Synthesis and characterization of new N-(diphenylphosphino)-naphthylamine chalcogenides: X-ray structures of (1-NHC10H7)P(Se)Ph 2 and Ph2P(S)OP(S)Ph2

Article abstract of DOI:10.1080/10426507.2012.668985

The reaction of 1-naphthylamine with one equivalent of chlorodiphenylphosphine in the presence of triethylamine gave the (1-NHC ₁₀H₇)PPh₂ (1) ligand. Refluxing of 1 with elemental sulfur or grey selenium in toluene (1:1 mo

Full text of DOI:10.1080/10426507.2012.668985

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Phosphorus, Sulfur, and Silicon and the
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Synthesis and Characterization of New
N-(Diphenylphosphino)-Naphthylamine
Chalcogenides: X-Ray Structures of (1-
NHC10H7)P(Se)Ph2 and Ph2P(S)OP(S)Ph2
Harbi Tomah Al-Masri a , Abdul-Hamid M. Emwas b , Zeyad A. Al-Talla
b & Mohamed H. Alkordi b
a Department of Applied Chemistry, Faculty of Applied Sciences,
Taibah University, Madinah, Kingdom of Saudi Arabia
b King Abdullah University of Science and Technology, Jeddah,
Thuwal, Kingdom of Saudi Arabia
Available online: 02 Mar 2012
To cite this article: Harbi Tomah Al-Masri, Abdul-Hamid M. Emwas, Zeyad A. Al-Talla & Mohamed
H. Alkordi (2012): Synthesis and Characterization of New N-(Diphenylphosphino)-Naphthylamine
Chalcogenides: X-Ray Structures of (1-NHC10H7)P(Se)Ph2 and Ph2P(S)OP(S)Ph2 , Phosphorus, Sulfur, and
Silicon and the Related Elements, 187:9, 1082-1090
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Phosphorus, Sulfur, and Silicon, 187:1082–1090, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2012.668985
SYNTHESIS AND CHARACTERIZATION OF NEW
N-(DIPHENYLPHOSPHINO)-NAPHTHYLAMINE
CHALCOGENIDES: X-RAY STRUCTURES OF
(1-NHC10H7)P(Se)Ph2 AND Ph2P(S)OP(S)Ph2
Harbi Tomah Al-Masri,1 Abdul-Hamid M. Emwas,2
Zeyad A. Al-Talla,2 and Mohamed H. Alkordi2
1Department of Applied Chemistry, Faculty of Applied Sciences, Taibah University,
Madinah, Kingdom of Saudi Arabia
2King Abdullah University of Science and Technology, Jeddah, Thuwal,
Kingdom of Saudi Arabia
GRAPHICAL ABSTRACT
Abstract The reaction of 1-naphthylamine with one equivalent of chlorodiphenylphosphine
in the presence of triethylamine gave the (1-NHC10H7)PPh2 (1) ligand. Refluxing of 1 with
elemental sulfur or grey selenium in toluene (1:1 molar ratio) afforded (1-NHC10H7)P(S)Ph2
(2) and (1-NHC10H7)P(Se)Ph2 (3), respectively. Moreover, the byproduct {Ph2P(S)}2O (4)
was isolated from the reaction of 1 with elemental sulfur. Compounds 1–3 were identified and
characterized by multinuclear (1H, 13C, 31P, 77Se) NMR spectroscopy, mass spectrometry, and
elemental analysis. Crystal structure determinations of 3 and 4 were carried out.
Keywords Aminophosphine; chalcogenides; chlorodiphenylphosphine; molecular structure;
phosphine
Received 11 December 2011; accepted 19 February 2012.
Address correspondence to Harbi Tomah Al-Masri, Department of Applied Chemistry, Faculty of Applied
Sciences, Taibah University, Madinah 1343, Kingdom of Saudi Arabia. E-mail: hmasri@taibahu.edu.sa
1082

