Alkylation of (η6-arene)Mn(CO)3 cations with organozinc reagents

Article abstract of DOI:10.1021/om010338h

Additions of allylic and benzylic zinc reagents to (η⁶-arene)Mn(CO)₃ cations proceed in an anti fashion to give the C-6 allylic- and benzylic-substituted (η⁵-cyclohexadienyl)Mn(CO)₃ neutral complexes, respectively. The reaction of less reactive primary organozinc reagents bearing an ester or a cyano group with the cations affords the α-alkylation products. Treatment of the organozinc reagent containing an acetoxy group with (η⁶-benzene)Mn(CO)₃⁺ complex in THF results in alkylation of the cation at the C-2 position of THF.

Full text of DOI:10.1021/om010338h

Organometallics 2001, 20, 4965-4968
4965
Notes
Alk yla tion of (η6-Ar en e)Mn (CO)3 Ca tion s w ith
Or ga n ozin c Rea gen ts
Ming-Chang P. Yeh,* Chong-Cheng Hwu, An-Tang Lee, and Ming-Shan Tsai
Department of Chemistry, National Taiwan Normal University,
88 Ding-J ou Road, Section 4, Taipei 117, Taiwan
Received April 24, 2001
Sch em e 1
Summary: Additions of allylic and benzylic zinc reagents
to (η6-arene)Mn(CO)3 cations proceed in an anti fashion
to give the C-6 allylic- and benzylic-substituted (η5-
cyclohexadienyl)Mn(CO)3 neutral complexes, respectively.
The reaction of less reactive primary organozinc reagents
bearing an ester or a cyano group with the cations
affords the R-alkylation products. Treatment of the
organozinc reagent containing an acetoxy group with (η6-
benzene)Mn(CO)3+ complex in THF results in alkylation
of the cation at the C-2 position of THF.
In tr od u ction
Nucleophilic additions to arenes coordinated to a
transition metal have attracted considerable interest in
organic synthesis.1 Transition metals, such as chro-
mium, manganese, iron, or ruthenium, have been used
to activate arenes toward nucleophilic substitution and
addition reactions. A wide range of nucleophiles add to
(η6-arene)Mn(CO)3+ complexes: lithium2 and Grignard
reagents,3 as well as ketone enolates, malonates, and
lithium aluminum hydride.3 Reports on the addition of
Resu lts a n d Discu ssion
Cations 1a -d were prepared by heating Mn(CO)5Br
and the corresponding arenes in the presence of AlCl3
according to a literature procedure.4 Addition of a THF
solution of allylic zinc reagent 2a or benzylic zinc
reagent 2b (2.0 mol equiv) to a stirred suspension of
cations 1a -d in THF at -10 °C under nitrogen gave
good yields (54-99%) of (η5-cyclohexadienyl)Mn(CO)3
complexes 3a -h (Scheme 1). The trans relationship
between the nucleophile and the metal moiety of
complexes 3 was assigned on the basis of chemical shifts
organozinc reagents to (η6-arene)Mn(CO)3 complexes
+
are not available. In this contribution, we report the
efficient addition of allylic and benzylic zinc reagents
to (η6-arene)Mn(CO)3 complexes in tetrahydrofuran
+
(THF), which proceeds in an anti fashion to afford the
C-6-substituted cyclohexadienyl complexes. When the
less reactive primary organozinc reagents bearing an
ester or a cyano group are used, the additions occur at
the R-carbon of the functionalized zinc reagents. The
reaction of the zinc reagent containing an acetoxy
1
at C-6 in their H NMR spectra. For example, the peak
at δ 2.57 (1H, m) assigned as an endo proton at the C-6
carbon for complex 3a is consistent with those of the
known3 exo C-6-substituted (η5-cyclohexadienyl)Mn-
(CO)3 complexes. As can be seen in Scheme 1, zinc
reagent addition to cation 1 is subject to substituent
directive effects. For example, addition of allylic or
benzylic zinc reagents to [(toluene)Mn(CO)3]+ (1b) fa-
vored the position meta to CH3 (to give 3b and 3f,
respectively), similar to that reported for Grignard3 and
lithium reagents.5 The zinc reagents added both ortho
and meta to the chloro substituent in [(C6H5Cl)Mn-
(CO)3]+ (1c) to afford 3c and 3g, respectively. The
addition of allylic zinc reagent (2a ) to [(C6H5OMe)Mn-
(CO)3]+ (1d ) occurred exclusively meta to the OMe to
functional group with (η6-benzene)Mn(CO)3 in THF
+
results in alkylation of the cation at the C-2 position of
THF to afford the C-6 exo THF-substituted (η5-cyclo-
hexadienyl)Mn(CO)3 neutral complex.
