Reaction of silylpentacarbonylmanganese with hydride-transfer reagents: Reduction of carbonyl ligands accompanied with Si-C and C-C coupling

Article abstract of DOI:10.1016/S0022-328X(02)01188-9

Treatment of Mn(CO)₅SiTol^p₂H (2) with an excess of LiAlH₄, NaBH₄, or NaBH₃(CN) in THF at room temperature gave hydrosilane H-SiTol^p₂H in high yield together with Mn₂(CO)₁₀. No reduction of CO ligands was observed. On the other hand, treatment of 2 with an excess of Red-Al ( = with LiAlH₄ in diethyl ether instead of hydrolysis gave alkylhydrosilanes (CH₃)SiTol^p₂H and (C₂H₅)SiTol^p₂H. The methyl and ethyl groups on silicon originate from the CO ligands in 2. These products clearly demonstrate that not only the Si-C coupling, but also C-C coupling occurs efficiently in this reaction.

Full text of DOI:10.1016/S0022-328X(02)01188-9

Journal of Organometallic Chemistry 650 (2002) 91–95
www.elsevier.com/locate/jorganchem
Reaction of silylpentacarbonylmanganese with hydride-transfer
reagents: reduction of carbonyl ligands accompanied with SiꢀC
and CꢀC coupling
Rie Shiozawa, Hiromi Tobita *, Hiroshi Ogino *
Department of Chemistry, Graduate School of Science, Tohoku Uni6ersity, Sendai 980-8578, Japan
Received 19 September 2001; received in revised form 6 December 2001; accepted 28 December 2001
Abstract
Treatment of Mn(CO)5SiTolp2H (2) with an excess of LiAlH4, NaBH4, or NaBH3(CN) in THF at room temperature gave
hydrosilane HꢀSiTol2pH in high yield together with Mn2(CO)10. No reduction of CO ligands was observed. On the other hand,
treatment of 2 with an excess of Red-Al (=Na[(CH3OCH2CH2O)2AlH2]) in toluene and subsequent addition of aqueous acidic
solution afforded alkylsilanols (CH3)SiTolp2(OH) and (C2H5)SiTolp2(OH). Treatment of the reaction mixture of 2 and Red-Al with
LiAlH4 in diethyl ether instead of hydrolysis gave alkylhydrosilanes (CH3)SiTolp2H and (C2H5)SiTolp2H. The methyl and ethyl
groups on silicon originate from the CO ligands in 2. These products clearly demonstrate that not only the SiꢀC coupling, but
also CꢀC coupling occurs efficiently in this reaction. © 2002 Elsevier Science B.V. All rights reserved.
Keywords: Silyl complexes; Carbonyl complexes; Manganese complexes; SiꢀC coupling; CꢀC coupling; Reduction
1. Introduction
and coupled with the Si atom to give the methylsilane.
We report herein the reaction of a silylpentacarbonyl-
manganese Mn(CO)5SiTolp2H (2) with several hydride-
transfer reagents. We found that the reaction of 2 with
Red-Al (=Na[(CH3OCH2CH2O)2AlH2]) in toluene in-
duces not only the SiꢀC, but also the CꢀC coupling
reactions (Scheme 1).
Reactions of hydride-transfer reagents with transition
metal carbonyl complexes have attracted much atten-
tion in relation to the Fischer–Tropsch reaction. Al-
though numerous reactions of this type have been
reported [1–5], there are few examples in which a
carbonyl ligand is not only reduced, but also coupled
with another ligand [6,7]. Recently we reported a novel
reaction of silyl(carbonyl)iron complexes CpFe(CO)2-
SiR3 (1) (Cp=h5-C5H5, R=aryl, alkyl, H) with
LiAlH4 that resulted in SiꢀC coupling to give methylsi-
lanes (CH3)SiR3 as a major product in moderate to
high yield [8]. The labeling experiments using LiAlD4
and CpFe(13CO)2SiTolp2R% (R%=H, Me, Tolp=p-
CH3C6H4) proved that a carbonyl ligand was reduced
2. Results and discussion
2.1. Reactions of 2 with se6eral hydride-transfer
reagents in THF
Treatment of Mn(CO)5SiTolp2H (2) with an excess of
LiAlH4, NaBH4, or NaBH3(CN) in THF at room
temperature afforded dihydrosilane HSiTolp2H (3) [9] in
high yield (54–91%) together with Mn2(CO)10 (Scheme
2) [10]. No reduction of CO ligands was observed. This
is perhaps because the basic solvent THF induces the
heterolysis of the MnꢀSi bond in 2 prior to the reaction
with the hydride-transfer reagents to give [HTolp2Si·
THF]+[Mn(CO)5]− in which the THF-coordinated silyl
cation is expected to be highly reactive toward hydride
nucleophiles. In fact, when pale yellow 2 was dissolved
Scheme 1.
