Syntheses and characterization of new tertiary phosphane ligands prepared from p-anisyl- and p-thioanisyldichlorophosphanes

Article abstract of DOI:10.1002/(SICI)1099-0682(199908)1999:8<1253::AID-EJIC1253>3.0.CO;2-H

The syntheses and spectroscopic parameters of the new tertiary phosphane ligands (p-MeOC₆H₄)(o-MeOC₆H₄)₂P (1), (p-MeOC₆H₄)(o-MeSC₆H₄)₂P (2), (p-M

Full text of DOI:10.1002/(SICI)1099-0682(199908)1999:8<1253::AID-EJIC1253>3.0.CO;2-H

FULL PAPER
Syntheses and Characterization of New Tertiary Phosphane Ligands
Prepared from p-Anisyl- and p-Thioanisyldichlorophosphanes
Riitta H. Laitinen,*[a] Helena Riihimäki,[a] Matti Haukka,[b] Sirpa Jääskeläinen,[b]
Tapani A. Pakkanen,[b] and Jouni Pursiainen[a]
Keywords: Phosphane ligands / 31P-NMR spectrometry / Substituent increments / Electronic and steric properties
The syntheses and spectroscopic parameters of the new
tertiary phosphane ligands (p-MeOC6H4)(o-MeOC6H4)2P (1),
(p-MeOC6H4)(o-MeSC6H4)2P (2), (p-MeSC6H4)(o-MeSC6H4)2P been determined. The dependence of the 31P-NMR chemical
H4)2P (5), and (p-MeSC6H4)(o-NC5H4)2P (6) are reported.
Single-crystal X-ray structures of all the compounds (1–6) have
(3), (p-MeSC6H4)(o-MeOC6H4)2P (4), (p-MeOC6H4)(o-NC5-
shifts on the substituent groups of the phosphanes is discussed.
phosphanes. FriedelϪCrafts reaction of phosphorus tri-
chloride with anisole or thioanisole in the presence of alu-
minium chloride as catalyst furnished the desired aryldich-
lorophosphanes.[8] These were then allowed to react with
ortho-substituted organolithium compounds, which were
obtained by halogenϪmetal interchange reactions.[9] Or-
ganolithium compounds bearing anisyl-, thioanisyl-, and
pyridyl groups were employed in order to modify the func-
tionality of the new ligands. These groups induce both
steric and electronic changes in the phosphane ligands. The
ligands thus obtained, bearing o-anisyl and o-thioanisyl
substituent groups, are potentially tridentate. However, ex-
perimental findings indicate that the o-thioanisyl ligands
behave as bidentate ligands in metal complexes,[10] while the
o-anisyl ligands behave mainly as monodentate li-
gands.[11][12] The o-pyridyl ligands are also potentially tri-
dentate, but in fact form either monodentate complexes or
behave as bridging ligands so as to form bimetallic coordi-
nation compounds.[13][14] The introduction of pyridyl
groups can also have a modifying effect on the solubilities
of phosphanes and their complexes.[15]
Introduction
Aromatic tertiary phosphanes, such as triphenylphos-
phane, are important ligands that find widespread use in
homogeneous organometallic catalysts. They stabilize the
low oxidation states of the metal centers and can be used
to modify both the electronic and steric properties of the
catalysts. The incorporation of substituents at the ortho-,
meta-, or para-positions of the aromatic rings offers a me-
ans of tailoring the properties of the ligands. Such substitu-
ents affect both the metalϪphosphorus bond lengths and
the associated angles.[1]
Ways of quantifying the electronic and steric properties
of phosphanes have been extensively studied since 1970.
TolmanЈs electronic and steric parameters (ν and θ, respec-
tively) have formed the basis for these studies over the last
30 years.[1,2,3] The improvements in NMR techniques and
molecular modelling have introduced new possibilities for
delineating the properties of phosphanes.[4,5,6,7]
In the present study, we have prepared and characterized
a series of new ligands derived from p-anisyl- and p-thioani-
syldichlorophosphanes. The ligands have been designed
with a view to modifying triphenylphosphane by introduc-
ing heteroatoms at various positions on the phenyl rings.
This should allow different coordination modes in metal
complexes. The electronic and steric properties of these li-
gands, assessed on the basis of their experimental 31P-NMR
shifts and crystal structures, are discussed.
31P-NMR Spectra
The behaviour of phosphanes as ligands is dependent on
the electron-donating and -accepting properties of the phos-
phorus atom. The catalytic properties of phosphanes are,
for example, regulated by the basicities of these ligands. 31P-
NMR spectrometry is an important tool for obtaining in-
formation concerning the chemical nature of the phos-
phorus atom. The 31P-NMR chemical shifts have been
shown to be dependent on the R groups of a phosphane
PR3.[16][17] Indeed, the chemical shifts of tertiary phos-
phane ligands can be estimated empirically (Equation
1):[16]
Results and Discussion
Syntheses
The new mixed ortho/para-substituted tertiary phosphane
ligands were prepared from para-substituted aryldichloro-
[a]
Department of Chemistry, University of Oulu,
P. O. Box 3000, FIN-90401 Oulu, Finland
Fax: (internat.) ϩ 358-8/552-1603
E-mail: Riitta.Laitinen@oulu.fi
[b]
Department of Chemistry, University of Joensuu,
P. O. Box 111, FIN-80101 Joensuu, Finland
Eur. J. Inorg. Chem. 1999, 1253Ϫ1258
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 1999
1434Ϫ1948/99/0808Ϫ1253 $ 17.50ϩ.50/0
1253

R. H. Laitinen et al.
FULL PAPER
Here, σP values are increments that are characteristic for pair on phosphorus on the chemical shift, which allows the
each substituent group. The reference value corresponds to electronic effects to dominate. However, it seems that within
PMe3 (δ ϭ Ϫ62 vs. 85% H3PO4).