(1) Pape, A. R.; Kaliappan, K. P.; Ku¨ndig, E. P. Chem. Rev. 2000,
100, 2917.
(2) (a) Semmelhack, M. F. In Comprehensive Organometallic Chem-
istry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon
Press: Oxford, U.K., 1995; Vol. 12, p 979. (b) Pauson, P. L.; Siegal, J .
A. J . Chem. Soc., Dalton Trans. 1975, 1683. (c) Rose-Munch, F.;
Gagliardini, V.; Renard, C.; Rose, E. Coord. Chem. Rev. 1998, 178-
180, 249. (d) Rose-Munch, F.; Rose, E. Curr. Org. Chem. 1999, 3, 445.
(e) Djukic, J .-P.; Rose-Munch, F.; Rose, E.; Vaissermann, J . Eur. J .
Inorg. Chem. 2000, 1295.
(3) (a) Balssa, F.; Gagliardini, V.; Rose-Munch, F.; Rose, E. Orga-
nometallics 1996, 15, 4373. (b) Chung, Y. K.; Williard, P. G.; Sweigart,
D. A. Organometallics 1982, 1, 1053. (c) Pike, R. D.; Sweigart, D. A.
Synlett 1990, 565.
(4) Coffield, T. H.; Sandel, V.; Closson, R. D. J . Am. Chem. Soc. 1957,
79, 5826.
(5) Semmelhack, M. F.; Clark, G. J . Am. Chem. Soc. 1977, 99, 1675.
10.1021/om010338h CCC: $20.00 © 2001 American Chemical Society
Publication on Web 10/04/2001

4966 Organometallics, Vol. 20, No. 23, 2001
Notes
provide complex 3d , while the addition of benzylic zinc
reagent (2b) to cation 1d favored the position meta to
OMe (o/m ) 1:7). The addition of lithium dimethylcu-
prate to cation 1a is known to occur exclusively at the
carbonyl ligand to afford the acyl complex 4 at -78 °C
and the alkyl complex 5 at 0 °C (eq 1).6 However,
reaction of zinc-copper reagents7 does not lead to the
formation of the acyl or alkyl complexes. For example,
in our preliminary results, addition of the zinc-copper
reagent (PhCH2Cu(CN)ZnI) to cation 1a occurs at the
arene ligand to generate complex 3e as the only isolated
product in good yields (70-80%) at both -78 and 0 °C.
tion of cation 1a at the C-2 position of THF to afford
complex 10 as the only product in 68% yield. Deproto-
nation occurred at the C-2 position of THF (Scheme 3)
to produce the zinc reagent 11, and anti addition of 11
to cation 1a furnished 10. The proof of the structure of
10 was accomplished by X-ray diffraction analysis
(Figure 1, Table 1).
Attempted alkylation of cation 1a using the function-
alized zinc-copper reagents derived from zinc reagents
2c-e failed to give any substituted cyclohexadienyl
complex under the same reaction conditions.
The reaction outlined herein demonstrates that the
addition of reactive allylic and benzylic zinc reagents
to (η6-arene)Mn(CO)3 cations proceeds in an anti fashion
to give the C-6 allylic- and benzylic-substituted (η5-
cyclohexadienyl)Mn(CO)3 neutral complexes, respec-
tively. While reaction of the cations with less reactive
ester- or cyano-functionalized organozinc reagents af-
fords the R-alkylation products, that with an acetoxy-
functionalized organozinc reagent in THF produces a
THF-substituted (η5-cyclohexadienyl)Mn(CO)3 neutral
complex.
