [5]. While complexes of the parent

thioformaldehyde are now known for most of the

transition metals [5] and even uranium [6], there are still

surprisingly few complexes of aliphatic thioaldehydes.

Some titanium and zirconium complexes originated

from an intramolecular deprotonation of thiolate li-

gands such as described by Eq. (4) [7]

[Ph₃C]PF₆

- Ph₃CH

ð7Þ

Re

C

Re

C

PF₆

ON

Ph₃P

ON

Ph₃P

S

R

S

H

O

SH

C O

C

Me₂

H

CO

C

S

P

CO

P

H

ð8Þ

W

P

H

Me₂

C

O

C

O

Here, we report an extension of this methodology to

the synthesis of tungsten complexes of aromatic as

well as aliphatic thioaldehydes. Furthermore, the

reactivity of these electron-rich complexes will be com-

pared with that of the cationic ruthenium complexes

[CpRu(PR₃)₂(S@CHR⁰)]^þ[11].

H

R

C

PMe₃

- CH₄

S

CH₂R

Zr

ð4Þ

Zr

S

CH₃

PMe₃

Thio- and selenoacetaldehyde complexes of cobalt

and rhodium were synthesized by Werner et al. [8] in

two rather unique ways: the half-sandwich cobalt com-

plexes resulted from a double nucleophilic substitution

(Eq. (5)), while the analogous rhodium complexes were

obtained from the corresponding vinylidene complex by

chalcogen addition followed by catalytic hydrogenation

as shown in Eq. (6)

2. Results and discussion

Addition of a slight excess of triﬂuoroacetic acid to a

THF solution containing 1 [10] or 2 [12] and the re-

spective benzaldehyde leads to an instantaneous colour

change to brown. Workup by column chromatography

provides the corresponding thiobenzaldehyde complexes

in high yields as orange-colored crystalline materials Eq.

(9)

H

CH₃CHBr₂

Co

CH₃

C

- CO

Me₃P

CO

Br

O

SH

W

R'CHO,

CF₃COOH

C

R₂

P

R₂

P

R'

H

CO

C

S

CO

- 2 NaBr,

- H₂E

W

2 NaEH

ð5Þ

P

R₂

P

R₂

THF, 20 ˚C,

5 min

C

O

C

O

1, 2

3a: 90%, 4a: 80%,

3b: 89%, 4b: 82%,

3c: 95%, 4c: 75%,

3d: 99%, 4d: 84%,

3e: 76%, 4e: 59%,

3f: 85%

H

C

E = S, Se

Co

R = Me: 1, 3; R = Ph: 2, 4

Me₃P

i-Pr₃P

CH₃

E

1

/₈E₈

CH₂

Rh

C

i-Pr₃P

C

R' C₆H₅3-C₆H₄F 4-C₆H₄F 4-C₆H₄Cl 4-C₆H₄OMe 4-C₆H₄NMe₂

E

CH₂

a

b

c

d

e

f

H₂Kat

ð6Þ

ð9Þ

The new compounds are soluble in most of the

common organic solvents except aliphatic hydrocar-

bons. In solution, the dppe derivatives 4 decompose

slowly while solutions of the dmpe complexes 3 are

perfectly stable at ambient temperature. The meridional

coordination geometry around the central tungsten

atom as well as the side-on coordination of the thioal-

dehyde ligand are readily inferred from the wavenum-

bers and intensity pattern of the m(CO) vibrations in the

IR spectra (Table 1). Further support comes from the

observation of a signal with ¹⁸³W satellites at d ¼ 50–60

in the ¹³CNMR spectra and the resonances of two non-

equivalent phosphorus nuclei in the ³¹P NMR spectra.

H

Rh

E

E = S, Se; Kat = [RhCl(PPh₃)₃]

C

i-Pr₃P

CH₃

A series of rhenium complexes including some car-

rying functional groups on the side chain were generated

by hydride abstraction (Eq. (7)) [9]. Recently we found

that AngeliciÕs condensation reaction [2] can be extended

to the synthesis of a thioformaldehyde complex of

tungsten by replacing two of the carbon monoxide li-

gands of the starting SH complex by the strongly elec-

tron donating chelate ligand Me₂PC₂H₄PMe₂(dmpe)

(Eq. (8)) [10]

1888

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

Table 1

Characteristic IR, ¹H and ¹³CNMR spectroscopic data of the thioaldehyde complexes mer-[W(CO)₃(R₂PC₂H₄PR₂)(g²-S@CHR⁰)]^a

R⁰

IR (THF)

¹H NMR (C₆D₆)

¹³C NMR (C₆D₆)

No.

R

m(CO) (cm^ꢀ1

)

d(C–H)

³J(P_A–H)

d(C@S)

²J(P_A–C) ²J(P_B–C)

3a

3b

3c

3d

3e

3f

Me

Ph

1994 (w)

1996 (w)

1994 (w)

1995 (w)

1992 (w)

1990 (w)

1991 (w)

1990 (w)

1988 (w)

1918 (s)

1920 (s)

1917 (s)

1919 (s)

1916 (s)

1913 (s)

1909 (s)

1905 (s)

1918 (s)

1927 (s)

1929 (s)

1926 (s)

1927 (s)

1923 (s)

1867 (vs)

1868 (vs)

1869 (vs)

1866 (vs)

1864 (vs)

1863 (vs)

1861 (vs)

1865 (vs)

1886 (vs)

1888 (vs)

1886 (vs)

1887 (vs)

1884 (vs)

5.83 (d)

5.65 (d)

5.69 (d)

5.61 (d)

5.86 (d)

6.02 (d)

4.70 (ddd)^c

4.92 (ddd)^d

4.90 (ddd)^f

5.21 (d)

5.61 (dd)ⁱ

5.88 (d)

5.73 (d)

5.79 (d)

5.74 (d)

5.72 (d)

3.1

2.7

2.8

2.9

3.4

2.7

2.2

2.6

2.8

2.4

2.7

2.2

2.7

52.7 (dd)^b

51.4 (d)

51.7 (dd)

51.7 (s)

1.0

1.9

2.8

1.9

3-C₆H₄F

4-C₆H₄F

4-C₆H₄Cl

4-C₆H₄OMe

4-C₆H₄NMe₂

Et

1.9

51.7 (d)

54.4 (dd)

58.7 (s)

56.8 (dd)^e

54.9 (d)^g

72.0 (dd)^h

55.5 (s)

2.3

2.1

2.0

1.9

3.1

3g

3h

3i

Pr

i-Bu

2.9

5.1

3.1

3k

3l

t-Bu

CHCHC₆H₄NMe₂1992 (w)

4a

4b

4c

4d

4e

Ph

2002 (w)

2004 (w)

2002 (w)

2003 (w)

2002 (w)

53.8 (s)

52.1 (s)

Ph

3-C₆H₄F

4-C₆H₄F

4-C₆H₄Cl

4-C₆H₄OMe

52.2 (s)

52.3 (s)

54.4 (s)

Ph

^aSee Section 4 for data of the corresponding fac isomers.

b

¹J(W–C) ¼ 16.2 Hz.

c

³J(H–H) ¼ 2.9, 9.9 Hz.

d

³J(H–H) ¼ 3.4, 9.4 Hz.

e

¹J(W–C) ¼ 16.2 Hz.

f

³J(H–H) ¼ 2.7, 10.5 Hz.

g

¹J(W–C) ¼ 17.3 Hz.

h

¹J(W–C) ¼ 24.8 Hz.

i

³J(H–H) ¼ 9.3 Hz.

Two fairly diﬀerent couplings ¹⁸³W–³¹P reﬂect the un-

ique positions of the phosphorus atoms trans to CO and

thioaldehyde, respectively (Table 2).

The thioformaldehyde complex mer-[W(CO)₃(Me₂

PC₂H₄PMe₂)(g²-S@CH₂)] was found to be in a 87:13

equilibrium in solution with its facial isomer [10]. Minor

additional signals in the IR and ³¹P NMR spectra of

complexes 3 and 4 (see Section 4) suggest a similar sit-

uation here although the fraction of the facial isomer is

signiﬁcantly smaller.

Treatment of 2 with aqueous formaldehyde or ali-

phatic aldehydes and acid did not lead to any isolable

products. However, reactions of 1 with a series of

aliphatic aldehydes in the presence of triﬂuoroacetic

acid gave, after chromatographic workup, the ex-

pected thioaldehyde complexes 3g–3k as well as the

Table 2

³¹P NMR spectroscopic data of the thioaldehyde complexes mer-[W(CO)₃(R₂PC₂H₄PR₂)(g²-S@CHR⁰)]^a

No.