AMINOPHOSPHINE CHALCOGENIDES
1083
INTRODUCTION
Aminophosphines possessing direct P N bonds and their derivatives play an impor-
tant role in the fight against cancer,1–4 as part of catalytic systems in industrially important
reactions,5–7 as well as herbicidal, neuroactive, and antimicrobial agents.8–11 This has
prompted us to extend our studies on the synthesis and solid-state structures of complexes
with N,O and N,N chelating ligends12 to the synthesis of new chelating phosphorus(III)
ligands containing P N linkages, which might be useful for transition metal chemistry and
catalytic applications.
As a part of our research program on this subject, we report the synthesis and
spectroscopic properties of the (1-NHC10H7)PPh2 (1) ligand, the corresponding sulfide
(1-NHC10H7)P(S)Ph2 (2), and selenide (1-NHC10H7)P(Se)Ph2 (3) as well as the crystal
structures of compounds 3 and 4.
RESULTS AND DISCUSSION
Synthesis
Scheme 1 summarizes the synthesis of compounds 1–3. The reaction of 1-naphthy
lamine with one equivalent of chlorodiphenylphosphine in the presence of triethylamine
proceeds in diethyl ether at room temperature under nitrogen atmosphere and gives (1-
NHC10H7)PPh2 (1) in 80% yield. The existence of compound 1 has been previously men-
tioned by Pudovik et al.13 Moreover, the reaction of aminophosphine 1 with one equivalent
of elemental sulfur or grey selenium in dry toluene under reflux conditions affords the
corresponding sulfide 2 and selenide 3, respectively.
Scheme 1 Preparation of compounds 1–3.
Refluxing of 1 with elemental sulfur without precaution to exclude H2O from the
starting material leads to the formation of the byproduct Ph2P(S)OP(S)Ph2 (4) in 10% yield.
The formation of 4 doubtlessly involves the hydrolysis of compound 2.14,15
Compounds 1–3 were isolated from the reaction solution and fully characterized by
elemental analysis, IR, MS, and multinuclear NMR spectroscopy. Furthermore, the molec-
ular structures of compounds 3 and 4 were elucidated by single crystal X-ray diffraction.
Spectroscopic Properties
The 31P NMR spectrum of 1 shows a single resonance at δ = 34.3, while the 31P
NMR signals of 2 and 3 appear each as a singlet at δ = 53.4 (2) and at δ = 48.1 (3). They
are shifted to lower field as compared to the signal of the parent organic ligand 1. With
decreasing electronegativity of the chalcogen from sulfur to selenium, the 31P NMR signal
moves to higher field. The 31P NMR signal of 3 is flanked by one pair of 77Se-satellites