Interestingly, with the less reactive ester-functional-
ized zinc reagent IZn(CH2)2CO2Et (2c), the alkylation
occurred at the R-carbon at 25 °C in THF to give the
stabilized cyclohexadienyl complex 6 as the major
product in 64% yield. The deprotonation of the R-pro-
ton may occur to give zinc-enolate 7 (Scheme 2), since
it was found that the addition of 7 to cation 1a pro-
duced complex 6 as the sole product. Similarly, treat-
ment of the cyano-functionalized organozinc reagent
IZn(CH2)2CN (2d ) with cation 1a also provided the
R-alkylated product 8 in 45% yield (eq 2). Rose and co-
workers reported that addition of the cyano-stabilized
lithium reagent 2-lithiopropionitrile to cation 1a at -78
°C in THF produces complex 8 and the dinuclear
complex 9 in a ratio of 7:1 in good yield (eq 3).8 The
formation of complex 9 was due to deprotonation of the
acidic proton, R to the cyano group of complex 8, under
basic reaction conditions. Unlike the lithium reagent,
the mild zinc reagent 2d does not abstract the R-proton
of complex 8 under the reaction conditions, and di-
nuclear species 9 is not formed.
Exp er im en ta l Section
Gen er a l Con sid er a tion s. All reactions were run under a
nitrogen atmosphere in oven-dried glassware unless otherwise
indicated. Anhydrous solvents or reaction mixtures were
transferred via an oven-dried syringe or cannula. Tetrahydro-
furan (THF) was distilled under nitrogen from a deep blue
sodium benzophenone ketyl solution. Cations 1a -d were
prepared by heating Mn(CO)5Br and the corresponding arenes
in the presence of AlCl3 according to literature procedures.4
Organozinc reagents were prepared according to literature
procedures.7 Flash column chromatography, following the
method of Still, was carried out with E. Merck silica gel
Reaction of the acetoxy-functionalized zinc reagent
IZn(CH2)3OAc (2e) with 1a in THF resulted in alkyla-
Sch em e 2
(6) Brookhart, M.; Pinhas, A. R.; Lukacs, A. Organometallics 1982,
1, 1730.
(7) (a) Knochel, P.; Yeh, M. C. P.; Berk, S.; Talbert, J . J . Org. Chem.
1988, 53, 2392. (b) Yeh, M. C. P.; Sheu, B. A.; Fu, H. W.; Tau, S. I.;
Chuang, L. W. J . Am. Chem. Soc. 1993, 115, 5941.
(8) Rose, E.; Corre-Susanne, C. L.; Rose-Munch, F.; Renard, C.;
Gagliardini, V.; Teldji, F.; Vaissermann, J . Eur. J . Inorg. Chem. 1999,
421.

Notes
Organometallics, Vol. 20, No. 23, 2001 4967
Ta ble 1. Cr ysta llogr a p h ic Da ta for 10
empirical formula
fw
C13H13MnO4
288.18
cryst syst
space group
a, Å
b, Å
c, Å
monoclinic
P21/c
9.930(2)
9.846(3)
13.158(3)
90.0(2)
91.95(2)
90.0(2)
1285.7(6)
4
R, deg
â, deg
γ, deg
V, Å3
Z
D(calcd), g cm-3
µ, cm-1
1.489
1.03
diffractometer
radiation λ, Å
temp, °C
2θ range, deg
no. of ind reflns (I > 2σ(I))
GOF on F2
Nonius (CAD4)
0.70930
20
16.42-25.70
2007
1.7850
0.044, 0.032
a
Rf,a Rw
Rf ) ∑(Fo - Fc)/∑(Fo) and Rw ) [∑(w(Fo - Fc)2)/∑(wFo2)]1/2
.