R

R⁰

³¹P NMR (C₆D₆)

d(P_A)

¹J(W–P_A)

d(P_B)

¹J(W–P_B)

²J(P_A–P_B)

3a

3b

3c

3d

3e

3f

Me

Ph

12.9

12.7

12.8

13.0

13.2

12.6

13.5

13.2

44.1

44.3

44.2

44.5

215

214

219

221

219

222

220

204

221

233

232

233

232

236

18.7

18.9

18.5

18.7

18.1

17.7

17.5

18.9

17.7

42.0

42.2

41.7

196

194

197

190

194

203

202

203

199

15

14

13

15

13

12

3-C₆H₄F

4-C₆H₄F

4-C₆H₄Cl

4-C₆H₄OMe

4-C₆H₄NMe₂

Et

3g

3h

3i

Pr

i-Bu

3k

3l

t-Bu

CHCHC₆H₄NMe₂

Ph

4a

4b

4c

4d

4e

Ph

3-C₆H₄F

4-C₆H₄F

4-C₆H₄Cl

4-C₆H₄OMe

Ph

^aSee Section 4 for data of the corresponding fac isomers.

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

1889

Table 3

thiocinnamaldehyde complex 3l (Eq. (10)). Their prop-

ꢀ

Selected bond lengths (A) and angles (°) for mer-[W(CO)₃(Me₂PC₂H₄-

PMe₂)(g²-S@CH-i-Bu)] (3i)

erties are very similar to those of the thiobenzaldehyde

complexes 3a–3f, including the presence in small quan-

tities of the corresponding facial isomers

W–S

2.501(2)

2.457(2)

2.489(2)

2.007(10)

2.021(9)

2.006(10)

W–C(6)

S–C(6)

2.286(8)

1.772(9)

1.480(13)

1.151(10)

1.133(9)

1.147(10)

W–P(1)

W–P(2)

W–C(3)

W–C(4)

W–C(5)

O

C(6)–C(7)

C(3)–O(3)

C(4)–O(4)

C(5)–O(5)

SH

W

R'CHO,

CF₃COOH

C

Me₂

P

Me₂

P

R'

H

CO

C

S

CO

W

P

Me₂

P

Me₂

THF, 20 ˚C,

5 min

C

O

C

O

S–W–C(6)

P(1)–W–S

P(2)–W–S

43.2(2)

C(3)–W–C(5)

C(3)–W–C(6)

C(4)–W–C(5)

C(4)–W–C(6)

C(5)–W–C(6)

W–S–C(6)

177.0(4)

85.7(4)

87.7(4)

73.5(3)

92.4(4)

61.9(3)

1

3g: 83%,

3h: 90%,

3i: 88%,

3k: 51%,

3l: 78%

162.60(7)

84.46(8)

79.14(8)

80.4(3)

R' Et n-Pr i-Bu t-Bu CH=CHC₆H₄NMe₂

P(1)–W–P(2)

P(1)–W–C(4)

C(3)–W–C(4)

g

h

i

k

l

93.8(4)

ð10Þ

An X-ray structure determination was carried out

on 3i, Fig. 1 shows a view of the molecule. As in the

corresponding thioformaldehyde complex [10], the

coordination geometry around the central tungsten

atom can be described as distorted pentagonal-bipy-

ramidal with the thioaldehyde ligand occupying two

adjacent sites. The largest angle deviation within the

pentagonal base is associated with the three-membered

W–S–C ring, all other angles between neighboring

bonds in this plane are in a range of 79 ꢁ 5° (Table 3).

As expected, all the bond lengths are almost equal to

those of the thioformaldehyde complex [10] with ex-

ception of the C–S bond which is slightly elongated

(by 3 pm). Of the two possible orientations of the i-

BuHC@S ligand the one with the sulfur atom pointing

towards one of the phosphorus atoms is obviously

preferred.

complex reacted smoothly with dimethylsulfate in ben-

zene (Eq. (11)). After salt metathesis with NH₄PF₆in

methanol, the corresponding S-methylated complexes

5a–5m were isolated in high yields

O

C

O

C

1. (MeO)₂SO₂,

C₆H₆, 12 h

Me₂

P

Me₂

P

R'

H

R'

H

CO

C

S

CO

C

S

W

PF₆

P

Me₂

P

Me₂

2. NH₄PF₆,

MeOH

C

O

C

O

Me

3a, c-m

R'

5a, c-m

No.

Yield

No.

R'

Et

Yield

ð11Þ

5a

5c

5d

5e

5f

C₆H₅

85%

97%

95%

89%

95%

5g

5h

5i

93%

90%

88%

85%

89%

81%

4-C₆H₄F

n-Pr

4-C₆H₄Cl

i-Bu

t-Bu

4-C₆H₄OMe

4-C₆H₄NMe₂

5k

5l

CHCHC₆H₄NMe₂

H

DFT calculations carried out on the parent thio-

formaldehyde complex mer-[W(CO)₃(Me₂PC₂H₄PMe₂)

(g²-S@CH₂)] have identiﬁed an energetically high

HOMO at )3.97 eV with the largest contribution arising

from a p orbital at sulfur [10]. In accord with this, the

dmpe complexes 3a–3l as well as the thioformaldehyde

5m

These are stable yellow crystalline compounds

which, as a consequence of their ionic composition, are

soluble only in polar organic media such as THF, di-

chloromethane or acetone. Their IR spectra in the

m(CO) region are similar in appearance to those of 3a–

3k but shifted to higher wavenumbers as a result of the

1

O(5)

C(5)

positive charge introduced by methylation. Both the H

and ¹³C signals of the thioformyl group are shifted

upﬁeld, and the newly introduced methyl group gives

resonances at d ¼ 2:9 (¹H) and d ¼ 31 (¹³C), respec-

tively (Table 4).

C(7)

S

P(2)

W

The methylated thiobenzaldehyde derivatives 5a–5f

were obtained as single isomers. NOE experiments

showed that the methyl group and the aryl substituent

occupy trans positions at the three-membered W–C–S

ring: Saturation of the aldehyde proton at d ¼ 5:2 en-

hanced both the methyl and aryl signals while irradia-

tion of the methyl signal at d ¼ 2:8 led to a gain of only

the aldehyde resonance, and saturation of the aryl res-

onances at d ¼ 7:5 enhanced only the thioaldehyde

signal. 5g–5k, on the other hand, were obtained as

C(6)

C(4)

H(6)

P(1)

C(3)

O(4)

O(3)

Fig. 1. ORTEP diagram of mer-[W(CO)₃(Me₂PC₂H₄PMe₂)(g²-

S@CH-i-Bu)] (3i). Hydrogen atoms except H(6) omitted.

1890

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

Table 4

Characteristic IR, ¹H and ¹³CNMR spectroscopic data of the methylated thioaldehyde complexes mer-[W(CO)₃(R₂PC₂H₄PR₂)(g²-E-

a

MeS@CHR⁰)]PF₆

IR (THF)

¹H NMR ([D₆]-acetone)

¹³C NMR ([D₆]-acetone)

No.

m(CO) (cm^ꢀ1

)

d(SCH₃)

d(C–H)

³J(P_A–H)

d(SCH₃)

d(C@S)

²J(P_B–C)

¹J(W–C)

5a

5c

5d

5e

5f

2027(w)

2025(w)

2023(w)

2024(w)

2023(w)

2024(w)

2029(w)

1961(s)

1959(s)

1958(s)

1956(s)

1955(s)

1960(s)

1962(s)

1902(vs)

1903(vs)

1900(vs)

1899(vs)

1897(vs)

1900(vs)

1901(vs)

2.87(s)

2.91(s)

2.87(s)

2.89(s)

2.90(s)

2.69(s)

2.68(s)

2.74(s)

2.69(s)

2.78(s)

2.64(s)

5.18(d)

5.25(d)

5.21(d)

5.19(d)

3.98(ddd)^c2.5

4.00(ddd)^d2.0

4.05(ddd)^e2.0

1.5

1.7

1.8

2.2

2.0

31.2(s)

31.3(s)

31.1(s)

31.3(d)^b

31.2(d)^b

30.8(s)

30.6(d)^b

31.0(d)^b

30.9(d)^b

30.6(s)

30.9(s)

45.8(d)

44.8(d)

44.5(d)

45.8(d)

46.7(d)

50.6(d)

47.9(d)

45.7(d)

61.0(d)

48.0(d)

22.9(s)ⁱ

5.0

4.8

5.1

4.8

6.1

4.8

5.7

4.8

18.3

23.8

20.3

19.1

17.2

22.4

21.9

21.0

24.8

18.1

5g

5h

5I

5k

5l

4.27(d)

1.5

2.0

4.88(dd)^f

3.18(d)^g

3.37(d)^g

h

5m

h

^aSee Section 4 for data of the corresponding Z isomers.

b

³J(P_A–C) ¼ 1.9 Hz.

c

³J(H–H) ¼ 10.6, 2.5 Hz.

d

³J(H–H) ¼ 11.2, 2.0 Hz.

e

³J(H–H) ¼ 11.4, 2.0 Hz.

f

³J(H–H) ¼ 10.2 Hz.

g

²J(H–H) ¼ 5.0 Hz.

^hj(P–H) not resolved.

