Chromium Cyclodienyl Complexes
Organometallics, Vol. 15, No. 15, 1996 3339
Ta ble 1. 1H a n d 13C{1H} NMR Sp ectr a l Da ta a
δ(1H)
complex
δ(13C{1H})
2a
2b
1.18 (3H, s, Me), 1.55 (3H, s, Me), 1.62 (1H, m, H9), 1.66
(1H, m, H8), 1.72 (1H, m, H8′), 1.90 (1H, m, H9′), 2.06 (3H, s,
Me), 2.07 (1H, dd, H7), 2.36 (1H, dd, H10), 3.11 (1H, dd, H4),
3.45 (1H, dd, H6), 3.87 (1H, s, H12), 3.94 (1H, s, H12′),
4.34 (1H, dd, H5)b
13.0, 16.1, 16.7 (Me), 26.0, 26.4 (C8,9), 38.9 (C10),
46.8 (C7), 47.0 (C1), 52.4 (C4), 62.9 (C5), 63.6 (C11),
67.3 (C6), 71.9 (C12), 82.0 (C2), 105.5 (C3),
233.4, 234.8, 235.6 (CO)
0.91 (3H, t, Me), 0.93 (3H, t, Me), 1.12 (3H, t, Me), 1.35 (2H, m,
CH2Me), 1.55 (2H, m, CH2Me), 1.62 (2H, m, H8,9), 1.90 (2H, m,
9.5, 13.7, 16.6, 17.2 (Me), 18.5, 22.7, 23.3 (CH2Me),
26.3 (C9), 31.5 (C8), 33.6 (C10), 47.1 (C7), 50.2 (C4),
52.7 (C1), 65.7 (C11), 66.3 (C5), 69.1 (C6), 92.5 (C12),
93.7 (C2), 107.5 (C3), 232.0, 233.7, 233.8 (CO)
H
7,8′), 2.08 (3H, d, Me), 2.17 (2H, m, H9′, CH2Me), 2.78 (1H, m,
CH2Me), 2.99 (1H, m, H10), 3.29 (1H, t, H4), 3.66 (1H, t, H6),
4.08 (1H, t, H5), 4.68 (1H, q, H12
)
3a
3b
1.28 (3H, s, Me), 1.61 (3H, s, Me), 1.65 (3H, s, Me), 1.87-2.00
(5H, m, H8,8′,9,9′,10), 2.78 (2H, m, H7,4), 4.67 (2H, s, H12′), 5.72
(1H, dd, H6), 5.74 (1H, dd, H5)
9.1 (Me), 13.1 (Me), 18.2 (Me), 25.1 (C8), 27.8 (C9),
45.1 (C7), 48.2 (C10), 51.4 (C1), 56.2 (C4),
105.3 (C12), 130.4 (C6), 132.2 (C5), 135.0 (C2),
137.4 (C3), 157 (C11)
9.7 (Me), 13.0 (Me), 13.1 (Me), 15.6 (Me), 17.9,
19.6, 20.7 (CH2), 26.9 (C8), 30.3 (C9), 35.5 (C7),
43.5 (C10), 53.2 (C4), 55.8 (C1), 113.0 (C12),
129.4 (C6), 133.2 (C5), 141.8 (C2), 143.0 (C3),
146.5 (C11)
0.86 (3H, t, Me), 0.98 (3H, t, Me), 0.99 (3H, t, Me), 1.49 (1H, m,
H8), 1.58 (3H, d, Me), 1.68-1.78 (2H, m, CH2), 1.84 (1H, m, H8′),
1.86 (1H, m, H9), 1.94 (1H, m, H9′), 2.0-2.2 (5H, m, CH2, H10),
2.94 (1H, t, H4), 3.24 (1H, m, H7), 5.20 (2H, q, H12), 5.68 (1H,
dd, H6), 5.72(1H, dd, H5)
4a
4b
5a
1.64 (1H, m, H8), 1.78 (3H, s, Me), 1.79 (1H, m, H8′), 1.83 (1H,
m, H9), 1.97 (1H, m, H9′), 2.42 (1H, t, H10), 3.08 (1H, dd,
H7), 3.52 (1H, t, H4), 4.68 (1H, s, H12), 5.07 (1H, s, H12′),
5.71 (1H, dd, H6), 5.83 (1H, t, H5), 7.20-7.44 (10H, m, Ph)
1.61 (1H, m, H8), 1.71 (3H, s, Me), 1.76 (1H, m, H8′), 1.82 (1H,
