Si-H-functionalized ferriodisiloxanes: Synthesis from the ferriodimethylsilanols C5R5(OC)2Fe-SiMe2OH (R = H, Me) and photoinduced transformation into μ2-disiloxanediyl-bridged dinuclear iron complexes

Article abstract of DOI:10.1002/1099-0682(200212)2002:12<3235::AID-EJIC3235>3.0.CO;2-A

Hydrolysis of the ferriochlorosilanes C₅R₅(OC)₂Fe-SiMe₂Cl [R = H (1a), Me (1b)] in the presence of Et₃N yields the corresponding ferriosilanols C₅R₅(OC)₂Fe-SiMe_2<

Full text of DOI:10.1002/1099-0682(200212)2002:12<3235::AID-EJIC3235>3.0.CO;2-A

FULL PAPER
Si؊H-Functionalized Ferriodisiloxanes: Synthesis from the
Ferriodimethylsilanols C5R5(OC)2Fe؊SiMe2OH (R ؍ H, Me) and
Photoinduced Transformation into µ2-Disiloxanediyl-Bridged Dinuclear
Iron Complexes[‡]
Wolfgang Malisch,*[a] Marco Hofmann,[a] Günter Kaupp,[a] Harald Käb,[a] and
Joachim Reising[a]
Keywords: Iron / Metallacycles / Oxidative addition / Silicon / Siloxanes
Hydrolysis of the ferriochlorosilanes C5R5(OC)2Fe−SiMe2Cl
with the chloro(organo)silanes R3SiCl (4a−d). Irradiation of
[R = H (1a), Me (1b)] in the presence of Et3N yields the cor- 5a and 5b results in CO elimination, followed by dimerization
responding ferriosilanols C5R5(OC)2Fe−SiMe2(OH) (2a and
2b). In addition, 2b is also obtained by oxo-functionalization
of C5Me5(OC)2Fe−SiMe2H (3) with dimethyldioxirane. The
ferriosilanol 2a can be converted into the ferriodisiloxanes
Cp(OC)2Fe−SiMe2OSiR3 [R3Si = Me2(H)Si (5a), pTol2(H)Si
(5b), Me3Si (5c) and pTol(Me)(H)Si (5d)] by condensation
to give the cyclic 1,5-diferratetrasiloxanes [µ2-SiMe2OSi(R)2]2
[Fe(H)(CO)Cp]2 [R = Me (6a) and pTol (6b)]. Compounds 2b
and 6b have been characterized by single-crystal X-ray
structure determination.
( Wiley-VCH Verlag GmbH, 69451 Weinheim, Germany,
2002)
Introduction
of the SiH unit to electronically unsaturated metal centres
to provide access to SiϪOϪSi-bridged dinuclear metal
complexes.[27]
This was strong motivation to perform the synthesis of
novel metallosilanols, especially with the well-known iron
fragments C5R5(OC)2Fe (R ϭ H, Me), and condensation
reactions to afford the corresponding disiloxanes. Further-
more, the SiH-functional derivatives were used for photoin-
duced transformation, providing novel eight-membered cyc-
lic dimetallasiloxanes.
Transition metal substituted silicon compounds have at-
tracted great attention in recent years, especially with regard
to the effect of the metal component on the reactivity of
the silicon unit.[2Ϫ5] In the context of our systematic studies
on the reactivity of functionalized siliconϪtransition metal
complexes[6Ϫ13] we have shown that metallosilanols with a
direct MϪSi bond of the general type LnMϪSi(R)3Ϫn(OH)n
(n ϭ 1Ϫ3)[14Ϫ30] are characterized by remarkably high
stability towards self-condensation, due to the electron-re-
leasing effect of the metal fragment. This property has per-
mitted the isolation of a number of transition metal substi-
tuted silanols,[14Ϫ26] mainly of the chromium and iron
groups, including examples with stereogenic metal and
silicon atoms[26] and even of metallosilanediols[27,28] and -si-
lanetriols.[29,30]
Results and Discussion
Access to the ferriodimethylsilanols 2a and 2b, the pre-
cursors for synthesis of the ferriodisiloxanes, is given by two
procedures Ϫ hydrolysis of chloroferriosilanes[14,18] and
oxo-functionalization of ferriosilanes.[16,20]
The reactivity of this special class of silanols has so far
not been explored in detail. However, preliminary studies
showed facile condensation with chlorosilanes as an effici-
ent route to metallosiloxanes.[22Ϫ24,26Ϫ30] In particular,
those bearing an SiH function at the γ-silicon atom offer
high synthetic potential in terms of the oxidative addition
Hydrolysis of the chloroferriodimethylsilanes 1a and 1b
in diethyl ether in the presence of the auxiliary base Et3N
at room temperature afforded the metallated silanols 2a and
2b in good yields [89% (2a), 70% (2b)] [Equation (1), route
a]. The C5Me5-substituted complex 1b undergoes ligand ex-
change (48 h) significantly more slowly than the Cp com-
pound 1a. This difference can be associated with the re-
duced electrophilicity of the silicon atom, deriving from the
greater electron-releasing effect of the permethylated Cp
ring. Controlled Cl/OH exchange can be performed without
an auxiliary base, as demonstrated for 2a, indicating that
the FeϪSi bonds in both 1a and 2a, in contrast to those in
[‡]
Synthesis and Reactivity of Silicon Transition Metal Com-
plexes, 51. Metallo-Silanols and Metallo-Siloxanes, 23. Part
