P - H-Functionalized 2-(Phosphanyl)ethanethiols, Their Titanocene Derivatives [Cp2Ti(SCH2CH2PHR)2] (R = Ph, 2,4,6-Me3C6H2, 2,4,6-iPr3C6H2) and Reaction of [Cp2Ti(SCH2CH2PHPh)2] with [Cu(CH3CN)4]BF4

Article abstract of DOI:10.1002/1099-0682(200109)2001:10<2587::AID-EJIC2587>3.0.CO;2-B

The P - H-functionalized 2-(phosphanyl)ethanethiols RHPCH2CH2SH [R = Ph (1), 2,4,6-Me3C6H2 (Mes) (2), 2,4,6-iPr3C6H2 (Tipp) (3)] were prepared by ring cleavage of ethylene sulfide with LiPHR, followed by hydrolytic workup and distillation. 1-3 react with [Cp2TiCl2] in the presence of excess NEt3 to yield a diastereomeric mixture (ratio ca. 1:1) of rac- and meso-[Cp2Ti(SCH2CH2PHR)2] [R = Ph (4), Mes (5), Tipp (6)]. 6 is not obtained in pure form. Compound 4 reacts with [Cu(CH3CN)4]BF4 to yield [Cu{P,P'-PHPhCH2CH2SB(FH)SCH2CH2PPh(B-P)}2]BF4 (7). 1-7 were characterized spectroscopically. 7 exhibits dynamic behavior in solution, as shown by 31P NMR soectroscopy. Crystal structure determinations were carried out on 5 and 7. In 5, both diastereomers cocrystallize in the asymmetric unit. Although the cation of 7 has six chiral centers, only the (R_P,R_P,R_P,R_P,R_B,R_B)/S_P,S_P,S_P,S_P,S_B,S_B) diastereomer is present in the solid state.

Full text of DOI:10.1002/1099-0682(200109)2001:10<2587::AID-EJIC2587>3.0.CO;2-B

FULL PAPER
P؊H-Functionalized 2-(Phosphanyl)ethanethiols, Their Titanocene Derivatives
[Cp2Ti(SCH2CH2PHR)2] (R ؍ Ph, 2,4,6-Me3C6H2, 2,4,6-iPr3C6H2) and
Reaction of [Cp2Ti(SCH2CH2PHPh)2] with [Cu(CH3CN)4]BF4
Satyajeet Chaudhury,[a] Steffen Blaurock,[a] and Evamarie Hey-Hawkins*[a]
Dedicated to Prof. M. Herberhold on the occasion of his 65th birthday
Keywords: PϪH-Functionalized 2-(phosphanyl)ethanethiols / Titanium / Metallocenes / Bis(phosphanylethanethiolates) /
Copper
The P−H-functionalized 2-(phosphanyl)ethanethiols RHPCH2- [Cu(CH3CN)4]BF4
to
yield
[Cu{P,PЈ-PHPhCH2CH2-
CH2SH [R = Ph (1), 2,4,6-Me3C6H2 (Mes) (2), 2,4,6-iPr3C6H2 SB(FH)SCH2CH2PPh(B−P)}2]BF4 (7). 1−7 were character-
(Tipp) (3)] were prepared by ring cleavage of ethylene sulfide ized spectroscopically. 7 exhibits dynamic behavior in solu-
with LiPHR, followed by hydrolytic workup and distillation.
tion, as shown by 31P NMR spectroscopy. Crystal structure
1−3 react with [Cp2TiCl2] in the presence of excess NEt3 to
determinations were carried out on 5 and 7. In 5, both dia-
yield a diastereomeric mixture (ratio ca. 1:1) of rac- and stereomers cocrystallize in the asymmetric unit. Although the
meso-[Cp2Ti(SCH2CH2PHR)2] [R = Ph (4), Mes (5), Tipp (6)].
6 is not obtained in pure form. Compound 4 reacts with
cation of 7 has six chiral centers, only the (RP,RP,RP,RP,RB,RB)/
(SP,SP,SP,SP,SB,SB) diastereomer is present in the solid state.
Introduction
plexes is known.[7,35,36] However, the use of mixed P,S li-
gands appears attractive for several reasons. Group-4 and
other early transition metals have well-established thiolato
complexes which can be employed in catalytic processes,[37]
while the late transition and coinage metals form stable
phosphane complexes which can also be used in catalysis.[38]
Thus, the possibility of bridging two different metal centers
by using ligands with mixed donor atoms appears feasible
and could conceivably result in metalϪmetal interaction[7]
and complexes with new and unique reactivity patterns. To
date, only a few heterobimetallic complexes in which a
phosphanylalkanethiolato ligand bridges an early and
While tertiary phosphanyl alcohols have been known and
employed as ligands in the synthesis of transition metal
complexes with catalytic properties for a long time,[1] the
synthetic potential of primary[2] and secondary[3] phos-
phanyl alcohols has only recently been recognized. The cor-
responding tertiary,[4Ϫ9] secondary[4,10,11] and primary[12]
phosphanylalkanethiols have received comparatively less at-
tention. The lack of investigations in this area reflects the
paucity of commercially available primary phosphanes, the
synthesis of which often requires tedious procedures.[13]
Catalytic reactions have been reported in which the trans-
ition metal center bears a neutral bidentate P,S ligand, such
as the chiral phosphanylalkyl thioether PR2CH2CHRЈSRЈЈ
(R, RЈ, RЈЈ ϭ alkyl or aryl).[8] However, these are rare due
to the possibility of metal poisoning by sulfur.
While several transition metal complexes with tertiary
phosphanylalkanethiolato ligands[4,6,7,14Ϫ28] are known,
mainly late ‘‘soft’’ transition metal complexes bearing prim-
ary (Ni, Pd, Pt,[12] Co, Rh[29]) or secondary phosphanyl-
alkanethiolato ligands (Ni,[4,30] Pd, Pt,[30] Co,[4,30,31] Cu,[30]
Rh[31]) have been described. Here, the phosphanylalkanethi-
olato ligand acts as a monoanionic bidentate S,P-chelating
ligand. In main-group metal chemistry, group-14 metal de-
rivatives Me2M(P,S-SCH2CH2PPh) (M ϭ Si,[11] Sn,[11,32]
Ge[11,33]) and Sn{S,P,S-SCH2CH2P(Ph)CH2CH2S}[34] are
known. Only a small number of early transition metal com-
a
late transition metal center are known, namely,
[Cp2Ti(SCH2CH2CH2PPh2)2Rh]ϩ or [Cp2Ti(SCH2CH2-
CH2PPh2)2Rh]0,[7] [Cp2Ti(SCH2CH2CH2PPh2)2Ni],[39]
[Cp2Ti(SCH2CH2CH2PPh2)2Ni(CO)2],[39]
CH2CH2PPh2)2Pd]2ϩ [39]
and
[Cp2Ti(SCH2-
,
[Cp2Ti(SCH2CH2-
PPh2)2Cu]ϩ.[35] Several homodi-[26,40Ϫ44] and -trinu-
clear[16,30,39,45] complexes and heterobimetallic bi-[46,47] and
trinuclear[39Ϫ41] complexes, in which the P,S ligand bridges
two late transition metal centers (Fe, Ni, Co, Pd, Pt, Cu,
Ag) have also been reported. Some of these complexes have
been structurally characterized.
