Synthesis and characterizaton of monoaminophosphine, bis(amino)phosphine derivatives, and their metal complexes

Article abstract of DOI:10.1080/15533174.2011.568464

Functionalized monoaminophosphine of the type Ph₂PNR₂ (1 and 3) and bis(amino)phosphine of the type PhP(NR₂)₂ (2) have been synthesized by treating Ph₂PCl or PhPCl₂ with corresponding amine

Full text of DOI:10.1080/15533174.2011.568464

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Synthesis and Characterizatıon of
Monoaminophosphine, Bis(Amino)Phosphine
Derivatives, and their Metal Complexes
Özlem Sarıöz a & Sena Öznergiz a
a Department of Chemistry, Faculty of Science-Arts, Niğde University, Niğde, Turkey
Version of record first published: 11 Jul 2011.
To cite this article: Özlem Sarıöz & Sena Öznergiz (2011): Synthesis and Characterizatıon of Monoaminophosphine,
Bis(Amino)Phosphine Derivatives, and their Metal Complexes, Synthesis and Reactivity in Inorganic, Metal-Organic, and
Nano-Metal Chemistry, 41:6, 698-703
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Synthesis and Reactivity in Inorganic, Metal-Organic, and Nano-Metal Chemistry, 41:698–703, 2011
Copyright ꢀ Taylor & Francis Group, LLC
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ISSN: 1553-3174 print / 1553-3182 online
DOI: 10.1080/15533174.2011.568464
Synthesis and Characterizatıon of Monoaminophosphine,
Bis(Amino)Phosphine Derivatives, and their Metal
Complexes
¨
¨
Ozlem Sarıo¨z and Sena Oznergiz
˘
˘
Department of Chemistry, Faculty of Science-Arts, Nigde University, Nigde, Turkey
of the general formula Ph2P(E)NR2 or PhP(E)(NR2)2 and their
transition metal complexes. The compounds were fully charac-
terized by IR, 1H NMR, and 31P NMR spectroscopic techniques,
and by elemental analysis.
Functionalized monoaminophosphine of the type Ph2PNR2 (1
and 3) and bis(amino)phosphine of the type PhP(NR2)2 (2) have
been synthesized by treating Ph2PCl or PhPCl2 with correspond-
ing amines. Ligands react with aqueous hydrogen peroxide, ele-
mental sulfur, or selenium to give the corresponding chalcogenides
in good yield. The metal complexes of the aminophosphines have
been obtained. All of the compounds were obtained in good yields
and were characterized by IR, NMR, and microanalysis.
EXPERIMENTAL
Reactions were routinely carried out using Schlenk-line tech-
niques under pure dry nitrogen gas. Solvents were dried and dis-
tilled prior to use. [Mo(CO)4(bipy)] and [Cr(CO)4(bipy)] were
prepared according to the literature procedures.[13] All other
chemicals were reagent grade, available commercially, and used
without further purification. Melting points were determined on
Keywords aminophosphines, complexation, oxidation, synthesis
INTRODUCTION
1
a Electrothermal A 9100 and are uncorrected. 31P-{ H} and
The coordination and organometallic chemistry of phos-
phorus bearing ligands possessing one (or more) P N
bond(s) has received some attention, especially of late.[1–7]
Although they possess two potential donor atoms, their
coordination compounds involve almost exclusively the
metal–phosphorus bond.[8] The transition metal chemistry
of aminophosphines is limited. This is partly due to the
sensitivity of the P(III)/N bonds towards acid or base
catalysed hydrolysis during complexation reactions.[2] Many
aminophosphine ligands and their complexes have been in-
vestigated in a number of catalytic processes.[5,9–12] The pres-
ence of P-N bidentate ligands enables many different and
important catalytic processes to occur, including asymmetric
hydroboration, carbonylation of alkynes, Stille coupling, and
asymmetric hydrogenation of highly substituted alkenes, to
name a few.[10] Some aminophosphines and derivatives have
also found application as anticancer drugs, herbicides, and an-
timicrobial agents, as well as neuroactive agents[9]
1H NMR spectra were taken on Bruker UltraShield-400 spec-
trophotometer. Infrared spectra were recorded on a Perkin Emler
FT-IR System Spectrum BX as KBr pellets. Elemental analysis
were performed in a CHNS-932 (LECO).
