Reaction of ruthenium complexes having both a phosphite and a group 14 element ligand with a lewis acid

Article abstract of DOI:10.1021/om990466u

Reactions of Cp(CO)(ER₃)Ru{PN(Me)CH₂CH₂NMe(OMe)} having an alkyl group (ER₃ = Me (1a), CH₂SiMe₃ (2a)), a silyl group (ER₃ = SiMe₃ (3a), SiMe₂SiMe₃ (4a)), a germyl group (ER₃ = GeMe₃ (5a)), or a stannyl group (ER₃ = SnMe₃ (6a), SnⁿBu₃ (7a), SnPh₃ (8a)) with a Lewis acid (BF₃·OEt₂ or Me₃SiOSO₂CF₃ (TMSOTf)) have been examined. In the reactions with BF₃·OEt₂, in any case except for 8a, an OMe abstraction as an anion uniformly takes place at the first stage to give the corresponding cationic phosphenium complex [Cp(CO)-(ER₃)Ru{PN(Me)CH₂CH₂NMe}]BF₄ (1b-Tb). The successive reaction depends on the type of ER₃ group. Alkyl complexes (1b and 2b) immediately undergo migratory insertion of the phosphenium ligand into the Ru-C bond, and a subsequent reaction with PPh₃ gives the cationic complex [Cp(CO)(PPh₃)Ru{PN(Me)CH₂CH₂NMe(ER ₃)}]BF₄ (ER₃ = Me (1c), CH₂-SiMe₃ (2c)). Silyl and germyl complexes (3b-5b) are stable with the Ru-Si and Ru-Ge bonds intact. In contrast, stannyl complexes (6b and 7b) undergo migration of one of the R groups on Sn to give the stannylene complex [Cp(CO){PN(Me)CH₂CH₂NMe(R)}Ru=SnR₂]-BF ₄ (R = Me (6e), ⁿBu (7e)). The reactions with another Lewis acid, TMSOTf, exhibit reactivities similar to those with BF₃·OEt₂, except when ER₃ is a stannyl group. In the reaction of 6a, 7a, or 8a with TMSOTf, one of the R groups on Sn is directly abstracted to give the corresponding stannylene complex [Cp(CO){PN(Me)CH₂CH₂NMe(OMe)}Ru=SnR₂]-OTf (R = Me (6f), ⁿBu (7t), Ph (8f)). 8f has been determined to be a doubly base stabilized stannylene complex by single-crystal X-ray diffraction.

Full text of DOI:10.1021/om990466u

Organometallics 1999, 18, 4785-4794
4785
Rea ction of Ru th en iu m Com p lexes Ha vin g both a
P h osp h ite a n d a Gr ou p 14 Elem en t Liga n d w ith a Lew is
Acid
Kazumori Kawamura, Hiroshi Nakazawa,* and Katsuhiko Miyoshi*
Department of Chemistry, Graduate School of Science, Hiroshima University,
Kagamiyama 1-3-1, Higashi-Hiroshima 739-8526, J apan
Received J une 15, 1999
Reactions of Cp(CO)(ER3)Ru{PN(Me)CH2CH2NMe(OMe)} having an alkyl group (ER3 )
Me (1a ), CH2SiMe3 (2a )), a silyl group (ER3 ) SiMe3 (3a ), SiMe2SiMe3 (4a )), a germyl group
(ER3 ) GeMe3 (5a )), or a stannyl group (ER3 ) SnMe3 (6a ), SnnBu3 (7a ), SnPh3 (8a )) with
a Lewis acid (BF3‚OEt2 or Me3SiOSO2CF3 (TMSOTf)) have been examined. In the reactions
with BF3‚OEt2, in any case except for 8a , an OMe abstraction as an anion uniformly takes
place at the first stage to give the corresponding cationic phosphenium complex [Cp(CO)-
(ER3)Ru{PN(Me)CH2CH2NMe}]BF4 (1b-7b). The successive reaction depends on the type
of ER3 group. Alkyl complexes (1b and 2b) immediately undergo migratory insertion of the
phosphenium ligand into the Ru-C bond, and a subsequent reaction with PPh3 gives the
cationic complex [Cp(CO)(PPh3)Ru{PN(Me)CH2CH2NMe(ER3)}]BF4 (ER3 ) Me (1c), CH2-
SiMe3 (2c)). Silyl and germyl complexes (3b-5b) are stable with the Ru-Si and Ru-Ge
bonds intact. In contrast, stannyl complexes (6b and 7b) undergo migration of one of the R
groups on Sn to give the stannylene complex [Cp(CO){PN(Me)CH2CH2NMe(R)}RudSnR2]-
BF4 (R ) Me (6e), nBu (7e)). The reactions with another Lewis acid, TMSOTf, exhibit
reactivities similar to those with BF3‚OEt2, except when ER3 is a stannyl group. In the
reaction of 6a , 7a , or 8a with TMSOTf, one of the R groups on Sn is directly abstracted to
give the corresponding stannylene complex [Cp(CO){PN(Me)CH2CH2NMe(OMe)}RudSnR2]-
n
OTf (R ) Me (6f), Bu (7f), Ph (8f)). 8f has been determined to be a doubly base stabilized
stannylene complex by single-crystal X-ray diffraction.
In tr od u ction
of transition metals regarding the syntheses and
structures,3c,4-11 but little has been studied with regard
to the reactivities of cationic phosphenium complexes.
There is growing interest in the chemistry of transi-
tion-metal complexes having a cationic phosphenium as
a ligand, because it can serve both as a strong π-acceptor
due to its empty p orbital and as a σ-donor and is
regarded as isolobal to a singlet carbene.1 In comparison
with the extensive development of the chemistry of
carbene complexes,2 little had been achieved in the
chemistry of the cationic phosphenium complexes until
the first report of Parry’s group in 1978.3a,b After that,
many such complexes were reported for several kinds
(4) (a) Muetterties, E. L.; Kirner, J . F.; Evans, W. J .; Watson, P. L.;
Abdel-Meguid, S. S.; Tavanaiepour, I.; Day, V. W. Proc. Natl. Acad.
Sci. U.S.A. 1978, 75, 1056. (b) Day, V. W.; Tavanaiepour, I.; Abdel-
Meguid, S. S.; Kirner, J . F.; Goh, L.-Y.; Muetterties, E. L. Inorg. Chem.
1982, 21, 657. (c) Choi, H. W.; Gravin, R. M.; Muetterties, E. L. J .
Chem. Soc., Chem. Commun. 1979, 1085.
(5) (a) Cowley, A. H.; Kemp, R. A.; Wilburn, J . C. Inorg. Chem. 1981,
20, 4289. (b) Cowley, A. H.; Kemp, R. A.; Ebsworth, E. A. V.; Rankin,
D. W.; Walkinshaw, M. D. J . Organomet. Chem. 1984, 265, C19.
(6) (a) McNamara, W. F.; Duesler, E. N.; Paine, R. T.; Ortiz, J . V.;
Ko¨lle, P.; No¨th, H. Organometallics 1986, 5, 380. (b) Hutchins, L. D,;
Reisachen, H.-U.; Wood, G. L.; Duesler, E. N.; Paine, R. T. J .
Organomet. Chem. 1987, 335, 229. (c) Lang, H.; Leise, M.; Zsolnai, L.
J . Organomet. Chem. 1990, 389, 325. (d) Malish, W.; Hirth, U.-A.;
Bright, T. A.; Ko¨b, H.; Erter, T. S.; Hu¨ckmann, S.; Bertagnolli, H.
Angew. Chem., Int. Ed. Engl. 1992, 31, 1525.
(1) (a) Cowley, A. H.; Kemp, R. A. Chem. Rev. 1985, 85, 367. (b)
Sanchez, M.; Mazieres, M. R.; Lamande, L.; Wolf, R. In Multiple Bonds
and Low Coordination in Phosphorus Chemistry; Regitz, M., Scherer,
O. J ., Eds.; Thieme: New York, 1990; Chapter D1. (c) Gudat, D. Coord.
Chem. Rev. 1997, 163, 71.
(2) (a) Doyle, M. P. In Comprehensive Organometallic Chemistry II;
Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press:
Oxford, U.K., 1995; Vol. 12. (b) Wulff, W. D. In Comprehensive
Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson,
G., Eds.; Pergamon Press: Oxford, U.K., 1995; Vol. 12. (c) Hegedus,
L. S. In Comprehensive Organometallic Chemistry II; Abel, E. W.,
Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: Oxford, U.K.,
1995; Vol. 12.
(3) (a) Montemayor, R. G.; Sauer, D. T.; Fleming, S.; Bennett, D.
W.; Thomas, M. G.; Parry, R. W. J . Am. Chem. Soc. 1978, 100, 2231.
(b) Bennett, D. W.; Parry, R. W. J . Am. Chem. Soc. 1979, 101, 755. (c)
Snow, S. S.; J iang, D.-X.; Parry, R. W. Inorg. Chem. 1987, 26, 1629.
(7) (a) Nakazawa, H.; Yamaguchi, Y.; Miyoshi, K. J . Organomet.
Chem. 1994, 465, 193. (b) Nakazawa, H.; Yamaguchi, Y.; Mizuta, T.;
Miyoshi, K. Organometallics 1995, 14, 4173. (c) Yamaguchi, Y.;
Nakazawa, H.; Itoh, T.; Miyoshi, K. Bull. Chem. Soc. J pn. 1996, 69,
983.
(8) (a) Nakazawa, H.; Ohta, M.; Miyoshi, K.; Yoneda, H. Organo-
metallics 1989, 8, 638. (b) Nakazawa, H.; Yamaguchi, Y.; Miyoshi, K.;
Nagasawa. A. Organometallics 1996, 15, 2517. (c) Yamaguchi, Y.;
Nakazawa, H.; Kishishita, M.; Miyoshi, K. Organometallics 1996, 15,
4383.
(9) Nakazawa, H.; Kishishita, M.; Yoshinaga, S.; Yamaguchi, Y.;
Mizuta, T.; Miyoshi, K. J . Organomet. Chem. 1997, 529, 423.
10.1021/om990466u CCC: $18.00 © 1999 American Chemical Society
Publication on Web 10/17/1999

4786 Organometallics, Vol. 18, No. 23, 1999
Kawamura et al.
We have recently developed a new method for the
preparation of cationic phosphenium transition-metal
complexes of Cr,7 Mo,7-9 W,7,9 and Fe,10,11 where an OR
group on a coordinating phosphorus compound is ab-
stracted by a Lewis acid such as BF3‚OEt2 or TMSOTf
(Me3SiOSO2CF3) (eq 1).
5% yield. Thus, we attempted an alternative synthesis
based on a photoreaction of Cp(CO)2RuCH2SiMe3 with
PNN(OMe) (eq 3), resulting in an improved yield (65%).
These complexes were characterized by IR and 1H,
13C, 29Si, 31P, and 119Sn NMR spectra as well as
elemental analysis. They were subjected to reaction with
a Lewis acid such as BF3‚OEt2 or TMSOTf (Me3SiOSO2-
CF3).
Rea ction of Alk yl Com p lexes w ith a Lew is Acid .
