Preparation and compounds of (8-methoxynaphth-1-yl)diphenylphosphine

Article abstract of DOI:10.1016/j.poly.2010.02.033

Reaction of 8-methoxy-1-naphthyllithium (2) with one equivalent of chlorodiphenylphosphine gives the novel (8-methoxynaphth-1-yl)diphenylphosphine (3) which was oxidised to the corresponding sulfide (4) and selenide (5) by reaction with sulfur and seleniu

Full text of DOI:10.1016/j.poly.2010.02.033

Polyhedron 29 (2010) 1849–1853
Contents lists available at ScienceDirect
Polyhedron
journal homepage: www.elsevier.com/locate/poly
Preparation and compounds of (8-methoxynaphth-1-yl)diphenylphosphine
*
Fergus R. Knight, Amy L. Fuller, Alexandra M.Z. Slawin, J. Derek Woollins
School of Chemistry, University of St. Andrews, St. Andrews, Fife KY16 9ST, UK
a r t i c l e i n f o
a b s t r a c t
Article history:
Reaction of 8-methoxy-1-naphthyllithium (2) with one equivalent of chlorodiphenylphosphine gives the
novel (8-methoxynaphth-1-yl)diphenylphosphine (3) which was oxidised to the corresponding sulfide
Received 11 February 2010
Accepted 26 February 2010
Available online 4 March 2010
(4) and selenide (5) by reaction with sulfur and selenium, respectively. The Pꢀ ꢀ ꢀO peri distance is signif-
0
icantly increased in 4 and 5 at 2.819(3) [2.793(3)] and 2.827(3) [2.806(3)] AÅ [values in square brackets are
for the second independent molecules in each case] relative to the value in 3 of 2.678(2) Å. There are
0
Keywords:
Ligand
Phosphorus
X-ray structure
Peri substitution
short Eꢀ ꢀ ꢀO interactions ie O(1)ꢀ ꢀ ꢀS(1) 3.165(3) [3.124(3)], O(1)ꢀ ꢀ ꢀSe(1) 3.247(3) [3.200(2)] AÅ and these
may be repulsive and responsible for the increased Pꢀ ꢀ ꢀO separation. The use of the naphthalene back-
bone in the synthesis of a potential hemilabile ligand is demonstrated by the synthesis and X-ray struc-
ture of (8-methoxynaphth-1-yl)diethoxyphosphine ruthenium p-cymene dichloride (6).
Ó 2010 Elsevier Ltd. All rights reserved.
Introduction
The molecular structure of 3 (Fig. 1) shows an intramolecular
non-bonded peri-distance between P(1) and O(1) of 2.678(2) Å. Se-
A number of groups have been investigating peri substituted
naphthalenes in efforts to understand the factors which influence
the degree of distortion [1–11]. The majority of the examples in-
volve two heavy atoms at the 1,8 positions but here we demon-
strate the facile synthesis of a new P,O system which may be of
value as a hemilabile ligand [12–23].
Lithiation of 1-methoxynaphthalene 1 with t-butyllithium in
anhydrous cyclohexane to produce 8-methoxy-1-naphthyllithium
(2) was reported by Shirley and Cheng in 1969 (Eq. (1)) [24,25].
lected bond lengths and bond angles are shown in Table 1.
In order to assess the impact of oxidation of the phosphorus
centre upon the peri distance we treated 3 with sulfur or selenium
to give P@S and P@Se, respectively (Eq. (3)). The 31P NMR of 4 and 5
display singlets at dP 53.08 and dP 43.3 (JP@Se(1) 741.4 Hz) whilst for
5 dSe = ꢁ150.9 (d, JSe(1)@P 741.4 Hz) in accord with the formulation
as P@S and P@Se, respectively. In 4 mP@S is observed at 645 cmꢁ1
whilst mP@Se in 5 is observed at 494 cmꢁ1
.
E
OMe
OMe Li
PPh2 OMe
PPh2 OMe
1. t-BuLi, cyclohexane, 24 h, 0-10 °C.
