DAL
TON
FULL P
APER
J. Chem. Soc., Dalton Trans., 1999, 4223–4230 4223
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
Reactions of [RuCp(L)(L⬘)(C᎐᎐᎐CPh)] (Cp = η5-C
5H5; L= PPh3, L⬘ = P(OMe)3 1a; LL⬘ = dppe = Ph2PCH2
-CH2PPh2 1b; L= PPh3, L⬘ = CN
tBu 1c) with H(Ph)C
᎐᎐C(CN)2 gave the cyclobutenyl complexes
[RuCp(L)-(L⬘){C᎐᎐C(Ph)CH(Ph)C(CN)2}] 2a, 2b and 2c which readily transform to the butadienyl complexes
[RuCp(L)(L⬘){C[᎐᎐C(CN)2]C(Ph)CH(Ph)}] 3a, 3b and 3c, respectively. Thermolysis of 3a in benzene afforded
the allylic complex [RuCp{P(OMe)3}[η
3-C[=C(CN)
2]C(Ph)CH(Ph)}] 4 in high yield. Reaction of 4 with
tBuNC
gave [RuCp{P(OMe)3}(CNtBu)[η1-C[᎐᎐C(CN)2]C(Ph)CH(Ph)}] 5. Treatment of 1a with Cl(Ph)C᎐᎐C(CN)2 afforded
the neutral vinylidene phosphonate complex [RuCp(PPh3){P(O)(OMe)2}{᎐᎐C᎐᎐C(Ph)C(Ph)C(CN)2}] 6. Reactions
of 1b and 1c, both lacking phosphite ligands, with Cl(Ph)C᎐᎐C(CN)2 gave the cationic vinylidene complexes
[RuCp(L)(L⬘){᎐᎐C᎐᎐C(Ph)C(Ph)C(CN)2}]⫹ 7b and 7c, respectively. Treatment of 1a with ICH2CN afforded
[RuCp(PPh3){P(OMe)3}{᎐᎐C᎐᎐C(Ph)CH2CN}]I 8a. In the presence of acid complex 8a decomposes to give the acyl
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.
Introduction
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⫹ 2] cycloaddition of the triple bond with unsaturated organic substrates.4 A few cycloadditions of
organic substrates such as CS2,5 (NC)2C᎐᎐C(CF3)2, (NC)2C᎐᎐
C(CN)2
6 and Ph 2C᎐᎐C᎐᎐O
7 to the acetylide ligand in various
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⫹ 2] cycloaddition. This was followed by a facile ring open-ing of the resultant ruthenium cyclobutenyl complex generatopen-ing the ruthenium butadienyl species. In some cases, subsequent displacement of a phosphine ligand led to the η3-allylic
prod-uct. For example, reactions between [RuCp(L)(L⬘)(C᎐᎐᎐CR)] (R= Me or Ph; L = PPh3; L⬘ = CO, PPh3 or P(OPh)3; LL⬘ =
dppe) and tetracyanoethylene gave cyclobutenyl [RuCp-(L)(L⬘){C᎐᎐CRC(CN)2C(CN)2}], butadienyl [RuCp(L)(L
⬘)-{C[᎐᎐C(CN)2]CRC᎐᎐C(CN)2}] and allylic [RuCp(PPh3){η3
-C(CN)2CRC᎐᎐C(CN)2}] complexes.6
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. † Supplementary data available: rotatable 3-D crystal structure diagram in CHIME format. See http://www.rsc.org/suppdata/dt/1999/4223/
Since then, Brauman and Golden10 have estimated that the
thermally allowed contrarotatory process for cyclobutenes is more favored (by 15.0 kcal mol⫺1) than the disrotatory process. This experimental estimate is in accord with values obtained by Breulet and Schaefer11 from ab initio calculations.
