Synthesis and derivatization, structures and transition metal chemistry of a new large bite bis(phosphinite) derived from bis(2-hydroxy-1-naphthyl)methane

Article abstract of DOI:10.1039/b206994f

Bis(2-hydroxy-1-naphthyl)methane reacts with chlorodiphenylphosphine to afford the bis(phosphinite), Ph₂P{(-OC₁₀H₆)(μ-CH₂)(C₁₀ H₆O-)}PPh₂ (1) in good yield. The bis(phosphinite) 1 reacts with elemental sulfur or selenium to give the corresponding disulfide or diselenide; the structure of the selenium derivative, Ph₂P(Se){(-OC₁₀H₆)(μ-CH₂)(C_{1 0}H₆O-)}P(Se)Ph₂ (3) is confirmed by X-ray crystal structure analysis. Treatment of the ligand 1 with platinum metal derivatives results in the formation of ten-membered chelate complexes with the ligand showing an η²-mode of coordination. The elucidation of the structures of the products is based on NMR (¹H and ³¹P) spectroscopic data. Molecular structures of [CpRuCl{η²-Ph₂P{(-OC₁₀H₆)(μ-C H₂)(C₁₀H₆O-)}PPh₂-κP,κP} ] (4) and [PtCl₂{η²-Ph₂P{(-OC₁₀H₆ )(μ-CH₂)(C₁₀H₆O-)}PPh₂- κP, κP}] (7) are determined by single crystal X-ray studies.

Full text of DOI:10.1039/b206994f

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Synthesis and derivatization, structures and transition metal
chemistry of a new large bite bis(phosphinite) derived from
bis(2-hydroxy-1-naphthyl)methane
Maravanji S. Balakrishna,*a Rashmishree Pandaa and Joel T. Magueb
a Department of Chemistry, Indian Institute of Technology, Bombay, Mumbai 400 076, India
b Department of Chemistry, Tulane University, New Orleans, Louisiana, LA 70118, USA
Received 17th July 2002, Accepted 11th October 2002
First published as an Advance Article on the web 12th November 2002
Bis(2-hydroxy-1-naphthyl)methane reacts with chlorodiphenylphosphine to afford the bis(phosphinite),
Ph2P{(–OC10H6)(µ-CH2)(C10H6O–)}PPh2 (1) in good yield. The bis(phosphinite) 1 reacts with elemental sulfur
or selenium to give the corresponding disulfide or diselenide; the structure of the selenium derivative, Ph2P(Se)-
{(–OC10H6)(µ-CH2)(C10H6O–)}P(Se)Ph2 (3) is confirmed by X-ray crystal structure analysis. Treatment of the
ligand 1 with platinum metal derivatives results in the formation of ten-membered chelate complexes with the
ligand showing an η2-mode of coordination. The elucidation of the structures of the products is based on NMR
(1H and 31P) spectroscopic data. Molecular structures of [CpRuCl{η2-Ph2P{(–OC10H6)(µ-CH2)(C10H6O–)}PPh2-
κP,κP}] (4) and [PtCl2{η2-Ph2P{(–OC10H6)(µ-CH2)(C10H6O–)}PPh2-κP,κP}] (7) are determined by single
crystal X-ray studies.
82.6 and 86.0 ppm, respectively. The diselenide derivative 3
Introduction
shows 1JPSe coupling of 827 Hz. The molecular structure of 3 is
also confirmed by single crystal X-ray analysis.
Many homogeneous catalysts used in industrial applications
include phosphine ligands with bulky substituents. In these
systems both steric and electronic effects are important with
the bulk of the ligands imposing regioselectivity during the
catalytic process.1,2 Transition metal complexes containing
bulky mono- and bis(phosphines) as catalysts in organic trans-
formations are well documented.3–8 Surprisingly, the utilization
of analogous bis(phosphinite) ligands in such reactions is
sparse although some of them are proved to be efficient
catalysts.5,9–13 As a part of our interest14–19 in designing new
phosphorus-based ligand systems, we describe in this paper the
synthesis of a new bis(phosphinite), Ph2P{(–OC10H6)(µ-CH2)-
(C10H6O–)}PPh2 (1). Compound 1 reacts with chalcogens to
give dichalcogenides; the molecular structure of the diselenide
is confirmed by an X-ray crystal study. Some transition metal
chemistry of 1 is also described with X-ray crystal structures of
ruthenium and platinum complexes.
