68
H. Ben Ammar et al. / Journal of Organometallic Chemistry 662 (2002) 63ꢀ69
/
4.41; Cl, 5.58. Found: C, 50.72; H, 4.65; N, 4.48; Cl,
5.84%. 1H-NMR: d 1.25 (d, 6H, Jꢄ
6.9 Hz, CH(CH3)2),
2.15 (s, 3H, CH3C6H4), 2.55 (s, 6H, 2 MeC6H3), 2.95
(sept, 1H, Jꢄ6.9 Hz, CH(CH3)2), 4.75 (d(AB), 1H,
JAB 20.5 Hz, CH2), 5.80 (d(AB), 1H, JAB 20.5 Hz,
CH2), 5.85 (d(AB), 2H, JAB 6.2 Hz, C6H4 p-cymene),
5.95 (d(AB), 2H JAB 6.2 Hz, C6H4 p-cymene) 7.28ꢀ
8.61 (m, 1H, 2C6H4). 13C-NMR: d 18.6 (MeC6H4), 22.4,
22.7 (CHMe2), 31.6 (CH2), 32.2 (CHMe2), 82.2, 83.5,
83.6, 85.0 (4CH p-cymene), 100.5 and 107.5 (2C p-
cymene), 112.3, 119.6, 122.7, 125.0, 126.2, 127.7, 127.9
(CH arom), 132.5, 135.8, 138.3, 142.6 (C arom), 160.3,
/
/
ꢄ
/
ꢄ
/
ꢄ
/
164.3 (2C Ä
1578 (n CÄ
cmꢂ1): 412 (1390), 280 (10 167), 273 (11 233), 240
(17 612). Electrochemistry (100 mV sꢂ1): E (Pc)ꢄ
1.532 V versus FeCp2.
/
N). IR (cmꢂ1): 1162 (n PÃ
N), 1609 (n CÄ
N). UV: l (nm) (o, l molꢂ1
/
F), 1539 (n CÄ
/C),
ꢄ
/
/
/
/
7.70 (m, 6H, 2C6H3). 13C-NMR: d 18.6 (MeC6H4), 21.9
(2 MeC6H3), 22.7 (CHMe2), 28.2 (CH2), 31.4 (CHMe2),
83.3 and 83.5 (4CH p-cymene), 100.5 and 107.1 (2C p-
cymene), 111.7, 119.3, 128.9 (3CH arom), 136.8, 139.3,
/
ꢂ
/
148.7 (3C arom), 160.0 (2C Ä
F), 1539 (n CÄC), 1578 (n CÄ
(nm) (o, l molꢂ1 cmꢂ1): 397 (7293), 281 (1489).
Electrochemistry (100 mV sꢂ1): E (Pc)ꢄ
1.326 V
/
N). IR (cmꢂ1): 1167 (n BÃ
N), 1619 (n CÄN). UV: l
/
6.6. Preparation of RuCl(2-(3H-benzoxazol-2-
ylidenemethyl)benzoxazole))(p-cymene) (4aꢀb)
/
/
/
/
/
ꢂ
/
A solution of complex 3a or 3b (one equivalent) in
CH2Cl2 (10 ml) was added to K2CO3 (three equivalents),
and the resulting suspension was stirred at r.t. for one
night. A brown solution was obtained, which was then
filtered through celite to remove salts, then evaporated.
versus FeCp2.
6.4. [RuCl(5,5?-dimethylbis(2-
benzoxazolyl)methane)(p-cymene)][BF4] (3c)
The crude complex was washed with Et2O (2ꢃ15 ml)
and dried under vacuum.
/
Complex 3c was prepared from [RuCl2(p-cymene)]2
(100 mg, 0.163 mmol), 5,5?-dimethylbis(2-benzoxa-
lyl)methane (91 mg, 0.32 mmol), and NH4BF4 (34 mg,
0.32 mmol) and isolated in 109 mg yield (97%). 1H-
6.7. RuCl(2-(3H-benzoxazol-2-
ylidenemethyl)benzoxazole))(p-cymene) (4a)
NMR: d 1.24 (d, 6H, Jꢄ
3H, CH3C6H4), 2.55 (s, 6H, 2 MeC6H3), 2.82 (sept, 1H,
Jꢄ6.9 Hz, CH(CH3)2), 4.90 (d(AB), 1H, JAB 19.2
Hz, CH2), 5.30 (d(AB), 1H, JAB 19.2 Hz, CH2), 5.80
(d(AB), 2 H, JAB 5.9 Hz, C6H4 p-cymene), 5.88
(d(AB), 2H JAB 7.73
/6.7 Hz, CH(CH3)2), 2.22 (s,
Complex 4a was prepared from complex 3a (50 mg,
0.082 mmol), K2CO3 (34 mg, 0.247 mmol) and isolated
/
ꢄ
/
ꢄ
/
1
in 42 mg yield (98%). H-NMR: d 1.15 (d, 6H, Jꢄ
/
6.9
ꢄ
/
Hz, CHMe2), 2.37 (s, 3H, MeC6H4), 2.43 (sept, 1H, Jꢄ
6.9 Hz, CHMe2), 4.75 (s, 1H, CH), 5.40 (d(AB), 2H,
JAB 6.2 Hz, C6H4 p-cymene), 5.55 (d(AB), 2H JAB
6.2 Hz, C6H4 p-cymene) 6.95ꢀ
7.40 (m, 8H, 2C6H4). 13C-
NMR: d 18.9 (MeC6H4), 22.7 (CHMe2), 30.7 (CHMe2),
77.2 (CÄCHÃCÄN), 82.3, 82.6 (4CH p-cymene), 97.3
and 99.9 (2C p-cymene), 108.9, 115.0, 120.9, 124.0,
138.6, 149.9 (CH arom), 158.3 (CÄCHÃC ÄN), 165.2
(CÄCHÃC Ä
N). Electrochemistry (100 mV sꢂ1): E
(Pc)ꢄ 1333 V versus FeCp2.
