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35
CH2Ã
H4ꢂPh), 7.94 (m, 2H, H5, H6), 8,49 (s, 1H, Ha). 31P
NMR (Me2CO-d6): 31.6 (s).
[Ni(iBu2dtc)(o-Ph2PC6H4CHÄ
obtained in 69% yield.
C31ClH40N2O4PS2Ni: C, 53.7; H, 5.8; N, 4.0; S, 9.2.
Found: C, 53.8; H, 5.8; N, 4.2; S, 9.3%. LMꢀ
135 Vꢄ1
cm2 molꢄ1. IR (cmꢄ1): 1615 (CÄ
N str), 1525 (CÃN str),
S str). H NMR (Me2CO-d6): 0.91 (s-br, 12H,
CH3-dtc), 1.26 (d, 6H, CH3ÃNP, Jꢀ6.3), 2.26 (m, 2H,
CH-dtc), 3.51 (s-br, 2H, CH2-dtc), 3.62 (s-br, 2H, CH2-
dtc), 4.34 (m, 1H, CHÃ
NP), 7.28 (m, 1H, H3), 7.72 (m,
11H, H4ꢂPh), 7.95 (m, 1H, H5), 8.07 (m, 1H, H6), 8,48
(d, 1H, Ha, Jꢀ
3.0). 31P NMR (Me2CO-d6): 33.6 (s).
[Ni(iBu2dtc)(o-Ph2PC6H4CHÄNtBu)][ClO4] (8) was
obtained in 75% yield. Anal. Calc. for
C32ClH42N2O4PS2Ni: C, 54.3; H, 6.0; N, 4.0; S, 9.1.
Found: C, 54.4; H, 6.1; N, 4.0; S, 9.1%. LMꢀ
145 Vꢄ1
cm2 molꢄ1. IR (cmꢄ1): 1608 (CÄ
N str), 1524 (CÃN str),
998 (CÃ
S str). 1H NMR (Me2CO-d6): 0.89 (d, 6H, CH3-
dtc, Jꢀ6.9), 0.93 (d, 6H, CH3-dtc, Jꢀ6.3), 1.54 (s, 9H,
CH3ÃNP), 2.24 (m, 2H, CH-dtc), 3.50 (d, 2H, CH2-dtc,
Jꢀ7.5), 3.60 (d, 2H, CH2-dtc, Jꢀ8.1), 7.27 (m, 1H,
H3), 7.75 (m, 11H, H4ꢂPh), 8.01 (m, 1H, H5), 8.05 (m,
1H, H6), 8,52 (d, 1H, Ha, Jꢀ5.1). 31P NMR (Me2CO-
d6): 33.2 (s).
/
NPꢂ
/
CH2-dtc), 7.27 (m, 1H, H3), 7.71 (m, 11H,
C24ClH25NO5PS2Ni: C, 48.3; H, 4.2; N, 2.3; S, 10.7.
Found: C, 48.1; H, 4.0; N, 2.2; S, 10.7%. LMꢀ
126 Vꢄ1
cm2 molꢄ1. IR (cmꢄ1): 1623 (CÄ
N str), 1226 (CÃO str),
1022 (CÃ
S str). 1H NMR (Me2CO-d6): 1.46 (m, 6H,
CH3-xan; CH3ÃNP), 3.72 (cd, 2H, CH2ÃNP, Jꢀ7.2),
4.73 (cd, 2H, CH2-xan, Jꢀ
6.9), 7.51 (m, 1H, H3), 7.71
(m, 11H, H4ꢂPh), 8.01 (m, 2H, H5, H6), 8.45 (s, 1H,
Ha). 31P NMR (Me2CO-d6): 31.3 (s).
[Ni(Etxan)(o-Ph2PC6H4CHÄ
NiPr)][ClO4] (11) was
obtained in 73% yield. Anal. Calc. for
C25ClH27NO5PS2Ni: C, 49.2; H, 4.5; N, 2.3; S, 10.5.
Found: C, 49.3; H, 4.2; N, 2.4; S, 10.3%. LMꢀ
99 Vꢄ1
cm2 molꢄ1. IR (cmꢄ1): 1621 (CÄ
N str), 1270 (CÃO str),
1025 (CÃ
S str). 1H NMR (Me2CO-d6): 1.23 (d, 6H,
CH3ÃNP, Jꢀ6.6), 1.40 (t, 3H, CH3-xan, Jꢀ7.1), 4.36
(m, 1H, CHÃ
/
/
/
/
/
NiPr)][ClO4] (7) was
Anal. Calc. for
/
/
/
/
/
/
/
/
/
1
997 (CÃ
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
/
NP), 4.71 (cd, 2H, CH2-xan, Jꢀ
/
7.1), 7.31
Ph), 7.95 (m, 1H, H5),
(m, 1H, H3), 7.73 (m, 11H, H4ꢂ
/
/
8.07 (m, 1H, H6), 8.48 (s, 1H, Ha). 31P NMR (Me2CO-
d6): 32.1 (s).
/
/
/
[Ni(Etxan)(o-Ph2PC6H4CHÄ
obtained in 72% yield.
C26ClH29NO5PS2Ni: C, 50.0; H, 4.7; N, 2.2; S, 10.3.
