M.I. Bruce et al. / Journal of Organometallic Chemistry 692 (2007) 2564–2574
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4.5. Fc(C„C)3Ru(dppe)Cp (2)
other bands at 1584w, 1573w, 1537m (sh), 1531m cmꢀ1
1H NMR:
2.40–2.65, 2.85–3.10 (2 · m, 2 · 2H,
.
d
A degassed solution of Fc(C„C)3SiMe3 (1011 mg,
3.04 mmol) in MeOH (50 ml) containing water (0.5 ml)
and dbu (1 drop) was added to a stirred mixture of
RuCl(dppe)Cp (1880 mg, 3.13 mmol) and KF (272 mg,
4.70 mmol). After heating at reflux point for 1 h and cool-
ing, the resulting precipitate was collected, dried in vacuum
and purified by column chromatography (basic alumina,
benzene) to give Fc(C„C)3Ru(dppe)Cp (2) (1365 mg,
53%) as a dark orange solid. Anal. Calc. for C47H38Fe-
P2Ru: C, 68.70; H, 4.66. Found: C, 68.67; H, 4.71%. M,
822. IR (nujol): m(C„C) 2108s, 1992s; other bands at
2 · CH2), 4.37 (s, 5H, Cp–Fe), 4.60, 4.69 (2 · m, 2 · 2H,
C5H4), 5.02 (s, 5H, Cp–Ru), 7.20–7.26, 7.33–7.43, 7.68–
7.72 (3 · m, 4H + 12H + 4H, Ph). 13C NMR: d 28.42–
28.73 (m, CH2), 60.56 (Fc ipso), 71.21 (Cp–Fe), 72.25,
73.40 (2 · C5H4), 84.43, 86.57 [2 · C(sp3) of cyclobutene],
86.26 (Cp–Ru), 112.07, 113.88, 115.42, 116.54, 119.77
(4 · CN + C), 128.04–128.43, 129.71, 130.29, 130.94–
131.08, 133.46–133.60 (6 · m, Ph), 134.89–134.23, 139.80–
140.35 (2 · m), 148.92 (C@C). 31P NMR: d 85.4 (dppe).
ES-MS (MeOH, positive ion, m/z): 973, [M+Na]+.
(b) With Co2(CO)8. A solution of Fc(C„C)3Ru(dp-
pe)Cp (35 mg, 0.043 mmol) and Co2(CO)8 (135 mg,
0.38 mmol) in dry thf (5 ml) was stirred overnight. After
removal of solvent in vacuum, the residue was purified by
preparative TLC (hexane/acetone 2/1) to give Fc{C2[Co2-
(CO)6]}2C„CRu(dppe)Cp (5) as a dark purple solid
(39 mg, 65%). Anal. Calc. for C59H38Co4FeO12P2Ru: C,
50.85; H, 2.75. Found: C, 50.96; H, 2.69%. M, 1394. IR
(CH2Cl2): m(CO) 2091w, 2070m, 2051s, 2044s (sh), 2023s
1
1585w, 1571w cmꢀ1. H NMR (C6D6): d 1.80–2.00, 2.30–
2.50 (2 · m, 2 · 2H, CH2), 3.76–3.77, 4.23–4.24 (2 · m,
2 · 2H, C5H4), 3.93 (s, 5H, Cp–Fe), 4.58 (s, 5H, Cp–Ru),
6.85–7.00, 7.05–7.30, 7.81–7.87 (3 · m, 7H + 8H + 5H,
Ph). 13C NMR: d 27.40–28.32 (m, 2 · CH2), 65.91, 68.17
(C5H4), 69.34, 69.69 (Cp–Fe), 70.71, 71.82 (C5H4), 74.85,
83.13 (Cp–Ru), 94.40, 123.13 [t, J(CP) 22.0 Hz], 129.47,
131.26–131.47, 133.27–134.48, 135.76–136.78, 141.02–
141.79 (5 · m, Ph). 31P: d 85.23 (dppe). ES-MS (MeOH +
NaOMe, positive ion, m/z): 845, [M+Na]+.
1
(sh), 2011s; other band at 1435w cmꢀ1. H NMR: d 2.56,
2.78 [2 · s (br), 2 · 2H, CH2], 4.22 [s (br), 5H, Cp–Fe],
4.40, 4.66 [2 · s (br), 2 · 2H, C5H4], 4.80 (br s, 5H, Cp–
Ru), 7.02–7.30, 7.76 (2 · m, 16H + 4H, Ph). 13C NMR: d
26.90–28.12 (m, CH2), 68.35, 71.36 (2 · m, C5H4), 69.74
(s, Cp–Fe), 83.68 (s, Cp–Ru), 88.09, 88.64, 89.39, 98.30,
98.88, 108.87, 127.90–128.17, 128.75, 131.06–131.12,
133.58–133.72, 136.19–136.87, 141.87–142.40 (6 · m, Ph),
156.74 [t, J 24.0 Hz, Ca], 199.57 (CO). 31P NMR: d 86.79
(dppe). ES-MS (MeOH, positive ion, m/z): 1417,
[M+Na]+; 1394, M+.