Bruce and his co-workers studied the transformations of cycloadducts of transition metal acetylides and activated olefins, such as C(CF3)2᎐᎐C(CN)2],
12 trans-CH(CO
2Me)
᎐᎐C(CN)-(CO2Me)13 and 4-(O2N)C6H4CH᎐᎐C(CN)R (R = CN or CO2
-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⫹ 2] cycloaddition is the first step and is followed by further additions of isothiocyanate to give a trimerization product. In this paper we report the reactions of H(Ph)C᎐᎐ C(CN)2 and Cl(Ph)C᎐᎐C(CN)2 with ruthenium acetylides. These
olefins were chosen because the presence of different electro-philic groups might enable further information to be obtained in the course of these reactions.
Results and discussion
Synthesis of cyclobutenyl and butadienyl complexes
Treatment of [RuCp(PPh3){P(OMe)3}(C᎐᎐᎐CPh)] 1a with
H(Ph)C᎐᎐C(CN)2 in CH2Cl2 at room temperature for 1 h
resulted in formation of a mixture of two complexes: [RuCp-(PPh3){P(OMe)3}{C᎐᎐C(Ph)CH(Ph)C(CN)2}] 2a and
[RuCp-(PPh3){P(OMe)3}{C[᎐᎐C(CN)2]C(Ph)CH(Ph)}] 3a in a ratio of
1 : 1 (Scheme 1). Prolonging the reaction time did not alter the ratio. However, if we carried out this reaction at 0⬚C 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
Scheme 1
single crystals of 3a, which converted into the mixture in solution.
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)2 to the
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-ing ones of 3a. In the 1H 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 the dppe ligand and the 1H 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 ⫺20 ⬚C
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-C
5H5
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
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}{3-C[᎐᎐C(CN)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}{η
3
-C[᎐᎐C(CN)2]C(Ph)CH(Ph)}] 4 by removal of a PPh3 ligand with
high yield (Scheme 1). The 1H 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.
Fig. 1 An ORTEP drawing of complex 3a with thermal ellipsoids,
(in all Figures) shown at the 30% probability level.
Table 1 Selected bond distances (Å) and angles (⬚) of [RuCp(PPh3
)-{P(OMe)3}{C[᎐᎐C(CN)2]C(Ph)᎐᎐CH(Ph)}] 3a Ru–P1 Ru–C1 C1–C2 C2–C10 C16–C17 C17–N1 P1–Ru–P2 P2–Ru–C1 Ru–C1–C2 C1–C2–C3 2.2364(23) 2.055(8) 1.506(11) 1.512(11) 1.428(11) 1.143(11) 92.33(8) 94.57(21) 122.2(5) 124.2(7) Ru–P2 C1–C16 C2–C3 C3–C4 C16–C18 C18–N2 P1–Ru–C1 Ru–C1–C16 C1–C2–C10 C3–C2–C10 2.3305(23) 1.384(11) 1.319(11) 1.455(11) 1.451(11) 1.131(11) 92.92(22) 126.1(6) 111.8(6) 123.9(7)
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-C
5H5 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 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).
Reaction of complex 4 with tBuNC in CH
2Cl2 at refluxing
temperature for 2 d afforded the butadienyl complex [RuCp-{P(OMe)3}(CNtBu){C[᎐᎐C(CN)2]C(Ph)CH(Ph)}] 5. The 31P
NMR spectrum displays a singlet resonance at δ 159.2 assign-able to the P(OMe)3 ligand. The 1H 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
Metal acetylide complexes are known to react readily with acti-vated olefins containing electron-withdrawing groups affording [2⫹ 2] cycloaddition products. We therefore treated vinyl chlor-ide with the acetylchlor-ide complex 1a to see if the reaction would proceed in a similar manner. The reaction of 1a with an excess of Cl(Ph)C᎐᎐C(CN)2 in CH2Cl2 at room temperature for 24 h
Fig. 2 An ORTEP drawing of complex 4.
