Reactions of ruthenium cyclopropenyl complexes containing pentamethylcyclopentadienyl ligands

Article abstract of DOI:10.1021/om000094l

Deprotonation of cationic pentamethylcyclopentadienyl dppp ruthenium vinylidene complexes containing electron-withdrawing groups at the vinylidene ligand yielded cyclopropenyl complexes [Ru]-C=C(Ph)CHR ([Ru] = (η⁵-C₅Me₅)(dppp)Ru, dppp = Ph₂PCH₂CH₂CH₂PPh₂, R = CN, 3a; R = CO₂CH₃, 3b). Insertion of acetone into the three-membered ring of 3a gave the neutral dihydrofuranyl complex [Ru]-C=C(Ph)CH(CN)CMe₂O (4). Electrophilic addition at C_β of 4 afforded cationic carbene complexes [[Ru]=CC(R′)(Ph)CH(CN)C(CH₃)₂O]⁺ (R′ = CH₂CN, 5a; R′ = CH₂CO₂CH₃, 5b; R′ = H, 7; R′ = HgCl, 8). Complexes 5a and 5b transformed to [[Ru]=CC(Ph)=C(CN)C(CH₃)₂O]⁺ (6) by elimination of small organic molecules. Reactivity of ruthenium complexes with a C₅Me₅ ligand is different from those with a C₅H₅ ligand and could be ascribed to electronic and steric effects. Reaction of [Ru]N₃ with ICH₂CN gave [Ru]-NCH₂I (11). Crystal structures of complexes 3a, 4, 6, 7, and 11 are also reported.

Full text of DOI:10.1021/om000094l

Organometallics 2000, 19, 3211-3219
3211
Rea ction s of Ru th en iu m Cyclop r op en yl Com p lexes
Con ta in in g P en ta m eth ylcyclop en ta d ien yl Liga n d s
Chao-Wan Chang,† Ying-Chih Lin,*,‡ Gene-Hsiang Lee,‡ and Yu Wang‡
National Overseas Chinese Student University Preparation School, Linkou, Taipei Hsien,
Taiwan, Republic of China, and Department of Chemistry, National Taiwan University,
Taipei, Taiwan 106, Republic of China
Received February 3, 2000
Deprotonation of cationic pentamethylcyclopentadienyl dppp ruthenium vinylidene com-
plexes containing electron-withdrawing groups at the vinylidene ligand yielded cyclopropenyl
complexes [Ru]-CdC(Ph)CHR ([Ru] ) (η5-C5Me5)(dppp)Ru, dppp ) Ph2PCH2CH2CH2PPh2,
R ) CN, 3a ; R ) CO2CH3, 3b). Insertion of acetone into the three-membered ring of 3a gave
the neutral dihydrofuranyl complex [Ru]-CdC(Ph)CH(CN)CMe2O (4). Electrophilic addition
at Câ of 4 afforded cationic carbene complexes [[Ru]dCC(R′)(Ph)CH(CN)C(CH3)2O]+ (R′ )
CH2CN, 5a ; R′ ) CH2CO2CH3, 5b; R′ ) H, 7; R′ ) HgCl, 8). Complexes 5a and 5b transformed
to [[Ru]dCC(Ph)dC(CN)C(CH3)2O]+ (6) by elimination of small organic molecules. Reactivity
of ruthenium complexes with a C5Me5 ligand is different from those with a C5H5 ligand and
could be ascribed to electronic and steric effects. Reaction of [Ru]N3 with ICH2CN gave [Ru]-
NCH2I (11). Crystal structures of complexes 3a , 4, 6, 7, and 11 are also reported.
In tr od u ction
vinylidene complexes indicated localization of electron
density on Câ (HOMO) and the electron deficiency at
CR.19,20 A study of the reaction of alcohols with ruthe-
nium vinylidene complexes indicated that electron-
withdrawing groups on the acetylide unit or on the
metal facilitate nucleophilic attack on CR.21
Recently we demonstrated that the presence of an
electron-withdrawing group at Cγ of the vinylidene
ligand combined with the cationic character of the
ruthenium complex enhances the acidity of the proton
at Cγ. Thus deprotonation of such complexes could be
readily achieved, and subsequent intramolecular cy-
cloaddition could lead to the formation of cyclopropenyl
complexes.1,2,22,23 For example, [Cp(PPh3)2RudCdC(Ph)-
CH2CN]+ was found to undergo deprotonation to afford
Metal vinylidene complexes have attracted consider-
able attention since they offer the possibility of develop-
ment of new types of organometallic intermediates that
may have unusual reactivity.1-4 Extensive reviews on
this subject have appeared recently.5-7 The best entry
into the transition metal vinylidene complexes is the
addition of electrophiles to the electron-rich carbon of
metal alkynyl complexes.8-18 A theoretical study of
† National Overseas Chinese Student University Preparation School.
‡ National Taiwan University.
(1) Ting, P. C.; Lin, Y. C.; Cheng, M. C.; Wang, Y. Organometallics
1994, 13, 2150.
(2) Chang, C. W.; Ting, P. C.; Lin, Y. C.; Lee, G. H.; Wang, Y. J .
Organomet. Chem. 1998, 553, 417.
(3) Chang, C. W.; Lin, Y. C.; Lee, G. H.; Huang, S. L.; Wang, Y.
Organometallics 1998, 17, 2534.
(4) Chang, C. W.; Lin, Y. C.; Lee, G. H.; Huang, S. L.; Wang, Y.
Organometallics 1999, 18, 982.
(5) Bruce, M. I. Chem. Rev. 1991, 91, 197.
(6) Bruce, M. I.; Swincer, A. G. Adv. Organomet. Chem. 1983, 22,
59.
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Chem. 1990, 30, 1.
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(10) Werner, H.; Hohn, A.; Schulz, M. J . Chem. Soc., Dalton Trans.
1991, 777.
the cyclopropenyl complex Cp(PPh3)2RuCdC(Ph)CHCN.
Unfortunately, without a methoxy substituent, the
three-membered ring readily undergoes electrophilic
addition to cause ring opening in the presence of acid
or other electrophiles. The presence of a methoxy
substituent in the cyclopropenyl ring enhances the
stability of the three-membered ring, and protonation
of such a ruthenium complex yields a cyclopropenylium
complex by loss of methanol. In our study, we also
noticed that replacement of the Cp ligand with a Tp
ligand23 makes one of the phosphines labile, and a facile
substitution reaction was observed for Tp ruthenium
cyclopropenyl complexes. To extend the breadth, we
(11) Schafer, M.; Wolf, J .; Werner, H. J . Chem. Soc., Chem. Com-
mun. 1991, 1341.
(12) Schneider, D.; Werner, H. Angew. Chem. 1991, 103, 710.
(13) Werner, H.; Dirnberger, T.; Hohn, A. Chem. Ber. 1991, 124,
1957.
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10, 3967.
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1992, 11, 4156.
(16) Nakanishi, S.; Goda, K.; Uchiyama, S.; Otsuji, Y. Bull Chem.
Soc. J pn. 1992, 65, 2560.
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H. J . Chem. Soc., Chem. Commun. 1993, 163.
(18) Watatuski, Y.; Koga, N.; Yamazaki, H.; Morokuma, K. J . Am.
Chem. Soc. 1994, 116, 8105.
(19) Kostic, N. M.; Fenske, R. F. Organometallics 1982, 1, 974.
(20) Werner, H.; Wolf, J .; Muller, G.; Kru¨ger, C. Angew. Chem., Int.
Ed. Engl. 1984, 28, 431.
(21) Bruce, M. I.; Swincer, A. G. Aust. J . Chem. 1980, 33, 1471.
(22) Ting, P. C.; Lin, Y. C.; Lee, G. H.; Cheng, M. C.; Wang, Y. J .
Am. Chem. Soc. 1996, 118, 6433.
(23) Lo, Y. H.; Lin, Y. C.; Lee, G. H.; Wang, Y. Organometallics 1999,
18, 982.
10.1021/om000094l CCC: $19.00 © 2000 American Chemical Society
Publication on Web 07/13/2000

3212 Organometallics, Vol. 19, No. 16, 2000
Chang et al.
Sch em e 1
Sch em e 2
have explored the effect of C5Me5 (Cp*) on the chemistry
of the ruthenium cyclopropenyl system. In this paper,
we report an unprecedented acetone insertion into the
cyclopropenyl ring, giving a dihydrofuranyl ligand and
the electrophilic addition at Câ of the five-membered
dihydrofuranyl ligand giving a carbene complex.
yield. The reaction gives yellow crystalline product in
analytically pure form. Single crystals of 3a , suitable
for X-ray diffraction analysis, were obtained when the
reaction is carried out at lower concentration. Complex
3a is stable in air and soluble in CH2Cl2, CHCl3, THF,
and benzene, slightly soluble in acetone and diethyl
ether, but insoluble in n-hexane, CH3CN, and MeOH.
The 31P NMR spectrum of 3a displays two doublet
Resu lts a n d Discu ssion
Syn th esis of Ru th en iu m Vin ylid en e Com p lexes.
