Reactions of ruthenium acetylide complexes with benzylidenemalonitrile

Article abstract of DOI:10.1039/a905788i

Reactions of [RuCp(L)(L′)(C≡CPh)] (Cp = η⁵-C₅H₅; L = PPh₃, L′ = P(OMe)₃ 1a; LL′ = dppe = Ph₂PCH₂CH₂PPh₂ 1b; L = PPh₃, L′ = CN^tBu 1c) w

Full text of DOI:10.1039/a905788i

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Reactions of ruthenium acetylide complexes with
benzylidenemalonitrile†
Chao-Wan Chang, Ying-Chih Lin,* Gene-Hsiang Lee and Yu Wang
Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, Republic of China.
E-mail: yclin@mail.ch.ntu.edu.tw
Received 19th July 1999, Accepted 18th October 1999
5
᎐
Reactions of [RuCp(L)(LЈ)(C᎐CPh)] (Cp = η -C H ; L = PPh , LЈ = P(OMe) 1a; LLЈ = dppe = Ph PCH -
᎐
5
5
3
3
2
2
CH PPh 1b; L = PPh , LЈ = CNtBu 1c) with H(Ph)C᎐C(CN) gave the cyclobutenyl complexes [RuCp(L)-
᎐
2
2
3
2
(LЈ){C᎐C(Ph)CH(Ph)C(CN) }] 2a, 2b and 2c which readily transform to the butadienyl complexes
᎐
2
[RuCp(L)(LЈ){C[᎐C(CN) ]C(Ph)CH(Ph)}] 3a, 3b and 3c, respectively. Thermolysis of 3a in benzene afforded
᎐
2
the allylic complex [RuCp{P(OMe)3}[η3-C[=C(CN)2]C(Ph)CH(Ph)}] 4 in high yield. Reaction of 4 with tBuNC
gave [RuCp{P(OMe) }(CNtBu)[η1-C[᎐C(CN) ]C(Ph)CH(Ph)}] 5. Treatment of 1a with Cl(Ph)C᎐C(CN) afforded
᎐
᎐
3
2
2
the neutral vinylidene phosphonate complex [RuCp(PPh ){P(O)(OMe) }{᎐C᎐C(Ph)C(Ph)C(CN) }] 6. Reactions
᎐ ᎐
3
2
2
of 1b and 1c, both lacking phosphite ligands, with Cl(Ph)C᎐C(CN) gave the cationic vinylidene complexes
᎐
2
[RuCp(L)(LЈ){᎐C᎐C(Ph)C(Ph)C(CN) }]ϩ 7b and 7c, respectively. Treatment of 1a with ICH CN afforded
᎐ ᎐
2
2
[RuCp(PPh ){P(OMe) }{᎐C᎐C(Ph)CH CN}]I 8a. In the presence of acid complex 8a decomposes to give the acyl
᎐ ᎐
3
3
2
complex [RuCp(PPh3){P(OMe)3}(COCH2Ph)] 10. The structures of 3a, 4, 6 and the latter complex have been
determined by single-crystal X-ray diffraction analysis.
Since then, Brauman and Golden10 have estimated that the
Introduction
thermally allowed contrarotatory process for cyclobutenes is
more favored (by 15.0 kcal molϪ1) than the disrotatory process.
This experimental estimate is in accord with values obtained by
Breulet and Schaefer11 from ab initio calculations.
Chemical reactivities of metal acetylide complexes have been
the focus of several recent works due to their wide applications
in many areas of organometallic1 and material chemistry.2 The
co-ordinated acetylide ligand on a transition metal is reactive
toward electrophiles, undergoing either alkylation or proton-
ation at the β-carbon to give a stable vinylidene complex. The
cycloaddition of alkynes with isocyanates has been reported in
nickel(0) complexes.3 This reaction possibly proceeds through
a metallacycle formed by the σ-co-ordinated acetylide and
isocyanate. One common reaction observed for the acetylide
ligand is the [2 ϩ 2] cycloaddition of the triple bond with
unsaturated organic substrates.4 A few cycloadditions of
organic substrates such as CS2,5 (NC) C᎐C(CF ) , (NC) C᎐
Bruce and his co-workers studied the transformations of
cycloadducts of transition metal acetylides and activated
olefins, such as C(CF ) ᎐C(CN) ],12 trans-CH(CO Me)᎐C(CN)-
᎐
᎐
3
2
2
(CO2Me)13 and 4-(O N)C H CH᎐C(CN)R (R =2CN or CO -
᎐
2
6
4
2
Et),14 using a substrate that permitted the stereochemistry to be
determined readily.
In a search for new chemical properties of the acetylide com-
plexes, we carried out reactions of isocyanate and isothiocy-
anate with two such ruthenium complexes and recently
reported15 sequential additions of the organic substrate to the
acetylide producing a novel heterocyclic ligand not observed
before. The [2 ϩ 2] cycloaddition is the first step and is followed
by further additions of isothiocyanate to give a trimerization
᎐
᎐
2
2
3
2
6
C(CN)2 and Ph C᎐C᎐O7 to the acetylide ligand in various
᎐ ᎐
2
metal complexes have also been reported. Addition of activ-
ated alkenes containing an electron-withdrawing group to
ruthenium acetylide complexes again resulted in a formal
[2 ϩ 2] cycloaddition. This was followed by a facile ring open-
ing of the resultant ruthenium cyclobutenyl complex generating
the ruthenium butadienyl species. In some cases, subsequent
product. In this paper we report the reactions of H(Ph)C᎐
᎐
C(CN) and Cl(Ph)C᎐C(CN) with ruthenium acetylides. These
᎐
2
2
olefins were chosen because the presence of different electro-
philic groups might enable further information to be obtained
in the course of these reactions.
displacement of a phosphine ligand led to the η3-allylic prod-
᎐
uct. For example, reactions between [RuCp(L)(LЈ)(C᎐CR)]
᎐
(R = Me or Ph; L = PPh3; LЈ = CO, PPh3 or P(OPh)3; LLЈ =
dppe) and tetracyanoethylene gave cyclobutenyl [RuCp-
Results and discussion
Synthesis of cyclobutenyl and butadienyl complexes
(L)(LЈ){C᎐CRC(CN) C(CN) }], butadienyl [RuCp(L)(LЈ)-
᎐
2
2
{C[᎐C(CN) ]CRC᎐C(CN) }] and allylic [RuCp(PPh3){η3-
᎐
᎐
2
2
C(CN) CRC᎐C(CN) }] complexes.6
Treatment of [RuCp(PPh ){P(OMe) }(C᎐CPh)] 1a with
᎐
᎐
᎐
2
2
3
3
The stereochemical studies by Criegee and co-workers8 on
the thermal ring opening of cis- and trans-1,2,3,4–
tetramethylcyclobutenes were the first to show unambiguously
the contrarotatory nature of the cyclobutene–butadiene elec-
trocyclic interconversion. In 1965 Woodward and Hoffmann9
proposed a theory to rationalize such electrocyclic reactions.
