Synthesis and characterization of aminophosphines, bis(amino)phosphine derivatives, and their molybdenum(0) complexes

Article abstract of DOI:10.1080/10426500802341275

Functionalized bis(amino)phosphines of the type PhP(NHR)2 (1a-c) and aminophosphines of the type Ph2PNHR (2a-c) have been synthesized by treating PhPCl2 or Ph2PCl with corresponding primary amines of H2N-R where R = -CH2SO3H, -C6H4SO3H, and benzo-15-crown-5. The molybdenum(0) complex of the aminophosphine (3) has been obtained by reacting cis-[Mo(CO)4(bipy)] with aminophosphine (2c). The synthesized aminophosphines, bis(amino)phosphines, and the molybdenum(0) complex have been characterized by IR, 1H NMR, 31P NMR, and MS spectroscopic techniques and by elemental analysis.

Full text of DOI:10.1080/10426500802341275

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Phosphorus, Sulfur, and Silicon
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Synthesis and Characterization
of Aminophosphines,
Bis(amino)phosphine
Derivatives, and Their
Molybdenum(0) Complexes
b
Özlem Sarıöz a , Osman Serindaĝ & Meysun İ.
Abdullah a
a Department of Chemistry, Faculty of Science-Arts,
Ni ĝde University, Niĝde, Turkey
b Department of Chemistry, Faculty of Science-Arts,
Çukurova University, Adana, Turkey
Published online: 22 Jun 2009.
To cite this article: Özlem Sarıöz , Osman Serindaĝ & Meysun İ. Abdullah (2009):
Synthesis and Characterization of Aminophosphines, Bis(amino)phosphine Derivatives,
and Their Molybdenum(0) Complexes, Phosphorus, Sulfur, and Silicon and the Related
Elements, 184:7, 1785-1795
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Phosphorus, Sulfur, and Silicon, 184:1785–1795, 2009
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500802341275
Synthesis and Characterization of Aminophosphines,
Bis(amino)phosphine Derivatives, and Their
Molybdenum(0) Complexes
1
2
¨
ˇ
¨
Ozlem Sarıoz, Osman Serindag,
1
˙
and Meysun I. Abdullah
1Department of Chemistry, Faculty of Science-Arts, Nigˇde University,
Nigˇde, Turkey
2Department of Chemistry, Faculty of Science-Arts, C¸ ukurova
University, Adana, Turkey
Functionalized bis(amino)phosphines of the type PhP(NHR) (1a–c) and
2
aminophosphines of the type Ph PNHR (2a–c) have been synthesized by treat-
2
ing PhPCl or Ph PCl with corresponding primary amines of H N-R where R =
2
2
2
-CH SO H, -C H SO H, and benzo-15-crown-5. The molybdenum(0) complex of
2
3
6
4
3
the aminophosphine (3) has been obtained by reacting cis-[Mo(CO) (bipy)] with
4
aminophosphine (2c). The synthesized aminophosphines, bis(amino)phosphines,
1
31
and the molybdenum(0) complex have been characterized by IR, H NMR,
P
NMR, and MS spectroscopic techniques and by elemental analysis.
Keywords Aminophosphine; bis(amino)phosphines; crown ethers; molybdenum(0)
complexes
INTRODUCTION
Phosphine ligands have many important applications in organometal-
lic chemistry and catalysis.1,2 It is not surprising that there contin-
ues to be considerable interest in synthesis of new phosphines that
have specific and well-characterized steric, electronic, and solubility
properties.3 Aminophosphines of the type R2PNR1R2 have been rela-
tively neglected as ligands, despite a number of potentially attractive
features. The mild conditions required for formation of P–N bond allow
facile incorporation of additional functionalities, and problems caused
Received 28 April 2008; accepted 14 July 2008.
We are grateful to the Research Foundation of The University of Nigˇde (NUAF) for
¨
financial support and the Chemistry Department of The University of C¸ ukurova for
providing research facilities.
