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I. Amour Morkan / Journal of Organometallic Chemistry 651 (2002) 132ꢁ
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3.1. Tricarbonyl(h6-N-cyanoazepine)metal(0)
C10H6N2O3W (386.02): Anal. Calc.: C, 31.12; H, 1.57;
N, 7.26. Found: C, 31.00; H, 1.60; N, 7.30%.
A solution of 1.0 g of (CO)3M(CH3CN)3 [M: Cr (6.65
mmol), Mo (4.52 mmol), W (3.24 mmol)] and 1.0 g of
N-cyanoazepine (8.46 mmol) in 150 ml of n-C6H14 is
irradiated [M: Cr (300 min), Mo (250 min), W (210 min)]
using a high pressure mercury lamp (Hg-Tauchlampe
TQ 150W, Quarzlampen GmbH, Hanau, Germany)
which is housed in a water-cooled glass jacket. The
resulting dark solution is filtered and then evaporated
under high vacuum (0.01 mmHg). The resulting solid is
3.5. Tricarbonyl{h4:2-7,8-diphenyl-9-N-cyano-9-
azabicyclo[4.2.1]-nona-2,4,7-triene}-chromium(0) (3a)
A solution of 2a (0.5 g, 1.97 mmol) and diphenyl
acetylene (0.5 g, 3.24 mmol) in 150 ml of C6H5CH3 was
irradiated at 263 K for 540 min using a high-pressure
mercury lamp. The residue was then filtered through
Celite and the solvent evaporated in high vacuum.
then purified by recrystallization from n-C6H14 at ꢃ
/
Recrystallization from n-C6H14ꢁ
3a as a reddish brown crystals.
Yield: 0.60 g (71% rel. 2a). C24H16CrN2O3 (432.40)
molar mass by MS 432 g molꢃ1. IR (n-C6H14): nꢂ
1985
(vs), 1894 (vs), 1720 (m) cmꢃ1 (CÄO); 2218 (w) cmꢃ1
(CÅ H-NMR (200 MHz, CDCl3): dꢂ4.56 (m,
N).*1
/CH2Cl2 (5:1) produced
78 8C. The dark orange crystals are best dried under
vacuum for 4 h and stored under nitrogen atmosphere
for analysis.
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3.2. Tricarbonyl(h6-N-cyanoazepine)chromium(0) (2a)
pale red solid
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2H, H2,5), 5.23 (m, 2H, H3,4), 5.28 (d, 1H, H1 or H6),
5.40 (d, 1H, H1 or H6), 7.26 (m, 6H, Ph), 7.60 (m, 4H,
C{1H}-NMR (100.62 MHz, C7D8): dꢂ
58.65,
59.60 (C1,6), 69.16, 69.80 (C2,5), 87.25, 88.90 (C7,8),
Ph).*13
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Yield: 1.20
C10H6CrN2O3 (254.17) molar mass by MS 254 g
molꢃ1 IR (n-C6H14): nꢂ
1996 (vs), 1938 (vs), 1912 (s)
cmꢃ1 (CÄO); 2217 (w) cmꢃ1 (CÅN).*1
H-NMR (200
MHz, CDCl3): dꢂ3.85 (m, 2H, H2,5), 4.30 (d, 2H, H1,6),
6.05 (m, 2H, H3,4).*13C{1H}-NMR (100.62 MHz,
C7D8): dꢂ72.20 (C1,6), 94.30 (C2,5), 97.15 (C3,4),
128.20 (NÃCN), 232.20, 226.05 (CÄO).*C10H6CrN2O3
g
(84% rel. (CO)3Cr(CH3CN)3).
/
94.80, 95.15 (C3,4), 127, 128, 129, 129.4, 130, 130.7 (Ph),
/
/
/
128.95 (CÅ
/
N), 228, 228.5, 232.6 (CÄ
/
O).*
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C24H16CrN2O3 (432.40): Anal. Calc.: C, 66.67; H,
3.73; N, 6.48. Found: C, 66.32; H, 3.76; N, 6.42%.
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3.6. Tricarbonyl{h4:2 -7,8-bis(trimethylsilyl)-9-N-cyano-
9-azabicyclo[4.2.1]-nona-2,4,7-triene}chromium(0)
(3b)
(254.17): Anal. Calc.: C, 47.25; H, 2.38; N, 11.02.