1084
H. T. AL-MASRI ET AL.
with a coupling constant 1JSeP of 765.2 Hz. The 77Se NMR spectrum of 3 shows a doublet
at δ = −238.8 ppm and the value of the coupling constant matches that resulting from
the 77Se-satellites in the 31P NMR spectrum of 3. This demonstrates the existence of the
monoselenide derivative.
1
The magnitude of the coupling constant JSeP can be used to evaluate the σ-donor
character and, hence, the basicity of the phosphine moiety. An increase of the coupling
constant is indicative of increasing s-character of the phosphorus lone-pair and hence
1
of lower basicity.16 The value of JSeP is in agreement with the few available literature
data on selenides of aminophosphines and larger than for the selenides of corresponding
diarylphosphines.17,18 This implies a lower basicity of the phosphine moiety in 1 due to the
higher electronegativity of the adjacent nitrogen atom.
The IR spectra of compounds 1−3 show bands in the range of 3245–3310 cm−1
,
1431–1439 cm−1, and 896–997 cm−1 due to υ(N H), υ(P Ph), and υ(P N) stretching,
respectively.19 For the P S double bond in 2 a band around 624 cm−1 is observed, whereas
the bands at around 560 cm−1 in the IR spectrum of compound 3 are characteristic of
the P Se moiety.20 In addition, the IR spectrum of 2 shows υ(N H) at 3245 cm−1; the
low-frequency shift of 65 cm−1 as compared to the ligand 1 (3310 cm−1) is attributed
to intermolecular hydrogen-bonding interactions between the amine proton and the sulfur
atom of the ligand.21
Molecular Structures of Compounds 3 and 4
Colorless crystals of 3 were obtained as described in the experimental section. Com-
pound 3 crystallizes in the triclinic space group P-1. Selected interatomic distances and
angles are contained in Table 2. The molecular◦structure is depicted in Figure 1. Colorless
crystals of 4 were obtained from toluene at 4 C. Compound 4 crystallizes in the mono-
clinic space group C2/c. Selected interatomic distances and angles are given in Table 3.
The molecular structure is depicted in Figure 2. Crystal data for compounds 3 and 4 and
details on structure refinement are summarized in Table 1.
The naphthyl skeleton in 3 is almost planar and the nitrogen atom resides almost
in the plane of the naphthyl ring [N1 C1 C10 C9 −0.48(2)◦]. The direction of the
P N bond is virtually perpendicular to the naphthyl plane and in the antiperiplanar sector
[P1 N1 C1 C10 168.70(2)◦]. On the other hand, the direction of the N−H bond is
in the naphthyl plane and in the synperiplanar sector [H N1 C1 C10 −11.30(4)◦], so
that the lone pair at N would be estimated to reside approximately at the borderline between
the synclinal and the anticlinal sectors, thus, minimizing Coulomb repulsion of the lone
pairs.22
The joint effects of Coulomb repulsion and the steric requirements would per-
mit to describe the environment of the phosphorus atom in 3 as distorted tetrahedral
[N P Se: 118.7(1)◦; Cph P−Se: 112.0(1) and 113.3(1)◦; N P Cph: 101.0(1) and
103.7(1)◦; Cph P Cph: 106.7(1)◦]. The smallest value belongs to the N P Cph angle
and the largest value to the N P Se angle.
The N P Se bond angle (Table 2) is larger than those observed for But2P(Se)
NHPrn (5) [111.7(2)◦], Ph2P(Se)NHPrn (6) [117.7(1)◦], [Et2P(Se)]2NPrn [117.7(1)◦] (7),23
Ph2P(Se)N(o-C6H4OMe)P(Se)Ph2 (8) [116.1(1) and 114.8(1)◦],24 Pri2P(Se)N(CH2Ph)CH2
CH2(CH2Ph)NP(Se)Pri2 (9) [111.9(1)◦],25 Ph2P(Se)NHNHpy (10) [109.2(2)◦],25
C6H4(NHP(Se)Ph2)2-1,2 (11) [115.8(5) and 114.3(5)◦], C10H6(NHP(Se)Ph2)2-1,8 (12)

AMINOPHOSPHINE CHALCOGENIDES
1085
Figure 1 ORTEP view of the molecular structure of the selenide 3; hydrogen atoms other than N H have been
omitted for clarity.
[114.2(1) and 116.8(2)◦],26 p-Ph2P(Se)NHCH2(C6H4)CH2NHP(Se)Ph2 (13) [116.8(2)◦],27
and (Ph2P(Se))2N-C6H3-(3,5-OCH3) (14) [115.6(1) and 115.1(1)◦].28 The N−P−Cph
bond angles [101.0(1) and 103.7(1)◦] are smaller than those in 5 [105.5(2) and 104.7(2)◦],
6 [103.8(2) and 104.0(2)◦], 7 [105.6(3) and 107.1(4)◦], 9 [105.6(2) and 109.8(2)◦], 10
[106.5(3) and 108.7(3)◦], and 11 [104.0(3) and 104.8(3)◦], while the Cph−P−Se bond angles
[112.0(1) and 113.3(1)◦] are larger than those observed for 11 [110.8(1) and 111.3(2)◦]
and similar to the one observed for 9 [112.5(1)◦].
The X-ray crystal structure of 3 (Figure 1, Table 2) shows a trigonal-planar sur-
roundings of the three-coordinate nitrogen atom (angle sum at nitrogen 360.03◦). The
P N CNaph bond angle [125.8(2)◦] is larger than those observed for 12 [122.8(3) and
120.8(3)◦] and in the range found for 11 [127.3(1) and 124.5(1)◦].
The values found for the P Se [2.110(1) Å], P N [1.671(2) Å], and P C
[1.819(3), 1.820(2) Å] bond lengths in 3 are within the ranges reported for those in com-
pounds 5–14. The P Se bond length in 3 is as expected longer than those observed
for the P S bond length in C6H4(NHP(S)Ph2)2-1,2 (15) [1.936(3) and 1.943(2) Å],
C10H6(NHP(S)Ph2)2-1,8 (16) [1.951(4) and 1.957(4) Å],26 1,4-[Ph2P(S)NHCH2]2C6H4
(17) [1.952(1) and 1.957(1) Å],27 Ph2P(S)N(Ph)C2H4N(Ph)P(S)PPh2 (18) [1.951(1) Å],
and Ph2P(S)N(C4H8)NP(S)PPh2 (19) [1.943(1) Å].29
The P N bond length in 3 [1.671(2) Å] is significantly shorter as compared to related
P(III) compounds like Ph2PNHNHpy [1.709(7) Å],25 Ph2PNH(C10H6)2NHPPh2 [1.704(2)