a
F igu r e 1. ORTEP drawing of complex 10 (at the 30%
probability level). Hydrogens are omitted for clarity. Se-
lected bond distances (Å): Mn-C5 ) 2.197(4), Mn-C6 )
2.120(4), Mn-C7 ) 2.115(4), C5-C6 ) 1.396(7), C6-C7 )
1.408(8), C4-C10 ) 1.537(5). Selected bond angles (deg):
Mn-C5-C4 ) 94.85(22), Mn-C6-C5 ) 74.18(23), Mn-
C7-C6 ) 70.77(24), C5-C4-C10 ) 112.2(3), C4-C5-C6
) 119.0(4), C10-O4-C13 ) 108.5(3).
dure, to a solution of cation 1a (0.36 g, 1.0 mmol) in 10 mL of
THF at -10 °C was added rapidly, neat, via syringe, allylic
zinc bromide (2a ) (2.0 mmol). The reaction was stirred at 0 °C
for 3 h (25 °C for functionalized zinc reagents 2c-e). The
reaction mixture was quenched with 5.0 mL of saturated
ammonium chloride solution via syringe needle and stirred
at 25 °C for 15 min, after which time the reaction mixture
was diluted with hexane (30 mL). The resultant solution was
washed with water (50 mL × 3) and brine (50 mL × 3), dried
over anhydrous magnesium sulfate (5.0 g), and concentrated
to give the crude mixture.
Sch em e 3
(6-exo-(P r o p e n -3-y l)c y c lo h e x a d ie n y l)t r ic a r b o n y l-
m a n ga n ese com p lex (3a ): yield 93% (0.24 g); IR (CH2Cl2)
3076, 2970, 2926, 2484, 2014, 1940, 1638, 1421, 1277, 994
1
cm-1; H NMR (400 MHz, CDCl3) δ 5.78 (t, J ) 5.4 Hz, 1 H),
5.49 (m, 1 H), 4.96 (d, J ) 10.8 Hz, 1 H), 4.92 (d, J ) 16.8 Hz,
1 H), 4.81 (dd, J ) 6.3, 5.4 Hz, 2 H), 3.20 (dd, J ) 7.3, 6.3 Hz,
2 H), 2.57 (m, 1 H), 1.46 (t, J ) 7.3 Hz, 2 H); 13C NMR (100.4
MHz, CDCl3) δ 222.94, 133.35, 116.76, 96.09, 79.67, 57.16,
46.86, 34.70; MS (20 eV) m/e 258 (M+, 1), 216 (100), 189 (75),
174 (100); HRMS (EI) m/e calcd for C12H11MnO3 258.0089,
found 258.0099.
(6-exo-(P r op en -3-yl)-2-m eth ylcycloh exa d ien yl)tr ica r -
bon ylm a n ga n ese com p lex (3b): 88% (0.24 g); IR (CH2Cl2)
3074, 2924, 2010, 1940, 1639, 1437, 1425, 1381, 1186, 997
(Kieselgel 60, 230-400 mesh) using the indicated solvents.9
All melting points were determined in open capillaries with a
Thomas-Hoover apparatus and are uncorrected. 1H nuclear
magnetic resonance (NMR) spectra were obtained with
J EOL-EX 400 (400 MHz) and Varian G-200 (200 MHz)
spectrometers. The chemical shifts are reported in parts per
million with either tetramethylsilane (0.00 ppm) or CHCl3
(7.26 ppm) as internal standard. 13C NMR spectra were
recorded with J EOL-EX 400 (100.4 MHz) and Varian G-200
(50 MHz) spectrometers with CDCl3 (77.0 ppm) as the internal
standard. Infrared (IR) spectra were recorded with a J ASCO
IR-700 spectrometer. Mass spectra were acquired on a J EOL
J MS-D 100 spectrometer at an ionization potential of 70 eV
and are reported as mass/charge (m/e) with percent relative
abundance. Satisfactory elemental analyses could not be
obtained for all complexes, and relevant NMRs are given in
the Supporting Information. High-resolution mass spectra
were obtained with an AEI MS-9 double-focusing mass spec-
trometer and a J EOL J MS-HX 110 spectrometer at the
Department of Chemistry, Central Instrument Center, Tai-
chung, Taiwan.