H(Ph)C᎐C(CN) in CH2Cl2 at room temperature for 1 h
᎐
2
resulted in formation of a mixture of two complexes: [RuCp-
(PPh ){P(OMe) }{C᎐C(Ph)CH(Ph)C(CN) }] 2a and [RuCp-
᎐
3
3
2
(PPh ){P(OMe) }{C[᎐C(CN) ]C(Ph)CH(Ph)}] 3a in a ratio of
᎐
3
3
2
1:1 (Scheme 1). Prolonging the reaction time did not alter the
ratio. However, if we carried out this reaction at 0 ЊC for 3 h the
ratio was about 2:1, which again changed to 1:1 at room tem-
perature. Complexes 2a and 3a cannot be separated by column
chromatography. Recrystallization of their mixture gave only
† Supplementary data available: rotatable 3-D crystal structure diagram
in CHIME format. See http://www.rsc.org/suppdata/dt/1999/4223/
J. Chem. Soc., Dalton Trans., 1999, 4223–4230
This journal is © The Royal Society of Chemistry 1999
4223

View Article Online
Scheme 1
Table 1 Selected bond distances (Å) and angles (Њ) of [RuCp(PPh3)-
single crystals of 3a, which converted into the mixture in
solution.
{P(OMe)3}{C[᎐C(CN)2]C(Ph)᎐CH(Ph)}] 3a
᎐
᎐
There was no obvious color change in the formation of
complexes 2a and 3a from 1a, so the reaction was monitored by
31P and 1H NMR spectra. For 1a the 31P NMR spectrum
displays two doublet resonances at δ 56.2 and 151.7 with
JP–P = 68.8 Hz assignable to PPh3 and P(OMe)3, respectively.
Upon addition of 3 equivalents of H(Ph)C᎐C(CN) to the
Ru–P1
Ru–C1
C1–C2
C2–C10
C16–C17
C17–N1
2.2364(23)
2.055(8)
1.506(11)
1.512(11)
1.428(11)
1.143(11)
Ru–P2
C1–C16
C2–C3
C3–C4
C16–C18
C18–N2
2.3305(23)
1.384(11)
1.319(11)
1.455(11)
1.451(11)
1.131(11)
᎐
2
CDCl3 solution of 1a, complexes 2a and 3a formed. The 31P
NMR spectrum of the mixture displays four doublet reson-
ances of which the two at δ 58.8 and 148.9 with JP–P = 70.2 Hz
are assigned to the PPh3 and P(OMe)3 of 2a, respectively, and
those at δ 58.3 and 148.2 with JP–P = 70.4 Hz to the correspond-
P1–Ru–P2
P2–Ru–C1
Ru–C1–C2
C1–C2–C3
92.33(8)
94.57(21)
122.2(5)
124.2(7)
P1–Ru–C1
92.92(22)
Ru–C1–C16 126.1(6)
C1–C2–C10 111.8(6)
C3–C2–C10 123.9(7)
1
ing ones of 3a. In the H NMR spectrum two singlet reson-
ances at δ 5.10 and 5.01 and a doublet resonance at δ 3.27 with
JH–P = 10.9 Hz are assigned to CH, Cp and OMe of 2a, respect-
ively. The corresponding resonances for 3a appear at δ 4.66 and
4.74 and 3.27 (doublet with JH–P = 10.9 Hz).
The reactions of complexes 1b and 1c with H(Ph)C᎐C(CN)
᎐
2
yielded kinetic and thermodynamic products. That of 1b in
CH2Cl2 in 1 h at room temperature afforded 2b which trans-
formed completely to 3b in 24 h. For 2b the 31P NMR spectrum
displays two broad resonances at δ 98.1 and 96.9 assignable to
1
the dppe ligand and the H NMR spectrum shows two singlet
resonances at δ 5.24 and 4.67 assignable to CHPh and Cp,
respectively. For 3b the 31P NMR spectrum displays two broad
resonances at δ 94.0 and 92.3 and the 1H NMR spectrum
displays the broad resonance at δ 5.95 assignable to CHPh and
the resonance at δ 4.43 to Cp. Treatment of 1c with H(Ph)C᎐
᎐
C(CN)2 in CH2Cl2 at room temperature for 10 min afforded 2c
in 87% yield (Scheme 1). If 2c was not isolated immediately the
ring-opening reaction proceeded and 3c formed. Attempts to
recrystallize 2b and 2c from CH2Cl2–hexane (1:2) at Ϫ20 ЊC
resulted in isolation of 3b and 3c, respectively. Complexes 2a
and 3a containing PPh3 and P(OMe)3 as their ancillary ligands
are in equilibrium. However, no such phenomenon was observed
for complexes 2b/3b and 2c/3c possibly because there is no
P(OMe)3 ligand in them.
The molecular structure of complex 3a has been determined
by a single-crystal X-ray diffraction analysis, an ORTEP16
drawing being shown in Fig. 1. Selected bond distances and
angles are listed in Table 1. The co-ordination about the
ruthenium is a distorted piano-stool geometry with the η5-C5H5
group being symmetrically attached to the metal. All Ru–C
(Cp) bond distances range within 2.231(2)–2.249(2) Å with an
average of 2.238 Å. The Ru–C1 bond distance of 2.055(8) Å is
relatively shorter. The butadienyl ligand is non-planar and there
Fig. 1 An ORTEP drawing of complex 3a with thermal ellipsoids,
(in all Figures) shown at the 30% probability level.
is no obvious delocalization between C–C single and C᎐C
᎐
double bonds (C1–C16 1.384; C1–C2 1.506; C2–C3 1.319 Å).
Synthesis and structure of [RuCp{P(OMe) }{ꢀ3-C[᎐C(CN) ]-
᎐
3
2
C(Ph)CH(Ph)}] 4
Thermolysis of complex 3a in benzene at refluxing temperature
for 2 d afforded the allylic complex [RuCp{P(OMe)3}{η3-
C[᎐C(CN) ]C(Ph)CH(Ph)}] 4 by removal of a PPh ligand with
᎐
2
3
1
high yield (Scheme 1). The H NMR spectrum of 4 displays a
singlet resonance at δ 4.94 and two doublet resonances at δ 3.63
(JH–P = 11.8) and 3.43 (JH–P = 12.3 Hz) attributed to Cp, OMe
and CH(Ph), respectively. The 31P NMR spectrum displays a
singlet resonance at δ 159.35 attributed to the P(OMe)3 ligand.
4224
J. Chem. Soc., Dalton Trans., 1999, 4223–4230

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Table 2 Selected bond distances (Å) and angles (Њ) of [RuCp-
Table 3 Selected bond distances (Å) and angles (Њ) of [RuCp-
{P(OMe)3}{η3-C(CN)2C(Ph)C᎐CH(Ph)}] 4
(PPh3){P(O)(OMe)2}{C᎐C(Ph)C(Ph)C(CN)2}]ؒ(OH)(Ph)C᎐C(CN)2 6
᎐
᎐
᎐
Ru–P
2.245(3)
Ru–C1
Ru–C3
C2–C3
C4–C5
C5–N1
2.250(9)
Ru–P1
Ru–C1
C2–C3
C3–C4
C4–C18
O4–H
2.3437(14)
1.790(5)
1.434(7)
1.373(7)
1.492(7)
1.45(5)
Ru–P2
C1–C2
C2–C5
C4–C17
O1–H
C17–N1
P2–O1
P2–O3
2.2965(16)
1.362(6)
1.501(7)
1.447(8)
1.00(5)
1.143(8)
1.475(3)
1.585(3)
Ru–C2
C1–C2
C3–C4
C4–C6
C6–N2
2.142(10)
1.422(14)
1.382(13)
1.399(14)
1.135(14)
1.934(10)
1.418(13)
1.439(14)
1.124(13)
C18–N2
P2–O2
1.136(7)
1.593(4)
P–Ru–C1
P–Ru–C3
C1–C2–C13
Ru–C3–C4
C3–C4–C6
Ru–C1–C7
80.7(3)
89.3(3)
128.8(8)
144.8(7)
122.7(9)
118.5(6)
P–Ru–C2
104.3(3)
111.1(9)
120.0(9)
120.6(9)
67.0(5)
C1–C2–C3
C3–C2–C13
C3–C4–C5
Ru–C1–C2
P1–Ru–P2
Ru–C1–C2
C2–C3–C4
C3–C4–C18
92.01(5)
173.9(4)
123.5(4)
122.6(5)
P1–Ru–C1
C1–C2–C3
C3–C4–C17
P2–O1–H
95.85(14)
120.4(4)
124.7(5)
171(3)
Fig. 2 An ORTEP drawing of complex 4.