¨
Address correspondence to Ozlem Sarıo¨z, Department of Chemistry, Faculty of
Science-Arts, Nigˇde University, 5100 Nigˇde, Turkey. E-mail: ozsarioz4@yahoo.com
1785

¨
O. Sarıo¨z et al.
1786
by the sensitivity of this bond to hydrolysis are often eliminated upon
coordination.4 The chemistry of aminophosphines containing direct P–
N bonds is one of the most challenging areas in main group chemistry.5
The coordination and organometallic chemistry of phosphorus bearing
ligands possessing one (or more) P–N bond(s) have received some at-
tention especially of late.4,6–11 Interest in phosphines with P–N bonds
arises from the different electronic properties transferred by the ni-
trogen center to the phosphorus center(s).12 P–N bond formation as
a method for ligand construction has become increasingly popular in
recent years.13 Potentially this ligand family is extremely attractive,
since preparative routes enable access to various structural modifica-
tions via simple P–N bond formation.9 Since both steric and electronic
effects exerted by a functional group on the amine play a significant
role on the outcome of the reaction,12 aminophosphines possessing P–N
bonds have attracted considerable interest in recent years because of
their versatile coordination chemistry. Although they posses two po-
tential donor atoms, their coordination compounds involve almost ex-
clusively the metal–phosphorus bond.14 Many aminophosphine ligands
and their complexes have been investigated in a number of catalytic
processes.5,9,15–17 Some aminophosphines and derivatives have also
found application as anticancer drugs, herbicides, and antimicrobial
agents, as well as neuroactive agents.5
In recent years the synthesis and coordination chemistry of phos-
phorus(III) ligands containing P–N linkages, generally derived by the
condensation of chlorophosphines with primary amines in the pres-
ence of a tertiary amine base, has received widespread attention.10
In the present article, we report the synthesis and metal complex
formation of new aminophosphine ligands. Ligands 1a–c and 2a–
c can be prepared from the corresponding commercially available
amines and dichlorophenylphosphine or chlorodiphenylphosphine ac-
cording to the literature.9,18,19 The synthesized aminophosphines,
bis(amino)phosphines, and the molybdenum(0) complex have been
1
characterized by IR, H NMR, 31P NMR, and MS spectroscopic tech-
niques and by elemental analysis.
RESULTS AND DISCUSSION
Synthesis and Spectroscopic Properties
of Bis(amino)phosphines
Earlier works had shown that primary amines react with alkyl-
or aryldichlorophosphines (RPCl2) in the presence of an HCl scav-
enger, either excess primary amines or added tertiary amine, to form

Aminophosphines and Bisaminophosphines
1787
bis(amino)phosphines.19 Bis(amino)phosphines (1a–c) were prepared
from dichlorophenylphosphine and primary amines (aminomethane-
sulfonic acid, sulfanilic acid, and 4-aminobenzo-15-crown-5) in the pres-
ence of triethylamine as is shown in Scheme 1.
NHR
Et3N
PhPCl2 + H2NR
PhP
-Et3N.HCl
NHR
1
-
+
CH SO Et3NH
a) R=
2
3
-
+
C H SO Et NH
b) R=
c) R=
6
4
3
3
O
O
O
O
O
SCHEME 1 Synthesis of bis(amino)phosphine ligands.
1
Compounds (1a–c) were characterized by 31P-{ H}, 1H-NMR, and IR
1
spectroscopic techniques and by elemental analysis. The 31P-{ H} NMR
spectra of the bis(amino)phosphines show singlets at 21.3 ppm (for 1a),
18.2 ppm (for 1b), and 18.7 ppm (for 1c). No 2JPH coupling is observed in
1
the 31P NMR spectra. The chemical shifts in the 31P-{ H} NMR spectra
are in accordance with the electronic properties of the substituents
on nitrogen and phosphorus. A similar chemical shift is observed for
bis(amino)phosphines (1a–c), suggesting that the difference in δ(P) is
primarily due to the presence of an alkyl group rather than a hydrogen
atom on the bis(amino)phosphine nitrogen atom.4 The electronic effect
of the quaternary ammonium functionality on the 31P chemical shift
is negligible. This is not unexpected, since electronic effects generally
contribute only slightly to the chemical shifts in similar compounds,
and the quarternized nitrogen is well removed from the phosphorus
atom.20 In the 31P NMR spectra, no peak is observed for unreacted
PPhCl2 compound around 160.2 ppm.21
1
In the H NMR spectra, the NH signals are observed as singlet at
2.6 ppm for 1a, as broad at 5.3 ppm for 1b, and as singlet at 2.2 ppm for
1
1c. H NMR spectra shows that 1a and 1b ligands are in SO3Et3NH
form. The signal at 12 ppm is assigned to the NH proton of Et3NH+.22
Methylenic (-CH2-) protons of the triethylamine counterion of 1a and
1b are observed 3.6 and 3.1 ppm, respectively, where methyl (CH3-
1
) protons are at 1.4 ppm.23 The H NMR of 1a shows a doublet for
the PNHCH2 protons at δ 1.9 (JPH = 29 Hz), which is consistent with
1
reported studies.9 In the H NMR spectra of 1c, while the resonances
due to aromatic protons appear in the range δ 6.6–7.8, NH signals