50/22: Ref.[1]
[a]
Institut für Anorganische Chemie der Universität Würzburg,
Am Hubland, 97074 Würzburg, Germany
Fax: (internat.) ϩ 49-931/888-4618
E-mail: Wolfgang.Malisch@mail.uni-wuerzburg.de
Eur. J. Inorg. Chem. 2002, 3235Ϫ3241  2002 WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim 1434Ϫ1948/02/1212Ϫ3235 $ 20.00ϩ.50/0 3235

W. Malisch, M. Hofmann, G. Kaupp, H. Käb, J. Reising
FULL PAPER
trialkylferriosilanes, are resistant towards cleavage with ganic substituents. A few examples show that, as far as the
HCl. formation of hydrogen bonds is concerned, the transition
In addition, the C5Me5-substituted ferriosilanol 2b was metal components show an effect analogous to that of or-
obtained by oxygenation of the corresponding ferriodime- ganic substituents, the difference being that the acidity of
thylsilane 3 with dimethyldioxirane [Equation (1), route b]. the OH hydrogen atom is reduced and the basicity of the
This method gave shorter reaction times and a more con- oxygen atom is increased.[16,22] Compound 2b, because of
venient workup procedure than the hydrolysis route. How- the bulkiness of the metal component, prefers hydrogen-
ever, the yield was significantly lower (36%), presumably bonded ‘‘dimerization’’, indicated by an oxygenϪoxygen
due to oxidation of the transition metal centre.[31]
distance of 2.889 A. This arrangement is similar to that
˚
found in C5Me5(OC)2RuϪSi(oTol)2OH.[22]
(1)
Figure 1. ORTEP Plot of 2b (O···O bond is dashed); selected bond
˚
lengths [A], angles [°] and torsion angles [°]: Fe1ϪC1 1.731(8),
The ferriodimethylsilanols 2a and 2b were obtained as
slightly air-sensitive, pale yellow solids, showing good solu-
bility in all kinds of organic solvents. Compounds 2a and
2b did not undergo self-condensation at room temperature
even in the presence of Et3N.
In order to gain an insight into the solid-state structure
of the ferriodimethylsilanols 2a and 2b, especially with re-
spect to hydrogen-bonded aggregation, an X-ray structure
determination of 2b was performed. Two molecules were
found in the asymmetric unit (Figure 1). For the central
iron atom a pseudo-octahedral coordination sphere is indi-
cated by the ligandϪironϪligand angles, which are close to
Fe1ϪC2 1.755(7), Fe1ϪSi1 2.313(2), O3ϪSi1 1.676(9), Si1ϪC14
1.864(7), Si1ϪC13 1.871(7), Fe2ϪC15 1.732(7), Fe2ϪC16 1.743(8),
Fe2ϪSi2 2.319(2), Si2ϪO17 1.653(6), Si2ϪC28 1.864(7), Si2ϪC27
1.894(7);
C1ϪFe1ϪC2
98.3(3),
C1ϪFe1ϪSi1
83.1(2),
C2ϪFe1ϪSi1 84.1(2), O3ϪSi1ϪC14 105.2(5), O3ϪSi1ϪC13
106.2(4), C14ϪSi1ϪC13 104.9(4), O3ϪSi1ϪFe1 111.6(4),
C16ϪFe2ϪC15 98.3(3), C15ϪFe2ϪSi2 83.9(2), C16ϪFe2ϪSi2
84.0(2), O17ϪSi2ϪC28 105.1(3), O17ϪSi2ϪC27 106.0(3),
C28ϪSi2ϪC27 104.8(3), O17ϪSi2ϪFe2 113.5(2), C28ϪSi2ϪFe2
113.8(2), C27ϪSi2ϪFe2 112.8(2); C1ϪFe1ϪSi1ϪO3 74.0(4),
C2ϪFe1ϪSi1ϪO3 173.1(4), C15ϪFe2ϪSi2ϪO17 Ϫ177.0(3),
C16ϪFe2ϪSi2ϪO17 Ϫ77.9(3)
Due to their high stabilities with respect to self-condensa-
90°. A larger angle exists between the carbonyl carbon tion, the ferriosilanols 2a and 2b are excellent starting mat-
atoms [98.3(3)°], while those between the CO ligands and erials for further reactions. Among these, condensation with
the silicon atom are diminished [83.1(2)°/84.1(2)° and chlorosilanes is of special interest for investigation of the
83.9(2)°/84.0(2)°]. Newman projection along the FeϪSi transition metal effect on the SiϪOϪSi bonding system and
bond reveals a staggered conformation of the substituents, the γ-silicon atom of the resulting ferriodisiloxanes. Treat-
with one of the methyl groups trans to the C5Me5 ring and ment of 2a with the chloro(organo)silanes 4aϪd in Et2O in
the OH group consequently occupying the space between the presence of the auxiliary base Et3N at room temper-
the C5Me5 ring and one carbonyl ligand. The FeϪSi dis- ature afforded the ferriodisiloxanes 5aϪd [34% (5c) to 95%
˚
˚
tances [2.313(2) A and 2.319(2) A] lie within the range ob- (5b) yield] after 1Ϫ12 h, these compounds being isolated as
served in known ironϪsilicon compounds.[32,33] The SiϪO pale yellow (5c) or orange (5a, 5b, 5d) oils displaying high
˚
˚
bond lengths [1.676(9) A and 1.653(6) A] are slightly greater solubility in benzene and n-pentane [Equation (2)].
than those in organosilanols,[34] indicating some electronic
Compounds 5a and 5d were also obtained in the absence
saturation of the silicon atom by the transition metal com- of triethylamine, but the reaction rate was significantly
ponent. The silicon atoms show a distorted tetrahedral co- lower [70% (5a)/10% (5d) conversion after 7 d].