A ruthenium-alkyl complex, Cp(CO)(Me)Ru{PNN-
(OMe)} (1a ), was treated with 2 equiv of BF3‚OEt2 at
room temperature and then with PPh3 at -78 °C in CH2-
Cl2 to afford the cationic complex [Cp(CO)Ru(PPh3)-
{PNN(Me)}]BF4 (1c) (eq 4). Complex 1c was character-
We also found some interesting facts that the cationic
phosphenium complexes thus formed exhibit the differ-
ent reactivities depending on the kind of the group 14
element ligand on the transition metal.9,10 For example,
in the reaction of the iron complex Cp(CO)(ER3)Fe-
{PNN(OMe)} (E ) group 14 element; PNN(OMe) stands
for PN(Me)CH2CH2NMe(OMe) in this paper) with a
Lewis acid such as BF3‚OEt2 or TMSOTf, OMe abstrac-
tion as an anion by a Lewis acid uniformly takes place
at the first stage to give the cationic phosphenium iron
complex [Cp(CO)(ER3)Fe{PNN}]+. When E is a carbon
atom, migratory insertion of the phosphenium ligand
into the Fe-C bond or, more simply, alkyl migration
from Fe to phosphenium P occurs to give the 16-electron
cationic complex [Cp(CO)Fe{PNN(CR3)}]+.10a,b When E
is a silicon or a germanium atom, the cationic phosphe-
nium complex is stable and the Fe-Si or an Fe-Ge bond
remains unreacted.10a,b,d In contrast, when E is a tin
atom, not SnR3 itself but one of its alkyl groups migrates
to the phosphenium P to give the stannylene complex
[Cp(CO){PNN(R)}FedSnR2]+.10b,c
ized by NMR and IR spectroscopy as well as elemental
analysis. In the IR spectrum, the absorption band
assigned to the CO stretching vibration was observed
at 1981 cm-1, which was 47 cm-1 higher in frequency
than that for the starting complex 1a , indicative of the
As an extension of our studies, we report here the
comparative reactions of Ru complexes Cp(CO)(ER3)-
Ru{PNN(OMe)} (E ) group 14 element) with a Lewis
acid such as BF3‚OEt2 or TMSOTf together with the
reactivity of the cationic ruthenium phosphenium com-
plexes.
1
formation of the cationic complex. The H and 13C NMR
spectra of 1c showed no resonance due to an OMe group
on the phosphorus atom. Instead, a new resonance was
1
observed at 1.58 ppm (2J PH ) 6.6 Hz) in the H NMR
spectrum and at 25.6 ppm (1J PC ) 13.1 Hz) in the 13C
NMR spectrum, suggesting the formation of a P-Me
direct bond. The 31P NMR spectrum showed two reso-
nances at 44.2 and 137.5 ppm as doublets (2J PP ) 44.1
Hz), which were assigned to PPh3 and PNN(Me),
respectively, indicating that both phosphine ligands
coordinate to the same ruthenium atom.
In the above reaction, it is considered that an Me
group on the phosphorus comes from the ruthenium
atom. In fact, the migration of an alkyl group from the
Ru to the P is proved by a parallel reaction of 2a , which
has a CH2SiMe3 group in place of an Me group on the
Ru in 1a (eq 4). The product, [Cp(CO)Ru(PPh3){PNN-
(CH2SiMe3)}]BF4 (2c), clearly shows that the OMe group
on the P is eliminated and the CH2SiMe3 group on the
Ru migrates to the P coordinating to the Ru.
Resu lts a n d Discu ssion
Ruthenium complexes having a group 14 element
ligand (ER3) and a diamino-substituted phosphite (PN-
N(OMe)) were prepared from the reaction of a ruthe-
n
nium-hydride complex with BuLi and then the corre-
sponding ER3X (E ) C, Si, Ge, Sn) reagent (eq 2).
Considering the products in the reactions of 1a and
2a , the reaction process shown in Scheme 1 could be
postulated. The cationic phosphenium complex b is
produced as an intermediate at the first stage in these
reactions, where an OMe group on the phosphorus
ligand is abstracted as an anion by BF3‚OEt2. However,
b is so reactive that an alkyl group on the ruthenium
atom immediately migrates to the phosphenium phos-
(Trimethylsilyl)methyl complex 2a was obtained in only
(10) (a) Nakazawa, H.; Yamaguchi, Y.; Mizuta, T.; Ichimura, S.;
Miyoshi, K. Organometallics 1995, 14, 4635. (b) Nakazawa, H.;
Yamaguchi, Y.; Kawamura, K.; Miyoshi, K. Organometallics 1997, 16,
4626. (c) Nakazawa, H.; Yamaguchi, Y.; Miyoshi, K. Organometallics
1996, 15, 1337. (d) Kawamura, K.; Nakazawa, H.; Miyoshi, K.
Organometallics 1999, 18, 1517.
(11) Mizuta, T.; Yamasaki, T.; Nakazawa, H.; Miyoshi, K. Organo-
metallics 1996, 15, 1093.

Reaction of Ruthenium Complexes with a Lewis Acid
Organometallics, Vol. 18, No. 23, 1999 4787
Sch em e 1
ppm lower magnetic field than that of the starting
complex. This large downfield shift strongly suggests
the formation of the cationic phosphenium complex.7,8,10
For example, the corresponding cationic phosphenium
complex of Fe, [Cp(CO)(SiMe3)Fe{PNN}]BF4, the struc-
ture of which was determined by X-ray analysis, exhib-
its a resonance in the 31P NMR spectrum at 309.9 ppm,
which is 132.7 ppm lower than that of the starting
complex, Cp(CO)(SiMe3)Fe{PNN(OMe)}.10a In the 1H
and 13C NMR spectra, a doublet assigned to an OMe
group on the phosphorus in 3a disappeared, indicating
that the OMe group was abstracted by a Lewis acid.
The 29Si NMR spectrum showed a doublet at 25.8 ppm
(25.2 ppm for the starting complex), indicating that the
SiMe3 ligand remains intact.
The cationic phosphenium complex 3b thus formed
is fairly stable in the reaction mixture, but several
attempts to isolate 3b as a solid have not been successful
to date. However, 3b could be converted, by the reaction
with PhCH2MgCl, into the isolable Cp(CO)(SiMe3)Ru-
{PNN(CH2Ph)} (3d ), which was fully characterized and
was shown to have the PhCH2 group bound to the
phosphorus atom (eq 5). This is further evidence that
3b is a cationic phosphenium complex.
The reaction of the ruthenium disilane complex 4a
with BF3‚OEt2 was also carried out. Ogino et al. have
reported for transition-metal disilane complexes with
CO ligands that photolysis initiates a loss of CO, and
then a terminal silyl group migrates to a coordinatively
unsaturated metal center with an Si-Si bond cleaved.12
Since a cationic phosphenium complex is also considered
to have an unsaturated site on the P, the migration of
the silyl group to the phosphenium P atom may well be
expected when the cationic phosphenium complex is
formed in the reaction of 4a .
In the reaction of 4a at -78 °C, the cationic phosphe-
nium complex 4b was formed quantitatively, but a
further reaction involving the cleavage of the Si-Si bond
was not observed at all. Warming the reaction mixture
to room temperature led to the formation of unassign-
able products. The cationic phosphenium complex 4b
is stable enough in the reaction mixture at -78 °C, but
the attempts to isolate it as a solid were all in vain
because of the accompanying decomposition. Instead,
the subsequent reaction with PhCH2MgCl gave the
stable neutral complex 4d (eq 5).
In the reaction of 3a or 4a , the silyl or methyl
migration product as found in the reaction of 1a or 2a
was not observed at all, even when PPh3 was added to
the reaction mixture. These results suggest that when
a group 14 element ligand coordinated to Ru is a silicon
atom, the phosphenium complex formed is compara-
tively stable, probably due to the Ru-Si bond being
stronger than the Ru-C bond. Similar results were
obtained when TMSOTf was used as a Lewis acid.
R ea ct ion of a Ger m yl Com p lex w it h a Lew is
Acid . The reaction of the germyl complex Cp(CO)-
(GeMe3)Ru{PNN(OMe)} (5a ) with BF3‚OEt2 or TMSOTf
gave a homogeneous solution, which showed spectro-
scopic data similar to those of the silyl complex 3a .
When BF3‚OEt2 is used, for example, a higher wave-
phorus to give the 16-electron cationic complex [Cp(CO)-
Ru{PNN(ER3)}]+. It is stabilized presumably by the
coordination of BF2OMe via oxygen present in the
solution.10a Such a species was observed in the 31P NMR
spectrum at 179.6 ppm as a singlet, but several at-
tempts to isolate it were not successful due to its
instability. BF2OMe is readily replaced by a stronger
base such as PPh3 to give the stable complex c. These
results obtained here were, as expected, similar to those
for the iron analogues.10a,b
It is generally accepted that a bond between a
transition metal and a main-group element becomes
stronger on going down the periodic table for transition
metals in the same group. With an expectation of
obtaining or detecting the cationic phosphenium com-
plex, we attempted the above reactions at -78 °C.
However, the resonance due to the cationic phosphe-
nium complex was not observed at all in the 31P NMR
spectrum. These results suggest that when a group 14
element ligand coordinated to Ru is a carbon atom, the
phosphenium complex as a whole is very reactive and
the further reaction proceeds immediately; i.e., migra-
tory insertion of the phosphenium ligand into the Ru-C
bond or, more simply, alkyl migration from the Ru to
the phosphenium P occurs to give a 16-electron cationic
complex. Similar results were obtained when TMSOTf
was used as a Lewis acid.
Rea ction of Silyl Com p lexes w ith a Lew is Acid .
In contrast to the reaction of alkyl complexes, the
reaction of a silyl complex, Cp(CO)(SiMe3)Ru{PNN-
(OMe)} (3a ), with BF3‚OEt2 resulted in the formation
of the cationic phosphenium complex [Cp(CO)(SiMe3)-
Ru{PNN}]BF4 (3b) (eq 5). In the 31P NMR spectrum, a
(12) (a) Tobita, H.; Kurita, H.; Ogino, H. Organometallics 1998, 17,
2844. (b) Tobita, H.; Ueno, K.; Shimoi, M.; Ogino, H. J . Am. Chem.
Soc. 1990, 112, 3415. (c) Lickiss, P. D. Chem. Soc. Rev. 1992, 21, 271.
singlet was observed at 286.6 ppm, which was at 135.0

4788 Organometallics, Vol. 18, No. 23, 1999
Kawamura et al.
number shift by 53 cm-1 is observed for νCO in the IR
spectrum compared with the starting complex 5a , the
31P NMR spectrum exhibits a singlet at 289.10 ppm
which is at more than 100 ppm lower magnetic field
electrophilic cleavage reactions.15 Therefore, it is ex-
pected that a cationic phosphenium complex with an
SnnBu3 group is more stable than that with an SnMe3
group, since the stronger Sn-nBu bond retards the
-
n
1
than that of 5a , and the H and 13C NMR spectra show
Bu migration from Sn to P.
the absence of an OMe group and the presence of a
GeMe3 group. Therefore, the product of the reaction is
strongly suggested to be a cationic phosphenium com-
plex, [Cp(CO)(GeMe3)Ru{PNN}]BF4 (5b) (eq 5).