certain chemically related groups of phosphanes, a relation-
The increments (σP) for the various substituent groups ship between 31P-NMR shifts and basicity can be found.
incorporated in the new tertiary phosphane ligands re- For example, the values for trialkylphosphanes correlate
ported herein can be calculated from the published 31P- quite well: P(tBu)3: ν(CO) ϭ 2056.1 cmϪ1 vs. δ ϭ 63;
NMR chemical shifts (Table 1). In these ligands, all three P(iPr)3: ν(CO) ϭ 2059.2 cmϪ1 vs. δ ϭ 19.4; PEt3: ν(CO) ϭ
substituent groups are similar. On using the aforementioned 2061.7 cmϪ1 vs. δ ϭ Ϫ20.0; PMe3: ν(CO) ϭ 2064.1 cmϪ1
increments to calculate theoretical 31P-NMR chemical vs. δ ϭ Ϫ62.[2][3]
shifts for the six new ligands prepared in this work, a rela-
A similar kind of correlation, although of opposite direc-
tively good agreement with the experimental values is ob- tion, can be noted in the series of anisyl-substituted phos-
served (Table 2). This indicates that with information on phane ligands. ν(CO) values of these ligands can be calcu-
the substituent increments at hand, the electronic properties lated by using the substituent contributions of o-C6H4-
of the phosphane can be predicted with reasonable accu- OCH3 (0.9 cmϪ1) and p-C6H4OCH3 (3.4 cmϪ1) reported
racy. This helps in the targeted modification of the phos- by Tolman.[2] When the experimental 31P-NMR shifts are
phanes towards known applications.
compared with these calculated ν(CO) values, a reasonably
good agreement is seen: (o-MeOC6H4)3P: ν(CO) ϭ 2058.8
cmϪ1 vs. δ ϭ Ϫ37.1; (p-MeOC6H4)(o-MeOC6H4)2P: ν(CO) ϭ
2061.3 cmϪ1 vs. δ ϭ Ϫ27.7; (p-MeOC6H4)3P: ν(CO) ϭ 2066.3
cmϪ1 vs. δ ϭ Ϫ10.2.
Table 1. Increments of substituted phenyl groups
Ligand
Empirical shift [ppm] σP increment [ppm]
The fairly good correlation of ν(CO) values and 31P-
NMR shifts in these examples suggests that 31P-NMR
chemical shifts give adequately reliable information con-
cerning the basicities of closely related phosphane ligands.
Therefore, the basicity order of the new ligands should be
6 > 5 > 3 > 2 > 4 > 1. This order is also supported by
the observation that electron-donating substituents increase
while electron-withdrawing substituents decrease the basic
strengths of the ligands.[2][24]
(o-MeSC6H4)3P
(p-MeSC6H4)3P
(o-MeOC6H4)3P
(p-MeOC6H4)3P
(o-NC5H4)3P
Ϫ30.2[18]
10.60
Ϫ8.3[19]
17.90
Ϫ37.1[18], Ϫ38.5[19]
Ϫ10.2[19], Ϫ9.60[20]
Ϫ1.3[21]
8.30, 7.83
17.27, 17.47
20.23
Table 2. Comparison of empirical and theoretical 31P-NMR shifts
of the new ligands
Ligand
Empirical shift [ppm]
Theoretical shift [ppm]
1
2
3
4
5
6
Ϫ27.7
Ϫ23.1
Ϫ21.1
Ϫ25.9
Ϫ2.3
Ϫ28.13
Ϫ23.53
Ϫ22.90
Ϫ27.50
Ϫ4.27
Molecular Structures
The X-ray crystal structures of all six ligands are essen-
tially very similar. There are no significant differences in
bond lengths or bond angles between the ligands. For ex-
ample, the CϪP bond lengths all fall within a range of just
Ϫ1.6
Ϫ3.64
Tolman[2] has estimated the electron-donating properties
of tertiary phosphanes by measuring the IR frequencies of
the carbonyl groups in Ni(CO)3(PR3). The frequencies ob-
tained with various ligands were compared to that with tri-
tert-butylphosphane, which proved to be the most basic li-
gand in the series. Based on the experimental results, Tol-
man calculated the substituent contributions (χi) of various
attached groups. The relationship can be expressed empiri-
cally by Equation 2:
˚
0.025 A. Similarly, the variations in the CaromϪO, Cme-
thylϪO, CaromϪS, and CmethylϪS bond lengths are relatively
small: 0.017, 0.021, 0.023, and 0.055 A, respectively. Fur-
˚
thermore, the relative orientation of the MeO or MeS
groups does not seem to have a systematic effect on the
bond lengths. The small geometrical variations suggest that
the structural impact of the ortho or para groups or the
pyridyl ring on the overall form of the ligands is only minor.
The X-ray crystal structures of the ligands 2 and 6 are pre-
sented in Figures 1 and 2.