¨
O. Sarıo¨z et al.
1788
were observed as singlet at 2.2 ppm. In addition, the resonances due to
O-CH2 protons of 1c appear in the region δ 3.0–4.1. The 1H NMR spectra
are consistent with the structure proposed.
In the IR spectra (KBr) of the ligands, the ν(NH) band is observed
at 3166 cm−1 (1a), 3234 cm−1 (1b), and 3347 cm−1 (1c).24,25 The ν(PN)
vibration is tentatively assigned to a very strong absorption at 856
cm−1 for 1a–b and 835 cm−1 for 1c respectively.18 The ν(PPh) bands
are observed in 1442 cm−1. The IR spectrum of 1a–b shows νSO3 bands
at 1186 and 1045 cm−1for 1a and 1178 and 1043 for 1b. The IR spectrum
of 1c shows νC−Oalifatic and νC−Oaromatic bands, respectively, at 1143 and
1253 cm−1
.
Synthesis and Spectroscopic Properties of Aminophosphines
Aminophosphines (2a–c) were prepared from chlorodiphenylphosphine
and primary amines (aminomethanesulfonic acid, sulfanilic acid, and
4-amino-benzo-15-crown-5) in the presence of triethylamine as was
shown in Scheme 2.
Et3N
Ph
Ph
Ph2PCl + H2NR
P
NHR
-Et3N.HCl
2
-
+
CH SO
a) R=
Et3NH
3
2
-
+
C H SO
Et3NH
3
b) R=
c) R=
6
4
O
O
O
O
O
SCHEME 2 Synthesis of aminophosphine ligands.
1
1
Compounds (2a–c) were characterized by 31P-{ H}, H-NMR, and
IR spectroscopic techniques and by elemental analysis. In phospho-
rus chemistry, 31P NMR spectroscopy has been widely used to mon-
itor reactions, which allows the rapid identification of product based
on characteristic signals in the spectrum. In general, diphenylphos-
phinoamines exhibit a singlet resonance typically around 64–70 ppm
(67.7 ppm in PhN(PPh2)2 and 65.6 ppm in C6H4(o-OCH3)N(PPh2)2].
Arylaminodiphenylphosphines also give rise to singlet resonances be-
tween 25 and 35 ppm (29.4 ppm in PhNH-PPh2, 26.4 ppm in PyNH-
PPh2, 27.2 ppm in C6H4(o-OCH3)NH-PPh2).12 A similar chemical shift
is observed for aminophosphines, suggesting that the difference in
δ(P) is primarily due to the presence of an alkyl group rather than a
1
hydrogen atom on the aminophosphine nitrogen atom.4 The 31P-{ H}

Aminophosphines and Bisaminophosphines
1789
NMR spectra of the aminophosphines show singlets at 22.7 ppm (for
2
2a), 22.5 ppm (for 2b), and 22.6 ppm (for 2c). No JPH coupling is
observed in the 31P NMR spectra. The 31P NMR spectra are con-
sistent with the structure proposed. The chemical shifts in the 31P-
1H NMR spectra are in accordance with the electronic properties of
the substituents on nitrogen and phosphorus. The electronic effect of
the quaternary ammonium functionality on the 31P chemical shift is
negligible.20 The absence of a signal at 81.5 ppm indicates that no
unreacted PPh2Cl remained.21
1
In the H NMR spectra, the NH signals are observed as broad res-
onances at 5.4 ppm for 2a and as a singlet at 1.7 ppm for 2b. 1H
NMR spectra shows that 2a and 2b ligands are in the –SO3Et3NH
form. In the 1H NMR of 2a–b, there are signals at δ 10.8 and 10.9
for Et3NH+.22,26 Peaks at 2.9 ppm (quartet) and 1.0 ppm (quartet)
for 2a and 3.1 ppm (multiple), 1.4 ppm (triplet) for 2b are due to
the methylenic (-CH2-) and methyl (CH3-) proton of the triethylamine
1
counterion.23 In addition, in the H NMR of 2a, a PNHCH2 signal is
observed at 2.9 ppm.