/
ꢄ
/
5.9 Hz, C6H4 p-cymene) 7.36ꢀ
/
(m, 6H, 2C6H3). 13C-NMR: d 18.7 (MeC6H4), 21.8 (2
MeC6H3), 22.7 (CHMe2), 28.4 (CH2), 31.3 (CHMe2),
83.3 and 83.6 (4CH p-cymene), 100.5 and 107.0 (2C p-
cymene), 112.2, 118.8, 127.7 (3CH arom), 136.9, 138.5,
ꢄ
/
ꢄ
/
/
150.6 (3C arom), 159.6 (2C Ä
F), 1539 (n CÄC), 1578 (n CÄ
(nm) (o, l molꢂ1 cmꢂ1): 396 (2062), 280 (1480).
Electrochemistry (100 mV sꢂ1): E (Pc)ꢄ
1.410 V
versus FeCp2.
/
N). IR (cmꢂ1): 1167 (n BÃ
N), 1619 (n CÄN). UV: l
/
/
/
/
/
/
/
/
/
/
/
/
/
/
ꢂ
/
/
ꢂ
/
6.5. [RuCl(2-benzothiazol-2-ylmethyl-benzoxazol)(p-
cymene)][PF6] (3d)
6.8. RuCl(5-methyl-2-(5-methyl-3H-benzooxazol-2-
ylidenemethyl)benzoxazole))(p-cymene) (4b)
Complex 3d was prepared from [RuCl2(p-cymene)]2
(100 mg, 0.163 mmol), 2-benzothiazol-2-ylmethyl-ben-
zoxazol (87 mg, 0.32 mmol), and NH4PF6 (53 mg, 0.32
mmol) and isolated in 97 mg yield (98%). Anal. Calc. for
C25H24ClF6N2ORuS: C, 44.03; H, 3.55; N, 4.11; Cl,
Complex 4b was prepared from complex 3b (55 mg,
0.086 mmol), K2CO3 (49 mg, 0.35 mmol) in 41 mg yield
1
(87%). H-NMR: d 1.12 (d, 6H, Jꢄ
/
6.9 Hz, CHMe2),
2.40 (s, 3H, CH3C6H4), 2.45 (s, 6H, MeC6H3), 2.47
(sept, 1H, Jꢄ6.9 Hz, CHMe2), 4.72 (s, 1H, CH), 5.41
(d(AB), 2 H, JAB 6.2 Hz, C6H4 p-cymene), 5.47
(d(AB), 2H JAB 6.2 Hz, C6H4 p-cymene) 6.79ꢀ6.86
(m, 2H, MeC6H3), 7.05ꢀ
7.18 (m, 4H, 2 MeC6H3). 13C-
NMR: 19.0 (MeC6H4), 21.8 (MeC6H3), 22.4
(CHMe2), 31.1 (CHMe2), 58.2 (CÄCHÃCÄN), 82.8,
/
1
5.20. Found: C, 44.08; H, 3.39; N, 3.98; Cl, 5.25%. H-
ꢄ
/
NMR: d 1.05 (d, 3H, Jꢄ
3H, Jꢄ6.9 Hz, CH(CH3)2), 2.18 (s, 3H, CH3C6H4),
2.80 (sept, 1H, Jꢄ6.9 Hz, CH(CH3)2), 5.01 (d(AB), 1H,
JAB 19.3 Hz, CH2), 5.20 (d(AB), 1H, JAB 19.2 Hz,
CH2), 5.71 (d(AB), 2 H, JAB 6.0 Hz, C6H4 p-cymene),
5.93 (d(AB), 2H JAB 6.0 Hz, C6H4 p-cymene) 7.15ꢀ
7.74 (m, 5H, 2C6H4), 7.84ꢀ7.97 (m, 5H, 2C6H4), 8.56ꢀ
/6.9 Hz, CH(CH3)2), 1.25 (d,
ꢄ
/
/
/
/
/
d
ꢄ
/
ꢄ
/
/
/
/
ꢄ
/
82.9 (4CH p-cymene), 99.9 and 103.5 (2C p-cymene),
ꢄ
/
/
108.6, 115.8, 122.0 (CH arom), 134.2, 143.8, 148.5 (C
N).
/
/
arom), 159.8 (CÄ
/
CHÃ
/
C Ä
/
N), 165.7 (CÄ
/
CHÃ
/
C Ä
/