ⁱJ(P–C) not resolved.

mixtures containing up to 10% of the respective Z iso-

mers. In this regard the thioaldehyde complexes 3 are

similar to the isostructural complexes of methyl and

benzyl dithioformate mer-[W(CO)₃(dmpe)g²-S@C(H)

(SR)] which upon alkylation also gave mixtures of E

and Z conﬁgured products [13]. The ³¹P NMR spectra

of complexes 5 (Table 5) show line broadening at 20°C.

Sharp spectra are obtained at )20°C and at +70°C. This

is obviously a result of a rapid rotation of the oleﬁn-like

ligand [14].

graphic workup, the thioether complexes fac-6a, c, e, m

were isolated in moderate to good yields (Eq. (12))

O

C

O

C

Me₂

P

Me₂

P

R'

H

LiAlH₄

CO

C

S

CO

W

PF₆

W

CH₂R'

P

Me₂

P

S

THF, 20 ˚C,

10 min

Me₂

C

O

C

O

Me

5a, c, e, m

mer-6a, c, e, m

A selection of the methylated thioaldehyde complexes

was treated with LiAlH₄in THF. After chromato-

Me

CH₂R'

S

Me₂

P

No.

R'

Yield

CO

W

Table 5

³¹P NMR spectroscopic data of the methylated thioaldehyde com-

fac-6a

fac-6c

fac-6e

fac-6m

C₆H₅

72%

53%

61%

67%

P

Me₂

C

O

4-C₆H₄F

4-C₆H₄OMe

H

a

plexes mer-[W(CO)₃(R₂PC₂H₄PR₂)(g²-E-MeS@CHR⁰)]PF₆

No.

d(P_A) ¹J(W–P_A)

d(P_B)

¹J(W–P_B)

²J(P_A–P_B)

fac-6a, c, e, m

5a

5c

5d

5e

5f

15.8

15.4

16.5

14.6

14.5

14.4

16.0

14.4

15.7

194

196

198

194

198

192

198

205

12.8

12.6

12.8

13.4

12.8

12.6

185

187

189

190

170

193

192

15

16

15

14

15

14

16

ð12Þ

6a–6m are light yellow crystalline materials which are

soluble without decomposition in most of the common

organic solvents. The fac coordination geometry is evi-

dent from the observation of three intense m(CO) ab-

sorptions in their IR spectra and a singlet phosphorus

NMR resonance (Table 6).

However, as the immediate result of a nucleophilic

hydride transfer to the meridional complexes 5, the

corresponding meridional thioether complexes should

be obtained. These could indeed be observed by re-

cording NMR spectra of the crude reaction mixtures.

5g

5h

5I

5k

5l

5m^b

^aRecorded in [D₆]-acetone; PF^ꢀ₆signal of all compounds:

d ¼ ꢀ144:1(sept), ¹J(P–F) ¼ 708 Hz; see Section 4 for data of the

corresponding Z isomers.

^bRecorded in CD₂Cl₂at )70 °C.

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

1891

Table 6

Characteristic IR and ³¹P NMR spectroscopic data of the thioether

complexes fac-[W(CO)₃(R₂PC₂H₄PR₂)(MeSCH₂R⁰)]^a

as THF solutions in 0.1 mm NaCl cells. NMR spectra

1

were recorded on a Jeol JNM-LA 300 instrument. H

(300.4 MHz) and ¹³C (75.45 MHz) chemical shifts are

reported relative to internal TMS; ³¹P (121.5 MHz)

chemical shifts are relative to external 85% H₃PO₄

with the deuterium signal of the solvent serving as

IR (THF)

No.

³¹P NMR (CD₂Cl₂)

m(CO)(cm^ꢀ1

)

d

¹J(W–P)

6a

6c

1924(s) 1834(s) 1815(s) 11.6

1924(s) 1832(s) 1816(s) 11.5

1924(s) 1832(s) 1814(s) 11.5

1925(s) 1833(s) 1815(s) 11.7

219

218

219

1

lock and internal reference. H and ¹³C NMR signals

6e

6m

of the phosphine ligands are uncharacteristic and have

therefore been omitted from the lists of spectroscopic

data. Also not listed here are data given already in the

tables. Analyses were carried out by the Microanalyt-

^aSee Section 4 for data of the corresponding mer isomers.

€

ical Laboratory of the Institut fur Anorganische

Chemie.

The mer isomers show resonances for two nonequivalent

P nuclei with the expected P–P coupling. The downﬁeld

resonance exhibits an unusually large ¹⁸³W–³¹P coupling

of ca. 300 Hz indicating that the phosphorus atom from

which it arises is situated trans to a weakly bonded li-

gand with a low structural trans inﬂuence [15]. The mer

to fac isomerization can easily be followed by NMR, in

solution at room temperature it is complete in less than

1 h.

4.1. Preparation of thioaldehyde complexes mer-

[W(CO)₃(Me₂PC₂H₄PMe₂)(g²-S@CHR⁰)] (3a–3l)

To a solution of the hydrogensulﬁdo complex 1 (200

mg, 0.20 mmol) in THF (10 ml) was added the respective

aldehyde (0.25 mmol) and CF₃COOH (15 ll, 0.20

mmol). An immediate color change to brownish-orange

was observed (the synthesis of 3l requires a reaction time

of 30 min). All volatiles were removed under vacuum,

and the sticky residue dissolved in hexanes and chro-

matographed using dichloromethane/acetone 40:1 as

eluent. The yellow fraction was collected and evaporated

to dryness. The residue was twice washed with 2-ml

portions of pentane and dried under vacuum giving a

yellow or orange crystalline powder.

3. Conclusions

The synthesis of thioaldehyde complexes by conden-

sation of aldehydes with transition metal–SH complexes

can be extended to the less electrophilic aliphatic alde-

hydes, provided that highly electron-rich anionic hy-

drogen sulﬁdo complexes are employed. The products

contain the newly formed thioaldehyde as a hapto-2 li-

gand which readily undergoes electrophilic addition.

This contrasts with the cationic ruthenium complexes

[CpRu(PR₃)₂(g¹-S@CHR⁰)]^þwhich can be obtained

similarly but react preferably with nucleophiles [11]. In

both cases further transformations are available to give

metal-coordinated thioethers.

mer-[W(CO)₃(dmpe){S@C(H)C₆H₅}](mer-3a): Yield:

97 mg (90%), m.p. 70 °C (dec.). Calc. for

C₁₆H₂₂O₃P₂SW (MW 540.2): C, 35.57; H, 4.10; S, 5.94.

1

Found: C, 35.41; H, 3.91; S, 5.72%. H NMR (C₆D₆):

d ¼ 6:91–7:76 (m, 5H, C₆H₅); ¹³C{¹H} NMR (C₆D₆):

d ¼ 125:8, 127.3, 129.1, 145.4 (s, C₆H₅), 197.3 (dd, ²J(P–

2

C) ¼ 7.5, 3.8 Hz, CO), 198.8 (dd, J(P–C) ¼ 6.5, 3.8 Hz,

2

CO), 211.5 (dd, J(P–C) ¼ 13.3, 9.6 Hz, CO).

fac-3a: IR, (m(CO), THF, cm^ꢀ1): 1976.

mer-[W(CO)₃(dmpe){S@C(H)(3-C₆H₄F)}] (mer-3b):

Yield: 99 mg (89%), m.p. 66 °C. Calc. for

C₁₆H₂₁FO₃P₂SW (MW 558.2): C, 34.43; H, 3.79; S,

5.74. Found: C, 34.25; H, 3.87; S, 5.65%. ¹H NMR

(C₆D₆): d ¼ 6:87–7:55 (m, 4H, C₆H₄F); ¹³C{¹H}NMR

4. Experimental

2

The complexes PPN[W(CO)₃(R₂PC₂H₄PR₂)(SH)] (1

[10], 2 [12], PPN ¼ Ph₃P@N@PPh₃) were prepared ac-

cording to published methods. Other chemicals were

obtained commercially and used without further puriﬁ-

cation. All experiments were carried out under an at-

mosphere of N₂in dried and deoxygenated solvents.

Reactions were routinely monitored by IR and NMR

spectroscopy. Chromatographic separations were car-

ried out using a 25 cm column of 2.5 cm diameter ﬁlled

with silica (Merck, grain size 0.06–0.20 mm) as sta-

tionary phase.