Table 2 Selected bond distances (Å) and angles (⬚) of
[RuCp-{P(OMe)3}{η3-C(CN)2C(Ph)C᎐᎐CH(Ph)}] 4 Ru–P Ru–C2 C1–C2 C3–C4 C4–C6 C6–N2 P–Ru–C1 P–Ru–C3 C1–C2–C13 Ru–C3–C4 C3–C4–C6 Ru–C1–C7 2.245(3) 2.142(10) 1.422(14) 1.382(13) 1.399(14) 1.135(14) 80.7(3) 89.3(3) 128.8(8) 144.8(7) 122.7(9) 118.5(6) Ru–C1 Ru–C3 C2–C3 C4–C5 C5–N1 P–Ru–C2 C1–C2–C3 C3–C2–C13 C3–C4–C5 Ru–C1–C2 2.250(9) 1.934(10) 1.418(13) 1.439(14) 1.124(13) 104.3(3) 111.1(9) 120.0(9) 120.6(9) 67.0(5)
gave an orange-red solution from which the neutral vinyl-idene complex [RuCp(PPh3){P(O)(OMe)2}{
᎐᎐C᎐᎐C(Ph)C(Ph)-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.
Evaporation of the solvent of the crude product caused formation of orange crystals. Complex 6 cocrystallized with (OH)(Ph)C᎐᎐C(CN)2, a product resulting from substitution of
the chlorine atom of excess of Cl(Ph)C᎐᎐C(CN)2. The structure
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)⬚. 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 (OH)(Ph)C᎐᎐C(CN)2 with O1–H and O4–H 1.00(5) and 1.45(5)
Å, respectively.
Lacking phosphite ligands, both complexes 1b and 1c, upon reacting with Cl(Ph)C᎐᎐C(CN)2, afforded in high yield the
cationic vinylidene complexes [RuCp(L)(L ⬘){᎐᎐C᎐᎐C(Ph)C(Ph)-C(CN)2}]Cl 7b, (LL⬘ = dppe) and 7c, (L = PPh3, L⬘ = CNtBu),
respectively. For 7b the 31P NMR spectrum displays a singlet
Fig. 3 An ORTEP drawing of complex 6.
Table 3 Selected bond distances (Å) and angles (⬚) of
[RuCp-(PPh3){P(O)(OMe)2}{C᎐᎐C(Ph)C(Ph)C(CN)2}]ⴢ(OH)(Ph)C᎐᎐C(CN)2 6 Ru–P1 Ru–C1 C2–C3 C3–C4 C4–C18 O4–H C18–N2 P2–O2 P1–Ru–P2 Ru–C1–C2 C2–C3–C4 C3–C4–C18 2.3437(14) 1.790(5) 1.434(7) 1.373(7) 1.492(7) 1.45(5) 1.136(7) 1.593(4) 92.01(5) 173.9(4) 123.5(4) 122.6(5) Ru–P2 C1–C2 C2–C5 C4–C17 O1–H C17–N1 P2–O1 P2–O3 P1–Ru–C1 C1–C2–C3 C3–C4–C17 P2–O1–H 2.2965(16) 1.362(6) 1.501(7) 1.447(8) 1.00(5) 1.143(8) 1.475(3) 1.585(3) 95.85(14) 120.4(4) 124.7(5) 171(3)
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 1H 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
Cl(Ph)C᎐᎐C(CN)2 behaved as a good leaving group and ended
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(PPh3){P(OMe)3}᎐᎐
C᎐᎐C(Ph)CH2CN}]I 8a in 64.8% yield (Scheme 2). In the 1H
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-(PPh3){P(O)(OMe)2}{᎐᎐C᎐᎐C(Ph)CH2CN}] 9a. Transformation
of the phosphite ligand to a phosphonate ligand was revealed by a significant shift of the 31P NMR resonance from δ 135.3 to
95.4. Formation of CH3I was seen in the 1H NMR spectrum.
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 I⫺ counter anion to give the phosphonate complex 9a.
Scheme 2
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
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 I⫺ 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)⬚) and O1–C1–C2 (111.0(4)⬚) 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.