In the IR spectra (KBr) of the ligands, the ν(NH) band is observed
at 3197 cm−1 (2a), 3230 cm −1 (2b), and 3393 cm−1 (2c).24,25 The ν(PN)
vibration is tentatively assigned to a very strong absorption at 850
cm−1 for 2a, 900 cm−1 for 2b, and 835 cm−1 for 2c.24 The ν(PPh) bands
are observed in 1442 cm−1 for 2a, 2c and 1438 cm−1 for 2b. The IR
spectrum of 2a–b shows νSO3 bands at 1187 and 1039 cm−1 for 2a and
1182 and 1030 for 2b. The IR spectrum of ligand 2c shows νC−Oaliphatic
and νC−Oaromatic bands, respectively, at 1132 and 1234 cm.−1
Synthesis and Characterization of
cis-[Mo(CO)4(Ph2PNH-benzo-15-crown-5)2]
The aminophosphine ligand 2c reacts readily with cis-[Mo(CO)4(bipy)]
to give cis- [Mo(CO)4(PPh2NH-benzo-15-crown-5)2] (3) in high yield as
shown in Scheme 3.
O
O
O
CO
Mo
CO
Mo
N
N
O
O
OC
OC
O
PPh2HN
PPh2HN
OC
OC
O
O
O
O
PPh2NH
+
O
reflux
CH2Cl2
CO
O
CO
O
O
O
3
SCHEME 3 Synthesis of cis-[Mo(CO)4(Ph2PNH-benzo-15-crown-5)2].

¨
O. Sarıo¨z et al.
1790
Molybdenum(0) complex (3) was characterized by microanalytical
data, infrared, mass, and NMR spectroscopic data. In the 1H NMR
spectra of complex 3, while the resonances due to aromatic protons
appear in the range δ 6.4–8.3, NH signals were observed as singlet
at 4.9 ppm. In addition, the resonances due to O-CH2 protons of the
complex appear in the region δ 3.3–4.3.27,28 The 31P-1H NMR spectra
of the complex shows singlet at 70.74 ppm, which is in accord with the
data reported for Mo(CO)4P analogous complexes.18,24 Ligands bearing
both amine and tertiary phosphine donors can behave as monodentate
ligand (via P or N) or bidentate ligand (via P and N).29 The P–N bond
in aminophosphines is essentially a single bond, so the lone pairs on ni-
trogen and phosphorus are available for donor bonding towards metal
atoms. The phosphorus chemical shift for complexes indicates P–Mo
interaction due to the low coordination shift value of complexes (ꢀδ). In
1
the 31P-{ H} NMR spectra, the complex exhibits singlet, which shows
the expected low-field shift relative to the uncoordinated ligand (ꢀδ =
48.1 ppm). The phosphorus chemical shifts at δ 70.74 ppm for the com-
plex indicates P–Mo interaction. IR spectrum of this complex has bands
at 3405, 1443, and 835 cm−1 due to NH, PPh, and PN vibrations, respec-
tively. The IR spectrum of the complex shows νC−Oaliphatic and νC−Oaromatic
bands, respectively, at 1137 and 1255 cm−1. NH bands also do not show
a significant shift with respect to that of the free ligand, suggesting
that ligation of 2c is through the phosphorus atom. Several of the ab-
sorption bands of phenylphosphines in infrared are very sensitive to
coordination; significant shifts are observed. The strong C–H phenyl
out-of-plane vibration at 750 cm−1 of the phenylphosphine group in the
IR spectra of the ligand shifts significantly upwards in the molybdenum
complex.30 The shift of this complex is 8 cm−1. The shift of the strong
C-H phenyl out-of-plane vibration of phenylphosphine group of ligand
2c in the molybdenum complex indicates that ligation of ligand 2c is
through phosphorus. The infrared spectra of the complex exhibits four
intense ν(CO) absorptions, typically in the region 1771–2009, consistent
with a cis tetracarbonylmolybdenum fragment.9,24,31–34 The generation
of Mo(CO)4L complexes may be used to as a rapid “spot test” for the
donor properties of new ligands. This attribute has been recognized
for many years, and an extensive literature exists for these complexes,