(C₆D₆): d ¼ 114:5–162:5 (m, C₆H₄F), 197.0 (dd, J(P–

2

C) ¼ 7.5, 3.8 Hz, CO), 198.7 (dd, J(P–C) ¼ 6.5, 3.8 Hz,

2

CO), 214.2 (dd, J(P–C) ¼ 13.4, 9.7 Hz, CO).

fac-3b: IR, (m(CO), THF, cm^ꢀ1): 1977.

mer-[W(CO)₃(dmpe){S@C(H)(4-C₆H₄F)}] (mer-3c):

Yield: 106 mg (95%), m.p. 76 °C (dec.). Calc. for

C₁₆H₂₁FO₃P₂SW (MW 558.2): C, 34.43; H, 3.79; S,

5.74. Found: C, 34.21; H, 3.51; S, 5.49%. ¹H NMR

(C₆D₆): d ¼ 6:87–7:55 (m, 4H, C₆H₄F); ¹³C{¹H}NMR

2

(C₆D₆): d ¼ 114:5–162:5 (m, C₆H₄F), 197.1 (dd, J(P–

2

C) ¼ 7.5, 3.8 Hz, CO), 198.8 (dd, J(P–C) ¼ 6.5, 3.5 Hz,

2

IR spectra of the m(CO) region were recorded on a

Bruker IFS-25 spectrometer with the samples prepared

CO), 211.5 (dd, J(P–C) ¼ 13.4, 9.7 Hz, CO).

fac-3c: IR, (m(CO), THF, cm^ꢀ1): 1977.

1892

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

2

mer-[W(CO)₃(dmpe){S@C(H)(4-C₆H₄Cl)}] (mer-3d):

CH₂), 49.9 (s, CH₂), 197.2 (dd, J(P–C) ¼ 7.6, 3.8 Hz,

2

Yield: 113 mg (98%), m.p. 76 °C. Calc. for

C₁₆H₂₁ClO₃P₂SW (MW 574.7): C, 33.44; H, 3.69; S,

5.58. Found: C, 33.39; H, 3.72; S, 5.51%. ¹H NMR

CO), 199.4 (dd, J(P–C) ¼ 7.6, 3.8 Hz, CO), 215.4 (dd,

²J(P–C) ¼ 12.4, 9.5 Hz, CO).

fac-3h: IR, (m(CO), THF, cm^ꢀ1): 1973; ¹H NMR

(C₆D₆): d ¼ 2:31–2:38 (m, 1H, CH₂), 3.15–3.22 (m, 1H,

3

(C₆D₆): d ¼ 7:20 (d, 2H, J(H–H) ¼ 8.4 Hz, C₆H₄Cl),

7.49 (d, 2H, ³J(H–H) ¼ 8.4 Hz, C₆H₄Cl); ¹³C{¹H}NMR

CH₂), 4.52 (ddd, 1H, J(H–H) ¼ 9.1 Hz, J(H–H) ¼ 3.2

3

2

3

(C₆D₆): d ¼ 130:1, 149.7 (s, C₆H₄Cl), 197.0 (dd, J(P–

Hz, J(P–H) ¼ 3.2 Hz, S@CH); ¹³C{¹H}NMR (C₆D₆):

2

C) ¼ 7.2, 3.8 Hz, CO), 198.8 (dd, J(P–C) ¼ 6.5, 3.5 Hz,

d ¼ 14:2 (s, CH₃), 32.1 (s, CH₂), 49.1 (s, CH₂), 67.5 (d,

²J(P–C) ¼ 3.8 Hz, ¹J(W–C) ¼ 14.3 Hz, S@CH);

2

CO), 214.3 (dd, J(P–C) ¼ 13.4, 9.7 Hz, CO).

fac-3d: IR, (m(CO), THF, cm^ꢀ1): 1976.

³¹P{¹H}NMR (C₆D₆): d ¼ 2:2 (s, J(W–P) ¼ 205 Hz),

1

mer-[W(CO)₃(dmpe){S@C(H)(4-C₆H₄OMe)}] (mer-

3e): Yield: 87 mg (76%), m.p. 69 °C (dec.). Calc. for

C₁₇H₂₄O₄P₂SW (MW 570.2): C, 35.81; H, 4.24; S, 5.62.

6.6 (s, J(W–P) ¼ 190 Hz).

mer-[W(CO)₃(dmpe){S@C(H)CH₂CH(CH₃)₂}] (mer-

3i): Yield: 92 mg (88%), m.p. 60 °C (dec.). Calc. for

C₁₄H₂₆O₃P₂SW (MW 520.2): C, 32.32; H, 5.04; S, 6.16.

1

Found: C, 35.32; H, 4.09; S, 5.18%. H NMR (C₆D₆):

3

1

d ¼ 3:25 (s, 3H, OCH₃), 6.88 (d, 2H, J(H–H) ¼ 8.4

Found: C, 32.17; H, 5.09; S, 6.06%. H NMR (C₆D₆):

3

Hz, C₆H₄), 7.75 (d, 2H, ³J(H–H) ¼ 8.4 Hz, C₆H₄);

¹³C{¹H}NMR (C₆D₆): d ¼ 54:7 (s, OCH₃), 113.6, 127.1,

143.0, 157.9 (s, C₆H₄), 197.4 (dd, ²J(P–C) ¼ 7.5, 3.8 Hz,

d ¼ 1:12 (d, 3H, J(H–H) ¼ 6.6 Hz, CH₃), 1.17 (d, 3H,

³J(H–H) ¼ 6.6 Hz, CH₃), 1.92–2.02 (m, 1H, CH₂), 2.09-

2.22 (m, 1H, CH), 3.07–3.19 (m, 1H, CH₂);

¹³C{¹H}NMR (C₆D₆): d ¼ 22:0 (s, CH₃), 23.6 (s, CH₃),

36.3 (s, CH₂), 57.0 (s, CH), 197.2 (dd, ²J(P–C) ¼ 7.1, 3.0

2

CO), 199.0 (dd, J(P–C) ¼ 6.5, 3.4 Hz, CO), 214.3 (dd,

²J(P–C) ¼ 12.8, 10.0 Hz, CO).

fac-3e: IR, (m(CO), THF, cm^ꢀ1): 1972.

Hz, CO), 199.3 (dd, J(P–C) ¼ 7.1, 3.0 Hz, CO), 215.4

2

mer-[W(CO)₃(dmpe){S@C(H)(4-C₆H₄NMe₂)}] (mer-

3f): Yield: 99 mg (85%), m.p. 74 °C (dec.). Calc. for

C₁₈H₂₇NO₃P₂SW (MW 583.3): C, 37.07; H, 4.67; N,

2.40; S, 5.50. Found: C, 36.66; H, 4.78; N, 2.36; S,

5.24%. ¹H NMR (C₆D₆): d ¼ 2:26 (s, 6H, N(CH₃)₂),

6.70 (d, 2H, ³J(H–H) ¼ 8.8 Hz, C₆H₄), 7.74 (d, 2H,

³J(H–H) ¼ 8.4 Hz, C₆H₄); ¹³C{¹H}NMR (C₆D₆):

d ¼ 40:6 (s, N(CH₃)₂), 113.0, 127.0, 139.2, 149.0 (s,

C₆H₄), 197.9 (dd, ²J(P–C) ¼ 7.2, 3.8 Hz, CO), 199.0 (dd,

(dd, J(P–C) ¼ 13.2, 10.2 Hz, CO).

fac-3i: IR, (m(CO), THF, cm^ꢀ1): 1973; ¹H NMR

(C₆D₆): d ¼ 4:52 (ddd, 1H, ³J(H–H) ¼ 9.9 Hz, ³J(H–

H) ¼ 2.7 Hz, J(P–H) ¼ 2.7 Hz, S@CH); ¹³C{¹H}NMR

3

(C₆D₆): d ¼ 22:1 (s, CH₃), 22.3 (s, CH₃), 35.5 (s, CH₂),

55.9 (s, CH); ³¹P{¹H}NMR (C₆D₆): d ¼ 2:0 (s, J(W–

1

P) ¼ 202 Hz), 6.4 (s, J(W–P) ¼ 191 Hz).

mer-[W(CO)₃(dmpe){S@C(H)C(CH₃)₃}]

(mer-3k):

Yield: 53 mg (51%), m.p. 50 °C (dec.). Calc. for

C₁₄H₂₆O₃P₂SW (MW 520.2): C, 32.32; H, 5.04; S, 6.16.

2

²J(P–C) ¼ 7.2, 3.8 Hz, CO), 215.1 (dd, J(P–C) ¼ 12.8,

1

10.7 Hz, CO).

fac-3f: IR, (m(CO), THF, cm^ꢀ1): 1968.

Found: C, 32.64; H, 5.14; S, 6.02%. H NMR (C₆D₆):

d ¼ 1:59 (s, 9H, CH₃); ¹³C{¹H}NMR (C₆D₆): d ¼ 33:5

2

mer-[W(CO)₃(dmpe){S@C(H)CH₂CH₃}] (mer-3g):

Yield: 82 mg (83%), m.p. 72 °C (dec.). Calc. for

C₁₂H₂₂O₃P₂SW (MW 492.2): C, 29.29; H, 4.51; S, 6.52.

(s, CH₃), 39.9 (s, CMe₃), 197.1 (dd, J(P–C) ¼ 7.5, 3.8

2

Hz, CO), 200.1 (dd, J(P–C) ¼ 6.5, 3.8 Hz, CO), 214.1

2

(dd, J(P–C) ¼ 14.12, 8.3 Hz, CO).