Our attempts to prepare similar vinylidene complexes with a trimethyl phosphite ligand all led to the corresponding neutral phosphonate complexes [RuCp(PPh3){P(᎐᎐O)(OMe)2}{᎐᎐C᎐᎐
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
doublet 31P NMR resonances at around δ 96 ± 2 and 49 ± 2
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.
Conclusion
The [2⫹ 2] cycloaddition of the unsymmetrical olefin HPhC᎐᎐
Fig. 4 An ORTEP drawing of complex 10.
Table 4 Selected bond distances (Å) and angles (⬚) of [RuCp(PPh3
)-{P(OMe)3}(COCH2Ph)] 10 Ru–P1 Ru–C1 C1–O1 P1–Ru–P2 P2–Ru–C1 Ru–C1–O1 C1–C2–C3 2.2153(15) 2.010(5) 1.326(7) 93.53(5) 93.06(15) 128.3(4) 119.0(5) Ru–P2 C1–C2 C2–C3 P1–Ru–C1 Ru–C1–C2 O1–C1–C2 2.3097(15) 1.518(7) 1.510(8) 93.53(15) 120.6(4) 111.0(4)
C(CN)2 to [RuCp(L)(L⬘)(C᎐᎐᎐CPh)] gave cyclobutenyl
complexes 2a–2c and butadienyl complexes 3a–3c. Further 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)2
proceeded through an Arbuzov-like dealkylation and resulted in formation of the neutral vinylidene complex [RuCp(PPh3
)-{P(O)(OMe)2}{᎐᎐C᎐᎐C(Ph)C(Ph)C(CN)2}] 6. The reaction of 1b
and 1c with Cl(Ph)C᎐᎐C(CN)2 afforded cationic vinylidene
complexes [RuCp(L)(L⬘){᎐᎐C᎐᎐C(Ph)C(Ph)C(CN)2}Cl 7. In
Cl(Ph)C᎐᎐C(CN)2, the two strong electron-withdrawing CN
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
vinylidene complexes [RuCp(PPh3){P(O)(OMe)2}{
᎐᎐C᎐᎐C(Ph)-CH2R}].
Experimental
General procedures
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 puri fi-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
were recorded on a JEOL SX-102A spectrometer. The com-plexes [RuCp(L)(L⬘)(C᎐᎐᎐CPh)] 1a [L = PPh3, L⬘ = P(OMe)3], 1b
(LL⬘ = 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.
Syntheses
[RuCp(PPh3){P(OMe)3}{C᎐᎐C(Ph)CH(Ph)C(CN)2}] 2a and
[RuCp(PPh3){P(OMe)3}{C[᎐᎐C(CN)2]C(Ph)CH(Ph)}] 3a. To a
solution of complex 1a (500 mg, 0.766 mmol) in CH2Cl2 (20 mL)
was added H(Ph)C᎐᎐C(CN)2 (354.3 mg, 2.29 mmol) and the
solution stirred for 1 h at room temperature. The 1H 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 (M⫹⫹ 1), 654.1 (M⫹⫺ PhHC᎐᎐C(CN)2) and 429.0 (M⫹⫺ PhHC᎐᎐C(CN)2
-CCPh). Spectroscopic data for 3a: 1H NMR (CDCl
3) 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 (M⫹⫹ 1), 654.1 (M⫹⫺ PhHC᎐᎐C(CN)2) and 429.0 (M⫹⫺ PhHC᎐᎐
C(CN)2-CCPh). Calc. for C44H40N2O3P2Ru: C, 65.42; H, 4.99;
N, 3.47. Found: C: 65.73; H, 4.85; N, 3.59%.