allowing ready comparison with a variety of other phosphorus (III) lig-
ands. The value νCO has been used to evaluate the ligand electronic
properties, and it has been found that for π-acceptor ligands, νCO is at
higher wave number than for σ-donor ligands. A shift to lower frequency
indicates a stronger donation of electron density from ligand to metal
to carbonyl ligand and thereby indicates a stronger σ-donor ability for

Aminophosphines and Bisaminophosphines
1791
the P–N ligands.1 We also have also re-prepared Mo(CO)4(Ph2PNHPh)2
and recorded its IR spectra to calibrate our values. It was found that in
the molybdenum complex 3, the CO stretching frequency (2009 cm−1
)
is significantly lower than in the Mo(CO)4(Ph2PNHPh)2 complex (2024
cm−1). The distinct CO strectching frequences can be explained due to
having a very electron-rich ligand. The new very electron-rich ligand
prepared here should, given its ease of preparation, be a useful tool in
organometallic chemistry and catalysis.
Elemental analysis data is in agreement with calculated values.
FAB+ mass spectrometry of the molybdenum complex (3) confirms the
proposed identity of the complex (3) by showing the expected parent-ion
peak. Electronic spectra of ligand 2c and their molybdenum complex (3)
were recorded in CHCl3 solution. In addition to the absorption bands of
the ligand, an absorption maximum is observed in the 547 nm for the
metal complex, which may be assigned to a charge transfer transition.
The reactions of cis-[Mo(CO)4(bipy)] with aminophosphines (1a–b
1
and 2a–b) were investigated, but in their 31P-{ H} NMR spectra, the
other molybdenum(0) complexes do not show any significant differences
between the coordinated and free ligand.
EXPERIMENTAL
Reactions were routinely carried out using Schlenk–line techniques un-
der pure dry dinitrogen. Solvents were dried and distilled prior to use.
Mo(CO)4(bipy) was prepared by reacting Mo(CO)6 with 2,2ꢀ bipyridine
in toluene and used in the synthesis of further molybdenum complexes.
All other chemicals were reagent grade, available commercially and
used without further purification. Melting points were determined on
1
1
a Electrothermal A 9100 and are uncorrected. 31P-{ H} and H NMR
spectra were taken on a Bruker Avance DPX-400 spectrometer. In-
frared spectra were recorded on a Jasco FTIR 300E spectrometer in
KBr. FAB-MS spectra were measured on a VG-Zapspec MS. Elemental
analyses were performed in a CHNS-932 (LECO). UV-Vis spectra were
recorded on a Shimadzu 160-A spectrophotometer.
Preparation of PhP(NHCH2SO3Et3NH)2 (1a)
Triethylamine (2.60 mL, 18.6 mmol) and PhPCl2 (0.61 mL, 4.5 mmol)
were sequentially added with stirring to a solution of NH2CH2SO3H
(1.00 g, 9.0 mmol) in THF (20 mL). The reaction mixture was stirred for
3 h and then filtered to remove NEt3HCl. The resulting solution was
evaporated under reduced pressure, and the product was extracted with

¨
O. Sarıo¨z et al.
1792
diethyl ether at –78◦C. The resulting solution was evaporated under re-
duced pressure to give a colorless powder. Yield 2.05 g (88%). Mp: 98 ◦C.
1H NMR (CDCl3, DMSO): 12.0 (b, NEt3H+, 2H), 6.7–8.6 (m, Ph, 5H),
1.9 (d, PNCH2,4H, JPH =29), 2.6 (s, NH, 2H), 3.6 (m, NH(CH2CH3)+,
3
+
1
12H), 1.4 (m, NH(CH2CH3)3 , 18H). 31P-{ H} NMR (CDCl3): 21.3 (s). IR
(KBr, cm−1): 856 (PN), 3166 (NH), 1442 (PPh), 3054 (CHaromatic), 2975
(CHalifatic), 1186 and 1045 (SO3). Elemental Analysis: C20H43PN4O6S2
(530.64 g) Found (Required): C, 45.53 (45.27); H, 8.18 (8.17); N, 10.44
(10.56) ; S, 11.82 (12.08).