1

Found: C, 29.17; H, 4.61; S, 6.44%. H NMR (C₆D₆):

3

fac-3k: IR, (m(CO), THF, cm^ꢀ1): 1970; ³¹P{¹H}NMR

2

d ¼ 1:47 (t, br, 3H, J(H–H) ¼ 8.7 Hz, CH₃), 1.89–2.03

(C₆D₆): d ¼ 17:5 (d, J(P–P) ¼ 13.4 Hz), 12.6 (d, J(P–

P) ¼ 13.4 Hz).

(m, 1H, CH₂), 3.10–3.23 (m, 1H, CH₂); ¹³C{¹H}NMR

(C₆D₆): d ¼ 23:3 (s, CH₃), 40.5 (s, CH₂), 197.2 (dd,

²J(P–C) ¼ 7.9, 3.8 Hz, CO), 199.5 (dd, ²J(P–C) ¼ 6.9, 3.5

mer-[W(CO)₃(dmpe){S@C(H)CH@CH(4-C₆H₄NM-

e₂)}] (mer-3l): Yield: 95 mg (78%), m.p. 79 °C (dec.).

Calc. for C₂₀H₂₉NO₃P₂SW (MW 609.3): C, 39.42; H,

4.80; N, 2.30; S, 5.26. Found: C, 39.28; H, 4.71; N, 2.33;

2

Hz, CO), 215.4 (dd, J(P–C) ¼ 13.1, 9.3 Hz, CO).

fac-3g: IR, (m(CO), THF, cm^ꢀ1): 1973; ¹H NMR

(C₆D₆): d ¼ 2:24–2:38 (m, 1H, CH₂), 3.01–3.10 (m, 1H,

1

S, 5.26%. H NMR (C₆D₆): d ¼ 2:43 (s, 6H, N(CH₃)₂),

3

CH₂), 4.40 (ddd, 1H, J(H–H) ¼ 9.0 Hz, J(H–H) ¼ 3.0

6.47 (m, 2H, C₆H₄), 6.72 (dd, 1H, J(H–H) ¼ 15.4, 9.3

Hz, J(P–H) ¼ 3.0 Hz, S@CH); ¹³C{¹H}NMR (C₆D₆):

Hz, CH), 6.86 (d, 1H, ³J(H–H) ¼ 15.4 Hz, CH), 7.42 (m,

2H, C₆H₄); ¹³C{¹H}NMR (C₆D₆): d ¼ 40:3 (s,

N(CH₃)₂), 112.8 (s, CH), 124.3 (s, CH), 113.0, 127.3,

140.9, 149.5 (s, C₆H₄), 197.0 (dd, ²J(P–C) ¼ 7.5, 3.8 Hz,

3

2

d ¼ 21:9 (s, CH₃), 39.9 (s, CH₂), 69.0 (d, J(P–C) ¼ 2.5

Hz, S@CH); ³¹P{¹H}NMR (C₆D₆): d ¼ 2:3 (s, J(W–

1

P) ¼ 202 Hz), 6.6 (s, J(W–P) ¼ 190 Hz).

2

mer-[W(CO)₃(dmpe){S@C(H)CH₂CH₂CH₃}] (mer-

3h): Yield: 91 mg (90%), m.p. 70 °C (dec.). Calc. for

C₁₃H₂₄O₃P₂SW (MW 506.2): C, 30.85; H, 4.78; S, 6.33.

CO), 199.1 (dd, J(P–C) ¼ 6.9, 3.5 Hz, CO), 213.4 (dd,

²J(P–C) ¼ 12.8, 10.7 Hz, CO).

fac-3l: IR, (m(CO), THF, cm^ꢀ1): 1970; H NMR (C₆

1

Found: C, 30.79; H, 4.81; S, 6.38%. H NMR (C₆D₆):

3

D₆): d ¼ 2:48 (s, 6H, N(CH₃)₂), 5.47 (dd, 1H, ³J(H–

H) ¼ 9.0, 4.4 Hz, S@CH); ³¹P{¹H}NMR (C₆D₆):

d ¼22:2 (d, ²J(P–P) ¼ 9.7 Hz), 15.7 (d, ²J(P–P) ¼ 9.7

Hz).

d ¼ 1:05 (t, 3H, J(H–H) ¼ 7.1 Hz, CH₃), 1.90-1.95 (m,

1H, CH₂), 2.01-2.10 (m, 2H, CH₂), 3.24-3.32 (m, 1H,

CH₂); ¹³C{¹H}NMR (C₆D₆): d ¼ 14:3 (s, CH₃), 32.1 (s,

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

1893

4.2. Preparation of thioaldehyde complexes mer-

[W(CO)₃(Ph₂PC₂H₄PPh₂)(g²-S@CHR⁰)] (4a–4e)

4.3. Preparation of methylated thioaldehyde complexes

mer-[W(CO)₃(Me₂PC₂H₄PMe₂)(g²-MeS@CHR⁰)]

PF₆(5a–5m)

To a solution of the hydrogensulﬁdo complex 2 (500

mg, 0.40 mmol) in THF (20 ml) was added the respective

aldehyde (0.50 mmol) and CF₃COOH (30 ll, 0.40 mmol).

An immediate color change to brownish-orange was ob-

served. All volatiles were removed under vacuum, and the

sticky residue dissolved in hexanes and chromatographed

using dichloromethane/acetone 40:1 as eluent. The yellow

fraction was collected and evaporated to dryness. The oily

residue was triturated with pentane, and the resulting

solid was twice washed with 5-ml portions of pentane and

dried under vacuum giving an orange crystalline powder.

mer-[W(CO)₃(dppe){S@C(H)C₆H₅}] (mer-4a): Yield:

250 mg (80%), m.p. 70 °C (dec.). Calc. for

C₃₆H₃₀O₃P₂SW (MW 788.5): C, 54.84; H, 3.84; S, 4.07.

Found: C, 54.63; H, 4.00; S, 3.88%. ¹³C{¹H}NMR

(C₆D₆): d ¼ 125:7–149:0 (m, C₆H₅), 198.2 (dd, ²J(P–

To a solution of the respective thioaldehyde complex

(0.20 mmol) in benzene (20 ml) was added dimethyl-

sulfate (21 ll, 0.22 mmol). After 12 h at 20 °C the

mixture was evaporated to dryness and the remaining oil

dissolved in methanol (10 ml). After addition of

NH₄PF₆(160 mg, 1.00 mmol) the mixture was stirred

for 15 min and again evacuated to dryness. The residue

was extracted with dichloromethane (10 ml) and ﬁltered

over celite. The ﬁltrate was taken to dryness and the

residue washed twice with pentane (5 ml). The product

remained as a yellow microcrystalline powder.

mer-[W(CO)₃(dmpe){MeS@C(H)C₆H₅}]PF₆

(5a):

Yield: 120 mg (85%), m.p. 143 °C (dec.). Calc. for

C₁₇H₂₅F₆O₃P₃SW (MW 700.2): C, 29.16; H, 3.60; S,

4.58. Found: C, 29.18; H, 3.68; S, 4.65%. ¹H NMR

([D₆]-acetone): d ¼ 7:10–7:32 (m, 5H, C₆H₅);

¹³C{¹H}NMR ([D₆]-acetone): d ¼ 125:8–145:4 (m,

C₆H₅), 197.8 (dd, ²J(P–C) ¼ 7.1, 5.1 Hz, CO), 198.8

(dd, ²J(P–C) ¼ 7.1, 4.1 Hz, CO), 211.5 (dd, ²J(P–

C) ¼ 16.3, 9.2 Hz, CO).

2

C) ¼ 6.5, 3.5 Hz, CO), 200.2 (dd, J(P–C) ¼ 6.5, 3.5 Hz,

2

CO), 213.6 (dd, J(P–C) ¼ 15.2, 12.1 Hz, CO).

fac-4a: IR, (m(CO), THF, cm^ꢀ1): 1976.

mer-[W(CO)₃(dppe){S@C(H)(3-C₆H₄F)}] (mer-4b):

Yield: 265 mg (82%), m.p. 78 °C. Calc. for

C₃₆H₂₉FO₃P₂SW (MW 806.5): C, 53.61; H, 3.62; S,

3.98. Found: C, 53.97; H, 3.86; S, 3.76%. ¹³C{¹H}NMR

mer-[W(CO)₃(dmpe){MeS@C(H)(4-C₆H₄F)}]PF₆(5c):

Yield: 140 mg (97%), m.p. 148 °C (dec.). Calc. for

C₁₇H₂₄F₇O₃P₃SW (MW 718.2): C, 28.43; H, 3.37; S,

4.46. Found: C, 28.43; H, 3.46; S, 4.61%. ¹H NMR

([D₆]-acetone): d ¼ 7:08–7:24 (m, 4H, C₆H₄F);¹³C{¹H}

NMR ([D₆]-acetone): d ¼ 115:8–163:4 (m, C₆H₄F),

2

(C₆D₆): d ¼ 122:2–159:0 (m, C₆H₄F), 198.1 (dd, J(P–

2

C) ¼ 5.7, 3.8 Hz, CO), 200.2 (dd, J(P–C) ¼ 5.7, 3.8 Hz,

2

CO), 213.6 (dd, J(P–C) ¼ 14.9, 12.0 Hz, CO).

fac-4b: IR, (m(CO), THF, cm^ꢀ1): 1979.