[RuCp(PPh3)(CNtBu){C᎐᎐C(Ph)CH(Ph)C(CN)2}] 2c. To a
solution of complex 1c (500 mg, 0.817 mmol) in CH2Cl2 (20 mL)
was added H(Ph)C᎐᎐C(CN)2 (377.5 mg, 2.45 mmol) and the
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 87%). Spectroscopic data for 2c: 1H NMR (C
6D6) 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, J C–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 (M⫹⫹ 1), 613.0 (M⫹⫺ PhHC᎐᎐C(CN) 2) and 512.0 (M⫹⫺ PhHC᎐᎐C(CN)2-CCPh). [RuCp(PPh3)(CNtBu){C[᎐᎐C(CN)2]C(Ph)CH(Ph)}] 3c. A
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
3c (186.0 mg, 93%). 1H NMR (CDCl 3): 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 (M⫹⫹ 1), 505.0 (M⫹⫹ 1 ⫺ PPh 3) and 422.0
(M⫹⫹ 1 ⫺ PPh3-tBuNC). Calc. for C40H46N3PRu: C, 72.04; H,
5.26; N, 5.48. Found: C, 72.66; H, 5.07; N, 5.33%.
[RuCp(dppe){C᎐᎐C(Ph)CH(Ph)C(CN)2}] 2b. This complex
(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. 1H NMR (C
6D6): 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 (CDCl 3): 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 (M⫹⫹ 1), 666.0 (M⫹⫺ PhHC᎐᎐C(CN)2) and 565.0 (M⫹⫺ PhHC᎐᎐C(CN)2-CCPh). Complex [RuCp(dppe){C[᎐᎐C(CN)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 and the reaction time was 8 h at room temperature. 1H 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 (CDCl 3): 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 (M⫹⫹ 1) and 565.0 (M⫹⫺ PhHC᎐᎐C(CN)2-CCPh). Calc.
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}{ 3-C[
᎐᎐C(CN)2]C(Ph)CH(Ph)}] 4. To a
solution of complex 1a (500 mg, 0.766 mmol) in benzene H(Ph)C᎐᎐C(CN)2 (345.3 mg, 2.29 mmol) was added and the
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 (CDCl
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),
71.3 (C(Ph)᎐᎐CH(Ph)) and 52.6 (d, JC–P= 7.67 Hz, OCH3); MS
(m/z, 102Ru): 546.1 (M⫹) and 291.0 (M⫹⫺ PhHC᎐᎐C(CN) 2
-CCPh). Calc. for C26H25N2O3PRu: C, 57.24; H, 4.62; N, 5.14.
Found: C, 57.65; H, 4.48; N, 5.03%.
[RuCp{P(OMe)3}(CN
tBu){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 (CDCl
3): 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 (M⫹),
505.1 (M⫹⫺ P(OMe)3) and 422.0 (M⫹⫺ 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%.
[RuCp(PPh3){P(O)(OMe)2}{᎐᎐C᎐᎐C(Ph)C(Ph)C(CN)2}] 6.
To a solution of complex 1a (150 mg, 0.230 mmol) in CH2Cl2,
Cl(Ph)C᎐᎐C(CN)2 (24.9 mg, 0.689 mmol) was added and
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)2 formed if the solvent slowly
evapor-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)2 (which could be formed by the reaction of
water in the solution and excess of Cl(Ph)C᎐᎐C(CN)2), the
pre-cipitate was further washed with 10 mL of diethyl ether and subsequently with 10 × 2 mL of hexane, then dried under vacuum giving 6 (160.0 mg, yield 87.9%). 1H NMR (CDCl
3): 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 (CDCl3): δ 339.8 (q, 1JC–P= 14.1, 2JC–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 (M⫹⫹ 1), 539.0 (M⫹⫺ CH᎐᎐C(CN) 2) and
428.9 (M⫹⫺ CH᎐᎐C(CN)2-P(O)(OMe)2). Calc. for C43H36N2
-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)2}][PF6] 7b
(83% yield) and [RuCp(PPh3)(tBuNC){
᎐᎐C᎐᎐C(Ph)C(Ph)-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 (CDCl 3) δ 7.78–6.92 (m, 25 H, Ph), 5.66 (s, Cp) and 1.17 (s, 9 H, C(CH3)3); 31P NMR (CDCl 3) δ 44.07; 13C NMR (CDCl 3) 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 (M⫹⫺ PF6), 540.0 (M⫹⫺ PF6⫺ CH᎐᎐C(CN)2⫹ CO) and
512.0 (M⫹⫺ PF6-CH᎐᎐C(CN)2). Calc. for C49H39F6N2P3Ru: C,
61.06; H, 4.08; N, 2.91. Found: C, 61.37; H, 3.96; N, 2.78%. Spectroscopic data for 7b: 1H NMR (CDCl
3) 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 (M⫹⫺ PF6), 593.0 (M⫹⫺ PF6-CH᎐᎐C(CN)2⫹CO), 565.0 (M⫹⫺ PF6-CH᎐᎐C(CN)2). Calc.