The steric effects of phosphanes as ligands are often ex-
pressed in terms of the Tolman cone angles θ.[1][3] These
Here, the frequency 2056.1 cmϪ1 is that seen with tri-tert- are estimated by assuming an average MϪP bond length of
˚
butylphosphane attached to Ni. The larger the χi value, the 2.28 A. Substituent groups in the para positions of the aryl
less basic the ligand.
rings do not significantly influence the steric properties of
Tolman and Allman recognized that there is no general the ligands. This is illustrated by the similar cone angles
correlation between basicity and 31P-NMR chemical shifts found for PPh3 and (pTol)3P, both θ ϭ 145°.[1] Of the li-
of phosphane ligands.[3][22] However, the basicities of the gands prepared in this work, (p-MeOC6H4)(o-NC5H4)2P (5)
corresponding phosphane oxides have been shown to be di- and (p-MeSC6H4)(o-NC5H4)2P (6) should therefore re-
rectly related to the 31P-NMR chemical shifts.[23] Phos- semble PPh3 from a steric point of view. The four other
phane oxides were chosen to minimize the effect of the lone ligands (p-MeOC6H4)(o-MeOC6H4)2P (1), (p-MeOC6H4)(o-
1254
Eur. J. Inorg. Chem. 1999, 1253Ϫ1258

Syntheses and Characterization of New Tertiary Phosphane Ligands
FULL PAPER
Scheme 1. Schematic structures of the reported ligands; numbering corresponds to the NMR data
ogous to (o-MeOC6H4)2PPh and (o-MeSC6H4)2PPh li-
gands. The steric requirements of these ligands are affected
by the conformations of the o-anisyl and o-thioanisyl
groups, and therefore the cone angles may not have strictly
defined values. The cone angles of these ligands have not
been determined
Experimental Section
The ligands were characterized mainly on the basis of 1H-, 13C-,
and 31P-NMR data. NMR spectra were recorded on Bruker
AM200 and Bruker DPX400 spectrometers. 1H- and 13C-NMR
spectra were referenced to TMS; 31P-NMR spectra to 85% H3PO4.
Ϫ Elemental analyses were carried out on a PerkinϪElmer 2400
Series II CHNS/O analyzer. Ϫ Exact mass peaks were measured
on a Kratos MS-80 spectrometer. Ϫ X-ray crystal structures were
determined with either an EnrafϪNonius Kappa-CCD or a Nicolet
R3m diffractometer. Ϫ Commercial reagents were used without
further purification. Diethyl ether was distilled from sodium/benzo-
phenone ketyl under nitrogen prior to use. Standard Schlenk tech-
niques were used for the syntheses.
Figure 1. X-ray crystal structure of (p-MeOC6H4)(o-MeSC6H4)2P
(2)
Starting Materials: p-Anisyldichlorophosphane and p-thioanisyld-
ichlorophosphane were prepared according to a published pro-
cedure for p-anisyldichlorophosphane.[25][26] The reaction time for
the preparation of p-thioanisyldichlorophosphane was extended to
90 h. p-Anisyldichlorophosphane was collected at 98Ϫ100°C/0.3
Torr; p-thioanisyldichlorophosphane at 125Ϫ126°C/0.15 Torr.
(p-Methoxyphenyl)bis(o-methoxyphenyl)phosphane (1): o-Bromoan-
isole (1.0 g, 0.7 mL, 5.4 mmol) was lithiated with n-butyllithium
(nBuLi) (2.2 mL, 2.5  in hexane, 5.4 mmol) in sodium-dried di-
ethyl ether (Et2O) (20 mL) at 0°C. The mixture was stirred for 1 h
at 0°C, and then a solution of p-anisyldichlorophosphane (0.6 g,
2.7 mmol) in Et2O (15 mL) was added. The resulting mixture was
stirred for a further 1 h at 0°C and the precipitate formed was
filtered off and dried in vacuo. The product (0.5 g, 1.5 mmol,
55.1%) was recrystallized from ethanol. Single crystals suitable for
Figure 2. X-ray crystal structure of (p-MeSC6H4)(o-NC5H4)2P (6)
MeSC6H4)2P (2), (p-MeSC6H4)(o-MeSC6H4)2P (3), and (p-
MeSC6H4)(o-MeOC6H4)2P (4) should be sterically anal- X-ray crystallographic analysis were obtained by slow evaporation
Eur. J. Inorg. Chem. 1999, 1253Ϫ1258 1255

R. H. Laitinen et al.
FULL PAPER
1
2
of the solvents from a dichloromethane/hexane solution at Ϫ20°C.
2 C, C9), 136.8 (d, JCϪP ϭ 8.7 Hz, 2 C, C1), 143.5 (d, JCϪP
ϭ
M.p. 146Ϫ149°C. Ϫ C21H21O3P: calcd. C 71.6, H 6.0; found C 27.6 Hz, 2 C, C2), 160.5 (s, 1 C, C10). Ϫ 31P{1H} NMR (162 MHz,
71.7, H 6.0. Ϫ 1H NMR (400 MHz, CDCl3): δ ϭ 3.7 (s, 6 H, H11), CDCl3): δ ϭ Ϫ23.1 (s).
3
3
3.8 (s, 3 H, H12), 6.7 (dd, JHϪH ϭ 6.0 Hz, JHϪP ϭ 2.2 Hz, 2 H,
(p-Thiomethylphenyl)bis(o-thiomethylphenyl)phosphane (3): o-Bro-
mothioanisole (2.0 g, 1.3 mL, 9.8 mmol) was lithiated with nBuLi
(3.9 mL, 2.5  in hexane, 9.8 mmol) in sodium-dried diethyl ether
(30 mL) at 0°C. The mixture was stirred for 2 h at 0°C, and then
a solution of p-thioanisyldichlorophosphane (1.1 g, 4.9 mmol) in
Et2O (20 mL) was added. The resulting mixture was stirred for a
further 2 h at 0°C and the precipitate formed was filtered off and
dried in vacuo. The product (0.9 g, 2.2 mmol, 45.0%) was twice
recrystallized, first from ethanol/toluene and then from hexane/
ethanol. Crystals were used for X-ray crystallographic analysis
without further crystallization. M.p. 144°C. Ϫ C21H21PS3: calcd.