1
cm-1; H NMR (400 MHz, CDCl3) δ 5.66 (d, J ) 5.4 Hz, 1 H),
5.49 (m, 1 H), 4.95 (d, J ) 10.3 Hz, 1 H), 4.81 (d, J ) 17.1 Hz,
1 H), 4.78 (t, J ) 5.4 Hz, 1 H), 3.16 (t, J ) 6.4 Hz, 1 H), 3.13
(d, J ) 5.9 Hz, 1 H), 2.59 (m, 1 H), 1.85 (s, 3 H), 1.49 (m, 2 H);
13C NMR (100.4 MHz, CDCl3) δ 223.05, 133.42, 111.20,
94.63, 80.48, 58.38, 57.34, 46.97, 36.00, 22.50; MS (20 eV) m/e
272 (M+, 1), 229 (100), 187 (70); HRMS (EI) m/e calcd for
C13H13MnO3 272.0245, found 272.0239.
(6-exo-(P r op en -3-yl)-2-ch lor ocycloh exa d ien yl)t r ica r -
b on ylm a n ga n ese (meta isomer of 3c): 66% (0.19 g); IR
(CH2Cl2) 3046, 2928, 2022, 1944, 1639, 1431, 1429, 1054 cm-1
;
1H NMR (400 MHz, CDCl3) δ 6.04 (d, J ) 5.9 Hz, 1 H), 5.46
(m, 1 H), 4.99 (d, J ) 9.8 Hz, 1 H), 4.90 (d, J ) 17.1 Hz, 1 H),
4.78 (dd, J ) 5.9, 6.3 Hz, 1 H), 3.51 (d, J ) 5.9 Hz, 1 H), 3.14
(dd, J ) 6.3, 6.8 Hz, 1 H), 2.73 (m, 1 H), 1.49 (m, 2 H); 13C
NMR (100.4 MHz, CDCl3) δ 223.71, 132.60, 117.51, 92.91,
79.73, 58.26, 58.15, 53.41, 46.53, 38.21; MS (20 eV) m/e 292
(M+, 1), 253 (33), 251 (100), 225 (5), 223 (15), 209 (28), 207
(80), 197 (13), 195 (31), 169 (13), 167 (39); HRMS (EI) m/e calcd
for C12H10ClMnO3 291.9699, found 291.9690.
Gen er a l P r oced u r e for Ad d ition of Or ga n ozin c Re-
a gen ts to (η6-Ar en e)Mn (CO)3 Ca tion s. In a typical proce-
(6-exo-(P r op en -3-yl)-2-m eth oxycycloh exa d ien yl)tr ica r -
bon ylm a n ga n ese com p lex (3d ): 54% (0.16 g); IR (CH2Cl2)
3058, 2928, 2002, 1920, 1603, 1493, 1465, 1217 cm-1; 1H NMR
(9) Still, W. C.; Kahn, M.; Mitra, A. J . Org. Chem. 1978, 43, 2923.

4968 Organometallics, Vol. 20, No. 23, 2001
Notes
(400 MHz, CDCl3) δ 5.71 (d, J ) 5.9 Hz, 1 H), 5.48 (m, 1 H),
4.96 (d, J ) 9.3 Hz, 1 H), 4.87 (d, J ) 17.1 Hz, 1 H), 4.83 (t, J
) 5.9 Hz, 1 H), 3.46 (s, 3 H), 3.12 (m, 2 H), 2.70 (m, 1 H), 1.45
(m, 2 H); 13C NMR (100.4 MHz, CDCl3) δ 222.65, 142.58,
133.42, 116.85, 92.45, 68.02, 57.52, 54.14, 47.36, 42.46, 37.41;
MS (20 eV) m/e 247 (M+ - CH2dCHCH2, 100), 204 (95), 164
(95); HRMS (EI) m/e calcd for C13H13MnO4 288.0194, found
288.0199.