Preparation of PPh2N(CH2C6H5)2 (1)
Triethylamine (1.8 mL, 13.05 mmol) and Ph2PCl (2.4 mL,
13.05 mmol) were sequentially added with stirring to a solution
of NH(CH2C6H5)2 (2.5 mL, 13.05 mmol) in THF (20 mL). The
reaction mixture was stirred for 3 h and then filtered to remove
Et3N.HCl. The resulting solution was evaporated under reduced
pressure and the product extracted with diethyl ether at –78◦C.
The solvent was removed under vacuum to give a white solid of
the crude product, which was crystallized from CH2Cl2/diethyl
ether mixture (2:1) at 0◦C. Yield 3.75 g (75%). m.p.: 83–85◦C.
1H NMR (CDCl3, δ, ppm): 7.01–8.02 (m, Ph, 20H), 4.10 (d, N-
1
CH2, 4H, JP-H = 8.2 Hz). 31P-{ H} NMR (CDCl3, δ, ppm): 66.5
(s). Selected IR (KBr, cm−1): 861 (PN), 1438 (PPh). Elemental
analysis: C26H24PN (381.45 gmol−1) Found (required): C, 81.74
(81.87); H, 6.15 (6.34); N, 3.52 (3.67).
Herein, we describe the synthesis of new aminophosphine
ligands and the corresponding aminophosphine chalcogenides
Preparation of PhP{N(CH2C6H5)2}2 (2)
Received 12 January 2011; accepted 15 February 2011.
The authors are grateful to Research Foundation of The University
of Nig˘de (NUAF) for financial support.
Address correspondence to Ozlem Sarıo¨z, Department of Chem-
istry, Faculty of Science-Arts, Nig˘de University, Nig˘de, Turkey. E-mail:
ozsarioz4@yahoo.com
A similar procedure to that described in 1 was used. Yield
6.0 g (65%). m.p.: 93–94◦C. 1H NMR (CDCl3, δ, ppm):
7.27–7.65 (m, Ph, 25H), 4.05 (d, NCH2, 8H, JP-H = 7.9 Hz).
¨
1
31P-{ H} NMR (CDCl3, δ, ppm): 24.3 (s). Selected IR (KBr,
cm−1): 850 (PN), 1443 (PPh). Elemental analysis: C34H33PN2
698

AMINOPHOSPHINES
699
(500.61 gmol−1) Found (required): C, 81.23 (81.57); H, 6.48 (516.61 gmol−1) Found (required): C, 78.87 (79.05); H, 6.22
(6.64); N, 5.49 (5.60).
(6.44); N, 5.28 (5.42).
Preparation of PPh2NHCH2SO3H (3)
Preparation of PhP(S){N(CH2C6H5)2}2 (8)
A similar procedure to that described in 1 was used. Yield
2.1 g (71%). m.p.: 147◦C. 1H NMR (CDCl3, δ, ppm): 6.90–8.01.
(m, PPh, SO3H, 11H), 5.41 (b, NH, 1H), 2.90 (d, PNCH2, 2H,
A similar procedure to that described in 5 was used. Yield
1
0.29 g (54%). m.p.: 113–114◦C. H NMR (CDCl3, δ, ppm):
7.22–7.32 (m, Ph, 25H), 4.12 (d, N CH2, 8H, JP-H = 6.8
1
JP-H = 29 Hz). 31P-{ H} NMR (CDCl3, δ, ppm): 30.3 (s). Se-
1
Hz). 31P-{ H} NMR (CDCl3, δ, ppm): 109.4 (s). Selected IR
lected IR (KBr, cm−1): 960 (PN), 1433 (PPh). Elemental analy-
sis: C13H14PNO3S (295.29 gmol−1) Found (required): C, 52.77
(52.88); H, 4.75 (4.78); N, 4.71 (4.74); S, 10.76 (10.86).
(KBr, cm−1): 850 (PN), 665 (PS), 1442 (PPh). Elemental anal-
ysis: C34H33PN2S (532.68 gmol−1) Found (required): C, 76.43
(76.66); H, 6.18 (6.24); N, 5.17 (5.26); S, 5.88 (6.02).