2

mer-[W(CO)₃(dppe){S@C(H)(4-C₆H₄F)}] (mer-4c):

Yield: 240 mg (75%), m.p. 59 °C. Calc. for

C₃₆H₂₉FO₃P₂SW (MW 806.5): C, 53.61; H, 3.62; S,

3.98. Found: C, 53.39; H, 3.64; S, 3.66%. ¹³C{¹H}NMR

197.7 (dd, J(P–C) ¼ 6.7, 4.8 Hz, CO), 198.7 (dd, J(P–

C) ¼ 7.2, 4.8 Hz, CO), 211.5 (dd, ²J(P–C) ¼ 16.2, 8.6 Hz,

CO).

mer-[W(CO)₃(dmpe){MeS@C(H)(4-C₆H₄Cl)}]PF₆(5d):

Yield: 140 mg (95%), m.p. 140 °C (dec.). Calc. for

C₁₇H₂₄ClF₆O₃P₃SW (MW 734.7): C, 27.79; H, 3.29; S,

4.36. Found: C, 27.56; H, 3.28; S, 4.65%. ¹H NMR

([D₆]-acetone): d ¼ 7:05–7:20 (m, 4H, C₆H₄Cl);¹³C{¹H}

NMR ([D₆]-acetone): d ¼ 125:4–142:1 (m, C₆H₄Cl),

2

(C₆D₆): d ¼ 128:7–164:7 (m, C₆H₄F), 198.2 (dd, J(P–

2

C) ¼ 5.7, 3.8 Hz, CO), 200.2 (dd, J(P–C) ¼ 5.7, 3.8 Hz,

2

CO), 213.7 (dd, J(P–C) ¼ 13.4, 12.4 Hz, CO).

fac-4c: IR, (m(CO), THF, cm^ꢀ1): 1977.

mer-[W(CO)₃(dppe){S@C(H)(4-C₆H₄Cl)}] (mer-4d):

Yield: 275 mg (84%), m.p. 57 °C. Calc. for

C₃₆H₂₉ClO₃P₂SW (MW 822.9): C, 52.54; H, 3.55; S,

3.90. Found: C, 52.67; H, 3.71; S, 3.55%. ¹³C{¹H}NMR

2

197.7 (dd, J(P–C) ¼ 7.1, 5.1 Hz, CO), 198.5 (dd, J(P–

C) ¼ 7.1, 4.1 Hz, CO), 211.4 (dd, ²J(P–C) ¼ 16.3, 8.1 Hz,

CO).

2

(C₆D₆): d ¼ 114:6–162:8 (m, C₆H₄Cl), 198.1 (dd, J(P–

mer-[W(CO)₃(dmpe){MeS@C(H)(4-C₆H₄OMe)}]PF₆

(5e): Yield: 130 mg (89%), m.p. 144 °C (dec.). Calc. for

C₁₈H₂₇F₆O₄P₃SW (MW 730.2): C, 29.61; H, 3.73; S,

4.39. Found: C, 29.77; H, 3.84; S, 4.49%. ¹H NMR

([D₆]-acetone): d ¼ 3:78 (s, 3H, OCH₃), 6.88-7.13 (m,

4H, C₆H₄); ¹³C{¹H}NMR ([D₆]-acetone): d ¼ 55:7 (s,

OCH₃), 114.6, 127.1, 137.0, 149.4 (s, C₆H₄), 197.8 (dd,

²J(P–C) ¼ 6.7, 4.8 Hz, CO), 198.9 (dd, ²J(P–C) ¼ 6.7, 4.8

2

C) ¼ 6.8, 3.6 Hz, CO), 200.2 (dd, J(P–C) ¼ 6.8, 3.6 Hz,

2

CO), 213.6 (dd, J(P–C) ¼ 15.1, 12.3 Hz, CO).

fac-4d: IR, (m(CO), THF, cm^ꢀ1): 1979.

mer-[W(CO)₃(dppe){S@C(H)(4-C₆H₄OMe)}] (mer-

4e): Yield: 190 mg (59%), m.p. 52 °C (dec.). This com-

pound, although spectroscopically pure, did not analyse

satisfactorily. Calc. for C₁₇H₂₄O₄P₂SW (MW 570.2): C,

1

2

35.81; H, 4.24; S, 5.62%. H NMR (C₆D₆): d ¼ 2:88 (s,

Hz, CO), 211.6 (dd, J(P–C) ¼ 16.2, 8.6 Hz, CO).

3H, OCH₃); ¹³C{¹H}NMR (C₆D₆): d ¼ 54:5 (s, OCH₃),

mer-[W(CO)₃(dmpe){MeS@C(H)(4-C₆H₄NMe₂)}] PF₆

(5f): Yield: 140 mg (95%), m.p. 149 °C (dec.). Calc. for

C₁₉H₃₀F₆NO₃P₃SW (MW 743.3): C, 30.70; H, 4.07; N,

1.88; S, 4.31. Found: C, 30.63; H, 4.00; N, 2.03; S,

4.43%. ¹H NMR ([D₆]-acetone): d ¼ 2:93 (s, 6H,

128.7–147.7 (m, C₆H₄), 198.3 (dd, ²J(P–C) ¼ 6.6, 3.8 Hz,

2

CO), 200.2 (dd, J(P–C) ¼ 6.6, 3.8 Hz, CO), 214.0 (dd,

²J(P–C) ¼ 13.4, 12.4 Hz, CO).

fac-4e: IR, (m(CO), THF, cm^ꢀ1): 1973.

1894

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

N(CH₃)₂), 6.68–7.05 (m, 4H, C₆H₄); ¹³C{¹H}NMR

([D₆]-acetone): d ¼ 40:4 (s, N(CH₃)₂), 112.8, 127.2,

132.2, 150.2 (s, C₆H₄), 197.8 (dd, ²J(P–C) ¼ 7.2, 3.8 Hz,

acetone): d ¼ 21:6 (s, CH₃), 23.3 (s, CH₃), 33.6 (s, CH),

2 1

37.9 (d, J(P–C) ¼ 5.7 Hz, J(W–C) ¼ 21 Hz, S@CH),

46.1 (s, CH₂); ³¹P{¹H}NMR ([D₆]-acetone): d ¼ 12:9 (d,

2

CO), 199.0 (dd, J(P–C) ¼ 6.7, 3.4 Hz, CO), 211.7 (dd,

²J(P–P) ¼ 14.9 Hz), 13.9 (d, J(P–P) ¼ 14.9 Hz).

²J(P–C) ¼ 15.3, 8.6 Hz, CO).

mer-[W(CO)₃(dmpe){MeS@C(H)CH₂C(CH₃)₃}]PF₆

(E-5k): Yield: 115 mg (85%), m.p. 69 °C (dec.). Calc. for

C₁₅H₂₉F₆O₃P₃SW (MW 680.2): C, 26.49; H, 4.30; S,

4.71. Found: C, 26.37; H, 4.24; S, 4.61%. ¹H NMR

([D₆]-acetone): d ¼ 1:30 (s, 9H, CH₃); ¹³C{¹H}NMR

([D₆]-acetone): d ¼ 32:4 (s, CH₃), 39.8 (s, CMe₃), 52.3 (s,

mer-[W(CO)₃(dmpe){MeS@C(H)CH₂CH₃}]PF₆(E-

5g): Yield: 120 mg (93%), m.p. 164 °C (dec.). Calc. for

C₁₃H₂₅F₆O₃P₃SW (MW 652.2): C, 23.94; H, 3.86; S,

4.92. Found: C, 23.95; H, 3.79; S, 4.96%. ¹H NMR

([D₆]-acetone): d ¼ 1:42 (dd, 3H, ³J(H–H) ¼ 7.1, 6.5 Hz,

CH₃), 1.49–1.64 (m, 2H, CH₂); ¹³C{¹H}NMR ([D₆]-

acetone): d ¼ 21:5 (s, CH₃), 36.4 (s, CH₂), 197.6 (dd,

²J(P–C) ¼ 7.1, 5.1 Hz, CO), 198.9 (dd, ²J(P–C) ¼ 6.6, 5.1

2

1

CH₂), 198.5 (dd, J(P–C) ¼ 6.7, 4.8 Hz, J(W–C) ¼ 130

2

1

Hz, CO), 200.1 (dd, J(P–C) ¼ 7.6, 5.7 Hz, J(W–C) ¼

2

1

134 Hz, CO), 214.1 (dd, J(P–C) ¼ 18.1, 6.6 Hz, J(W–

C) ¼ 125 Hz, CO).