We now report on the synthesis and spectroscopic studies
of the soft-soft PϪH-functionalized 2-(phosphanyl)ethane-
thiols RHPCH2CH2SH [R ϭ Ph (1), 2,4,6-Me3C6H2 (Mes)
(2), 2,4,6-iPr3C6H2 (Tipp) (3)]. The synthesis of 1 from
NaPHPh and ethylene sulfide in liquid ammonia, followed
by hydrolysis with hydrochloric acid was reported by Issleib
et al. in 1967.[4] However, characterization of the product
was limited to elemental analysis and IR-spectroscopic
studies.
[a]
Institut für Anorganische Chemie der Universität Leipzig,
Johannisallee 29, 04103 Leipzig, Germany
Eur. J. Inorg. Chem. 2001, 2587Ϫ2596
WILEY-VCH Verlag GmbH, 69451 Weinheim, 2001
1434Ϫ1948/01/1010Ϫ2587 $ 17.50ϩ.50/0
2587

S. Chaudhury, S. Blaurock, E. Hey-Hawkins
FULL PAPER
7.8 Hz). The methylene protons of the HPCH2CH2SH frag-
ment appear as complex multiplets due to 1HϪ1H and
1HϪ31P coupling. The PϪH signal is a doublet of doublets
of doublets (1 and 2) or a doublet of triplets (3) at δ ഠ
Results and Discussion
Synthesis and Characterization of the 2-
(Phosphanyl)ethanethiols RHPCH2CH2SH [R ؍ Ph (1),
Mes (2), Tipp (3)]
3
4.0Ϫ4.3 (1JPϪH ϭ 209Ϫ217, JHϪH ϭ 7Ϫ9 Hz). In the 13C
NMR spectra, the PϪCH2 and SϪCH2 groups give rise to
The PϪH-functionalized 2-(phosphanyl)ethanethiols
RHPCH2CH2SH [R ϭ Ph (1), Mes (2), Tipp (3)] were pre-
pared by nucleophilic ring cleavage of ethylene sulfide with
the lithium phosphanides LiPHR, prepared in situ from
RPH2 and BuLi, followed by hydrolytic workup and distil-
lation (Scheme 1). A stoichiometric amount of ethylene sul-
fide had to be employed to prevent further reaction to
RP(CH2CH2SH)2.[6] 1Ϫ3 were obtained in good yields and
gave satisfactory elemental analyses. They are readily oxid-
ized by air. At room temperature, the 2-(phosphanyl)-
ethanethiols are colorless oils that solidify at Ϫ30 °C.
1
doublets at δ ϭ 24.4Ϫ24.8 (PϪC, JCϪP ϭ 7.1 and 7.8 Hz
for 1 and 2, 12.6 Hz for 3) and δ ϭ 27.7 Ϫ30.4 (PϪCϪCϪS,
2JCϪP ca. 15.8Ϫ17.0 Hz). For all compounds, molecular ion
peaks were observed in the mass spectra. In the IR spectra,
the SϪH stretching band is observed around 2560 cmϪ1
,
and ν(PϪH) is found in the 2280 to 2340 cmϪ1 region (cf.
ref.[4]).
Synthesis and Characterization of rac- and meso-
[Cp2Ti(SCH2CH2PHR)2] [R ؍ Ph (4), Mes (5), Tipp (6)]
The PϪH-functionalized 2-(phosphanyl)ethanethiols
1Ϫ3 react with [Cp2TiCl2] in the presence of excess triethyl-
amine
to
give
the
disubstituted
products
[Cp2Ti(SCH2CH2PHR)2] [R ϭ Ph (4), Mes (5), Tipp (6)],
and (NEt3H)Cl (Scheme 2). In the 31P{1H} NMR spectra
(Table 2), two singlets of equal intensity are present, in ac-
Scheme 1
The 2-(phosphanyl)ethanethiols 1Ϫ3 were characterized cordance with the presence of two diastereomers due to the
spectroscopically (1H, 31P, 13C NMR spectroscopy; MS; chiral center at the phosphorus atom. Separation of the di-
and IR spectroscopy). A comparison of the 1H, 31P and 13
C
astereomers was not achieved, even after repeated recrystal-
data for 1؊3 is given in Table 1. In the proton-coupled 31P lization. The chemical shifts of the 2-(phosphanyl)ethane-
NMR spectra, 1؊3 give rise to doublets, and the signals thiols and of the titanium complexes are similar, the latter
of 1 are downfield relative to those of 2 and 3 (1 Ͻ 2 Ͻ exhibiting a downfield shift of only δ ഠ 2.5. This indicates
3; Table 1).
no TiϪP interaction in solution. In complexes in which the
1
In the H NMR spectra, the SϪH proton gives rise to a phosphanylalkanethiolato ligand acts as bidentate ligand,
triplet (1 and 2) or multiplet (3) at δ ϭ 1.2Ϫ1.3 (3JHϪH
ϭ
a downfield shift of δ ഠ 80 is observed in the 31P NMR
Table 1. NMR-spectroscopic data for compounds 1Ϫ3
PhPHCH2CH2SH (1)
MesPHCH2CH2SH (2)
TippPHCH2CH2SH (3)
3
3
1H
1.31 (t, 1 H, JHϪH ϭ 7.8, SH)
1.21 (t, 1 H, JHϪH ϭ 7.8, SH)
1.19 (br, s, 6 H, CH3 in o-iPr)
1.21 (br, s, 6 H, CH3 in o-iPr)
1.28 (br, s, 3 H, CH3 in p-iPr)
1.30 (br, s, 3 H, CH3 in p-iPr)
1.25Ϫ1.30 (m, 1 H, SH)
1.72 (m, 1 H, PϪCH2)
δ/ppm, J/Hz
1.69 (m, 1 H, PϪCH2)
1.83 (m, 1 H, PϪCH2)
2.27 (m, 2 H, SϪCH2)
1.59 (m, 1 H, PϪCH2)
1.83 (m, 1 H, PϪCH2)
2.08 (s, 3 H, p-CH3 in Mes)
2.24 (m, 2 H, SϪCH2)
2.31 (s, 6 H, o-CH3 in Mes)
4.24 (d/d/d, 1 H, JPϪH ϭ 216.5,
3JHϪH ϭ 8.5, PH)
6.71 (s, 2 H, m-H in Mes)
1
4.04 (d/d/d, 1 H, JPϪH ϭ 209.6,
3JHϪH ϭ 8.8, PH)
3
1
7.06 (d, 1 H, JHϪH ϭ 4.0, p-H in Ph)
1.97 (m, 1 H, PϪCH2)
7.26 (m, 4 H, o- and m-H in Ph)
2.31 (m, 2 H, SϪCH2)
2.75 (sept, 1 H, CH in p-iPr, JHϪH ϭ 6.9)
3
3
3.71 (sept, 2 H, CH in o-iPr, JHϪH ϭ 6.5)
1
3
4.13 (d/t, 1 H, JPϪH ϭ 216.5, JHϪH ϭ 7.1, PH)
7.12 (s, 2 H, m-H in Tipp)
31P
Ϫ54.0 (d, JPϪH ϭ 210.2, PH)
Ϫ88.8 (d, JPϪH ϭ 216.5, PH)
-97.1 (d, JPϪH ϭ 215.4, PH)
1
1
1
δ/ppm, J/Hz
13C[a]
δ/ppm, J/Hz
1
1
24.58 (d, JCϪP ϭ 7.1, PϪCH2)
21.67 (s, p-CH3 in Mes)
24.48 (d, JPϪC ϭ 12.6, PϪCH2)
2
3
3
29.30 (d, JCϪP ϭ 15.9, SϪCH2
23.83 (d, JPϪC ϭ 10.9, o-CH3 in Mes)
24.77 (d, JPϪC ϭ 4.7, CH3 in o-iPr)
1
129.08 (s, ipso-C in Ph)
129.43 (d, JPϪC ϭ 5.5, m-C in Ph)
24.80 (d, JPϪC ϭ 7.8, PϪCH2)
25.09 (s, CH3 in o-iPr)
25.72 (s, CH3 in p-iPr)
3
2
27.73 (d, JPϪC ϭ 17.0, SϪCH2)
2
3
2
134.51 (d, JPϪC ϭ 15.4, o-C in Ph)
130.07 (d, JPϪC ϭ 2.8, m-C in Mes)
30.04 (d, JPϪC ϭ 15.8, SϪCH2)
4
3
135.4 (d, JPϪC ϭ 11.9, p-C in Ph)
138.66 (s, p-C in Mes)
33.70 (d, JPϪC ϭ 13.7, CH in o-iPr)
2
142.45 (d, JPϪC ϭ 20.8, o-C in Mes)
35.39 (s, CH in p-iPr)
122.42 (d, JPϪC ϭ 3.0, m-C in Tipp)
3
150.68 (s, p-C in Tipp)
2
153.91 (d, JPϪC ϭ 11.1, o-C in Tipp)
[a]
ipso-C signal of Ph (for 1), Mes (for 2) and Tipp (for 3) obscured by solvent or not observed.