Preparation of PhP(NHC6H4SO3Et3NH)2 (1b)
A similar procedure to that described in 1a was used. Yield 1.90
g (50%). Mp: 118◦C. 1H NMR (CDCl3): 12.0 (b, NEt3H+, 2H), 6.9–
8.2 (m, Ph, 13H), 5.3 (bs, NH, 2H), 3.1 (q, NH(CH2CH3)+,12 H), 1.4
3
(t, NH(CH2CH3)+, 18H). 31P-{ H} NMR (CDCl3): 18.22 (s). IR (KBr,
1
cm−1): 856 (PN),33234 (NH), 1442 (PPh), 3050 (CHaromatic), 1178 and
1043 (SO3). Elemental Analysis: C30H47PN4O6S2 (654.77 g) Found (Re-
quired): C, 54.45 (55.03); H, 6.98 (7.23); N, 8.47 (8.56) ; S, 9.38 (9.79).
Preparation of PhP(NH-benzocrown-5)2 (1c)
A similar procedure to that described in 1a was used. Yield 0.20 g (87%).
1
Mp: 135◦C. H NMR (CDCl3, ppm): 6.6–7.8 (m. Ph, 11H), 2.2 (s, NH,
2H), 3.0–4.1 (m, O-CH2, 32 H). 31P-1H NMR (CDCl3, ppm): 18.74 (s);
IR (KBr, cm−1): 835 (PN), 3347 (NH), 1442 (PPh), 3053 (CHaromatic),
2937 (CHalifatic), 1143 (COCalifatic) and 1253 (COCaromatic). Elemental
Analysis: C34H45PN2O10 (672.63 g) Found (Required): C, 60.42 (60.71);
H, 6.52 (6.74); N, 4.22 (4.16).
Preparation of PPh2NHCH2SO3Et3NH (2a)
Triethylamine (2.50 mL, 18.0 mmol) and Ph2PCl (1.65 mL, 9.0 mmol)
were sequentially added with stirring to a solution of NH2CH2SO3H
(1.00 g, 9.0 mmol) in THF (20 mL). The reaction mixture was stirred for
3 h and then filtered to remove NEt3HCl. The resulting solution was
evaporated under reduced pressure, and the product was extracted
with diethyl ether at –78◦C. The resulting solution was evaporated un-
der reduced pressure to give a colorless powder. Yield 2.50 g (70%).
Mp: 147◦C. 1H NMR (CDCl3, ppm): 10.8 (b, NEt3H+, 1H), 6.9–8.0.
(m, PPh, 10H), 5.4 (b, NH, 1H), 2.9 (q, NH(CH2CH3)+, PNCH2, 8H),
3
+
1
1.0 (q, NH(CH2CH3)3 , 9H). 31P-{ H} NMR (CDCl3, ppm): 22.7 (s). IR

Aminophosphines and Bisaminophosphines
1793
(KBr, cm−1): 850 (PN), 3197 (NH), 2680 (NCH2), 1442 (PPh), 3054
(CHaromatic), 2973 (CHalifatic), 1187 and 1039 (SO3). Elemental Analy-
sis: C19H29PN2O3S (396.45 g) Found (Required): C, 57.43 (57.56); H,
7.25 (7.37); N, 7.26 (7.07) ; S, 7.98 (8.09).
Preparation of PPh2NHC6H4SO3Et3NH (2b)
A similar procedure to that described in 2a was used. Yield 1.90 g
1
(39%). Mp: 122◦C. H NMR (DMSO, ppm): 10.9 (b, NEt3H+, 1H), 6.6–
8.0 (m, Ph, 14H), 1.7 (s, NH, 1H), 3.1 (m, NH(CH2CH3)+, 6H), 1.4 (t,
3
+
1
NH(CH2CH3)3 , 9H). 31P-{ H} NMR (CDCl3, ppm): 22.50 (s). IR (KBr,
cm−1): 900 (PN), 3230 (NH), 1438 (PPh), 3050 (CHaromatic), 1182 and
1030 (SO3). Elemental Analysis: C24H31PN2O3S (458.51 g) Found (Re-
quired): C, 62.58 (62.86); H, 6.69 (6.81); N, 5.74 (6.12) ; S, 6.37 (6.99).