ordination with reduced angles between the methyl and hy-
Comparison of the spectroscopic data of the ferriosilanol
droxy substituents [104.8(3)Ϫ106.2(4)°] and enlarged ones 2a and of the ferriosiloxanes 5aϪd shows no significant ef-
to the metal component [111.6(4)Ϫ115.5(3)°]. Triorgano- fect concerning the ν(CO)sym and ν(CO)asym frequencies of
silanols often show interesting hydrogen-bonded super- the CO ligands, while for the 29Si NMR resonance a high-
structures,
forming
chains,[35,36]
tetramers[37]
or field shift for the iron-bound silicon atom from δ ϭ 66.05
dimers,[38Ϫ40] depending on the steric demand of the or- ppm (2a) to δ ϭ 58.73 (5a), 61.45 (5b) or 59.97 ppm (5d) is
3236
Eur. J. Inorg. Chem. 2002, 3235Ϫ3241

SiϪH-Functionalized Ferriodisiloxanes
FULL PAPER
(2)
found. The ν˜(SiH) absorptions of 5a, 5b and 5d
(2123Ϫ2112 cmϪ1) lie in the normal range of SiϪH func-
tional organosilanes or organosiloxanes, showing that the
‘‘transition metal effect’’ on the silicon atom in the γ-posi-
tion is negligible. This finding implies that for these systems
the known reactivity behaviour of SiϪH-functional silanes
Ϫ photoinduced oxidative addition of SiH functions to co-
ordinatively unsaturated metal centres, for example, re-
sulting in the formation of M(H)ϪSi units Ϫ may be ex-
pected.[5] Indeed, irradiation of 5a and 5b with UV light in
cyclohexane for 7 h/20 h resulted in controlled CO elimina-
tion, followed by SiϪH addition to the iron atom. The re-
˚
Figure 2. ORTEP Plot of 6b; selected bond lengths [A], angles [°]
and torsion angles [°]: Fe1ϪSi1 2.339(1), Fe1ϪSi2 2.311(1),
Fe1ϪH1 1.4644(5), Si1ϪO2A 1.636(2), Si2ϪO2 1.635(2), Si1ϪC21
1.868(4),
Si2ϪC110
1.891(3);
Si1ϪFe1ϪSi2
109.43(4),
Si2ϪFe1ϪH1 55.88(3), Si1ϪFe1ϪH1 62.03(3), C1ϪFe1ϪH1
102.4(2), Si2ϪO2ϪSi1A 153.6(1), Fe1ϪSi1ϪO2A 110.81(9);
Fe1ϪSi2ϪO2 111.75(9), Fe1ϪSi1ϪC21 116.0(2), C21ϪSi1ϪC22
Fe1ϪSi2ϪO2ϪSi1A
Ϫ128.18(8), H1ϪFe1ϪSi2ϪO2 Ϫ51.09(8), Si1ϪFe1ϪSi2ϪO2
Ϫ18.29(7)
107.5(3),
Fe1ϪSi2ϪC110
114.4(1),
sulting eight-membered cyclic ferriodisiloxanes 6a and 6b and lie within the range of known bis(silyl)iron com-
were obtained as white (6a) and beige (6b) solids in 19% plexes.[47,48] The SiϪO distances [1.636 (Si1) and 1.635 A
˚
(6a) and 10% (6b) yields [Equation (3)].
(Si2)] are significantly shorter than those in four-membered
cyclo-metalladisiloxanes {e.g., (Ph3P)2(OC)(H)Ir(SiMe2O-
2
[44]
˚
SiMe2-κ -Si) [d(SiϪO) ϭ 1.690/1.678 A]
or (dppe)Pt(Si-
˚
Me2OSiMe2-κ -Si) [d(SiϪO) ϭ 1.693/1.689 A][49]} and im-
ply a partial double bond character for the SiϪO
bond.[50Ϫ55] The value of 153.6(1)° for the SiϪOϪSi angle
is similar to that in cyclic organotetrasiloxanes.[32] The iron
atoms show a pseudo-square-pyramidal arrangement, with
the Cp ligand in the apical position and the two Si atoms
at the tetragonal base arranged trans to each other
[Si1ϪFe1ϪSi2 109.43(4)°] as well as the CO and H ligands
[C1ϪFe1ϪH1 102.4(2)°]. The silicon atoms show distorted
tetrahedral coordination with different FeϪSiϪC angles de-
pending on the nature of the organic ligand [114.4(1)/
111.3(1)° FeϪSiϪC(pTol); 116.0(2)/109.2(2)° FeϪSiϪ
C(Me)], with the FeϪSiϪC(Me) angles showing stronger
deviation from the ideal value.
2
(3)
The structures of 6a and 6b were confirmed by the FeϪH
1
resonance in the H NMR at δ ϭ Ϫ13.31 (6a)/Ϫ12.54 ppm
2
(6b), with J(HFeSi) coupling constants of 23.6 (6a)/24.0
Hz (6b) excluding agostic FeHSi interaction.[5] In addition,
the 29Si{1H} NMR spectra show singlets at δ ϭ 45.11 (6a)
and 46.71 (6b) ppm, indicating chemical equivalence of the
methyl-substituted silicon atoms.
Intramolecular cyclization to the four-membered cyclo-
ferradisiloxanes Cp(OC)(H)Fe-(SiMe2OSiR2-κ2-Si)[41Ϫ45]
can be ruled out, as shown by the X-ray structure deter-
mination of 6b. This type of siloxane is obviously disfa-
voured, due to high ring strain.
For (R2SiO)4 rings a variety of conformations (Ci chair,
C2 boat, S4 boat) has been found in the solid state,[32] with
(tBu2SiOSiMe2O)2 representing an exception, due to the
planarity of the ring.[56] The eight-membered Fe2Si4O2 ar-
rangement of 6b adopts a chair conformation with both
metal components bent in opposite directions out of the
plane defined by the four silicon atoms (Figure 3). An
identical situation holds for the oxygen atoms.