ð1Þ
ð3Þ
2. S, toluene 2hrs
2
1
4 E = S
3. Se, toluenere flux
3
5 E = Se
Reaction of 8-methoxy-1-naphthyllithium (2) with one equiva-
lent of chlorodiphenylphosphine produced the novel compound
(8-methoxynaphth-1-yl)diphenylphosphine (3) (Eq. (2)). This com-
pound was characterised by elemental analysis, infra red spectros-
copy, 1H, 13C, and 31P NMR spectroscopy and mass spectrometry.
The 31P NMR spectrum showed a singlet at d = 2.44 ppm.
The X-ray structures of 4 and 5 (Fig. 2 and Table 2) are isomor-
phous and both contain two independent molecules in the unit
cell. Interestingly, the Pꢀ ꢀ ꢀO peri distance is significantly increased
0
in 4 and 5 at 2.819(3) [2.793(3)] and 2.827(3) [2.806(3)] ÅA [values
in square brackets are for the second independent molecules in
each case] relative to the value in 3 of 2.678(2) Å. Interestingly,
OMe
OMe PPh2
there are short Eꢀ ꢀ ꢀO interactions ie O(1)ꢀ ꢀ ꢀS(1) 3.165(3)
0
[3.124(3)], O(1)ꢀ ꢀ ꢀSe(1) 3.247(3) [3.200(2)] AÅ and these may be
repulsive and responsible for the increased Pꢀ ꢀ ꢀO separation.
In order to test the ability of 1,8 P, O naphthalene derivatives to
act as ligands we prepared a simple example of a metal complex 6
according to Eq. (4) without isolation of the ligand. Compound 6
was characterised spectroscopically and by X-ray crystallography
1. t-BuLi, cyclohexane, 24 h, 0-10 °C.
ð2Þ
2. ClPPh2, Et2O, 0-10 °C.
3
1
(Fig. 3 and Table 3). The complex is essentially octahedral with
* Corresponding author.
0
E-mail address: jdw3@st-and.ac.uk (J. Derek Woollins).
monodentate P coordination (the Ruꢀ ꢀ ꢀO separation is 3.563(2) ÅA)
0277-5387/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.poly.2010.02.033

1850
F.R. Knight et al. / Polyhedron 29 (2010) 1849–1853
Fig. 2. The crystal structure of the two independent molecules of (8-meth-
oxynaphth-1-yl)diphenylphosphine selenide (5), the sulfide (4) is isomorphous
and is not illustrated.
Fig. 1. The crystal structure of (8-methoxynaphth-1-yl)diphenylphosphine (3).
Experimental
Table 1
All experiments were carried out under an oxygen- and mois-
ture-free nitrogen atmosphere using standard Schlenk techniques
and glassware. Reagents were obtained from commercial sources
and used as received. Dry solvents were collected from a MBraun
solvent system. Elemental analyses were performed by the Univer-
sity of St. Andrews School of Chemistry Microanalysis Service. In-
fra-red spectra were recorded as KBr discs in the range 4000–
300 cmꢁ1 on a Perkin–Elmer System 2000 Fourier transform spec-
trometer. 1H and 13C NMR spectra were recorded on a Jeol GSX
270 MHz spectrometer with d(H) and d(C) referenced to external
tetramethylsilane. 31P and 77Se NMR spectra were recorded on a
Jeol GSX 270 MHz spectrometer with d(P) and d(Se) referenced to
external phosphoric acid and dimethylselenide, respectively.
Assignments of 13C and 1H NMR spectra were made with the help
of H–H COSY and HSQC experiments. All measurements were per-
formed at 25 °C. All values reported for NMR spectroscopy are in
parts per million (ppm). Coupling constants (J) are given in Hertz
(Hz). Mass spectrometry was performed by the University of St.
Andrews Mass Spectrometry Service. Electron impact mass spec-
trometry (EIMS) and Chemical Ionisation Mass Spectrometry
(CIMS) was carried out on a Micromass GCT orthogonal accelera-
tion time of flight mass spectrometer. Electrospray Mass Spectrom-
etry (ESMS) was carried out on a Micromass LCT orthogonal
accelerator time of flight mass spectrometer.