C 63.0, H 5.3, S 24.0; found C 62.9, H 5.4, S 24.0. Ϫ 1H NMR
(200 MHz, CDCl3): δ ϭ 2.4 (s, 6 H, H11), 2.5 (s, 3 H, H12), 6.7 (dd,
3JHϪH ϭ 7.3 Hz, 2 H, H6), 7.1 (m, 2 H, H5), 7.2 (m, 4 H, H8 and
H9), 7.3 (m, 4 H, H3 and H4). Ϫ 13C{1H} NMR (50 MHz, CDCl3):
H6), 6.8 (m, 6 H, H3, H5, and H9), 7.2 (t, JHϪH ϭ 7.6 Hz, 2 H,
3
H8), 7.3 (t, JHϪH 7.7 Hz, 2 H, H4). Ϫ 13C{1H} NMR (100 MHz,
3
CDCl3): δ ϭ 55.1 (s, 1 C, C12), 55.6 (s, 2 C, C11), 110.1 (s, 2 C, C3),
113.9 (d, JCϪP ϭ 7.9 Hz, 2 C, C8), 120.8 (s, 2 C, C5), 125.7 (d,
2
1JCϪP ϭ 12.3 Hz, 2 C, C1), 126.8 (d, JCϪP ϭ 6.9 Hz, 1 C, C7),
1
130.0 (s, 2 C, C4), 133.5 (s, 2 C, C6), 135.6 (d, JCϪP ϭ 22.5 Hz, 2
3
C, C9), 160.1 (s, 1 C, C10), 161.2 (d, JCϪP ϭ 15.9 Hz, 2 C, C2). Ϫ
2
31P{1H} NMR (162 MHz, CDCl3): δ ϭ Ϫ27.7 (s).
(p-Methoxyphenyl)bis(o-thiomethylphenyl)phosphane (2): o-Bromo-
thioanisole (2.0 g, 1.3 mL, 9.8 mmol) was lithiated with nBuLi
(3.9 mL, 2.5  in hexane, 9.8 mmol) in sodium-dried diethyl ether
(20 mL) at 0°C. The mixture was stirred for 2 h at 0°C, and then
a solution of p-anisyldichlorophosphane (1.0 g, 4.9 mmol) in Et2O
(20 mL) was added. The resulting mixture was stirred for a further
2 h at 0°C and the precipitate formed was filtered off and dried in
vacuo. The product (1.1 g, 2.9 mmol, 59.2%) was recrystallized
from ethanol/toluene. Single crystals suitable for X-ray crystallo-
graphic analysis were obtained by slow evaporation of the solvents
from a dichloromethane/hexane solution. M.p. 155Ϫ157°C. Ϫ
C21H21OPS2: calcd. C 65.6, H 5.5, S 16.7; found C 65.5, H 5.5, S
16.3. Ϫ 1H NMR (200 MHz, CDCl3): δ ϭ 2.4 (s, 6 H, H11), 3.8 (s,
δ ϭ 15.1 (s, 1 C, C12), 17.3 (d, JCϪP ϭ 8.7 Hz, 2 C, C11), 125.3 (s,
4
2
3
2 C, C5), 126.1 (d, JCϪP ϭ 8.7 Hz, 2 C, C8), 126.8 (d, JCϪP
ϭ
4.4 Hz, 2 C, C3), 129.3 (s, 2 C, C4), 131.3 (d, JCϪP ϭ 10.2 Hz, 1
1
C, C7), 133.3 (s, 2 C, C6), 134.7 (d, JCϪP ϭ 20.3 Hz, 2 C, C9),
3
136.2 (d, JCϪP ϭ 10.2, 2 C, C1), 140.0 (s, 1 C, C10), 143.7 (d,
1
2JCϪP ϭ 29.1 Hz, 2 C, C2). Ϫ 31P{1H} NMR (162 MHz, CDCl3):
δ ϭ Ϫ21.1 (s).