A perspective view of the molecular structure of the com-
pound 3 with the atomic numbering scheme is shown in the Fig.
1. Crystal data and the details of the structure determination
are given in Table 4. Selected parameters are listed in Table 1.
Results and discussion
The reaction of bis(2-hydroxy-1-naphthyl)methane with chloro-
diphenylphosphine in the ratio 1 : 2 in THF in the presence of
a catalytic amount of 4-dimethylaminopyridine affords the
expected bis(naphthol) derivative, Ph2P{(–OC10H6)(µ-CH2)-
(C10H6O–)}PPh2 (1) in good yield. Stoichiometric reaction of
the new bis(phosphinite) (1) with two molar equivalents
of elemental sulfur or selenium powder in toluene under
reflux conditions gives the corresponding disulfide, Ph2P(S)-
{(–OC10H6)(µ-CH2)(C10H6O–)}P(S)Ph2 (2) or diselenide,
Ph2P(Se){(–OC10H6)(µ-CH2)(C10H6O–)}P(Se)Ph2 (3) as shown
in Scheme 1. The disulfide derivative 2 was formed very rapidly
within 15 minutes at 60 ЊC whereas the formation of the
diselenide derivative was slow and took nearly 8 h for the com-
pletion of the reaction. The progress of the reaction can be
readily followed visually by the disappearance of sulfur in the
case of 2 and the black colour of selenium in the case of 3.
The elucidation of the structures of ligand 1 and the chal-
cogen derivatives 2 and 3 are based on NMR (1H and 31P{1H})
spectroscopic data and elemental analyses. The 31P{1H} NMR
spectra of compounds 1–3 exhibit single resonances at 112.2,
Fig. 1 Perspective view of compound 3 showing the atom numbering
scheme. Thermal ellipsoids are drawn at the 50% probability level and
hydrogen atoms are omitted for clarity.
Compound 3 crystallizes in the monoclinic crystal system in
the extended conformation. The P᎐Se bond lengths (P(1)–Se(1),
᎐
2.0722(9) Å; P(2)–Se(2), 2.0699(9) Å) compare well with those
found in Ph2P(Se)NHP(Se)Ph2 (P(1)–Se(1), 2.085(1); P(2)–
Se(2), 2.101(1) Å).20 The two selenium atoms are in an
approximately syn disposition with the Se(1)–P(1) and Se(2)–
P(2) vectors making an angle of 26.6Њ when projected down
P(1) ؒ ؒ ؒ P(2).
Here the P(1) and P(2) centers are distinctly pyramidal with
sum of the angles 344.70(10) and 346.60(10)Њ, respectively. The
average P–O distance of 1.618(2) Å is closer to the values
(ca.1.62 Å) typically found for P–O bond distances in
phosphites.1
The complexation behavior of the phosphinoxy derivative 1
has been investigated by its reactions with platinum metal
DOI: 10.1039/b206994f
J. Chem. Soc., Dalton Trans., 2002, 4617–4621
This journal is © The Royal Society of Chemistry 2002
4617

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Scheme 1
Table 2 Selected bond distances (Å) and bond angles (Њ) for 4
Table 1 Selected bond distances (Å) and bond angles (Њ) for 3
Se(1)–P(1)
Se(2)–P(2)
P(1)–O(1)
P(2)–O(2)
P(1)–C(1)
P(1)–C(7)
P(2)–C(34)
2.072(9)
2.070(9)
1.624(2)
1.612(2)
1.800(3)
1.804(3)
1.811(3)
P(2)–C(40)
O(1)–C(13)
O(2)–C(33)
C(13)–C(22)
C(22)–C(23)
C(23)–C(24)
C(24)–C(33)
1.799(3)
Ru–Cl
2.424(3)
2.254(18)
2.254(2)
2.229(10)
2.223(8)
2.216(8)
2.212(11)
2.196(13)
P(1)–O(1)
P(2)–O(2)
1.635(4)
1.645(5)
1.423(8)
1.385(11)
1.366(10)
1.520(9)
1.531(12)