Figure 2 shows that 6b can be regarded as deriving from
the well-known cyclic organotetrasiloxanes by replacement
of the oxygen atoms in the 1- and 5-positions with the isolo-
bal iron fragment Cp(OC)(H)Fe.[46]
˚
The FeϪSi bond lengths of 2.339(1) A (Fe1ϪSi1) and
˚
2.311(1) A (Fe1ϪSi2) show the expected decrease on going
from the methyl- to the tolyl-substituted metalϪsilicon unit Figure 3. Chair conformation of the eight-membered ring of 6b
Eur. J. Inorg. Chem. 2002, 3235Ϫ3241 3237

W. Malisch, M. Hofmann, G. Kaupp, H. Käb, J. Reising
FULL PAPER
Ϫ COϩ], 248 (26) [C5Me5(CO)Fe Ϫ SiHϩ], 191 (100) [C5Me5Feϩ].
Conclusions
3.
[Dicarbonyl(η5-cyclopentadienyl)ferrio]dimethylsilanol
(2a):
The γ-SiH-functionalized ferriodisiloxanes presented in
this paper proved to be synthetically valuable precursors for
the simple synthesis of SiϪOϪSi-bridged homodinuclear
Cp(OC)2FeϪSiMe2Cl (1a, 256 mg, 0.96 mmol), dissolved in 25 mL
of Et2O, was treated with Et3N (144 mg, 1.44 mmol) and H2O (100
mg, 5.55 mmol). After 45 min of stirring at room temperature, the
iron complexes. Further investigation is currently being di- precipitate of [Et3NH]Cl was separated, the orange solution was
concentrated to dryness, and the resulting ferriosilanol was washed
five times with 2 mL of n-pentane and dried in vacuo. Yield 215
mg (89%). Light yellow, microcrystalline powder. M.p. 45 °C (de-
comp.). 1H NMR (200 MHz, [D6]benzene): δ ϭ 4.27 (s, 5 H, H5C5),
1.77 (br. s, 1 H, HO), 0.70 ppm (s, 6 H, H3C). 29Si{1H} NMR (18
MHz, [D6]benzene): δ ϭ 66.05 ppm (s). IR (cyclohexane): ν˜ ϭ 3690
cmϪ1 [br, w, ν(OH)], 1998 (s), 1947 (vs) [ν(CO)]. C9H12FeO3Si
(252.13): calcd. C 42.88, H 4.80; found C 42.14, H 4.79.
rected towards heteronuclear derivatives with metal com-
plexes characterized by a high tendency towards oxidative
addition of SiH functions, such as Pt or Ir. Another aspect
concerns the introduction of hydroxy groups at the γ-silicon
atom, giving access to metallosiloxanols. These compounds
are of special interest for further condensation to afford
transition metal fragment substituted oligosiloxanes. We re-
gard these species as model compounds for catalytic sys-
tems immobilized on a silica surface.
4. Synthesis of 2a in the Absence of an Auxiliary Base: H2O (1000
mg, 55.6 mmol) was added to a solution of Cp(OC)2FeϪSiMe2Cl
(1a, 270 mg, 1.00 mmol) in Et2O (20 mL). After 2 h of stirring at
room temperature, the organic layer was separated and concen-
trated in vacuo. The resulting 2a was washed twice with 2 mL of
n-pentane and dried in vacuo. Yield 242 mg (96%).
Experimental Section
General Remarks: All reactions were performed under purified ni-
trogen. Solvents were dried by conventional procedures, distilled
and saturated with N2 prior to use. 1H, 13C{1H} and 29Si{1H}
NMR spectra were recorded with Jeol FX 90Q, Bruker AC 200
and Bruker AMX 400 spectrometers; δ(29Si) chemical shifts are
measured relative to external Me4Si; δ(1H)/(13C) are reported
downfield from Me4Si, referenced to the residual proton signal (1H)
or natural-abundance carbon signal of C6D6 (13C). Infrared spectra
were recorded with a PerkinϪElmer 283 grating spectrometer. The
solutions were measured in NaCl cells of 0.1 mm path length with
a resolution of about 2 cmϪ1. Melting points: differential thermal
analysis (Du Pont 9000 Thermal Analysis System). Literature pro-
cedures were employed to synthesize Cp(OC)2FeϪSiMe2Cl (1a)[57]
and dimethyldioxirane.[58] Me2Si(H)Cl (4a), Me3SiCl (4c), Et3N
and 18-crown-6 were obtained commercially and were distilled
prior to use.
5.
[Dicarbonyl(η5-pentamethylcyclopentadienyl)ferrio]dimethyl-
silanol (2b): The preparation was as described under 3., from
C5Me5(OC)2FeϪSiMe2Cl (1b, 235 mg, 0.69 mmol), H2O (12 mg,
0.69 mmol) and Et3N (730 mg, 7.2 mmol) (48 h). Yield 155 mg
1
(70%). Yellow microcrystalline powder. M.p. 72 °C (decomp.). H
NMR (400 MHz, [D6]benzene): δ ϭ 1.55 [s, 15 H, (H3C)5C5], 1.02
(s, 1 H, HO), 0.67 ppm [s, 6 H, (H3C)2Si]. 13C{1H} NMR (101
MHz, [D6]benzene): δ ϭ 217.62 (s, CO), 95.13 [s, C5(CH3)5], 9.96
[s, (CH3)2Si], 9.80 ppm [s, (CH3)5C5]. 29Si{1H} NMR (80 MHz,
[D6]benzene): δ ϭ 66.83 ppm (s). IR (toluene): ν˜ ϭ 3629 cmϪ1 [w,
br, ν(OH)], 1979 (vs), 1922 (vs) [ν(CO)]. C14H22FeO3Si (322.26):
calcd. C 52.18, H 6.88; found C 52.63, H 7.15.