1086
H. T. AL-MASRI ET AL.
Figure 2 ORTEP view of the molecular structure of compound 4; hydrogen atoms have been omitted for clarity.
Å], and Pri2PN(CH2Ph)CH2CH2(CH2Ph)NPPri2 [1.704(2) Å], which is somewhat coun-
terintuitive and suggests that in 3 there may be some antibonding π-character in the P N
linkage.25
The molecular structure of 4 (Figure 2, Table 3) shows a distorted tetrahedral geometry
around the phosphorus atoms with angles between 99.1(1) and 116.1(1)◦. The smallest value
corresponds to the O P Cph angle and the largest value to the O P S angle.
A comparison of the structural data of the O P S [116.1(1)◦] and CPh P CPh
[105.9(1)◦] bond angles in 4 with those observed in the bisphosphinites Ph2P(S)O
(C6H10)OP(S)PPh2 (20)30 and (Ph2P(S)O)2–C10H6N2 (21)31 shows that the O P S bond
angle in 4 is slightly larger than those found in 21 [115.0(2) and 115.9(2)◦] and similar to
those observed in 20 [116.1(1)◦], while the CPh P CPh bond angle is larger than those
observed in 21 [106.4(1) and 106.3(1)◦] and is quite comparable with those found for 20
[105.1(1)◦]. Moreover, the O P CPh bond angle ranges in 20 [from 100.6(1) to 105.0(1)◦]
and in 21 [from 99.9(1) to 104.3(1)◦] are larger than the range observed in 4 [from 99.1(1)
to 102.2(1)◦].
The average P CPh bond distances in 4 [1.797 Å] are comparable with those found
in 20 [av. 1.809 Å] and 21 [av. 1.805 Å]. The bisphosphinite 21 has similar P O [1.620(4),
1.621(4) Å] and P S [1.915(2), 1.908(2) Å] distances as 4 [P O: 1.618(3); P S: 1.900(1)