Fig. 3 An ORTEP drawing of complex 6.
No similar reaction was observed for 3b or 3c. The weak bond-
ing of the PPh3 ligand in 3a could possibly be owing to the
presence of the P(OMe)3 ligand. The Ru–P bonds in 3b and 3c
should be relatively stronger.
The structure of complex 4 has been determined by a single-
crystal X-ray diffraction analysis. An ORTEP drawing is shown
in Fig. 2. Selected bond distances and angles are listed in Table
2. The co-ordination sphere consists of a η5-C5H5 group (Ru–
C(Cp) 2.183–2.253 Å, average 2.214 Å), a P(OMe)3 ligand (Ru–
P 2.245(3) Å) and a η3-allylic ligand (Ru–C1 2.250(9), Ru–C2
2.142(10), Ru–C3 1.934(10) Å). The η3-allylic ligand is formed
by co-ordination of the C1–C2 bond of the butadienyl ligand
gave an orange-red solution from which the neutral vinyl-
idene complex [RuCp(PPh ){P(O)(OMe) }{᎐C᎐C(Ph)C(Ph)-
᎐ ᎐
3
2
C(CN)2}] 6 was obtained in 88% yield. The 1H NMR spectrum
displays inequivalent OMe resonances at δ 3.20 and 2.96 both
with JH–P = 11.6 Hz. Two doublet 31P resonances appear at
δ 105.6 and 43.7 with JP–P = 47.8 Hz, the former shifted signifi-
cantly from δ 158.3 of P(OMe)3 in 1a indicating that an
Arbuzov-like dealkylation16 of the P(OMe)3 ligand could have
occurred in the reaction. The 13C NMR spectrum displays a
doublet of doublet resonance at δ 339.8 attributed to Cα, indi-
cating the presence of a vinylidene ligand. The product is thus
assumed to have a neutral vinylidene structure and a phos-
phonate ligand.
and there is delocalization between C–C single and C᎐C double
᎐
bonds (C2–C3 1.418(13); C1–C2 1.422(14); C3–C4 1.382(13)
Å).
Evaporation of the solvent of the crude product caused
formation of orange crystals. Complex 6 cocrystallized with
t
Reaction of complex 4 with BuNC in CH2Cl2 at refluxing
temperature for 2 d afforded the butadienyl complex [RuCp-
(OH)(Ph)C᎐C(CN)2, a product resulting from substitution of
᎐
{P(OMe) }(CNtBu){C[᎐C(CN) ]C(Ph)CH(Ph)}] 5. The 31P
᎐
3
2
the chlorine atom of excess of Cl(Ph)C᎐C(CN) . The structure
᎐
2
NMR spectrum displays a singlet resonance at δ 159.2 assign-
of 6 was fully characterized by a single-crystal X-ray diffraction
analysis. An ORTEP drawing is shown in Fig. 3. Selected bond
distances and angles are listed in Table 3. The short Ru–C1
bond of 1.790(5) Å is typical of a ruthenium vinylidene system
and so is the C1–C2 bond of 1.362(6) Å.18 The ruthenium–
vinylidene linkage is nearly linear; the bond angle Ru–C1–C2 is
173.9(4)Њ. The relatively short bond length P2–O1 (1.475(3) Å)
with no methyl group bound to O1 indicates the presence of a
phosphonate ligand. The bonds P2–O2 and P2–O3 (1.593(4)
and 1.585(3) Å) are relatively longer. There is an intermolecular
hydrogen bond between the phosphonate ligand of 6 and
1
able to the P(OMe)3 ligand. The H NMR spectrum displays
three singlet resonances at δ 5.97, 4.63 and 1.34 assignable to
CHPh, Cp and C(CH3)3, respectively, and a doublet resonance
at δ 3.57 with JH–P = 11.6 Hz assignable to P(OMe)3. The η3-
allylic ligand in 4 became η1 bonding and the co-ordination site
was replaced by a donor tert-butyl cyanide ligand. Complex 5 is
thermally more stable than 3b and 3c. Thermolysis of complex
5 in benzene at refluxing temperature for two days did not
remove the phosphite or the isocyanide ligand.
Reaction of ruthenium acetylides with Cl(Ph)C᎐C(CN)
᎐
2
(OH)(Ph)C᎐C(CN) with O1–H and O4–H 1.00(5) and 1.45(5)
᎐
2
Metal acetylide complexes are known to react readily with acti-
vated olefins containing electron-withdrawing groups affording
[2 ϩ 2] cycloaddition products. We therefore treated vinyl chlor-
ide with the acetylide complex 1a to see if the reaction would
proceed in a similar manner. The reaction of 1a with an excess
Å, respectively.
Lacking phosphite ligands, both complexes 1b and 1c, upon
reacting with Cl(Ph)C᎐C(CN) , afforded in high yield the
᎐
2
cationic vinylidene complexes [RuCp(L)(LЈ){᎐C᎐C(Ph)C(Ph)-
᎐ ᎐
C(CN)2}]Cl 7b, (LLЈ = dppe) and 7c, (L = PPh3, LЈ = CNtBu),
respectively. For 7b the 31P NMR spectrum displays a singlet
of Cl(Ph)C᎐C(CN) in CH Cl at room temperature for 24 h
᎐
2
2
2
J. Chem. Soc., Dalton Trans., 1999, 4223–4230
4225

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resonance at δ 77.4 assignable to the dppe ligand. In the 13C
NMR spectrum the triplet resonance at δ 351.8 with JC–P = 14.8
Hz is assigned to Cα. The H NMR spectrum of 7c displays
resonances at δ 5.66 and 1.17 attributed to Cp and C(CH3)3,
respectively, and the 31P NMR spectrum displays a singlet
resonance at δ 44.1 assignable to the PPh3 ligand. The 13C
NMR spectrum displays a doublet resonance at δ 345.2 with
JC–P = 12.0 Hz assignable to Cα of the vinylidene ligand and a
doublet resonance at δ 198.6 with JC–P = 16.3 Hz assignable to
the CNtBu. It is not surprising that the chloride atom of
Table 4 Selected bond distances (Å) and angles (Њ) of [RuCp(PPh3)-
{P(OMe)3}(COCH2Ph)] 10
1
Ru–P1
Ru–C1
C1–O1
2.2153(15)
2.010(5)
1.326(7)
Ru–P2
C1–C2
C2–C3
2.3097(15)
1.518(7)
1.510(8)
P1–Ru–P2
P2–Ru–C1
Ru–C1–O1
C1–C2–C3
93.53(5)
93.06(15)
128.3(4)
119.0(5)
P1–Ru–C1
Ru–C1–C2
O1–C1–C2
93.53(15)
120.6(4)
111.0(4)
Cl(Ph)C᎐C(CN) behaved as a good leaving group and ended
᎐
2
up as a counter anion after the formation of the cationic vinyl-
idene complexes; NH4PF6 was added to exchange the counter
anion after the reaction was completed.