3
3 H, H12), 6.7 (dd, JHϪH ϭ 7.5 Hz, 3JHϪP ϭ 3.8 Hz, 2 H, H6), 6.9
3
3
(d, JHϪH ϭ 7.7 Hz, 2 H, H9), 7.1 (m, 2 H, H5), 7.2 (t, JHϪH
ϭ
(p-Thiomethylphenyl)bis(o-methoxyphenyl)phosphane (4): o-Bromo-
anisole (1.9 g, 1.2 mL, 9.8 mmol) was lithiated with nBuLi (3.9 mL,
7.8 Hz, 2 H, H8), 7.3 (m, 4 H, H3 and H4). Ϫ 13C{1H} NMR
(50 MHz, CDCl3): δ ϭ 17.3 (d, JCϪP ϭ 8.7 Hz, 2 C, C11), 55.1 (s, 2.5  in hexane, 9.8 mmol) in sodium-dried diethyl ether (30 mL)
4
2
1 C, C12), 114.4 (d, JCϪP ϭ 8.7 Hz, 2 C, C8), 125.3 (s, 2 C, C5),
at 0°C. The mixture was stirred for 1 h at 0°C, and then a solution
125.9 (d, JCϪP ϭ 7.3 Hz, 1 C, C7), 126.8 (d, JCϪP ϭ 4.4 Hz, 2 C, of p-thioanisyldichlorophosphane (1.1 g, 4.9 mmol) in Et2O (20
1
3
C3), 129.2 (s, 2 C, C4), 133.1 (s, 2 C, C6), 136.1 (d, 3JCϪP ϭ 23.2 Hz,
mL) was added. The resulting mixture was stirred for a further 2
Table 3. Crystallographic data
Ligand
1
2
3
4
5
6
Chemical formula
C21H21O3P
352.35
C21H21OPS2
384.47
C21H21PS3
400.53
C21H21O2PS
368.41
C17H15N2OP
294.28
C17H15N2PS
310.34
Molecular weight [g molϪ1
]
Crystal size [mm]
0.2 ϫ 0.2 ϫ 0.2 0.3 ϫ 0.3 ϫ 0.3 0.1 ϫ 0.1 ϫ 0.3 0.4 ϫ 0.4 ϫ 0.2 0.4 ϫ 0.4 ϫ 0.2 0.3 ϫ 0.3 ϫ 0.2
Color
Colorless
Monoclinic
P21/c
Colorless
Monoclinic
P21/c
Colorless
Triclinic
P-1
Colorless
Triclinic
P-1
Colorless
Monoclinic
P21/n
Colorless
Monoclinic
P21/c
Crystal system
Space group
Unit cell dimensions [°]
a [nm]
b [nm]
c [nm]
α [°]
7.678(2)
30.928(6)
7.780(2)
90
8.002(2)
14.917(3)
16.304(3)
90
8.083(2)
10.110(2)
13.454(3)
72.09(3)
74.97(3)
82.52(3)
1008.9(4)
2
8.357(2)
11.126(2)
11.786(2)
103.57(3)
107.60(3)
104.49(3)
952.5(3)
2
8.300(2)
10.944(2)
16.967(3)
90
9.406(2)
9.350(2)
17.877(4)
90
β [°]
102.45(3)
90
92.63(3)
90
100.84(3)
90
98.50(3)
90
γ [°]
Volume [nm3]
Z
1804.1(6)
4
1.297
0.169
1944.1(7)
4
1.314
0.362
1513.7(5)
4
1.291
0.181
1554.9(6)
4
1.326
0.305
Densitycalcd. [Mg mϪ3
]
1.319
1.285
Absorption coefficient
0.448
0.265
µ [mmϪ1
F(000)
]
744
808
420
388
616
648
θ range [°]
2.72Ϫ24.99
Ϫ8 Ǟ 9
Ϫ36 Ǟ 29
Ϫ9 Ǟ 8
7645
2.50Ϫ25.00
0 Ǟ 9
0 Ǟ 17
Ϫ19 Ǟ 19
3749
3.03Ϫ25.00
Ϫ9 Ǟ 9
Ϫ12 Ǟ 12
Ϫ15 Ǟ 15
6761
2.01Ϫ28.22
Ϫ11 Ǟ 11
Ϫ13 Ǟ 14
Ϫ15 Ǟ 15
12254
3.07Ϫ26.00
Ϫ10 Ǟ 10
Ϫ13 Ǟ 13
Ϫ20 Ǟ 20
18305
2.46Ϫ26.00
0 Ǟ 11
0 Ǟ 11
Ϫ22 Ǟ 21
3047
h range
k range
l range
No. of collected reflns.
No. of unique reflns.
3068
3409
3488
4456
2952
3047
No. of obsd. reflns., I > 2σ(I) 2317
1404
2163
3894
2637
2705
No. of parameters
Final R indices I > 2σ(I)
wR2 I > 2σ(I)
227
227
227
227
235
190
0.0651
0.1586
1.094
120(2)
0.0730
0.1076
1.006
0.0551
0.1305
1.045
0.0523
0.1448
1.055
0.0371
0.0984
1.037
0.0333
0.0821
1.048
Goodness-of-fit
T [K]
293(2)
293(2)
293(2)
293(2)
293(2)
1256
Eur. J. Inorg. Chem. 1999, 1253Ϫ1258

Syntheses and Characterization of New Tertiary Phosphane Ligands
FULL PAPER
˚
Table 4. Selected bond lengths [A]
(1)
(2)
(3)
(4)
(5)
(6)
P(1)ϪC(1)
P(1)ϪC(7)
P(1)ϪC(13)
C(2)ϪS(1)
C(8)ϪS(2)
C(16)ϪS(3)
C(16)ϪO(3)
S(1)ϪC(19)
S(2)ϪC(20)
S(3)ϪC(21)
C(2)ϪO(1)
C(8)ϪO(2)
C(16)ϪS(3)
O(1)ϪC(19)
O(2)ϪC(20)
O(3)ϪC(21)
N(1)ϪC(1)
N(1)ϪC(5)
N(2)ϪC(7)
N(2)ϪC(11)
1.842(4)