Complex 5b is stable at room temperature in the
reaction mixture and does not undergo germyl migration
from Ru to the phosphenium P. The subsequent reaction
with PhCH2MgCl gave the isolable complex 5d , which
was fully characterized.
As expected, in the reaction of 7a at -78 °C, the
cationic phosphenium complex 7b was cleanly formed
and was stable in the reaction mixture at -78 °C.
Although 7b could not be isolated as a solid, the
spectroscopic data were fully obtained and they con-
firmed 7b to be a cationic phosphenium complex. The
treatment of 7b with PhCH2MgCl at -78 °C yielded 7d
quantitatively, which was isolated and fully character-
ized (eq 6). This is another evidence that 7b is a cationic
phosphenium complex.
Rea ction of Sta n n yl Com p lexes w ith BF 3‚OEt2.
The product in the reaction of stannyl complexes
depends on the kind of Lewis acid used. In the reaction
of the SnMe3 complex Cp(CO)(SnMe3)Ru{PNN(OMe)}
(6a ) with 2 equiv of BF3‚OEt2, the 31P NMR spectrum
showed singlet signals at 286.2 and 185.0 ppm at the
beginning of the reaction. The former resonance, which
is at 134.3 ppm lower magnetic field than that of the
starting complex 6a , can be assigned to a cationic
phosphenium complex where an OMe group on the P is
eliminated as an anion (vide supra). This signal disap-
peared within 30 min, and only the signal at 185.0 ppm
was left. At the same time, the 119Sn NMR spectrum
showed a broad signal at 664.4 ppm, which is at
considerably lower field than that (58.4 ppm) of 6a . This
very low chemical shift strongly suggests the formation
of an RudSn fragment.10b,c,13,14 For example, the stan-
nylene complex [Cp(CO){PNN(Me)}FedSnMe2]OTf ex-
hibits a resonance in the 119Sn NMR spectrum at 495.8
ppm10b,c and (CO)5CrdSn(SCH2CH2)2NtBu at 622.8
ppm.14 On the basis of these results and the formation
of a stannylene complex in the reaction of the corre-
sponding iron complex,10c the product would be best
formulated as [Cp(CO){PNN(Me)}RudSnMe2]BF4 (6e),
where one of the methyl groups on the Sn migrates to
the phosphenium P atom (eq 6). However, 6e has proved
too reactive to isolate as a solid to date.
When 7b was gradually warmed to room temperature
in the reaction mixture, the 31P and 119Sn NMR spectra
showed the disappearance of the resonance due to 7b.
Instead, a new resonance probably due to a stannylene
complex 7e appeared at 194.8 ppm in the 31P NMR
spectrum and at 674.67 ppm in the 119Sn NMR spec-
trum. However, several attempts to isolate 7e were also
unsuccessful due to its instability.
Similarly, reaction of the SnPh3 complex 8a with BF3‚
119
OEt2 was also attempted. In this case, the 31P and
-
Sn NMR measurements revealed the formation of
several kinds of complexes. The Sn-C bond15 for 8a is
the weakest among 6a -8a , which may cause the
complicated reactions involving Sn-Ph bond cleavage
(vide infra). We did not analyze the products in detail.
In the reaction of stannyl complexes 6a and 7a with
BF3‚OEt2, it is clearly shown that an OMe group on the
phosphorus is first abstracted as an anion to give a
cationic phosphenium complex. Then it undergoes alkyl
migration from Sn to P to give a stannylene complex.
Rea ction of Sta n n yl Com p lexes w ith Tr im eth -
ylsilyl Tr ifla te (TMSOTf). In contrast to the reaction
with BF3‚OEt2, the reaction of stannyl complexes with
TMSOTf gave a different product. In the reaction of the
SnMe3 complex 6a in hexane, the stannylene complex
[Cp(CO){PNN(OMe)}RudSnMe2]OTf (6f) was obtained
as a white powder (eq 7), which was characterized by
NMR and IR spectroscopy as well as elemental analysis.
The IR spectrum of 6f showed a CO stretching absorp-
tion at 1939 cm-1, which is 22 cm-1 higher than that of
the starting complex 6a , suggesting that the product
has cationic character. In the 119Sn NMR spectrum, a
doublet was observed at 494.1 ppm (J PSn ) 311.2 Hz),
which is at 435.7 ppm lower magnetic field than that
of 6a . This large downfield shift suggests the formation
of the stannylene complex (vide supra).10b,c,13,14 The 31P
NMR spectrum did not exhibit any significant change
in the chemical shift, indicating that the phosphite
ligand coordinated to Ru remained intact in the reac-
The reaction of the SnnBu3 complex 7a with BF3‚OEt2
was also carried out. It has been reported that an Sn-
nBu bond is less reactive than an Sn-Me bond in
(13) Tzschach, A.; J urkschat, K.; Scheer, M.; Meunier-Piret, J .; van
Meerssche, M. J . Organomet. Chem. 1983, 259, 165.
(14) (a) Lappert, M. F.; Rowe, R. S. Coord. Chem. Rev. 1990, 100,
267. (b) Petz, W. Chem. Rev. 1986, 86, 1019.
(15) Wardell, J . L. In Chemistry of Tin; Harrison, P. G., Ed.;
Chapman and Hall: New York, 1989; Chapter 5, p 170.

Reaction of Ruthenium Complexes with a Lewis Acid
Organometallics, Vol. 18, No. 23, 1999 4789
F igu r e 1. ORTEP drawing of 8a showing the atom-
numbering scheme. The thermal ellipsoids are drawn at
the 50% probability level.
F igu r e 2. ORTEP drawing of 8f showing the atom-
numbering scheme. The thermal ellipsoids are drawn at
the 50% probability level.
1
tion, which was also confirmed by the H and 13C NMR
Ta ble 1. Su m m a r y of Cr ysta l Da ta for 8a a n d 8f
spectra. In the 1H NMR spectrum, it was confirmed that
one of methyl groups on Sn was eliminated. Similar
results were obtained in the reactions of 7a and 8a to
give the corresponding stannylene complexes 7f and 8f,
respectively (eq 7), and the X-ray analysis established
the structure for 8f, which is found to be a stannylene
complex stabilized by both an OTf anion and an OMe
oxygen (vide infra).
8a
8f
formula
fw
cryst syst
space group
a, Å
C29H33N2O2RuPSn C24H28F3N2O5RuPSSn
692.30
monoclinic
P21/n
18.024(7)
15.546(6)
10.621(5)
101.50(3)
2916(2)
4
764.31
monoclinic
P21/n
18.487(8)
12.007(6)
13.997(5)
105.56(3)
2993(2)
4
b, Å
c, Å
â, deg
V, Å3
In solution, there may be an equilibrium for these
stannylene complexes obtained here between a base-
stabilized stannylene form and a base-free one. For
Z
Dcalcd, g cm-3
µ, cm-1
1.58
1.80
14.5
14.9
cryst size, mm
radiation (λ, Å)
scan technique
scan range, deg
0.37 × 0.37 × 0.20 0.30 × 0.30 × 0.25
1
example, the H and 13C NMR spectra of 6f show that
Mo KR (0.710 73) Mo KR (0.710 73)
ω-2θ
ω-2θ
the two Me groups on Sn are magnetically equivalent,
indicating that when an OTf anion is freed from the Sn,
fast rotation of the SnMe2 group takes place around the
Ru-Sn bond.
3 < 2θ < 57
3 < 2θ < 53
7533
no. of unique data 9358
no. of unique data 5269
with Fo > 3σ(Fo)
R
Rw
5098
0.034
0.041
0.031
0.032
In the reaction with TMSOTf, an OMe elimination
reaction observed on treatment with BF3‚OEt2 was not
observed at all; however, one of the R groups on Sn is
selectively abstracted. Although it is not easy to eluci-
date where the selectivity comes from, it should be noted
that an OTf anion can encourage the cleavage of an
Sn-R bond, as is shown in the following example.
Addition of NaOTf to a solution containing a cationic
phosphenium iron complex, [Cp(CO)(SnnBu3)Fe{PNN}]-
BF4, promotes a migration of one nBu group from the
Sn to the phosphenium P to give a stannylene complex,
[Cp(CO){PNN(nBu)}FedSnnBu2]OTf.10b Coordination of
the OTf oxygen to the Sn to give a five-coordinated Sn
(hypervalent Sn) may trigger an R migration from Sn
to P. Therefore, it may be considered that the coordina-
tion ability of OTf- is responsible for the interesting
selectivity found here.
In the reaction of Cp(CO)(SnR3)M{PNN(OMe)} with
TMSOTf, an R group is abstracted from a stannyl group
for the ruthenium complex, whereas an OMe group is
abstracted from a phosphite ligand for the iron complex.10b,c
This may be explained from the following differences
between the Fe and Ru complexes: (i) in the O atom
basicity of an OMe group, (ii) in the strength of an Sn-R
bond, (iii) in the thermodynamic stability of the product,
and (iv) in the energy of the transition state of the
reaction, for example. However, where the difference in
the reactivity comes from is not clear at present.
Cr ysta l Str u ctu r es of 8a and 8f. X-ray structure
analyses of 8a and 8f were undertaken. The ORTEP
drawings of 8a and 8f are displayed in Figures 1 and 2,
respectively. Crystal data and selected bond distances
and angles are summarized in Tables 1-3.
These complexes have normal piano-stool configura-
tions; the ruthenium has a cyclopentadienyl ligand
bonded in an η5 fashion, a terminal CO ligand, a
diamino-substituted phosphite ligand, and a tin ligand.
Comparison of the structures of 8a and 8f reveals that
the Ru-Sn bond is ca. 0.04 Å shorter for 8f than for
8a . However, the Ru-Sn bond (2.577 Å) for 8f is not
shortened in comparison with various Ru-SnR3 com-
plexes previously reported, where Ru-Sn single-bond
lengths between 2.55 and 2.69 Å have been measured.16
(16) Holt, M. S.; Wilson, W. L.; Nelson, J . H. Chem. Rev. 1989, 89,
11.

4790 Organometallics, Vol. 18, No. 23, 1999
Kawamura et al.