Preparation of Ph2P(O)N(CH2C6H5)2 (4)
Preparation of PhP(Se){N(CH2C6H5)2}2 (9)
A THF solution (10 mL) of 1 (0.75 g, 1.96 mmol) and aque-
ous H2O2 (30% w/w, 0.2 mL) was stirred for 2 h at room tem-
perature. The reaction mixture was concentrated to ca. 1–2 mL
in vacuo and diethylether (20 mL) was added. The precipitate
was fıltered and dried in air to yield 4. Yield 0.33 g (42%).
m.p.: 195–196◦C. 1H NMR (CDCl3, δ, ppm): 7.12–8.07 (m, Ph,
A similar procedure to that described in 6 was used. Yield
1
0.34 g (59%). m.p.: 103–105◦C. H NMR (CDCl3, δ, ppm):
7.25–7.58 (m, Ph, 25H), 3.94 (d, N CH2, 8H, JP-H = 8.1 Hz).
1
31P-{ H} NMR (CDCl3, δ, ppm): 102.2 (s, JPSe = 746 Hz).
Selected IR (KBr, cm−1): 851 (PN), 578 (PSe), 1443 (PPh).
Elemental analysis: C34H33PN2Se (579.57 gmol−1) Found (re-
quired): C, 70.23 (70.46); H, 5.55 (5.74); N, 4.66 (4.83).
1
20H), 4.11 (s, N-CH2, 4H). 31P-{ H} NMR (CDCl3, δ, ppm):
31.4 (s). Selected IR (KBr, cm−1): 897 (PN), 1438 (PPh), 1199
(P = O). Elemental analysis: C26H24PNO (397.45 gmol−1
)
Preparation of Ph2P(O)NHCH2SO3H (10)
Found (required): C, 78.21 (78.57); H, 5.95 (6.09); N, 3.66
(3.52).
A similar procedure to that described in 4 was used. Yield
1
0.29 g (55%). m.p.: 165–167◦C. H NMR (DMSO, δ, ppm):
Preparation of Ph2P(S)N(CH2C6H5)2 (5)
7.21–7.82 (m, PPh, SO3H, 11H), 4.29 (s, NH, 1H), 3.11 (s,
1
PNCH2, 2H). 31P-{ H} NMR (CDCl3, δ, ppm): 22.9 (s). Se-
Ligand 1 (0.71 g, 1.87 mmol) and S8 (0.06 g, 1.87 mmol)
were refluxed in toluene (20 mL) for 5 h. The reaction mix-
ture was concentrated to ca. 1–2 mL in vacuo and diethylether
(20 mL) was added. The precipitate was fıltered and dried in air
to yield 5. Yield 0.44 g (57%). m.p.: 90–91◦C. 1H NMR (CDCl3,
lected IR (KBr, cm−1): 937 (PN), 1205 (P O), 1438 (PPh).
Elemental analysis: C13H14PNO4S (311.29 gmol−1) Found (re-
quired): C, 50.06 (50.16); H, 4.47 (4.53); N, 4.56 (4.50); S,
10.35 (10.30).
δ, ppm): 7.10–8.01 (m, Ph, 20H), 4.19 (d, N-CH2, 4H, JP-H
=
1
7.2 Hz). 31P-{ H} NMR (CDCl3, δ, ppm): 70.8 (s). Selected IR
(KBr, cm−1): 896 (PN), 633 (PS), 1437 (PPh). Elemental anal-
ysis: C26H24PNS (413.51 gmol−1) Found (required): C, 75.33
(75.52); H, 5.72 (5.85); N, 3.22 (3.39); S, 7.56 (7.75).
Preparation of Ph2P(Se)NHCH2SO3H (11)
A similar procedure to that described in 6 was used. Yield
1
0.4 g (63%). m.p.: 191–192◦C. H NMR (CDCl3, δ, ppm):
7.15–7.80 (m, PPh, SO3H, 11H), 3.79 (s, NH, 1H), 2.37 (s,
1
PNCH2, 2H). 31P-{ H} NMR (CDCl3, δ, ppm): 61.4 (s, JPSe
=
Preparation of Ph2P(Se)N(CH2C6H5)2 (6)
747 Hz). Selected IR (KBr, cm−1): 957 (PN), 567 (PSe), 1435
Ligand 1 (0.50 g, 1.30 mmol) and grey Se (0.10 g, 1.30 mmol)
were refıuxed in toluene (20 mL) for 5 h. The reaction mix-
ture was concentrated to ca. 1–2 mL in vacuo and diethylether
(20 mL) was added. The precipitate was fıltered and dried in
(PPh). Elemental analysis: C13H14PSeNO3S (374.25 gmol−1
)
Found (required): C, 41.63 (41.72); H, 3.66 (3.77); N, 3.66
(3.74); S, 8.48 (8.57).
