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K. Pachhunga et al. / Inorganica Chimica Acta 361 (2008) 3294–3300
and filtered to remove sodium chloride. The filtrate upon
concentration to a minimum volume ca. 5 ml and addition
of excess hexane gave the orange-yellow complexes 5–7,
which were separated and dried under vacuum.
2.6. Preparation of complexes
[(g6-C6H6)Ru(L\L){N3C2HCN}] L\L = O,O0-acac (10);
O,O0-bzac (11); O,O0-dbzm (12)
(Caution: This complex should be handled with extreme
care and usage of spatula is avoided).
To a round-bottom flask charged with the azido com-
plex 5 (0.1 g, 0.31 mmol) was added fumaronitrile (0.05 g,
0.63 mmol) and 20 ml of dichloromethane–methanol mix-
ture. The solution was stirred at room temperature for
24 h. The solvent was reduced to ca. 5 ml and an excess
of n-pentane added to give a chocolate color precipitate.
The powder compound was collected and washed with n-
pentane (3 · 10 ml) and dried under vacuum.
Complex [(g6-C6H6)Ru(O,O0-acac)N3] (5): Yield:
42 mg, 41%. IR (KBr, cmꢀ1): 2026 (mN3); 1568, 1387
(mC@O + C@C). 1H NMR (CDCl3, d): 2.20 (s, 6H, CH3),
5.69 (s, 1H, cH), 5.81 (s, 6H, C6H6), 7.37–7.42 (m, Ph).
Complex [(g6-C6H6)Ru(O,O0-bzac)N3] (6): This com-
plex was prepared by following a similar method employed
in the preparation of [(g6-C6H6)Ru(O,O0-acac)N3] (5),
using Na(O,O0-bzac) Æ H2O instead of Na(O,O0-aca-
Complex [(g6-C6H6)Ru(O,O0-acac){N3C2HCN}] (10):
Yield: 50 mg, 43.14%. IR (KBr, cmꢀ1): 2236 (mC„N),
c) Æ H2O. Yield: 49 mg, 51%. IR (KBr, cmꢀ1): 2025 (mN ),
1580, 1520 (mC@N + mC@C). H NMR (CDCl3, d): 2.25 (s,
1
3
1
1553, 520 (mC@O + mC@C). H NMR (CDCl3, d): 2.02 (s,
6H, CH3), 5.59 (s, 1H, cH), 6.02 (s, 6H, C6H6); 6.82 (s,
1H, CH).
3H, CH3), 5.59 (s, 1H, cH), 5.91 (s, 6H, C6H6), 7.02–7.28
(m, 5H, Ph).
Complex [(g6-C6H6)Ru(O,O0-bzac){N3C2HCN}] (11):
Yield: 54 mg, 47.64%. Elemental Anal. (%), Calc. for
C19H16N4O2Ru: C, 52.66; H, 3.69; N, 12.93. Found: C,
52.03; H, 3.96; N, 13.15%. IR (KBr, cmꢀ1): 2234 (mC@N),
Complex [(g6-C6H6)Ru(O,O0-dbzm)N3] (7): This com-
plex was prepared by following the similar procedure as
described in the preparation of complex [(g6-
C6H6)Ru(O,O0-acac)N3] (5) using Na(O,O0-dbzm) Æ H2O
instead of Na(O,O0-acac) Æ H2O. Yield: 56 mg, 58%. IR
1
1572, 1520 (mC@N + mC@C). H NMR (CDCl3, d): 2.12 (s,
3H, (bzac–CH3), 5.75 (s, 1H, cH), 5.79 (s, 6H, C6H6);
6.86 (s, 1H, CH); 7.24–7.52 (m, 5H).
(KBr, cmꢀ1): 2022, 1646, 1573 (mN ), (mC@O, C@C). 1H
3
NMR (CDCl3, d): 5.47 (s, 1H, cH), 5.89 (s, 6H, C6H6),
7.30–7.62 (m, 10H, Ph).