* Corresponding authors. Fax: +81-22-217-6543 (H.T.).
E-mail address: tobita@inorg.chem.tohoku.ac.jp (H. Tobita).
0022-328X/02/$ - see front matter © 2002 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(02)01188-9

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R. Shiozawa et al. / Journal of Organometallic Chemistry 650 (2002) 91–95
gave deuteriosilanols (CH3)SiTolp2(OD) (4-d) (ca. 80
atom% D) and (C2H5)SiTolp2(OD) (5-d) (ca. 80 atom%
D) in 40 and 25% yields, respectively. Although isola-
tion of the primary products was unsuccessful, we infer
that the primary products were neutral silyl manganese
complexes containing SiTolp2(CH3) and SiTol2p(C2H5)
ligands in which the methyl and ethyl groups on silicon
originate from the CO ligands in 2. These complexes
were then hydrolyzed through heterolysis of the MnꢀSi
bonds [12] to give 4 and 5. In fact, acid hydrolysis of
the model complex Mn(CO)5SiTolp2(CH3) proceeded
Scheme 2.
in THF, the solution changed to red instantaneously.
The IR spectrum of the solution showed two weak but
distinct bands assigned to wCO at extremely low
wavenumber region (1900 and 1865 cm−1) in addition
to strong wCO bands of 2 (2092, 1998 and 1983 cm−1).
The intensity ratio of the former bands and those of 2
did not change in the course of time. The former values
are almost identical with those of Na+[Mn(CO)5]−
(1898 and 1863 cm−1) [11]. These facts suggest that
when 2 is dissolved in THF, it quickly reaches to
equilibrium with [HTolp2Si·THF]+[Mn(CO)5]− where 2
is the major component.
smoothly
at
room
temperature
to
give
(CH3)SiTolp2(OH) (4) in 90% yield. This primary forma-
tion of neutral silyl manganese complexes was further
supported by the following experiment. Treatment of
the reaction mixture of 2 and Red-Al with excess
LiAlH4 in diethyl ether instead of hydrolysis gave
methylsilane (CH3)SiTolp2H (6) and ethylsilane
(CH3CH2)SiTolp2H (7) in 41 and 28% yields, respectively
(Scheme 4). Use of excess LiAlD4 instead of LiAlH4
gave deuteriosilanes (CH3)SiTolp2D (6-d) (ca. 55 atom%
D) and (CH3CH2)SiTolp2D (7-d) (ca. 53 atom% D) in 41
and 28% yields, respectively. The yields of methylsilane
6 and ethylsilane 7 are almost identical with those of
the corresponding hydrolysis products methylsilanol 4
and ethylsilanol 5. Thus, these yields apparently reflect
the proportion of the introduction of methyl and ethyl
groups in the silyl ligands in primary products.
2.2. Reactions of 2 with Red-Al in toluene
By contrast, treatment of 2 with excess Red-Al in
toluene at room temperature for 1 day and subsequent
addition of aqueous acidic solution gave silanols
(CH3)SiTolp2(OH) (4) and (C2H5)SiTolp2(OH) (5) in 43
and 33% yields, respectively (Scheme 3). Neither forma-
tion of dihydrosilane 3 nor that of methylsilane 6 and
ethylsilane 7 (vide infra) was observed by GC/MS. The
formation of 4 and 5 clearly demonstrates that not only
the SiꢀC coupling, but also the CꢀC coupling occurred
efficiently in this reaction.