Treatment of [Ru]CtPh (1, [Ru] ) Cp*(dppp)Ru, Cp*
) η5-C5Me5, dppp ) Ph2PCH2CH2CH2PPh2) with ICH2-
CN in CH2Cl2 afforded the cationic vinylidene complex
[[Ru]dCdC(Ph)CH2CN]+ (2a ) in 85% yield (Scheme 1).
Unlike other vinylidene complexes,5 which are generally
prepared at room temperature, 2a is prepared by
heating a CH2Cl2 solution of 1 and ICH2CN at reflux
for 1 day. The steric effect of the Cp* ligand may hinder
the electrophilic addition, therefore requiring mild heat-
ing and longer reaction times. Similarly, preparations
of vinylidene complexes [[Ru]dCdC(Ph)CH2R]+ (R )
CO2CH3, 2b; R ) C6F5, 2c; R ) C6H5, 2d ; R ) p-C6H4-
CN, 2e; R ) p-C6H4CF3, 2f) have produced high yields.
All these reactions required mild heating and gave
analytically pure complexes of various colors. The
characteristic deshielded CR resonances in the 13C NMR
spectra of these vinylidene complexes appear as triplets
in the region of δ ) 343 ( 3. The 31P NMR resonance
appears as a singlet at δ ) 35 ( 1 in CDCl3 at room
temperature due to the fluxional behavior of the vin-
ylidene ligand.24,25
2
resonances at δ 48.13 and 45.15 with J P-P ) 49.76 Hz
in CDCl3 arising from the presence of a stereogenic
center in the three-membered ring. In the 1H NMR
spectrum of 3a , the resonance of the methine proton
appears at δ 1.07, and in the 13C{1H} NMR spectrum,
2
the triplet at δ 133.96 with J C-P ) 5.74 Hz is assigned
to CR.
The deprotonation/cyclopropenation reaction also oc-
curs for 2b, giving [Ru]CdC(Ph)CHCO2CH3 (3b) in 77%
yield. This reaction can only be carried out in acetone
and only by using n-Bu4NOH as a proton abstractor.
Previously we reported that deprotonation of the analo-
gous complex22 [(η5-C5H5)(PPh3)2RudCdC(Ph)CH2CO2-
CH3]+ gave the cyclopropenyl complex as a kinetic
product, which transformed to the furanyl complex in
1 h at room temperature. However, we did not observe
such a transformation for 3b in benzene after 3 days at
room temperature. This could be due to steric repulsion
between Cp* and the phenyl substituent on the cyclo-
propenyl ligand. The 31P NMR spectrum of 3b also
displays two doublet resonances at δ 47.73 and 43.00
Cyclop r op en a t ion of Vin ylid en e Com p lexes.
Deprotonation of 2a by n-Bu4NOH is followed by the
expected cyclization, yielding the cyclopropenyl complex
2
1
with J P-P ) 50.18 Hz. In the H NMR spectrum of 3b,
the resonance of the methine proton appears at δ 1.60.
Facile deprotonation of 2a and 2b indicates the acidic
nature of the methylene protons, which may be ascribed
to the combined effect of the cationic character and
electron-withdrawing substituents of the vinylidene
complexes. However, a similar reaction is not observed
for complexes 2c-f with n-Bu4NF, DBU, or KOH.
Analogous Cp vinylidene complexes undergo a depro-
tonation reaction to yield cyclization products.22 There-
[Ru]CdC(Ph)CHCN (3a ) (Scheme 1). Use of acetone or
acetonitrile as a solvent gives a good yield, and use of
other bases such as n-Bu4NF (1 M in THF), DBU (1,8-
diazabicyclo[5.4.0]undecene), or KOH (dissolved in a
minimum amount of H2O) also gives 3a in comparable
(24) Allen, D. L.; Gibson, V. C.; Green, M. L.; Skinner, T. F.;
Bashikin, J .; Grebenik, P. D. J . Chem. Soc., Chem. Commun. 1985,
895.
(25) Consiglio, G.; Morandini, F. Chem. Rev. 1987, 87, 761.

Reactions of Ru Cyclopropenyl Complexes
Organometallics, Vol. 19, No. 16, 2000 3213
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) of (η5-C5Me5)(d p p p )Ru CdC(P h )CHCN (3a )
Ru-P1
Ru-C1
C1-C2
C2-C10
C3-C4
2.2956(5)
2.048(2)
1.601(3)
1.448(3)
1.469(3)
Ru-P2
C1-C3
C2-C3
N1-C10
2.2934(5)
1.313(3)
1.506(3)
1.154(3)
P1-Ru-P2
Ru-C1-C3
C1-Ru-P1
C2-C1-C3
C1-C3-C4
C3-C2-C10
92.45(2)
160.4(3)
88.88(5)
61.3(1)
155.5(2)
118.2(2)
Ru-C1-C2
C1-C2-C3
C1-Ru-P2
C2-C3-C1
C2-C3-C4
C1-C2-C10
136.1(1)
49.9(1)
81.88(5)
68.8(1)
135.4(2)
121.8(2)
single bond, and the C1-C3 distance of 1.313(3) Å is a
regular CdC double bond, indicating coordination of one
sp2 carbon of the cyclopropenyl ligand. Both bond angles
Ru-C1-C3 and C1-C3-C4 (160.4(2)° and 155.5(2)°,
respectively) are greater than that of an idealized sp2
hybridization. The C1-C2 and C2-C3 bond lengths of
1.601(3) and 1.506(3) Å, respectively, are significantly
different, conforming to the favorable cleavage of the
C1-C2 bond.
In ser tion of Aceton e in to th e Cyclop r op en yl
Rin g of 3a . If the bright yellow solution of 3a in acetone
is stored at room temperature for 2 days, the color of
the solution turns yellow-brown. The 31P NMR spectrum
of the mixture indicated formation of two new complexes
F igu r e 1. ORTEP drawing of 3a with thermal ellipsoids
shown at the 30% probability level. For phenyl groups on
dppp, only the ipso carbons are shown.
fore, we conclude that, in the vinylidene system with a
Cp* ligand, a strong electron-withdrawing group on the
vinylidene ligand is necessary to enhance acidity of the
methylene protons for deprotonation.
Previous studies on metal cyclopropenyl deriva-
tives26-30 include the synthesis of iron derivatives from
the reaction of metal carbonylate anions with cyclopro-
penylium cations reported by Bartmann and Gomp-
per,27,31 as well as CO insertion and ring-opening studies
of such systems28,29 by Hughes and co-workers. We
reported the synthesis and chemical reactivity of several
neutral ruthenium cyclopropenyl complexes1,2,22-23 in
which the metal bonds to one C(sp2) atom of the three-
membered cyclopropenyl ring. A few structurally dif-
ferent cyclopropenylidene complexes, mostly prepared
from dichlorocyclopropene,32,33 and a number of π-cy-
clopropene complexes34-37 are also known. The acidity
of the aliphatic protons on the coordinated dppe ligand
in a cationic iron vinylidene complex38 has been em-
ployed for inducing the intramolecular cyclization be-
tween the dppe and the vinylidene ligand.
in a ratio of 2:1. The major product, [Ru]CdC(Ph)CH-
(CN)C(CH3)2O (4), is formed by addition of an acetone
molecule to the three-membered ring of 3a , which is
confirmed by single-crystal X-ray diffraction analysis.
Complex 4 is air stable and soluble in THF, CH2Cl2,
CHCl3, and benzene, moderately soluble in acetone,
acetonitrile, and methanol, and insoluble in hexane.
Thermolysis of 4 at 60 °C afforded 1. The organic portion
from this reaction was not isolated. In the 31P NMR
spectrum of the mixture, two doublet resonances at δ
45.38 and 39.11 with J P-P ) 52.12 Hz are assigned to
1
4. The H NMR spectrum of 4 displays resonances at δ
The molecular structure of 3a has been confirmed by
a single-crystal X-ray diffraction study. An ORTEP
diagram is shown in Figure 1, and selected bond
distances and angles are listed in Table 1. This complex
adopts a distorted three-leg piano stool geometry. The
Ru-C1 distance of 2.048(2) Å is typical for a Ru-C
1.09, 1.22, and 1.57 that are assignable to Cp*, 2CH3,
and CH, respectively.
Complex 4 was recrystallized from THF/hexane (1:3)
to give single crystals, and its molecular structure was
determined by a single-crystal X-ray diffraction study.
An ORTEP diagram is shown in Figure 2, and selected
bond distances and bond angles are given in Table 2.
Complex 4 adopts a distorted three-leg piano stool
geometry with the P1-Ru-P2, P1-Ru-C1, and P2-
Ru-C1 angles being 90.78(8)°, 88.5(2)°, and 86.3(3)°,
respectively. Insertion of an acetone molecule is clearly
seen in the coordinated five-membered dihydrofuranyl
ligand. The Ru-C1 distance of 2.101(7) Å is typical for
a Ru-C single bond, and the C1-C3 distance of 1.371-
(10) Å indicates a CdC double bond. The O1-C1 and
O1-C4 single bond lengths of 1.431(8) and 1.455(9) Å,
respectively, are comparable. The Ru-C1-C2 bond
angle of 136.7(5)° is slightly greater than an sp2
hybridization bond angle; thus O1-C1-C2 and Ru-
C1-O1 bond angles of 108.6(6)° and 113.8(4)°, respec-
tively, are smaller.