1.834(4)
1.836(4)
1.842(6)
1.833(6)
1.826(6)
1.759(6)
1.768(6)
1.843(3)
1.838(3)
1.829(4)
1.759(4)
1.753(4)
1.762(4)
1.8332(16)
1.8283(17)
1.8352(17)
1.8395(16)
1.8392(16)
1.8194(16)
1.8373(16)
1.8439(17)
1.8288(16)
1.7763(19)
1.7613(17)
1.377(5)
1.366(7)
1.783(6)
1.769(6)
1.360(2)
1.795(4)
1.756(5)
1.740(5)
1.776(3)
1.365(2)
1.368(2)
1.7763(19)
1.423(2)
1.414(3)
1.780(2)
1.375(5)
1.369(5)
1.7613(17)
1.429(5)
1.435(5)
1.431(5)
1.426(7)
1.422(3)
1.345(2)
1.337(2)
1.343(2)
1.338(2)
1.351(2)
1.333(2)
1.347(2)
1.341(3)
Table 5. Selected bond angles [°]
(1)
(2)
(3)
(4)
(5)
(6)
C(1)ϪP(1)ϪC(7)
C(1)ϪP(1)ϪC(13)
C(7)ϪP(1)ϪC(13)
C(16)ϪO(3)ϪC(21)
C(16)ϪS(3)ϪC(21)
C(2)ϪO(1)ϪC(19)
C(8)ϪO(2)ϪC(20)
C(2)ϪS(1)ϪC(19)
C(8)ϪS(2)ϪC(20)
102.57(18)
101.8(3)
100.3(3)
103.4(3)
117.5(5)
102.74(15)
102.04(8)
103.03(7)
103.02(7)
103.57(7)
118.98(16)
102.52(7)
103.36(7)
100.63(7)
100.94(18)
102.60(18)
116.4(3)
100.74(15)
103.38(16)
101.12(8)
103.81(8)
103.7(2)
103.30(12)
118.54(17)
118.51(19)
104.77(10)
117.5(3)
117.5(3)
104.4(3)
104.5(3)
103.44(19)
105.6(2)
h at 0°C and then the precipitate formed was filtered off and dried tracted from the aqueous phase with diethyl ether. The solvent was
in vacuo. The product (1.1 g, 3.1 mmol, 62.0%) was recrystallized
from ethanol. Single crystals suitable for X-ray crystallographic
analysis were obtained by slow evaporation of the solvent from a
evaporated from the combined extracts and the oily crude product
was washed with methanol. The product (3.06 g, 10.4 mmol,
83.2%) was dried in vacuo. Single crystals were grown by vapor
dichloromethane solution. M.p. 151Ϫ152°C.
Ϫ C21H21O2PS: diffusion of hexane into a methanol/dichloromethane solution of
calcd. C 68.5, H 5.8, S 8.7; found C 68.0, H 5.5, S 9.1. Ϫ 1H NMR
the pyridylphosphane. M.p. 100Ϫ101°C. Ϫ 1H NMR (200 MHz,
(200 MHz, CDCl3): δ ϭ 2.5 (s, 3 H, H12), 3.7 (s, 6 H, H11), 6.7 (dd, CDCl3): δ ϭ 3.8 (s, 3 H, H12), 7.0 (d, JHϪH ϭ 8.5 Hz, 2 H, H9),
3
3JHϪH ϭ 7.3 Hz, 3JHϪP ϭ 1.7 Hz, 2 H, H6), 6.8 (t, 3JHϪH ϭ 7.7 Hz,
7.3 (m, 4 H, H6 and H8), 7.5 (t, JHϪH ϭ 7.3 Hz, 2 H, H4), 7.7 (t,
3
2 H, H5), 6.9 (t, 3JHϪH ϭ 5.1 Hz, 2 H, H3), 7.2 (d, 3JHϪH ϭ 4.3 Hz, 3JHϪH ϭ 7.7 Hz, JHϪP ϭ 1.7 Hz, 2 H, H5), 8.6 (m, 2 H, H3). Ϫ
4
3
4 H, H8 and H9), 7.3 (t, JHϪH ϭ 6.8 Hz, 2 H, H4). Ϫ 13C{1H} 13C{1H} NMR (50 MHz, CDCl3): δ ϭ 55.5 (s, 1 C, C12), 115.2 (d,
NMR (100 MHz, CDCl3): δ ϭ 15.2 (s, 1 C, C12), 55.7 (s, 2 C, C11), 2JCϪP ϭ 8.7 Hz, 2 C, C8), 123.1 (s, 2 C, C4), 127.0 (d, JCϪP
ϭ
1
1
2
110.2 (s, 2 C, C3), 120.9 (s, 2 C, C5), 125.1 (d, JCϪP ϭ 12.2 Hz, 2 7.3 Hz, 1 C, C7), 128.7 (d, JCϪP ϭ 18.9 Hz, 2 C, C6), 136.4 (d,
C, C1), 125.8 (d, 2JCϪP ϭ 7.0 Hz, 2 C, C8), 130.1 (s, 2 C, C4), 132.4
3JCϪP ϭ 2.9 Hz, 2 C, C5), 137.7 (d, JCϪP ϭ 23.2 Hz, 2 C, C9),
3
1
3
3
(d, JCϪP ϭ 9.7 Hz, 1 C, C7), 133.7 (s, 2 C, C6), 134.4 (d, JCϪP
ϭ
150.8 (d, JCϪP ϭ 11.6 Hz, 2 C, C3), 162.0 (s, 1 C, C10), 164.8 (d,
2
21.6 Hz, 2 C, C9), 139.1 (s, 1 C, C10), 161.3 (d, JCϪP ϭ 15.9 Hz, 2 1JCϪP ϭ 4.4 Hz, 2 C, C1). Ϫ 31P{1H} NMR (162 MHz, CDCl3):
C, C2). Ϫ 31P{1H} NMR (162 MHz, CDCl3): δ ϭ Ϫ25.9 (s).