2588
Eur. J. Inorg. Chem. 2001, 2587Ϫ2596

Titanocene Derivatives of 2-(Phosphanyl)ethanethiols
FULL PAPER
Table 2. NMR-spectroscopic data for compounds 4Ϫ6
[Cp2Ti(SCH2CH2PHPh)2] (4)
[Cp2Ti(SCH2CH2PHMes)2] (5)
[Cp2Ti(SCH2CH2PHTipp)2] (6)[a]
[a]
1H
1.98 (m, 2 H, PϪCH2)
1.87 (m, 2 H, PϪCH2)
2.10 (s, 2 H ϩ 6 H, PϪCH2
and p-CH3 in Mes)
δ/ppm, J/Hz 2.09 (m, 2 H, PϪCH2)
3.24 (m, 4 H, SϪCH2)
1
4.32 (d/t, 2 H, JPϪH ϭ 208.0,
2.52 (m, 12 H, o-CH3 in Mes)
3.23 (m, 4 H, SϪCH2)
3JHϪH ϭ 7.0, PH)
1
5.62 (s, 10 H, Cp)
4.51 (d, br, 2 H, JPϪH ϭ 215, PH)
7.09 (m, 6 H, o- and p-H in Ph)
5.59 (s, 10 H, Cp)
3
7.46 (t, 4 H, JHϪH ϭ 6.8, m-H in Ph)
6.80 (s, 4 H, m-H in Mes)
1
3
1
1
31P
Ϫ51.64 (d/t, JPϪH ϭ 207, JPϪH ϭ 5, PH)
Ϫ86.14 (d, JPϪH ϭ 215, PH)
Ϫ94.8 (d, JPϪH ϭ 203, PH)
1
3
1
1
δ/ppm, J/Hz Ϫ51.67 (d/t, JPϪH ϭ 207, JPϪH ϭ 5, PH)
Ϫ86.30 (d, JPϪH ϭ 215, PH)
Ϫ94.9 (d, JPϪH ϭ 203, PH)
(ratio ca. 1:1)
(ratio 1:1)
21.72 (s, CH3 in Mes)
23.6 (br, PϪCH2)
(ratio 4:3)
[a]
13C
27.84 (br, t, PϪCH2)
1
δ/ppm, J/Hz 44.22 (t, JC1ϪH ϭ 139, SϪCH2)
111.93 (d/t, JCϪH ϭ 176 Hz, JCϪH ϭ 5.8 Hz, Cp) 44.87 (SϪCH2)
1
126.33 (d, JCϪH ϭ 161, m-C in Ph)
111.84 (Cp)
130.09 (m-C in Mes)
138.43 (p-C in Mes)
129.20 (o-C in Ph)[b]
1
134.71 (d, JCϪH ϭ 146, p-C in Ph)
138 (br. s, ipso-C in Ph)
142.6 (br, o-C in Mes)
[c]
[a]
[b]
1
Impurity of TippPHCH2CH2SH present; therefore the H and 13C NMR spectroscopic data could not be unambiguously assigned. Ϫ
[c]
Obscured by solvent signal. Ϫ ipso-C signal obscured by solvent signal.
spectrum.[12] In the 13C NMR spectra of 4 and 5, the signal failure to separate them by fractional crystallization. Both
of the SϪCH2 group is shifted downfield by ca. 19 ppm diastereomers have similar bond lengths and bond angles.
The titanium atom is coordinated in a pseudotetrahedral
fashion by two Cp rings and the S atoms of 2-(phosphanyl)-
ethanethiolato ligands. The TiϪS bond lengths of 2.3699(7)
relative to the free ligand.
˚
˚
to 2.4155(7) A [average 2.3925(7) A] and the SϪTiϪS bond
angles of 96.04(2) and 96.09(3)° are slightly larger than
those of the related complex [Cp2Ti(SCH2CH2CH2PPh2)2]
[TiϪS 2.378(6), 2.384(6) A, SϪTiϪS 93.3(2)°].[7] One of the
˚
CϪSϪTi bond angles in 5 is large [C(11)ϪS(1)ϪTi(1)
114.6(1); C(43)ϪS(3)ϪTi(2) 114.70(9)°], and the other is
smaller, by ca. 5 to 7° [C(22)ϪS(2)ϪTi(1) 109.08(8);
C(54)ϪS(4)ϪTi(2) 107.63(8)°]. This suggests some degree
of backbonding from S(1) and S(3) to Ti, which are also
involved in the shorter TiϪS bonds [Ti(1)ϪS(1) 2.3899(6);
Scheme 2
For 4 and 6, separation of the titanium complex and the
2-(phosphanyl)ethanethiol could not be achieved by col-
umn chromatography or recrystallization. When the purple
oil was heated to ca. 46 °C at 10Ϫ3 Torr (4) or ca. 113 °C
at 10Ϫ3 Torr (6), the 2-(phosphanyl)ethanethiol could be
distilled off, but decomposition of the titanium complex
also occurred.
˚
Ti(2)ϪS(3) 2.3699(7) A]. In [Cp2Ti(SCH2CH2CH2PPh2)2],
the CϪSϪTi bond angles are similar, 109.7(6) and
110.0(6)°.[7] In the titanocene dithiolato complexes,
[Cp2RTi(SRЈ)2][48] (CpR ϭ Cp, RЈ ϭ Me,[49] Et,[50] tBu,[51]
Ph;[52] CpR ϭ C5H4SiMe3, RЈ ϭ C6F5 [53]) and [Cp*
2Ti(SH)2] (Cp* ϭ C5Me5),[54] the TiϪS bond lengths range
The related Ti complexes [Cp2Ti(SCH2CH2CH2PPh2)2][7]
and [Cp2Ti(SCH2CH2PPh2)2][35] were obtained in a similar
way, as a purple solid and a viscous purple oil that could
not be crystallized, respectively. The difference in chemical
shifts [∆δ31P(complex Ϫ ligand) ϭ 1.3 or 0.9 ppm] is com-
parable to that observed for 4؊6 relative to 1؊3.