(26) Lowe, C.; Shklover, V.; Bosch, H. W.; Berke, H. Chem. Ber.
1993, 126, 1769.
(27) Gompper, R.; Bartmann, E. Angew. Chem., Int. Ed. Engl. 1978,
17, 456.
(28) DeSimone, D. M.; Derrosiers, P. J .; Hughes, R. P. J . Am. Chem.
Soc. 1982, 104, 4842.
(29) Hughes, R. P.; Donaldson, W. A. J . Am. Chem. Soc. 1982, 104,
4846.
(30) Weiss, R.; Priesner, C. Angew. Chem., Int. Ed. Engl. 1978, 17,
457.
(31) Gompper, R.; Bartmann, E. Angew. Chem., Int. Ed. Engl. 1985,
24, 209.
(32) Miki, S.; Ohno, T.; Iwasaki, H.; Yoshida, Z. I. J . Phys. Org.
Chem. 1988, 1, 333.
(33) Yoshida, Z. I. Pure Appl. Chem. 1982, 54, 1059.
(34) Schrock, R. R. Acc. Chem. Res. 1986, 19, 342.
(35) Hughes, R. P.; Reisch, J . W.; Rheingold, A. L. Organometallics
1985, 4, 1754.
(36) Hughes, R. P.; Klaui, W.; Reisch, J . W.; Muller, A.; Rheingold,
A. L. Organometallics 1985, 4, 1761.
(37) Mealli, C,; Midollini, S.; Moneti, S.; Sacconi, L.; Silvestre, J .;
Albright, T. A. J . Am. Chem. Soc. 1982, 104, 59.
(38) Adams, R. D.; Davison, A.; Selegue, J . P. J . Am. Chem. Soc.
1979, 101, 7232.
Acetone is the only reagent found to undergo an
insertion reaction to give 4. Methyl isobutyl ketone,
2-butanone, and 3-pentanone have been used as sol-

3214 Organometallics, Vol. 19, No. 16, 2000
Chang et al.
F igu r e 2. ORTEP drawing of 4 with thermal ellipsoids
shown at the 30% probability level. For phenyl groups on
dppp, only the ipso carbons are shown.
F igu r e 3. ORTEP drawing of 6 with thermal ellipsoids
shown at the 30% probability level. For phenyl groups on
dppp, only the ipso carbons are shown.
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) of
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) of
(η5-C5Me5)(d p p p )Ru CdC(P h )CH(CN)C(CH3)2O (4)
(η5-C5Me5)(d p p p )Ru dCC(P h )dC(CN)C(CH3)2O (6)
Ru-P1
Ru-C1
C2-C3
C3-C11
C1-O1
C4-C12
2.321(2)
2.101(7)
1.55(1)
1.50(2)
1.431(8)
1.46(1)
Ru-P2
C1-C2
C3-C4
C11-N1
C4-O1
C4-C13
2.283(2)
1.37(1)
1.55(1)
1.13(1)
1.455(9)
1.45(1)
Ru-P1
Ru-C1
C2-C3
C3-C4
C3-C11
C4-C12
2.333(1)
1.953(5)
1.378(7)
1.481(8)
1.421(8)
1.514(9)
Ru-P2
C1-C2
O1-C1
O1-C4
C11-N1
C4-C13
2.333(1)
1.500(7)
1.375(6)
1.462(6)
1.136(7)
1.517(7)
Ru-C1-C2
C2-C1-O1
C2-C3-C4
C11-C3-C4
C13-C4-O1
O1-C3-C4
C1-Ru-P2
C3-C2-C5
C3-C4-C13
136.7(5)
108.6(6)
102.9(7)
113.4(9)
108.2(8)
100.9(6)
86.3(3)
Ru-C1-O1
C1-C2-C3
C1-C2-C5
C11-C3-C2
O1-C4-C12
C1-Ru-P1
P1-Ru-P2
C3-C4-C12
C12-C4-C13
113.8(4)
108.0(7)
134.6(8)
110.8(8)
110.9(7)
88.5(2)
90.78(8)
110.0(9)
108.6(9)
C1-Ru-P2
P1-Ru-P2
Ru-C1-C2
C2-C3-C4
C1-C2-C3
C3-C2-C5
C11-C3-C4
C12-C4-C3
C3-C4-C13
C12-C4-C13
86.4(2)
91.97(5)
137.1(4)
111.8(5)
108.5(4)
119.6(5)
121.1(5)
111.5(5)
115.8(5)
111.7(5)
P1-Ru-C1
O1-C1-C2
O1-C1-Ru
C1-O1-C4
C1-C2-C5
C2-C3-C11
O1-C4-C3
O1-C4-C12
O1-C4-C13
86.9(1)
103.1(4)
119.7(3)
116.3(4)
131.2(5)
126.6(5)
99.9(4)
117.2(7)
118.0(8)
108.3(5)
108.8(4)
vents for the reaction of 2a with n-Bu4NOH. In these
solvent systems, 3a formed in good yield, but no
insertion product was observed at room temperature.
Addition of PhNCO, PhNCS, (CF3)2CO, or formaldehyde
to a benzene solution of 3a resulted in ring opening,
yielding 2a , and addition of propanal resulted in de-
composition of 3a , leading to 1. The minor product of
the reaction of 2a with base in the presence of acetone
was not isolated due to decomposition to 1 during
chromatography. However, on the basis of the 31P NMR
spectrum of the mixture displaying two doublet 31P
resonances at δ 28.67, 11.77 (J P-P ) 52.21 Hz) assign-
able for this minor product and the mass spectrum of
the mixture displaying only parent peaks of 4, the
tivity. This is possibly due to the steric effect of the Cp*
ligand. Spectroscopic data of 5 consist of a strongly
deshielded CR resonance as a triplet at around δ 290 in
the 13C NMR spectrum.
Elimination of CH3CN from 5a in CDCl3 generated
the new cationic cyclic carbene complex [[Ru]dCC(Ph)d
C(CN)C(CH3)2O][I] (6) (Scheme 2). The reaction was
complete in 3 days at room temperature, and heating
the solution accelerated the reaction. Complex 5b also
transformed to 6 in solution after 1 week at room
temperature and in refluxing CHCl3 after 1 day. Com-
plex 6 can also be obtained directly by thermolysis of 4
in the presence ICH2CN or BrCH2CO2CH3. The 31P
NMR spectrum of 6 displays a singlet at δ 37.1, and, in
the 13C NMR spectrum of 6, the deshielded triplet CR
resonance at δ 275.0 is characteristic of a carbene
complex.
inverted insertion mode giving [Ru]CdC(Ph)CH(CN)-
OC(CH3)2 (4′) is speculated.
Electr op h ilic Ad d ition s of Ru th en iu m Cyclo-
p en ten yl Com p lex 4. Treatment of 4 with organic
halides XCH2R afforded cationic cyclic carbene com-
The molecular structure of 6 has been confirmed by
a single-crystal X-ray diffraction study. An ORTEP
diagram is shown in Figure 3, and selected bond
distances and bond angles are given in Table 3. This
complex adopts a three-leg piano stool geometry with
the P1-Ru-P2, P1-Ru-C1, and P2-Ru-C1 angles
being 91.97(5)°, 86.93(14)°, and 86.4(2)°, respectively.
The Ru-C1 distance of 1.953(5) Å is typical for a Rud
C double bond. In the five-membered ring, the C2-C3
bond distance of 1.378(7) Å indicates a double bond. The
plexes [[Ru]dCC(CH2R)(Ph)CH(CN)C(CH3)2O][X] (R )
CN, X ) I, 5a ; R ) CO2CH3, X ) Br, 5b) in high yields.
Both 31P NMR spectra display two doublet resonances:
δ 37.30, 31.45 with J P-P ) 48.02 Hz and δ 37.38, 31.94
with J P-P ) 52.91 Hz, assignable to 5a and 5b,
respectively. The five-membered ring contains two ste-
reogenic carbon centers, and two diastereomers were
expected. However, for each compound, we see only one
set of two 31P doublets, indicating high diastereoselec-

Reactions of Ru Cyclopropenyl Complexes
Organometallics, Vol. 19, No. 16, 2000 3215
shorter O1-C1 bond lengths of 1.375(6) Å, relative to
that of O1-C4 of 1.462(6) Å, indicates contribution of
the lone pair of oxygen, thus leading to a stronger
C(sp2)-O single bond. The C1-C2-C5 and C2-C3-
C11 bond angles of 131.2(5)° and 126.6(5)°, respectively,
are consistent with sp2 hybridization for C2 and C3.