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for 8a
Sch em e 2
Bond Distances
Sn(1)-Ru(1)
Sn(1)-C(12)
Sn(1)-C(18)
Sn(1)-C(24)
Ru(1)-P(1)
Ru(1)-C(1)
P(1)-O(2)
2.617(1)
2.177(2)
2.181(3)
2.164(3)
2.239(1)
1.858(3)
1.612(3)
1.665(3)
P(1)-N(2)
O(1)-C(1)
O(2)-C(2)
N(1)-C(3)
N(1)-C(4)
N(2)-C(5)
N(2)-C(6)
C(4)-C(5)
1.662(3)
1.148(4)
1.438(2)
1.421(5)
1.447(5)
1.423(6)
1.440(6)
1.447(6)
P(1)-N(1)
Bond Angles
Ru(1)-Sn(1)-C(12)
Ru(1)-Sn(1)-C(18)
Ru(1)-Sn(1)-C(24)
C(12)-Sn(1)-C(18)
C(12)-Sn(1)-C(24)
C(18)-Sn(1)-C(24)
Sn(1)-Ru(1)-P(1)
Sn(1)-Ru(1)-C(1)
P(1)-Ru(1)-C(1)
Ru(1)-P(1)-O(2)
Ru(1)-P(1)-N(1)
Ru(1)-P(1)-N(2)
O(2)-P(1)-N(1)
111.6(1)
117.5(1)
121.0(1)
99.0(1)
101.1(1)
103.3(1)
93.3(1)
85.1(1)
88.9(1)
111.4(1)
119.0(2)
118.9(2)
108.3(2)
O(2)-P(1)-N(2)
N(1)-P(1)-N(2)
P(1)-O(2)-C(2)
P(1)-N(1)-C(3)
P(1)-N(1)-C(4)
C(3)-N(1)-C(4)
P(1)-N(2)-C(5)
P(1)-N(2)-C(6)
C(5)-N(2)-C(6)
Ru(1)-C(1)-O(1)
N(1)-C(4)-C(5)
N(2)-C(5)-C(4)
105.0(2)
92.0(2)
121.0(3)
125.2(3)
114.5(3)
120.1(3)
114.6(3)
124.4(3)
119.2(4)
177.5(3)
108.4(4)
109.9(4)
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for 8f
Bond Distances
Sn(1)-Ru(1)
Sn(1)‚‚‚O(2)
Sn(1)-O(3)
Sn(1)-C(7)
Sn(1)-C(13)
Ru(1)-P(1)
Ru(1)-C(1)
P(1)-O(2)
2.577(1)
2.711(2)
2.253(3)
2.147(3)
2.147(3)
2.251(1)
1.841(4)
1.632(2)
1.653(3)
P(1)-N(2)
O(1)-C(1)
O(2)-C(2)
N(1)-C(3)
N(1)-C(4)
N(2)-C(5)
N(2)-C(6)
C(4)-C(5)
1.649(3)
1.144(5)
1.443(5)
1.434(6)
1.450(6)
1.445(5)
1.444(5)
1.463(6)
complex of ruthenium. These results are very similar
to those of an iron analogue, [Cp(CO){PNN(Me)}Fed
SnMe2]OTf,10c except in the manner of stabilization of
the stannylene Sn by a base, where one of the nitrogen
atoms on P acts as a donor in place of an OMe oxygen
in 8f.
P(1)-N(1)
Bond Angles
Ru(1)-Sn(1)‚‚‚O(2)
Ru(1)-Sn(1)-O(3)
Ru(1)-Sn(1)-C(7)
Ru(1)-Sn(1)-C(13)
O(2)‚‚‚Sn(1)-O(3)
O(3)-Sn(1)-C(7)
O(3)-Sn(1)-C(13)
C(7)-Sn(1)-C(13)
Sn(1)-Ru(1)-P(1)
Sn(1)-Ru(1)-C(1)
P(1)-Ru(1)-C(1)
Ru(1)-P(1)-O(2)
Ru(1)-P(1)-N(1)
Ru(1)-P(1)-N(2)
O(2)-P(1)-N(1)
71.9(1)
108.2(1)
128.6(1)
121.9(1)
168.8(1)
87.4(1)
97.2(1)
103.2(1)
83.3(1)
86.1(1)
91.4(2)
105.1(1)
121.6(2)
120.7(1)
107.9(2)
O(2)-P(1)-N(2)
N(1)-P(1)-N(2)
Sn(1)‚‚‚O(2)-P(1)
Sn(1)‚‚‚O(2)-C(2)
P(1)-O(2)-C(2)
P(1)-N(1)-C(3)
P(1)-N(1)-C(4)
C(3)-N(1)-C(4)
P(1)-N(2)-C(5)
P(1)-N(2)-C(6)
C(5)-N(2)-C(6)
Ru(1)-C(1)-O(1)
N(1)-C(4)-C(5)
N(2)-C(5)-C(4)
108.1(2)
92.5(2)
92.2(1)
Con clu sion
The results in reactions of ruthenium complexes Cp-
(CO)(ER3)Ru{PNN(OMe)} (a ) (E ) group 14 element)
with a Lewis acid are summarized in Scheme 2. When
BF3‚OEt2 is used, a cationic phosphenium complex (b)
is obtained with an OMe group abstraction in the initial
step irrespective of the kind of E. However, the succes-
sive reaction depends on the kind of E. When E is a
carbon atom, migratory insertion of the phosphenium
ligand into the Ru-C bond takes place, and a subse-
quent reaction with PPh3 gives c. When E is a silicon
or a germanium atom, the cationic phosphenium com-
plex (b) is comparatively stable and an Ru-Si or an
Ru-Ge bond remains unreacted. When E is a tin atom,
one of R groups on the Sn migrates to the phosphenium
P to give a stannylene complex (e). These observations
are very similar to those of the iron analogues. The
reactions with another Lewis acid, TMSOTf, exhibit
reactivities similar to those with BF3‚OEt2, except when
E is a tin atom. In the reaction of a stannyl complex of
Ru with TMSOTf, one of the R groups on the Sn is
directly abstracted to give another stannylene complex
(f). This result is quite different from that of the iron
case.
140.7(2)
122.4(2)
124.7(3)
114.3(3)
120.9(4)
115.5(3)
125.6(3)
118.8(3)
177.5(3)
108.8(3)
107.7(4)
For 8f, the tin atom is five-coordinate with a geometry
described best as distorted trigonal bipyramidal, with
two oxygens (O(2) and O(3)) occupying the axial sites:
the Ru(1)Sn(1)C(7)C(13) unit is nearly planar (the sum
of angles around Sn amounts to 353.7°), and the O(2)-
Sn(1)-O(3) angle is 168.8°. In comparison with the
structures of O-base-stabilized stannylene complexes
reported previously,10c,14,17 the Sn(1)-O(2) bond length
(2.253 Å) is reasonable, whereas the Sn(1)-O(3) bond
is slightly longer (2.711 Å) but significantly shorter than
the sum of van der Waals radii (3.70 Å).18 Therefore, 8f
is best described as a doubly base stabilized stannylene
Exp er im en ta l Section
(17) For example: (a) Balch, A. L.; Oram, D. E. Organometallics
1988, 7, 155. (b) Almedia, J . F.; Dixon, K. R.; Eaborn, C.; Hitchcock,
P. B.; Pidcock, A.; Vinaixa, S. J . Chem. Soc., Chem. Commun. 1982,
1315.
(18) Huheey, J . E. In Inorganic Chemistry; Harper & Row: New
York, 1983.
Gen er a l Rem a r k s. All reactions were carried out under
an atmosphere of dry nitrogen by using standard Schlenk tube
techniques. All solvents were purified by distillation: ether,
THF, and benzene were distilled from sodium/benzophenone,

Reaction of Ruthenium Complexes with a Lewis Acid
Organometallics, Vol. 18, No. 23, 1999 4791
heptane, hexane, and pentane were distilled from sodium
metal, and CH2Cl2 and ClCH2CH2Cl were distilled from P2O5.
All solvents were stored under a nitrogen atmosphere. BF3‚
OEt2 and TMSOTf were distilled prior to use. PNN(OMe) was
prepared according to the literature method.19 Other reagents
employed in this research were used as received. Column
chromatography was carried out quickly in the air on Merck
aluminum oxide 90 (No. 1.01097).
mg, 0.70 mmol, 71%). Anal. Calcd for C12H21N2O2PRu: C,
40.33; H, 5.92; N, 7.84. Found: C, 40.35; H, 5.82; N, 7.82. IR
1
(νCO, cm-1, in CH2Cl2): 1924. H NMR (δ, in CDCl3): 0.13 (d,
J PH ) 3.9 Hz, 3H, RuCH3), 2.65 (d, J PH ) 11.0 Hz, 3H, NCH3),
2.68 (d, J PH ) 10.5 Hz, 3H, NCH3), 3.08 (m, 2H, NCH2), 3.28
(d, J PH ) 11.6 Hz, 3H, OCH3), 3.33 (m, 2H, NCH2), 4.98 (s,
5H, C5H5). 13C NMR (δ, in CDCl3): -33.18 (d, J PC ) 13.7 Hz,
RuCH3), 33.25 (d, J PC ) 11.8 Hz, NCH3), 33.89 (d, J PC ) 12.4
Hz, NCH3), 51.23 (s, NCH2), 51.39 (d, J PC ) 1.3 Hz, NCH2),
51.48 (d, J PC ) 9.4 Hz, OCH3), 85.67 (d, J PC ) 3.1 Hz, C5H5),
207.07 (d, J PC ) 28.7 Hz, CO). 31P NMR (δ, in CDCl3): 152.10
(s).
IR spectra were recorded on a Shimadzu FTIR-8100A
spectrometer. A J EOL LA-300 multinuclear spectrometer was
used to obtain 1H, 13C, 29Si, 31P, and 119Sn NMR spectra. The
reference was as follows: for 1H and 13C NMR data, Si(CH3)4
as an internal standard; for 29Si NMR data, Si(CH3)4 as an
external standard; for 31P NMR data, 85% H3PO4 as an
external standard; for 119Sn NMR data, SnMe4 as an external
standard. Elemental analyses were performed on a Perkin-
Elmer 2400CHN elemental analyzer.
2a was obtained from ClCH2SiMe3 as a colorless crystal.
Yield: 5%. Anal. Calcd for C15H29N2O2PRuSi: C, 41.94; H,
6.81; N, 6.52. Found: C, 42.22; H, 7.03; N, 6.23. IR (νCO, cm-1
,
in CH2Cl2): 1914. 1H NMR (δ, in CDCl3): -0.65 (dd, J PH
12.1 Hz, J HH ) 2.9 Hz, 1H, RuCH2), -0.04 (s, 9H, SiCH3), 0.04
(dd, J PH ) 12.1 Hz, J HH ) 2.4 Hz, 1H, RuCH2), 2.65 (d, J PH
)
)
P r ep a r a tion of Cp (CO)(H)Ru {P NN(OMe)}. Ru3(CO)12
(1000 mg, 1.56 mmol) was added to a solution of CpH (1.30
mL, 15.8 mmol) in heptane (100 mL) in a Schlenk tube, and
the reaction mixture was heated under reflux for 2 h. The
initial deep red solution became a clear yellow solution,
indicating the formation of Cp(CO)2RuH.20 To this solution,
which was cooled to room temperature, was added PNN(OMe)
(0.69 mL, 4.69 mmol), and the reaction mixture was heated
to 100 °C for 10 min to complete the reaction. After filtration
to remove insoluble materials, the filtrate was concentrated
to ca. 10 mL under reduced pressure to give a yellow suspen-
sion. The supernatant was removed by cannula, and the
resulting residue was washed with pentane and dried in vacuo
to yield a yellow powder of the title compound (1157 mg, 3.37
mmol, 72%). Although the 1H NMR spectrum showed that the
product includes a small amount of impurity probably due to
cyclopentadiene, it was used for the following reactions as a
starting complex without further purification.
