T. S. Lobana, G. Bawa, R. J. Butcher, C. W. Liu
ARTICLE
NHPh, 2H); 6.91Ϫ7.51 (m, C4,5,6 ϩ Ph-H 36H). 31P NMR(CDCl3, δ):
Ϫ56.67; Δδ(δcomplexϪδPPh3) ϭ 56.7 {δPPh3 ϭ Ϫ113.15}.
[Ru(η2-N2, S-pytsc)2{(p-tolyl)3P}2] (2). To a solution of Hpytsc
(0.0186 g; 0.1 mmol) in methanol (30 mL) was added solid
RuCl2{(p-tolyl)3P}3 (0.050 g; 0.046 mmol) followed by NEt3 base
(0.5 mL). The mixture was stirred for 4 h. and yellow solid sepa-
rated was filtered, washed with methanol, and dried. The
Et3NHϩClϪ salt remained in the solution. The compound was
recrystallized from dichloromethane-acetonitrile mixture. Mp.
180Ϫ82 °C, bright orange, yield, 76 %. Anal. calc. C56H56N8P2RuS2;
C 61.98 (calc. 62.90); H 5.58 (5.2); N 10.57 (10.40) %.
IR bands (KBr, pellets, cmϪ1) : ν(N-H) 3444w, 3437s (-NH2-); ν(C-H) 3012w;
ν(CϭN) ϩ δNH2 ϩ ν(CϭC) 1592sh, 1600s, 1581s; ν(P-C) 1085s; ν(C-S),
808s. 1H NMR (CDCl3, δ): 8.67 (s, C2H, 2H), 6.53 (d, C7H, 1H), 7.44Ϫ7.54
(m, C5,6H, 4H), 6.76Ϫ7.44 (m, Ph-H ϩ C4), 5.45 (s, -NH2, 4H), 2.2 (s, -CH3,
18H). 31P NMR(CDCl3, δ): Ϫ58.74, Δδ(δcomplexϪδ(p-tolyl)3P
{δ(p-tolyl)3P ϭ Ϫ115.6}.
) ϭ 56.86;
Compounds 3 and 4 were prepared by a method similar to 2.
[Ru(η2-N2, S-Hstsc)2{(p-tolyl)3P}2] (3). Mp. 182Ϫ185 °C, yellow,
yield, 76 %. Anal. Calc. for C58H56N6O2P2RuS2 : C 63.30 (calc.
63.50); H 5.35 (5.10); N 7.54 (7.66) %.
IR bands (KBr, pellets, cmϪ1): ν(N-H) 3377s; ν(C-C) 3012w; ν(CϭN) ϩ
δNH2 1622sh, 1600s, 1581s; ν(C-S), 808s; ν(P-C) 1085s. 1H NMR (CDCl3,
δ): 10.65 (s, -OH, 2H), 8.78 (s, C2H, 2H), 7.13Ϫ7.19 (m, m, p-PhϩC4,5,6,7),
6.78Ϫ6.85 (m, O-H), 4.75(s, -NH2, 4H), 2.20 (s, -CH3, 18H). 31P
NMR(CDCl3, δ): Ϫ58.41, Δδ(δcomplexϪδ(p-tolyl)3P) ϭ 57.19.
Chart 1.
[Ru(η2-N2, S-btsc)2{(p-tolyl)3P}2] (4). Mp. 155Ϫ160 °C, yellow,
yield, 60 %. Anal. calc. for C58H58N6P2S2Ru : C 65.26 (calc. 65.10);
H 5.52 (5.40); N 8.30 (7.80) %.
IR bands (KBr, pellets, cmϪ1) : ν(N-H) 3376s, 3233 (-NH2); ν(CϭN) ϩ
δNH2 ϩ ν(CϭC) 1605s, 1592sh; ν(P-C) 1085s; ν(C-S) 824s; 1H NMR
(CDCl3, δ): 8.64 (s, C2H, 2H), 7.25 (s, C6H, 2H), 7.07 (m, C4ϩ8H, 2H),
6.8 (dd, C5H, 2H), 5.15 (s, -NH2, 4H), 2.20 (s, -CH3, 18H), 7.07Ϫ7.19
(m, o, m-H, 24H), 6.78 (d, m-H, 12H); 31P NMR(CDCl3, δ) : Ϫ57.36,
Δδ(δcomplexϪδp-tolyl)3P) ϭ 58.24.