1.368(10)
1.393(4)
1.400(4)
1.377(4)
1.517(4)
1.521(3)
1.371(4)
Ru–P(1)
Ru–P(2)
Ru–C(46)
Ru–C(47)
Ru–C(48)
Ru–C(49)
Ru–C(50)
O(1)–C(13)
O(2)–C(33)
C(13)–C(22)
C(22)–C(23)
C(23)–C(24)
C(24)–C(33)
Se(1)–P(1)–O(1)
Se(1)–P(1)–C(1)
Se(1)–P(1)–C(7)
O(1)–P(1)–C(1)
O(1)–P(1)–C(7)
C(1)–P(1)–C(7)
Se(2)–P(2)–O(2)
Se(2)–P(2)–C(34)
Se(2)–P(2)–C(40)
O(2)–P(2)–C(34)
O(2)–P(2)–C(40)
C(34)–P(2)–C(40)
117.25(9)
115.58(11)
114.97(11)
102.21(13)
98.63(13)
106.04(15)
116.70(9)
114.25(11)
115.65(11)
104.23(13)
97.50(13)
106.59(15)
P(1)–O(1)–C(13)
P(2)–O(2)–C(33)
129.6(2)
129.2(2)
116.3(2)
117.8(2)
120.2(2)
121.9(2)
116.3(3)
119.1(2)
122.2(2)
120.3(3)
117.2(2)
Cl–Ru–P(1)
Cl–Ru–P(2)
P(1)–Ru–P(2)
Ru–P(1)–O(1)
Ru–P(2)–O(2)
P(1)–O(1)–C(13)
95.39(8)
89.53(8)
93.94(7)
113.84(16)
121.5(2)
131.4(4)
P(2)–O(2)–C(33)
128.7(4)
114.9(5)
118.8(7)
121.1(6)
114.7(6)
121.1(8)
O(1)–C(13)–C(22)
C(13)–C(22)–C(21)
C(13)–C(22)–C(23)
C(21)–C(22)–C(23)
O(2)–C(33)–C(24)
C(22)–C(23)–C(24)
C(23)–C(24)–C(25)
C(23)–C(24)–C(33)
C(25)–C(24)–C(33)
O(1)–C(13)–C(22)
O(2)–C(33)–C(24)
C(13)–C(22)–C(23)
C(22)–C(23)–C(24)
C(23)–C(24)–C(33)
at 85.9 ppm (∆δ = Ϫ26.3 Hz) with 195Pt satellites. Phosphorus
resonance in Pt() complexes are upfield of those for Ru()
complexes of the same ligands. The large 1JPtP coupling of 4155
Hz is attributed to a cis configuration of the coordinated phos-
phorus centers.14,21,22 Spectroscopic studies on complex 6 could
not be carried out because of its poor solubility in most organic
solvents. The molecular structures23 of the complexes 4 and 7
are further confirmed by single crystal X-ray diffraction studies.
A perspective view of 4 with the numbering scheme is shown
in Fig. 2(a) and the central core is shown in Fig. 2(b). The
crystallographic data are given in Table 4. Selected bond lengths
and bond angles are listed in Table 2. The complex adopts
the well-known piano-stool structure that consists of an η5-
cyclopentadienyl ring, a chlorine atom and the two phosphorus
centers. The average Ru–P bond distance of 2.254(10) Å
is shorter than those observed in analogous complexes24–28
containing organophosphines. This may be attributed to the
better π-acceptor nature of the phosphite ligands compared to
organophosphines. In addition, it may also be due to the steric
factors and the size of the chelate ring in the complex; the
M–P distances are sensitive to the bulkiness of the phosphine
ligands.29 The chlorine atom is bent towards the P(2) atom:
Cl–Ru–P(1) 95.39(8)Њ, Cl–Ru–P(2) 89.53(8)Њ, to avoid steric
interactions with one of the phenyl rings bound to P(1). The
organometallic derivatives containing one or two labile ligands
(Scheme 1). The reaction of 1 with one equivalent of [CpRu-
(PPh3)2Cl] in toluene at refluxing temperature gives the
monomeric complex [CpRuCl{η2-Ph2P{(–OC10H6)(µ-CH2)-
(C10H6O–)}PPh2-κP,κP}] (4) in which the bis(phosphinoxy)
ligand shows chelating bidentate mode of coordination.
Treatment of a solution of 1 in THF with an equimolar ratio
of the Ru() derivative, [Cp*Ru(COD)Cl] afforded
a
similar ten-membered chelating complex [Cp*RuCl{η2-Ph2P-
{(–OC10H6)(µ-CH2)(C10H6O–)}PPh2-κP,κP}] (5) in 83% yield.