10.4 Hz, 3H, NCH3), 2.71 (d, J PH ) 10.6 Hz, 3H, NCH3), 3.11
(m, 2H, NCH2), 3.32 (d, J PH ) 11.6 Hz, 3H, OCH3), 3.35 (m,
2H, NCH2), 4.97 (s, 5H, C5H5). 13C NMR (δ, in CDCl3): -30.11
(d, J PC ) 10.0 Hz, RuCH2), 2.49 (s, SiCH3), 33.39 (d, J PC
)
11.2 Hz, NCH3), 33.81 (d, J PC ) 13.0 Hz, NCH3), 51.36 (s,
NCH2), 51.50 (d, J PC ) 9.3 Hz, OCH3), 51.52 (s, NCH2), 85.38
(d, J PC ) 3.1 Hz, C5H5), 207.38 (d, J PC ) 29.2 Hz, CO). 29Si
NMR (δ, in CDCl3): 8.49 (s). 31P NMR (δ, in CDCl3): 151.33
(s).
3a was obtained from ClSiMe3 as a white powder. Yield:
72%. Anal. Calcd for C14H27N2O2PRuSi: C, 40.47; H, 6.55; N,
6.74. Found: C, 40.53; H, 6.38; N, 6.75. IR (νCO, cm-1, in CH2-
1
Cl2): 1917. H NMR (δ, in CDCl3): 0.25 (s, 9H, SiCH3), 2.63
(d, J PH ) 11.6 Hz, 3H, NCH3), 2.71 (d, J PH ) 11.0 Hz, 3H,
NCH3), 3.08 (m, 2H, NCH2), 3.22 (d, J PH ) 11.9 Hz, 3H, OCH3),
3.33 (m, 2H, NCH2), 4.95 (d, J PH ) 0.6 Hz, C5H5). 13C NMR (δ,
in CDCl3): 9.36 (s, SiCH3), 33.70 (d, J PC ) 11.8 Hz, NCH3),
33.71 (d, J PC ) 11.8 Hz, NCH3), 50.69 (d, J PC ) 1.2 Hz, NCH2),
50.95 (d, J PC ) 12.4 Hz, OCH3), 51.43 (d, J PC ) 1.9 Hz, NCH2),
84.92 (d, J PC ) 2.5 Hz, C5H5), 206.32 (d, J PC ) 24.2 Hz, CO).
29Si NMR (δ, in CDCl3): 25.21 (d, J PSi ) 17.3 Hz). 31P NMR
(δ, in CDCl3): 153.64 (s).
It is possible to obtain the title compound as a pure form.
The yellow powder obtained above was loaded on an alumina
column, the colorless band eluted with benzene/hexane (1/1)
was collected, and the solvents were removed in vacuo to give
a white powder. Crystallization from a hot hexane solution
gave a colorless crystal of the title compound. Yield: <10%.
Anal. Calcd for C11H19N2O2PRu: C, 38.48; H, 5.58; N, 8.16.
Found: C, 38.65; H, 5.49; N, 8.08. IR (νCO, cm-1, in benzene):
1935. 1H NMR (δ, in C6D6): -11.67 (d, J PH ) 33.3 Hz, 1H,
RuH), 2.54 (d, J PH ) 12.1 Hz, 3H, NCH3), 2.62 (d, J PH ) 12.1
Hz, 3H, NCH3), 2.64 (m, 2H, NCH2), 2.88 (m, 2H, NCH2), 3.07
(d, J PH ) 11.7 Hz, 3H, OCH3), 4.99 (d, J PH ) 0.7 Hz, 5H, C5H5).
13C NMR (δ, in C6D6): 33.86 (d, J PC ) 11.8 Hz, NCH3), 34.21
(d, J PC ) 13.1 Hz, NCH3), 50.72 (s, NCH2), 50.79 (s, NCH2),
51.16 (d, J PC ) 9.9 Hz, OCH3), 83.08 (d, J PC ) 2.5 Hz, C5H5),
205.10 (d, J PC ) 24.2 Hz, CO). 31P NMR (δ, in C6D6): 163.44.
4a was obtained from ClSiMe2SiMe3 as a colorless crystal.
Yield: 66%. Anal. Calcd for C16H33N2O2PRuSi2: C, 40.57; H,
7.02; N, 5.91. Found: C, 40.59; H, 6.88; N, 5.98. IR (νCO, cm-1
,
in CH2Cl2): 1922. 1H NMR (δ, in CDCl3): 0.05 (s, 9H,
RuSiSiCH3), 0.28 (s, 3H, RuSiCH3), 0.38 (s, 3H, RuSiCH3), 2.65
(d, J PH ) 11.6 Hz, 3H, NCH3), 2.71 (d, J PH ) 11.2 Hz, 3H,
NCH3), 3.08 (m, 2H, NCH2), 3.23 (d, J PH ) 11.9 Hz, 3H, OCH3),
3.34 (m, 2H, NCH2), 4.97 (d, J PH ) 0.6 Hz, 5H, C5H5). 13C NMR
(δ, in CDCl3): -0.29 (s, RuSiSiCH3), 3.46 (s, SiCH3), 5.26 (s,
SiCH3), 33.69 (d, J PC ) 12.8 Hz, NCH3), 33.81 (d, J PC ) 13.1
Hz, NCH3), 50.75 (s, NCH2), 50.93 (d, J PC ) 12.4 Hz, OCH3),
51.43 (s, NCH2), 84.72 (d, J PC ) 2.5 Hz, C5H5), 205.46 (d, J PC
) 25.5 Hz, CO). 29Si NMR (δ, in CDCl3): -11.54 (s, RuSiSi),
-0.84 (d, J PSi ) 15.5 Hz, RuSiSi). 31P NMR (δ, in CDCl3):
151.26 (s).
P r ep a r a tion of Cp (CO)(ER3)Ru {P NN(OMe)} (ER3
)
Me (1a ), CH2SiMe3 (2a ), SiMe3 (3a ), SiMe2SiMe3 (4a ),
GeMe3 (5a ), Sn Me3 (6a ), Sn n Bu 3 (7a ), Sn P h 3 (8a )) fr om
Cp (CO)(H)Ru {P NN(OMe)}. In a typical procedure, nBuLi
(0.63 mL, 1.57 M of hexane solution, 0.99 mmol) was added to
a solution of Cp(CO)(H)Ru{PNN(OMe)} (340 mg, 0.99 mmol)
in THF (5 mL) at -78 °C. The solution was stirred for 20 min,
and then MeI (0.062 mL, 0.99 mmol) was added. The reaction
mixture was warmed to room temperature and stirred for 3
h. After the volatiles were removed under reduced pressure,
the residue was loaded on an alumina column and the column
eluted with CH2Cl2. The yellow band developed was collected
and was reloaded on an alumina column. The colorless band
eluted with CH2Cl2/hexane (1/4) was collected, and the solvents
were removed in vacuo to give a colorless crystal of 1a (251
5a was obtained from ClGeMe3 as a white powder. Yield:
78%. Anal. Calcd for C14H27GeN2O2PRu: C, 36.55; H, 5.92; N,
6.09. Found: C, 36.75; H, 5.84; N, 5.96. IR (νCO, cm-1, in CH2-
1
Cl2): 1917. H NMR (δ, in CDCl3): 0.33 (s, 9H, GeCH3), 2.64
(d, J PH ) 10.6 Hz, 3H, NCH3), 2.68 (d, J PH ) 10.1 Hz, 3H,
NCH3), 3.07 (m, 2H, NCH2), 3.21 (d, J PH ) 11.9 Hz, 3H, OCH3),
3.30 (m, 2H, NCH2), 4.92 (d, J PH ) 0.8 Hz, 5H, C5H5). 13C NMR
(δ, in CDCl3): 7.93 (s, GeCH3), 33.64 (d, J PC ) 13.7 Hz, NCH3),
33.69 (d, J PC ) 13.5 Hz, NCH3), 50.66 (s, NCH2), 50.87 (d, J PC
) 12.4 Hz, OCH3), 51.34 (d, J PC ) 2.5 Hz, NCH2), 83.88 (d,
J PC ) 2.5 Hz, C5H5), 206.14 (d, J PC ) 25.5 Hz, CO). 31P NMR
(δ, in CDCl3): 153.26 (s).
6a was obtained from ClSnMe3 as a white powder. Yield:
78%. Anal. Calcd for C14H27N2O2PRuSn: C, 33.22; H, 5.38; N,
5.53. Found: C, 33.21; H, 5.46; N, 5.43. IR (νCO, cm-1, in CH2-
(19) Ramirez, F.; Patwardham, A. V.; Kugler, H. J .; Smith, C. P. J .
Am. Chem. Soc. 1967, 89, 6276.
(20) Humphries, A. P.; Knox, S. A. R. J . Chem. Soc., Dalton Trans.
1975, 1710.
1
Cl2): 1917. H NMR (δ, in CDCl3): 0.15 (s, with Sn satellites,

4792 Organometallics, Vol. 18, No. 23, 1999
Kawamura et al.
J SnH ) 42.9, 41.3 Hz, 9H, SnCH3), 2.63 (d, J PH ) 10.6 Hz, 3H,
NCH3), 2.67 (d, J PH ) 11.7 Hz, 3H, NCH3), 3.03 (m, 2H, NCH2),
3.21 (d, J PH ) 11.9 Hz, 3H, OCH3), 3.34 (m, 2H, NCH2), 4.91
(d, J PH ) 0.4 Hz, 5H, C5H5). 13C NMR (δ, in CDCl3): -4.34 (s,
with Sn satellites, J SnC ) 210.1, 201.4 Hz, SnCH3), 33.73 (d,
J PC ) 13.7 Hz, NCH3), 33.86 (d, J PC ) 13.1 Hz, NCH3), 50.67
(s, NCH2), 51.06 (d, J PC ) 11.8 Hz, OCH3), 51.34 (d, J PC ) 1.9
Similarly, the formations of 4b, 5b, and 7b were confirmed
when 4a , 5a , and 7a were respectively used as starting
complexes. 4b: IR (νCO, cm-1, in CH2Cl2) 1967. 13C NMR (δ,
in CH2Cl2): -1.67 (s, RuSiSiCH3), 3.90 (s, RuSiCH3), 5.04 (s,
RuSiCH3), 33.74 (d, J PC ) 14.3 Hz, NCH3), 51.67 (s, NCH2),
87.58 (d, J PC ) 3.7 Hz, C5H5), 200.54 (d, J PC ) 19.9 Hz, CO);
29Si NMR (δ, in CH2Cl2) -13.03 (s, RuSiSi), -3.46 (d, J PSi
)
Hz, NCH2), 82.28 (d, J PC ) 2.5 Hz, C5H5), 205.74 (d, J PC
)
16.7 Hz, RuSiSi); 31P NMR (δ, in CH2Cl2) 286.13 (s). 5b: IR
24.9 Hz, CO). 31P NMR (δ, in CDCl3): 151.92 (s, with Sn
satellites, J SnP ) 200.5, 191.6 Hz). 119Sn NMR (δ, in CDCl3):
58.39 (d, J PSn ) 202.3 Hz).