δ ϭ Ϫ2.3 (s). Ϫ MS: Exact mass: 294.0886.
(p-Methoxyphenyl)bis(o-pyridyl)phosphane (5): A solution of nBuLi
(10 mL, 2.5  in hexane, 25 mmol) in sodium-dried diethyl ether
(p-Thiomethoxyphenyl)bis(o-pyridyl)phosphane (6): A solution of
nBuLi (4 mL, 2.5  in hexane, 10 mmol) in sodium-dried diethyl
(40 mL) was cooled to Ϫ100°C by means of an ethanol/liquid ni- ether (20 mL) was cooled to Ϫ100°C by means of an ethanol/liquid
trogen bath. A solution of o-bromopyridine (2.5 mL, 25 mmol) in
diethyl ether (30 mL) was then rapidly added and the mixture was
stirred for 1.5 h at Ϫ100°C. A solution of p-anisyldichlorophos-
nitrogen bath. A solution of o-bromopyridine (1.0 mL, 10 mmol)
in diethyl ether (20 mL) was then rapidly added and the mixture
was stirred for 75 min at Ϫ100°C. A solution of p-thioanisyldichlo-
phane (2.61 g, 12.5 mmol) in diethyl ether (30 mL) was then added rophosphane (1.13 g, 5 mmol) in diethyl ether (20 mL) was then
dropwise and stirring was continued at Ϫ100°C for 1 h. After
added dropwise and stirring was continued at Ϫ100°C for 1 h.
slowly warming to room temperature, the light-brown mixture was
After slowly warming to room temperature, the light-yellow mix-
extracted with H2SO4 (2 , 30 mL) and the aqueous layer was sepa- ture was extracted with H2SO4 (2 , 30 mL) and the aqueous layer
rated and made alkaline with NaOH. The crude product was ex-
was separated and made alkaline with NaOH. The white solid
1257
Eur. J. Inorg. Chem. 1999, 1253Ϫ1258

R. H. Laitinen et al.
FULL PAPER
[4]
C. J. Elsevier, B. Kowall, H. Kragten, Inorg. Chem. 1995, 34,
4836Ϫ4839.
S. Song, E. C. Alyea, Can. J. Chem. 1996, 74, 2304Ϫ2320.
T. L. Brown, K. J. Lee, Coord. Chem. Rev. 1993, 128, 89Ϫ116.
J. M. Smith, B. C. Taverner, N. J. Coville, J. Organomet. Chem.
1997, 530, 131Ϫ140.
J. A. Miles, M. T. Beeny, K. W. Ratts, J. Org. Chem. 1975, 40,
343Ϫ347.
R. G. Jones, H. Gilman, Org. React. 1951, 6, 339Ϫ356.
L. Hirsivaara, M. Haukka, S. Jääskeläinen, R. H. Laitinen, E.
Niskanen, T. A. Pakkanen, J. Pursiainen, J. Organomet. Chem.,
in press.
product was obtained by extraction of the aqueous phase with di-
ethyl ether. The product (0.60 g, 1.93 mmol, 38.7%) was dried in
vacuo. Single crystals were grown by vapor diffusion of hexane into
a methanol/dichloromethane solution of the pyridylphosphane.
M.p. 122Ϫ123°C. Ϫ 1H NMR (200 MHz, CDCl3): δ ϭ 2.5 (s, 3 H,
[5]
[6]
[7]
[8]
H12), 7.2 (m, 6 H, H6, H8, and H9), 7.4 (t, JHϪH ϭ 7.7 Hz, 2 H,
3
3
4
H4), 7.6 (t, JHϪH ϭ 7.7 Hz, JHϪP ϭ 1.9 Hz, 2 H, H5), 8.7 (d,
[9]
3JHϪH ϭ 4.7 Hz, 2 H, H3). Ϫ 13C{1H} NMR (50 MHz, CDCl3):
[10]
δ ϭ 14.8 (s, 1 C, C12), 123.3 (s, 2 C, C4), 126.5 (d, JCϪP ϭ 8.7 Hz,
2
2
1
2 C, C8), 128.9 (d, JCϪP ϭ 20.3 Hz, 2 C, C6), 132.3 (d, JCϪP
ϭ
[11]
[12]
L. Hirsivaara et al., to be published.
10.2 Hz, 1 C, C7), 136.2 (s, 2 C, C5), 136.6 (d, JCϪP ϭ 2.9 Hz, 2
3
K. R. Dunbar, J. S. Sun, S. C. Haefner, J. H. Matonic, Or-
ganometallics 1994, 13, 2713Ϫ2720.
C, C9), 142.0 (s, 1 C, C10), 150.9 (d, JCϪP ϭ 11.6 Hz, 2 C, C3),
3
[13]
[14]
[15]
[16]
1
164.1 (d, JCϪP ϭ 4.4 Hz, 2 C, C1). Ϫ 31P{1H} NMR (162 MHz,
J. P. Farr, M. M. Olmstead, A. L. Balch, J. Am. Chem. Soc.
1980, 102, 6654Ϫ6656.
CDCl3): δ ϭ Ϫ1.6 (s). Ϫ MS: Exact mass: 310.0727.
A. Maisonnet, J. P. Farr, M. M. Olmstead, C. T. Hunt, A. L.
Balch, Inorg. Chem. 1982, 21, 3961Ϫ3967.