The stoichiometric reactions of [M(COD)Cl2] (M= Pd, Pt) with
1 : 1 molar proportions of 1 in CH2Cl2 at ambient temperature
give the chelate complexes [MCl2{η2-Ph2P{(–OC10H6)-
(µ-CH2)(C10H6O–)}PPh2-κP,κP}] (M = Pd, 6; Pt, 7).
The chemical compositions of complexes 4–7 are established
by elemental analyses and the proposed structures are con-
sistent with their spectroscopic data. The 31P{1H} NMR spectra
of 4 and 5 show single resonances at 153.5 and 154.0 ppm,
respectively, with coordination shifts (∆δ) of 41.3 and 42.0
ppm. The 31P resonance due to the platinum complex 7 appears
4618
J. Chem. Soc., Dalton Trans., 2002, 4617–4621

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Table 3 Selected bond distances (Å) and bond angles (Њ) for 7
explanation. The average P–O bond distance of 1.611(8) Å is
slightly shorter than the normally accepted P–O single bond
distance of 1.62 Å.
Pt–Cl(1)
Pt–Cl(2)
Pt–P(1)
Pt–P(2)
P(1)–O(1)
P(2)–O(2)
2.346(3)
2.324(3)
2.229(3)
2.224(2)
1.606(8)
1.616(8)
O(1)–C(13)
O(2)–C(33)
C(13)–C(22)
C(22)–C(23)
C(23)–C(24)
C(24)–C(33)
1.413(12)
1.408(12)
1.355(14)
1.537(14)
1.521(13)
1.380(14)
Conclusion
The new bis(phosphinite) ligand prepared in high yield can be
readily oxidized with chalcogens to give the corresponding
dichalcogenides and chelate complexes with transition metal
Cl(1)–Pt–Cl(2)
Cl(1)–Pt–P(2)
Cl(1)–Pt–P(2)
Cl(2)–Pt–P(1)
Cl(2)–Pt–P(2)
P(1)–Pt–P(2)
Pt–P(1)–O(1)
Pt–P(2)–O(2)
87.23(11)
178.30(10)
84.91(10)
92.58(10)
171.54(11)
95.37(9)
O(1)–C(13)–C(22)
P(1)–O(1)–C(13)
P(2)–O(2)–C(33)
C(13)–C(22)–C(23)
C(22)–C(23)–C(24)
C(23)–C(24)–C(33)
O(2)–C(33)–C(24)
116.9(9)
123.8(7)
124.2(6)
120.4(9)
116.9(8)
119.8(9)
117.1(8)
114.1(3)
111.9(3)
Fig. 3 (a) Perspective view of complex 7 showing the atom numbering
scheme. Thermal ellipsoids are drawn at the 50% probability level and
hydrogen atoms are omitted for clarity. (b) Plot of the central core of
the complex 7.
derivatives. The ruthenium complex adopts a well-known
piano-stool structure whereas the structure of platinum com-
plex shows a typical square-planar geometry. Diphosphines
with large bite angles are useful in catalysis and further research
in this direction is in progress.
Fig. 2 (a) Perspective view of complex 4 showing the atom numbering
scheme. Thermal ellipsoids are drawn at the 50% probability level and
hydrogen atoms are omitted for clarity. (b) Plot of the central core of
the complex 4.
Experimental
All experimental manipulations were carried out under an
atmosphere of dry nitrogen or argon using Schlenk techniques.
Solvents were dried and distilled prior to use by conventional
methods. PPh2Cl, elemental sulfur and selenium powder
were used as purchased. Bis(2-hydroxy-1-naphthyl)methane,32
[CpRu(PPh3)2Cl],33 [Cp*Ru(COD)Cl2],34 [M(COD)Cl2] (M =
average P–O bond distance of 1.64(5) Å is in agreement with
the typical value of P–O single bonds in other related
phosphites.
A perspective view of molecule 7 with the numbering scheme
is shown in Fig. 3(a) and the central core is shown in Fig. 3(b).