˚
from 2.387(3) (RЈ ϭ Et) to 2.438(2) A (RЈ ϭ C6F5), and
the SϪTiϪS angles from 93.6(1) (RЈ ϭ Me) to 100.6(1)°
(RЈ ϭ C6F5). The values observed for 5 fall inside this
range. In titanocene complexes with chelating S,S ligands,
the SϪTiϪS angles are smaller (ca. 83°) due to the geomet-
ric requirements.[48,51,55,56]
Molecular Structure of [Cp2Ti(SCH2CH2PHMes)2] (5)
The related heterobimetallic complexes [Cp2Ti-
[7]
Dark purple crystals of 5 were obtained from a saturated (SCH2CH2CH2PPh2)2Rh]ϩ [TiϪS 2.409(3), 2.438(3) A],
˚
hexane solution at room temperature. 5 crystallizes in the [Cp2Ti(SCH2CH2CH2PPh2)2Ni] [TiϪS 2.484(5), 2.483(5)
[39]
˚
¯
centrosymmetric triclinic space group P1 with four molec- A],
[Cp2Ti(SCH2CH2CH2PPh2)2Ni(CO)2]
[TiϪS
[39]
and [Cp2Ti(SCH2CH2PPh2)2Cu]ϩ
˚
ules in the unit cell. Both diastereomers, rac- and meso- 2.398(2), 2.398(4) A],
[Cp2Ti(SCH2CH2PHMes)2], are present in the asymmetric [TiϪS 2.465(2), 2.484(3) A]
[35]
˚
have been structurally char-
unit (Figure 1, Table 3). Cocrystallization of the two dia- acterized. Here, the TiϪS bonds are longer when the S
stereomers would appear to be the major reason for the atom is also bonded to a second transition metal.
Eur. J. Inorg. Chem. 2001, 2587Ϫ2596
2589

S. Chaudhury, S. Blaurock, E. Hey-Hawkins
FULL PAPER
[CpЈ2Ti{η2-S,S-SP(S)(R)P(S)(R)S}] and [CpЈ2Ti{η2-S,S-
S2P(S)R}] (CpЈ ϭ C5H4Me, R ϭ p-OMeC6H4),[57] in the
(phosphane sulfide)titanocene compounds [Cp2Ti(SPCy2)2]
and [Cp2Ti{η2-S,S-S2PCy2}][58] and in the inorganic tita-
nium(IV) complexes [TiCl2{η2-S,S-S2PEt2}2].[59] In
[57]
[CpЈ2Ti{η2-S,S-S2P(S)R}] [2.4898(8), 2.4639(8) A],
˚
[58]
2
˚
[Cp2Ti{η -S,S-S2PCy2}] [2.586(4) and 2.611(5) A],
and
[TiCl2{η -S,S-S2PEt2}2] [2.503(3) and 2.442(3) A],[59] which
contain chelating P,S ligands, the TiϪS bond lengths are in
the range of dinuclear complexes in which the S atom of
the thiolato substituent is bonded to two metal atoms. In
the complex [Cp2Ti(SPCy2)2], with a nonchelating S,P li-
2
˚
[58]
˚
gand, the TiϪS bond lengths [2.420(3), 2.427(3) A]
in the range observed for 5.
are
Reaction of [Cu(CH3CN)4]BF4 with [Cp2Ti(SCH2CH2-
PHPh)2] (4) ؊ Molecular Structure of [Cu{P,PЈ-
PHPhCH2CH2SB(FH)SCH2CH2PPh(B؊P)}2]BF4 (7)
When 4 was treated with [Cu(CH3CN)4]BF4 we expected
the formation of the heterodinuclear complex
[Cp2Ti(SCH2CH2PHPh)2Cu]BF4, analogous to the forma-
tion of the green-black complex [Cp2Ti(SCH2CH2-
PPh2)2Cu]BF4 (obtained in 55% yield).[35] However, al-
though the experiment was carried out in exactly the same
way as that leading to the heterodinuclear TiϪCu complex,
we were unable to isolate a heterodinuclear complex. In-
stead, we observed the formation of a CuI complex,
[Cu{P,PЈ-PHPhCH2CH2SB(FH)SCH2CH2PPh(BϪP)}2]-
BF4 (7), in a low yield. Apparently this was formed in a
complex reaction in which ligand exchange between the
Ϫ
BF4 anion and the titanium complex occurred with the
formation of [PHPhCH2CH2SB(F2)SCH2CH2PHPh]Ϫ, fol-
lowed by the substitution of one fluoride atom by the phos-
phanyl group with the transfer of the PϪH proton to the
remaining fluoride, to give the cyclized ligand PHPhCH2-
CH2SB(FH)SCH2CH2PPh(BϪP). Coordination of this
bis(phosphane) ligand to CuI gives the cation [Cu{P,PЈ-
PHPhCH2CH2SB(FH)SCH2CH2PPh(BϪP)}2]ϩ
(7)
Figure 1. Molecular structure of [Cp2Ti(SCH2CH2PHMes)2] (5)
showing the atom numbering scheme employed (ORTEP, 50%
probability, SHELXTL PLUS; XP);[70] a) rac isomer; b) meso iso-
mer; hydrogen atoms (other than PϪH) are omitted for clarity
(Scheme 3). Elimination of HX from the adducts
R2BXϪPHRЈ2, with the formation of BϪP single bonds,
has been observed before.[60]
Ϫ
Other related mononuclear transition metal complexes
The participation of the BF4 anion in the reaction was
with S,P chelating phosphanylalkanethiolato ligands which rather unexpected and, to the best of our knowledge, is un-
Ϫ
have been structurally characterized include [MoX(S,P- precedented. The only reaction reported involving BF4 is
SCH2CH2PPh2)2]nϩ (n ϭ 0, X ϭ O;[18] n ϭ 1, X ϭ Cp[36]), that with difluorophosphoric acid (HPO2F2) in P2O3F4 to
[Re(SCH2Ph)(S,P-SCH2CH2PPh2)2],[22]
[Tc(S,P-SC6H4- give HB(PO2F2)4.[61] In addition, Stephan et al. were able
PPh2)3],[14] [Tc(S,P-SCH2CH2PPh2)2(S-SCH2CH2POPh2)],[15] to
synthesize
the
heterodinuclear
complexes
[FeCl(CO)(PPh3)(S,P-SC{(tBu)(SCOMe)}CH2PPh2)],[21] [Fe- [Cp2Ti(SCH2CH2CH2PPh2)2Rh]ϩ
and [Cp2Ti(SCH2-
[7]
{η2-C(OMe)S}P(OMe)3(S,P-SC(tBu)ϭCHPPh2)],[24] [Ir(H)- CH2PPh2)2Cu]ϩ
in ca. 60% yield starting from
[35]
Ϫ
(S,P-SCH2CH2PPh2)(S,P-HSCH2CH2PPh2)(CO)]ϩ,[17] [Ni- the corresponding BF4 salts of [Rh(NBD)2]ϩ (NBD ϭ
(S,P-SCH2CH2PR2)2] (R ϭ Me,[23] Ph[25]). Complexes with norbornadiene) and [Cu(CH3CN)4]ϩ. However, when
tri-, tetra- or hexadentate phosphanylalkanethiolato ligands [Ni(CH3CN)4](BF4)2
which also have been studied are [Mo{S,P,S- (SCH2CH2CH2PPh2)2], the trinuclear Ni complex
(SCH2CH2)2PPh}2],[6] [Ni{S,S,P,P-SCH2CH2P(Ph)CH2- [Ni{(SCH2CH2PPh2)2Ni}2]2ϩ was obtained in a 75% yield
CH2CH2P(Ph)CH2CH2S}],[20] [Os{P,P,S,S,S,S- due to ligand exchange.[39] Other heterodinuclear complexes
and