Before hydrolysis, silanols 4 and 5 were not detected
in the reaction mixture by GC/MS. Thus the OH group
of 4 and 5 originated from water. Actually, treatment
of the reaction mixture of 2 and Red-Al with DCl/D2O
In comparison with the iron analogue 1 that did not
react with Red-Al but reacted with LiAlH4 to give
methylsilane (CH3)SiTolp2H (6) [8b], manganese com-
plex 2 was reduced under milder conditions and more
than one CO ligand were participated in the reaction.
These differences are attributable to the following fac-
tors: (1) 2 has more CO ligands than iron analogue 1;
and (2) the CO ligands in 2 are more reactive toward
nucleophiles than those in 1 because the back-donation
to each CO ligand in 2 is weaker than 1.
Scheme 3.
Scheme 4.

R. Shiozawa et al. / Journal of Organometallic Chemistry 650 (2002) 91–95
93
3. Experimental
removal of solvent in vacuo, the residue was extracted
with hexane and the extract was filtered through a
Celite pad under nitrogen. The solvent was removed in
vacuo and the residue was subjected to silica gel flash
chromatography (12 mm o.d.×30 mm) with 1/5 tolu-
ene–hexane as eluent to give Tolp2SiH2 (504 mg, 1.77
mmol) as a colorless liquid in 91% yield together with
Mn2(CO)10 (87.1 mg, 223 mmol) as a bright yellow
powder in 23% yield.
All manipulations were carried out under a dry nitro-
gen atmosphere. Reagent-grade hexane, Et2O, and
THF were distilled from sodium–benzophenone ketyl
immediately before use. Benzene-d6 and acetone-d6 were
dried with molecular sieves 4A. Na[Mn(CO)5] [13] and
Tolp2SiRCl (R=H, Me) [8b] were prepared according
to
the
literature
procedures.
Na[(CH3OCH2-
CH2O)2AlH2] (Red-Al) was purchased from Aldrich.
Other chemicals were purchased from Wako Pure
Chemical Industries, Ltd. and used as received. All
NMR spectra were recorded in a Brucker ARX-300
3.3. Reaction of Mn(CO)5SiTolp2H (2) with NaBH4 in
THF
1
spectrometer. H-, 13C- and 29Si-NMR data were refer-
To a suspension of NaBH4 (308 mg, 8.11 mmol) in
THF (15 ml) was added a THF solution (5 ml) of 2
(804 mg, 1.98 mmol) at −43 °C. The mixture was
allowed to warm to r.t. and was stirred for 1 day. The
reaction mixture was worked up in a manner similar to
that for the reaction with LiAlH4 to give Tolp2SiH2 (475
mg, 1.67 mmol) in 84% yield together with Mn2(CO)10
(122 mg, 312 mmol) in 32% yield.
enced to Me4Si. 29Si-NMR spectra were obtained by
the DEPT pulse sequence. IR spectra were recorded in
a Horiba FT-200 spectrometer. Mass spectra were
recorded on Shimadzu GCMS-QP5050A and JEOL
HX-110 mass spectrometers. The D contents in the
deuterated products were determined by mass
spectroscopy.
3.1. Synthesis of Mn(CO)5SiTolp2H (2)
3.4. Reaction of Mn(CO)5SiTolp2H (2) with
NaBH3(CN) in THF
A THF solution of Na[Mn(CO)5] (0.99 M, 20 ml,
19.9 mmol) prepared from Mn2(CO)10 and Na/Hg was
slowly cannulated into a two-necked flask connected to
a vacuum line and the solvent was removed in vacuo.
Then Ar gas was introduced into the reaction vessel
and the deoxygenated solution of Tolp2SiHCl (4.65 g,
18.8 mmol) in hexane (20 ml) was added to it by a
syringe at −43 °C. The reaction mixture was stirred at
room temperature (r.t.) for 12 h and filtered through a
Celite pad under nitrogen. The filtrate was evaporated
under reduced pressure and the residue was recrystal-
lized from pentane to give 2 (3.33 g, 8.20 mmol, 44%
yield) as pale yellow crystals. 1H-NMR (300 MHz,
C6D6) l 7.71–7.73, 7.01–7.04 (AB q, J=8 Hz, 4H×2;
p-CH3C6H4), 5.68 (s, 1H; SiꢀH), 2.05 (s, 6H; p-
CH3C6H4). 13C-NMR (75.5 MHz, C6D6) l 213.2 (CO),
139.1, 135.1, 134.9, 129.3 (p-CH3C6H4), 21.3 (p-
CH3C6H4). 29Si-NMR (59.6 MHz, C6D6) l 7.84. IR
(cm−1, KBr pellet): w(SiꢀH) 2108, w(CO) 2092, 1998,
1983. Mass (EI, 70 eV); m/z: 406 (M+, 2), 378 (M+−
CO, 9), 322 (M+−3CO, 5), 211 (M+−Mn(CO)5,
100). Anal. Found: C, 56.23; H, 3.59. Calc. for
C19H15MnO5Si: C, 56.16; H, 3.72%.