AMINOPHOSPHINE CHALCOGENIDES
1087
Table 1 Crystal data and structure refinement for 3 and 4
3
4
Formula
Mr
Temp. (K)
Crystal system
Space group
a(Å)
C22H18NPSe
406.30
296(2)
Triclinic
P-1
9.6164(7)
9.8096(7)
10.9768(8)
98.749(3)
110.372(3)
94.731(3)
949.1(1)
2
C24H20OP2S2
450.46
273(2)
Monoclinic
C2/c
15.4809(13)
9.0479(10)
17.290(2)
90
113.537(6)
90
2220.4(4)
4
b(Å)
c(Å)
α(◦)
β(◦)
γ (◦)
V(Å3)
Z
ρcalcd (Mg m−3
F(000)
)
1.422
412
3.486
1. 348
936
3.634
µ(mm−1
)
Reflns. total
Reflns. unique
Rint
9619
2918
0.0304
227
2883
1254
0.0281
132
Params.
R1 (I > 2σ(I))
wR2 (all data)
0.0541
0.1968
0.628
0.0713
0.2837
0.341
(
(
/ρ)max (e Å−3
)
/ρ)min (e Å−3
)
−0.939
−0.472
CCDC depos. No.
844302
844303
Å], while 20 displays a smaller P O [1.590(4) Å] and a larger P S [1.928(2) Å] distance
as compared to those found in compound 4.
Interestingly, the P S bond length of 1.900(1)) Å is shorter than those observed in
the amine derivatives 15–19. The aromatic rings in 3 and 4 display bond lengths and angles
as expected.
EXPERIMENTAL
All experiments were carried out under purified dry nitrogen using standard Schlenk
and vacuum line techniques. Solvents were dried and freshly distilled under nitrogen.32
Chlorodiphenylphosphine and 1-naphthylamine were used as purchased. Infrared spectra
were recorded with a Perkin-Elmer System 2000 FT-IR spectrophotometer in the range
between 4000 and 400 cm−1 using KBr pellets. Microanalyses were performed with a
Table 2 Selected bond lengths (Å) and bond angles (◦) for 3
P
P
P
N
N
Se
CPh
CNaph
1.671(2)
2.110(1)
1.819(3), 1.820(2)
1.418(3)
106.7(1)
P
N
Se
N
P
P
CNaph
CPh
CPh
Se
125.8(2)
103.7(1), 101.0(1)
112.0(1), 113.3(1)
118.7(1)
N
P
ꢀ
CPh
P
CPh
angles at N
360.03

1088
H. T. AL-MASRI ET AL.
Table 3 Selected bond lengths (Å) and bond angles (◦) for 4
P
P
P
O
S
CPh
1.618(1)
1.900(1)
1.787(9), 1.806(8)
105.9(1)
P
O
P
P
P
P
136.6(1)
O
O
O
CPh
CPh
S
99.1(1), 102.2(1)
115.7(1), 115.7(1)
116.1(3)
CPh
P CPh
Flash 2000 elemental analyzer. Mass spectra were recorded with a LTQ Orbitrap Velos
mass spectrometer in the positive ion mode. The NMR spectra were recorded at 25 ◦C with
a Bruker AVANCE III 600 or a Bruker AVANCE II 400 NMR spectrometer operating at
the appropriate frequencies using tetramethylsilane for 1H, 85% H3PO4 for 31P, and Me2Se
for 77Se as external standards. CDCl3 was used as both solvent and internal lock. Melting
points were determined with a Gallenkamp Model apparatus in open capillaries.
N-(Naphthalen-1-yl)-1,1-diphenylphosphinamine (1)
Chlorodiphenylphosphine (4.89 g, 22.20 mmol) was added dropwise to a solution of
1-naphthylamine (3.20 g, 22.20 mmol) and triethylamine (2.25 g, 22.20 mmol) in diethyl
ether (150 mL) at room temperature with vigorous stirring. After completion of the addition,
the reaction mixture was stirred at room temperature for 12 h and then the white precipitate
(triethylammonium hydrochloride) was filtered off through a sintered Schlenk tube. The
volume of the filtrate was reduced to 50 mL and the reaction mixture was cooled to –30 ◦C
when a white solid was obtained, which was recrystallized from diethylether at –4 ◦C to give
◦
1
aminophosphine 1 as colorless crystals in 80% yield. Mp 135–137 C. H NMR (400.13
MHz, CDCl3): δ = 3.26 (br., 1H, N−H), 6.50−8.2 (m, 17H, C10H7, and C6H5). 13C NMR
(100.63 MHz, CDCl3): δ = 115.2, 119.7, 122.6, 125.6, 126.2, 126.3, 128.9, 129.0, 131.8,
132.3, 133.3, 133.9, 134.3, 135.3 (C10H7 and C6H5). 31P NMR (161.97 MHz, CDCl3): δ =
34.3 (s). Selected IR data (KBr pellet): υ = 3310 cm−1 (N H), 1431 cm−1 (P Ph), 896
cm−1 (P N). ESI-MS (positive): m/z = 328.12 [M+H]+. Calcd. for C22H18NP (327.37).
Found: C 80.74, H 5.58, N 4.30. Calcd. C 80.72, H 5.54, N 4.28%.
N-(Naphthalen-1-yl)-P,P-diphenylphosphinothioic Amide (2)
A mixture of 1 (0.5 g, 1.39 mmol) and elemental sulfur (0.05 g, 1.39 mmol) in dry
toluene (50 mL) was heated under reflux for 4 h. The solution was filtered through celite
while hot to remove a small amount of insoluble material. The volume of the filtrate was
reduced to 10 mL and the solution was kept at room temperature to afford colorless crystals
of 2 in 80% yield. Mp 165–167 ◦C. 1H NMR (600 MHz, CDCl3): δ = 5.42 (d, 2JPH = 6.2 Hz,
1H, N H), 6.94–8.15 (m, 17H, C10H7, and C6H5). 13C NMR (150 MHz, CDCl3): δ = 115.9,
120.0, 122.7, 125.6, 126.20, 126.24, 128.8, 128.9, 131.7, 132.1, 133.2, 134.0, 134.3, 135.3
(C10H7 and C6H5). 31P NMR (242.94 MHz, CDCl3): δ = 53.4 (s). Selected IR data (KBr
pellet): υ = 3245 cm−1 (N H), 1437 cm−1 (P Ph), 997 cm−1 (P N), 624 cm−1 (P S).
ESI-MS (positive): m/z 360.09 [M+H]+. Calcd. for C22H18NPS (359.43). Found: C 73.54,
H 5.10, N 3.93. Calcd. C 73.52, H 5.05, N 3.90%.