Selected bond lengths (Å) and angles (°) for (8-methoxynaphth-1-yl)diphenylphos-
phine (3).
14
15
16
13
12
21 22
11
23
8
20
P
O1
9
17
1
1
19 18
10
2
7
3
5
4
6
3
P(1)ꢀ ꢀ ꢀO(1)
2.678(2)
1.860(3)
1.362(4)
1.433(5)
122.8(2)
124.6(3)
114.3(2)
P(1)–C(1)
O(1)–C(9)
O(1)–C(23)
P(1)–C(1)–C(10)
C(1)–C(10)–C(9)
O(1)–C(9)–C(10)
R
= 361.7
Distance from naphthalene mean plane
P(1)
O(1)
0.1197(37)
0.0332(39)
Torsion angle
C(6)–C(5)–C(10)–C(1)
C(4)–C(5)–C(10)–C(9)
179.5(2)
ꢁ178.1(2)
(8-Methoxynaphth-1-yl)diphenylphosphine (3)
and like in 4 and 5 the substitution at phosphorus results in an en-
0
tert-Butyllithium in pentane (22 mL, 1.5 M, 33 mmol, CARE this
material is pyrophoric and should be handled with care) was added
to a solution of 1-methoxynaphthalene (4.75 g, 30 mmol) in dry
cyclohexane (60 mL) under a nitrogen atmosphere. The mixture
larged Pꢀ ꢀ ꢀO separation (2.875(3) ÅA) compared to 3. This separation
coupled with the sum of three internal angles of the C3PO ‘ring’
gives an indication of the degree of steric strain enforced upon
the naphthalene system by the substitution at phosphorus.
Cl
Cl2
1
Ru1
O
ð4Þ
OMe P(OEt)2
2
OMe
P
O1
8
1
1
O3
2
1. [Ru(pCy)Cl2]2, DCM.
8a
4a
1. t-BuLi, cyclohexane, 24 h, 0-10 °C.
7
2. ClP(OEt)2, Et2O, 0-10 °C.
6 6
3
3
1
4
5

F.R. Knight et al. / Polyhedron 29 (2010) 1849–1853
1851
Table 2
Selected bond lengths (Å) and angles (°) for the independent molecules of (8-methoxynaphth-1-yl)diphenylphosphine sulfide (4) and selenide (5). A dash implies the deviation
from the mean plane is less than the relevant esd ie it is not statistically variant from zero.
14
14
15
16
15
16
13
12
13
12
21 22
21 22
11
11
23
23
S1
Se1
20
20
P
O1
P
1
O1
17
1
17
1
9
1
9
19 18
19 18
10
5
10
5
2
2
8
7
8
7
3
3
4
4
6
6
4A & 4B
5A & 5B
P(1)ꢀ ꢀ ꢀO(1)
2.819(3)
1.839(3)
1.362(4)
3.165(3)
1.427(4)
1.9598(14)
125.4(2)
125.4(3)
115.5(3)
2.793(3)
P(1)ꢀꢀꢀO(1)
P(1)–C(1)
O(1)–C(9)
O(1)ꢀꢀꢀSe(1)
O(1)–C(23)
Se(1)@P(1)
P(1)–C(1)–C(10)
C(1)–C(10)–C(9)
O(1)–C(9)–C(10)
2.827(3)
2.806(3)
1.837(3)
1.354(4)
3.200(2)
1.426(4)
2.1157(8)
125.6(2)
125.2(3)
115.1(3)
P(1)–C(1)
1.832(4)
1.353(5)
3.124(3)
1.422(4)
1.9589(12)
126.0(2)
124.7(3)
115.0(4)
1.837(3)
1.356(3)
3.247(3)
1.427(4)
2.1175(9)
125.6(2)
124.8(2)
116.0(3)
O(1)–C(9)
O(1)ꢀꢀꢀS(1)
O(1)–C(23)
S(1)=P(1)
P(1)–C(1)–C(10)
C(1)–C(10)–C(9)
O(1)–C(9)–C(10)
R
= 366.1
R
= 365.7
R
= 366.4
R
= 365.9
Distance from naphthalene mean plane