Other phosphonate vinylidene complexes
Treatment of complex 1a with ICH2CN in CH2Cl2 for 10 min
afforded the vinylidene complex [RuCp(PPh ){P(OMe) }᎐
᎐
3
3
1
C᎐C(Ph)CH CN}]I 8a in 64.8% yield (Scheme 2). In the H
᎐
2
Fig. 4 An ORTEP drawing of complex 10.
In the presence of acid the newly formed carbon–carbon
bond of complex 8a is easily cleaved. Since NH4PF6 was used in
the preparation, it was converted into HPF6. Thus complex 8a
Ϫ
with PF6 counter anion prepared at room temperature is
unstable particularly in CH2Cl2 solution. It decomposes to give
the acyl complex [RuCp(PPh3){P(OMe)3}(COCH2Ph)] 10.
With IϪ anion, 8a is stable for one day and then the Arbuzov-
like dealkylation occurs to give neutral vinylidene complex 9a.
The presence of HPF6 is required for the formation of acyl
complex 10. In fact, in 1980, Bruce and Swincer20 reported a
similar reaction and proposed a possible mechanism.
The molecular structure of complex 10 has been determined
by an X-ray diffraction study. An ORTEP drawing is shown in
Fig. 4. Selected bond distances and bond angles are listed in
Table 4. The bond distance of Ru–C1 (2.010(5) Å) is typical for
a Ru–C single bond and that of C1–O1 (1.326(7) Å) is typical
for a C–O double bond. The bond angles of Ru–C1–O1
(128.3(4)Њ) and O1–C1–C2 (111.0(4)Њ) are slightly deviated from
that of a typical C (sp2) hybidization which may be due to the
steric effect between the phenyl group of the acyl ligand and the
bulky PPh3 ligand.
Scheme 2
Our attempts to prepare similar vinylidene complexes with a
trimethyl phosphite ligand all led to the corresponding neutral
NMR spectrum the two dd resonances at δ 3.27 and 3.17 are
assigned to the two non-equivalent methylene protons. Length-
ening the reaction time caused Arbuzov-like dealkylation to
occur, leading to formation of the phosphonate complex [RuCp-
phosphonate complexes [RuCp(PPh ){P(᎐O)(OMe) }{᎐C᎐
᎐
᎐ ᎐
3
2
C(Ph)CH2R}], R = C6F5 9b; R = C6H5 9c; p-NCC6H4 9d; R =
p-F3CC6H4 9e; 1-C10H7 9f or CO2CH3 9g in high yield (Scheme
2). The most characteristic spectroscopic data of these vinyl-
idene complexes again consist of a strongly deshielded reson-
ance as a triplet at δ 348 3 in the 13C NMR spectrum and two
(PPh ){P(O)(OMe) }{᎐C᎐C(Ph)CH CN}] 9a. Transformation
᎐ ᎐
3
2
2
of the phosphite ligand to a phosphonate ligand was revealed
by a significant shift of the 31P NMR resonance from δ 135.3 to
doublet 31P NMR resonances at around δ 96 2 and 49
2
1
95.4. Formation of CH3I was seen in the H NMR spectrum.
attributed to P(O)(OMe)2 and PPh3, respectively. Complexes
9a–9g are all deep red oils, possibly because of the presence of
phosphonate ligand and are stable in solution and in air for
more than one month. Attempted deprotonation failed to give
a cyclopropenyl complex, possibly due to lack of a positive
charge.
The observation of the sequential transformation seems to
indicate that formation of the phosphonate ligand required
halide ion. The most characteristic spectroscopic data of the
two vinylidene complexes consist of a strongly deshielded Cα
resonance as a doublet of doublet at δ 348.6 2.5 in the 13C
NMR spectrum.19 Since 8a is a cationic complex containing a
P(OMe)3 ligand, it is not surprising to see an Arbuzov-like
dealkylation in the presence of IϪ counter anion to give the
phosphonate complex 9a.
Conclusion
The [2 ϩ 2] cycloaddition of the unsymmetrical olefin HPhC᎐
᎐
4226
J. Chem. Soc., Dalton Trans., 1999, 4223–4230

View Article Online
᎐
C(CN)2 to [RuCp(L)(LЈ)(C᎐CPh)] gave cyclobutenyl
C(CN)2-CCPh). Calc. for C44H40N2O3P2Ru: C, 65.42; H, 4.99;
᎐
complexes 2a–2c and butadienyl complexes 3a–3c. Further
N, 3.47. Found: C: 65.73; H, 4.85; N, 3.59%.
pyrolysis of 2a and 3a gave the η3-allylic complex 4 by loss
of a PPh3 ligand. The reaction of 1a with ClPhC᎐C(CN)
proceeded through an Arbuzov-like dealkylation and resulted
in formation of the neutral vinylidene complex [RuCp(PPh3)-
[RuCp(PPh )(CNtBu){C᎐C(Ph)CH(Ph)C(CN) }] 2c. To a
solution of complex 1c (500 mg, 0.817 mmol) in CH2Cl2 (20 mL)
᎐
2
᎐
3
2
was added H(Ph)C᎐C(CN) (377.5 mg, 2.45 mmol) and the
᎐
2
{P(O)(OMe) }{᎐C᎐C(Ph)C(Ph)C(CN) }] 6. The reaction of 1b
᎐ ᎐
2
2
solution was stirred for 10 min at room temperature. Removal
of the solvent under vacuum followed by addition of hexane
gave a yellow precipitate. After filtration, the solid was further
washed with 2 × 20 mL of hexane and 10 mL of diethyl ether
and dried under vacuum to give the product 2c (544.5 mg, yield
and 1c with Cl(Ph)C᎐C(CN) afforded cationic vinylidene
᎐
2
complexes [RuCp(L)(LЈ){᎐C᎐C(Ph)C(Ph)C(CN) }Cl 7. In
᎐ ᎐
2
Cl(Ph)C᎐C(CN) , the two strong electron-withdrawing CN
᎐
2
groups make the chlorine atom a good leaving group. The
Arbuzov-like dealkylation reaction is not uncommon for such a
ruthenium entity with a vinylidene ligand. The reaction of 1a
with organic halide XCH2R afforded neutral phosphonate
1
87%). Spectroscopic data for 2c: H NMR (C6D6) δ 7.89–6.90
(m, 25 H, Ph), 4.98 (s, Cp), 4.85 (s, 1 H, CH) and 1.21 (s, 9 H,
C(CH3)3); 31P NMR (CDCl3) δ 59.2; 13C NMR (CDCl3) δ 243.3
(d, CNtBu, JC–P = 10.1), 167.2 (d, Cα, JC–P = 9.9Hz), 158.7
(CPh), 137.8–125.0 (Ph), 117.6, 115.5 (2CN), 84.0 (Cp), 82.4
(C(CN)2), 58.1 (CHPh), 56.6 (C(CH3)3) and 30.4 (C(CH3)3);
MS (m/z, 102Ru) 767.2 (Mϩ ϩ 1), 613.0 (Mϩ Ϫ PhHC᎐C(CN) )
vinylidene complexes [RuCp(PPh ){P(O)(OMe) }{᎐C᎐C(Ph)-
᎐ ᎐
3
2
CH2R}].
Experimental
General procedures
᎐
2
and 512.0 (Mϩ Ϫ PhHC᎐C(CN) -CCPh).
᎐
2
[RuCp(PPh )(CNtBu){C[᎐C(CN) ]C(Ph)CH(Ph)}] 3c.
A
All manipulations were performed under nitrogen using
vacuum-line, dry-box, and standard Schlenk techniques.