Selected bond lengths and bond angles are listed in Table 3 and
the crystallographic data are given in Table 4. The structure of
the complex shows a typical square-planar environment around
the metal center with the bis(phosphinoxy) ligand, and two
chlorine atoms in a mutually cis-disposition. The average Pt–P
distance is 2.226(3) Å. The Cl(2)–Pt–P(1) angle is 92.58(10)Њ
whereas the Cl(1)–Pt–P(2) angle is 84.91(10)Њ which clearly
indicates some distortion at the metal center. The P(1)–Pt–P(2)
angle (95.37(9)Њ) appears to have increased from the square-
planar value of 90Њ to an extent limited by the development
of phosphine–chlorine interactions. The PtP2Cl2 plane is per-
pendicular to two of the four phenyl rings. The average Pt–Cl
bond distance of 2.335(3) Å is comparable with that observed
(2.33–2.35 Å) in analogous Pt–phosphine complexes.30,31 It is
interesting to note that the longer Pt–Cl distance is paired with
the shorter Pt–P distance and vice versa but there is no obvious
1
Pd,35 Pt36) were prepared by the cited procedures. The H and
31P{1H} NMR (δ in ppm) spectra were obtained on a VXR
300S spectrometer operating at frequencies of 300 and 121
MHz, respectively. The spectra were recorded in CDCl3
solutions with CDCl3 as an internal lock; TMS and 85% H3PO4
1
were used as external standards for H and 31P{1H} NMR,
respectively. Positive shifts lie downfield of the standard in all
cases. Melting points of all compounds were determined
on Veego melting point apparatus and were uncorrected.
Microanalyses were carried out on a Carlo Erba Model 1106
elemental analyzer.
Synthesis of Ph2P{(–OC10H6)(ꢀ-CH2)(C10H6O–)}PPh2 (1)
A solution of PPh2Cl (4.63 g, 20 mmol) in diethyl ether/THF
(1: 2, 30 mL) was added dropwise to a mixture of bis(2-
J. Chem. Soc., Dalton Trans., 2002, 4617–4621
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Table 4 Crystallographic data for 3, 4 and 7
3
4
7
Empirical formula
Formula weight
Crystal system
Space group
a/Å
b/Å
c/Å
C45H34O2P2Se2
826.58
C50H39ClO2P2RuؒCH2Cl2ؒ0.5H2O
964.25
C45H34Cl2O2P2PtؒCH2Cl2ؒH2O
1037.68
Monoclinic
P21/c (no. 14)
15.357(3)
11.005(2)
26.594(4)
106.300(10)
4314(1)
4
1.598
2056
3.6
0.30 × 0.40 × 0.43
293
Monoclinic
C2/c (no. 15)
44.656(3)
11.1275(9)
15.5265(18)
99.753(8)
7603.8(12)
8
1.444
3344
2.067
0.23 × 0.40 × 0.40
293
Monoclinic
C2/c (no. 15)
41.312(2)
12.8234(17)
22.770(2)
122.897(8)
10128.4(18)
8
1.265
3944
0.568
0.26 × 0.40 × 0.40
293
β/Њ
V/Å3
Z
Dc/g cmϪ3
F(000)
µ(Mo-Kα)/cmϪ1
Crystal size/mm
T /K
λ(Mo-Kα)/Å
θmin–max/Њ
Total no. reflections
No. unique reflections
Observed data
Rint
0.71073
1.9–25.1
6871
6778
4413
0.71073
1.7–25.1
9164
9030
5018
0.71073
1.6–25.1
7934
7630
5065
0.023
0.051
0.138
R
Rw
0.0353
0.1078
0.0619
0.2354
0.0605
0.1858
hydroxy-1-naphthyl)methane (3.0 g, 10 mmol), a catalytic
amount of 4-dimethylaminopyridine (0.015 g) and triethyl-
amine (2.02 g, 20.1 mmol) also in THF (50 mL) at 0 ЊC with
vigorous stirring. Then the solution was allowed to warm
to room temperature and stirring was continued for 20 h. The
triethylamine hydrochloride was removed by filtration. The
solvent was removed under vacuum to give a white solid of the
crude product, which was recrystallized from dichloromethane/
petroleum ether (2 : 1, bp range for petroleum ether: 60–80 ЊC).