P(1)
O(1)
S(1)
ꢁ0.2149(47)
–
P(1)
O(1)
Se(1)
–
–
0.0381(49)
0.0839(50)
1.6333(57)
0.0794(44)
–
0.0620(46)
1.8474(51)
ꢁ1.9366(54)
Torsion angle
C(6)–C(5)–C(10)–C(1)
C(4)–C(5)–C(10)–C(9)
ꢁ179.3(3)
176.6(3)
177.2(3)
C(6)–C(5)–C(10)–C(1)
C(4)–C(5)–C(10)–C(9)
ꢁ179.8(3)
176.9(3)
177.3(3)
179.4(3)
178.6(3)
was then stirred at room temperature for 24 h. 8-Lithio-1-
methoxynaphthalene precipitated and was filtered off under nitro-
gen using a sintered glass filter attached to the reaction vessel. The
solid was washed with anhydrous cyclohexane (40 mL), washed
back into the vessel with anhydrous ether (100 mL) and the sus-
pension cooled to ꢁ78 °C in a solid CO2–acetone bath. To this solu-
tion was added chlorodiphenylphosphine (6.62 g, 5.4 mL,
30 mmol). The mixture was stirred for a further 24 h at room tem-
perature. The solvent was removed in vacuo and hexane (40 mL)
was added to precipitate out unwanted salts. The solution was fil-
tered under nitrogen and the solvent removed in vacuo. The crude
yellow oil obtained was recrystallised from hexane. Yield 4.63 g,
(45%); (Anal. Calc. for C23H19OP: C, 80.70; H, 5.60. Found C,
2610w, 2156w, 1688s, 1584s, 1482w, 1437vs, 1311w, 1181vs,
1127vs, 1067s, 959vs, 857s, 755s, 727vs, 693vs, 553vs, 525s,
491w, 433vs, 329vs; dH (270 MHz, CDCl3) 7.76 (1 H, d, J 8.2 Hz,
nap 4-H), 7.49–7.43 (1 H, m, nap 5-H), 7.41–7.22 (12 H, m, nap
2,3-H, 2 ꢂ PPh2 2-6-H), 6.92–6.85 (1 H, m, nap 6-H), 6.76 (1 H,
dd, J 1.1 and 7.4 Hz, nap 7-H), 3.53 (3 H, s, –OCH3); dC (67.9 MHz,
Table 3
Selected bond lengths (Å) and angles (°) for (8-methoxynaphth-1-yl)diphenylphos-
phine ruthenium p-cymene dichloride (6).
22
18
19
20
17
16
78.81; H, 5.56%.); mmax (KBr tablet)/cmꢁ1
: 3406br s, 3075s,
24
23
25
13
21
12
Cl1
Cl2
Ru1
11
O
14
2
P
O1
9
1
15
O3
2
1
10
5
8
7
3
6
4
6
P(1)ꢀ ꢀ ꢀO(1)
P(1)–C(1)
O(1)–C(9)
O(1)–C(23)
2.875(3)
1.852(5)
1.382(7)
Ru(1)–P(1)
2.3272(12)
2.4177(10)
2.4081(15)
1.722(1)
Ru(1)–Cl(2)
Ru(1)–Cl(3)
Ruꢀ ꢀ ꢀCentroid
P(1)–C(1)–C(10)
C(1)–C(10)–C(9)
O(1)–C(9)–C(10)
128.5(4)
124.6(5)
115.0(4)
Cl(2)–Ru(1)–Cl(3)
Cl(2)–Ru(1)–P(1)
Cl(3)–Ru(1)–P(1)
86.39(4)
88.49(3)
93.43(5)
R
= 368.1
Distance from naphthalene mean plane
P(1)
O(1)
ꢁ0.1455(65)
0.2516(70)
Torsion angle
C(6)–C(5)–C(10)–C(1)
C(4)–C(5)–C(10)–C(9)
174.0(4)
173.7(4)
Fig. 3. The crystal structure of (8-methoxynaphth-1-yl)diethoxyphosphine ruthe-
nium p-cymene dichloride (6).