Complex [(g6-C6H6)Ru(O,O0-dbzm){N3C2HCN}] (12):
Yield: 56 mg, 50.3%. IR (KBr, cmꢀ1): 2225 (mC„N), 1571,
1
1520 (mC@N + mC@C). H NMR (CDCl3, d): 5.81 (s, 1H,
2.4. Preparation of triazolato complex
[(g6-C6H6)Ru(O,O0-acac){N3C2(CO2CH3)2}] (8)
cH), 5.94 (s, 6H, C6H6), 6.83 (s, 1H, CH); 7.28–7.42 (m,
10H, Ph).
To a round-bottom flask charged with the corresponding
azido complex [(g6-C6H6)Ru(O,O0-acac)N3] (0.1 g, 0.31
mmol) was added a fivefold excess of dimethylacetylenedi-
carboxylate and CH2Cl2 (20 ml). The mixture was stirred
at room temperature for 14–15 h. The solution was evapo-
rated to ca. 5 ml. To this solution was added 30 ml of hex-
ane, whereby the compound was precipitated out as a
yellow solid. The solid compound was collected by filtration
and washed with 2 · 20 ml of hexane and dried under vac-
uum to gave the triazolato complexes [(g6-C6H6)Ru-
(L\L){N3C2(CO2CH3)2}]. Yield: 52 mg, 34%. IR (KBr,
cmꢀ1): 1437–1446 (mN@N), 1580, 1529 (mC@O+C@C). 1H
NMR (CDCl3, d): 1.91(s, 6H, acac–Me); 2.87 (s, 6H,
OCH3); 5.47 (s, 1H, acac-cH); 5.69 (s, 6H, C6H6).
Table 1
Crystal data and experimental details for [(g6-C6H6)Ru(O,O0-acac)-
{N3C2(CO2C2H5)2}] (9)
Chemical formula
Formula weight
Crystal system
C19H24N3O6Ru
491.48
monoclinic
P21/c (no. 14)
red block
0.42 · 0.22 · 0.10
11.265(2)
7.2910(10)
24.976(5)
98.36(3)
Space group
Crystal colour and shape
Crystal size
˚
a (A)
˚
b (A)
˚
c (A)
b (o)
3
˚
V (A )
2029.6(6)
4
173(2)
Z
2.5. Preparation of triazolato complexes
[(g6-C6H6)Ru(O,O0-acac){N3C2(CO2C2H5)2}] (9)
T (K)
Dcalc (g cmꢀ3
)
1.608
l (mmꢀ1
)
0.813
The complex is prepared by following the same proce-
dure for the preparation of [(g6-C6H6)Ru(O,O0-acac){N3-
C2(CO2CH3)2}] (8), where diethylacetylenedicarboxylate
is used instead of dimethylacetylenedicarboxylate. Yield:
55 mg, 39%. IR (KBr, cmꢀ1): 1437–1446 (mN@N), 1533
(mC@O+C@C). 1H NMR (CDCl3, d): 1.92 (s, 6H, (acac–
Me), 2.35 (q, 6H, {OCH2(CH3)2}, 2.62 (t, 6H, CH2(CH3)2);
3.65 (q, 4H, (–CH2 of OCH2 (CH3)2); 5.85 (s, 1H, (acac-
cH), 5.94 (s, 6H, C6H6).
Scan range (ꢁ)
2.28 < h < 25.97
3941
2772
Unique reflections
Reflections used [I > 2r(I)]
Rint
Final R indices [I > 2r(I)]*
R indices (all data)
Goodness-of-fit
0.0481
0.0364, wR2 = 0.0894
0.0574, wR2 = 0.0951
1.038
ꢀ3
˚
Maximum, minimum Dq/e (A
)
0.794, ꢀ0.549
2
2 1=2
*
Structures were refined on F 2o : wR2 ¼ ½R½wðF o2 ꢀ F c2Þ ꢁ=RwðF 2oÞ ꢁ
;
2
where wꢀ1 ¼ ½RðF o2Þ þ ðaPÞ þ bPꢁ and P ¼ ½maxðF o2; 0Þ þ 2F 2c ꢁ=3.