1
air to yield 6. Yield 0.40 g (62%). m.p.: 84–86◦C. H NMR
Preparation of cis-[Mo(CO)4(PPh2N(CH2C6H5)2)2] (12)
Ligand 1 (0.73 g, 1.92 mmol) and [Mo(CO)4(bipy)]
(0.35 g, 0.96 mmol) were refluxed in 20 mL CH2Cl2 for 5 h. The
solution was concentrated in vacuo, and the purple product was
precipitated with diethylether (30 mL). The residue was washed
with toluene (3×5 mL). Yield: 0.77 g (83%). m.p.: 139–141◦C
(decomp).1H NMR (CDCl3, δ, ppm): 7.00–7.96 (m. Ph, 40H),
(CDCl3, δ, ppm): 7.11–8.01 (m, Ph, 20H), 4.21 (d, N-CH2, 4H,
1
JP-H = 11.7 Hz). 31P-{ H} NMR (CDCl3, δ, ppm): 70.4 (s, JPSe
= 755 Hz). Selected IR (KBr, cm−1): 896 (PN), 566 (PSe), 1436
(PPh). Elemental analysis: C26H24PNSe (460.41 gmol−1) Found
(required): C, 67.63 (67.83); H, 5.14 (5.25); N, 2.86 (3.04).
Preparation of PhP(O){N(CH2C6H5)2}2 (7)
1
4.05 (s, CH2, 8H). 31P-{ H} NMR (CDCl3, δ, ppm): 102.4. Se-
A similar procedure to that described in 4 was used. Yield
lected IR (KBr, cm−1): 894 (PN), 1437 (PPh), 2011, 1910, 1871
and 1818 (CO). Elemental analysis: C56H48P2N2O4Mo (970.88
gmol−1) Found (required): C, 69.13 (69.28); H, 4.78 (4.98); N,
2.57 (2.88).
1
0.20 g (40%). m.p.: 117–120◦C. H NMR (CDCl3, δ, ppm):
1
7.29–7.57 (m, Ph, 25H), 3.95 (s, N-CH2, 8H). 31P-{ H} NMR
(CDCl3, δ, ppm): 18.9 (s). Selected IR (KBr, cm−1): 856 (PN),
1429 (PPh), 1209 (P O). Elemental analysis: C34H33PN2O

¨ ¨ ¨ ˙
O. SARIOZ AND S. OZNERGIZ
700
Preparation of cis-[Mo(CO)4(PhP{N(CH2C6H5)2}2)2] (13) Preparation of [Co(PPh2NHCH2SO3H)2Cl2] (18)
A similar procedure to that described in 12 was used. Yield:
CoCl2.2H2O (0.14 g, 0.84 mmol) and PPh2NHCH2SO3H
0.45 g (75%). m.p.: 150–151◦C (decomp).1H NMR (DMSO, δ, (0.5 g, 1.69 mmol) were refluxed in 20 mL THF for 5
1
ppm): 7.40–7.98 (m, Ph, 50H), 4.13 (s, CH2, 16H). 31P-{ H} h. The solvent was removed under vacuum to give a blue
NMR (CDCl3, δ, ppm): 73.7. Selected IR (KBr, cm−1): 858 solid of the crude product, which was crystallized from
(PN), 1440 (PPh), 2009, 1865 and 1813 (CO). Elemental anal- dichloromethane/diethylether (2:1). Yield: 0.42 g (69%). m.p.:
ysis: C72H66P2N2O4Mo (1209.21 gmol−1) Found (required): C, 227–228◦C (decomp). 1H NMR (CDCl3, δ, ppm): 7.10–7.70 (m,
71.33 (71.51); H, 5.38 (5.50); N, 4.37 (4.63).