(6-exo-B e n zylc y c lo h e x a d ie n y l)t r ic a r b o n ylm a n g a -
n ese com p lex (3e): 96% (0.30 g); IR (CH2Cl2) 3078, 3030,
2958, 2862, 2014, 1939, 1601, 1493, 1077 cm-1; 1H NMR (400
MHz, CDCl3) δ 7.00-7.26 (m, 5 H), 5.83 (t, J ) 5.4 Hz, 1 H),
4.86 (dd, J ) 5.9, 5.4 Hz, 2 H), 3.16 (t, J ) 5.9 Hz, 2 H), 2.73
(m, 1 H), 1.96 (d, J ) 7.3 Hz, 2 H); 13C NMR (100.4 MHz,
CDCl3) δ 222.84, 137.13, 129.05, 128.24, 126.05, 96.07, 79.84,
56.99, 48.58, 36.77; MS (20 eV) m/e 308 (M+, 1), 216 (65), 217
(100), 160 (45); HRMS (EI) m/e calcd for C16H13MnO3 308.0244,
found 308.0238.
(dd, J ) 5.9, 7.3 Hz, 1 H), 2.99 (d, J ) 6.3 Hz, 1 H), 2.83 (m,
1 H), 2.06 (m, 1 H), 1.92 (m, 1 H); 13C NMR (100.4 MHz, CDCl3)
δ 222.44, 142.58, 137.14, 129.10, 128.26, 126.09, 92.55, 68.26,
57.32, 54.09, 49.09, 42.29, 39.55; MS (20 eV) m/e 254 (M+
-
3CO, 100), 246 (100), 190 (80), 162 (80); HRMS (EI) m/e calcd
for C14H15Mn 254.0516, found 254.0508.
(6-exo-(Eth yl p r op ion a te-2-yl)cycloh exa d ien yl)tr ica r -
bon ylm a n ga n ese com p lex (6): 64% (0.20 g); IR (CH2Cl2)
3064, 2932, 2856, 2014, 1937, 1723, 1456, 1373, 1049 cm-1
;
1H NMR (400 MHz, CDCl3) δ 5.80 (t, J ) 5.4 Hz, 1 H), 4.89
(dd, J ) 6.4, 5.4 Hz, 2 H), 4.12 (q, J ) 7.3 Hz, 2 H), 3.22 (dd,
J ) 6.4, 7.3 Hz, 2 H), 2.73 (m, 1 H), 1.64 (m, 1 H), 1.27 (t, J )
7.3 Hz, 3 H), 0.90 (d, J ) 7.3 Hz, 3 H); 13C NMR (100.4 MHz,
CDCl3) δ 222.52, 173.91, 96.59, 96.29, 80.24, 60.29, 55.29,
53.57, 50.32, 37.57, 14.27, 12.28; MS (20 eV) m/e 318 (M+, 1),
234 (75), 217 (100); HRMS (EI) m/e calcd for C14H15MnO5
318.0299, found 318.0290.
(6-exo-(Tet r a h yd r ofu r a n yl-2-yl)cycloh exa d ien yl)t r i-
ca r b on ylm a n ga n ese com p lex (10): 64% (0.20 g); mp
85-87 °C; IR (CH2Cl2) 3065, 2932, 2856, 2012, 1937, 1732,
(6-exo-B e n zy l-2-m e t h y lc y c lo h e x a d ie n y l)t r ic a r b o -
n ylm a n ga n ese com p lex (3f): 92% (0.30 g); IR (CH2Cl2) 3074,
2936, 2020, 1937, 1606, 1459, 1424, 1276, 1153 cm-1; 1H NMR
(400 MHz, CDCl3) δ 6.93-7.29 (m, 5 H), 5.66 (d, J ) 5.4 Hz,
1 H), 4.81 (dd, J ) 5.4, 6.6 Hz, 1 H), 3.11 (m, 2 H), 2.75 (m, 1
H), 1.95 (dd, J ) 12.1, 7.3 Hz, 2 H), 1.85 (s, 3 H); 13C NMR
(100.4 MHz, CDCl3) δ 222.90, 137.25, 129.07, 128.16, 125.98,
111.19, 94.67, 80.57, 58.30, 57.19, 48.70, 38.14, 22.49; MS (20
eV) m/e 322 (M+, 1), 238 (100), 231 (100), 204 (50); HRMS (EI)
m/e calcd for C17H15MnO3 322.0402, found 322.0410.