P(CH2CH2S)(CH2CH2SSCH2CH2)2P(CH2CH2S)}].[9]
was
treated
with
[Cp2Ti-
with phosphanylalkanethiolato bridges are [Ni(µ-
P,S ligands without a carbon spacer between P and S SCH2CH2PPh2)2Mo(CO)4],[47] accessible from [Ni(S,P-
are present in thiophosphoryltitanocene complexes such as SCH2CH2PPh2)2] and [Mo(CO)4(NBD)], and [Pt{µ-
2590
Eur. J. Inorg. Chem. 2001, 2587Ϫ2596

Titanocene Derivatives of 2-(Phosphanyl)ethanethiols
˚
FULL PAPER
Table 3. Selected bond lengths [A] and angles [°] in 5 (CEN ϭ center of the corresponding cyclopentadienyl ring)
Molecule 1
Molecule 2
Ti(1)ϪS(1)
Ti(1)ϪS(2)
S(1)ϪC(11)
S(2)ϪC(22)
P(1)ϪC(13)
P(1)ϪC(12)
P(1)ϪH(1P)
2.3899(6)
2.3945(7)
1.827(3)
1.821(2)
1.832(3)
1.855(3)
1.33(5)
Ti(2)ϪS(3)
Ti(2)ϪS(4)
S(3)ϪC(43)
S(4)ϪC(54)
P(3)ϪC(45)
P(3)ϪC(44)
P(3)ϪH(3P)
2.3699(7)
2.4155(7)
1.825(3)
1.819(2)
1.830(3)
1.859(3)
1.25(4)
P(2)ϪC(24)
P(2)ϪC(23)
P(2)ϪH(2P)
1.838(2)
1.858(3)
1.22(4)
P(4)ϪC(56)
P(4)ϪC(55)
P(4)ϪH(4P)
1.842(2)
1.850(3)
1.34(5)
C(11)ϪC(12)
C(22)ϪC(23)
Ti(1)ϪC(Cp)
C(Cp)ϪC(Cp)
1.490(4)
1.515(3)
2.356(2) to 2.413(3)
1.380(4) to 1.407(4)
96.04(2)
132.6(1)
114.6(1)
109.08(8)
102.9(1)
98(2)
C(43)ϪC(44)
C(54)ϪC(55)
Ti(2)ϪC(Cp)
C(Cp)ϪC(Cp)
1.492(4)
1.513(3)
2.372(3) to 2.417(2)
1.380(4) to 1.407(4)
96.09(3)
132.6(1)
114.70(9)
107.63(8)
101.0(1)
102(2)
S(1)ϪTi(1)ϪS(2)
CEN(1)ϪTi(1)ϪCEN(2)
C(11)ϪS(1)ϪTi(1)
C(22)ϪS(2)ϪTi(1)
C(13)ϪP(1)ϪC(12)
C(13)ϪP(1)ϪH(1P)
C(12)ϪP(1)ϪH(1P)
C(24)ϪP(2)ϪC(23)
C(24)ϪP(2)ϪH(2P)
C(23)ϪP(2)ϪH(2P)
C(12)ϪC(11)ϪS(1)
C(11)ϪC(12)ϪP(1)
C(18)ϪC(13)ϪP(1)
C(14)ϪC(13)ϪP(1)
C(23)ϪC(22)ϪS(2)
C(22)ϪC(23)ϪP(2)
C(25)ϪC(24)ϪP(2)
C(29)ϪC(24)ϪP(2)
S(3)ϪTi(2)ϪS(4)
CEN(3)ϪTi(2)ϪCEN(4)
C(43)ϪS(3)ϪTi(2)
C(54)ϪS(4)ϪTi(2)
C(45)ϪP(3)ϪC(44)
C(45)ϪP(3)ϪH(3P)
C(44)ϪP(3)ϪH(3P)
C(56)ϪP(4)ϪC(55)
C(56)ϪP(4)ϪH(4P)
C(55)ϪP(4)ϪH(4P)
C(44)ϪC(43)ϪS(3)
C(43)ϪC(44)ϪP(3)
C(50)ϪC(45)ϪP(3)
C(46)ϪC(45)ϪP(3)
C(55)ϪC(54)ϪS(4)
C(54)ϪC(55)ϪP(4)
C(61)ϪC(56)ϪP(4)
C(57)ϪC(56)ϪP(4)
94(2)
100.7(1)
107(2)
103(2)
100.7(1)
102(2)
103(2)
106(2)
111.7(2)
115.8(2)
122.0(2)
119.2(2)
110.0(2)
112.9(2)
119.4(2)
121.5(2)
112.0(2)
113.9(2)
120.8(2)
121.1(2)
111.6(2)
112.9(2)
119.7(2)
121.3(2)
SCH2CH2PEt2)2Ag}]ϱ(NO3)ϱ,[46] which is obtained from
[Pt(S,P-SCH2CH2PEt2)2] and AgNO3.
At room temperature, two broad sets of signals are ob-
served at δ ഠ Ϫ32 and δ ഠ Ϫ43 in the 31P NMR spectrum
of 7. The absence of a signal in the EPR spectrum indicates
the presence of CuI. The signals at δ ഠ Ϫ43 show further
proton coupling and are thus assigned to the PHPh groups.
In 7, there are six chiral centers present (two boron and four
phosphorus atoms), and hence numerous diastereomers (26
enantiomers) can be formed resulting in the observation of
a large number of signals in the appropriate region of the
NMR spectrum. Additionally, (phosphane)CuI complexes
exhibit dynamic behavior in solution, and Cu has a quadru-
pole moment, hence broad signals are usually observed in
the 31P NMR spectra.
Only one singlet at δ ϭ Ϫ0.97 is observed in the 11B
Ϫ
NMR spectrum of 7 in CDCl3. This is assigned to the BF4
anion by comparison with the starting material,
[Cu(CH3CN)4]BF4.[62] Apparently, the signal for the boron
atom of the bis(phosphane) ligand is too broad to be ob-
served, and this is probably due to the quadrupole moment
of boron, the observed dynamic behavior, and the presence
of several possible diastereomers in solution.
7 crystallizes in the monoclinic space group P21/n with
four formula units in the unit cell. One molecule of CH2Cl2
Scheme 3
Eur. J. Inorg. Chem. 2001, 2587Ϫ2596
2591

S. Chaudhury, S. Blaurock, E. Hey-Hawkins
FULL PAPER
is present in the asymmetric unit. The BF4Ϫ anion is highly
disordered. Although the cation of 7 has six chiral centers
(two boron and four phosphorus atoms) and numerous di-
astereomers are observed in solution, there is only one dias-
tereomer present in the solid state. In this diastereomer, all
six chiral centers have either (R) or (S) configuration (Fig-
˚
Table 4. Selected bond lengths [A] and bond angles [°] of 7
Cu(1)ϪP(1)
Cu(1)ϪP(3)
P(1)ϪB(1)
P(1)ϪC(1)
P(2)ϪC(9)
2.287(1)
2.295(1)
1.872(4)
1.823(5)
1.824(4)
1.31(5)
1.830(5)
1.830(5)
1.820(5)
1.844(5)
1.823(7)
1.821(5)
1.538(7)
1.43(6)
Cu(1)ϪP(2)
Cu(1)ϪP(4)
P(3)ϪB(2)
P(1)ϪC(7)
P(2)ϪC(15)
P(4)ϪH(4P)
P(3)ϪC(23)
P(4)ϪC(31)
S(2)ϪC(8)
S(2)ϪB(1)
S(4)ϪC(32)
S(4)ϪB(2)
B(2)ϪF(2)
F(2)ϪH(2F)
C(15)ϪC(16)
C(31)ϪC(32)
2.268(1)
2.276(1)
1.877(5)
1.826(5)
1.843(5)
1.48(5)
1.839(5)
1.850(5)
1.804(6)
1.817(4)
1.830(6)
1.840(5)
1.546(7)
1.30(6)
1.507(7)
1.514(7)
104.00(4)
116.90(5)
101.15(4)
104.0(2)
112.90(1)
124.6(2)
122.4(2)
93(2)
ure 2, Table 4). The two enantiomers are related by a crys- P(2)ϪH(2P)
P(3)ϪC(17)
tallographic center of inversion in the centrosymmetric
P(4)ϪC(25)
space group P21/n. To the best of our knowledge, this is the
S(1)ϪC(16)
first structurally characterized chiral bis(diphosphane)cop-
S(1)ϪB(1)
S(3)ϪC(24)
S(3)ϪB(2)
B(1)ϪF(1)
F(1)ϪH(1F)
C(7)ϪC(8)
C(23)ϪC(24)
P(2)ϪCu(1)ϪP(4)
P(4)ϪCu(1)ϪP(1)
P(4)ϪCu(1)ϪP(3)
C(1)ϪP(1)ϪC(7)
C(7)ϪP(1)ϪB(1)
C(7)ϪP(1)ϪCu(1)
C(9)ϪP(2)ϪC(15)
C(15)ϪP(2)ϪCu(1) 114.6(2)
C(15)ϪP(2)ϪH(2P) 104(2)
C(17)ϪP(3)ϪC(23) 104.8(3)
per(I) complex.