6. Synthesis of 2b by Oxygenation of C5Me5(OC)2Fe؊SiMe2H (3)
with Dimethyldioxirane: A solution of dimethyldioxirane in acetone
(0.10 , 10 mL) was added dropwise at Ϫ78 °C to a solution of
C5Me5(OC)2FeϪSiMe2H (3, 265 mg, 0.87 mmol) in 20 mL of tolu-
ene. After 1 h of stirring, the mixture was allowed to warm to room
temperature and the solvent was evaporated in vacuo. The orange
residue was extracted with 10 mL of n-pentane, and 2b crystallized
at Ϫ78 °C. Yield 100 mg (36%).
1. Chloro[dicarbonyl(η5-pentamethylcyclopentadienyl)ferrio]dimeth-
ylsilane (1b): Me2SiCl2 (1680 mg, 13.03 mmol) was added to a sus-
pension of Na[Fe(CO)2C5Me5] (880 mg, 3.26 mmol) in 50 mL of
cyclohexane and the mixture was vigorously stirred for 40 h at
room temperature. After filtration, the solvent was removed in va-
cuo, the red residue was extracted three times with 10 mL of n-
pentane, and 1b crystallized at Ϫ78 °C. Yield 410 mg (37%). Or-
ange, microcrystalline powder. M.p. 96 °C. 1H NMR (60 MHz,
[D6]benzene): δ ϭ 1.60 [s, 15 H, (H3C)5C5], 0.97 ppm (s, 6 H,
H3CSi). IR (n-pentane): ν˜ ϭ 1993 cmϪ1 (vs), 1941 (vs) [ν(CO)].
C14H21ClFeO2Si (340.74): calcd. C 49.35, H 6.23, Cl 10.40; found
C 49.07, H 5.91, Cl 10.60.
7. Chlorobis(4-methylphenyl)silane (4b):
A Grignard solution,
freshly prepared from Mg (2.43 g, 0.1 mol) and 4-bromotoluene
(1.71 g, 0.1 mol) in 50 mL of diethyl ether, was added dropwise
over 1 h to a cooled solution (0 °C) of HSiCl3 (6.77 g, 0.05 mol)
in 100 mL of Et2O. After the mixture had been stirred for 1 h at
room temperature, the precipitate was filtered off and the resulting
dark brown, oily residue was fractionally distilled. Yield 12.69 g
(51%). Colourless liquid. B.p. 105Ϫ107 °C/0.01 Torr. 1H NMR (60
2. [Dicarbonyl(η5-pentamethylcyclopentadienyl)ferrio]dimethylsilane
(3): The preparation was as described under 1., from Na[Fe(C-
O)2C5Me5] (700 mg, 2.59 mmol) and Me2Si(H)Cl (735 mg, 7.77
mmol) in 100 mL of cyclohexane (20 h). Further purification of 3
was performed by sublimation at 83Ϫ85 °C (10Ϫ2 Torr). Yield 420
3
MHz, [D6]benzene): δ ϭ 7.53 [d, JHCCH ϭ 8.0 Hz, 4 H, H-3/5 of
3
H4C6], 6.97 [d, JHCCH ϭ 8.0 Hz, 4 H, H-2/6 of H4C6], 5.90 (s, 1
H, HSi), 1.92 ppm (s, 6 H, H3C). IR (cyclohexane): ν˜ ϭ 2159 cmϪ1
[s, ν(SiH)].
1
mg (53%). Yellow, microcrystalline powder. M.p. 43 °C. H NMR
(60 MHz, [D6]benzene): δ ϭ 4.72 [sept, 3J(HSiCH) ϭ 3.6 Hz, 1 H,
8. 1-[Dicarbonyl(η5-cyclopentadienyl)ferrio]-1,1,3,3-tetramethyldi-
siloxane (5a)
3
HSi], 1.50 [s, 15 H (H3C)5C5], 0.62 ppm [d, J(HCSiH) ϭ 3.6 Hz,
6 H, (H3C)2Si]. 13C{1H} NMR (50 MHz, [D6]benzene): δ ϭ 217.27
(s, CO), 94.57 [s, C5(CH3)5], 9.45 [s, (CH3)5C5], 2.79 ppm [s, a) From Cp(OC)2Fe؊SiMe2OH (2a), Me2Si(H)Cl (4a) and Et3N:
(CH3)2Si]. 29Si{1H} NMR (18 MHz, [D6]benzene): δ ϭ 28.36 ppm
(s). IR (cyclohexane): ν˜ ϭ 2043 cmϪ1 [w, ν(SiH)], 1984 (vs), 1931
(vs) [ν(CO)]. C14H22FeO2Si (306.3): calcd. C 54.90, H 7.24; found
A solution of Cp(OC)2FeϪSiMe2OH (2a, 224 mg, 0.89 mmol) in
20 mL of Et2O was treated with Et3N (101 mg, 1.00 mmol) and
Me2Si(H)Cl (4a, 308 mg, 2.84 mmol). After the mixture had been
C 54.72, H 6.95. MS (30 °C): m/z (%) ϭ 306 (3) [Mϩ], 278 (36) [M stirred for 1 h at room temperature, the precipitate of [Et3NH]Cl
3238
Eur. J. Inorg. Chem. 2002, 3235Ϫ3241

SiϪH-Functionalized Ferriodisiloxanes
FULL PAPER
was filtered off and all volatiles were removed in vacuo. The red
oily residue was extracted with 3 mL of n-pentane, the solvent was
removed, and 5a was dried in vacuo. Yield 218 mg (79%).