X-ray Crystallography: X-ray diffraction data were collected with
an EnrafϪNonius Kappa-CCD (compounds 1 and 3؊6) or a Nico-
let R3m (compound 2) diffractometer using Mo-Kα radiation (λ ϭ
A. S. C. Chan, C. C. Chen, R. Cao, M. R. Lee, S. M. Peng, G.
H. Lee, Organometallics 1997, 16, 3469Ϫ3473.
J. G. Verkade, L. D. Quin (Eds.), Phosphorus-31 NMR Spec-
troscopy in Stereochemical Analysis, VCH Publishers, Inc., De-
erfield Beach, FL, U.S.A., 1987, p. 88Ϫ92.
˚
0.71073 A). For 2, cell parameters were obtained from 25 automati-
cally centered reflections. Data collection (ω scan mode), data re-
duction, and cell refinement were carried out with the P3/P4 dif-
fractometer program V4.27.[27] For the other compounds, the data
were collected using ␾ or combined ␾Ϫω scans with the Collect[28]
data collection program. Denzo and Scalepack[29] programs were
used for cell refinements and data reduction. All structures were
solved by direct methods using either SHELXS-97[30] or SIR-97[31]
programs with the WinGX[32] graphical user interface, or by using
the SHELXTL v5.1[33] program package. Structure refinements
were carried out with SHELXL-97.[34] All non-hydrogen atoms
were refined anisotropically. For compounds 1؊5, the hydrogens
were constrained to ride on their parent atom [Uiso ϭ 1.2(Ceq) for
aromatic hydrogens and Uiso ϭ 1.5(Ceq) for methyl H atoms]. For
compound 6, all hydrogens were located from the difference Four-
ier map and refined isotropically with constant Uiso ϭ 0.05 for
aromatic hydrogens and Uiso ϭ 0.08 for methyl hydrogens. Crystal-
lographic data are summarized in Table 3 and selected bond lengths
and angles are given in Tables 4 and 5.
[17]
S. O. Grim, W. McFarlane, E. F. Davidoff, J. Org. Chem 1967,
31, 781Ϫ784.
[18]
[19]
P. Suomalainen, R. H. Laitinen et al., to be published.
S. O. Grim, A. W. Yankowsky, Phosphorus and Sulfur 1977, 3,
191Ϫ195.
[20]
[21]
Y. Yamashoji, T. Matsushita, M. Tanaka, T. Shono, Polyhedron
1989, 8, 1053Ϫ1059.
R. J. Bowen, A. C. Garner, S. J. Berners-Price, I. D. Jenkins, R.
E. Sue, J. Organomet. Chem. 1998, 554, 181Ϫ184.
T. Allman, R. G. Goel, Can. J. Chem. 1982, 60, 716Ϫ722.
T. T. Derencsenyi, Inorg. Chem. 1981, 20, 665Ϫ670.
C. A. Streuli, Anal. Chem. 1960, 32, 985Ϫ987.
A. Michaelis, Annalen 1896, 293, 249Ϫ257.
[22]
[23]
[24]
[25]
[26]
[27]
W. C. Davies, F. G. Mann, J. Chem. Soc. 1944, 276Ϫ283.
P3/P4 Diffractometer Program V4.27, Siemens Analytical X-ray
Instruments, 1989؊1991.
Collect, Data collection software, EnrafϪNonius, Delft, The
Netherlands, 1998.
[28]
[29]
Z. Otwinowski, W. Minor, Processing of X-ray Diffraction Data
Collected in Oscillation Mode, Methods in Enzymology, Vol.
276, Macromolecular Crystallography, Part A (Eds.: C. W.
Carter, Jr., R. M. Sweet), Academic Press, 1997, p. 307Ϫ326.
G. M. Sheldrick, SHELXS-97, Program for Crystal Structure
Determination, University of Göttingen, Germany, 1997.
A. Altomare, C. Cascarano, C. Giacovazzo, A. Guagliardi, A.
G. G. Moliterni, M. C. Burna, G. Polidori, M. Camalli, R.
Spagna, SIR-97, A Package for Crystal Structure Solution by
Direct Methods and Refinement, University of Bari, Italy, 1997.
L. J. Farrugia, WinGX Ϫ A Windows Program for Crystal Struc-
ture Analysis, University of Glasgow, Scotland, 1998.
G. M. Sheldrick, SHELXTL Version 5.1, Bruker Analytical X-
ray Systems, Inc., Madison, Wisconsin, USA, 1998.
G. M. Sheldrick, SHELXL-97, Program for Crystal Structure
Refinement, University of Göttingen, Germany, 1997.
Received February 8, 1999
[30]
[31]
Crystallographic data (excluding structure factors) for the struc-
tures reported in this paper have been deposited with the Cam-
bridge Crystallographic Data Centre as supplementary publication
nos. CCDC-114003 to CCDC-114008. Copies of the data can be
obtained free of charge on application to CCDC, 12 Union Road,
Cambridge CB2 1EZ, U.K. [Fax: (internat.) ϩ44 (0)1223/ 336033;
E-mail: deposit@ccdc.cam.ac.uk].
[32]
[33]
[34]
[1]
C. A. Tolman, Chem. Rev. 1977, 77, 313Ϫ348.
[2]
C. A. Tolman, J. Am. Chem. Soc. 1970, 92, 2953Ϫ2956.
[3]
C. A. Tolman, J. Am. Chem. Soc. 1970, 92, 2956Ϫ2965.
[I99042]
1258
Eur. J. Inorg. Chem. 1999, 1253Ϫ1258