Ph, SO3H, 22H), 4.52 (b, NH, 2H), 2.66 (s, PNCH2, 4H). 31P-
{ H} NMR (CDCl3, δ, ppm): 45.8. Selected IR (KBr, cm−1): 945
1
Preparation of cis-[Cr(CO)4(PhP{N(CH2C6H5)2}2)2] (14)
(PN), 1438 (PPh). Elemental analysis: CoC26H28P2N2O6S2Cl2
(720.43 gmol−1) Found (required): C, 43.03 (43.35); H, 3.88
(3.92); N, 3.78 (3.89); S, 8.98 (8.90).
A similar procedure to that described in 12 was used. Yield:
1
0.38 g (65%). m.p.: 147–149◦C (decomp). H NMR (CDCl3,
δ, ppm): 7.32–8.11 (m, Ph, 50H), 3.66 (s, CH2, 16H). 31P-
{ H} NMR (CDCl3, δ, ppm): 102.2. Selected IR (KBr, cm−1):
1
RESULTS AND DISCUSSION
885 (PN), 1440 (PPh), 2002, 1871 and 1813 (CO). Elemental
analysis: C72H66P2N4O4Cr (1165.26 gmol−1) Found (required):
C, 73.98 (74.21); H, 5.58 (5.71); N, 4.57 (4.81).
Earlier works had shown that primary and secondary
amines react with chlorophosphines in the presence of a ter-
tiary amine base to form aminophosphines.[14] Ligands 1–3
can be prepared from corresponding commercially available
amine and dichlorophenylphosphine or chlorodiphenylphos-
phine according to the literature.[15] Synthesis of mono- and
bis(amino)phosphine ligands (1–3) and their oxidation reactions
are shown in Figure 1.
Preparation of [Cu(Ph2PN(CH2C6H5)2)2Cl2] (15)
Ligand 1 (0.45 g, 1.20 mmol) and CuCl2.2H2O (0.10 g,
0.59 mmol) and were refluxed in 20 mL THF for 3 h. The solu-
tion was concentrated in vacuo, and the green product was pre-
cipitated with diethylether (30 mL). Yield: 0.38 g (70%). m.p.:
1
272–274◦C (decomp). H NMR (CDCl3, δ, ppm): 7.21–7.74
The structure of the compounds (1–3) was confirmed by
spectroscopic analysis. The spectroscopic data for synthesized
1
(m, Ph, 40H), 4.06 (s, CH2, 8H). 31P-{ H} NMR (CDCl3, δ,
ppm): 80.8. Selected IR (KBr, cm−1): 894 (PN), 1437 (PPh).
Elemental analysis: CuC52H48P2N2Cl2 (897.35 gmol−1) Found
(required): C, 69.43 (69.60); H, 5.18 (5.39); N, 2.99 (3.12).
1
compounds is shown in Table 1. The 31P-{ H} NMR spectra
of the aminophosphines and the bis(amino)phosphine show sin-
glets at 66.5 ppm for 1, 24.3 ppm for 2, and 30.3 ppm for
3.[16–19] The absence of a signal at 81.5 or 160.2 ppm indicates
that no unreacted PPh2Cl or PPhCl2 remained.[20] The 31P NMR
spectra are consistent with the proposed structure. The chemical
Preparation of [Cu{(CH3COO)2(PhP{N(CH2C6H5)2}2)2}]
(16)
1
shifts in the 31P-{ H} NMR spectra are in accordance with the
Ligand 2 (0.50 g, 1.0 mmol) and Cu(CH3COO)2H2O (0.10 g,
0.50 mmol) were refluxed in 20 mL CH2Cl2 for 4 h. The solution
was concentrated in vacuo, and the green product was precip-
itated with diethylether (30 mL). Yield: 0.40 g (68%). m.p.:
253–254◦C (decomp).1H NMR (CDCl3, δ, ppm): 6.91–7.56 (m,
Ph, 50H), 3.57 (s, CH2, 16H), 2.22 (s, CH3COO, 6H). 31P-
electronic properties of the substituents on nitrogen and phos-
phorus.[16–19]
Among the routes used to prepare aminophosphines, the
most frequently used method involves aminolysis of a phos-
phine chloride. The reaction of phosphine chloride and the pri-
mary amine usually provides the target compound, RNHPR2, in
high yield.[18] The reactions of some primary amine derivatives
with Ph2PCl in the presence of triethylamine have been thor-
oughly studied, and different substances were obtained, depend-
ing on the relative ratio of the reagents, the electron-withdrawing
groups, and their positions on the aromatic ring and solvents
suchas diethyl ether and dichloromethane.[19] Aminophosphines
(Ph2PNHR) are found as the main products, and when the re-
action conditions changed, diphosphinoamines (RN(PPh2)2) or
iminodiphosphines (RN = PPh2PPh2) are also formed as the
major products.[19] The substituents at the amine backbone can
also play an important role in determining the outcome of the
products.[21]
{ H} NMR (CDCl3, δ, ppm): 80.8. Selected IR (KBr, cm−1):
1
850 (PN), 1443 (PPh). Elemental analysis: CuC72H72P2N4O4
(1182.86 gmol−1) Found (required): C, 72.93 (73.11); H, 5.98
(6.13); N, 4.44 (4.74).