4.6. Reactions of Fc(C„C)3Ru(dppe)Cp
(a) With tcne. A mixture of Fc(C„C)3Ru(dppe)Cp
(104 mg, 0.127 mmol) and tcne (19 mg, 0.15 mmol) in dry
CH2Cl2 (5 ml) was sonicated at r.t. for 8 h. Removal of sol-
vent in vacuum and purification by preparative TLC
(CH2Cl2) gave FcC„CC„C{C[@C(CN)2]}2Ru(dppe)Cp
(3) as a dark blue solid (Rf = 0.3; 12 mg, 10%). The base-
line material was recovered and extracted several times
with diethyl ether and purified by a second TLC (5%
acetone-CH2Cl2) to give the green cyclobutenyl complex
FcC„CC„C{C@CC(CN)2C(CN)2}Ru(dppe)Cp (4) (Rf =
0.3; 50 mg, 41%).
(c) With Co2(l-dppm)(CO)6.
A
solution of
Fc(C„C)3Ru(dppe)Cp (38 mg, 0.046 mmol) and Co2-
(l-dppm)(CO)6 (39 mg, 0.58 mmol) in dry thf (20 ml) ws
heated at reflux point overnight. After removal of solvent
under vacuum, preparative TLC of the residue (hexane/
acetone 3/2) afforded the mono adduct FcC2{Co2(l-
dppm)(CO)4}C„CC„C Ru(dppe)Cp (6) as a brown solid
(60 mg, 91%). Anal. Calc. for C76H60Co2FeO4P4Ru: C,
63.57; H, 4.21. Found: C, 63.41; H, 4.09%. M, 1436. IR
(CH2Cl2): m(CC) 2113w; m(CO) 2009m, 1992s, 1964m,
For 3: Anal. Calc. for C53H38FeN4P2Ru: C, 67.02; H,
4.03; N, 5.90. Found: C, 67.08; H, 3.93; N, 5.96%. M,
950. IR (CH2Cl2): m(C„N) 2226w, 2207w; m(C„C)
2181s, 2135w; other bands at 1605m, 1502m cmꢀ1 1H
.
NMR: d 2.30–2.50, 2.50–2.70 (2 · m, 2 · 2H, CH2), 4.31
(s, 5H, Cp–Fe), 4.42 [m (br), 2H, C5H4], 4.62, 4.66
(2 · m, 2 · 1H, C5H4), 4.93 (s, 5H, Cp–Ru), 6.63–6.69,
7.12–7.34, 7.50–7.73, 7.97–8.03 (4 · m, Ph). 13C NMR: d
26.28–26.96, 29.02–29.67(2 · m, CH2), 60.75 (C5H4 ipso),
70.01, 71.01 (Cp–Fe), 71.24, 72.18, 73.24, 73.45 [d, J(CP)
3.2 Hz], 77.20, 81.27, 86.04 (Cp–Ru), 95.72 [d, J(CP)
6.8 Hz], 96.87, 97.39, 111.93, 112.36, 112.88, 118.12
(4 · CN), 127.78–128.24, 128.64–128.76, 130.54, 131.26–
131.74 (4 · m, Ph), 134.52, 135.03, 136.13, 136.72, 140.07,
140.49, 163.63 (C@C). 31P NMR: d 66.4 [d, J(PP)
22.2 Hz], 81.8 [d, J(PP) 22.2 Hz]. ES-MS (MeOH +
NaOMe, positive ion, m/z): 973, [M+Na]+.
1945w; other band at 1435w cmꢀ1 1H NMR: d 1.95–
.
2.15, 2.60–2.80 (2 · m, 2 · 2H, 2 · CH2 of dppe), 2.95–
3.15, 3.70–3.85 (2 · m, 2 · 1H, CH2 of dppm), 4.16 (m,
2H, C5H4), 4.41 (s, 5H, Cp–Fe), 4.71 (m, 7H,
C5H4 + Cp–Ru), 6.77–7.27, 7.53, 7.91–7.97 (3 · m,
31H + 5H + 4H, Ph). 13C NMR: d 27.95–28.56 (m,
2 · CH2 of dppe), 31.42 [t, J(CP) 21.6 Hz, CH2 of dppm],
63.48, 67.63, 69.71 (2 · s, C5H4), 69.30 (s, Cp–Fe), 77.21,
83.25 (Cp–Ru), 91.02, 91.74 [t, J(CP) 2.6 Hz], 96.25,
125.99 [t, J(CP) 24.8 Hz, Ca], 127.80–128.13, 128.64,
128.97, 129.46–129.52, 130.98–131.14, 131.41–131.55,
132.71–132.91, 136.11–136.79, 141.62–142.13 (8 · m, Ph),
134.37 [t, J(CP) 15.9 Hz], 138.60 [t, J(CP) 23.6 Hz],
202.22 (CO), 206.68 (CO). 31P NMR: d 9.5 (dppm), 85.5
(dppe). ES-MS (MeOH, positive ion, m/z): 1436, M+.
For 4: Anal. Calc. for C53H38FeN4P2Ru: C, 67.02; H,
4.03; N, 5.90. Found: C, 66.94; H, 3.97; N, 6.02%. M,
950. IR (nujol): m(C„N) 2208m; m(C„C) 2163s, 1978vs;