m, H9), 1.92 (1H, m, H9′), 2.64 (1H, t, H10), 3.06 (1H, dd, H7),
3.11 (1H, t, H4), 4.00 (1H, s, H12), 5.00 (1H, s, H12′), 5.84 (1H,
dd, H6), 5.88 (1H, t, H5), 7.02-7.67 (10H, m, Ph)
1.11 (s, Me), 1.53 (s, Me), 1.77 (s, Me), 1.82 (t, H9), 1.91 (m, H9′),
2.06 (s, Me), 2.10 (m, H7,10), 2.20, (m, H15), 2.40 (m, H15′),
2.65-3.00 (m, H14,14′,16,16′,8), 3.04 (t, H4), 3.78 (s, H12), 3.81
(s, H12′), 3.84 (d, H6), 4.15 (t, H5)
12.7 (Me), 18.0 (C8), 26.8 (C9), 45.1 (C7), 53.0 (C10),
56.0 (C4), 64.3 (C1), 110.7 (C12), 126.0, 127.0,
128.2, 128.5, 128.8, 129.0 (Ph), 131.5, 132.2 (C5,6),
138.0 (C2), 140.5, 142.0 (Ph), 147.0 (C3), 151.9 (C11)
13.5, 13.7, 16.6, 16.7, 20.5, 20.6 (Me), 25.5-29.2
(C8, C9, C14-16, Me-13), 39.2, 41.5 (C10), 47,
47.3, 48.2, 48.7, 49.8 (C4, C7, C13), 52.3, 53.5, 54.1,
(C13, C1), 61.0, 62.2 (C5), 63.7, 64.4 (C11), 66.3,
68.0 (C6), 71.5, 73.0 (C12), 83.5 (C2), 95, 98.2 (C3),
232.2, 234.4, 235.1, 236.0 (CO)c
5b
5c
1.14 (s, Me), 1.48 (s, Me), 1.74 (s, Me), 1.81 (t, H8), 1.93 (m, H8′),
2.05 (s, Me), 2.10 (m, H7,10), 2.20, (m, H15), 2.40 (m, H15′),
2.65-3.00 (m, H14,14′,16,16′,4,9), 3.52 (d, H6), 3.74 (s, H12),
3.76 (s, H12′), 4.09 (t, H5)
1.11 (3H, s, Me), 1.18 (1H, m, H8), 1.44 (3H, s, Me), 1.71 (1H,
m, H8′), 1.94 (1H, m, H7), 2.03 (3H, s, Me), 2.07 (1H,
dd, H10), 2.58 (1H, dd, H9), 3.29 (1H, t, H4), 3.45 (1H, t,
H6), 3.63 (1H, s, H12), 3.72 (1H, s, H12′), 3.83 (1H, d, CHPh2),
4.21 (1H, t, H5), 7.18-7.35 (10H, m, Ph)
1.30, (s, Me), 1.31 (s, Me), 1.40 (m, H9′), 1.44 (s, Me), 1.57 (s, Me),
1.58 (s, Me), 1.60 (s, Me), 1.72-2.00 (m, H8,9,10,8′), 2.55 (dd, H7),
2.68-2.78 (m, H4,7), 3.17 (m, H4), 3.75 (d, CHPh2), 4.00 (d,
CHPh2), 4.50 (s, H12′), 4.62 (s, H12′), 4.74 (s, H12), 4.76 (s,
13.2, 17.0, 24.3 (Me), 26.5 (C8), 41.7, 42.0 (C9, C10),
47.2 (C1), 47.2 (C7), 52.5 (C4), 55.2 (CHPh2),
61.0 (C5), 64.0 (C11), 68.5 (C6), 72.2 (C12), 82.2 (C2),
98.5 (C3), 126.2, 126.8, 127.5, 128.1, 128.7, 129.1,
143.1, 143.4 (Ph), 232.2, 234.0, 234.5 (CO)
6a ,b
H
12), 5.50 (t, H6), 5.78 (t, H5), 5.88-5.91 (m, H5,6),
7.1-7.4 (m, Ph)d
8a
8b
0.93 (3H, s, 10-Me), 1.18 (3H, s, 1-Me), 1.81 (1H, m, H13),
1.88 (3H, s), 1.89, (3H, s), 1.93 (3H, s, 2-Me, 3-Me, 11-Me),
2.00 (2H, m, H8, H13′), 2.37 (1H, m, brd, H7), 2.51 (1H, m,
brd, H9), 2.70 (2H, m, H12, H14), 2.96 (2H, m, H12′, H14′),