Found: C, 50.0; H, 4.6; N, 2.3; S, 10.4%. LMꢀ
105 Vꢄ1
cm2 molꢄ1. IR (cmꢄ1): 1613 (CÄ
N str), 1236 (CÃO str),
S str). H NMR (Me2CO-d6): 1.40 (t, 3H, CH3-
xan, Jꢀ6.1), 1.51 (s, 9H, CH3ÃNP), 4.67 (cd, 2H, CH2-
xan, Jꢀ Ph),
/
NtBu)][ClO4] (12) was
Anal. Calc. for
/
/
/
/
/
/
/
/
/
1
/
996 (CÃ
/
/
/
/
6.1), 7.31 (m, 1H, H3), 7.73 (m, 11H, H4ꢂ
/
2.3. Preparation of the complexes [Ni(R?xan)(o-
Ph2PC6H4CHÄNR)][ClO4] [R?ꢀEt; RꢀMe (9), Et
Pr; RꢀMe (13), Et
8.02 (m, 2H, H5, H6), 8.55 (s, 1H, Ha). 31P NMR
/
/
/
(Me2CO-d6): 32.2 (s).
i
t
(10), Pr (11), Bu (12); R?ꢀi
/
/
[Ni(iPrxan)(o-Ph2PC6H4CHÄ
/
NMe)][ClO4] (13) was
Anal. Calc. for
C24ClH25NO5PS2Ni: C, 48.3; H, 4.2; N, 2.3; S, 10.7.
Found: C, 48.4; H, 4.2; N, 2.5; S, 10.8%. LMꢀ
139 Vꢄ1
cm2 molꢄ1. IR (cmꢄ1): 1634 (CÄ
N str), 1250 (CÃO str),
1020 (CÃ
S str). 1H NMR (Me2CO-d6): 1.44 (d, 6H,
CH3-xan, Jꢀ6,0), 3.64 (s, 3H, CH3ÃNP), 5.60 (m, 1H,
Ph), 7.94
i
t
(14), Pr (15), Bu (16)]
obtained
in
65%
yield.
The complexes were obtained by reacting Ni(ClO4)2,
the bis(xanthate) precursor [Ni(R?xan)2] and the corres-
ponding iminophosphine in ethanol according to the
following general method. To an ethanolic solution (10
ml) of fine pulverized Ni(ClO4)2 (0.062 g, 0.172 mmol)
and fine pulverized [Ni(R?xan)2] (0.172 mmol) was
added the calculated amount of iminophosphine (0.172
mmol) in ethanol solution previously prepared. After 30
minutes stirring at room temperature the resulting
solutions were concentrated under reduced pressure to
half volume. The addition of diethyl ether caused
precipitation of the new brown complexes, which were
filtered off, washed with diethyl ether and air dried.
/
/
/
/
/
/
CH-xan), 7.51 (m, 1H, H3), 7.76 (m, 11H, H4ꢂ
/
(m, 2H, H5, H6), 8.45 (s, 1H, Ha). 31P NMR (Me2CO-
d6): 31.6 (s).
[Ni(iPrxan)(o-Ph2PC6H4CHÄ
was obtained in 72% yield. Anal. Calc. for
C25ClH27NO5PS2Ni: C, 49.1; H, 4.5; N, 2.3; S, 10.5.
/
CHÄ/NEt)][ClO4] (14)
Found: C, 49.3; H, 4.5; N, 2.3; S, 10.5%. LMꢀ
cm2 molꢄ1. IR (cmꢄ1): 1614 (CÄ
N str), 1280 (CÃ
1020 (CÃ
S str). 1H NMR (Me2CO-d6): 1.47 (m, 9H,
CH3-xa; CH3ÃNP), 3.70 (m, 2H, CH2ÃNP), 5.55 (m,
Ph),
/
104 Vꢄ1
O str),
/
/
/
[Ni(Etxan)(o-Ph2PC6H4CHÄ/NMe)][ClO4] (9) was ob-
/
/
tained in 69% yield. Anal. Calc. for C23ClH23NO5PS2Ni:
C, 47.4; H, 4.0; N, 2.4; S, 11.0. Found: C, 47.6; H, 4.0;
1H, CH-xan), 7.37 (m, 1H, H3), 7.80 (m, 11H, H4ꢂ
/
8.01 (m, 2H, H5, H6), 8.53 (s, 1H, Ha). 31P NMR
N, 2.6; S, 11.1%. LMꢀ
1616 (CÄ
NMR (Me2CO-d6): 1.43 (t, 3H, CH3-xan, Jꢀ
(s, 3H, CH3ÃNP), 4.73 (cd, 2H, CH2-xan, Jꢀ
(m, 1H, H3), 7.71 (m, 11H, H4ꢂPh), 8.01 (m, 2H, H5,
H6), 8.45 (s, 1H, Ha). 31P NMR (Me2CO-d6): 31.5 (s).
[Ni(Etxan)(o-Ph2PC6H4CHÄNEt)][ClO4] (10) was
obtained in 65% yield. Anal. Calc. for
/
109 Vꢄ1 cm2 molꢄ1. IR (cmꢄ1):
(Me2CO-d6): 31.3 (s).
1
/
N str), 1226 (CÃ
/
O str), 1024 (CÃ
/
S str). H
[Ni(iPrxan)(o-Ph2PC6H4CHÄ
/
NiPr)][ClO4] (15) was
Anal. Calc. for
C26ClH29NO5PS2Ni: C, 50.0; H, 4.7; N, 2.2; S, 10.3.
Found: C, 50.1; H, 4.7; N, 2.4; S, 10.5%. LMꢀ
95 Vꢄ1
cm2 molꢄ1. IR (cmꢄ1): 1617 (CÄ
N str), 1276 (CÃO str),
1026 (CÃ
S str). 1H NMR (Me2CO-d6): 1.27 (d, 6H,
CH3ÃNP, Jꢀ6.3), 1.45 (d, 6H, CH3-xan, Jꢀ6.3), 4.39
/7.0), 3.64
obtained
in
71%
yield.
/
/
7.0), 7.51
/
/
/
/
/
/
/
/
/