Preparation of Ph2PNH-benzocrown-5 (2c)
A similar procedure to that described in 2a was used. Yield 0.40 g (86%).
1
31P-{ H} NMR (CDCl3, ppm): 22.60 (s); IR (KBr, cm−1): 835 (PN), 3393
(NH), 1442 (PPh), 3067 (CHaromatic), 2949 (CHalifatic), 1132 (COCalifatic
)
and 1234 (COCaromatic). Elemental Analysis: C26H30PNO5 (467.45 g)
Found (Required): C, 66.65 (66.80); H, 6.16 (6.47); N, 3.35 (2.99).
Preparation of cis-[Mo(CO)4(Ph2PNH-benzocrown-5)2] (3)
Ligand (0.20 g, 0.43 mmol) and [Mo(CO)4(bipy)] (0.08 g, 0.22 mmol)
were refluxed in 20 mL CH2Cl2 for 5 h. The solution was con-
centrated in vacuo, and the purple product was precipitated with
30 mL diethylether. The purple residue was separated by filtra-
tion, washed with toluene (3 × 5 mL) and recrysallized from
◦
CH2Cl2-diethylether. Yield: 0.20 g (83%). Mp: 189–191 C (decomp).1
H NMR (CDCl3, ppm): 6.4–8.3 (m. Ph, 26H), 4.9 (s, NH, 2H),
1
3.3–4.3 (m, O-CH2, 32 H). 31P-{ H} NMR (CDCl3, ppm): 70.74.
MS [m:z, %]: 955 [Mo (Ph2PNH-benzocrown-5)(PhPNH-benzocrown-
5)+, 4), 763 [Mo(Ph2PNH-benzocrown-5)(PhPNHC6H3)+, 4), 506
[Mo(CO)3(PPh2NH)(PhPNH)+, 100], 490 [Mo(CO)3(PPh2N)(PhP)+, 35],
467 (Ph2PNH-benzocrown-5+, 12), 313 [PNH-benzocrown-5+, 7), 282
[NH-benzocrown-5+, 7), 200 [PPh2NH, 6] and fragmentation prod-
ucts thereof. IR (KBr, cm−1): 835 (PN), 3405 (NH), 1443 (PPh),
3060 (CHaromatic), 2933 (CHalifatic), 1137 (COCal), 1255 (COCar), 2009,
1913, 1820 and 1771 (CO). Elemental Analysis: C56H60MoN2O14P2

¨
O. Sarıo¨z et al.
1794
(1142.98 g) Found (Required): C, 58.53 (58.84); H, 5.58 (5.31); N, 2.37
(2.45).
REFERENCES
[1] M. R. Zubiri, M. L. Clarke, D. F. Foster, D. J. Cole-Hamilton, A. M. Z. Slawin, and
J. D. Woollins, J. Chem. Soc., Dalton Trans., 969 (2001).
[2] M. R. Zubiri, H. L. Milton, D. J. Cole-Hamilton, A. M. Z. Slawin, and J. D. Woollins,
Inorg. Chem. Commun., 7, 201 (2004).
[3] L. A. Barg, R. W. Byrn, M. D. Carr, D. H. Nolan, and B. N. Storhoff, Organometallics,
17, 1340 (1998).
[4] A. D. Burrows, M. F. Mahon, and M. T. Palmer, J. Chem. Soc., Dalton Trans., 3615
(2000).
¨
[5] F. Durap, N. Biricik, B. Gu¨mgu¨m, S. Ozkar, W. H. Ang, Z. Fei, and R. Scopelliti,
Polyhedron, 27(1), 196 (2008).
[6] S. Priya, M. S. Balakrishna, and J. T. Mague, J. Organomet. Chem., 679, 116 (2003).
[7] M. Necas, M. R. S. J. Foreman, D. Dastych, and J. Novosad, Inorg. Chem. Commun.,
4, 36 (2001).