Preparation of [Ni(PPh2NHCH2SO3H)2Cl2] (17)
A mixture of NiCl2.6H2O (0.13 g, 0.88 mmol) and
PPh2NHCH2SO3H (0.50 g, 1.7 mmol) in THF (10 ml) was
stirred at r.t. for 1 h. The solution was evaporated under re-
duced pressure and the orange product was precipitated with
diethylether (20 mL). Yield: 0.44 g (72%). m.p.: 178–180◦C
(decomp). 1H NMR (CDCl3, δ, ppm): 6.91–8.56 (m, Ph, SO3H,
1
22H), 3.45 (b, NH, 2H), 2.83 (s, PNCH2, 4H). 31P-{ H}
NMR (CDCl3, δ, ppm): 47.2. Selected IR (KBr, cm−1): 943
(PN), 1436 (PPh). Elemental analysis: NiC26H28P2N2O6S2Cl2
(720.19 gmol−1) Found (required): C, 43.21 (43.36); H, 4.18
(3.92); N, 3.98 (3.89); S, 8.82 (8.90).
We investigated the aminolysis reaction of aminomethane-
sulfonic acide with Ph2PCl in the presence of Et3N in thf. The
1
31P-{ H} NMR spectrum of product 3 shows that the com-
pound displays the characteristic signal of aminophosphine at

AMINOPHOSPHINES
701
TABLE 1
The spectroscopic data for synthesized compounds
υ
Compound
δ P
ꢀδ
PN
PPh
P O
P S
P Se
PPh2N(CH2C6H5)2
66.5
24.3
30.3
31.4
70.8
70.4
18.9
109.4
102.2
22.9
61.4
102.4
80.8
73.7
102.2
80.8
47.2
45.8
–
–
–
–
–
–
–
–
–
861
850
960
897
896
896
856
850
851
937
957
894
894
858
885
850
943
945
1438
1443
1433
1438
1437
1436
1429
1442
1443
1438
1435
1437
1437
1440
1440
1443
1436
1438
PhP{N(CH2C6H5)2}2
PPh2NHCH2SO3H
Ph2P(O)N(CH2C6H5)2
Ph2P(S)N(CH2C6H5)2
Ph2P(Se)N(CH2C6H5)2
1199
1209
1205
633
665
566
PhP(O){N(CH2C6H5)2}
PhP(S){N(CH2C6H5)2}22
PhP(Se){N(CH2C6H5)2}2
Ph2P(O)NHCH2SO3H
578
567
–
–
Ph2P(Se)NHCH2SO3H
cis-[Mo(CO)4(PPh2N(CH2C6H5)2)2]
[Cu(Ph2PN(CH2C6H5)2)2Cl2]
cis-[Mo(CO)4(PhP{N(CH2C6H5)2}2)2]
cis-[Cr(CO)4(PhP{N(CH2C6H5)2}2)2]
[Cu{(CH3COO)2(PhP{N(CH2C6H5)2}2)2}]
[Ni(PPh2NHCH2SO3H)2Cl2]
[Co(PPh2NHCH2SO3H)2Cl2]
35.9
14.3
49.4
77.9
56.5
16.9
15.5
CH2
P
CH2
CH2
CH2
CH2
PhPCl2
CH2
CH2
Ph2PCl
N
H
N
N
P
N
CH2
2
1
H2O2/S8/Se
H2O2/S8/Se
E
E
CH2
N
CH2
CH2
P
CH2
CH2
P
CH2
N
N
7-9
4-6
E=O (7), S (8), Se (9)
E=O (4), S (5), Se (6)
E
H2O2/S8/Se
Et3N
Ph
Ph
Ph2PCl + H2NCH2SO3H
P
NHCH2SO3H
P NHCH2SO3H
-Et3N.HCl
Ph
Ph
10-11
E=O (10), Se (11)
FIG. 1. Synthesis of mono- and bis(amino)phosphine ligands (1–3) and their oxidation reactions.