(νCO, cm-1, in CH2Cl2) 1970; H NMR (δ, in CH2Cl2) 0.43 (s,
1
9H, GeCH3), 2.89 (d, J PH ) 13.2 Hz, 6H, NCH3), 3.71 (m, 4H,
NCH2), 5.39 (s, 5H, C5H5); 13C NMR (δ, in CH2Cl2) 8.26 (s,
GeCH3), 33.62 (d, J PC ) 14.3 Hz, NCH3), 51.79 (s, NCH2), 87.36
(s, C5H5), 200.86 (d, J PC ) 21.8 Hz, CO); 31P NMR (δ, in CH2-
Cl2) 289.10 (s). 7b: IR (νCO, cm-1, in CH2Cl2) 1962; 13C NMR
(δ, in CH2Cl2) 14.66 (s, with Sn satellites, J SnC ) 273.5, 260.4
Hz, SnCH2CH2CH2CH3), 15.23 (s, SnCH2CH2CH2CH3), 27.57
(s, with Sn satellites, J SnC ) 66.5 Hz, SnCH2CH2CH2CH3),
30.02 (s, with Sn satellites, J SnC ) 19.9 Hz, SnCH2CH2CH2-
CH3), 33.96 (d, J PC ) 14.9 Hz, NCH3), 51.92 (s, NCH2), 85.47
(d, J PC ) 2.5 Hz, C5H5), 200.86 (d, J PC ) 19.9 Hz, CO); 31P
NMR (δ, in CH2Cl2) 287.64 (s, with Sn satellites, J SnP ) 182.7
Hz); 119Sn NMR (δ, in CH2Cl2) 88.46 (d, J PSn ) 185.2 Hz).
P r ep a r a tion of [Cp (CO)(P P h 3)Ru {P NN(Me)}]BF 4 (1c).
BF3‚OEt2 (0.023 mL, 0.18 mmol) was added to a solution of
1a (33 mg, 0.092 mmol) in CH2Cl2 (1.5 mL) at room temper-
ature, and the solution was stirred for 30 min. After it was
cooled to -78 °C, the solution was treated with PPh3 (48 mg,
0.18 mmol), warmed to room temperature, stirred for 2 h, and
then loaded on an alumina column. After elution with CH2-
Cl2, the colorless band eluted with CH2Cl2/acetone (4/1) was
collected and dried in vacuo to give a white powder. Crystal-
lization from a CH2Cl2/ether layer gave a colorless crystal of
1c (25 mg, 0.037 mmol, 40%). Anal. Calcd for C29H33BF4N2-
OP2Ru: C, 51.57; H, 4.92; N, 4.15. Found: C, 51.55; H, 4.87;
N, 4.12. IR (νCO, cm-1, in CH2Cl2): 1981. 1H NMR (δ, in
CDCl3): 1.58 (d, J PH ) 6.6 Hz, 3H, PCH3), 2.25 (d, J PH ) 12.5
Hz, 3H, NCH3), 2.52 (d, J PH ) 12.1 Hz, 3H, NCH3), 2.60 (m,
1H, NCH2), 2.84 (m, 3H, NCH2), 5.23 (s, 5H, C5H5), 7.34 (s,
6H, C6H5), 7.45 (s, 9H, C6H5). 13C NMR (δ, in CDCl3): 25.57
(d, J PC ) 13.1 Hz, PCH3), 32.93 (d, J PC ) 8.1 Hz, NCH3), 33.52
(d, J PC ) 7.5 Hz, NCH3), 50.73 (s, NCH2), 51.13 (s, NCH2),
89.16 (s, C5H5), 128.65 (d, J PC ) 11.2 Hz, m-C6H5), 131.05 (d,
J PC ) 2.5 Hz, p-C6H5), 133.24 (d, J PC ) 11.2 Hz, o-C6H5), 134.18
(d, J PC ) 51.0 Hz, ꢀ-C6H5), 202.10 (dd, J PC ) 19.9, 18.0 Hz,
CO). 31P NMR (δ, in CDCl3): 47.05 (d, J PP ) 34.0 Hz, PPh3),
137.20 (d, J PP ) 33.9 Hz, PNN(Me)).
7a was obtained from ClSnnBu3 as a white powder. Yield:
79%. Anal. Calcd for C23H45N2O2PRuSn: C, 43.68; H, 7.17; N,
4.43. Found: C, 43.91; H, 7.41; N, 4.34. IR (νCO, cm-1, in CH2-
1
Cl2): 1915. H NMR (δ, in CDCl3): 0.88 (m, 6H, SnCH2CH2-
CH2CH3), 0.90 (t, J HH ) 7.3 Hz, 9H, SnCH2CH2CH2CH3), 1.32
(sext, J HH ) 7.3 Hz, 6H, SnCH2CH2CH2CH3), 1.48 (m, 6H,
SnCH2CH2CH2CH3), 2.64 (d, J PH ) 11.2 Hz, 3H, NCH3), 2.67
(d, J PH ) 11.7 Hz, 3H, NCH3), 3.05 (m, 2H, NCH2), 3.21 (d,
J PH ) 11.7 Hz, 3H, OCH3), 3.34 (m, 2H, NCH2), 4.94 (s, 5H,
C5H5). 13C NMR (δ, in CDCl3): 13.66 (s, with Sn satellites, J SnC
) 217.5, 208.8 Hz, SnCH2CH2CH2CH3), 13.82 (s, SnCH2CH2-
CH2CH3), 27.94 (s, with Sn satellites, J SnC ) 54.7 Hz, SnCH2-
CH2CH2CH3), 30.37 (s, with Sn satellites, J SnC ) 16.8 Hz,
SnCH2CH2CH2CH3), 33.81 (d, J PC ) 12.4 Hz, NCH3), 33.89 (d,
J PC ) 12.4 Hz, NCH3), 50.78 (s, NCH2), 50.97 (d, J PC ) 13.1
Hz, OCH3), 51.44 (d, J PC ) 1.9 Hz, NCH2), 81.89 (d, J PC ) 2.5
Hz, C5H5), 205.97 (d, J PC ) 24.9 Hz, CO). 31P NMR (δ, in
CDCl3): 154.76 (s, with Sn satellites, J SnP ) 182.7, 173.8 Hz).
119Sn NMR (δ, in CDCl3): 75.15 (d, J PSn ) 181.7 Hz).
8a was obtained from ClSnPh3 as a colorless crystal. Yield:
74%. Anal. Calcd for C29H33N2O2PRuSn: C, 50.31; H, 4.80; N,
4.05. Found: C, 50.44; H, 4.69; N, 4.03. IR (νCO, cm-1, in CH2-
Cl2): 1929. 1H NMR (δ, in CDCl3): 2.34 (d, J PH ) 11.2 Hz,
3H, NCH3), 2.55 (d, J PH ) 11.7 Hz, 3H, NCH3), 2.82 (m, 2H,
NCH2), 2.97 (d, J PH ) 12.2 Hz, 3H, OCH3), 3.12 (m, 2H, NCH2),
4.97 (s, 5H, C5H5), 7.19 (m, 9H, C6H5), 7.54 (m, 6H, C6H5). 13
C
NMR (δ, in CDCl3): 33.34 (d, J PC ) 12.4 Hz, NCH3), 33.55 (d,
J PC ) 12.4 Hz, NCH3), 50.64 (s, NCH2), 51.15 (d, J PC ) 12.4
Hz, OCH3), 51.18 (d, J PC ) 1.2 Hz, NCH2), 82.78 (d, J PC ) 2.5
Hz, C5H5), 126.67 (s, with Sn satellites, J SnC ) 8.8 Hz, p-C6H5),
127.21 (s, with Sn satellites, J SnC ) 38.5 Hz, m-C6H5), 137.23
(s, with Sn satellites, J SnC ) 36.0 Hz, o-C6H5), 137.23 (s, with
Sn satellites, J SnC ) 303.3 Hz, 289.6 Hz, ꢀ-C6H5), 205.44 (d,
J PC ) 24.2 Hz, CO). 31P NMR (δ, in CDCl3): 149.63 (s, with
Sn satellites, J SnP ) 231.7, 220.5 Hz). 119Sn NMR (δ, in
CDCl3): 10.11 (d, J PSn ) 229.7 Hz).
Alt er n a t ive P r ep a r a t ion of Cp (CO)(CH2SiMe3)R u -
{P NN(OMe)} (2a ). Cp(CO)2RuCH2SiMe3 (151 mg, 0.49 mmol),
benzene (10 mL), and PNN(OMe) (0.080 mL, 0.54 mmol) were
placed in a Pyrex Schlenk tube, and the solution was irradiated
with a 400 W medium-pressure mercury arc lamp at 0 °C for
4 h. After the solvent was removed under reduced pressure,
the resulting residue was loaded on an alumina column and
eluted with CH2Cl2. The yellow band developed was collected
and was reloaded on an alumina column. The colorless band
eluted with CH2Cl2/hexane (1/9) was collected, and the solvents
were removed in vacuo to give a white powder of 2a (137 mg,
0.32 mmol, 65%).
Typ ica l P r ep a r a tion of [Cp (CO)(ER3)Ru {P NN}]BF 4
(ER3 ) SiMe3 (3b), SiMe2SiMe3 (4b), GeMe3 (5b), Sn n Bu 3
(7b)). In a typical procedure, a solution of 3a (147 mg, 0.38
mmol) in CH2Cl2 (1.5 mL) was cooled to -78 °C, and then BF3‚
OEt2 (0.096 mL, 0.76 mmol) was added. After the solution was
warmed to room temperature, it was directly subjected to
spectroscopic measurements, which confirmed the formation
of 3b. IR (νCO, cm-1, in CH2Cl2): 1971. 13C NMR (δ, in CH2-
Cl2): 9.43 (d, J PC ) 1.9 Hz, SiCH3), 33.96 (d, J PC ) 13.1 Hz,
NCH3), 52.13 (s, NCH2), 88.40 (s, C5H5), 201.26 (d, J PC ) 20.5
Hz, CO). 29Si NMR (δ, in CH2Cl2): 25.78 (d, J PSi ) 18.4 Hz).
31P NMR (δ, in CH2Cl2): 286.63 (s).
P r ep a r a tion of [Cp (CO)(P P h 3)Ru {P NN(CH2SiMe3)}]-
BF 4 (2c). Complex 2c was prepared from 2a , BF3‚OEt2, and
PPh3 in the same manner as that of 1c. Yield: 46%. Anal.
Calcd for C32H41BF4N2OP2RuSi: C, 51.41; H, 5.53; N, 3.75.
Found: C, 51.20; H, 5.66; N, 3.73. IR (νCO, cm-1, in CH2Cl2):
1
1971. H NMR (δ, in CDCl3): -0.03 (s, 9H, SiCH3), 1.13 (dd,
J PH ) 15.6 Hz, J HH ) 6.2 Hz, 1H, PCH2), 1.38 (dd, J PH ) 15.6
Hz, J HH ) 6.2 Hz, 1H, PCH2), 2.35 (d, J PH ) 11.9 Hz, 3H,
NCH3), 2.50 (d, J PH ) 11.9 Hz, 3H, NCH3), 2.90 (m, 1H, NCH2),
3.07 (m, 3H, NCH2), 5.22 (s, 5H, C5H5), 7.44 (m, 15H, C6H5).