for C46H39F6N3P2Ru: C, 60.66; H, 4.32; N, 4.61. Found: C,
61.04; H, 4.40; N, 4.08%.
[RuCp(PPh3){P(OMe)3}{᎐᎐C᎐᎐C(Ph)CH2CN}]I 8a. A Schlenk
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 (CDCl 3): 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 NMR (CDCl3): δ 351.7 (q, Cα, 2JC–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
(M⫹⫺ I), 553.1 (M⫹⫺ I-CH2CN-CCPh) and 429.1 (M⫹⫺
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(PPh3){P(O)(OMe)2}{᎐᎐C᎐᎐C(Ph)CH2CN}] 9a. A
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, 90% yield). 1H NMR (CDCl 3): 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 (CDCl 3): 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 (M⫹⫹
1), 539.1 (M⫹⫺ CH2CN-CCPh) and 429.1 (M⫹⫺ CH2
CN-CCPh⫺ 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 complexes [RuCp(PPh3){P(᎐᎐O)(OMe)2}{᎐᎐C᎐᎐C(Ph)CH2R}]
(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 (CDCl 3) 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 (M⫹⫹ 1), 539.1
(M⫹-CH2C6F5-CCPh) and 429.1 (M⫹⫺ 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 (CDCl 3) δ 97.5 and 51.2 (2d, JP–P= 48.7 Hz); 13C NMR (CDCl 3) 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
(M⫹⫹ 1), 539.1 (M⫹⫺ CH2Ph-CCPh) and 429.1 (M⫹⫺ 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, OCH3). 31P NMR (CDCl3) δ 95.9, 50.8 (2d, JP–P= 47.5 Hz); 13C 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 (M⫹⫹ 1), 539.1 (M⫹⫺ CH2C6H4CN-CCPh) and 429.1 (M⫹⫺ CH2C6H4
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}{η
3-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
Formula M Crystal system Space group T/K a/Å b/Å c/Å α/⬚ β/⬚ γ/⬚ V/Å3 Z µ/cm⫺1 Measured reflections Observed reflections R, R⬘ 3a C44H40N2O3P2Ru 807.82 Monoclinic P21/c 298 11.3426(14) 31.489(5) 11.0026(15) 104.206(12) 3809.6(10) 4 5.262 4954 2517 0.043, 0.040 4 C26H25N2O3PRu 546.54 Monoclinic P21/c 298 12.1184(18) 14.917(8) 13.498(3) 92.155(14) 2438.2(14) 4 7.877 4271 2169 0.058, 0.052 6 C53H42N4O4P2Ru 961.95 Triclinic P1¯ 298 10.4298(14) 13.883(3) 18.082(4) 107.468(22) 91.791(20) 108.375(15) 2347.2(8) 2 4.392 8273 4526 0.044, 0.035 10 C34H36O4P2Ru 935.01 Monoclinic P21/c 298 18.016(3) 10.071(3) 22.979(4) 105.838(14) 4011.1(15) 4 7.646 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: 1H NMR (CDCl
3) δ 7.76–6.89 (m, Ph), 5.27 (s, 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 (M⫹⫹ 1), 539.1 (M⫹⫺ CH2C6H4CF3-CCPh) and 429.1
(M⫹⫺ 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 (CDCl
3) 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 (M⫹⫹ 1), 539.1 (M⫹⫺ CH2C10H7-CCPh) and 429.1
(M⫹⫺ 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 (CDCl 3) 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 (CDCl 3) δ 350.8 (t, Cα, 2J C–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 (M⫹⫹ 1),