3

¨ ¨ ¨ ˙
O. SARIOZ AND S. OZNERGIZ
702
30.3 ppm, and the result is in agreement with the earlier stud-
ies.[19] In general, aminodiphenylphosphines RNHPPh2 give
rise to singlet resonances between 25 and 35 ppm. Diphos-
phinoamines (R-N(PPh2)2) also exhibit a singlet resonance, but
at higher frequency, typically around 64–70 ppm.[19] There was
no evidence for the formation of iminobiphosphine, producing
two sets of doublets at ∼ +10 to ∼ −20 ppm.[22] The 1H NMR
spectra are consistent with the proposed structure. In the IR
spectra (KBr) of the ligands, the υ(PN) vibration is tentatively
assigned to a very strong absorption at 861 cm−1 for 1, 850
cm−1 for 2, and 960 cm−1 for 3, respectively [16,21]. The υ(PPh)
bands are observed in 1438 cm−1 for 1, 1443 cm−1 for 2, and
1433 cm−1 for 3, respectively.[23]
CO
M
OC
OC
L
L
12 (L=PPh2N(CH2Ph)2), M=Mo)
13
(L=PPh(N(CH2Ph)2)2), M=Mo)
14 (L=PPh(N(CH2Ph)2)2), M=Cr)
CO
12-14
FIG. 2. Proposed structures of cis-[M(CO)4(L)2] complexes.
a single bond, so the lone pairs on nitrogen and phosphorus are
available for donor bonding towards metal atoms. However, no
examples have been synthesized where both P and N have acted
as donor atoms. It is only P that acts as the donor atom. The
phosphorus chemical shift for complexes indicates P-M interac-
tion due to the low coordination shift value of complexes (ꢀδ).
Oxidation of 1–3 aqueous hydrogen peroxide or elemental
sulfur or selenium gave the corresponding oxides (4, 7, and
10), sulfıdes (5 and 8), and selenides (6, 9, and 11), respec-
tively (Scheme 1). Oxidation of 1–3 using aqueous H2O2 was
very rapid even at ambient temperature. However, the reaction
with elemental sulfur or selenium had to be carried out at el-
evated temperatures as expected because elemental sulfur and
selenium are weaker oxidizing agents than hydrogen peroxide,
especially towards phosphorus atoms with bulky phenyl groups.
Compound 3 does not react even at elevated temperature with
elemental sulfur. As is typical of P(V) = E compounds, 31P
chemical shifts of compounds 4–11 occured in the δ 18.9–109.4
ppm range, and the chemical shift region is quite consistent
with the literature for analogous derivatives.[21,24–26] As indi-
cated in the literature, coupling constants of 1JPSe 746–755 Hz
In the 31P-{ H} NMR spectra, 12, 13, and 14 exhibit singlets that
1
show the expected low-fıeld shifts relative to the uncoordinated
ligands [12: 102.4 ppm (ꢀδ = 35.9 ppm), 13: 73.7 ppm (ꢀδ =
49.4 ppm), 14: 102.2 ppm (ꢀδ = 77.9 ppm)].[16] The phosphorus
chemical shifts for the complexes indicate P–M interaction. The
coordination chemical shift value decreases considerably from
chromium to molybdenum, as expected.[2,27] In the IR spectra
of the metal carbonyl complexes, the υ(PN) vibration is tenta-
tively assigned to a very strong absorption at 894 cm−1 for 12,
858 cm−1 for 13, and 885 cm−1 for 14, respectively, which is
shifted to higher wavenumbers for 12 (ꢀυ = 33 cm−1), 13 (ꢀυ
= 8 cm−1), and 14 (ꢀυ = 35 cm−1) compared with their free
ligands.[28] The υ(PPh) bands are observed in 1437 cm−1 for
12, 1440 cm−1 for 13 and 14, respectively. The infrared spec-
tra of the complexes [M(CO)4L2] exhibit three or four intense
ν(CO) absorptions, in the carbonyl region (1813–2011 cm−1),
characteristic of the presence of cis -[M(CO)4] with C2v symme-
try.[5,18,27,29,30] 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, allow-
ing ready comparison with a variety of other phosphorus (III)
ligands. The value υCO has been used to evaluate the ligand
electronic properties, and it has been found that for π-acceptor
ligands, υCO is at higherwave number than for σ-donor ligands.