Protonation of 4 with CF3COOH occurs also at Câ of
the five-membered ring, yielding the carbene complex
[[Ru]dCCH(Ph)CH(CN)C(CH3)2O][CF3COO] (7) (Scheme
2). This reaction is faster compared to the reaction of 4
with XCH2R (5 min vs 24 h at room temperature). The
protonation resulted in formation of two diastereomers,
giving two sets of doublets of doublets at δ 38.63, 32.97
(J P-P ) 48.03 Hz) and δ 37.09, 31.93 (J P-P ) 48.93 Hz)
in a ratio of 20:1 in the 31P NMR spectrum. Purification
by recrystallization gave only the major isomer. The
characteristic CR resonance of the major isomer of 7
appears as a triplet at δ 290.5 in the 13C NMR spectrum,
F igu r e 4. ORTEP drawing of 7 with thermal ellipsoids
shown at the 30% probability level. For phenyl groups on
dppp, only the ipso carbons are shown.
1
and, in the H NMR spectrum, two singlets appear at δ
Ta ble 4. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) of
5.13 and δ 1.59, assignable to the CHPh and CHCN
groups of the five-membered ring, respectively. The FAB
mass spectrum displays a parent peak at m/e 848.3
attributed to (M+ - CF3COO). In solution, 7 slowly
transformed to 6 by elimination of H2. After 14 days at
room temperature the transformation was not complete
and the ratio of 7:6 was 4:1. Thermolysis of the solution
caused decomposition of 7.
(η5-C5Me5)(d p p p )Ru dCCH(P h )CH(CN)C(CH3)2O (7)
Ru-P1
Ru-C1
C2-C3
C3-C4
C4-C5
C4-C6
2.341(2)
1.943(8)
1.55(1)
1.54(1)
1.50(1)
1.52(1)
Ru-P2
C1-C2
O1-C4
O1-C1
C3-C13
N1-C13
2.331(2)
1.55(1)
1.49(1)
1.33(1)
1.45(1)
1.14(1)
Addition of HgCl2 to 4 resulted in immediate forma-
P1-Ru-P2
P2-Ru-C1
Ru-C1-C2
C2-C3-C4
C3-C2-C7
C1-C2-C7
C3-C4-O1
C3-C2-C7
C3-C4-C5
O1-C4-C5
C5-C4-C6
89.96(8)
89.9(2)
P1-Ru-C1
Ru-C1-O1
O1-C1-C2
C1-C2-C3
C4-C3-C13
C1-O1-C4
C2-C3-C13
C4-C3-C13
C3-C4-C6
O1-C4-C6
87.3(3)
125.2(6)
106.2(7)
103.3(6)
112.5(7)
117.1(6)
115.3(8)
112.5(7)
112.9(8)
105.6(7)
tion of the blue carbene complex [[Ru]dCC(HgCl)(Ph)-
128.2(6)
105.0(7)
116.3(7)
114.1(7)
100.7(6)
116.3(7)
117.0(8)
107.7(7)
111.6(7)
CH(CN)C(CH3)2O][Cl] (8). The presence of two stereo-
genic carbon centers in the cyclic ligand resulted in two
sets of doublets of doublets at δ 37.8, 32.2 with J P-P
)
50.85 Hz and δ 37.75, 31.83 with J P-P ) 48.01 Hz in a
ratio of 10:1 in the 31P NMR spectrum. The minor
isomer escaped from purification by recrystallization
again, since only the major one was obtained. The 13C
NMR spectrum of the major isomer of 8 consists of
strongly deshielded CR resonance as a triplet at δ 309.7
in CDCl3 at room temperature. No transformation of 8
to 6 is observed in CDCl3 after 14 days. The lower
diastereoselectivity of the mercuric chloride addition to
4 relative to that in protonation is somewhat surprising,
and we do not have rationalization for this observation.
The molecular structure of 7 was confirmed by a
single-crystal X-ray diffraction study. An ORTEP dia-
gram is shown in Figure 4, and selected bond distances
and bond angles are listed in Table 4. The Ru-C1
distance of 1.943(8) Å is typical for a Ru carbene system,
and the C2-C3 bond length of 1.554(12) Å is a C-C
single bond. The different O1-C1 and O1-C4 bond
lengths of 1.33(1) and 1.49(1) Å, respectively, are
consistent with other similar carbene complexes.39
The Ru1-C1-C2 and O1-C1-Ru1 bond angles of
128.2(6)° and 125.2(6)°, respectively, are slightly greater
than an sp2 hybridization bond angle. The O1-C1-C2,
C1-C2-C3, C2-C3-C4, and C3-C4-O1 bond angles
of 106.2(7)°, 103.3(6)°, 105.0(7)°, and 100.7(6)°, respec-
tively, are slightly smaller than a typical pentagonal
angle (108°). Formation of carbene complexes 5, 7, and
8 occurs by selective addition of electrophile (XCH2R,
H+, and HgCl2) to the nucleophilic Câ of the five-
membered ring in 4. Possibly because of steric crowding
around Câ and Cγ, it is inclined to form a more stable
carbene complex 6 by elimination of a small molecule.
Rea ction s of Ru th en iu m Cyclop r op en yl Com -
p lex 3a . Reactions of CF3COOH with 3a and 3b readily
gave 2a and 2b, respectively, indicating the basic
character of the methine carbon of the three-membered
ring. This protonation is different from the acid-induced
demethoxylation of the iron cyclopropenyl complex
Cp(CO)2Fe[C3(OMe)(Ph)2], containing a methoxy group
on the three-membered ring.31
Treatment of 3a with HgCl2 produced the vinylidene
complex [[Ru]dCdC(Ph)CH(CN)(HgCl)][Cl] (9) in 86%
yield. As expected, the 31P NMR spectrum of 9 displays
two doublets at δ 37.88 and 32.82 with J P-P ) 50.39
Hz. Formation of 9 occurs by selective cleavage of the
cyclopropenyl single bond near the metal center. At-
tempts to carry out cyclopropenation of 9 by using n-Bu4-
NOH, n-Bu4NF, and DBU resulted in cleavage of the
C-Hg bond, yielding 3a (Scheme 3).
(39) Bruce, M. I.; Swincer, A. G.; Thomson, B. J .; Wallis, R. C. Aust.
J . Chem. 1980, 33, 2605. (b) Garner, J .-A. M.; Irving, A.; Moss, J . R.
Organometallics 1990, 9, 2836. (c) Adams, H.; Bailey, N. A.; Grayson,
M.; Ridgway, C.; Smith, A. J .; Taylor, P.; Winter, M. J .; Housecroft, C.
E. Organometallics 1990, 9, 2621.
The addition of 5 equiv of Me3SiN3 (TMSN3) to 3a in
THF at room temperature initiated a color change from
the light yellow solution of 3 to red initially, then

3216 Organometallics, Vol. 19, No. 16, 2000
Chang et al.
Sch em e 3
F igu r e 5. ORTEP drawing of 11 with thermal ellipsoids
shown at the 30% probability level. For phenyl groups on
dppp, only the ipso carbons are shown.
Ta ble 5. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) of [(η5-C5Me5)(d p p p )Ru NCCH2I][I3] (11)
Ru-P1
Ru-N1
C2-C3
2.334(2)
2.027(5)
1.45(1)
Ru-P2
N1-C2
C3-I1
2.334(1)
1.155(8)
2.188(9)
becoming a light orange after ca. 30 min, and, after 1
h, turning yellow again. The final product was recovered
as [Ru]N3 (10) (Scheme 3) in 78% yield. Recently40 we
reported reactions of Cp ruthenium cyclopropenyl com-
plexes with TMSN3. The reaction of 3a with TMSN3
may proceed similarly, i.e., via electrophilic addition of
a TMS group to the sp3 carbon of the cyclopropenyl ring
followed by hydrolysis. Nucleophilic addition of an N3
anion at CR and electrophilic addition of a second TMS
unit at Câ followed by loss of N2 then gives an N-
coordinated nitrile complex. Substitution of the nitrile
P1-Ru-P2
P2-Ru-N1
N1-C2-C3
86.09(5)
87.2(1)
176.1(9)
P1-Ru-N1
Ru-N1-C2
C2-C3-I1
89.0(1)
173.1(5)
109.8(5)
single bond, respectively. The N1-C2-C3 angle of
176.1(9)° is close to linear, indicating a C(sp) hybridiza-
tion. The C2-C3-I1 angle of 109.8(5)° is typical for that
of an idealized C(sp3) hybridization.
-
ligand by N3 occurs finally after 1 h to give 10. The
Con clu sion s
proton source of the reaction is believed to come from
the small amount of water in solvent and in TMSN3 (no
attempt was made to dry TMSN3 due to potential
hazards) and protons incorporated into the product
through hydrolysis of the TMS substituents. No attempt
was made to isolate the organic product.
Facile preparation of two neutral C5Me5-dppp-Ru
cyclopropenyl complexes was achieved by deprotonation
of cationic vinylidene complexes with electron-with-
drawing substituents such as -CN and -CO2CH3 in
acetone. Treatment of cationic vinylidene complexes
containing relatively weaker electron-withdrawing sub-
stituents such as C6F5, Ph, p-C6H4CN, and p-C6H4CF3
with base failed to give similar result. Protonation of
the ruthenium cyclopropenyl complexes regenerated the
vinylidene complexes, showing the nucleophilic nature
of the antecedent Cγ carbon of the cyclopropenyl ligand.