1852
F.R. Knight et al. / Polyhedron 29 (2010) 1849–1853
ꢀ
CDCl3) 134.0(d, J 19.7 Hz), 133.0(d, J 3.1 Hz), 129.2(s), 128.7(s),
128.6(d, J 7.3 Hz), 126.3(s), 126.0(s), 121.5(s), 106.3(s), 54.7(s); dP
(109 MHz, CDCl3) 2.81; m/z (ES+) 343.12 ([M+H]+, 50%).
C23H19OPSe, formula weight = 421.34, triclinic, space group P1,
a = 9.8572(17), b = 11.841(3), c = 17.750(5) Å,
a = 85.944(19),
b = 77.638(18),
c
l
= 71.454(16)°, U = 1918.6(8) Å3, Z = 4, DCalc
= 1.459 Mg mꢁ3
,
= 2.049 mmꢁ1, F(0 0 0) = 856. Of 21 068 mea-
ꢀ
C23H19OP, formula weight = 342.38, triclinic, space group P1,
a = 8.8248(8), b = 10.7137(10), c = 11.1950(10) Å,
a
= 102.816(3),
sured data, 6645 were unique (Rint = 0.037) and 6211 observed
b = 112.641(3),
c
= 103.520(3)°, U = 890.62(14) Å3, Z = 2, DCalc
(I > 2 (I)]) to give R1 = 0.0386 and wR2 = 0.1372. CCDC 752702.
r
= 1.277 Mg mꢁ3
,
l
= 0.161 mmꢁ1, F(0 0 0) = 360. Of 7630 measured
data, 3138 were unique (Rint = 0.047) and 2463 observed (I > 2
to give R1 = 0.0631 and wR2 = 0.1355. CCDC 752700.
r(I)])
Ruthenium complex 6
tert-Butyllithium (1.7 M) in pentane (19.4 mL, 33 mmol, CARE,
pyrophoric handle with caution) was added to a solution of 1-
methoxynaphthalene (4.75 g, 30 mmol) in dry cyclohexane
(60 mL). The solution was stirred at room temperature for 24 h.
8-Lithio-1-methoxynaphthalene precipitated and was filtered off
under nitrogen using a sintered glass filter attached to the reaction
vessel. The solid was washed with dry cyclohexane (40 mL),
washed back into the reaction vessel with dry diethyl ether
(100 mL) and the suspension was cooled to ꢁ78 °C. Chlorodieth-
oxyphosphine (30 mmol, 4.3 mL) was added dropwise to the sus-
pension which was stirred overnight. The solvent was removed
in vacuo and hexane (100 mL) was added to precipitate out un-
wanted salts. The solution was filtered under nitrogen and the sol-
vent removed in vacuo. The crude ligand has dP = 7.3 ppm. To a
schlenk tube containing ligand (8-methoxynaphthyl-1-yl)dieth-
oxyphosphine (0.299 g, 1.08 mmol) and [Ru(pcym)Cl2]2 (0.329 g,
0.54 mmol) was added dichloromethane (5 mL). The reaction was
stirred for 2 h. Removal of the solvent and recrystallisation of the
red oil from dichloromethane/pentane gave red crystals. Yield
1.02 g (24%); (Anal. Calc. for C25H33O3PRuCl2: C, 51.40; H, 5.70.