Dichloromethane was distilled from CaH2 and diethyl ether
and THF from sodium diphenylketyl. All other solvents and
reagents were of reagent grade used without further purifi-
cation. The NMR spectra were recorded on Bruker AC-200
and AM-300WB FT-NMR spectrometers at room temper-
ature (unless stated otherwise) and are reported in units of
δ with residual protons in the solvents as an initial stand-
ard (CDCl3, δ 7.24: acetone-d6, δ 2.04). The FAB mass spectra
᎐
3
2
CH2Cl2 solution of complex 2c (200 mg, 0.261 mmol) was
stirred at room temperature for 2 h. Removal of the solvent
under vacuum followed by addition of hexane gave a yellow
precipitate which was dried under vacuum, giving the product
1
3c (186.0 mg, 93%). H NMR (CDCl3): δ 7.89–6.72 (m, 25 H,
Ph), 5.33 (s, H), 4.40 (s, Cp) and 1.05 (s, 9 H, C(CH3)3). 31P
NMR (CDCl3): δ 56.0. 13C NMR (CDCl3): δ 233.8 (d,
JC–P = 10.1, CNtBu), 158.3 (d, Cα, JC–P = 9.9 Hz), 155.1 (CPh),
137.4–115.5 (Ph), 113.6, 112.5 (2CN), 88.9 (C(CN)2), 84.2 (Cp),
57.0 (C(CH3)3), 56.7 (CHPh) and 30.5 (C(CH3)3); MS (m/z,
102Ru): 767.2 (Mϩ ϩ 1), 505.0 (Mϩ ϩ 1 Ϫ PPh3) and 422.0
(Mϩ ϩ 1 Ϫ PPh3-tBuNC). Calc. for C40H46N3PRu: C, 72.04; H,
5.26; N, 5.48. Found: C, 72.66; H, 5.07; N, 5.33%.
were recorded on a JEOL SX-102A spectrometer. The com-
᎐
plexes [RuCp(L)(LЈ)(C᎐CPh)] 1a [L = PPh , LЈ = P(OMe) ], 1b
᎐
3
3
(LLЈ = dppe) and 1c (L = PPh3, L = CNtBu) were prepared
following the methods reported.21 Elemental analyses and
X-ray diffraction studies were carried out at the Regional
Center of Analytical Instrument located at the National
Taiwan University.
[RuCp(dppe){C᎐C(Ph)CH(Ph)C(CN) }] 2b. This complex
᎐
2
(523.3 mg, 0.638 mmol, yield 85%) was prepared from 1b (500
mg, 0.751 mmol) using the same procedure as that for 2c and a
reaction time of 1 h at room temperature. H NMR (C6D6):
Syntheses
1
δ 8.17–6.63 (m, 30 H, Ph), 5.24 (s, 1 H, CH), 4.67 (s, Cp) and
2.68–2.40 (m, CH2CH2). 31P NMR (CDCl3): δ 98.1 and 96.9
(2br). 13C NMR (CDCl3): δ 164.9 (t, Cα, JC–P = 17.0), 157.1
(CPh), 136.8–122.8 (Ph), 119.1, 117.4 (2CN), 84.9 (Cp), 82.3
(C(CN)2), 30.1 and 29.5 (2d, JC–P = 18.0 Hz); MS (m/z, 102Ru)
821.1 (Mϩ ϩ 1), 666.0 (Mϩ Ϫ PhHC᎐C(CN) ) and 565.0 (Mϩ Ϫ
[RuCp(PPh ){P(OMe) }{C᎐C(Ph)CH(Ph)C(CN) }] 2a and
᎐
3
3
2
[RuCp(PPh ){P(OMe) }{C[᎐C(CN) ]C(Ph)CH(Ph)}] 3a. To a
᎐
3
3
2
solution of complex 1a (500 mg, 0.766 mmol) in CH2Cl2 (20 mL)
was added H(Ph)C᎐C(CN) (354.3 mg, 2.29 mmol) and the
᎐
2
1
solution stirred for 1 h at room temperature. The H and 31P
NMR spectra of the product indicated formation of two major
products 2a and 3a in a ratio of 1:1. Reduced the solvent to ca.
3 mL under vacuum followed by addition of hexane gave yellow
precipitates. After filtration, the solid was further washed with
2 × 20 mL of hexane and 10 mL of diethyl ether and dried
under vacuum to give a mixture of 2a and 3a (544.5 mg, 0.674
mmol) in a total yield of 75%. Crystallization of the mixture
from CH2Cl2–hexane (1:3) gave yellow crystals. At room tem-
perature 3a in CDCl3 solution was converted into a mixture of
2a and 3a (1:1) in 30 min. Spectroscopic data for 2a: 1H NMR
(CDCl3): δ 7.90–6.35 (m, 25 H, Ph), 5.10 (s, 1 H, CH), 5.01 (s,
Cp) and 3.27 (d, 9 H, JH–P = 10.93 Hz, OCH3); 31P NMR
(CDCl3) δ 148.9 and 58.8 (2d, JP–P = 70.2 Hz); 13C NMR
(CDCl3) δ 164.6 (q, Cα, JC–P = 12.6, 7.2), 163.0 (CPh), 137.4–
123.0 (Ph), 113.7, 112.5 (2CN), 82.9 (C(CN)2), 82.6 (Cp) and
52.2 (d, JC–P = 9.0 Hz, OCH3); MS (m/z, 102Ru) 809.1 (Mϩ ϩ 1),
654.1 (Mϩ Ϫ PhHC᎐C(CN) ) and 429.0 (Mϩ Ϫ PhHC᎐C(CN) -
᎐
2
PhHC᎐C(CN) -CCPh). Complex [RuCp(dppe){C[᎐C(CN) ]-
᎐
᎐
2
2
C(Ph)CH(Ph)}] 3b (180.0 mg, yield 90%) was prepared from 2b
(200 mg, 0.244 mmol) using the same procedure as that for 3c
1
and the reaction time was 8 h at room temperature. H NMR
(C6D6): δ 7.91–6.97 (m, 30H, Ph), 5.95 (br, 1H, CH), 4.43 (s,
Cp) and 2.70–2.05 (m, CH2CH2). 31P NMR (CDCl3): δ 94.0 and
92.3 (2br). 13C NMR (CDCl3): δ 164.9 (t, Cα, JC–P = 17.0), 157.1
(CPh), 136.8–122.8 (Ph), 119.1, 117.4 (2CN), 84.9 (Cp), 82.3
(C(CN)2), 30.1 and 29.5 (2d, JC–P = 18.0 Hz); MS (m/z, 102Ru)
821.1 (Mϩ ϩ 1) and 565.0 (Mϩ Ϫ PhHC᎐C(CN) -CCPh). Calc.
᎐
2
for C49H40N2P2Ru: C, 71.78; H, 4.92; N, 3.42. Found: C, 72.05;
H, 4.75; N, 3.32%.