(6-exo-B e n zy l-2-c h lo r o c y c lo h e x a d ie n y l)t r ic a r b o -
n ylm a n ga n ese (meta isomer of 3g): 64% (0.22 g); IR (CH2-
1606, 1456, 1367, 1273 cm-1 1H NMR (400 MHz, CDCl3) δ
;
5.79 (t, J ) 5.4 Hz, 1 H), 4.78 (t, J ) 6.4 Hz, 2 H), 3.57-3.74
(m, 2 H), 3.30 (dd, J ) 5.9, 7.3 Hz, 1 H), 2.97 (dd, J ) 5.9, 7.3
Hz, 1 H), 2.83 (m, 1 H), 2.52 (m, 1 H), 1.73 (m, 3 H), 1.28 (m,
1 H); 13C NMR (100.4 MHz, CDCl3) δ 222.77, 97.03, 96.79,
85.12, 79.76, 67.73, 55.79, 52.02, 39.88, 27.17, 25.17; MS (20
eV) m/e 288 (M+, 1), 217 (100), 204 (10), 199 (30), 181 (30),
161 (40); HRMS (EI) m/e calcd for C13H13MnO4 288.0194, found
288.0191. Crystals suitable for X-ray diffraction were grown
from CH2Cl2.
1
Cl2) 3034, 2928, 2022, 1938, 1604, 1427, 1251, 1055 cm-1; H
NMR (400 MHz, CDCl3) δ 6.97-7.32 (m, 5 H), 6.05 (d, J ) 5.2
Hz, 1 H), 4.81(dd, J ) 6.7, 6.0 Hz, 1 H), 3.42 (d, J ) 6.0 Hz, 1
H), 3.08 (dd, J ) 6.7, 6.1 Hz, 1 H), 2.87 (m, 1 H), 2.02 (d, J )
7.1 Hz, 2 H); 13C NMR (100.4 MHz, CDCl3) δ 221.53, 136.49,
129.06, 128.36, 126.30, 115.49, 92.94, 79.81, 58.00, 48.27,
40.26; MS (20 eV) m/e 342 (M+, 1), 260 (6), 258 (17), 253 (14),
251 (47), 197 (8), 195 (20), 92 (11), 90 (36), 55 (100); HRMS
(EI) m/e calcd for C16H12ClMnO3 341.9855, found 341.9833.
(6-exo-Be n zyl-2-m e t h oxycycloh e xa d ie n yl)t r ica r b o-
n ylm a n ga n ese (meta isomer of 3h ): 59% (0.20 g); IR (CH2-
Ack n ow led gm en t. This work was supported by a
grant from the National Science Council (NSC 89-2113-
M-003-004).
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates, bond lengths, bond angles, and anisotropic ther-
mal parameters for complex 10, analytical data for complexes
o-3c, o-3g, and o-3h , and additional NMR spectra for 3a , o-3c,
3e, o-3g, m-3g, m-3h , 6, and 10. This material is available
free of charge via the Internet at http://pubs.acs.org.
1
Cl2) 3058, 2928, 2002, 1920, 1603, 1493, 1465, 1217 cm-1; H
NMR (400 MHz, CDCl3) δ 6.97-7.28 (m, 5 H), 5.73 (d, J ) 5.9
Hz, 1 H), 4.87 (dd, J ) 5.9, 6.4 Hz, 1 H), 3.40 (s, 3 H), 3.08
OM010338H