[8] H. Liu, N. A. G. Banderia, M. J. Calhorda, M. G. B. Drew, V. Felix, J. Novosad, F. F.
de Biani, and P. Zanello, J. Organomet. Chem., 689, 2808 (2004).
[9] K. G. Gaw, M. B. Smith, and J. D. Steed, J. Organomet. Chem., 664, 294 (2002).
[10] P. Bhattacharyya, T. Q. Ly, A. M. Z. Slawin, and J. D. Woollins, Polyhedron, 20, 1803
(2001).
[11] R. Guo, X. Li, J. Wu, W. H. Kwok, J. Chen, M. C. K. Choi, and A. S. C. Chan,
Tetrahedron Lett., 43, 6803 (2002).
[12] Z. Fei, R. Scopelliti, and P. J. Dyson, J. Chem. Soc., Dalton Trans., 2772 (2003).
[13] P. Bhattacharyya, A. M. Z. Slawin, and J. D. Woollins, Inorg. Chem. Commun., 4,
198 (2001).
¨
¨
[14] B. Gu¨mgu¨m, O. Akba, F. Durap, L. T. Yıldırım, D. Ulku¨, and S. Ozkar, Polyhedron,
25, 3133 (2006).
[15] A. M. Z. Slawin, J. Wheatley, M. V. Wheatley, and J. D. Woollins, Polyhedron, 22,
1397 (2003).
[16] C. Saluzzo, J. Breuzard, S. Pellet-Rostaing, M. Vallet, F. Le Guyader, and M.
Lemaire, J. Organomet. Chem., 643–644, 98 (2002).
[17] J. Cheng, F. Wang , J. Xu, Y. Pan, and Z. Zhang, Tetrahedron Lett., 44, 7095 (2003).
[18] T. Q. Ly, A. M. Z. Slawin, and J. D. Woolins, J. Chem. Soc., Dalton Trans., 1611
(1997).
[19] T. G. Hill, R. C. Haltiwanger, T. R. Prout, and A. D. Norman, Inorg. Chem., 28, 3461
(1989).
[20] R. T. Smith and M. C. Baird, Inorg. Chim. Acta, 62, 135 (1982).
[21] A. Hessler and O. Stelzer, J. Org. Chem., 62, 2362 (1997).
[22] N. O. Brace and S. G. Mull, J. Fluorine Chem., 121, 33 (2003).
[23] P. C. Zachariadis, S. K. Hadjikakou, N. Hadjiliadis, A. Michaelides, S. Skoulika, Y.
Ming, and Y. Xiaolin, Inorg. Chim. Acta, 343, 361 (2003).
[24] O. Ku¨hl, S. Blaurock, J. Sieler, and E. Hey-Hawkins, Polyhedron, 20, 111 (2001).
[25] F. Tisato, G. Pilloni, F. Rofozco, G. Bandoli, C. Corvaja, and B. Corain, Inorg. Chim.
Acta, 275–276, 401 (1998).
[26] M. S. Rahman, J. W. Steed, and K. K. Hii, Synthesis, 1320 (2000).
¨
[27] A. Gu¨l and O. Bekarolu, J. Chem. Soc., Dalton Trans., 2537 (1983).

Aminophosphines and Bisaminophosphines
1795
[28] C. Nataro, H. M. Baseski, C. M. Thomas, B. J. Wiza, and K. M. Rourke, Polyhedron,
20, 1023 (2001).
¨
[29] A. Baysal, M. Aydemir, F. Durap, B. Gu¨mgu¨m, S. Ozkar, and L. T. Yıldırım, Polyhe-
dron, 26, 3373 (2007).
[30] G. Westermark and L. Persson, Colloids and Surfaces A: Physicochemical and En-
gineering Aspects, 144, 149 (1998).
[31] M. S. Balakrishna and R. McDonald, Inorg. Chem. Commun., 5, 782 (2002).
[32] C. L. Thurner, M. Barz, M. Spiegler, and W. R. Thiel, J. Organomet. Chem., 541, 39
(1997).
[33] M. S. Balakrishna, R. M. Abhyankar, and J. T. Mague, J. Chem. Soc., Dalton Trans.,
1407 (1999).
[34] E. Lindner, M. Mohr, C. Nachtigal, R. Fawzi, and G. Henkel, J. Organomet. Chem.,
595, 166 (2000).