Thus other electrophiles could also be added to this Cγ
site by reactions with cyclopropenyl complexes. No
conversion of 3b to the ruthenium furanyl complex was
observed regardless of much higher strain energy of the
cyclopropenyl ring. An acetone insertion reaction was
observed in the cyclopropenyl complex 3a , yielding a
neutral five-membered dihydrofuranyl complex 4 in
moderate yield.
Electrophilic addition to 4 affords the cationic carbene
complexes 5a and 5b. Complexes 5a and 5b are trans-
formed to 6 by elimination of a small organic molecule.
The significantly different reactivity of ruthenium com-
plexes with a Cp* ligand from those with a C5H5 ligand
may due to the electronic and steric effects. Treatment
of 3 with (CH3)3SiN3 afforded 10, and subsequent
reaction of 10 with ICH2CN produced a novel N-
coordinated nitrile complex 11.
Interestingly, treatment of yellow complex 10 with
excess ICH2CN at room temperature afforded the brown
N-coordinated iodoacetonitrile complex {[Ru]NC-CH2I}-
[I3] (11) (Scheme 3). Surprisingly, no iodide addition was
observed; instead the coordinated N3- is readily replaced
by ICH2CN without cleavage of the C-I bond. In the
1H NMR spectrum of 11, two singlet resonances at δ
4.50 and 1.54 are assigned to CH2 and Cp*, respectively.
The 31P NMR spectrum displays a singlet resonance at
δ 35.01. In the 13C NMR spectrum, resonances at δ
119.4, 50.9, and 9.7 are assigned to CN, CH2, and Cp*,
respectively. Complex 11 is stable in air and soluble in
most polar solvents such as CH2Cl2, acetone, aceto-
nitrile, THF, and MeOH and moderately soluble in
n-pentane and n-hexane.
The molecular structure of 11 was confirmed by a
single-crystal X-ray diffraction study. An ORTEP dia-
gram is shown in Figure 5, and selected bond distances
and bond angles are given in Table 5. The metal center
is coordinated to the nitrile nitrogen atom of ICH2CN,
and the counteranion is I3-. The Ru-N1 bond length of
2.027(5) Å is typical for a Ru-N dative bond. The N1-
C2 bond length of 1.155(8) Å is typical for a C-N triple
bond. The C2-C3 and C3-I1 bond lengths of 1.453(10)
and 2.188(9) Å indicate a C-C single bond and C-I
Exp er im en ta l Section
Gen er a l P r oced u r es. All manipulations were performed
(40) Chang, K. H.; Lin, Y. C. Chem. Commun. 1998, 1441.
under nitrogen using vacuum-line, drybox, and standard

Reactions of Ru Cyclopropenyl Complexes
Organometallics, Vol. 19, No. 16, 2000 3217
(PCH2CH2), 32.6 (CH2C6H4CN), 10.6 (5CH3); MS (m/z, Ru102
Schlenk techniques. CH2Cl2 was distilled from CaH2, and
diethyl ether and THF were distilled from sodium diphen-
ylketyl. All other solvents and reagents were of reagent grade
and were used without further purification. NMR spectra were
recorded on Bruker AC-200 and AM-300WB FT-NMR spec-
trometers at room temperature (unless stated otherwise) and
are referenced to residual protons in the solvents (CDCl3, δ
7.24: acetone-d6, δ 2.04). FAB mass spectra were recorded on
a J EOL SX-102A spectrometer. Complex [Ru]CtCPh, 1, was
prepared following the methods reported in the literature.41
Elemental analyses and X-ray diffraction studies were carried
out at the Regional Center of Analytical Instruments located
at the National Taiwan University.
)
946.2 (M+ - Br), 750.2 (M+ - Br - CH2C6H4CN), 649.1 (M+
- Br - CH2C6H4CN - CCPh). Anal. Calcd for C53H52NP2-
RuBr: C, 67.30; H, 5.54; N, 1.48. Found: C, 68.35; H, 5.67; N,
1.35. Spectroscopic data for 2f are as follows: 1H NMR (CDCl3)
δ 7.59-6.83 (m, 25H, Ph), 3.89 (s, 2H, CH2), 2.77 (m, 2PCH2),
2.05 (m, PCH2CH2), 1.61 (s, 15H, 5CH3); 31P NMR (CDCl3) δ
35.61; 13C NMR (CDCl3) δ 345.0 (t, CR, J C-P ) 16.3 Hz), 142.5-
125.1 (Ph and Câ), 103.8 (Cp), 32.4 (CH2C6H4CN), 29.2
(t, PCH2, J C-P ) 19.5 Hz), 21.9 (PCH2CH2), 10.6 (5CH3); MS
(m/z, Ru102) 989.2 (M+ - Br), 750.2 (M+ - Br - CH2C6H4CF3),
649.1 (M+ - Br - CH2C6H4CF3 - CCPh). Anal. Calcd for
C
53H52F3P2RuBr: C, 64.37; H, 5.30. Found: C, 64.58; H, 5.49.
Syn th esis of [[Ru ]dCdC(P h )CH2CN][I] (2a ). A Schlenk
flask was charged with ICH2CN (240 µL, 3.3 mmol) and 1 (250
mg, 0.33 mmol) in 10 mL of CH2Cl2. The mixture was heated
to reflux for 24 h. After the solution was allowed to cool, the
solvent was reduced to about 3 mL under vacuum and was
added to 20 mL of a vigorously stirred diethyl ether solution.
The pink powders thus formed were filtered and washed with
20 mL of n-hexane and 20 mL of diethyl ether and dried under
vacuum to give the product 2a (260 mg, 85% yield). Spectro-
scopic data for 2a are as follows: 1H NMR (CDCl3) δ 7.47-
6.82 (m, 25H, Ph), 3.22 (s, 2H, CH2), 2.65 (m, 2PCH2), 1.93
(m, PCH2CH2), 1.58 (s, 15H, 5CH3); 31P NMR (CDCl3) δ 34.35;
13C NMR (CDCl3) δ 341.8 (t, CR, J C-P ) 17.9 Hz), 133.3-127.8
Syn th esis of [Ru ]CdC(P h )CHCN (3a ). To a 15 mL
acetonitrile solution of complex 2a (1.70 g, 1.854 mmol) was
added an aliquot of nBu4NOH (1 M in MeOH, 2 mL) . The
mixture was stirred at room temperature for 30 min to give
bright yellow precipitates. The precipitate was filtered and
washed with 2 × 10 mL of acetonitrile and dried under vacuum
to give the product 3a (1.33 g, 91% yield). Spectroscopic data
for 3a are as follows: 1H NMR (CDCl3) δ 7.72-7.03 (m, 25H,
Ph), 2.65 (m, 2PCH2), 1.93 (m, PCH2CH2), 1.35 (s, 15H, 5CH3),
1.07 (s, 1H, CH); 31P NMR (CDCl3) δ 48.13, 45.52 (AB, J P-P
)
49.76 Hz); 13C NMR (CDCl3) δ 135.2-122.7 (Ph, and Câ), 134.0
(t, CR, J C-P ) 5.74 Hz), 114.0 (CN), 94.0 (Cp), 29.9 (t, PCH2,
J C-P ) 28.1 Hz), 24.1 (PCH2CH2), 13.7 (CH), 10.0 (5CH3); MS
(m/z, Ru102) 790.1 (M+ + 1), 751.2 (M+-CHCN), 649.1 (M+-
CHCN-CCPh). Anal. Calcd for C47H47NP2Ru: C, 71.55; H,
6.01; N, 1.78. Found: C, 72.31; H, 6.37; N, 1.55.
(Ph), 119.4 (Câ), 118.6 (CN), 104.7 (Cp), 29.4 (t, PCH2, J C-P
)
17.9 Hz), 21.3 (PCH2CH2), 17.4 (CH2CN), 10.3 (5CH3); MS
(m/z, Ru102) 790.2 (M+ - I), 750.2 (M+ - I - CH2CN), 649.1
(M+ - I - CH2CN - CCPh). Anal. Calcd for C47H48NP2RuI:
C, 61.57; H, 5.28; N, 1.53, Found: C, 62.37; H, 5.45; N, 1.44.