Yield: 94% (6.3 g). Mp 182–184 ЊC. Anal. Calc. for C45H34O2P2:
Ar), 8.03 (d, 2H, Ar), 8.00 (d, 2H, Ar), 7.62 (d, 2H, Ar),
7.41–7.54 (m, 20H, OPPh2), 7.25 (t, 2H, Ar), 7.20 (t, 2H, Ar),
4.81 (s, 2H, Ar–CH2–Ar). 31P{1H} NMR (300 MHz, CDCl3):
δ 86.0 (s), 1JPSe = 827 Hz.
Synthesis of [CpRuCl{ꢁ2-Ph2P{(–OC10H6)(ꢀ-CH2)(C10H6O–)}-
PPh2-ꢂP,ꢂP}] (4)
A mixture of [CpRu(PPh3)2Cl] (0.038 g, 0.05 mmol) and the
bis(phosphine) 1 (0.035 g, 0.05 mmol) in toluene (10 mL) was
heated under reflux for 18 h. The orange–yellow solution was
then cooled to room temperature. Solvent was removed under
reduced pressure and the residue was extracted with cold
diethyl ether to remove PPh3. The remaining residue was
recrystallized from CH2Cl2/diethyl ether (1 : 1) solution to
afford orange yellow crystalline 4. Yield: 86% (0.039 g). Mp
250 ЊC (decomp.). Anal. Calc. for C50H39ClO2P2RuؒCH2Cl2ؒ
0.5H2O: C, 63.52; H, 4.39. Found: C, 63.28; H, 4.33%. 1H NMR
(300 MHz, CDCl3): δ 8.10 (br s, 2H, Ar), 7.75 (d, 2H, Ar), 7.68
(br s, 2H, Ar), 7.24–7.42 (m, 20H, OPPh2), 7.16 (br s, 2H, Ar),
6.98 (br s, 2H, Ar), 6.86 (br s, 2H, Ar), 4.86 (ABq, 2H,
1
C, 80.82; H, 5.12. Found: C, 80.71; H, 5.03%. H NMR (300
MHz, CDCl3): δ 8.27 (d, 2H, Ar), 7.65–7.71 (m, 4H, Ar), 7.61
(d, 2H, Ar), 7.47–7.51 (m, 2H, Ar), 7.34–7.41 (m, 20H, OPPh2),
7.19 (t, 2H, Ar), 4.89 (s, 2H, Ar–CH2–Ar). 31P{1H} NMR (300
MHz, CDCl3): δ 112.2 (s).
Synthesis of Ph2P(S){(–OC10H6)(ꢀ-CH2)(C10H6O–)}P(S)Ph2 (2)
A mixture of the bis(phosphine) 1 (0.14 g, 0.021 mmol) and
sulfur (0.014 g, 0.043 mmol) in toluene (10 mL) was heated to
80 ЊC for 5 min to give a clear solution. Solvent was removed
under reduced pressure to give a pale white residue. The residue
was dissolved in CH2Cl2 (1.5 mL), layered with 1 mL of petrol-
eum ether (bp 60–80 ЊC) and kept at room temperature to give
X-ray quality colorless crystals of 2. Yield: 97% (0.15 g). Mp
214–216 ЊC. Anal. Calc. for C45H34O2P2S2: C, 73.76; H, 4.68.
Found: C, 73.69; H, 4.61%. 1H NMR (300 MHz, CDCl3): δ 8.09
(d, 2H, Ar), 8.01 (d, 2H, Ar), 7.97 (d, 2H, Ar), 7.65 (d, 2H, Ar),
7.39–7.52 (m, 20H, OPPh2), 7.29 (t, 2H, Ar), 7.23 (t, 2H, Ar),
4.78 (s, 2H, Ar–CH2–Ar). 31P{1H} NMR (300 MHz, CDCl3):
δ 82.6 (s).
2
Ar–CH2–Ar, JHH = 15.1 Hz), 4.31 (s, 5H, Cp). 31P{1H} NMR
(300 MHz, CDCl3): δ 153.5 (s).
Synthesis of [Cp*RuCl{ꢁ2-Ph2P{(–OC10H6)(ꢀ-CH2)(C10H6O–)}-
PPh2-ꢂP,ꢂP}] (5)
A solution of the bis(phosphine) 1 (0.05 g, 0.07 mmol) in THF
(5 mL) was added dropwise to a solution of [Cp*Ru(COD)Cl]
(0.025 g, 0.066 mmol) also in THF (5 mL). The reaction
mixture was stirred at room temperature for 12 h. Solvent was
removed completely under reduced pressure and the product
was extracted with petroleum ether (bp 60–80 ЊC, 10 mL). The
solution was concentrated to 3 mL, which upon cooling to 0 ЊC
gave analytically pure sample of 5. Yield: 83% (0.051 g). Mp
238–240 ЊC (melts with decomposition). Anal. Calc. for
C55H49ClO2P2Ru: C, 70.23; H, 5.25. Found: C, 70.05; H, 5.19%.