[RuCp{P(OMe) }{ꢀ3-C[᎐C(CN) ]C(Ph)CH(Ph)}] 4. To
a
᎐
3
2
solution of complex 1a (500 mg, 0.766 mmol) in benzene
H(Ph)C᎐C(CN) (345.3 mg, 2.29 mmol) was added and the
᎐
᎐
᎐
2
2
2
1
CCPh). Spectroscopic data for 3a: H NMR (CDCl3) δ 7.76–
6.44 (m, 25 H, Ph), 4.66 (s, 1 H, CH), 4.74 (s, Cp) and 3.37
(d, 9 H, JH–P = 11.13 Hz, OCH3); 31P NMR (CDCl3) δ 148.2 and
58.3 (2d, JP–P = 70.35 Hz); 13C NMR (CDCl3) δ 165.8 (q,
Cα, JC–P = 15.7, 8.9), 162.9 (CPh), 139.6–118.2 (Ph), 117.1,
116.6 (2CN), 84.2 (C(CN)2), 82.7 (Cp), 60.5 (CHPh) and
52.1 (d, JC–P = 9.0 Hz, OCH3); MS (m/z, 102Ru) 809.1 (Mϩ ϩ
1), 654.1 (Mϩ Ϫ PhHC᎐C(CN) ) and 429.0 (Mϩ Ϫ PhHC᎐
solution refluxed for 48 h. Removal of benzene solution under
vacuum followed by addition of 50 mL of hexane gave a yellow
precipitate. After filtration, the solid was further washed with
20 × 2 mL of hexane, 10 mL of diethyl ether and dried under
vacuum, giving the product 4 (368 mg) in 88% yield. 1H NMR
(CDCl3): δ 7.45–6.72 (m, 10 H, Ph), 4.94 (s, Cp), 3.63 (d, 9 H,
JH–P = 11.75, OCH3) and 3.43 (d, 1 H, CH(Ph), JH–P = 12.30
Hz). 31P NMR (CDCl3): δ 159.35 (P(OMe)3). 13C NMR (CDCl3):
᎐
᎐
2
J. Chem. Soc., Dalton Trans., 1999, 4223–4230
4227

View Article Online
δ 223.5 (d, JC–P = 14.6, Cα), 141.6, 137.0, 131.0–126.0 (Ph),
118.2, 113.0 (2CN), 86.1 (Cp), 78.6 (d, JC–P = 8.68, C(CN)2),
for C46H39F6N3P2Ru: C, 60.66; H, 4.32; N, 4.61. Found: C,
61.04; H, 4.40; N, 4.08%.
71.3 (C(Ph)᎐CH(Ph)) and 52.6 (d, JC–P = 7.67 Hz, OCH3); MS
᎐
(m/z, 102Ru): 546.1 (Mϩ) and 291.0 (Mϩ Ϫ PhHC᎐C(CN) -
[RuCp(PPh ){P(OMe) }{᎐C᎐C(Ph)CH CN}]I 8a. A Schlenk
᎐
᎐ ᎐
2
3
3
2
CCPh). Calc. for C26H25N2O3PRu: C, 57.24; H, 4.62; N, 5.14.
Found: C, 57.65; H, 4.48; N, 5.03%.
flask was charged with ICH2CN (0.20 mL, 1.53 mmol), com-
plex 1a (0.20 g, 0.31 mmol) and 10 mL of CH2Cl2. The mixture
was stirred at room temperature for 10 min. The solvent was
reduced to about 3 mL under vacuum and 20 mL of ether were
added resulting in an orange precipitation. The mixture was
filtered and the solid portion was washed with 20 mL of
n-pentane and 20 mL of diethyl ether and dried under vacuum
to give 8a (0.163 g, 64.8% yield). 1H NMR (CDCl3): δ 7.49–7.06
(m, 20 H, Ph), 5.54 (s, Cp), 3.37 (d, 9 H, JH–P = 11.1,
P(OMe)3), 3.27 and 3.17 (dd, CH2CN, JH–H = 17.8 Hz). 31P
NMR (CDCl3): δ 135.4 and 44.8 (2d, JP–P = 49.30 Hz). 13C
[RuCp{P(OMe)3}(CNtBu){C[C(CN)2]C(Ph)CH(Ph)}] 5. To a
solution of complex 4 (100 mg, 0.183 mmol) in CH2Cl2, tBuCN
(62.1 µL, 0.550 mmol) was added and the solution refluxed
for 48 h. Removal of the solvent under vacuum followed by
addition of 30 mL of hexane gave a yellow precipitate. After
filtration, the solid was further washed with 10 × 2 mL of
hexane, 10 mL of diethyl ether and dried under vacuum, giving
the product 5 (82.7 mg, yield 72%). 1H NMR (CDCl3): δ 7.65–
6.96 (m, 25 H, Ph), 5.97 (s, 1 H, CH), 4.63 (s, Cp), 3.57 (d, 9 H,
JH–P = 11.55 Hz, OCH3) and 1.34 (s, C(CH3)3). 31P NMR
(CDCl3): δ 159.2. 13C NMR (CDCl3): δ 236.0 (d, CNtBu,
JC–P = 17.9), 154.5, 138.7–117.8 (Ph, Cβ and Cγ), 119.6, 115.3
(2CN), 85.2 (Cp), 57.0 (s, C(CH3)3), 51.8 (d, JC–P = 3.8 Hz,
OCH3) and 29.6 (s, C(CH3)3); MS (m/z, 102Ru): 629.1 (Mϩ),
505.1 (Mϩ Ϫ P(OMe)3) and 422.0 (Mϩ Ϫ P(OMe)3-tBuNC).
Calc. for C31H34N3O3PRu: C, 59.22; H, 5.45; N, 6.68. Found:
C, 59.76; H, 5.32; N, 6.47%.
2
NMR (CDCl3): δ 351.7 (q, Cα, JC–P = 13.9, 20.0), 133.1–126.4
(m, Ph), 118.2 (CN), 116.4 (Cβ), 93.0 (Cp), 54.2 (d, JC–P = 9.6
Hz, P(OMe)3) and 12.3 (CH2CN); MS (m/z, 102Ru): 694.1
(Mϩ Ϫ I), 553.1 (Mϩ Ϫ I-CH2CN-CCPh) and 429.1 (Mϩ Ϫ
I-CH2CN-CCPh-P(OMe)3). Calc. for C36H36INO3P2Ru: C,
52.69; H, 4.42; N, 1.71. Found: C, 52.89; H, 4.36; N, 1.65%.
[RuCp(PPh ){P(O)(OMe) }{᎐C᎐C(Ph)CH CN}]
᎐ ᎐
9a.
A
3
2
2
Schlenk flask was charged with ICH2CN (0.20 mL, 1.53 mmol),
complex 1a (200 mg, 0.31 mmol) and 10 mL of CH2Cl2. The
mixture was heated to reflux for 1 h. The solvent was removed
under vacuum and the residue washed with hexane and dried
under vacuum to give the red oily product 9a (186.9 mg,
[RuCp(PPh ){P(O)(OMe) }{᎐C᎐C(Ph)C(Ph)C(CN) }]
6.