(50 MHz, [D6]benzene): δ ϭ 215.49 (s, CO), 139.75 (s, C-1 of
C6H4), 134.98 (s, C-4 of C6H4), 133.91 (s, C-2/6 of C6H4), 129.06
(s, C-3/5 of C6H4), 83.55 (s, C5H5), 21.48 (s, CH3C6H4), 11.03 (s,
CH3SiFe), 1.02 ppm (s, CH3SiH). 29Si{1H} NMR (18 MHz,
[D6]benzene): δ ϭ 59.97 (s, SiFe), Ϫ15.39 ppm (s, SiH). IR (cyclo-
hexane): ν˜ ϭ 2112 cmϪ1 [w, ν(SiH)], 1999 (s), 1947 (vs) [ν(CO)].
C17H22FeO3Si2 (386.38): calcd. C 52.85, H 5.74; found C 52.17,
H 5.78.
b) From Cp(OC)2Fe؊SiMe2OH (2a), NaH and Me2Si(H)Cl (4a):
A cooled solution (Ϫ78 °C) of Cp(OC)2FeϪSiMe2OH (2a, 100 mg,
0.40 mmol) in 10 mL of toluene was treated with NaH (10 mg,
0.40 mmol) and 18-crown-6 (10 mg) and stirred for 30 min. After
addition of Me2Si(H)Cl (4a, 47 mg, 0.50 mmol) the mixture was
allowed to warm to room temperature and stirred for another 10
min. After filtration through a Celite pad, the solvent was removed
and 5a was washed at Ϫ78 °C with 3 mL of n-pentane and dried
12. Treatment of Cp(OC)2Fe؊SiMe2OH (2a) with Me2Si(H)Cl (4a)
or pTol(Me)Si(H)Cl (4d) in the Absence of an Auxiliary Base: A
solution of Cp(OC)2FeϪSiMe2OH (2a, 151 mg, 0.60 mmol) and
in vacuo. Yield 104 mg (84%). Orange oil. M.p. Ϫ37 °C. 1H NMR either Me2Si(H)Cl (4a, 300 mg, 3.17 mmol) or pTol(Me)Si(H)Cl
(400.1 MHz, [D6]benzene): δ ϭ 5.04 [sept, 3J(HSiCH) ϭ 2.7,
1JSiH ϭ 202.0 Hz, 1 H, HSi], 4.12 (s, 5 H, H5C5), 0.63 (s, 6 H, temperature. After 7 d, conversion into 5a/5d was 70%/10% com-
(4d, 258 mg, 1.51 mmol) in 15 mL of Et2O was stirred at room
H3CSiFe), 0.23 ppm [d, 3J(HSiCH) ϭ 2.7 Hz, 6 H, H3CSiH].
29Si{1H} NMR (79.5 MHz, [D6]benzene): δ ϭ 58.73 (s, SiFe),
Ϫ8.27 ppm (s, SiH). IR (n-pentane): ν˜ ϭ 2117 cmϪ1 [w, ν(SiH)],
1998 (s), 1957 (vs) [ν(CO)]. C11H18FeO3Si2 (310.28): calcd. C 42.58,
H 5.85; found C 42.29, H 5.82.
plete.
13.
Bis(µ-1,1,3,3-tetramethyldisiloxane-1,3-diyl)bis[carbonyl(η5-
cyclopentadienyl)hydridoiron(IV)] (6a): A solution of Cp(OC)2FeϪ
SiMe2OSiMe2H (5a, 581 mg, 1.87 mmol) in 40 mL of cyclohexane
was irradiated with UV light (quartz lamp TQ 718, 700 W, Hanau)
for 7 h. After removal of the solvent in vacuo, the residue was
9. 1-[Dicarbonyl(η5-cyclopentadienyl)ferrio]-1,1-dimethyl-3,3-bis(4-
methylphenyl)disiloxane (5b): The preparation was as described un- purified by column chromatography (20 ϫ 1 cm, silica gel,
der 8a., from Cp(OC)2FeϪSiMe2OH (2a, 699 mg, 2.77 mmol), 0.063Ϫ0.2 mm, 20 °C, cyclohexane/benzene, 2:1). The eluate from
Et3N (722 mg, 7.14 mmol) and (pTol)2Si(H)Cl (4b, 1026 mg, 4.16 the yellow zone was concentrated to dryness, the residue was stirred
mmol) in 60 mL of diethyl ether (5 h). Yield 1214 mg (95%). Or- with 2 mL of ice-cold n-pentane, and the precipitate of 6a separated
1
ange oil. M.p. Ϫ20 °C. H NMR (400.1 MHz, [D6]benzene): δ ϭ and dried in vacuo. Yield: 100 mg (19%). White microcrystalline
3
7.69 [d, JHCCH ϭ 6.8 Hz, 2 H, H-3/H-5 of H4C6], 7.07 [d, powder. M.p. 126 °C (decomp.). 1H NMR (60 MHz, [D6]benzene):
1
3JHCCH ϭ 6.8 Hz, 2 H, H-2/H-6 of H4C6], 5.87 [s, JSiH ϭ 211.3
δ ϭ 3.94 (s, 10 H, H5C5), 0.80 (s, 12 H, H3C), 0.65 (s, 12 H, H3C),
Hz, 1 H, HSi], 4.13 (s, 5 H, H5C5), 2.11 (s, 6 H, H3CC6H4), 0.71 Ϫ13.31 ppm [s, J(HFeSi) ϭ 23.6 Hz, 2 H, HFe]. 13C{1H} NMR
2
ppm (s, 6 H, H3CSi). 13C{1H} NMR (100.6 MHz, [D6]benzene): (50 MHz, [D6]benzene): δ ϭ 212.98 (s, CO), 82.46 (s, C5H5), 13.37
δ ϭ 215.42 (s, CO), 140.00 (s, C-1 of C6H4), 134.76 (s, C-3/C-5 of
(s, CH3), 12.97 ppm (s, CH3). 29Si{1H} NMR (18 MHz, [D6]ben-
C6H4), 133.48 (s, C-4 of C6H4), 129.11 (s, C-2/C-6 of C6H4), 83.64 zene): δ ϭ 45.31 ppm (s). IR (cyclohexane): ν˜ ϭ 1955 cmϪ1 [vs,
(s, C5H5), 21.52 (s, CH3C6H4), 11.08 ppm (s, CH3Si). 29Si{1H}
NMR (79.5 MHz, [D6]benzene): δ ϭ 61.45 (s, SiFe), Ϫ22.76 ppm
ν(CO)], 1257 (m), 1247 (m) [ν(SiCH3)], 1070 (s), 1065 (m, sh) [νas(-
SiOSi)], 576 (m), 565 (m) [νs(SiOSi)]. C20H36Fe2O4Si4 (564.542):
[s, Si(pTol)2H]. IR (n-pentane): ν˜ ϭ 2123 cmϪ1 [w, ν(SiH)], 2000 calcd. C 42.55, H 6.43; found C 42.24, H 6.50.