1H NMR (300 MHz, CDCl3): δ 7.88 (br s, 2H, Ar), 7.65 (br s,
2H, Ar), 7.54 (br s, 2H, Ar), 7.40 (t, 2H, Ar), 7.16–7.35 (m,
20H, OPPh2), 7.11 (t, 2H, Ar), 6.38 (d, 2H, Ar), 4.61 (ABq, 2H,
Ar–CH2–Ar, 2JHH = 14.8 Hz), 1.16 (s, 15H, Cp*). 31P{1H} NMR
(300 MHz, CDCl3): δ 155.0 (s).
Synthesis of Ph2P(Se){(–OC10H6)(ꢀ-CH2)(C10H6O–)}P(Se)Ph2
(3)
A mixture of the bis(phosphine) 1 (0.14 g, 0.021 mmol) and
selenium powder (0.034 g, 0.043 mmol) in toluene (10 mL) was
heated under reflux for 8 h. The solution was then cooled to
room temperature and filtered to remove any undissolved
material. The solvent was removed under reduced pressure to
give a sticky residue. The residue was dissolved in 3 mL of
CH2Cl2, layered with 1 mL of petroleum ether (bp 60–80 ЊC)
and kept at room temperature to afford colorless crystals of 3
suitable for X-ray analysis. Yield: 96% (0.17 g). Mp 208–210 ЊC.
Anal. Calc. for C45H34O2P2Se2: C, 65.39; H, 4.15. Found: C,
Synthesis of [PdCl2{ꢁ2-Ph2P{(–OC10H6)(ꢀ-CH2)(C10H6O–)}-
PPh2-ꢂP,ꢂP}] (6)
1
65.27; H, 4.09%. H NMR (300 MHz, CDCl3): δ 8.12 (d, 2H,
A solution of the bis(phosphine) 1 (0.13 g, 0.194 mmol) in
4620
J. Chem. Soc., Dalton Trans., 2002, 4617–4621

View Article Online
CH2Cl2 (5 mL) was added dropwise to a solution of
[Pd(COD)Cl2] (0.055 g, 0.194 mmol) also in CH2Cl2 (3 mL) and
the reaction mixture was stirred at room temperature for 16 h.
The solution was concentrated to 3 mL, and 1 mL of petroleum
ether (bp 60–80 ЊC) was added. Cooling this solution to 0 ЊC
gave yellow crystalline, analytically pure sample of 6. Yield:
85% (0.14 g). Mp 270 ЊC (decomp.). Anal. Calc. for
C45H34Cl2O2P2Pd: C, 63.88; H, 4.05. Found: C, 63.75; H, 3.93%.
Department, Tulane University, New Orleans, Louisiana, USA
for the support of the Crystallography Laboratory. We also
thank the Regional Sophisticated Instrumentation Center
(RSIC), Bombay for recording NMR spectra.