539.1 (M⫹⫺ CH2CO2CH3-CCPh) and 429.1 (M⫹⫺ CH2CO2
-CH3-CCPh-P(O)(OMe)2). Calc. for C36H36O5P2Ru: C, 60.75; H,
5.10. Found: C, 61.03; H, 5.02%.
[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
for 24 h. Then the solvent was removed under vacuum and the residue washed with 20 × 2 mL of hexane and 20 × 2 mL of ether to give the pale yellow product 10 (168.3 mg, 82% yield).
1H NMR (CD
3COCD3): δ 7.65–6.80 (m, 20 H, Ph), 5.27 (s, Cp),
4.77, 4.68 (dd, JH–H= 17.65, CH2) and 3.53 (d, 9 H, JH–P= 10.87
Hz, P(OMe)3). 31P NMR (CD3COCD3): δ 154.2 and 55.8 (2d,
JP–P= 61.1 Hz); MS (m/z, 102Ru) 672.1 (M⫹), 553.1 (M⫹⫺
COCH2Ph) and 429.1 (M⫹⫺ COCH2Ph-P(OMe)3).
X-Ray analysis of complex 3a
Single crystals of complex 3a were grown as mentioned above. A single crystal was mounted on an Enraf-Nonius CAD4 dif-fractometer. Cell constant and other pertinent data are col-lected in Table 5. The NRCC structure determination package21
was used for crystallographic computations. Merging of
equiv-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 R⬘ = 0.040. The procedures for the structure determination of 4, 6, and 10 were similar.
CCDC reference number 186/1698.
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.
References
1 W. Beck, B. Niemer and M. Wieser, Angew. Chem., Int. Ed. Engl., 1993, 32, 923; L. S. Hegedus, in Organometallics in Synthesis, ed. M. Schlosser, Wiley, New York, 1994, p. 383; T. Bartik, B. Bartik, M. Brady, R. Dembinski and J. A. Gladysz, Angew.
Chem., 1996, 3S 414; P. C. Ting, Y. C. Lin, G. H. Lee, M. C. Cheng
and Y. Wang, J. Am. Chem. Soc., 1996, 118, 6433.
2 L. K. Myers, C. Langhoff and M. B. Thompson, J. Am. Chem. Soc.,
1992, 114, 7560; T. Kaharu, H. Matsubara and S. Takahashi,
J. Mater. Chem., 1992, 2, 43; O. Lavastre, M. Even, P. H. Dixneuf,
A. Pacreau and J. P. Vairon, Organometallics, 1996, 15, 1530; I. Y. Wu, J. T. Lin, J. Luo, S. S. Sun, C. S. Lee, K. J. Lin, C. Tsai, C. C. Hsu and J. L. Lin, Organometallics, 1997, 16, 2038.
3 H. Hoberg and B. W. Oster, J. Organomet. Chem., 1983, 252, 359. 4 M. I. Bruce, T. W. Hambley, M. J. Leddell, M. R. Snow, A. G.
Swincer and R. T. Tiekink, Organometallics, 1990, 9, 96. 5 I. P. Selegue, J. Am. Chem. Soc., 1982, 104, 119.
6 A. Davison and J. P. Solar, J. Organomet. Chem., 1979, 166, C13; M. I. Bruce, T. W. Hambley, M. R. Snow and A. G. Swincer,
Organometallics, 1985, 4, 501.
7 P. Hong, K. Sonogashira and N. Hagihara, J. Organomet. Chem., 1981, 219, 363; A. G. M. Barrett, N. E. Carpenter, J. Mortier and M. Sabat, Organometallics, 1990, 9, 151.
8 R. Criegee and K. Noll, Leibigs Ann. Chem., 1959, 627, 1; R. Criegee, D. Seebach, R. E. Winter, B. Borretzen and H. A. Brune,
Chem. Ber., 1965, 98, 2339.