Complexes [[Ru]dCdC(Ph)CH2R][Br] (R ) CO2CH3, 2b
(85% yield); R ) C6F5, 2c (82% yield); R ) Ph, 2d (79% yield);
R ) p-C6H4CN, 2e (83% yield); R ) p-C6H4CF3, 2f (87% yield))
were prepared from the reaction of 1 with BrCH2CO2CH3,
BrCH2C6F5, BrCH2C6H5, BrCH2(p-C6H4CN), and BrCH2(p-
C6H4CF3), respectively, using a procedure similar to that of
2a . Spectroscopic data for 2b are as follows: 1H NMR (CDCl3)
δ 7.62-6.84 (m, 25H, Ph), 3.56 (s, 3H, OCH3), 3.27 (s, 2H, CH2),
Syn th esis of [Ru ]CdC(P h )CH(CO2CH3) (3b). To a 10 mL
acetone solution of complex 2b (500 mg, 0.554 mmol) was
added an aliquot of (nBu)4NOH (1 M in MeOH, 1.0 mL). The
mixture was stirred at room temperature for 30 min to give
bright yellow precipitates, which were filtered and washed
with 2 × 5 mL of acetone, then dried under vacuum to give
the product 3b (340 mg, 77% yield). Spectroscopic data for 3b
are as follows: 1H NMR (CDCl3) δ 7.63-6.89 (m, 25H, Ph),
3.43 (s, 3H, OCH3), 2.43 (m, 4H, PCH2), 2.02 (m, PCH2CH2),
1.60 (s, 1H, CH), 1.34 (s, 15H, 5CH3); 31P NMR (CDCl3) δ 47.73,
43.00 (AB, J P-P ) 50.18 Hz); 13C NMR (CDCl3) δ 183.6 (CO2),
134.0-119.4 (Ph and CR), 104.2 (Câ), 89.1 (Cp), 52.1 (OCH3),
26.8 (t, J C-P ) 13.7 Hz, PCH2), 21.5 (PCH2CH2), 10.0 (CH),
10.5 (5CH3), 9.7 (CH); MS (m/z, Ru102) 823.1 (M+ + 1), 750.2
(M+ - CHCO2CH3), 649.1 (M+ - CHCO2CH3 - CCPh). Anal.
Calcd for C48H50O2P2Ru: C, 70.14; H, 6.13. Found: C, 71.23;
H, 6.37.
2.71 (m, 2PCH2), 2.02 (m, PCH2CH2), 1.56 (s, 15H, 5CH3); 31
NMR (CDCl3) δ 35.10; 13C NMR (CDCl3) δ 345.1 (t, CR, J C-P
P
)
14.0 Hz), 171.5 (CO2), 133.3-121.5 (Ph and Câ), 104.1 (Cp),
52.0 (OCH3), 33.3 (CH2), 29.1 (t, PCH2, J C-P ) 18.4 Hz), 21.7
(PCH2CH2), 10.4 (5CH3); MS (m/z, Ru102) 823.3 (M+ - Br),
750.2 (M+ - Br - CH2CO2CH3), 649.1 (M+ - Br - CH2CO2-
CH3 - CCPh). Anal. Calcd for C48H51O2P2BrRu: C, 63.85; H,
5.69. Found: C, 64.22; H, 5.83. Spectroscopic data for 2c are
as follows: 1H NMR (CDCl3) δ 7.44-6.76 (m, 25H, Ph), 3.97
(s, 2H, CH2), 2.80 (m, 2PCH2), 2.65 (m, PCH2CH2), 1.59 (s, 15H,
5CH3); 31P NMR (CDCl3) δ 35.86; 13C NMR (CDCl3) δ 341.8 (t,
CR, J C-P ) 14.5 Hz), 134.1-123.7 (Ph), 119.4 (Câ), 104.2 (Cp),
29.1 (t, PCH2, J C-P ) 18.8 Hz), 21.8 (PCH2CH2), 20.1 (CH2C6F5),
10.5 (5CH3); MS (m/z, Ru102) 931 (M+ - Br), 750.2 (M+ - Br -
CH2C6F5), 649.1 (M+ - Br - CH2C6F5 - CCPh). Anal. Calcd
for C52H48F5P2BrRu: C, 61.78; H, 4.79. Found: C, 62.35; H,
4.93. Spectroscopic data for 2d are as follows: 1H NMR (CDCl3)
δ 7.90-6.86 (m, 25H, Ph), 3.82 (s, 2H, CH2), 2.70 (m, 2PCH2),
2.17 (m, PCH2CH2), 1.63 (s, 15H, 5CH3); 31P NMR (CDCl3) δ
35.77; 13C NMR (CDCl3) δ 345.4 (t, CR, J C-P ) 10.1 Hz), 137.7-
125.7 (Ph and Câ), 103.7 (Cp), 32.7 (CH2C6H5), 29.2 (t, PCH2,
Syn th esis of [Ru ]CdC(P h )CH(CN)C(CH3)2O (4). To a
15 mL acetone solution of 2a (500 mg, 0.634 mmol) was added
an aliquot of nBu4NOH (1 M in MeOH, 1.0 mL). The mixture
was stirred at room temperature for 5 min to give a bright
yellow solution of 3a . The solution was stirred at room
temperature for 5 days, and then the solvent was reduced to
2 mL under vacuum. To the residue, 30 mL of MeOH was
added, and yellow precipitates thus formed were filtered and
washed with 2 × 5 mL of MeOH. The 31P NMR spectrum
indicates the presence of two products in a ratio of 2:1. Thus
the product was passed through a silica gel-packed column
eluted with 1:1 ethyl acetate/hexane, and only a yellow band
was collected. After the solvent was removed under vacuum
the yellow band gave a single product, 4 (280 mg, 52% yield).
The minor product decomposed in the column. Spectroscopic
data for 4 are as follows: 1H NMR (CDCl3) δ 7.58-6.17 (m,
25H, Ph), 2.86 (t, PCH2, J H-P ) 9.85 Hz), 2.54 (m, PCH2CH2),
2.86 (t, PCH2, J H-P ) 13.57 Hz), 1.57 (s, 1H, CH), 1.22 (s, 6H,
2CH3), 1.08 (s, 15H, 5CH3); 31P NMR (CDCl3) δ 45.43, 39.11
(AB, J P-P ) 52.21 Hz); 13C NMR (CDCl3) δ 145.2 (OC(CH3)2),
135.1-123.6 (Ph, CR and Câ), 113.1 (CN), 93.3 (Cp), 31.9 (t,
PCH2, J C-P ) 18.7 Hz), 22.1 (PCH2), 9.6 (CH), 10.4 (5CH3);
MS (m/z, Ru102) 848.3 (M+ + 1), 790.2 (M+ - CH3COCH3), 751.2
J C-P ) 19.2 Hz), 21.9 (PCH2CH2), 10.7 (5CH3); MS (m/z, Ru102
)
841.4 (M+ - Br), 750.2 (M+ - Br - CH2C6H5), 649.1 (M+ - Br
- CH2C6H5 - CCPh). Anal. Calcd for C52H53P2RuBr: C, 67.82;
H, 5.80. Found: C, 68.25; H, 5.93. Spectroscopic data for 2e
are as follows: 1H NMR (CDCl3) δ 7.62-6.79 (m, 25H, Ph),
3.94 (s, 2H, CH2), 2.77 (m, 2PCH2), 2.13 (m, PCH2CH2), 1.59
(s, 15H, 5CH3); 31P NMR (CDCl3) δ 35.46; 13C NMR (CDCl3) δ
344.6 (t, CR, J C-P ) 14.1 Hz), 134.1-124.8 (Ph), 119.2 (Câ),
118.7 (CN), 103.8 (Cp), 29.2 (t, PCH2, J C-P ) 18.9 Hz), 21.8
(41) Oshima, N.; Suzuki, H.; Moro-oka, Y. Chem. Lett. 1984, 1161.

3218 Organometallics, Vol. 19, No. 16, 2000
Chang et al.
(M+ - CH3COCH3 - CHCN), 649.1 (M+ - CH3COCH3
-
Spectroscopic data for 7 are as follows: 1H NMR (CD3COCD3)
δ 7.63-6.16 (m, 25H, Ph), 5.13 (s, 1H, CHPh), 3.20 (t, 1H, J H-P
) 10.19 Hz, CH2), 2.93 (t, 1H, J H-P ) 13.14 Hz, CH2), 2.82-
2.45 (m, 2H, PCH2), 2.19-2.08 (m, 2H, PCH2), 1.59 (s, 1H,
CHCN), 1.24, 1.09 (s, 3H, 2CH3), 1.15 (s, 15H, 5CH3); 31P NMR
(CDCl3) δ 38.63, 32.97 (2d, J P-P ) 48.03 Hz); 13C NMR (CDCl3)
δ 290.5 (t, J C-P ) 12.7 Hz, CR), 138.2-128.3 (Ph and Câ), 116.3
(CN), 102.2 (Cp), 97.3 (OC(CH3)2), 70.2 (CHPh), 30.7, 30.2
CHCN - CCPh). Anal. Calcd for C50H53NOP2Ru: C, 70.90; H,
6.31; N, 1.65. Found: C, 71.33; H, 6.45; N, 1.65. 31P NMR data
of the minor product 4′: 31P NMR (CDCl3) δ 28.67, 11.77 (J P-P
) 50.23 Hz).
Syn th esis of [[Ru ]dCC(P h )(CH2CN)CH(CN)C(CH3)2O]-
[I] (5a ). A Schlenk flask was charged with ICH2CN (520 µL,
0.590 mmol) and 4 (100 mg, 0.118 mmol) in 10 mL of CH2Cl2.
The mixture was stirred at room temperature for 8 h. The
solvent was reduced to about 2 mL under vacuum, and the
residue was added to 20 mL of vigorously stirred diethyl ether.
