114 Keles¸, Altan, and Serindagˇ
amine)); 742–684 (m, monosubstitued P-Ph2). 1H
NMR (CDCI3, 25◦C): δ 7.34–7.18 [m, 20 H, 4 Ph], 3.42
[br, 4 H, 2 (P-CH2-N)], 1.21 [s, 9H, 2 (N-C-(CH3)3)]
ppm. 31P NMR (CDCI3, 25◦C): δ −27.2 [s, PPh2-CH2]
ppm.
EXPERIMENTAL
General
All reactions were carried out under nitrogen at-
mosphere using conventional Schlenk glassware.
Methyl alcohol, ethyl alcohol, dichloromethane,
tetrahydrofuran (THF), and diethyl ether were used
as solvents, which were dried using established
procedures and then immediately distilled under
nitrogen atmosphere before use. Tetrabutylammo-
nium perchlorate (TBAP) was purchased from Fluka
and [PdCI2(COD)] complex was prepared as de-
scribed in literature [7].
[(Ph2PCH2)2NPhm-SO3Na] (2): Et3N (0.8 mL,
5.84 mmol) was added to a stirred solution
of [Ph2P(CH2OH)2]Cl (0.5 g, 1.77 mmol) in 2:1
H2O/MeOH (15 mL) followed by addition of sodium
3-aminobenzenesulfonate (0.175 g, 0.9 mmol) dis-
solved in CH2Cl2, and then the mixture was refluxed
for 2 h. The product was extracted with CH2Cl2 and
dried over MgSO4. The solvent was removed under
vacuum. Yield: 0.346 g (66%). Elemental analysis
calculation for [(Ph2PCH2)2NPhSO3Na]: C, 64.97%;
H, 4.74%; N, 2.37%. Found: C, 65.40%; H, 4.57%; N,
2.53%. FT-IR (KBr): ν 3040 (m, Ar-H); 2932 (m, R-H);
1574 (m, C C (Ph); 1465 (m, C H); 1126 (m, C-N (t-
amine)); 1077 (m, S(O)); 810–747-686 (m, mono-and
disubstituted Ar-H). 1H NMR (CDCI3, 25◦C): δ 7.52–
7.32 [m, 20H, 4P-Ph], δ 6.90 [m, 4H, N-Ph], 3.50 [br,
4H, P-CH2-N] ppm. 31P NMR (CDCI3, 25◦C): δ −26.36
[s, PPh2-CH2] ppm.
The metal contents of the complexes were de-
termined using a Hitachi 180-80 Polarized Zeiman
atomic absorption spectrometer. Elemental analy-
ses were performed using a LECO CHNS 932 ana-
lyzer. FT-IR spectra were recorded as KBr pellets in a
4000–450 cm−1 range using a Perkin-Elmer RX1 FT-
1
IR system. H and 31P NMR spectra were recorded
at 25◦C in DMSO-d6 and CDCl3 using Varian Mer-
cury 200 MHz NMR spectrometer. 31P NMR spectra
were recorded with complete proton decoupling and
are reported in ppm using 85% H3PO4 as an external
standard. The hydrogenated product was analyzed
on a Shimadzu GC 14 A gas chromatograph using a
30 m × 0.25 mm ZB-5 column.
[NiCl2(Ph2PCH2)2NC(CH3)3](3): Ligand
1
(0.103 g, 0.22 mmol) was added to a stirred solution
of NiCl2·6H2O (0.052 g, 0.22 mmol) in ethanol (10
mL). An orange precipitated formed immediately
and the mixture was stirred for 30 min. The orange
product was filtered, washed with diethyl ether, and
finally dried. Yield: 0.122 g (93%). Elemental anal-
ysis calculation for [NiCl2(Ph2PCH2)2NC(CH3)3]: C,
60.13%; H, 5.51%; N, 2.34%. Found: C, 59.89%;
H, 5.80%; N, 2.45%. FT-IR (KBr): ν 3074 (m,
Ar-H); 2870 (m, R-H); 1520 (m, C C (Ph); 1478
(m, C H); 1020 (m, C-N (t-amine)); 725–638 (m,
monosubstitued Ar-H). 1H NMR (CDCI3, 25◦C): δ
7.70–7.40 [m, 20H, 4Ph], 3.58 [d, 4H, P-CH2-N],
A conventional three-electrode electrochemical
cell setup using a CHI 660B electrochemical ana-
lyzer was used to investigate the electrochemical be-
haviors of complexes. A platinum electrode was used
as the working electrode, an Ag/AgCl electrode was
utilized as the reference electrode, and a platinum
wire was used as the counter electrode, respectively.
Electrochemical tests were conducted in THF, and
0.1 M TBAP was used as the supporting electrolyte.
Synthesis of Bis(diphenylphosphinomethyl)amino
Ligands and Metal Complexes
2 J(HP) 3.35 Hz. 1.27 [s, 9H, N-C, (CH )3] ppm. 31
P
3
[(Ph2PCH2)2NC(CH3)3] (1): Phosphonium salt
([Ph2P(CH2OH)2]CI) (0.260 g, 0.92 mmol), which
was prepared according to literature procedure [8],
was dissolved in 2:1 H2O/MeOH (15 mL). Triethy-
lamine (Et3N) (0.5 mL, 3.65 mmol) was added to
a stirred solution of [Ph2P(CH2OH)2]CI, followed
by addition of t-butylamine (46 µL, 0.46 mmol).
The mixture was refluxed for 1 h, and then the
product was extracted with CH2CI2 and dried over
MgSO4. The solvent was removed under vacuum.
Yield: 0.173 g (80%). Elemental analysis calculation
for [(Ph2PCH2)2NC(CH3)3]: C, 76.75%; H, 7.04%; N,
2.98%. Found: C, 77.14%; H, 7.15%; N, 3.07%. FT-
IR (KBr): ν 3052 (m, Ar-H); 2985 (m, R-H); 1584
(m, C C (Ph); 1476 (m, C H); 1094 (m, C N (t-
NMR (CDCI3, 25◦C): δ 30.4 [br, Ni-PPh2] ppm.
[NiCl2(Ph2PCH2)2N-m-PhSO3Na] (4): Ligand 2
(0.1 g, 0.169 mmol) was added to a stirred solu-
tion of NiCl2·6H2O (0.05 g, 0.21 mmol) in ethanol
(10 mL). An orange precipitate formed immediately
and the mixture was stirred for 30 min. The prod-
uct was washed with diethyl ether and dried. Yield:
0.09 g (74%). Elemental analysis calculation for
[NiCl2(Ph2PCH2)2NPhSO3Na]: C, 53.28%; H, 3.89%;
N, 1.94%. Found: C, 53.57%; H, 4.13%; N, 2.05%. FT-
IR (KBr): ν 3069 (m, Ar-H); 2915 (m, R-H); 1523 (m,
C C (Ph); 1435 (m, C H); 1085 (m, C-N (t-amine));
1065 (m, S(O)); 790–675 (m, mono-, and disub-
1
stitued Ar-H). H NMR (CDCI3, 25◦C): δ 7.63–7.38
Heteroatom Chemistry DOI 10.1002/hc