Found: C, 51.70; H, 5.49%.); vmax (KBr tablet)/cmꢁ1: 3442br,
3032s, 2961s, 2925s, 2896s, 2824s, 2433w, 1943w, 1742w,
1615w, 1561s, 1502s, 1461vs, 1367vs, 1323s, 1261vs, 1201s,
1148s, 1116vs, 1092s, 1023vs, 941vs, 861s, 823s, 776vs, 760vs,
734s, 634s, 604w, 545vs, 519vs, 465s, 424s, 288s; dH (270 MHz,
CDCl3) 8.07-8.00 (1 H, m, nap 4-H), 7.93 (1 H, d, J 8.1 Hz, nap 2-
H), 7.89 (1 H, d, J 8.2 Hz, nap 5-H), 7.59–7.53 (1 H, m, nap 3-H),
7.47–7.37 (4 H, m, nap 6,7-H, 2 ꢂ Ar-H), 6.95–6.89 (2 H, m, 2 x
Ar-H), 4.16–4.07 (4 H, m, –P(OCH2CH3)2), 3.97 (3 H, s, –OCH3),
2.85 (1 H, q, J 6.9 Hz, Ar-CH(CH3)2), 1.84 (3 H, s, Ar-CH3), 1.25–
1.15 (6 H, m, –P(OCH2CH3)2), 1.10 (6 H, d, J 7.0 Hz, Ar-CH(CH3)2);
(8-Methoxynaphth-1-yl)diphenylphosphine sulfide (4)
To a solution of (8-methoxynaphth-1-yl)diphenylphosphine
(0.317 g, 0.927 mmol) in toluene (10 mL) powdered sulfur
(0.03 g, 0.927 mmol) was added in small batches at 0 °C. The mix-
ture was stirred for ½ h at 0 °C and another 2 h at ambient temper-
ature. The resulting cloudy solution was filtered, the solvent was
removed in vacuo and the remaining oil vigorously stirred with
hexane (10 mL) over night, which resulted in a thick suspension.
The solid product was collected by filtration and recrystallised
from dichloromethane/pentane. Yield 0.236 g, (68%); (Anal. Calc.
for C23H19OPS: C, 73.78; H, 5.12. Found C, 73.10; H, 4.57%.); vmax
(KBr tablet)/cmꢁ1: 3053s, 2929s, 2829s, 2268w, 1960w, 1893s,
1826w, 1753w, 1683w, 1639w, 1613s, 1563vs, 1502vs, 1457vs,
1434vs, 1367vs, 1328vs, 1264vs, 1211s, 1186s, 1152s, 1116vs,
1051s, 1023s, 995vs, 911vs, 847w, 819vs, 763vs, 746vs, 716vs,
690vs, 654vs, 634vs, 595s, 553w, 517vs, 483s, 450s, 416vs; dH
(270 MHz, CDCl3) 7.96–7.88 (1 H, m, nap 4-H), 7.88–7.71 (4 H, m,
2 ꢂ PPh2 2,6-H), 7.51–7.34 (8 H, m, nap 5,6-H, 2 ꢂ PPh2 3-5-H),
7.34–7.22 (2 H, m, nap 2,3-H), 6.76 (1 H, dd, J 1.1 and 7.3 Hz, nap
7-H), 3.24 (3 H, s, –OCH3); dC (67.9 MHz, CDCl3) 135.4(d, J
11.4 Hz), 132.9(d, J 3.1 Hz), 131.6(d, J 10.4 Hz), 130.5(d, J 3.2 Hz),
128.2(d,
J 12.4 Hz), 127.2(s), 125.1(d, J 14.6 Hz), 121.3(s),
107.1(s), 53.0(s); dP (109 MHz, CDCl3) 53.08; m/z (ES+) 343.07
([M–S]+, 100%).
ꢀ
C23H19OPS, formula weight = 374.44, triclinic, space group P1,
a = 9.7972(12), b = 11.7887(18), c = 17.681(3) Å,
a = 86.043(13),
b = 77.168(12),
c
= 71.227(10)°, U = 1885.1(5) Å3, Z = 2, DCalc
= 1.318 Mg mꢁ3
,
l
= 0.265 mmꢁ1, F(0 0 0) = 784. Of 19 723 mea-
sured data, 6507 were unique (Rint = 0.073) and 5702 observed
(I > 2 (I)]) to give R1 = 0.0788 and wR2 = 0.1353. CCDC 752701.
dC (67.9 MHz, CDCl3) 136.0(d,
J 6.2 Hz), 132.4(s), 131.0(d, J
r
8.3 Hz), 127.1(s), 124.7(d, J 10.4 Hz), 121.2(s), 106.9(s), 63.9(–
P(OCH2CH3)2), 57.9(–OCH3), 30.1(Ar-CH(CH3)2), 21.7(Ar-CH(CH3)2),
17.9(Ar-CH3), 16.1(–P(OCH2CH3)2); dP (109 MHz, CDCl3) 138.1; m/z
(ES+) 549.10 ([M–Cl]+, 100%).