9 R. B. Woodward and R. Hoffmann, J. Am. Chem. Soc., 1965, 87,
4388.
10 J. I. Brauman and D. M. Golden, J. Am. Chem. Soc., 1968, 90, 1920. 11 J. Breulet and H. F. Schaefer, J. Am. Chem. Soc., 1984, 106, 1221. 12 F. Minzani, C. Pelizzi and G. Predieri, J. Organomet. Chem., 1982,
231, C6; M. I. Bruce, M. J. Liddell, M. R. Snow and E. R. T.
Tiekink, Organometallics, 1988, 7, 343.
13 M. I. Bruce, D. N. Duffy, M. J. Liddell, M. R. Snow and R. T.
Tiekink, Organometallics, 1992, 11, 1527.
14 M. I. Bruce, P. A. Humphrey, M. R. Snow, A. G. Swincer and R. T. Tiekink, J. Organomet. Chem., 1986, 303, 417.
15 C. W. Chang, Y. C. Lin, G. H. Lee, S. L. Huang and Y. Wang,
Organometallics, 1998, 17, 2534.
16 C. K. Johnson, ORTEP II, Report ORNL-5138, Oak Ridge National Laboratory, Oak Ridge, TN, 1976.
17 T. B. Brill and S. Landon, Chem. Rev., 1984, 84, 577; H. Nakazawa and K. Miyoshi, Trends Organomet. Chem., 1994, 1, 295.
18 A. G. Maki and R. A. Toth, J. Mol. Spectrosc., 1965, 17, 136. 19 D. L. Allen, V. G. Gibson, M. L. Green, T. F. Skinner, J. Bashikin
and P. D. Grebenik, J. Chem. Soc., Chem. Commun., 1985, 895; G. Consiglio and F. Morandini, Chem. Rev., 1987, 87, 761.
20 M. I. Bruce and A. G. Swincer, Aust. J. Chem., 1980, 33, 1471. 21 K. Schulze, B. Schulze and C. Richter, Chem. Abstr., 1989, 111,
6889d.
22 E. J. Gabe, F. L. Lee and Y. Lepage, in Crystallographic Computing
3, eds. G. M. Sheldrick, C. Kruger and R. Goddard, Clarendon
Press, Oxford, 1985, p. 167.
23 International Tables for X-ray Crystallography, Reidel, Dordrecht, Boston, 1974, vol. IV.
![Table 4 Selected bond distances (Å) and angles ( ⬚) of [RuCp(PPh 3 )- )-{P(OMe) 3 }(COCH 2 Ph)] 10 Ru–P1 Ru–C1 C1–O1 P1–Ru–P2 P2–Ru–C1 Ru–C1–O1 C1–C2–C3 2.2153(15)2.010(5)1.326(7)93.53(5)93.06(15)128.3(4)119.0(5) Ru–P2 C1–C2C2–C3 P1–Ru–C1 Ru–C1–C2 O1–C1–C2](https://thumb-ap.123doks.com/thumbv2/9libinfo/8695570.198735/4.919.87.438.394.884/table-selected-bond-distances-angles-rucp-pph-coch.webp)
![Table 5 Crystal data and structure re finement for [RuCp(PPh 3 ){P(OMe) 3 }{C[ ᎐᎐C(CN) 2 ]C(Ph) ᎐᎐CH(Ph)}] 3a, [RuCp{P(OMe) 3 }{ η 3 -C(CN) 2 - -C(Ph)C ᎐᎐CH(Ph)}] 4, [RuCp(PPh 3 ){P(O)(OMe) 2 }{ ᎐᎐C᎐᎐C(Ph)C(Ph)C(CN) 2 }] 6 and [RuCp(PPh 3 ){P(OMe) 3 }(COC](https://thumb-ap.123doks.com/thumbv2/9libinfo/8695570.198735/7.919.89.836.106.360/table-crystal-structure-finement-rucp-rucp-rucp-rucp.webp)