2

Hz, CO), 211.8 (dd, J(P–C) ¼ 16.3, 8.1 Hz, CO).

Z-5g: ¹H NMR ([D₆]-acetone): d ¼ 1:35 (dd, 3H,

³J(H–H) ¼ 7.1, 7.1 Hz, CH₃), 2.61 (s, 3H, SCH₃);

¹³C{¹H}NMR ([D₆]-acetone): d ¼ 22:7 (s, CH₃), 30.9 (s,

CH₂), 42.2 (d, ²J(P–C) ¼ 6.1 Hz, S@CH), 195.1 (dd,

²J(P–C) ¼ 7.1, 5.1 Hz, CO), 200.3 (dd, ²J(P–C) ¼ 6.1, 5.1

Hz, CO), 212.0 (dd, ²J(P–C) ¼ 16.3, 8.1 Hz, CO);

³¹P{¹H}NMR ([D₆]-acetone): d ¼ 12:9 (d, ²J(P–P) ¼

15.1 Hz, ¹J(W–P) ¼ 177 Hz), 14.0 (d, ²J(P–P) ¼ 15.1 Hz,

¹J(W–P) ¼ 199 Hz).

Z-5k: ³¹P{¹H}NMR ([D₆]-acetone): d ¼ 12:6 (d,

²J(P–P) ¼ 15.3 Hz), 14.5 (d, J(P–P) ¼ 15.3 Hz).

2

mer-[W(CO)₃(dmpe){MeS@C(H)CH@CH(4-C₆H₄N

Me₂)}]PF₆(E-5l): Yield: 140 mg (89%), m.p. 70 °C

(dec.). Calc. for C₂₁H₃₂F₆NO₃P₃SW (MW 769.3): C,

32.79; H, 4.19; N, 1.82; S, 4.17. Found: C, 33.05; H,

4.30; N, 2.03; S, 3.86%. ¹H NMR ([D₆]-acetone):

d ¼ 2:92 (s, 6H, N(CH₃)₂), 5.93 (dd, 1H, ³J(H–

H) ¼ 15.5, 10.2 Hz, CH), 6.65–6.71 (m, 2H, C₆H₄), 6.84

(d, 1H, ³J(H–H) ¼ 15.5 Hz, CH), 7.21–7.24 (m, 2H,

C₆H₄); ¹³C{¹H}NMR ([D₆]-acetone): d ¼ 40:4 (s,

N(CH₃)₂), 112.6 (s, CH), 125.3 (s, CH), 113.1, 128.0,

139.5, 151.2 (s, C₆H₄), 197.1 (dd, ²J(P–C) ¼ 6.7, 4.8 Hz,

mer-[W(CO)₃(dmpe){MeS@C(H)CH₂CH₂CH₃}]PF₆

(E-5h): Yield: 120 mg (90%), m.p. 128 °C (dec.). Calc.

for C₁₄H₂₇F₆O₃P₃SW (MW 666.2): C, 25.24; H, 4.09; S,

4.81. Found: C, 25.20; H, 4.15; S, 4.95%. ¹H NMR

([D₆]-acetone): d ¼ 1:03 (dd, 3H, ³J(H–H) ¼ 7.4, 7.1 Hz,

2

CO), 198.8 (dd, J(P–C) ¼ 6.7, 4.8 Hz, CO), 210.6 (dd,

CH₃),

1.50–1.54,

1.73–1.89

(m,

4H,

CH₂);

²J(P–C) ¼ 15.3, 8.6 Hz, CO).

¹³C{¹H}NMR ([D₆]-acetone): d ¼ 13:9 (s, CH₃), 45.3

(d, ²J(P–C) ¼ 2.0 Hz, CH₂), 197.5 (dd, ²J(P–C) ¼ 7.1,

4.7 Hz, CO), 198.9 (dd, ²J(P–C) ¼ 6.7, 3.8 Hz, CO),

Z-5l: ¹H NMR ([D₆]-acetone): d ¼ 2.81 (s, 3H,

SCH₃), 2.94 (s, 6H, N(CH₃)₂), 4.92 (dd, 1H, ³J(H–H) ¼

10.1, ³J(P–H) ¼ 2.2 Hz, S@CH), 6.05 (dd, 1H, ³J(H–

H) ¼ 15.2, 10.1 Hz, CH), 6.71–6.73 (m, 2H, C₆H₄), 6.91

(d, 1H, ³J(H–H) ¼ 15.2 Hz, CH), 7.31–7.34 (m, 2H,

C₆H₄); ¹³C{¹H}NMR ([D₆]-acetone): d ¼ 40:3 (s,

2

211.8 (dd, J(P–C) ¼ 16.2, 7.6 Hz, CO).

Z-5h: ¹H NMR ([D₆]-acetone): d ¼ 2:61 (s, 3H,

SCH₃); ¹³C{¹H}NMR ([D₆]-acetone): d ¼ 14:0 (s, CH₃),

2

1

2

1

39.5 (s, CH₂), 39.8 (d, J(P–C) ¼ 5.7 Hz, J(W–C) ¼ 22

N(CH₃)₂), 48.0 (d, J(P–C) ¼ 3.8 Hz, J(W–C) ¼ 18 Hz,

S@CH), 112.6 (s, CH), 125.3 (s, CH), 113.0, 128.3,

139.5, 151.5 (s, C₆H₄), 196.9 (dd, ²J(P–C) ¼ 7.6, 5.7 Hz,

Hz, S@CH), 195.5 (dd, ²J(P–C) ¼ 7.1, 4.7 Hz, CO),

2

200.3 (dd, J(P–C) ¼ 6.7, 3.8 Hz, CO), 212.0 (dd, J(P–

C) ¼ 16.2, 8.6 Hz, CO); ³¹P{¹H}NMR ([D₆]-acetone):

d ¼ 12:9 (d, ²J(P–P) ¼ 15.1 Hz), 14.0 (d, ²J(P–P) ¼ 15.1

Hz).

2

CO), 198.3 (dd, J(P–C) ¼ 7.6, 4.8 Hz, CO), 210.4 (dd,

²J(P–C) ¼ 15.3, 8.6 Hz, CO); ³¹P{¹H}NMR ([D₆]-ace-

tone): d ¼ 12:9 (d, ²J(P–P) ¼ 14.9 Hz), 15.3 (d, ²J(P–

P) ¼ 14.9 Hz).

mer-[W(CO)₃(dmpe){MeS@C(H)CH₂CH(CH₃)₂}] PF₆

(E-5i): Yield: 120 mg (88%), m.p. 138 °C (dec.). Calc. for

C₁₅H₂₉F₆O₃P₃SW (MW 680.2): C, 26.49; H, 4.30; S,

4.71. Found: C, 26.44; H, 4.16; S, 4.97%. ¹H NMR

([D₆]-acetone): d ¼ 1:06 (d, 3H, ³J(H–H) ¼ 6,8 Hz,

mer-[W(CO)₃(dmpe){MeS@CH₂}]PF₆(5m): Yield:

100 mg (81%), m.p. 109 °C. Calc. for C₁₁H₂₁F₆O₃P₃SW

(MW 624.1): C, 21.17; H, 3.39; S, 5.14. Found: C, 21.45;

H, 3.26; S, 5.11%. ¹³C{¹H}NMR (CD₂Cl₂, )80 °C):

3

2

CH₃), 1.12 (d, 3H, J(H–H) ¼ 6,8 Hz, CH₃), 1.41–1.51

d ¼ 193:2 (dd, J(P–C) ¼ 6.7, 4.8 Hz, CO), 198.4 (dd,

(m, 2H, CH₂); ¹³C{¹H} NMR ([D₆]-acetone): d ¼ 21:9

(s, CH₃), 23.0 (s, CH₃), 35.2 (s, CH), 52.3 (s, CH₂), 197.4

(dd, ²J(P–C) ¼ 7.2, 4.8 Hz, CO), 198.9 (dd, ²J(P–

C) ¼ 6.7, 3.8 Hz, CO), 212.0 (dd, ²J(P–C) ¼ 16.2, 8.6 Hz,

CO).

²J(P–C) ¼ 6.7, 4.8 Hz, CO), 207.6 (dd, J(P–C) ¼ 16.2,

2

6.7 Hz, CO).

4.4. Preparation of thioether complexes fac-[W(CO)₃

(Me₂PC₂H₄PMe₂)(MeSCH₂R⁰)] (6a, c, e, m)

Z-5i: ¹H NMR ([D₆]-acetone): d ¼ 1:07 (d, 3H, ³J(H–

H) ¼ 6.4 Hz, CH₃), 1.17 (d, 3H, ³J(H–H) ¼ 6.4 Hz,

CH₃), 2.63 (s, 3H, SCH₃), 4.12 (ddd, 1H, ³J(H–

H) ¼ 10.3, 2.8, 2.8 Hz, S@CH); ¹³C{¹H}NMR ([D₆]-

To a solution of the methylated thioaldehyde com-

plex (0.20 mmol) in THF (10 ml) was added LiAlH₄(40

mg, 1.0 mmol) and the mixture stirred for 10 min at 20

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

1895

Table 7

Crystal data and structure reﬁnement for mer-[W(CO)₃(Me₂PC₂H₄-

PMe₂)(g²-S@CH-i-Bu)] (3i)

°C. Excess hydride reagent was quenched by careful

addition of water. The mixture was evaporated to dry-

ness and the residue extracted with dichloromethane (10

ml). Rapidly recorded NMR spectra showed the pres-

ence of 30–40% mer isomer at this stage. The ﬁltered

extract was chromatographed using dichloromethane as

eluent, and the yellow band collected and taken to

dryness. The residue was washed twice with pentane (2

ml) and dried under vacuum.