References and notes
1 C. A. McAuliffe, in Comprehensive Coordination Chemistry, eds.
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2 C. A. McAuliffe and A. G. Mackie, in Encyclopedia of Inorganic
Chemistry, ed. R. B. King, John Wiley and Sons, New York, 1994,
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Synthesis of [PtCl2{ꢁ2-Ph2P{(–OC10H6)(ꢀ-CH2)(C10H6O–)}-
PPh2-ꢂP,ꢂP}] (7)
A solution of the bis(phosphine) 1 (0.1 g, 0.15 mmol) in CH2Cl2
(5 mL) was added dropwise to a solution of [Pt(COD)Cl2]
(0.056 g, 0.15 mmol) also in CH2Cl2 (3 mL). The reaction mix-
ture, which turned light yellow during the reaction, was stirred
at room temperature for 12 h. The solution was concentrated
to 3 mL, and 1 mL of petroleum ether (bp 60–80 ЊC) was added
to it. Cooling this solution to 0 ЊC afforded the product 7 as
colorless crystals suitable for X-ray analysis. Yield: 90%
(0.126 g). Mp 145 ЊC (decomp.). Anal. Calc. for C45H34-
Cl2O2P2PtؒCH2Cl2ؒH2O: C, 53.70; H, 3.72. Found: C, 53.51; H,
3.66%. 1H NMR (300 MHz, CDCl3): δ 7.94 (br s, 2H, Ar), 7.68
(d, 2H, Ar), 7.52 (br s, 2H, Ar), 7.44 (t, 2H, Ar), 7.28–7.40 (m,
20H, OPPh2), 7.14 (br s, 2H, Ar), 6.54 (d, 2H, Ar), 4.76 (ABq,
3 D. E. C. Corbridge, Phosphorus: An Outline of its Chemistry,
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2
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23 The complexes 4 and 7 did not crystallize well from very dry
solvents. However, when air was bubbled for a few seconds through a
dichloromethane/hexane (1 : 1) solution of the complex followed by
cooling to 0 ЊC, X-ray quality crystals were obtained containing
both dichloromethane and water of solvation.
24 W. H. Pearson, J. E. Shade, J. E. Brown and T. E. Bitterwolf, Acta
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X-Ray crystal structure
Crystals of compounds 3, 4 and 7, suitable for X-ray crystal
analyses were obtained from slow evaporation of CH2Cl2
solutions, layered with petroleum ether (bp 60–80 ЊC), at room
temperature. The crystals were coated with an epoxy resin
and mounted on Pyrex filaments on a Enraf-Nonius CAD-4
diffractometer. General procedures for crystal orientation, unit
cell determination, refinement and collection of intensity data
have been published.37 Intensity data were collected at room
temperature using graphite-monochromated Mo-Kα (λ =
0.71073 Å) radiation with a Enraf-Nonius CAD-4 diffract-
ometer. Intensities were corrected for Lorentz–polarisation
effects (XCAD4)38 and for absorption. The structures were
solved by direct methods (SHELXS-97). Refinements were
done by full-matrix least squares based on F 2 using the
SHELXTL-PLUS39 program package. Details of the data
collections and refinements specific to these compounds are
summarized in Table 4. In ruthenium compound 4 there is an
ordered CH2Cl2 molecule at 50% occupancy (Cl1s–C1s–Cl2s)
and a second one disordered over two sites having Cl3 in com-
mon (Cl3s–C4sa–Cl4a and Cl3s–C4sb–Cl4b). The hydrogen
atoms on these carbon atoms were not included because of the
disorder. Besides this, there are two isolated areas of electron
density that were modeled by solvent water (with ∼25%
occupancy). Although hydrogen atoms were not identified
clearly, O1s is 2.84 and 3.07 Å, respectively, from the alternate
disordered locations for O2s (at 1.5Ϫx, 1.5Ϫy, 2Ϫz and x,
yϪ1, z), both of which seem reasonable distances for hydrogen
bonding. In the platinum complex 7 there is a CH2Cl2 molecule
at full occupancy and a water molecule (O3). Hydrogen atoms
attached to O3 could not be reliably located, however, O3 is
2.64 Å from O3 at (2Ϫx, Ϫy, 2Ϫz) which is a reasonable
separation for two waters H-bonded together.
CCDC reference numbers 190092–190094.
See http://www.rsc.org/suppdata/dt/b2/b206994f/ for crystal-
lographic data in CIF or other electronic format.
34 P. J. Fagan, W. S. Maloney, J. C. Calabrese and I. D. Williams,
Organometallics, 1990, 1843.
35 D. Drew and J. R. Doyle, Inorg. Synth., 1972, 13, 52.
36 D. Drew and J. R. Doyle, Inorg. Synth., 1972, 13, 48.
37 J. T. Mague and C. L. Lloyd, Organometallics, 1988, 7, 983.
38 K. Harms and S. Wocadlo, CAD-4 Files, Program to Extract
Intensity Data from Enraf-Nonius, Delft, 1987.
Acknowledgements
We thank the Department of science and Technology (DST),
New Delhi, for financial support of the work done at the Indian
Institution of Technology, Bombay and the Chemistry
39 Bruker AXS, SHELXTL-PLUS, Version 5.1, Madison, WI, 1997.
J. Chem. Soc., Dalton Trans., 2002, 4617–4621
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