Preparation of [Fe(CO)4(CNR)]
[R~C6H4C6H4O(O)CC6H4OCnH2nz1
,
C6H4O(O)CC6H4C6H4OCnH2nz1
C6H4C(O)OC6H4C6H4OCnH2nz1
,
]
To
a
mixture of [Fe(CO)5] (0.3 mmol), CoCl2?2H2O
(0.03 mmol) and 15 mL of toluene at 60 ³C, was added
dropwise the corresponding isocyanide (0.39 mmol) in 20 mL
of toluene, under nitrogen. After stirring for 20 minutes, the
reaction mixture was cooled to room temperature and the
solvent was removed under vacuum. Recrystallisation from
CH2Cl2/hexane at 215 ³C afforded air stable yellow crystals of
the product.
Yields, IR and analytical data
Fig. 3 Comparison of the transition temperatures of [Fe(CO)4(CNR)]
(LA),
R~C6H4C6H4O(O)CC6H4OCnH2nz1 (Fe±LA). n~6: Yield
59%. IR (CH2Cl2) n(CMN): 2163 m, n(CO): 2055 s, 1998 m,
1970 s. Anal. Calcd. for C30H25FeNO7: C, 63.51; H, 4.44; N,
2.47. Found: C, 62.99; H, 4.72; N, 2.35. n~8: Yield 42%. IR
(CH2Cl2) n(CMN): 2162 m, n(CO): 2055 s, 1998 m, 1970 s. Anal.
Calcd. for C32H29FeNO7: C, 64.55; H, 4.91; N, 2.35. Found: C,
64.86; H, 5.15; N, 2.34. n~10: Yield 54%. IR (CH2Cl2) n(CMN):
2165 m, n(CO): 2055 s, 1995 m, 1967 s. Anal. Calcd. for
C34H33FeNO7: C, 65.51; H, 5.33; N, 2.25. Found: C, 64.95; H,
5.42; N, 2.10. n~12: Yield 46%. IR (CH2Cl2) n(CMN): 2163,
n(CO): 2055 s, 1998 m, 1971 s. Anal. Calcd. for C36H37FeNO7:
C, 66.36; H, 5.72; N, 2.15. Found: C, 66.65; H, 5.93; N, 2.12.
[R~C6H4C6H4O(O)CC6H4OCnH2nz1
C6H4O(O)CC6H4-
C6H4OCnH2nz1 (LB), C6H4C(O)OC6H4C6H4OCnH2nz1 (LC)] com-
plexes. The bars are labelled Fe±Ln; Ln denotes the isocyanide.
dried over MgSO4 and ®ltered. The solvent was removed on a
rotary evaporator to obtain the product as yellow solid (90%
yield).
Preparation of 4-isocyanobiphenyl-4'-yl 4-alkoxybenzoate
The procedure described by Ugi and Meyr48 was followed,
using triphosgene as the dehydrating agent. To a solution of
4-formamidobiphenyl-4'-yl 4-alkoxybenzoate (6.71 mmol),
prepared by reaction of the amine with formic acid, and
triethylamine (3.40 mmol) in 50 ml of CH2Cl2 was added
dropwise a solution of triphosgene (2.25 mmol) in 25 ml of
CH2Cl2. The mixture was stirred for 1 h and then the solvent
was removed on a rotary evaporator. The resulting residue was
chromatographed (silica gel, CH2Cl2/hexane, 4 : 1 as eluent)
and the solvent was evaporated to obtain the product as a white
solid (60% yield).
R~C6H4O(O)CC6H4C6H4OCnH2nz1 (Fe±LB). n~6: Yield
56%. IR (CH2Cl2) n(CMN): 2165 m, n(CO): 2055 s, 1996 m,
1967 s. Anal. Calcd. for C30H25FeNO7: C, 63.51; H, 4.44; N,
2.47. Found: C, 63.03; H, 4.55; N, 2.38. n~8: Yield 45%. IR
(CH2Cl2) n(CMN): 2161 m, n(CO): 2055 s, 2000 m, 1973 s. Anal.
Calcd. for C32H29FeNO7: C, 64.55; H, 4.91; N, 2.35. Found: C,
64.21; H, 4.98; N, 2.35. n~10: Yield 49%. IR (CH2Cl2) n(CMN):
2164 m, n(CO): 2055 s, 1996 m, 1967 s. Anal. Calcd. for
C34H33FeNO7: C, 65.51; H, 5.33; N, 2.25. Found: C, 65.23; H,
5.18; N, 2.15. n~12: Yield 45%. IR (CH2Cl2) n(CMN): 2166,
n(CO): 2055 s, 1996 m, 1967 s. Anal. Calcd. for C36H37FeNO7:
C, 66.36; H, 5.72; N, 2.15. Found: C, 66.01; H, 5.82; N, 2.14.