3.72 (1H, t, H5), 4.20 (1H, t, H4), 4.94 (1H, t, H6)
0.71 (3H, t), 0.95 (3H, t), 1.04 (3H, t), 1.16 (3H, t, 1-Me, 2-Me,
3-Me, 10-Me), 1.47, 1.55 (4H, m, CH2), 1.77 (1H, m, H13),
1.86 (3H, s, 11-Me), 1.94 (2H, m, brd, H8, H13′), 2.32,
2.40 (4H, m, CH2), 2.55 (1H, s, brd, H7), 2.67 (2H, m,
-1.7 (C10), 13.7, 14.1 (1-Me, 10-Me), 20.4, 23.2,
25.3 (2-Me, 3-Me, 11-Me), 26.7, 26.8, 28.6 (C12,
C13, C14), 46.2 (C9), 46.7 (C8), 49.9 (C7), 54.8
(C4), 60.7 (C1), 68.8 (C5), 79.3 (C6), 86.6 (C3),
99.9 (C2), 236.2, 239.6 (CO)
7.1 (C10), 10.3, 12.9, 14.7, 15.9 (Me), 21.2, 22.3,
22.5 (CH2), 25.3 (Me), 26.6, 26.8 (C12, C14), 28.3,
28.5 (CH2, C13), 42.0 (C9), 43.4 (C8), 47.6 (C7),
49.8 (C11), 51.0 (C4), 65.8 (C1), 71.5 (C5),
81.1 (C6), 96.2 (C3), 105.4 (C2), 235.8, 240.4 (CO)
H
12, H14), 2.75 (1H, s, brd, H9), 2.92 (2H, m, H12′, H14′),
3.63 (1H, t, H5), 4.27 (1H, t, H4), 4.88 (1H, t, H6)
a
b
d
See eqs 2, 4, and 6 for labeling; in CDCl3 unless stated otherwise. In CD3NO2. c Spectrum of the mixture of 5a ,b. Spectrum of the
mixture of 6a ,b.
2a in yield similar to that obtained from 1a 24 along with
trimethyltin hydride as the byproduct.25
Decom p lexa t ion of t h e Or ga n ic Liga n d fr om
2a ,b. When acetonitrile solutions of 2a ,b are heated
to reflux for 15-30 min, the tricyclic organic ligands are
cleanly decomplexed from the metal with concomitant
formation of [Cr(CO)3(CH3CN)3] (eq 2). Evaporation of
the solvent in vacuo and extraction of the residue with
hexane gave crude 3a ,b as colorless oils. Pure samples
were isolated in good yield following chromatography
on silica gel. The new organic compound 3a is 1,2,3-
trimethyl-11-methylenetricyclo[5.3.1.04,10]undeca-2,5-di-
ene, whereas 3b is 1,2,3-triethyl-11-(E-ethylidene)-
tricyclo[5.3.1.04,10]undeca-2,5-diene.
The isolation of the bis(alkyne)-dienyl cycloadducts
as Cr(CO)3 complexes rather than the free organic
species is dependent upon the alkyne used as well as
the nature of the substituents on the C7 ring. In some
(24) Wang, C. Ph.D. Thesis, Rutgers University, 1993.
(25) GCMS analysis of the reaction mixture showed Me3SnH was
present as well as species of molecular mass consistent with products
derived from the insertion of excess 2-butyne into the SnH bond, e.g.
Me3SnC(Me)dCHMe.