(8-Methoxynaphth-1-yl)diphenylphosphine selenide (5)
solution of (8-methoxynaphth-1-yl)diphenylphosphine
A
C25H33O3PCl2Ru, formula weight = 584.48, triclinic, space group
ꢀ
(7.363 g, 21.5 mmol) and Se (1.70 g, 21.5 mmol) were heated under
reflux in toluene (20 mL) for 2 h. The resulting cloudy solution was
filtered, the solvent was removed in vacuo and the remaining oil
vigorously stirred with hexane (10 mL) over night, which resulted
in a thick suspension. The solid product was collected by filtration
and recrystallised from dichloromethane/pentane. Yield 7.17 g,
(79%); (Anal. Calc. for C23H19OPSe: C, 65.57; H, 4.55. Found C,
64.67; H, 4.07%.); vmax (KBr tablet)/cmꢁ1: 2930br s, 1968w,
1898w, 1825w, 1776w, 1674w, 1587w, 1572w, 1476s, 1433vs,
1386w, 1334w, 1308s, 1273w, 1180s, 1157s, 1107vs, 1067w,
1023s, 994w, 953w, 892vs, 779w, 744vs, 718s, 703vs, 686vs,
613w, 590w, 558vs, 494s, 468w, 445w, 392w, 361s, 323w; dH
(270 MHz, CDCl3) 7.95–7.70 (5 H, m, nap 4-H, 2 ꢂ PPh2 2,6-H),
7.55–7.34 (8 H, m, nap 5,6-H, 2 ꢂ PPh2 3-5-H), 7.34–7.15 (2 H, m,
nap 2,3-H), 6.69 (1 H, dd, J 2.4 and 6.5 Hz, nap 7-H), 3.19 (3 H, s,
–OCH3); dC (67.9 MHz, CDCl3) 135.5(d, J 11.5 Hz), 133.2(d, J
4.3 Hz), 132.5(d, J 10.0 Hz), 131.0(d, J 2.5 Hz), 128.6(d, J 12.5 Hz),
P1, a = 9.916(4), b = 10.349(4), c = 13.298(7) Å,
a
= 88.26(3),
1265.3(10) Å3, Z = 2, DCalc
= 0.918 mmꢁ1, F(0 0 0) = 600. Of 14 990 mea-
sured data, 4401 were unique (Rint = 0.041) and 4279 observed
(I > 2 (I)]) to give R1 = 0.0482 and wR2 = 0.1398. CCDC 752703.
b = 89.46(3),
c
,
= 68.07(2)°,
l
U
=
= 1.534 Mg mꢁ3
r
Supplementary data
CCDC 752700–752703 contains the supplementary crystallo-
graphic data for 3–6. These data can be obtained free of charge
via http://www.ccdc.cam.ac.uk/conts/retrieving.html, or from the
Cambridge Crystallographic Data Centre, 12 Union Road, Cam-
bridge CB2 1EZ, UK; fax: (+44) 1223-336-033; or e-mail:
deposit@ccdc.cam.ac.uk.
References
127.6(s), 125.4(d,
J 14.3 Hz), 121.6(s), 107.5(s), 53.0(s); dP
[1] H.E. Katz, J. Am. Chem. Soc. 107 (1985) 1420.
[2] R.W. Alder, P.S. Bowman, W.R.S. Steel, D.R. Winterman, Chem. Commun.
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(109 MHz, CDCl3) 43.32 (JP@Se(1) 741.4 Hz); dSe (51.5 MHz, CDCl3)
ꢁ150.9 (d, JSe(1)@P 741.4 Hz); m/z (CI+) 423.04 ([M+H]+, 100%).

F.R. Knight et al. / Polyhedron 29 (2010) 1849–1853
1853
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