To a suspension of NaBH3(CN) (673 mg, 8.10 mmol)
in THF (15 ml) was added a THF solution (5 ml) of 2
(798 mg, 1.97 mmol) at −43 °C. The mixture was
allowed to warm to r.t. and was stirred for 2 days. The
reaction mixture was worked up in a manner similar to
that for the reaction with LiAlH4 to give Tolp2SiH2 (302
mg, 514 mmol) in 54% yield together with Mn2(CO)10
(200 mg, 514 mmol) in 52% yield.
3.5. Reaction of Mn(CO)5SiTolp2H (2) with Red-Al and
subsequent hydrolysis
A toluene solution of Red-Al (3.4 M, 30 ml, 102
mmol) was added dropwise to a solution of 2 (4.09 g,
10.1 mmol) in toluene (50 ml) over a period of 30 min
and then stirred for 1 day at r.t. The reaction mixture
was cooled in an ice bath, and EtOAc (10 ml) was
added dropwise to destroy an excess of Red-Al. Then
aqueous HCl solution (1 M, 200 ml) was added and the
organic layer was washed with saturated NaHCO3 solu-
tion, water, and saturated NaCl solution, and then
dried over anhydrous MgSO4. Removal of solvent in
vacuo gave a mixture of (CH3)SiTolp2(OH) (4) (1.05 g,
4.34 mmol), and (C2H5)SiTolp2(OH) (5) (853 mg, 3.33
mmol) in 43 and 33% yields, respectively. All the prod-
ucts were identified by comparing the 29Si-NMR and
GC/MS data with those of the authentic samples.
Yields were determined by quantitative analysis with
GC/MS.
3.2. Reaction of Mn(CO)5SiTolp2H (2) with LiAlH4 in
THF
To a suspension of LiAlH4 (298 mg, 7.83 mmol) in
THF (15 ml) was added a THF solution (5 ml) of 2
(789 mg, 1.94 mmol) at −43 °C. The mixture was
allowed to warm to r.t. and was stirred for 4 h. After

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R. Shiozawa et al. / Journal of Organometallic Chemistry 650 (2002) 91–95
3.6. Reaction of Mn(CO)5SiTolp2H (2) with Red-Al
and subsequent treatment with DCl/D2O
aqueous solution until the solution was neutralized. The
mixture was placed in a separatory funnel. The organic
layer was separated, washed with 1 M HCl aqueous
solution (10 ml×3), saturated NaHCO3 solution (10
ml), water (10 ml×3), and saturated NaCl solution (10
ml), and then dried over anhydrous MgSO4. The solvent
was removed in vacuo to give 4 (4.50 g, 18.6 mmol) in
93% yield as a colorless oil. 1H-NMR (300 MHz,
acetone-d6) l 7.20–7.23, 7.59–7.62 (AB q, J=8.1 Hz,
4H×2; p-CH3C6H4), 5.62 (br, 1H; SiꢀOH), 2.34 (s, 6H;
p-CH3C6H4), 0.65 (s, 3H; SiꢀMe). 13C-NMR (75.5
MHz, acetone-d6) l 139.6, 135.9, 134.7, 129.1 (p-
CH3C6H4), 21.5 (p-CH3C6H4), −0.56 (SiꢀMe). 29Si-
NMR (59.6 MHz, acetone-d6) l −0.84. Mass (EI, 70
eV); m/z: 242 (M+, 37), 227 (M+−Me, 100). Exact
mass found: 242.1126. Calc. for C15H18OSi: 242.1127.