13C NMR (δ, in CDCl3): 0.16 (s, SiCH3), 33.57 (d, J PC ) 9.3
Hz, NCH3), 34.21 (d, J PC ) 9.4 Hz, NCH3), 35.30 (d, J PC ) 11.2
Hz, PCH2), 50.71 (s, NCH2), 50.85 (s, NCH2), 89.40 (s, C5H5),
128.77 (d, J PC ) 10.5 Hz, m-C6H5), 131.10 (s, p-C6H5), 133.30
(d, J PC ) 11.2 Hz, o-C6H5), 134.50 (d, J PC ) 49.6 Hz, ꢀ-C6H5),
203.04 (t, J PC ) 19.2 Hz, CO). 29Si NMR (δ, in CDCl3): -0.62
(d, J PSi ) 12.5 Hz). 31P NMR (δ, in CDCl3): 47.23 (d, J PP
)
29.2 Hz, PPh3), 139.39 (d, J PP ) 29.2 Hz, PNN(CH2SiMe3)).
P r ep a r a tion of Cp (CO)(SiMe3)Ru {P NN(CH2P h )} (3d ).
BF3‚OEt2 (0.13 mL, 1.04 mmol) was added to a solution of 3a
(235 mg, 0.57 mmol) in CH2Cl2 (5.0 mL) at -78 °C, and the
solution was stirred for 30 min. The solution was treated with
PhCH2MgCl (0.40 mL, 2.0 M of THF solution, 0.80 mmol) at
-78 °C, warmed to room temperature, and stirred for 1 h. After
the volatiles were removed in vacuo, the residue was extracted

Reaction of Ruthenium Complexes with a Lewis Acid
Organometallics, Vol. 18, No. 23, 1999 4793
with pentane (10 mL × 4). After the pentane extract was
evaporated to dryness under reduced pressure, the resulting
residue was loaded on an alumina column. The colorless band
eluted with CH2Cl2 was collected and dried in vacuo. Crystal-
lization from hexane gave a colorless crystal of 3d (131 mg,
0.28 mmol, 49%). Anal. Calcd for C20H31N2OPRuSi: C, 50.51;
powder of 7d . Yield: 45%. Anal. Calcd for C29H49N2OPRuSn:
C, 50.30; H, 7.13; N, 4.05. Found: C, 50.13; H, 7.28; N, 3.75.
1
IR (νCO, cm-1, in CH2Cl2): 1907. H NMR (δ, in CDCl3): 0.89
(t, J HH ) 7.2 Hz, 9H, SnCH2CH2CH2CH3), 0.95 (m, 6H, SnCH2-
CH2CH2CH3), 1.33 (sext, J HH ) 7.2 Hz, 6H, SnCH2CH2CH2-
CH3), 1.50 (m, 6H, SnCH2CH2CH2CH3), 2.26 (m, 2H, NCH2),
2.64 (m, 2H, NCH2), 2.66 (d, J PH ) 11.4 Hz, 3H, NCH3), 2.73
(d, J PH ) 11.4 Hz, 3H, NCH3), 3.13 (m, 2H, PCH2), 4.92 (s,
5H, C5H5), 7.00 (m, 2H, C6H5), 7.17 (m, 3H, C6H5). 13C NMR
(δ, in CDCl3): 13.71 (s, with Sn satellites, J SnC ) 211.7, 202.5
Hz, SnCH2CH2CH2CH3), 13.79 (s, SnCH2CH2CH2CH3), 27.92
(s, with Sn satellites, J SnC ) 53.1 Hz, SnCH2CH2CH2CH3),
30.43 (s, with Sn satellites, J SnC ) 18.3 Hz, SnCH2CH2CH2-
CH3), 34.34 (d, J PC ) 12.8 Hz, NCH3), 34.73 (d, J PC ) 12.8 Hz,
NCH3), 50.57 (s, NCH2), 51.18 (s, NCH2), 51.81 (d, J PC ) 13.7
Hz, PCH2), 82.66 (s, C5H5), 125.63 (d, J PC ) 2.8 Hz, p-C6H5),
127.79 (d, J PC ) 2.8 Hz, m-C6H5), 129.94 (d, J PC ) 3.7 Hz,
H, 6.57; N, 5.89. Found: C, 50.24; H, 6.54; N, 5.88. IR (νCO
,
cm-1, in CH2Cl2): 1910. 1H NMR (δ, in CDCl3): 0.34 (s, 9H,
SiCH3), 2.34 (m, 2H, NCH2), 2.70 (m, 2H, NCH2), 2.70 (d, J PH
) 11.2 Hz, 3H, NCH3), 2.73 (d, J PH ) 11.2 Hz, 3H, NCH3),
3.07 (dd, J PH ) 14.7 Hz, J HH ) 2.2 Hz, 1H, PCH2), 3.27 (dd,
J PH ) 14.7 Hz, J HH ) 2.2 Hz, 1H, PCH2), 4.97 (s, 5H, C5H5),
7.02 (m, 2H, C6H5), 7.19 (m, 3H, C6H5). 13C NMR (δ, in
CDCl3): 9.92 (s, SiCH3), 34.18 (d, J PC ) 12.4 Hz, NCH3), 34.52
(d, J PC ) 11.2 Hz, NCH3), 50.51 (s, NCH2), 50.96 (d, J PC ) 10.6
Hz, PCH2), 51.16 (s, NCH2), 85.56 (s, C5H5), 125.58 (s, p-C6H5),
127.76 (s, m-C6H5), 129.87 (d, J PC ) 3.1 Hz, o-C6H5), 137.02
(d, J PC ) 10.0 Hz, ꢀ-C6H5), 206.90 (d, J PC ) 20.5 Hz, CO). 29Si
NMR (δ, in CDCl3): 22.89 (d, J PSi ) 14.9 Hz). 31P NMR (δ, in
CDCl3): 153.55 (s).
o-C6H5), 137.15 (d, J PC ) 11.0 Hz, ꢀ-C6H5), 206.77 (d, J PC
)
20.2 Hz, CO). 31P NMR (δ, in CDCl3): 154.76 (s, with Sn
satellites, J SnP ) 151.5 Hz). 119Sn NMR (δ, in CDCl3): 63.38
(d, J PSn ) 154.3 Hz).
P r ep a r a tion of Cp (CO)(SiMe2SiMe3)Ru {P NN(CH2P h )}
(4d ). Complex 4d was prepared from 4a , BF3‚OEt2, and
PhCH2MgCl in the same manner as that of 3d . The crude
product was purified by alumina column chromatography. The
colorless band eluted with CH2Cl2/hexane (1/1) was collected
and dried in vacuo. Crystallization from hexane gave a
colorless crystal of 4d . Yield: 46%. Anal. Calcd for C22H37N2-
OPRuSi2: C, 49.51; H, 6.99; N, 5.25. Found: C, 49.71; H, 6.95;
N, 5.00. IR (νCO, cm-1, in CH2Cl2): 1913. 1H NMR (δ, in
CDCl3): 0.08 (s, 9H, RuSiSiCH3), 0.36 (s, 3H, RuSiCH3), 0.45
(s, 3H, RuSiCH3), 2.33 (m, 2H, NCH2), 2.69 (m, 2H, NCH2),
2.69 (d, J PH ) 11.0 Hz, 3H, NCH3), 2.73 (d, J PH ) 11.0 Hz, 3H,
NCH3), 3.07 (dd, J PH ) 14.7 Hz, J HH ) 3.5 Hz, 1H, PCH2),
3.27 (dd, J PH ) 14.7 Hz, J HH ) 3.5 Hz, 1H, PCH2), 4.97 (s, 5H,
C5H5), 7.01 (m, 2H, C6H5), 7.18 (m, 3H, C6H5). 13C NMR (δ, in
CDCl3): -0.04 (s, RuSiSiCH3), 4.37 (s, RuSiCH3), 5.02 (s,
RuSiCH3), 34.13 (d, J PC ) 12.4 Hz, NCH3), 34.72 (d, J PC ) 11.2
Hz, NCH3), 50.61 (s, NCH2), 50.69 (d, J PC ) 10.6 Hz, PCH2),
51.17 (s, NCH2), 85.43 (d, J PC ) 0.9 Hz, C5H5), 125.65 (d, J PC
) 2.5 Hz, p-C6H5), 127.80 (d, J PC ) 1.9 Hz, m-C6H5), 129.90
(d, J PC ) 3.7 Hz, o-C6H5), 136.97 (d, J PC ) 10.6 Hz, ꢀ-C6H5),
206.20 (d, J PC ) 21.8 Hz, CO). 29Si NMR (δ, in CDCl3): -11.03
(s, PSiSi), 22.89 (d, J PSi ) 13.7 Hz, PSiSi). 31P NMR (δ, in
CDCl3): 152.45 (s).
P r epar ation of [Cp(CO){P NN(Me)}Ru dSn Me2]BF4 (6e).
A solution of 6a (89 mg, 0.18 mmol) in CH2Cl2 (1.0 mL) was
cooled to -78 °C, and then BF3‚OEt2 (0.088 mL, 0.70 mmol)
was added. After the solution was warmed to room tempera-
ture, it was directly subjected to spectroscopic measurements.
31P NMR (δ, in CH2Cl2): 184.95 (s, with Sn satellites, J SnP
230.6 Hz). 119Sn NMR (δ, in CH2Cl2): 664.1 (br).
)
P r ep a r a t ion of [Cp (CO){P NN(n Bu )}R u dSn n Bu 2]BF 4
(7e). A solution of 7a (232 mg, 0.37 mmol) in CH2Cl2 (1.5 mL)
was cooled to -78 °C, and then BF3‚OEt2 (0.093 mL, 0.74
mmol) was added. After the solution was warmed to room
temperature, it was directly subjected to spectroscopic mea-
surements. 31P NMR (δ, in CH2Cl2): 194.78 (s, with Sn
satellites, J SnP ) 195.6 Hz). 119Sn NMR (δ, in CH2Cl2): 674.67
(br).
P r ep a r a t ion of [Cp (CO){P NN(OMe)}R u dSn Me2]OTf
(6f). TMSOTf (0.043 mL, 0.24 mmol) was added to a solution
of 6a (120 mg, 0.24 mmol) in hexane (5.0 mL), and the solution
was stirred for 2 days at room temperature to give a white
suspension. The supernatant was removed by cannula, and
the residue was washed with ether and pentane and dried in
vacuo to give a white powder of 6f (97 mg, 0.15 mmol, 64%).
Anal. Calcd for C14H24F3N2O5PRuSSn: C, 26.27; H, 3.78; N,
4.38. Found: C, 26.29; H, 3.43; N, 4.33. IR (νCO, cm-1, in CH2-
P r ep a r a tion of Cp (CO)(GeMe3)Ru {P NN(CH2P h )} (5d ).