To a solution of complex 1a (150 mg, 0.230 mmol) in CH2Cl2,
᎐ ᎐
3
2
2
Cl(Ph)C᎐C(CN) (24.9 mg, 0.689 mmol) was added and
᎐
2
1
the solution stirred at room temperature for 24 h, the solution
changing from yellow to red. At this stage, crystals of 6 contain-
ing (OH)PhC᎐C(CN) formed if the solvent slowly evapor-
90% yield). H NMR (CDCl3): δ 7.50–6.86 (m, 20H, Ph), 5.32
(s, Cp), 3.45, 3.37 (2d, JH–H = 12.4, CH2CN), 3.31 and 2.95
(2d, 6 H, JH–P = 11.5 Hz, OCH3). 31P NMR (CDCl3): δ 95.4 and
48.1 (2d, JP–P = 47.0 Hz). 13C NMR (CDCl3): δ 346.2 (t, Cα,
JC–P = 16.0), 133.5–119.7 (m, Ph), 117.8 (CN), 116.7 (Cβ),
92.3 (Cp), 50.3 (d, JC–P = 8.4, P(OMe)3), 49.8 (d, JC–P = 9.4
Hz, P(OMe)3) and 12.3 (CH2); MS (m/z, 102Ru): 680.1 (Mϩ ϩ
1), 539.1 (Mϩ Ϫ CH2CN-CCPh) and 429.1 (Mϩ Ϫ CH2CN-
CCPh Ϫ P(O)(OMe)2). Calc. for C35H33NO3P2Ru: C, 61.94;
H, 4.90; N, 2.06. Found: C, 62.09; H, 4.72; N, 1.68%. The
᎐
2
ated in the air. The solvent was reduced to ca. 5 mL then
the mixture was added to a 50 mL solution of diethyl ether
yielding orange-red precipitates of 6. In order to remove
(OH)PhC᎐C(CN) (which could be formed by the reaction of
᎐
2
water in the solution and excess of Cl(Ph)C᎐C(CN) ), the pre-
᎐
2
cipitate was further washed with 10 mL of diethyl ether and
subsequently with 10 × 2 mL of hexane, then dried under
1
vacuum giving 6 (160.0 mg, yield 87.9%). H NMR (CDCl3):
complexes
[RuCp(PPh ){P(᎐O)(OMe) }{᎐C᎐C(Ph)CH R}]
᎐
᎐ ᎐
3
2
2
δ 7.80–7.14 (m, 25 H, Ph), 5.33 (s, Cp), 3.20 (d, 3 H,
JH–P = 11.61, OCH3) 2.96 (d, 3 H, JH–P = 11.63 Hz, OCH3). 31P
NMR (CDCl3): δ 105.6 and 43.7 (2d, JP–P = 47.8 Hz). 13C NMR
(R = C6F5 9b; Ph 9c; p-NCC6H4CN 9d; p-F3CC6H4 9e; 1-C10H7
9f or CO2CH3 9g) were prepared from the reaction of 1a (0.20
g, 0.31 mmol) with BrCH2C6F5, BrCH2Ph, BrCH2(C6H4CN-p),
BrCH2(C6H4CF3-p), BrCH2(1-C10H7) or BrCH2CO2CH3 using
a similar procedure to that for 9a. Spectroscopic data for 9b: 1H
NMR (CDCl3) δ 7.86–6.82 (m, 20 H, Ph), 5.28 (s, Cp), 3.89,
3.65 (2d, JH–H = 15.6, CH2), 3.16 and 2.99 (2d, 6 H, JH–P = 11.5
Hz, OCH3); 31P NMR (CDCl3) δ 97.9 and 50.4 (2d, JP–P = 45.5
Hz); 13C NMR (CDCl3) δ 346.4 (t, Cα, 2JC–P = 17.4), 146.3–125.8
(m, Ph), 123.0 (Cβ), 92.1 (Cp), 50.2, 49.7 (2d, JC–P = 7.3 Hz,
OCH3) and 17.2 (CH2); MS (m/z, 102Ru) 821.1 (Mϩ ϩ 1), 539.1
(Mϩ-CH2C6F5-CCPh) and 429.1 (Mϩ Ϫ CH2C6F5-CCPh-P(O)-
(OMe)2). Calc. for C35H33F5O3P2Ru: C, 58.61; H, 4.06. Found:
C, 58.97; H, 3.92%. Spectroscopic data for 9c: 1H NMR
(CDCl3) δ 7.76–6.89 (m, 20 H, Ph), 5.29 (s, Cp), 3.84, 3.68 (2d,
JH–H = 16.2, CH2), 3.30 and 3.06 (2d, 6 H, JH–P = 11.6 Hz,
OCH3); 31P NMR (CDCl3) δ 97.5 and 51.2 (2d, JP–P = 48.7 Hz);
13C NMR (CDCl3) δ 347.1 (t, Cα, JC–P = 16.2, 15.7), 133.5–119.7
(m, Ph), 117.8 (CN), 116.7 (Cβ), 92.3 (Cp), 50.3, 49.8 (2d,
JC–P = 8.93 Hz, OCH3) and 12.3 (CH2); MS (m/z, 102Ru) 732.1
(Mϩ ϩ 1), 539.1 (Mϩ Ϫ CH2Ph-CCPh) and 429.1 (Mϩ Ϫ CH2-
Ph-CCPh-P(O)(OMe)2). Calc. for C40H38O3P2Ru: C, 65.83; H,
5.25. Found: C, 66.01; H, 5.16%. Spectroscopic data for 9d: 1H
NMR (CDCl3) δ 7.77–6.82 (m, Ph), 5.24 (s, Cp), 3.91, 3.68 (2d,
JH–H = 16.4, CH2), 3.15 and 2.98 (2d, 6 H, JH–P = 11.2 Hz,
1
2
(CDCl3): δ 339.8 (q, JC–P = 14.1, JC–P = 4.7, Cα), 167.6 (Cβ),
134.4–127.8 (Ph), 114.8, 114.0 (2CN), 94.2 (Cp), 85.6 (Cγ),
78.2 (C(CN)2) and 52.3 (t, JC–P = 11.2 Hz, P(O)(OCH3)2); MS
(m/z, 102Ru): 793.0 (Mϩ ϩ 1), 539.0 (Mϩ Ϫ CH᎐C(CN) ) and
᎐
2
428.9 (Mϩ Ϫ CH᎐C(CN) -P(O)(OMe) ). Calc. for C H N -
᎐
2
2
43 36
2
O3P2Ru: C, 65.22; H, 4.58; N, 3.54. Found: C, 65.56; H, 4.77; N,
3.34%.
Complexes [RuCp(dppe){᎐C᎐C(Ph)C(Ph)C(CN) }][PF ] 7b
᎐ ᎐
2
6
(83% yield) and [RuCp(PPh )(tBuNC){᎐C᎐C(Ph)C(Ph)-
᎐ ᎐
3
C(CN)2}][PF6] 7c (76% yield) were prepared using the same
procedure as that for 6 and NH4PF6 was added to exchange the
counter anion after the reaction was complete. Spectroscopic
data for 7c: 1H NMR (CDCl3) δ 7.78–6.92 (m, 25 H, Ph), 5.66
(s, Cp) and 1.17 (s, 9 H, C(CH3)3); 31P NMR (CDCl3) δ 44.07;
13C NMR (CDCl3) δ 345.2 (d, JC–P = 12.0, Cα), 198.6 (d,
JC–P = 16.3, CNtBu), 164.7 (Cα), 137.1–126.0 (Ph), 113.7, 112.4
(2CN), 94.9 (Cp), 85.5 (d, JC–P = 13.74 Hz, Cγ), 78.3 (C(CN)2),
60.5 (C(CH3)3) and 29.8 (s, C(CH3)3); MS (m/z, 102Ru): 766.1
(Mϩ Ϫ PF6), 540.0 (Mϩ Ϫ PF Ϫ CH᎐C(CN) ϩ CO) and
᎐
6
2
512.0 (Mϩ Ϫ PF -CH᎐C(CN) ). Calc. for C H F N P Ru: C,
᎐
6
2
49 39
6
2
3
61.06; H, 4.08; N, 2.91. Found: C, 61.37; H, 3.96; N, 2.78%.
1
Spectroscopic data for 7b: H NMR (CDCl3) δ 7.81–6.49 (m,
30H, Ph), 5.46 (s, Cp) and 3.70–3.15 (m, 4H, CH2CH2); 31P
NMR (CDCl3) δ 77.4; 13C NMR (CDCl3) δ 351.8 (t, JC–P = 14.8,
Cα), 166.0 (Cβ), 135.8–126.2 (Ph), 114.1, 113.2 (2CN), 93.9
(Cp), 85.6 (Cγ), 80.3 (C(CN)2) and 28.9 (t, JC–P = 22.9 Hz,
PCH2CH2P); MS (m/z, 102Ru) 819.1 (Mϩ Ϫ PF6), 593.0 (Mϩ Ϫ
PF -CH᎐C(CN) ϩCO), 565.0 (Mϩ Ϫ PF -CH᎐C(CN) ). Calc.