[Ru(η2-N2, S-Hstsc)2(dppb)] (5). To a solution of H2stsc (0.022 g;
0.12 mmol) in methanol (30 mL) was added solid [Ru2Cl4(dppb)3]
(0.05 g; 0.03 mmol) followed by addition of NEt3 (0.5 mL).
The mixture was stirred for about 24 h. The yellow solid formed
was filtered, washed with methanol and dried (Et3NHϩClϪ re-
mained in mother liquor being soluble). Crystals were grown from
dichloromethane-acetonitrile-methanol. Mp. 218Ϫ220 °C, color,
yellow, yield, 62 %. Anal. calc. for C45H44.50N6O4P2RuS2: C 55.8
(calc. 56.2); H 4.8 (4.60); N 9.2 (8.8) %.
IR bands (KBr, pellets, cmϪ1): ν(N-H) 3479b, 3375s, 3292s (-NH2); ν(CϭN)
ϩ δNH2 ϩ ν(CϭC) 1618sh, 1589s, 1514s; ν(P-CPh) 1091s; ν(C-S) 810s; 1H
NMR (CDCl3, δ): 10.65 (s, -OH, 2H), 8.93 (s, C2H, 2H), 7.60 (s br, C5H,
2H), 6.8 (m, C7,8H, 4H), 7.07Ϫ7.60(m, C4H ϩ PhH), 4.76 (s, -NH2, 4H),
2.8 (s, -CH2, 2H), 2.51 (s, -CH2, 2H). 31P NMR (CDCl3, δ) : Ϫ57.54 ppm,
Δδ(δcomplexϪδdppb) ϭ 66.35 ppm. (δdppb ϭ Ϫ123.89 ppm).
Chart 2.
paratus U.V spectra were recorded using UV-1601PC Shimadzu.
IR spectra were recorded using KBr pellets on a PyeϪUnicam SP3-
300 spectrophotometer. 1H NMR spectra were recorded on a JEOL
AL300 FT spectrometer at 300 MHz in CDCl3 with TMS as in-
ternal reference. 31P NMR spectra were recorded at 121.5 MHz
with TMP {(CH3O)3P} as external reference taken as zero position.
[Ru(η2-N2, S-pytsc-NPh)2(PPh3)2]·1.5CH3CN (1). To a solution of
Hpytsc-NPh (0.019 g; 0.10 mmol) in methanol (20 mL) was added
RuCl2(PPh3)3 (0.050 g; 0.052 mmol) and Et3N (0.5 mL) followed
by stirring for 2 h, during which clear orange colored solution was
formed. The solution was filtered and kept for evaporation, orange
crystalline product starts forming after few days. It was recrystal-
lised from acetonitrile. Mp. 150Ϫ152 °C, orange, yield, 70 %. Anal.
calc. C65H56.50N9.50P2RuS2; C 64.87 (calc. 65.10); H5.79 (4.71); N
10.97 (11.10) %.
Compounds 6, 7, 8 were prepared similarly.
[Ru(η2-N2, S-btsc)2(dppb)] (6). Mp. 175Ϫ177 °C, yellow, yield,
55 %. Anal. calc. for C44H44N6P2S2Ru : C 59.2 (calc. 59.90); H 5.04
(5.00); N 10.05 (9.53) %.
IR bands (KBr, pellets, cmϪ1) : ν(N-H) ϩ ν(O-H), 3457m, 3360Ϫ3300m,
3150w, ν(CϭN) ϩ δNH2 ϩ ν(CϭC) ϩ δ(OH2), 1585s, 1573sh, 1562sh; ν(P-
C) 1093s; ν(C-S) 817s. 1H NMR (CDCl3, δ) : 8.80 (s, C2H, 2H), 8.52 (d, C7H,
2H), 7.10Ϫ7.66 (m, Ph-H ϩ C4,5,6 H, 26H), 5.46 (s, NH2, 4H), 1.26Ϫ2.89
(-CH2-, 8H); 31P NMR (CDCl3, δ) : Ϫ58.213 ppm, Δδ(δcomplexϪδligand) ϭ
65.48 ppm.
IR bands (KBr, pellets, cmϪ1) : ν(N-H) 3340s, 3217 (-NH2-); ν(C-H) 3010w;
ν(CϭN) ϩ δNH2 ϩ ν(CϭC) 1589s, 1558; ν(P-CPh) 1089m; ν(C-S) 760s; 1H
NMR (CDCl3, δ): 9.00 (s, C2H, 2H); 8.52 (d, C7H, 2H, J ϭ 1.125); 8.34 (s,
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© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2009, 355Ϫ360