(vs), 1949 (vs) [ν(CO)], 1252 [vw, ν(SiCH3)], 1042 [m, br, νas(-
14. Bis[µ-1,1-dimethyl-3,3-bis(4-methylphenyl)disiloxane-1,3-diyl]-
SiOSi)], 597 [s, νs(SiOSi)]. C23H26FeO3Si2 (462.474): calcd. C 59.73,
bis[carbonyl(η5-cyclopentadienyl)hydridoiron(IV)] (6b): The prepara-
tion was as described under 13., from Cp(OC)2FeϪ
H 5.67; found C 59.84, H 5.80.
10.
1-[Dicarbonyl(η5-cyclopentadienyl)ferrio]-1,1,3,3,3-pentameth- SiMe2OSi(pTol)2H (5b, 998 mg, 2.16 mmol) in 40 mL of cyclohex-
yldisiloxane (5c): The preparation was as described under 8a., from
ane (20 h). Crystallization of 6b occurred at Ϫ78 °C in n-pentane.
Cp(OC)2FeϪSiMe2OH (2a, 366 mg, 1.43 mmol), Et3N (211 mg, Yield: 90 mg (10%). Beige, microcrystalline powder. M.p. 179 °C
1
2.09 mmol) and Me3SiCl (4c, 244 mg, 2.25 mmol) in 15 mL of Et2O (decomp.). H NMR (60 MHz, [D6]benzene): δ ϭ 8.01, 7.90 [2 d,
(12 h). Further purification of 5c was performed by distillation at
3JHCCH ϭ 7.7/7.6 Hz, 8 H, H-3/H-5 of H4C6], 7.25, 7.19 [2 d,
3JHCCH ϭ 7.6/7.7 Hz, 8 H, H-2/H-6 of H4C6], 3.93 (s, 10 H, H5C5),
50 °C (10Ϫ4 Torr). Yield 153 mg (34%). Pale yellow oil. M.p. Ϫ32
°C. 1H NMR (60 MHz, [D6]benzene): δ ϭ 4.21 (s, 5 H, H5C5), 0.63 2.26, 2.19 (2 s, 12 H, H3CC6H4), 0.70, 0.63 (2 s, 12 H, H3C), Ϫ12.54
[s, 6 H, (H3C)2SiFe], 0.19 ppm [s, 9 H, (H3C)3Si]. 29Si{1H} NMR
ppm [s, 2J(HFeSi) ϭ 24.0 Hz, 2 H, HFe]. 13C{1H} NMR (50 MHz,
[D6]benzene): δ ϭ 213.17 (s, CO), 142.97, 142.22 (2 s, C-1 of C6H4),
(79.5 MHz, [D6]benzene): δ ϭ 55.50 (s, SiFe), 5.44 ppm (s, SiMe3).
IR (benzene): ν˜
ϭ
1994 cmϪ1 (vs), 1936 (vs) [ν(CO)]. 138.14, 138.03 (2 s, C-4 of C6H4), 135.38, 134.61 (2 s, C-3/C-5 of
C12H20FeO3Si2 (324.31): calcd. C 44.44, H 6.22; found C 44.90, H C6H4), 128.72, 128.37 (2 s, C-2/C-6 of C6H4), 83.99 (s, C5H5),
5.77. MS: m/z ϭ 324 [Mϩ].
21.47, 21.43 (2 s, CH3C6H4), 13.57, 13.17 ppm (2 s, CH3Si).
29Si{1H} NMR (18 MHz, [D6]benzene): δ ϭ 46.71 ppm [s,
Si(CH3)2], Si(pTol)2 signal not detected. IR (cyclohexane): ν˜ ϭ 1956
cmϪ1 (vs), 1945 (m, sh) [ν(CO)], 1258 [m, br, ν(SiCH3)], 1051 (s,
br), 1020 (m, br) [νas(SiOSi)], 574 (m), 565 (w) [νs(SiOSi)].
C44H52Fe2O6Si2 (868.929): calcd. C 60.82, H 6.03; found C 60.85,
H 5.88.