Found: C, 47.55; H, 2.30; N, 11.20%.
3.3. Tricarbonyl(h6-N-cyanoazepine)molybdenum(0)
(2b) pale red solid
A solution of 2a (0.5 g, 1.97 mmol) and bis(trimethyl-
silyl)acetylene (0.66 g, 0.88 ml, 3.90 mmol) in 150 ml of
C6H5CH3 was irradiated with UV light at 263 K for 690
min. The resulting solution was then filtered through
Celite and the solvent evaporated in high vacuum. The
brown residue was then chromatographed on silica gel
Yield: 1.0
C10H6MoN2O3 (298.11) molar mass by MS 298 g
molꢃ1. IR (n-C6H14): nꢂ
1998 (vs), 1938 (vs), 1910 (s)
cmꢃ1 (CÄO); 2219 (w) cmꢃ1 (CÅN).*1
H-NMR (200
MHz, CDCl3): dꢂ3.85 (m, 2H, H2,5), 4.32 (d, 2H, H1,6),
6.03 (m, 2H, H3,4).*13C{1H}-NMR (100.62 MHz,
C7D8): dꢂ73.10 (C1,6), 94.65 (C2,5), 97.05 (C3,4),
128.35 CÅN), 227.30, 215.45 (CÄO).*
(NÃ
g
(74% rel. (CO)3Mo(CH3CN)3).
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by using a n-C6H14ꢁ
/
CH2Cl2ꢁC3H6O (10:9:1) mixture.
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The orange elute was collected and evaporated in
vacuum. The resulting residue was recrystallized from
/
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n-C6H14 at ꢃ78 8C for one night. Decantation of the
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solvent and drying of the residue in vacuum produced 3b
as dark red crystals which were stored under nitrogen
atmosphere for analysis.
C10H6MoN2O3 (298.11): Anal. Calc.: C, 40.29; H,
2.03; N, 9.40. Found: C, 41.00; H, 2.11; N, 9.45%.
Yield: 0.55 g (66% rel. 2a). C24H16CrN2O3 (424.57)
3.4. Tricarbonyl(h6-N-cyanoazepine)tungsten(0) (2c)
pale red solid
molar mass by MS 424 g molꢃ1. IR (n-C6H14): nꢂ
/
1972
O), 2219 (w) cmꢃ1
H-NMR (200 MHz, CDCl3): dꢂ0.40 (s,
(vs), 1896 (vs), 1722 (m) cmꢃ1 (CÄ
/
(CÅ
/
N).*1
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/
Yield: 0.75
C10H6N2O3W (386.02) molar mass by MS 386 g
molꢃ1. IR (n-C6H14): nꢂ
1995 (vs), 1934 (vs), 1908 (s)
(CÄ H-NMR (200
O) cmꢃ1; 2217 (w) cmꢃ1 (CÅN).*1
MHz, CDCl3): dꢂ3.94 (m, 2H, H2,5), 4.38 (d, 2H, H1,6),
6.02 (m, 2H, H3,4).*13C{1H}-NMR (100.62 MHz,
C7D8): dꢂ65.80 (C1,6), 93.20 (C3,4), 93.75 (C2,5),
128.90 CÅN), 217.15, 206.20 (CO).*
(NÃ
g
(59.9% rel. (CO)3W(CH3CH)3).
18H, SiMe3), 4.58 (m, 2H, H2,5), 4.87 (m, 2H, H3,4),
4.84 (m, 1H, H1 or H6), 5.86 (d, 1H, H1 or
/
H6).*13
/
C{1H}NMR (100.62 MHz, C7D8): dꢂ
/
1.00
(SiMe3), 59.20, 59.56 (C1,6), 71.80, 72.10 ( C2,5), 74.30,
75.10 (C7,8), 95.80, 96.40 (C3,4), 128.42 (CÅN), 229,
229.7, 233.4 (CÄO).*C24H16CrN2O3 (424.57): Anal.
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Calc.: C, 50.92; H, 5.70; N, 6.60. Found: C, 51.30; H,
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5.52; N, 6.48%.