A toluene solution of the reaction mixture of 2 (215
mg, 529 mmol) and Red-Al (3.4 M, 0.3 ml, 1.02 mmol)
was added dropwise to DCl/D2O solution (1 M, 200
ml). The reaction mixture was worked up in a manner
similar to that for the reaction with HCl/H2O to give a
mixture of (CH3)SiTolp2(OD) (4-d: ca. 80 atom% D)
(51.6 mg, 212 mmol) and (C2H5)SiTolp2(OD) (5-d: ca. 80
atom% D) (34.0 mg, 132 mmol) in 40 and 25% yields,
respectively.
3.7. Acid hydrolysis of Mn(CO)5SiTolp2(CH3)
To a Et2O solution (50 ml) of Mn(CO)5SiTolp2(CH3)
(563 mg, 1.34 mmol) was added aqueous HCl (1 M, 200
ml) at r.t. and then stirred for 1 day. The mixture was
placed in a separatory funnel. The organic layer was
separated, washed with saturated NaHCO3 solution,
water, and saturated NaCl solution, and then dried over
anhydrous MgSO4. The solvent was removed in vacuo
to give (CH3)SiTolp2(OH) (4) (292 mg, 121 mmol) in 90%
yield.
3.11. Preparation of Tolp2SiEt(OH) (5)
A 2 l four-necked flask was equipped with a con-
denser, a mechanical stirrer, and a dropping funnel.
EtSiCl3 (78.5 g, 480 mmol) and THF (650 ml) were
placed in the flask. A THF solution of TolpMgCl (1.00
M, 800 ml, 800 mmol) was added dropwise from the
dropping funnel into the flask over a period of 1 h, and
then the mixture was refluxed for an additional 5 h.
After the reaction mixture was allowed to cool to r.t., it
was filtered and the salt was washed with Et2O (3 l). The
filtrate was concentrated and the residue was distilled
under reduced pressure to give Tolp2SiEtCl (61.3 g, 223
mmol, 46%) as a colorless oil, b.p. 134 °C/0.3 mmHg.
1H-NMR (300 MHz, C6D6) l 7.57–7.59, 6.99–7.02 (AB
q, J=8 Hz, 4H×2; p-CH3C6H4), 2.08 (s, 6H; p-
CH3C6H4), 1.19 (quartet, 3J(H,H)=7 Hz, 2H;
SiꢀCH2CH3), 1.09 (t, 3J(H,H)=7 Hz, 3H; SiꢀCH2CH3).
13C-NMR (75.5 MHz, C6D6) l 140.6, 134.8, 130.6, 129.2
(p-CH3C6H4), 21.5 (p-CH3C6H4), 9.10, 7.02 (SiꢀEt).
29Si-NMR (59.6 MHz, C6D6) l 13.0. Mass (EI, 70 eV);
m/z: 274 (M+, 12), 245 (M+−Et, 100).
3.8. Reaction of Mn(CO)5SiTolp2H (2) with Red-Al and
subsequent treatment with LiAlH4
A toluene solution of Red-Al (3.4 M, 7.3 ml, 24.8
mmol) was added dropwise to a solution of 2 (912 mg,
2.25 mmol) in toluene (20 ml) over a period of 10 min
and then stirred for 18 h at r.t. The reaction mixture was
added dropwise to a Et2O solution (30 ml) of LiAlH4
(997 mg, 26.2 mmol) at r.t. and stirred for 3 h. Hydrol-
ysis and workup in a manner similar to those in Section
3.5 gave a mixture of (CH3)SiTolp2H (6) [8b] (208 mg,
920 mmol) and (CH3CH2)SiTolp2H (7) (151 mg, 629
mmol) in 41 and 28% yields, respectively.
3.9. Reaction of Mn(CO)5SiTolp2H (2) with Red-Al and
subsequent treatment with LiAlD4
Hydrolysis of Tolp2SiEtCl (5.64 g, 20.5 mmol) in a
manner analogous to that for 4 gave Tolp2SiEt(OH) (5)
1
(4.85 g, 18.9 mmol, 92%) as a colorless oil. H-NMR
A toluene solution of the reaction mixture of 2 (387
mg, 952 mmol) and Red-Al (3.4 M, 0.5 ml, 1.70 mmol)
was added dropwise to a Et2O solution (10 ml) of
LiAlD4 (339 mg, 8.07 mmol). The reaction mixture was
worked up in a manner similar to that for the reaction
with LiAlH4 to give a mixture of (CH3)SiTolp2D (6-d: ca.