IR and analytical data
CNC6H4C6H4O(O)CC6H4OCnH2nz1 (LA).
n~6: IR
(CH2Cl2) n(CMN): 2128 s. Anal. Calcd. for C26H25NO3: C,
78.17; H, 6.31; N, 3.51. Found: C, 77.92; H, 6.50; N, 3.44. n~8:
IR (CH2Cl2) n(CMN): 2128 s. Anal. Calcd. for C28H29NO3: C,
78.66; H, 6.84; N, 3.28. Found: C, 78.44; H, 6.89; N, 3.41.
n~10: IR (CH2Cl2) n(CMN): 2128 s. Anal. Calcd. for
C30H33NO3: C, 79.09; H, 7.30; N, 3.07. Found: C, 78.89; H,
7.31; N, 3.12. n~12: IR (CH2Cl2) n(CMN): 2128 s. Anal. Calcd.
for C32H37NO3: C, 79.47; H, 7.71; N, 2.90. Found: C, 79.08; H,
7.76; N, 2.85.
R~C6H4C(O)OC6H4C6H4OCnH2nz1 (Fe±LC). n~6: Yield
59%. IR (CH2Cl2) n(CMN): 2153 m, n(CO): 2052 s, 2004 m,
1977 s. Anal. Calcd. for C30H25FeNO7: C, 63.51; H, 4.44; N,
2.47. Found: C, 63.65; H, 4.53; N, 2.47. n~8: Yield 56%. IR
(CH2Cl2) n(CMN): 2159 m, n(CO): 2054 s, 1999 m, 1968 s. Anal.
Calcd. for C32H29FeNO7: C, 64.55; H, 4.91; N, 2.35. Found: C,
64.43; H, 5.03; N, 2.30. n~10: Yield 61%. IR (CH2Cl2) n(CMN):
2159 m, n(CO): 2054 s, 1999 m, 1968 s. Anal. Calcd. for
C34H33FeNO7: C, 65.51; H, 5.33; N, 2.25. Found: C, 66.07; H,
5.60; N, 2.13. n~12: Yield 46%. IR (CH2Cl2) n(CMN): 2158,
n(CO): 2054 s, 2000 m, 1971 s. Anal. Calcd. for C36H37FeNO7:
C, 66.36; H, 5.72; N, 2.15. Found: C, 66.28; H, 5.92; N, 2.03.
CNC6H4O(O)CC6H4C6H4OCnH2nz1 (LB).
n~6: IR
(CH2Cl2) n(CMN): 2130 s. Anal. Calcd. for C26H25NO3: C,
78.17; H, 6.31; N, 3.51. Found: C, 77.82; H, 6.36; N, 3.44. n~8:
IR (CH2Cl2) n(CMN): 2130 s. Anal. Calcd. for C28H29NO3: C,
78.66; H, 6.84; N, 3.28. Found: C, 78.22; H, 6.74; N, 3.23.
n~10: IR (CH2Cl2) n(CMN): 2130 s. Anal. Calcd. for
C30H33NO3: C, 79.09; H, 7.30; N, 3.07. Found: C, 78.87; H,
7.24; N, 3.09. n~12: IR (CH2Cl2) n(CMN): 2130 s. Anal. Calcd.
for C32H37NO3: C, 79.47; H, 7.71; N, 2.90. Found: C, 79.21; H,
7.67; N, 2.89.
Acknowledgements
We are indebted to the ComisioÂn Interministerial de Ciencia y
TecnologÂõa (Project MAT99-0971) and to the Junta de Castilla
y LeoÂn (Projects VA16/99 and VA15/00B) for ®nancial
support.
CNC6H4C(O)OC6H4C6H4OCnH2nz1 (LC).
n~6: IR
(CH2Cl2) n(CMN): 2127 s. Anal. Calcd. for C26H25NO3: C,
78.17; H, 6.31; N, 3.51. Found: C, 77.97; H, 6.35; N, 3.38. n~8:
IR (CH2Cl2) n(CMN): 2128 s. Anal. Calcd. for C28H29NO3: C,
78.66; H, 6.84; N, 3.28. Found: C, 78.40; H, 6.87; N, 3.24.
n~10: IR (CH2Cl2) n(CMN): 2128 s. Anal. Calcd. for
C30H33NO3: C, 79.09; H, 7.30; N, 3.07. Found: C, 78.68; H,
7.19; N, 3.18. n~12: IR (CH2Cl2) n(CMN): 2128 s. Anal. Calcd.
for C32H37NO3: C, 79.47; H, 7.71; N, 2.90. Found: C, 79.28; H,
7.57; N, 2.85.
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