W. Tully et al. / Journal of Organometallic Chemistry 690 (2005) 3348–3356
3355
was further characterised by a single crystal X-ray struc-
ture determination (see below).
(1H, d, J = 7.7 Hz, H300), 7.52 (2H, m, H40, H500), 7.41
(1H, t, J = 5.6 Hz, H4000), 4.43 (1H, t, J = 3.7 Hz, H3),
4.24 (1H, s, H2); 4.13 (1H, dd, J = 14.1, 4.3 Hz, H4a),
4.02 (1H, dd, J = 14.1, 3.0 Hz, H4b). 13C NMR
(CD3COCD3): d 213.3 (s, CO), 209.9 (s, C1), 201.7 (s,
C5), 189.6 (s, C30), 173.0 (s, C200), 153.2 (d, C600), 142.9
(s, C200), 140.8 (s, C20), 140.0 (d, C400), 138.7 (d, C3000),
137.1 (d, C40), 135.9 (d, C5000), 133.3 (d, C50), 129.9 (d,
C4000), 123.5 (d, C500), 123.4 (d, C300), 55.3 (d, C2), 44.8
(d. C3), 43.2 (t, C4).
Second product: [1,5-Diphenyl-jC2-3-(2-pyridyl)pen-
tane-1,5-dione-jO1jO5]bis-(tetracarbonylmanganese)
(7a): Yellow crystals (15%), decomp. 170 ꢁC, identified
by spectra only: IR: m(CO) 2082 (m), 1995 (s, br), 1938
(s, br) cmꢁ1
.
1H NMR (CDCl3): d 8.38 (1H, d,
J = 4.2 Hz, H600), 8.05 (2H, d, J = 7.5 Hz, H30), 7.86
(2H, d, J = 7.8 Hz, H60), 7.54 (1H, dt, J = 7.6, 1.7 Hz,
H400), 7.39 (2H, dt, J = 7.4, 1.2 Hz, H40), 7.15 (2H, dt,
J = 7.5, 1.0 Hz, H50), 7.06 (2H, m, H300,500), 4.02 (1H,
m, H3),3.62 (2H, dd, J = 16.2, 8.9 Hz, H2a,4a), 3.30
(2H, dd, J = 16.2, 5.6 Hz, H2b,4b). 13C NMR (CDCl3):
d 216.9 (s, C1,5), 194.3 (s, C20), 160.4 (s, C200), 149.5 (d,
C600), 145.1 (s, C10), 141.6 (d, C30), 136.5 (d, C400), 134.0
(d, C40), 131.4 (s, C60), 123.9 (d, C50), 123.6 (d, C300),
122.2 (d, C500), 42.0 (t, C2,4), 40.3 (d, C3).
No second product was obtained on cooling the fil-
trate solution in this case.
3.2.2.4. 1,5-Di-(3-thienyl)-3-(2-pyridyl)pentane-1,5-dione
(5c) with 2.5 mol PhCH2Mn(CO)5. First product. [1,5-
Di(3-thienyl-jC2)-3-(2-pyridyl-jN)pentan-2-yl-jC2-1,5-
dione-jO1jO5]tetracarbonylmanganesetricarbonylman-
ganese (6c): Yellow crystals (27%), decomp. 198 ꢁC. IR:
m(CO) 2084 (m), 2015 (vs), 1999 (s, br), 1919 (vs, br)
3.2.2.2. 1,5-Diphenyl-3-(2-pyridyl)pentane-1,5-dione
(5a) with 3 mol PhCH2Mn(CO)5. First product. 6a
cmꢁ1 1H NMR (CDCl3): d 8.78 (1H, d, J = 5.4 Hz,
.
(58%): spectral data as above.
H600), 8.12 (1H, d, J = 1.6 Hz, H2000), 7.79 (1H, t,
J = 7.6 Hz, H400), 7.62 (1H, d, J = 5.0 Hz, H40), 7.50
(2H, m, H300, H4000), 7.43 (1H, d, J = 5.0 Hz, H50), 7.36
(1H, m, H5000), 7.22 (1H, t, J = 7.0 Hz, H500), 4.15 (1H,
dd, J = 4.7, 3.0 Hz, H3), 3.87 (1H, s, H2); 3.51 (2H,
ddd, J = 16.7, 4.7, 3.0 Hz, H4a, H4b), 4.02 (1H, dd,
J = 14.1, 3.0 Hz, H4b). 13C NMR (CDCl3): d 214.4 (s,
C20), 208.9 (s, C1), 200.7 (s, C5), 172.3 (s, C200), 152.5
(d, C600), 140.3 (s, C30 or C3000), 134.4 (d, C2000), 131.4
(d, C50), 127.4 (d, C5000), 126.6 (d, C4000), 124.5 (d, C40),
122.3 (d, C500), 121.8 (d, C300), 54.8 (d, C2), 44.2 (d.
C3), 43.5 (t, C4).
0
000
Second product. ½1; 5-Diphenyl-jC2 jC2 -3-ð2-pyridyl-
jNÞpentan-2-yl-jC2-1; 5-dione-jO1jO5ꢀtris-ðtetracarbo-
nylmanganeseÞ (8a): Mustard yellow crystals (19%),
decomp. 178 ꢁC. Anal. Found: C, 49.05; H, 1.70.