1.526(7)
1.518(8)
117.44(5) P(2)ϪCu(1)ϪP(1)
115.26(5) P(2)ϪCu(1)ϪP(3)
101.36(5) P(1)ϪCu(1)ϪP(3)
106.8(2)
95.1(2)
111.0(2)
102.2(2)
C(1)ϪP(1)ϪB(1)
C(1)ϪP(1)ϪCu(1)
B(1)ϪP(1)ϪCu(1)
C(9)ϪP(2)ϪCu(1)
C(9)ϪP(2)ϪH(2P)
Cu(1)ϪP(2)ϪH(2P) 117(2)
C(17)ϪP(3)ϪB(2) 103.6(2)
C(17)ϪP(3)ϪCu(1) 116.3(2)
B(2)ϪP(3)ϪCu(1) 121.0(2)
C(23)ϪP(3)ϪB(2)
95.7(2)
C(23)ϪP(3)ϪCu(1) 112.6(2)
C(25)ϪP(4)ϪC(31) 105.8(2)
C(31)ϪP(4)ϪCu(1) 113.9(2)
C(31)ϪP(4)ϪH(4P) 103(2)
C(25)ϪP(4)ϪCu(1) 121.5(2)
C(25)ϪP(4)ϪH(4P) 94(2)
Cu(1)ϪP(4)ϪH(4P) 116(2)
C(16)ϪS(1)ϪB(1)
B(2)ϪS(3)ϪC(24)
104.2(2)
97.2(3)
C(8)ϪS(2)ϪB(1)
C(32)ϪS(4)ϪB(2)
F(1)ϪB(1)ϪS(1)
F(1)ϪB(1)ϪP(1)
S(1)ϪB(1)ϪP(1)
F(2)ϪB(2)ϪS(4)
F(2)ϪB(2)ϪP(3)
S(4)ϪB(2)ϪP(3)
B(2)ϪF(2)ϪH(2F)
C(6)ϪC(1)ϪP(1)
C(7)ϪC(8)ϪS(2)
C(14)ϪC(9)ϪP(2)
C(15)ϪC(16)ϪS(1)
C(18)ϪC(17)ϪP(3)
C(23)ϪC(24)ϪS(3)
C(30)ϪC(25)ϪP(4)
C(31)ϪC(32)ϪS(4)
98.4(2)
105.4(2)
113.2(3)
117.0(3)
107.2(2)
113.5(3)
114.5(3)
109.1(2)
111(3)
123.5(4)
112.0(4)
120.5(4)
112.4(4)
124.1(4)
112.5(4)
119.3(4)
111.6(4)
Figure 2. Molecular structure of (RP,RP,RP,RP,RB,RB)/ F(1)ϪB(1)ϪS(2)
108.4(3)
105.0(2)
105.2(2)
109.5(3)
104.6(2)
104.9(2)
115(2)
118.7(4)
113.4(4)
121.8(4)
(SP,SP,SP,SP,SB,SB)-[Cu{P,PЈ-PHPhCH2CH2SB(FH)SCH2-
CH2PPh(BϪP)}2]BF4 (7) showing the atom numbering scheme em-
ployed (ORTEP, 50% probability, SHELXTL PLUS; XP);[70] only
the cation is shown; hydrogen atoms (other than PϪH or FϪH)
are omitted for clarity
S(2)ϪB(1)ϪS(1)
S(2)ϪB(1)ϪP(1)
F(2)ϪB(2)ϪS(3)
S(3)ϪB(2)ϪS(4)
S(3)ϪB(2)ϪP(3)
B(1)ϪF(1)ϪH(1F)
C(2)ϪC(1)ϪP(1)
C(8)ϪC(7)ϪP(1)
C(10)ϪC(9)ϪP(2)
C(16)ϪC(15)ϪP(2) 114.0(4)
C(22)ϪC(17)ϪP(3) 118.1(4)
C(24)ϪC(23)ϪP(3) 112.9(4)
C(26)ϪC(25)ϪP(4) 121.2(4)
C(32)ϪC(31)ϪP(4) 110.6(4)
In 7, the copper(I) center is coordinated in a distorted
tetrahedral fashion to four P atoms of two neutral chelating
bis(phosphane) ligands, PHPhCH2CH2SB(FH)SCH2CH2-
PPh(BϪP). The CuϪP bond lengths of the secondary phos-
phane groups [Cu(1)ϪP(2) 2.268(1), Cu(1)ϪP(4) 2.276(1)
˚
A] in 7 are slightly smaller than those of the other two
phosphane ligands [Cu(1)ϪP(1) 2.287(1), Cu(1)ϪP(3)
˚
2.295(1) A]. The PϪCuϪP bond angles of the chelating
phosphanes are large [P(4)ϪCu(1)ϪP(1) 115.26(5),
P(2)ϪCu(1)ϪP(3) 116.90(5)°], as is the P(2)ϪCu(1)ϪP(4) bis(diphosphane)CuI complexes to date], the bite angles of
bond angle [117.44(5)°]. The other PϪCuϪP angles range 115.26(5), 116.90(5)° are the largest observed so far. Di-
from 101.15(4) to 104.00(4)°.
nuclear CuI complexes with bridging bis(phosphane) li-
and bis(diphos- gands are generally formed when the chain length of the
[63]
Several (tetraphosphane)copper(I)
phane) complexes[64] have been structurally characterized bis(phosphane) increases to six [PPh2CH2(CH2)2CH2PPh2]
(Table 5). The CuϪP bond lengths are comparable with or eight atoms [PPh2CH2(CH2)4CH2PPh2].[64c]
those of 7, while the PϪCuϪP bite angle of the chelating
The bis(phosphane) ligands in 7 contain PϪB bonds, pre-
phosphanes is dependent on the ring size. Thus, five-mem- sumably formed by elimination of HF. The PϪB bond
˚
bered rings exhibit PϪCuϪP bond angles ranging from lengths of 1.872(4) and 1.877(5) A agree well with those of
88.3(1) to 90.9(1)°, while these angles are larger in other phosphanidoboranes of the general formula
[Cu(PPh2CH2CH2CH2PPh2)2]X, which has a six-membered R2BϪPRЈ2.[60] In 7, the BϪS bond lengths of 1.817(4)
ring [X ϭ ClO4: 94.56(9), 96.94(9)°;[64c] BF4: 97.66(5), [S(2)ϪB(1)], 1.844(5) [S(1)ϪB(1)], 1.821(5) [S(3)ϪB(2)] and
98.22(5)°[64a]]. In 7, which has a seven-membered ring [the 1.840(5) A [S(4)ϪB(2)] are in the range observed for
˚
largest chelate ring reported for structurally characterized thioboranes.[65]
2592
Eur. J. Inorg. Chem. 2001, 2587Ϫ2596

Titanocene Derivatives of 2-(Phosphanyl)ethanethiols
FULL PAPER
Table 5. Comparison of CuϪP bond lengths and PϪCuϪP bond angles in 7 and related bis(diphosphane)copper(I) complexes
˚
Complex
CuϪP [A]
PϪCuϪP bite angle [°]
115.26(5), 116.90(5)
88.3(1), 88.6(1)
89.6
Ref.