The brown powder thus formed was filtered and washed with
2 × 5 mL of diethyl ether and dried under vacuum to give the
product 5a (98.5 mg, 82% yield). Spectroscopic data for 5a are
as follows: 1H NMR (CDCl3) δ 7.74-6.18 (m, 25H, Ph), 5.28
(s, 2H, CH2), 2.84 (m, 2H, CH2), 2.59, 2.13 (m, 2H, PCH2), 1.46
(s, 1H, CHCN), 1.14 (s, 6H, 2CH3), 1.17 (s, 15H, 5CH3); 31P
NMR (CDCl3) δ 37.30, 31.45 (AB, J P-P ) 48.02 Hz); 13C NMR
(CDCl3) δ 290.6 (t, CR, J C-P ) 11.6 Hz), 139.0-127.7 (Ph),
116.1, 115.2 (CN), 102.0 (Cp), 97.5 (OC(CH3)2), 70.0 (CH2), 28.8
(dd, J C-P ) 29.9, 6.4 Hz, PCH2), 27.6 (dd, J C-P ) 30.7, 5.3 Hz,
PCH2), 22.6, 21.1 (2CH3), 20.4 (CH2), 14.0 (s, CHCN), 10.3
(5CH3); MS (m/z, Ru102) 887.3 (M+ - I), 649.1 (M+ - I - CH3-
COCH3 - CHCN - CCPh - CH2CN). Anal. Calcd for
C52H55N2OP2RuI: C, 61.60; H, 5.47; N, 2.76. Found: C,
62.03; H, 5.64; N, 2.42.
(2CH3), 28.7 (dd, J C-P ) 28.6, 6.0 Hz, PCH2), 28.3 (dd, J C-P
28.6, 5.8 Hz, PCH2), 27.8 (CHCN), 20.3 (PCH2CH2), 10.1
(5CH3); MS (m/z, Ru102) 849.3 (M+ - CF3COO), 649.1 (M+
CH3COCH3 - CHCN - CCPh - H). Anal. Calcd for C52H54
)
-
-
NO3F3P2Ru: C, 64.99; H, 5.39; N, 1.44. Found: C, 65.38; H,
5.61; N, 1.25.
Syn th esis of [[Ru ]dCC(P h )(HgCl)CH(CN)C(CH3)2O]-
[Cl] (8). A Schlenk flask was charged with HgCl2 (160 mg,
0.59 mmol) and 4 (100 mg, 0.118 mmol) in 10 mL of CH2Cl2.
The mixture was stirred at room temperature for 30 min.
Excess HgCl2 was filtered, and the solvent was reduced to
about 2 mL under vacuum. The residue was added to a 20
mL solution of vigorously stirred diethyl ether. The black-blue
powder thus formed was filtered and washed with 2 × 5 mL
of diethyl ether and dried under vacuum to give 8 (115 mg,
90% yield). Spectroscopic data for 8 are as follows: 1H NMR
(CD3COCD3) δ 7.67-6.92 (m, 25H, Ph), 3.20 (s, 1H, CHCN),
2.43 (m, 2H, PCH2CH2), 2.00 (t, 2H, J H-P ) 15.80 Hz, PCH2),
1.80 (t, 2H, J H-P ) 13.80 Hz, PCH2), 1.61 (s, 6H, 2CH3), 1.21
(s, 15H, 5CH3); 31P NMR (CDCl3) δ 37.83, 32.23 (J P-P ) 50.85
Hz); 13C NMR (CDCl3) δ 309.7 (t, J C-P ) 14.6 Hz, CR), 137.3-
125.1 (Ph and Câ), 118.5 (CN), 92.5 (Cp), 89.2 (OC(CH3)2), 30.7
(t, J C-P ) 23.1 Hz, 2PCH2), 27.8, 27.4 (2CH3), 21.4 (PCH2CH2),
Complex [[Ru]dC-C(Ph)(CH2CO2CH3)CH(CN)C(CH3)2O]-
[Br] (5b) (100 mg, 88% yield) was prepared from 4 (100 mg,
0.118 mmol) with BrCH2CO2CH3 (56 µL, 0.590 mmol) using a
procedure similar to that of 5a . Spectroscopic data of 5b are
as follows: 1H NMR (CD3COCD3) δ 7.77-6.18 (m, 25H, Ph),
3.81 (s, 2H, CH2), 3.76 (s, 3H, OCH3), 3.34 (t, 2H, J H-H ) 13.42
Hz, PCH2), 2.95 (m, 2H, PCH2CH2), 2.18 (t, 2H, J H-H ) 13.42
Hz, PCH2), 1.79 (s, 6H, 2CH3), 1.59 (s, 1H, CH), 1.17 (s, 15H,
10.3 (CHCN), 9.3 (5CH3); MS (m/z, Ru,102 Hg202) 1049.3 (M+
-
Cl), 649.1 (M+ - Cl - CH3COCH3 - CHCN - HgCl - CCPh).
Anal. Calcd for C50H53Cl2P2RuHg: C, 55.17; H, 4.91. Found:
C, 56.33; H, 5.02.
5CH3); 31P NMR (CDCl3) δ 37.38, 31.94 (J P-P ) 52.91 Hz); 13
C
NMR (CDCl3) δ 291.1 (t, CR, J C-P ) 12.2 Hz), 167.7 (CO2),
139.1-127.7 (Ph), 119.4 (Câ), 115.3 (CN), 102.0 (Cp), 97.4
(OC(CH3)2), 70.3 (CH2), 28.9 (dd, J C-P ) 30.8, 5.5 Hz, PCH2),
27.3 (dd, J C-P ) 29.1, 6.0 Hz, PCH2), 21.1 (PCH2CH2), 20.5
(2CH3), 13.7 (CHCN), 10.2 (5CH3); MS (m/z, Ru102) 920.3 (M+
- Br), 649.1 (M+ - Br - CH3COCH3 - CHCN - CCPh - CH2-
CO2CH3). Anal. Calcd for C53H58NO3P2RuBr: C, 63.66; H, 5.85;
N, 1.40. Found: C, 64.18; H, 6.01; N, 1.23.
Syn th esis of [[Ru ]dCdC(P h )CH(CN)(HgCl)][Cl] (9). A
Schlenk flask was charged with HgCl2 (170 mg, 0.634 mmol)
and 3a (100 mg, 0.127 mmol) in 10 mL of CH2Cl2. The mixture
was stirred at room temperature for 30 min. Excess HgCl2 was
filtered, and the solvent was reduced to about 2 mL under
vacuum. The residue was added to a 20 mL solution of
vigorously stirred diethyl ether. The pink powder thus formed
was filtered and washed with 2 × 5 mL of diethyl ether and
dried under vacuum to give 9 (116 mg, 86% yield). Spectro-
scopic data for 9 are as follows: 1H NMR (CDCl3) δ 7.84-6.54
(m, 25H, Ph), 3.66 (s, 1H, CH), 2.95 (m, 2H, PCH2), 2.81 (m,
2H, PCH2), 2.70 (m, 2H, PCH2CH2), 1.59 (s, 15H, 5CH3); 31P
NMR (CDCl3) δ 37.88, 32.82 (2d, J P-P ) 50.39 Hz); 13C NMR
(CDCl3) δ 340.7 (t, J C-P ) 14.6 Hz, CR), 134.1-128.0 (Ph and
Câ), 122.1 (CN), 104.6 (Cp), 31.2 (d, J C-P ) 35.3 Hz, PCH2),
29.9 (CH), 28.7 (d, J C-P ) 32.9 Hz, PCH2), 21.8 (PCH2CH2),
10.6 (5CH3); MS (m/z, Ru,102 Hg202) 991.3 (M+ - Cl), 649.1 (M+
- Cl - CHCN - HgCl - CCPh). Anal. Calcd for C47H47NP2-
Cl2RuHg: C, 52.23; H, 4.47; N, 1.32. Found: C, 52.55; H, 4.75;
N, 1.20.
Syn th esis of [[Ru ]dCC(P h )dC(CN)C(CH3)2O][I] (6). A
Schlenk flask was charged with ICH2CN (510 µL, 0.590 mmol)
and 4 (100 mg, 0.118 mmol) and 10 mL of CH2Cl2. The mixture
was heated to reflux for 24 h. Then the solvent was reduced
to about 2 mL under vacuum, and the residue was added to
20 mL of vigorously stirred n-hexane. The brown powders thus
formed were filtered and washed with 2 × 5 mL of diethyl
ether and dried under vacuum to give 6 (75 mg, 65% yield).
Spectroscopic data for 6 are as follows: 1H NMR (CDCl3) δ
7.71-6.18 (m, 25H, Ph), 2.84 (t, 2H, J H-H ) 14.15 Hz,
PCH2CH2), 2.62, 2.08 (2m, 4H, PCH2), 1.14 (s, 6H, 2CH3), 1.06
(s, 15H, 5CH3); 31P NMR (CDCl3) δ 36.78. 13C NMR (CDCl3) δ
275.0 (t, CR, J C-P ) 12.2 Hz), 163.0 (Câ), 139.6-128.9 (Ph),
120.6 (Cγ), 114.1 (CN), 103.5 (Cp), 102.1 (OC(CH3)2), 29.1 (t,
J C-P ) 18.3 Hz, PCH2), 22.3 (PCH2CH2), 12.1 (5CH3), 11.5
(2CH3); MS (m/z, Ru102) 846.2 (M+ - I), 649.1 (M+ - I - CH3-
COCH3 - CCN - CCPh). Anal. Calcd For C50H52NOP2IRu: C,
61.73; H, 5.39; N, 1.44. Found: C, 62.17; H, 5.52; N, 1.17.