C34H16NO14Mn3 calc.: C, 49.39; H, 1.95%. IR: m(CO)
2083 (m), 2074 (m), 1993 (s, br), 1944 (s, br), 1929 (s,
br) cmꢁ1 1H NMR (CDCl3): d 9.00 (1H, d, J =
.
5.6 Hz, H600), 8.23 (1H, d, J = 7.5 Hz, H3000), 8.14 (3H,
m, J = 7.7 Hz, H30, H400, H6000), 7.80 (1H, d,
J = 7.9 Hz, H60), 7.62 (3H, m, H300, H500, H5000), 7.47
(1H, dt, H40), 7.34 (1H, dt, J = 8.0, 1.0 Hz, H4000), 7.23
(1H, dt, J = 7.3, 1.2 Hz, H50), 4.86 (1H, m, H3), 4.76
(1H, d, J = 9.9 Hz, H2), 4.31 (1H, dd, J = 19.5, 3.8 Hz,
H4a); 3.84 (1H, dd, J = 19.5, 4.4 Hz, H4b). 13C NMR
(CDCl3): d 222.2 (s, CO), 221.9 (s, CO), 219.1 (s, C1),
217.1 (s, C5), 215.0 (s, CO), 214.0 (s, CO), 213.6 (s,
CO), 213.4 (s, CO), 212.8 (s, CO), 212.3 (s, CO), 193.0
(s, C200), 186.9 (s, C20), 172.5 (s, C200), 155.0 (d, C600),
146.7 (s, C10 or C50), 146.5 (S, C10 or C50), 141.9, (d,
C30 or C3000), 141.7 (d, C30 or C3000), 139.4 (d, C400),
135.0 (d, C4000), 133.0 (d, C40), 132.7 (d, C6000), 128.1 (d,
C60), 124.8 (d, C5000), 124.3 (d, C300), 124.2 (d, C50),
123.7 (d, C500), 48.6 (d, C2), 46.9 (d, C3), 42.9 (t, C4).
Second product. [1,5-Di(3-thienyl-jC2)-3-(2-pyridyl)-
pentane-1,5-dione-jO1jO5]bis-(tetracarbonylmanganese)
(7c): Yellow crystals (35%), m.p. 130 ꢁC. Anal. Found:
C, 47.38; H, 2.26; N, 2.18. C26H13S2NO10Mn2 calc.:C,
47.50; H, 1.99; N, 2.13%. IR: m(CO) 2092 (m), 2009
(vs, br), 1950 (vs) cmꢁ1 1H NMR (CDCl3): d 8.42
.
(1H, d, J = 4.3 Hz, H600), 7.49 (1H, dd, J = 7.7, 7.5 Hz,
H400), 7.45 (2H, d, J = 5.0 Hz, H40), 7.36 (2H, d,
J = 5.0 Hz, H50), 7.04 (1H, dd, J = 7.7, 4.3 Hz, H500),
7.01 (1H, d, J = 7.5 Hz, H300), 3.99 (1H, m, H3), 3.46
(2H, dd, J = 15.3, 8.9 Hz, H2a,4a), 3.18 (2H, dd,
J = 15.3, 5.7 Hz, H2b,4b); 13C NMR (CDCl3): d 219.7
(s, CO), 213.0 (s, CO), 212.7 (s, C20), 209.2 (s, CO),
208.9 (s, CO), 206.2 (s, C1), 160.5 (s, C200), 150.0 (d,
C30), 149.5 (d, C600), 136.4 (d, C400), 132.8 (d, C50),
126.2 (d, C40), 123.3 (d, C300), 122.1 (d, C500), 43.1 (t,
C2), 41.1 (d, C3).
3.2.2.3. 1,5-Di-(2-thienyl)-3-(2-pyridyl)pentane-1,5-dione
(5b) with 2.5 mol PhCH2Mn(CO)5. First product.
[1,5-Di(2-thienyl-jC3)-3-(2-pyridyl-jN)pentan-2-yl-jC2-
1,5-dione-jO1jO5]tetracarbonylmanganesetricarbonyl-
manganese (6b): Yellow crystals (84%), decomp.
174 ꢁC. Anal. Found: C, 47.99; H, 2.94; N, 2.28.
C26H13S2NO10Mn2 calc.: C, 47.71; H, 2.08; N, 2.23%.
IR: m(CO) 2078 (m), 2015 (vs), 1990 (s, br), 1921 (vs,
3.2.3. Manganation of b-(2-pyridyl)chalcones
Using standard Schlenk equipment, (E)-1-(2,6-
dimethoxyphenyl)-3-(2-pyridyl)prop-2-en-1-one
and
br) cmꢁ1
.
1H NMR (CD3COCD3): d 9.02 (1H, d,
benzylpentacarbonylmanganese (1.05 mol) in petroleum
spirit (b.p. 60–80 ꢁC) were heated under reflux for 2.5 h.
On cooling, [1-(2,6-dimethoxyphenyl)-3-(2-pyridyl-
J = 5.3 Hz, H600), 8.24 (1H, d, J = 4.7 Hz, H3000), 8.13
(2H, m, H400, H5000), 7.99 (1H, d, J = 5.0 Hz, H50), 7.91