55 atom% D) [8b] (88.7 mg, 390 mmol) and
(CH3CH2)SiTolp2D (7-d: ca. 53 atom% D) (64.5 mg, 267
mmol) in 41 and 28% yields, respectively.
(300 MHz, acetone-d6) l 7.50–7.52, 7.16–7.19 (AB q,
J=8 Hz, 4H×2; p-CH3C6H4), 5.52 (br, 1H; SiꢀOH),
2.30 (s, 6H; p-CH3C6H4), 1.02 (br s, 5H; SiꢀEt). 13C-
NMR (75.5 MHz, acetone-d6) l 139.7, 135.0, 134.9,
129.1 (p-CH3C6H4), 21.4 (p-CH3C6H4), 7.94, 7.10
(SiꢀEt). 29Si-NMR (59.6 MHz, acetone-d6) l −0.90.
Mass (EI, 70 eV); m/z: 256 (M+, 5), 227 (M+−Et,
100). Exact mass found: 256.1281. Calc. for C16H20OSi:
256.1283.
3.10. Preparation of Tolp2SiMe(OH) (4)
3.12. Preparation of Tolp2SiHEt (7)
To a Et2O solution (30 ml) of Tolp2SiMeCl (5.23 g,
20.1 mmol) and phenolphthalein was added 1 M NaOH
To a Et2O solution of EtMgBr (0.875 M, 120 ml, 105
mmol) was added a Et2O solution (60 ml) of Tolp2SiHCl

R. Shiozawa et al. / Journal of Organometallic Chemistry 650 (2002) 91–95
95
(13.0 g, 52.4 mmol) over a period of 5 min. The mixture
was stirred at r.t. for 1.5 h and then cooled in an ice
bath. Water (20 ml) was added dropwise to hydrolyze
an excess of EtMgBr and then 6 M HCl (100 ml) was
added to dissolve the salt. The aqueous layer was
extracted with two 50 ml portions of ether and the
combined organic layer was washed with saturated
NaHCO3 solution (200 ml), water (200 ml), and satu-
rated NaCl solution (200 ml) and then dried over
anhydrous MgSO4. After removal of solvent, the
residue was distilled under reduced pressure to give 7
(10.9 g, 45.4 mmol, 87%) as a colorless oil, b.p. 114 °C/
Japan Society for the Promotion of Science (JSPS) for
the award of a JSPS Research Fellowship for Young
Scientists to R.S. We are grateful to Dow Corning
Torey Silicon Co., Ltd. and Shin-Etsu Chemical Co.,
Ltd. for gifts of silicon compounds.
References
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1
0.2 mmHg. H-NMR (300 MHz, C6D6) l 7.51–7.53,
7.02–7.05 (AB q, J=8 Hz, 4H×2; p-CH3C6H4), 5.10
(t, 3J(H,H)=4 Hz, 1H; SiꢀH), 2.10 (s, 6H; p-
CH3C6H4), 1.08 (br s, 5H; SiꢀEt). 13C-NMR (75.5
MHz, C6D6) l 139.4, 135.6, 131.2, 129.1 (p-CH3C6H4),
21.4 (p-CH3C6H4), 8.40, 4.77 (SiꢀEt). 29Si-NMR (59.6
MHz, C6D6) l −11.6. IR (cm−1, NaCl plate): w(SiꢀH)
2110. Mass (EI, 70 eV); m/z: 240 (M+, 37), 211 (M+−
Et, 100), 148 (M+−H−Tolp, 42), 119 (M+−H−
Et−Tolp, 18). Anal. Found: C, 79.79; H, 8.44. Calc.
for C16H20Si: C, 79.93; H, 8.38%.
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Acknowledgements
This work was supported by Grants-in-Aid for Scien-
tific Research (Nos. 09239105, 09440245, and
12042210) from the Ministry of Education, Culture,
Sports, Science and Technology of Japan. We thank the