Syn th esis of [Ru ]N3 (10). A Schlenk flask was charged
with (CH3)3SiN3 (78 µL, 0.590 mmol) and 3a (100 mg, 0.127
mmol) and 10 mL of THF. The mixture was stirred at room
temperature for 3 h. The solvent was reduced to about 2 mL
under vacuum and added to 20 mL of vigorously stirred
n-hexane. The yellow powder thus formed was filtered and
washed with 2 × 5 mL of n-hexane and dried under vacuum
to give the product 10 (68 mg, 78% yield). Spectroscopic data
for 10 are as follows: 1H NMR (CDCl3) δ 7.65-6.94 (m, 25H,
Ph), 2.56 (t, 4H, J H-P ) 13.33 Hz, PCH2), 2.31 (m, 2H,
Syn t h esis of [[R u ]dCCH (P h )CH (CN)C(CH3)2O][CF 3-
COO] (7). A Schlenk flask was charged with CF3COOH (95
µL, 1.18 mmol) and 4 (100 mg, 0.118 mmol) in 10 mL of CH2-
Cl2. The mixture was stirred at room temperature for 1 h. The
solvent was reduced to about 2 mL under vacuum, and 20 mL
of diethyl ether was added to the residue. The brown powder
thus formed was filtered and washed with 2 × 5 mL of diethyl
ether and dried under vacuum to give 7 (85 mg, 75% yield).
PCH2CH2), 1.37 (s, 15H, 5CH3); 31P NMR (CDCl3) δ 38.26. 13
C
NMR (CDCl3) δ 138.6-127.5 (Ph, CR and Câ), 89.6 (Cp), 27.9
(t, J C-P ) 13.8 Hz, PCH2), 21.2 (PCH2CH2), 9.6 (5CH3); MS
(m/z, Ru102) 692.3 (M+ + 1), 675.3 (M+ - N - 1), 649.3 (M+
-

Reactions of Ru Cyclopropenyl Complexes
Organometallics, Vol. 19, No. 16, 2000 3219
Ta ble 6. Cr ysta l a n d In ten sity Collection Da ta for (C5Me5)(d p p p )Ru CdC(P h )CHCN (3a ),
(C5Me5)(d p p p )Ru CdC(P h )CH(CN)C(CH3)2O (4), [(C5Me5)(d p p p )Ru dC-C(P h )dC(CN)C(CH3)2O][I]‚2CHCl3 (6),
[(C5Me5)(d p p p )Ru dCCH(P h )CH(CN)C(CH3)2O][CF 3COO]‚1/2CF 3COOH (7), a n d [(C5Me5)(d p p p )Ru NCCH2I][I3]
(11)
C47H47NP2Ru,
C50H53NOPRu,
C52H53Cl6INOP2Ru,
C54H55.5Cl3F4.5NO4P2Ru,
C39H43I4NP2Ru,
3a
4
6
7
11
space group
cryst syst
a, Å
b, Å
c, Å
P21/n
P212121
orthorhombic
11.2771(3)
17.8994(4)
23.8595(5)
90
90
90
P21/c
P1h
P21/c
monoclinic
16.1153(3)
12.2925(1)
19.9973(4)
90
95.010(1)
90
3946.28(11)
4
monoclinic
21.4873(4)
13.2421(3)
19.5952(4)
90
105.965(1)
90
5360.5(2)
4
triclinic
monoclinic
15.5340(1)
13.2322(1)
21.3003(2)
90
103.684(1)
90
4253.98(6)
4
12.1587(5)
19.1984(8)
24.7050(9)
69.400(1)
76.820(1)
89.762(1)
5237(6)
R, deg
â, deg
γ, deg
V, Å3
4816.1(2)
4
Z
4
cryst dimens,
mm
0.40 × 0.22 × 0.18
0.35 × 0.15 × 0.12
0.35 × 0.30 × 0.05
0.20 × 0.18 × 0.04
0.36 × 0.34 × 0.05
2θ range, deg
total no. of reflns
final R indices
[I > 2σ(I)]
R indices
(all data)
1.56 to 27.50
9047
R1 ) 0.0279,
wR2 ) 0.0715
R1 ) 0.0394,
wR2 ) 0.0779
1.42 to 26.37
9796
R1 ) 0.0702,
wR2 ) 0.1702
R1 ) 0.1166
wR2 ) 0.1928
1.83 to 26.37
10 542
R1 ) 0.0542,
wR2 ) 0.1282
R1 ) 0.0945,
wR2 ) 0.1456
0.91 to 25.00
17 577
R1 ) 0.0964,
wR2 ) 0.1848
R1 ) 0.1487,
wR2 ) 0.2080
1.35 to 26.40
8552
R1 ) 0.0491,
wR2 ) 0.1162
R1 ) 0.0593,
wR2 ) 0.1245
N3). Anal. Calcd for C37H41N3P2Ru: C, 64.33; H, 5.98; N, 6.08.
Found: C, 64.46; H, 6.10; N, 5.93.
processed and the structures were solved and refined by the
SHELXTL44 program. The structure was solved using direct
methods and confirmed by Patterson methods refining on
intensities of all data (20 610 reflections) to give wR1 ) 0.0579
and wR2 ) 0.122145 for 20 610 unique observed reflections
(I > 2σ(I)). Hydrogen atoms were placed geometrically using
the riding model, with thermal parameters set to 1.2 times
that for the atoms to which the hydrogen is attached and 1.5
times that for the methyl hydrogens. The procedures for the
structure determination of 4, 6, 7, and 11 were similar to that
of 3a . Crystal data of these complexes are listed in Table 6.
Syn th esis of [[Ru ]NCCH 2I][I3] (11). A Schlenk flask was
charged with ICH2CN (100 µL, 1.45 mmol) and 10 (100 mg,
0.145 mmol) in 10 mL of CH2Cl2. The mixture was stirred at
room temperature for 3 h. The solvent was reduced to about 2
mL under vacuum and added to 20 mL of vigorously stirred
n-pentane. The orange-yellow powder thus formed was filtered
and washed with 5 mL of n-pentane and dried under vacuum
to give 11 (66 mg, 56% yield). Spectroscopic data for 11 are as
follows: 1H NMR (CDCl3) δ 8.07-6.83 (m, 25H, Ph), 4.50 (s,
2H, CH2), 2.59 (m, 2H, PCH2), 2.43 (m, 2H, PCH2CH2), 2.00
(m, 2H, PCH2), 1.54 (s, 15H, 5CH3); 31P NMR (CDCl3) δ 35.01;
13C NMR (CDCl3) δ 133.8-124.7 (Ph, CR and Câ), 119.4 (CN),
93.2 (Cp), 50.9 (CH2), 29.4 (t, J C-P ) 8.22 Hz, PCH2), 20.3
(PCH2CH2), 9.7 (5CH3); MS (m/z, Ru102) 816.2 (M+ + 1 - I3),
776.1 (M+ - I3 - CH2CN), 649.3 (M+ - I4 - CH2CN). Anal.
Calcd for C39H42NP2RuI4: C, 39.18; H, 3.54; N, 1.17. Found:
C, 40.25; H, 3.73; N, 1.06.
X-r a y An a lysis of 3a . Single crystals of 3a suitable for
X-ray diffraction study were grown as mentioned above. A
single crystal of dimensions 0.32 × 0.08 × 0.05 mm3 was glued
to a glass fiber and mounted on a SMART CCD diffractometer.
The data were collected using 3 kW sealed-tube molybdenum
KR radiation (T ) 295 K). Exposure time was 5 s per frame.42
SADABS43 (Siemens area detector absorption) absorption
correction was applied, and decay was negligible. Data were
Ack n ow led gm en t. Financial support by the Na-
tional Science Council of Taiwan, the Republic of China,
is gratefully acknowledged. We thank Nathan T. Allen
for helpful discussions.
Su p p or tin g In for m a tion Ava ila ble: Details of the struc-
tural determination for complexes 3a , 4, 6, 7, and 11 including
crystal and intensity collection data, positional and anisotropic
thermal parameters, and all of the bond distances and angles.
This material is available free of charge via the Internet at
http://pubs.acs.org.
OM000094L
(44) SHELXTL: Structure Analysis Program, version 5.04; Siemens
Industrial Automation Inc.: Madison, WI, 1995.
(42) SAINT (Siemens Area Detector Integration) program; Siemens
Analytical X-ray: Madison, WI, 1995.
(43) The SADABS program is based on the method of Blessing;
see: Blessing, R. H. Acta Crystallogr., Sect. A 1995, 51, 33.
(45) GOF ) [∑[w(F2 - F2c)2]/(n - p)]1/2, where n and p denote the
o
number of data and parameters. R1 ) (∑||Fo| - |Fc||)/∑|Fo|, wR2 ) [∑-
[w(F2 - F2c)2]/∑[w(F2o)2]]1/2 where w ) 1/[σ2(F2o) + (aP)2 + bP] and P
o
) [(max; 0, F2o) + 2F2c]/3.