1

2

Empirical formula

Formula weight

Temperature (K)

C₁₄H₂₆O₃P₂SW ꢂ C₆H₁₄

556.23

143(2)

0.71073

ꢀ

Wavelength (A)

Crystal size (mm)

Crystal system, space group

0.2 ꢃ 0.1 ꢃ 0.1

monoclinic, P2₁=c

9.7636(3)

ꢀ

a (A)

ꢀ

b (A)

13.5384(4)

16.9630(5)

fac-[W(CO)₃(dmpe){MeSCH₂C₆H₅}] (6a): Yield: 80

mg (72%), m.p. 76 °C (dec.). Calc. for C₁₇H₂₆O₃P₂SW

(MW 556.3): C, 36.71; H, 4.71; S, 5.76. Found: C, 36.04;

ꢀ

c (A)

b (°)

Volume (A )

92.634(1)

2239.9(2)

3

ꢀ

1

Z, calculated density (Mg m^ꢀ3

)

4, 1.649

5.398

H, 4.37; S, 5.52%. H NMR (CD₂Cl₂): d ¼ 2:32 (s, 3H,

Absorption coeﬃcient (mm^ꢀ1

Reﬂections collected/unique

Final R indices ½I > 2rðIÞꢄ

R indices (all data)

)

SCH₃), 3.91 (s, 2H, SCH₂), 7.23–7.31 (m, 5H, C₆H₅);

3

21,806/3209

R₁¼ 0:038, wR₂¼ 0:083

0.807 and )0.798

¹³C{¹H}NMR (CD₂Cl₂): d ¼ 26:9 (t, J(P–C) ¼ 4.8 Hz,

3

SCH₃), 52.0 (t, J(P–C) ¼ 4.8 Hz, SCH₂), 128.7, 129.0,

2

129.4, 137.3 (s, C₆H₅), 212.5 (t, J(P–C) ¼ 5.7 Hz, CO),

Largest diﬀerential peak and

ꢀ3

2

ꢀ

hole (e A

)

217.2 (dd, J(P–C) ¼ 30.5, 5.7 Hz, CO).

1

4

mer-6a: H NMR (CD₂Cl₂): d ¼ 2:44 (d, 3H, J(P–

H) ¼ 1.1 Hz, SCH₃), 3.93 (s, 2H, SCH₂); ³¹P{¹H}NMR

(CD₂Cl₂): d ¼ 5:3 (d, ²J(P–P) ¼ 10.9 Hz, ¹J(W–P) ¼ 218

2

1

Hz), 19.1 (d, J(P–P) ¼ 10.9 Hz, J(W–P) ¼ 302 Hz).

SCH₃); ¹³C{¹H}NMR (CD₂Cl₂): d ¼ 30:7 (t, ³J(P–

C) ¼ 5.1 Hz, SCH₃), 212.7 (t, ²J(P–C) ¼ 6.1 Hz, CO),

fac-[W(CO)₃(dmpe){MeSCH₂(4-C₆H₄F)}]

(6c):

Yield: 60 mg (53%), m.p. 96 °C (dec.). Calc. for

C₁₇H₂₅FO₃P₂SW (MW 574.2): C, 35.56; H, 4.39; S,

5.58. Found: C, 35.74; H, 4.46; S, 5.48%. ¹H NMR

(CD₂Cl₂): d ¼ 2:32 (s, 3H, SCH₃), 3.90 (s, 2H, SCH₂),

7.00–7.33 (m, 4H, C₆H₄F); ¹³C{¹H}NMR (CD₂Cl₂):

d ¼ 26:9 (t, ³J(P–C) ¼ 4.8 Hz, SCH₃), 51.2 (t, ³J(P–

2

217.4 (dd, J(P–C) ¼ 30.0, 6.1 Hz, CO).

4.5. Structure determination of mer-[W(CO)₃(Me₂

PC₂H₄PMe₂)(g²-S@CH-i-Bu)] (3i)

2

C) ¼ 4.8 Hz, SCH₂), 115.8 (d, J(F–C) ¼ 20 Hz, CH),

Yellow crystals of 3i suitable for structure determi-

nation were obtained by diﬀusion of hexane into a tol-

uene solution at 0 °C. X-ray data were collected on a

Bruker Smart-Apex CCD diﬀractometer using Mo Ka

radiation. The crystal data are summarized in Table 7.

The structure was solved using the direct methods pro-

vided within ^SHELXS97 [16] and reﬁned by full-matrix

least squares methods using ^SHELXL97 [16]. Half a

disordered molecule of hexane per formula unit was

found but could not be fully reﬁned.

130.8 (d, ³J(F–C) ¼ 9 Hz, CH), 133.2 (s, CH), 162.6 (d,

¹J(F–C) ¼ 245 Hz, CF), 212.5 (t, ²J(P–C) ¼ 5.7 Hz, CO),

2

217.2 (dd, J(P–C) ¼ 30.5, 5.7 Hz, CO).

1

4

mer-6c: H NMR (CD₂Cl₂): d ¼ 2:45 (d, 3H, J(P–

H) ¼ 1.3 Hz, SCH₃), 3.94 (s, 2H, SCH₂); ³¹P{¹H}NMR

(CD₂Cl₂): d ¼ 5:3 (d, ²J(P–P) ¼ 10.9 Hz, ¹J(W–P) ¼ 218

2

1

Hz), 19.0 (d, J(P–P) ¼ 10.9 Hz, J(W–P) ¼ 302 Hz).

fac-[W(CO)₃(dmpe){MeSCH₂(4-C₆H₄OMe)}] (6e):

Yield: 70 mg (61%), m.p. 38 °C (dec.). Calc. for

C₁₈H₂₈O₄P₂SW (MW 586.3): C, 36.88; H, 4.81; S, 5.47.

Found: C, 36.63; H, 4.67; S, 5.27%. ¹H NMR (CD₂Cl₂):

d ¼ 2:31 (s, 3H, SCH₃), 3.67 (s, 3H, OCH₃), 3.86 (s, 2H,

SCH₂), 6.81–7.25 (m, 4H, C₆H₄); ¹³C{¹H}NMR

(CD₂Cl₂): d ¼ 26:7 (t, ³J(P–C) ¼ 4.8 Hz, SCH₃), 51.5 (t,

³J(P–C) ¼ 4.8 Hz, SCH₂), 55.6 (s, OCH₃), 114.3, 129.3,

5. Supplementary material

Further details of the structure determination are

available from the Cambridge Crystallographic Data

Centre, CCDC reference number 223075.

2

130.6, 159.6 (s, C₆H₄), 212.6 (t, J(P–C) ¼ 5.7 Hz, CO),

2

217.3 (dd, J(P–C) ¼ 30.0, 5.7 Hz, CO).

1

4

mer-6e: H NMR (CD₂Cl₂): d ¼ 2:44 (d, 3H, J(P–

H) ¼ 1.1 Hz, SCH₃), 3.77 (s, 3H, OCH₃), 3.88 (s, 2H,

SCH₂); ³¹P{¹H}NMR (CD₂Cl₂): d ¼ 5:2 (d, J(P–P) ¼

2

10.9 Hz, ¹J(W–P) ¼ 218 Hz), 19.1 (d, ²J(P–P) ¼ 10.9 Hz,

¹J(W–P) ¼ 303 Hz).

Acknowledgements

fac-[W(CO)₃(dmpe){SMe₂}] (6m): Yield: 65 mg

(67%), m.p. 53 °C (dec.). Calc. for C₁₁H₂₂O₃P₂SW (MW

480.2): C, 27.52; H, 4.62; S, 6.68. Found: C, 27.10; H,

4.49; S, 6.14%. ¹H NMR (CD₂Cl₂): d ¼ 2:51 (s, 6H,

This work was supported by the Deutsche Fors-

chungsgemeinschaft within the Sonderforschungsber-

eich 347 ‘‘Selective Reactions of Metal-Activated

Molecules’’.

1896

W.A. Schenk et al. / Inorganica Chimica Acta 357 (2004) 1886–1896

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Article Doi

Tungsten complexes of aromatic and aliphatic thioaldehydes

DOI: 10.1016/j.ica.2003.11.032

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