OCH3). 31P NMR (CDCl3) δ 95.9, 50.8 (2d, JP–P = 47.5 Hz); 13
C
NMR (CDCl3) δ 349.4 (t, Cα, 2JC–P = 16.0), 147.5–118.3 (m, Ph),
117.8 (CN), 116.7 (Cβ), 92.1 (Cp), 50.3, 49.9 (2d, JC–P = 9.0 Hz,
OCH3) and 29.8 (CH2); MS (m/z, 102Ru) 757.1 (Mϩ ϩ 1), 539.1
(Mϩ Ϫ CH2C6H4CN-CCPh) and 429.1 (Mϩ Ϫ CH2C6H4CN-
CCPh-P(O)(OMe)2). Calc. for C41H37NO3P2Ru: C, 65.24; H,
᎐
᎐
6
2
6
2
4228
J. Chem. Soc., Dalton Trans., 1999, 4223–4230

View Article Online
Table 5 Crystal data and structure refinement for [RuCp(PPh3){P(OMe)3}{C[᎐C(CN)2]C(Ph)᎐CH(Ph)}] 3a, [RuCp{P(OMe)3}{η3-C(CN)2-
᎐
᎐
C(Ph)C᎐CH(Ph)}] 4, [RuCp(PPh3){P(O)(OMe)2}{᎐C᎐C(Ph)C(Ph)C(CN)2}] 6 and [RuCp(PPh3){P(OMe)3}(COCH2Ph)} 10
᎐
᎐ ᎐
3a
4
6
10
Formula
M
C44H40N2O3P2Ru
807.82
C26H25N2O3PRu
546.54
C53H42N4O4P2Ru
961.95
C34H36O4P2Ru
935.01
Crystal system
Space group
Monoclinic
P21/c
Monoclinic
P21/c
Triclinic
P1
Monoclinic
P21/c
¯
T/K
a/Å
b/Å
c/Å
α/Њ
β/Њ
298
298
298
298
11.3426(14)
31.489(5)
11.0026(15)
12.1184(18)
14.917(8)
13.498(3)
10.4298(14)
13.883(3)
18.082(4)
107.468(22)
91.791(20)
108.375(15)
2347.2(8)
2
18.016(3)
10.071(3)
22.979(4)
104.206(12)
92.155(14)
105.838(14)
γ/Њ
V/Å3
3809.6(10)
4
5.262
2438.2(14)
4
7.877
4011.1(15)
4
7.646
Z
µ/cmϪ1
4.392
Measured reflections
Observed reflections
R, RЈ
4954
2517
0.043, 0.040
4271
2169
0.058, 0.052
8273
4526
0.044, 0.035
7034
4591
0.045, 0.047
4.94; N, 1.86. Found: C, 65.53; H, 4.78; N, 1.77%. Spectroscopic
data for 9e: H NMR (CDCl3) δ 7.76–6.89 (m, Ph), 5.27 (s,
alent and duplicate reflections gave a total of 4954 unique data,
from which 2517 were considered observed (I > 2σ(I)). The
structure was solved by the heavy atom method then refined via
standard least-squares and Fourier-difference techniques. The
analytical forms of the scattering factor tables for the neutral
atoms were used.23 Final refinement converged smoothly to
values of R = 0.043 and RЈ = 0.040. The procedures for the
structure determination of 4, 6, and 10 were similar.
CCDC reference number 186/1698.
1
Cp), 3.91, 3.68 (2d, JH–H = 16.3, CH2), 3.25 and 3.01 (2d, 6 H,
JH–P = 11.6 Hz, OCH3); 31P NMR (CDCl3) δ 96.6, 50.9 (2d,
JP–P = 42.8 Hz); 13C NMR (CDCl3) δ 350.2 (t, Cα, 2JC–P = 17.1),
145.7–124.9 (m, Ph, Cβ), 92.1 (Cp), 50.4 (d, JC–P = 8.75, OCH3),
49.9 (d, JC–P = 9.21 Hz, OCH3) and 29.4 (CH2); MS (m/z, 102Ru)
800.1 (Mϩ ϩ 1), 539.1 (Mϩ Ϫ CH2C6H4CF3-CCPh) and 429.1
(Mϩ Ϫ CH2C6H4CF3-CCPh-P(O)(OMe)2). Calc. for C35H33F5-
O3P2Ru: C, 61.73; H, 4.68. Found: C, 61.98; H, 4.55%. Spectro-
scopic data for 9f: 1H NMR (CDCl3) δ 7.75–6.84 (m, Ph), 5.24
(s, Cp), 3.89, 3.71 (2d, JH–H = 16.4, CH2), 3.23 and 2.99 (2d, 6 H,
JH–P = 11.5 Hz, OCH3); 31P NMR (CDCl3) δ 97.0 and 50.0 (2d,
JP–P = 48.4 Hz); 13C NMR (CDCl3) δ 351.0 (t, Cα, 2JC–P = 16.4),
138.8–124.3 (m, Ph), 117.1 (Cβ), 92.0 (Cp), 50.2, 49.8 (2d,
JC–P = 9.2 Hz, OCH3) and 29.8 (CH2); MS (FAB, 102Ru)
m/z 782.1 (Mϩ ϩ 1), 539.1 (Mϩ Ϫ CH2C10H7-CCPh) and 429.1
(Mϩ Ϫ CH2C10H7-CCPh-P(O)(OMe)2). Calc. for C44H40O3P2-
Ru: C, 67.77; H, 5.17. Found: C, 67.95; H, 5.06%. Spectroscopic
data for 9g: 1H NMR (CDCl3) δ 7.84–6.88 (m, 20 H, Ph), 5.22
(s, Cp), 3.89, 3.75 (2d, JH–H = 16.5, CH2CO2CH3), 3.17 and 2.90
(2d, 6 H, JH–P = 11.6 Hz, OCH3); 31P NMR (CDCl3) δ 96.9 and
50.2 (2d, JP–P = 49.1 Hz); 13C NMR (CDCl3) δ 350.8 (t, Cα,
2JC–P = 15.6), 173.1 (CO2CH3), 135.5–124.8 (m, Ph), 121.0 (Cβ),
92.1 (Cp), 50.0, 49.6 (2d, JC–P = 8.7 Hz, OCH3), 51.5 (CH2-
CO2CH3) and 28.7 (CO2CH3); MS (m/z, 102Ru) 712.1 (Mϩ ϩ 1),
539.1 (Mϩ Ϫ CH2CO2CH3-CCPh) and 429.1 (Mϩ Ϫ CH2CO2-
CH3-CCPh-P(O)(OMe)2). Calc. for C36H36O5P2Ru: C, 60.75; H,
5.10. Found: C, 61.03; H, 5.02%.
See http://www.rsc.org/suppdata/dt/1999/4223/ for crystallo-
graphic files in .cif format.
Acknowledgements
We are grateful for support of this work by the National
Science Council, Taiwan, Republic of China.
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[RuCp(PPh3){P(OMe)3}{COCH2Ph)] 10. A Schlenk flask
was charged with ICH2CN (0.20 mL, 1.53 mmol), complex 1a
(200 mg, 0.31 mmol), NH4PF6 (74.8 mg, 0.459 mmol), and 20
mL of CH2Cl2. The solution was stirred at room temperature
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X-Ray analysis of complex 3a
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Paper 9/05788I
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J. Chem. Soc., Dalton Trans., 1999, 4223–4230