7
2.287(1), 2.268(1),
2.295(1), 2.276(1)
2.320(4), 2.305(4)
this work
[64h]
[Cu(PPh2CH2CH2PPh2)2]
[Cu(Mes)2]
[Cu(PPh2CH2CH2PPh2)2]2
[Cu6Fe4(CO)16]
[64g]
[64a]
[64f]
[64d]
[64b]
[64e]
[64c]
[64a]
2.285
[Cu(PPh2CH2CH2PPh2)2]ClO4
2.259(2), 2.301(2),
2.300(2), 2.270(2)
2.248(3), 2.250(3),
2.254(3), 2.248(3)
2.286(6), 2.280(7),
2.293(7), 2.277(7)
2.305(1), 2.324(1),
2.322(1), 2.320(1)
2.276(2), 2.288(2),
2.289(2), 2.287(2)
2.316(3), 2.312(3)
2.311(3), 2.330(2)
2.303(1), 2.298(1)
2.296(1), 2.317(1)
90.34(7), 90.58(7)
90.9(1)
[Cu(PMe2CH2CH2PMe2)2]
[Cu{Co(CO)4}2]
[Cu(PMe2CH2CH2PMe2)2][CpTi(SCH2CH2S)2]
90.5(2)
[CuL12]PF6
91.68(4), 91.26(4)
89.69(7), 89.90(7)
94.56(9), 96.94(9)
97.66(5), 98.22(5)
[a]
[Cu(PPh2CHϭCHPPh2)2]PF6
[Cu(PPh2CH2CH2CH2PPh2)2]ClO4
[Cu(PPh2CH2CH2CH2PPh2)2]BF4
[a]
L1 ϭ 2,3-bis(diphenylphosphanyl)maleic anhydride
IR [cmϪ1]: ν˜ ϭ 2564 m (νSH; ref.[4]: 2560 cmϪ1 ), 2285 vs (νPH;
ref.[4]: 2290 cmϪ1). Ϫ C8H11PS (170.2): calcd. C 56.45, H 6.51, S
18.8; found C 55.00, H 6.59, S 17.6.
We are presently further investigating the potential of
1Ϫ3 as thiolato- and/or phosphanido ligands in transition
metal chemistry.
Preparation of 2-(Mesitylphosphanyl)ethanethiol (2): MesPH2
(4.88 g, 32 mmol) was dissolved in degassed THF (250 mL), and
the solution cooled to Ϫ70 °C. BuLi (22 mL of a 1.48  solution,
32.6 mmol) in hexane was added dropwise over 30 min. The color
of the solution changed to turbid orange. After stirring for 1 h at
room temp., the solution was cooled again to Ϫ70 °C, and ethylene
sulfide (2 mL, 33.2 mmol) was added slowly. The color of the solu-
tion became clear yellow. After stirring for 30 min at room temp.,
about 0.8 mL of degassed water was added. The solution turned
turbid white due to the formation of LiOH, which was filtered off.
The solvent was then evaporated, and the colorless viscous residue
distilled to give 2 (4.3 g, 63%, b.p. 100 °C/10Ϫ2.5 Torr). Ϫ EI MS:
Experimental Section
General: All experiments were carried out under purified dry argon.
Solvents were dried and freshly distilled under argon. Ϫ NMR
spectra: Avance DRX 400 (Bruker), standards: 1H NMR
(400 MHz): trace amounts of protonated solvent, C6D6; 13C NMR
(100.6 MHz): internal solvent; 31P NMR (162 MHz): external 85%
H3PO4. Ϫ The IR spectra were recorded as KBr mulls with a
PerkinϪElmer FT-IR spectrometer System 2000 in the range
350Ϫ4000 cmϪ1. Ϫ The mass spectra were recorded with a Sektor-
feldgerät AMD 402 (AMD Intectra GmbH; EI, 70 eV). Ϫ The
melting points were determined in sealed capillaries under argon
m/z (%) ϭ 212 (84) [Mϩ], 208 (8) [Mϩ Ϫ 2 H2], 179 (47) [Mϩ
Ϫ
SH], 151 (73) [PHMesϩ], and fragments thereof. Ϫ IR [cmϪ1]: ν˜ ϭ
2560 m (νSH), 2334 vs (νPH). Ϫ C11H17PS (212.3): calcd. C 62.23,
H 8.67; found C 61.9, H 8.21.
and are uncorrected. RPH2 (R ϭ Ph,[66] Mes,[67] Tipp[13]), and
[68]
[Cu(CH3CN)4]BF4
were prepared according to literature pro-
Preparation of 2-(Triisopropylphenylphosphanyl)ethanethiol (3):
TippPH2 (5.18 g, 22 mmol) was dissolved in degassed THF (250
mL), and the solution cooled to Ϫ70 °C. BuLi (18.7 mL of a 1.17
 solution, 22 mmol) in hexane was added dropwise over a period
cedures. [Cp2TiCl2] and ethylene sulfide are commercially avail-
able (Aldrich).
Preparation of 2-(Phenylphosphanyl)ethanethiol (1): PhPH2 (5 mL,
45 mmol) was dissolved in degassed THF (250 mL) and cooled to of 30 min. The color of the solution changed to yellow, and LiPH-
Ϫ70 °C. BuLi (30.7 mL of a 1.48  solution, 45 mmol) in hexane Tipp precipitated from the solution. This was isolated by filtration
was added dropwise over 30 min. The color of the solution changed (3 g, 57.2%, confirmed by 31P NMR[13]). LiPHTipp (2 g,
to turbid orange. After stirring for 1 h at room temp., the solution
8.35 mmol) was then dissolved in THF (200 mL), and the solution
was cooled again to Ϫ70 °C, and ethylene sulfide (3 mL,
cooled to Ϫ70 °C. Ethylene sulfide (0.5 mL, 8.39 mmol) was added
49.9 mmol) was added slowly. The color of the solution became slowly. The color of the solution became light yellow. After stirring
clear yellow. After stirring for 30 min at room temp., about 2 mL for 30 min at room temp., about 0.2 mL of degassed water was
of degassed water was added. The solution turned turbid white due
to the formation of LiOH, which was filtered off. The solvent was
then evaporated, and the colorless viscous residue distilled to give
added, and the solution turned turbid white due to the formation
of LiOH, which was filtered off. The solvent was then evaporated,
and the colorless viscous residue distilled to give 3 (2.1 g, 83%, b.p.