11. 1-[Dicarbonyl(η5-cyclopentadienyl)ferrio]-1,1,3-trimethyl-3-(4-
methylphenyl)disiloxane (5d): The preparation was as described un-
der 8a., from Cp(OC)2FeϪSiMe2OH (2a, 302 mg, 1.20 mmol),
Et3N (203 mg, 2.01 mmol) and pTol(Me)Si(H)Cl (4d, 420 mg, 2.46
mmol) in 20 mL of Et2O (1 h). Further purification of 5d was
performed by column chromatography (20 ϫ 2 cm, Al2O3, activity
1
IV, cyclohexane). Yield 270 mg (70%). Orange oil. M.p. 4 °C. H
15. X-ray Crystal Structure Determination of 2b: Colourless crystals
of 2b suitable for X-ray diffraction were grown by slow diffusion
NMR (60 MHz, [D6]benzene): δ ϭ 7.64 [d, 3JHCCH ϭ 8.5 Hz, 2 H,
3
H-3/5 of H4C6], 7.12 [d, JHCCH ϭ 8.5 Hz, 2 H, H-2/6 of H4C6], of n-pentane into a benzene solution of 2b at room temperature.
3
1
5.47 [q, J(HSiCH) ϭ 2.8, JSiH ϭ 207.0 Hz, 1 H, HSi], 4.08 (s, 5
Crystal data: C28H44Fe2O6Si2, M ϭ 644.52, monoclinic, space
˚
˚
H, H5C5), 2.10 (s, 3 H, H3CC6H4), 0.68, 0.67 (2 s, 6 H, H3CSiFe), group P21 (no. 5), a ϭ 9.042(10) A, b ϭ 13.941(5) A, c ϭ 13.125(9)
3
3
0.49 ppm [d, J(HSiCH) ϭ 2.8 Hz, 3 H, H3CSiH]. 13C{1H} NMR A, β ϭ 104.14(4)°, V ϭ 1604.2(22) A , Z ϭ 4, dcalcd. ϭ 1.334
˚
˚
Eur. J. Inorg. Chem. 2002, 3235Ϫ3241
3239

W. Malisch, M. Hofmann, G. Kaupp, H. Käb, J. Reising
FULL PAPER
[6]
[7]
[8]
[9]
g·cmϪ3, CAD4 diffractometer (EnrafϪNonius), radiation type:
Mo-Kα, wavelength: λ ϭ 0.71073 A, graphite monochromator, crys-
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˚
tal size: 0.19 ϫ 0.10 ϫ 0.07 mm, temperature: 293 K, ω/Θ-scan,
scale range: 1.60° Ͻ Θ Ͻ 22.50°, F(000) ϭ 680, total reflections:
2373, independent reflections: 2211 with I Ͼ 2.0σ(I), absorption
coefficient: µ ϭ 1.018 mmϪ1, empirical absorption correction
(Tmin./Tmax. ϭ 0.8779/0.9978), structure solution: SHELXS-86[59]
by direct methods, structure refinement: SHELXL-93[60] (369 para-
meters), R1 ϭ 0.0293, wR2 ϭ 0.0683. The positions of the OH
hydrogen atoms were located and isotropically refined, while the
remaining hydrogen atoms were geometrically positioned
and subsequently refined with a riding model. CCDC-158196
contains the supplementary crystallographic data for this
compound. These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge
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16. X-ray Crystal Structure Determination of 6b: Pale yellow crys-
tals of 6b suitable for X-ray diffraction were grown by slow dif-
fusion of n-pentane into a toluene solution of 6b at Ϫ35 °C. Crystal
[18]
¯
data: C26H31FeO2Si2, M ϭ 487.54, triclinic, space group: P1 (no.
˚
˚
˚
˚
2), a ϭ 8.882(3) A, b ϭ 9.241(6) A, c ϭ 15.243(9) A, α ϭ
3
87.423(12)°, β ϭ 79.07(2)°, γ ϭ 86.49(2)°, V ϭ 1225.5(11) A , Z ϭ
2, dcalcd. ϭ 1.321 g·cmϪ3, CAD4 diffractometer (EnrafϪNonius),
[19]
[20]
[21]
[22]
[23]
˚
radiation type: Mo-Kα, wavelength: λ ϭ 0.71073 A, graphite mon-
ochromator, crystal size: 0.50 ϫ 0.40 ϫ 0.20 mm, temperature: 293
K, ω/Θ-scan, scale range: 2.20° Ͻ Θ Ͻ 26.91°, F(000) ϭ 514, total
reflections: 5545, independent reflections: 4314 with I Ͼ 2σ(I), ab-
sorption coefficient: µ ϭ 0.735 mmϪ1, empirical absorption correc-
tion (Tmin/Tmax ϭ 0.9433/0.9965), structure solution: SHELXS-
86[59] by direct methods, structure refinement: SHELXL-93[60] (371
parameter), R1 ϭ 0.0405, wR2 ϭ 0.1189. The positions of all hydro-
gen atoms except those of the pTol methyl groups were located
and isotropically refined, while the remaining hydrogen atoms were
geometrically positioned and subsequently refined with a riding
model. In addition, one toluene molecule with a disordered CH3
group was found in the unit cell. CCDC-158197 contains
the supplementary crystallographic data for this compound.
These data can be obtained free of charge at
www.ccdc.cam.ac.uk/conts/retrieving.html or from the Cambridge
Crystallographic Data Centre, 12, Union Road, Cambridge
[24]
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CB2 1EZ, UK [Fax: (internat.)
deposit@ccdc.cam.ac.uk].
ϩ 44-1223/336-033; E-mail:
Acknowledgments
[31]
[32]
We gratefully acknowledge financial support from the Deutsche
Forschungsgemeinschaft (Schwerpunktprogramm ‘‘Spezifische
Phänomene in der Siliciumchemie’’) as well as from the Fonds der
Chemischen Industrie.
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