Complex 5d was prepared from 5a , BF3‚OEt2, and PhCH2MgCl
in the same manner as that of 3d . The crude product was
purified by alumina column chromatography. The colorless
band eluted with CH2Cl2/hexane (1/1) was collected and dried
in vacuo. Crystallization from hexane gave a white powder of
5d . Yield: 35%. Anal. Calcd for C20H31GeN2OPRu: C, 46.18;
1
Cl2): 1939. H NMR (δ, in CDCl3): 0.77 (s, with Sn satellites,
J SnH ) 38.1 Hz, 6H, SnCH3), 2.66 (d, J PH ) 11.4 Hz, 3H, NCH3),
2.68 (d, J PH ) 12.5 Hz, 3H, NCH3), 3.10 (m, 2H, NCH2), 3.21
(d, J PH ) 11.7 Hz, 3H, OCH3), 3.36 (m, 2H, NCH2), 5.13 (s,
C5H5). 13C NMR (δ, in CDCl3): 7.15 (s, with Sn satellites, J SnC
) 174.4 Hz, SnCH3), 33.22 (d, J PC ) 12.5 Hz, NCH3), 33.75 (d,
J PC ) 12.4 Hz, NCH3), 50.86 (s, NCH2), 51.09 (s, NCH2), 52.21
H, 6.01; N, 5.39. Found: C, 46.44; H, 6.02; N, 5.15. IR (νCO
,
cm-1, in CH2Cl2): 1911. 1H NMR (δ, in CDCl3): 0.36 (s, 9H,
GeCH3), 2.28 (m, 2H, NCH2), 2.60 (m, 2H, NCH2), 2.63 (d, J PH
) 11.2 Hz, 3H, NCH3), 2.64 (d, J PH ) 11.2 Hz, 3H, NCH3),
3.00 (dd, J PH ) 14.7 Hz, J HH ) 2.6 Hz, 1H, PCH2), 3.15 (dd,
J PH ) 14.7 Hz, J HH ) 2.6 Hz, 1H, PCH2), 4.97 (s, 5H, C5H5),
6.95 (m, 2H, C6H5), 7.14 (m, 3H, C6H5). 13C NMR (δ, in
CDCl3): 8.45 (s, GeCH3), 34.27 (d, J PC ) 12.4 Hz, NCH3), 34.56
(d, J PC ) 12.4 Hz, NCH3), 50.52 (d, J PC ) 9.3 Hz, PCH2), 50.58
(s, NCH2), 51.17 (s, NCH2), 84.66 (d, J PC ) 1.9 Hz, C5H5),
125.60 (d, J PC ) 2.5 Hz, p-C6H5), 127.78 (d, J PC ) 1.9 Hz,
(d, J PC ) 11.8 Hz, OCH3), 83.23 (s, C5H5), 119.15 (q, J FC
)
317.8 Hz, CF3), 203.43 (d, J PC ) 22.3 Hz, CO). 31P NMR (δ, in
CDCl3): 150.18 (s, with Sn satellites, J SnP ) 313.5, 300.1 Hz).
119Sn NMR (δ, in CDCl3): 494.06 (d, J PSn ) 311.2 Hz).
P r ep a r a tion of [Cp (CO){P NN(OMe)}Ru dSn n Bu 2]OTf
(7f). TMSOTf (0.085 mL, 0.47 mmol) was added to a solution
of 7a (297 mg, 0.47 mmol) in ClCH2CH2Cl (10 mL). The
solution was heated to 60 °C and stirred for 12 h. After the
reaction mixture was concentrated to ca. 2 mL, it was directly
subjected to spectroscopic measurements, which confirmed the
1
m-C6H5), 129.91 (d, J PC ) 3.7 Hz, o-C6H5), 137.03 (d, J PC
)
formation of 7f. H NMR (δ, in ClCH2CH2Cl): 2.53 (d, J PH
)
10.6 Hz, ꢀ-C6H5), 206.90 (d, J PC ) 20.5 Hz, CO). 31P NMR (δ,
in CDCl3): 152.58 (s).
11.6 Hz, 3H, NCH3), 2.58 (d, J PH ) 12.5 Hz, 3H, NCH3), 3.00
(m, 2H, NCH2), 3.10 (d, J PH ) 11.7 Hz, 3H, OCH3), 3.24 (m,
2H, NCH2), 5.07 (s, 5H, C5H5). Detailed assignments of the
SnnBu2 resonances were not possible, due to interference by
resonances of the nBu protons abstracted by a Lewis acid
present in the solution. 13C NMR (δ, in ClCH2CH2Cl): 8.85 (s,
with Sn satellites, J SnC ) 312.6, 299.0 Hz, SnCH2CH2CH2CH3),
13.71 (s, SnCH2CH2CH2CH3), 27.57 (s, with Sn satellites, J SnC
P r ep a r a tion of Cp (CO)(Sn n Bu 3)Ru {P NN(CH2P h )} (7d ).
Complex 7d was prepared from 7a , BF3‚OEt2, and PhCH2MgCl
in the same manner as that of 3d . The crude product was
purified by alumina column chromatography. The colorless
band that eluted with CH2Cl2/hexane (1/1) was collected and
dried in vacuo. Crystallization from hexane gave a white

4794 Organometallics, Vol. 18, No. 23, 1999
Kawamura et al.
) 52.2 Hz, SnCH2CH2CH2CH3), 29.41 (s, with Sn satellites,
J SnC ) 19.3 Hz, SnCH2CH2CH2CH3), 33.07 (d, J PC ) 12.4 Hz,
NCH3), 33.60 (d, J PC ) 12.4 Hz, NCH3), 50.94 (s, NCH2), 51.25
(s, NCH2), 51.98 (d, J PC ) 11.8 Hz, OCH3), 83.31 (d, J PC ) 2.5
Hz, C5H5), 204.10 (d, J PC ) 22.4 Hz, CO). The CF3 carbon was
not observed. 31P NMR (δ, in ClCH2CH2Cl): 150.89 (s, with
Sn satellites, J SnP ) 284.1, 276.2 Hz). 119Sn NMR (δ, in ClCH2-
CH2Cl): 532.09 (d, J PSn ) 281.2 Hz).
dimensions were obtained by least squares from the angular
setting of 29 accurately centered reflections with 32° < 2θ <
35° for 8a and from that of 24 such reflections with 32° < 2θ
< 35° for 8f. P21/n was selected as the space group for both
8a and 8f, which led to successful refinements. Reflection
intensities were collected in the usual manner at 25 ( 1 °C,
and 3 reflections checked after every 200 reflections showed
no decrease in intensity.
The structures were solved by a direct method with the
program SIR92.21 The positions of the hydrogen atoms were
calculated by assuming idealized geometries. Absorption and
extinction corrections were then applied,22,23 and several cycles
of full-matrix least-squares refinement with anisotropic tem-
perature factors for non-hydrogen atoms led to final values of
P r ep a r a t ion of [Cp (CO){P NN(OMe)}R u dSn P h 2]OTf
(8f). TMSOTf (0.051 mL, 0.28 mmol) was added to a solution
of 8a (197 mg, 0.28 mmol) in CH2Cl2 (10 mL) at -78 °C. The
solution was warmed to room temperature and stirred for 12
h. The solution was then concentrated to ca. 2 mL under
reduced pressure. After slow addition of hexane (10 mL), it
was kept in a refrigerator to give colorless crystals, which were
collected by filtration, washed with ether and hexane, and
dried in vacuo, yielding 8f (104 mg, 0.14 mmol, 48%). Anal.
Calcd for C24H28F3N2O5PRuSSn: C, 37.72; H, 3.69; N, 3.67.
Found: C, 37.70; H, 3.51; N, 3.66. IR (νCO, cm-1, in CH2Cl2):
1950. 1H NMR (δ, in CDCl3): 2.28 (d, J PH ) 11.4 Hz, 3H,
NCH3), 2.69 (d, J PH ) 12.5 Hz, 3H, NCH3), 3.01 (m, 2H, NCH2),
3.03 (d, J PH ) 11.7 Hz, 3H, OCH3), 3.22 (m, 2H, NCH2), 5.35
(d, J PH ) 1.5 Hz, 5H, C5H5), 7.36 (m, 6H, C6H5), 7.65 (m, 4H,
C6H5), 13C NMR (δ, in CDCl3): 32.73 (d, J PC ) 11.8 Hz, NCH3),
33.58 (d, J PC ) 12.4 Hz, NCH3), 50.85 (s, NCH2), 51.03 (s,
NCH2), 52.07 (d, J PC ) 11.8 Hz, OCH3), 83.45 (d, J PC ) 2.5
Hz, C5H5), 128.14 (s, with Sn satellites, J SnC ) 44.3 Hz,
m-C6H5), 128.73 (s, with Sn satellites, J SnC ) 10.0 Hz, p-C6H5),
135.50 (s, with Sn satellites, J SnC ) 47.9 Hz, o-C6H5), 150.18
R ) 0.034 and Rw ) 0.041 for 8a and R ) 0.031 and Rw
)
0.032 for 8f. All calculations were performed on an SGI Indy
R5000 computer using the program system CRYSTAN-GM24
with neutral atom scattering factors from Cromer and Waber.25
Ack n ow led gm en t. This work was supported by
Grant-in-Aid for Science Research (Grant No. 10440195
and No. 11‚05085) and a Grant-in-Aid on Priority Area
of Interelement Chemistry (Grant No. 11120235) from
the Ministry of Education, Science, Sports and Culture
of J apan.
Su p p or tin g In for m a tion Ava ila ble: Tables giving posi-
tional and thermal parameters for 8a and 8f. This material is
available free of charge via the Internet at http://pubs.acs.org.
(s, ꢀ-C6H5), 203.48 (d, J PC ) 21.8 Hz, CO). The CF3 carbon was
119
not observed. In principle, satellite peaks due to 117Sn and
-
OM990466U
Sn for the ꢀ-C6H5 carbon should be observed. However, they
were not observed due to the low concentration of the sample.
(21) Altomare, A.; Cascarano, G.; Giacovazzo, C.; Gurgliardi, A.;
Burla, M. C.; Polidori, G.; Camalli, M. SIR-92; University of Bari, Bari,
Italy, 1992.
(22) Katayama, C. Acta Crystallogr., Sect. A 1986, A42, 19.
(23) Coppens, P.; Hamilton, W. C. Acta Crystallogr., Sect. A 1970,
A26, 71.
(24) Crystan-GM: A Computer Program for the Solution and
Refinement of Crystal Structures from X-ray Diffraction Data; Mac-
Science Co., Ltd., Yokohama, J apan, 1995.
(25) Cromer, D. T.; Waber, J . T. In International Tables for X-ray
Crystallography; Kynoch Press: Birmingham, U.K., 1974; Vol. IV,
Table 2.2 A.
31P NMR (δ, in CDCl3): 148.04 (s, with Sn satellites, J SnP
)
329.7 Hz). 119Sn NMR (δ, in CDCl3): 306.96 (d, J PSn ) 332.6
Hz).
X-r a y Str u ctu r e Deter m in a tion for 8a a n d 8f. Crystal-
lographic and experimental details of X-ray crystal structure
analysis for 8a and 8f are given in Table 1. The suitable
crystals of 8a and 8f were individually mounted on a Mac
Science MXCκ diffractometer and irradiated with graphite-
monochromated Mo KR radiation (λ ) 0.710 73 Å). Unit-cell