AMINOPHOSPHINE CHALCOGENIDES
1089
N-(Naphthalen-1-yl)-P,P-diphenylphosphinoselenoic Amide (3)
A similar procedure to that described for 2 was used, except that grey selenium (0.11 g,
1.39 mmol) was employed instead of elemental sulfur. Compound 3 was obtained as
colorless crystals in 75% yield. Mp 189−192 ◦C. 1H NMR (600 MHz, CDCl3): δ = 5.28
(d, 2JPH = 5 Hz, 1H, N H), 6.50−8.52 (m, 17H, C10H6, and C6H5). 13C NMR (150 MHz,
CDCl3): δ = 110.9, 119.9, 121.8, 124.6, 126.5, 129.5, 129.9, 130.0, 131.9, 131.6, 132.6,
133.3, 134.3, 135.5 (C10H7 and C6H5). 31P NMR (242.94 MHz, CDCl3): δ = 48.1 (s, 1JSeP
=
765.2 Hz). 77Se NMR (114.4 MHz, CDCl3): δ = −238.8 (d, 1JSeP = 767.6 Hz). Selected
IR data (KBr pellet): υ = 3275 cm−1 (N H), 1439 cm−1 (P Ph), 996 cm−1 (P N), 560
cm−1 (P Se). ESI-MS (positive): m/z 407.04 [M+H]+. Calcd. for C22H18NPSe (406.33).
Found: C 65.07, H 4.43, N 3.48. Calcd. C 65.03, H 4.47, N 3.45%.
Data Collection and Structure Determination
Crystallographic data of compounds 3 and 4 are given in Table 1. Data [λ(CuKα) =
1.54178 Å] were collected with a Bruker-AXS SMART-APEX CCD diffractometer. All
observed reflections were used for determination of the unit cell parameters. Indexing
was performed using SMART.33 Frames were integrated with SAINT software package.34
Absorption correction was performed by multiscan method implemented in SADABS.35
Crystal structures were solved using SHELXS-97 and refined using SHELXL-97 contained
in SHELXTL and WinGX-1.70.01 program packages.36 All nondisordered nonhydrogen
atoms were refined with anisotropic displacement parameters. All H-atoms bonded to car-
bon atoms were placed in geometrically optimized positions and refined with an isotropic
displacement parameter relative to the attached atoms. Crystallographic data for the struc-
tural analysis have been deposited with the Cambridge Crystallographic Data Centre, CCDC
Nos. 844302 for 3 and 844303 for 4. These data can be obtained from Cambridge Crystal-
lographic Data Centre, 12, Union Road, Cambridge CB2 1EZ, UK; fax: (internat.) +44-
1223/336-033; E-mail: deposit@ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk.
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