1 (5.4 g, 70%, b.p. 46 °C/10Ϫ3 Torr; ref.[4]: b.p. 135Ϫ137 °C/10 113 °C/10Ϫ3 Torr). Ϫ EI MS: m/z (%) ϭ 296 (19) [Mϩ], 263 (100)
Torr). Ϫ EI MS: m/z (%) ϭ 170 (57) [Mϩ], 142 (14) [Mϩ Ϫ 2 CH2], [Mϩ Ϫ SH], 235 (17) [PHTippϩ], and fragments thereof. Ϫ
137 (82) [Mϩ Ϫ SH], 109 (100) [PHPhϩ], and fragments thereof. Ϫ
C17H29PS (296.4): calcd. C 68.88, H 9.86; found C 69.30, H 9.96.
Eur. J. Inorg. Chem. 2001, 2587Ϫ2596
2593

S. Chaudhury, S. Blaurock, E. Hey-Hawkins
FULL PAPER
Preparation of [Cp2Ti(SCH2CH2PHPh)2] (4): PhPHCH2CH2SH changed from red to purple. (Et3NH)Cl was separated by filtration.
(0.60 g, 3.5 mmol) was added to a solution of [Cp2TiCl2] (0.35 g, The solvent was removed from the filtrate in vacuum. The oily
1.4 mmol) in THF (25 mL). A solution of triethylamine (0.9 mL, residue was dissolved in 25 mL hexane and filtered. The resulting
6.4 mmol) in THF (25 mL) was added dropwise over 30 min. The oily residue was recrystallized repeatedly from hexane. However,
solution was stirred for 24 h during which its color changed from
the NMR spectra showed the presence of an impurity of 3, which
red to purple. (Et3NH)Cl was removed by filtration, and the solvent could not be eliminated by recrystallization or heating to ca. 113
was removed from the filtrate in vacuum. The oily residue was °C at 10Ϫ3 Torr (decomp. of 6 occurred).
washed three times with 10 mL of hexane, then recrystallized from
toluene/hexane to give 4 as a viscous oil. Yield: 0.65 g (90%). NMR
spectra showed that there is a minor impurity of 1 present which
could not be eliminated by recrystallization or heating to ca. 46 °C
at 10Ϫ3 Torr (decomp. of 4 occurred). Ϫ EI MS: m/z (%) ϭ 347 (9)
[Mϩ Ϫ SCH2CH2PHPh], 109 (52) [PHPhϩ], and fragments thereof.
Reaction of [Cu(CH3CN)4BF4] with [Cp2Ti(SCH2CH2PHPh)2] (4):
A solution of 4 (0.18 g, 0.35 mmol) in acetonitrile (20 mL) was
added dropwise to
a solution of [Cu(CH3CN)4]BF4 (0.11 g,
0.35 mmol) in acetonitrile (10 mL). The solution was stirred over-
night, after which it was concentrated under vacuum, and diethyl
ether was added. A brownish solid precipitated. This was isolated,
dissolved in CH2Cl2, layered with hexane and then connected to
another flask containing toluene. Some yellow crystals formed over
a black residue. The yellow crystals were isolated.
Ϫ IR [cmϪ1]: ν ϭ 2281 vs (νPH).
˜
Preparation of [Cp2Ti(SCH2CH2PHMes)2] (5): MesPHCH2CH2SH
(1.1 g, 5.1 mmol) was added to a solution of [Cp2TiCl2] (0.59 g,
2.3 mmol) in THF (25 mL). A solution of triethylamine (1.0 mL,
7.1 mmol) in THF (25 mL) was added dropwise over 30 min. The
solution was stirred for 24 h during which its color changed from
red to purple. (Et3NH)Cl was separated by filtration. The solvent
was removed from the filtrate in vacuum. The oily residue was dis-
solved in 25 mL hexane and filtered. At room temperature, crystals
of 5 formed. Yield: 0.45 g (32%), m.p. 105Ϫ108 °C. Ϫ EI MS: m/
z (%) ϭ 600 (2) [Mϩ], 389 (17) [Mϩ Ϫ SCH2CH2PHMes], 212 (57)
[HSCH2CH2PHMesϩ], 178 (32) [Cp2Tiϩ], 152 (58) [PH2Mesϩ], 119
(100) [Mesϩ], and fragments thereof. Ϫ C32H42P2S2Ti (600.62):
calcd. C 63.99, H 7.05, S 10.68; found C 63.9, H 6.57, S 10.5.
Data Collection and Structural Refinement of 5 and 7: Crystallo-
˚
graphic data are given in Table 6. Data [λ(Mo-Kα) ϭ 0.71073 A]
were collected with a Siemens CCD (SMART) diffractometer. All
observed reflections were used for the determination of the unit
cell parameters. Empirical absorption correction with SADABS.[69]
The structures were solved by direct methods (SHELXTL
PLUS[70]). Restrictions for 5: Zr, S, P, and C atoms anisotropic;
restrictions for 7: Cu, P, B, F, S, and C atoms anisotropic; H atoms
located by difference maps and refined isotropically. Crystallo-
graphic data (excluding structure factors) for the structures re-
Preparation of [Cp2Ti(SCH2CH2PHTipp)2] (6). TippPHCH2- ported in this paper have been deposited with the Cambridge Crys-
CH2SH (1.03 g, 3.4 mmol) was added to a solution of [Cp2TiCl2]
(0.39 g, 1.5 mmol) in THF (25 mL). A solution of triethylamine
tallographic Data Centre (5: CCDC-159594; 7: CCDC-159593).
Copies of the data can be obtained free of charge on application
(1.0 mL, 7.1 mmol) in THF (25 mL) was added dropwise over to CCDC, 12 Union Road, Cambridge, CB2 1EZ, UK [Fax: (in-
30 min. The solution was stirred for 24 h during which its color ternat.) ϩ 1223/336-033; E-mail: deposit@ccdc.cam.ac.uk].
Table 6. Crystal data and structure refinement for 5 and 7
5
7
Empirical formula
Mr
C32H42P2S2Ti
600.62
220(2)
C32H40B3CuF6P4S4·CH2Cl2
971.66
220(2)
monoclinic
P21/n
10.7405(2)
20.1003(5)
20.3827(6)
90
97.289(1)
90
4364.8(2)
4
Temperature [K]
Crystal system
Space group
triclinic
¯
P1
˚
a [A]
12.9752(2)
15.5545(2)
17.2252(1)
65.836(1)
89.180(1)
84.942(1)
3158.57(7)
4[a]
˚
b [A]
˚
c [A]
α [°]
β [°]
γ [°]
3
˚
V [A ]
Z
ρcalcd. [Mg mϪ3
F(000)
]
1.263
1272
1.479
1984
Crystal size [mm]
Abs. coeff. [mmϪ1
2Θmax [°]
0.50 ϫ 0.40 ϫ 0.20
0.524
56.0
0.50 ϫ 0.40 ϫ 0.30
1.012
55.1
]
Refl. collected
18002
23877
Independent reflections
Rint
Parameters
12971
0.0354
955
9090
0.0412
683
R [I Ͼ 2σ(I)]
wR2 (all data)
0.0398
0.0951
0.373
Ϫ0.359
0.0566
0.1740
0.993
Ϫ3
˚
(∆/ρ)min. [e·A
]
]
Ϫ3
˚
(∆/ρ)max. [e·A
Ϫ0.833
[a]
Both diastereomers are present in the asymmetric unit.
2594
Eur. J. Inorg. Chem. 2001, 2587Ϫ2596

Titanocene Derivatives of 2-(Phosphanyl)ethanethiols
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S. C. thanks the Department of Science and Technology (DST)
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