A shift to lower frequency indicates a stronger donation of elec-
tron density from ligand to metal to carbonyl ligand and thereby
indicates a stronger σ-donor ability for the P–N ligands.[31] The
position of υCO for the molybdenum complexes (12 and 13) is
shown in Table 2. It was found that in the molybdenum complex
13, the CO stretching frequency (2009 cm−1) is lower than in
the molybdenum complex 12 (2011 cm−1). Hence the ligand 2
is stronger σ-donor and more electron rich than the ligand 1.
The chromium complex 14, the CO stretching frequency (2002
1
are often seen for E = Se.[24] The H NMR spectra are con-
sistent with the proposed structure. In the IR spectra of 4–11,
−1
the υ(PN) vibration is observed at 897 cm−1 (4), 896 cm
(5), 896 cm−1 (6), 856 cm−1 (7), 850 cm−1 (8), 851 cm−1 (9),
937 cm−1 (10), and 957 cm−1 (11).[16,21] The υ(PPh) bands are
observed in region of 1429–1443 cm−1. The IR spectra of 4, 7,
and 10 show υP = O vibration at 1199 for 4, 1209 cm−1 for
7, and 1205 cm−1 for 10, respectively.[25] In the IR spectra of
the compounds, while the υP O vibration is observed in very
narrow range, the υP-N vibration is observed in relatively wide
range, suggesting that P(III)-N bonds are quite sensitive to the
substituents attached to them. The structures of the oxidized
derivatives (4,7,10), sulfıdes (5 and 8), and selenides (6,9,11)
were further confırmed by using microanalysis, and found to be
in good agreement with the theoretical values.
The metal carbonyl derivatives, cis-[M(CO)4(L)2] (M = Mo,
L = Ph2PN(CH2Ph)2, 12; M = Mo, L = PhP(N(CH2Ph)2)2, 13;
M = Cr, L = PhP(N(CH2Ph)2)2, 14) were obtained by the dis-
placement of bipyridine from the [M(CO)4(bipy)]. Compound 3
does not react even at elevated temperature. The metal carbonyl
derivatives are shown in Figure 2.
The metal carbonyl derivatives, cis-[M(CO)4(L)2] (12–14)
were characterized by IR, NMR, and elemental analysis. Lig-
ands bearing both amine and tertiary phosphine donors can
behave as monodentate ligand (via P or N) or bidentate ligand
(via P and N). The P N bond in aminophosphines is essentially
cm−1) is lower than in the molybdenum complex 13 (2009 cm−1
)
as expected.[2]
When
a THF solution of CuCl2.2H2O is treated
with a THF solution of Ph2PN(CH2C6H5)2, the com-

AMINOPHOSPHINES
703
TABLE 2
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CONCLUSIONS
In conclusion, the new monoaminophosphines and
bis(amino)phosphine and their oxides, sulfıdes, selenides, and
transition metal complexes have been prepared. The compounds
were characterized. Although aminophosphines possess two
potential donor atoms, their coordination compounds involve
the metal–phosphorus bond. The coordination through phos-
phorus is attributed to the low basicity of the amine nitrogen
because of the P–N π interaction between the phosphorus dπ
and nitrogen pπ orbitals.
32. Said, M.; Hughes, D.L.; Bochmann, M. Polyhedron 2006, 25, 843–
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