Reactions of alkynyl-ruthenium complexes with the ketene dithioacetal, (MeS)2C=C(CN)2

Article abstract of DOI:10.1021/om7011437

Reactions of several alkynyl-ruthenium complexes with the ketene dithioacetal (MeS)₂C=C(CN)₂ (2) are described. The first examples of metalated 6-alkylthio-6-azafulvenes, Ru(C=CRC-(SMe)=C(CN)C=N(SMe)) (PPh₃)Cp [R = Ph (5a)

Full text of DOI:10.1021/om7011437

3556
Organometallics 2008, 27, 3556–3563
Reactions of Alkynyl-Ruthenium Complexes with the Ketene
Dithioacetal, (MeS)2CdC(CN)2
David J. Armitt,† Michael I. Bruce,*,† Brian W. Skelton,‡ and Allan H. White‡
School of Chemistry and Physics, UniVersity of Adelaide, Adelaide, South Australia 5005, and
Chemistry M313, SBBCS, UniVersity of Western Australia,
Crawley, Western Australia 6009
ReceiVed NoVember 13, 2007
Reactions of several alkynyl-ruthenium complexes with the ketene dithioacetal (MeS)2CdC(CN)2
(2) are described. The first examples of metalated 6-alkylthio-6-azafulvenes, Ru{CdCRC-
(SMe)dC(CN)CdN(SMe)}(PPh3)Cp [R ) Ph (5a), Fc (5b)], were obtained from Ru(Ct CR)(PPh3)2Cp,
while Ru(Ct CPh)(CO)(PPh3)Cp gave dienyl complexes Ru{C(SMe)dCPhC(SMe)dC(CN)2}(CO)-
(PPh3)nCp [n ) 1 (8), 0 (9)]. Yields of the azafulvenes were increased under conditions conducive to
radical formation. The reaction between 5 and Ru(Ct CCt CPh)(PPh3)2Cp afforded the alkynyl-dienyl
Ru{C(SMe)dC(Ct CPh)C(SMe)dC(CN)2}(PPh3)Cp (11) and the dienynyl Ru{Ct CC(SMe)dCPhC-
(SMe)dC(CN)2}(PPh3)2Cp (12), formed by formal insertion of either Ct C triple bond into one C-S
bond. The reaction of Ru(Ct CPh)(PPh3)2Cp with dimethyl 2,3-dicyanofumarate (3) afforded diastereomers
of the η3-dienyl complex Ru{η3-C(CN)(CO2Me)CPhCdC(CN)(CO2Me)}(PPh3)Cp (13). XRD structural
determinations of 5a, 8, 9, 11, and one diastereomer of 13 are reported.
Scheme 1
Introduction
The reaction between tetracyanoethene (tcne, 1) and a
σ-alkynyl-transition metal complex was first described in
1979.1 Since that time, many other reactions of this type have
been studied, both by this group2 and by others.3–6 In general,
the products arise from a formal [2 + 2]-cycloaddition leading
to cyclobutenes (A), which can then undergo electrocyclic ring
* Corresponding author. Fax: + 61 8 8303 4358. E-mail: michael.bruce@
adelaide.edu.au.
opening to give σ-1,3-butadienyl (B) or 1,2,3-η3-butadienyl
complexes (C) (Scheme 1). In some cases A can be isolated,
and independent experiments have shown that a smooth
conversion to B occurs more or less rapidly on warming.
† University of Adelaide.
‡ University of Western Australia.
(1) Davison, A.; Solar, J. P. J. Organomet. Chem. 1979, 166, C13-
C16.
(2) (a) Bruce, M. I.; Hambley, T. W.; Snow, M. R.; Swincer, A. G.
Organometallics 1985, 4, 494–500. (b) Bruce, M. I.; Hambley, T. W.; Snow,
M. R.; Swincer, A. G. Organometallics 1985, 4, 501–508. (c) Bruce, M. I.;
Duffy, D. N.; Liddell, M. J.; Snow, M. R.; Tiekink, E. R. T. J. Organomet.
Chem. 1987, 335, 365–378. (d) Bruce, M. I.; Cifuentes, M. P.; Snow, M. R.;
Tiekink, E. R. T. J. Organomet. Chem. 1989, 359, 379–399. (e) Bruce,
M. I.; Ke, M.; Low, P. J.; Skelton, B. W.; White, A. H. Organometallics
1998, 17, 3539–3549. (f) Bruce, M. I.; Low, P. J.; Skelton, B. W.; White,
A. H. New J. Chem. 1998, 22, 419–422. (g) Bruce, M. I.; Hall, B. C.; Kelly,
B. D.; Low, P. J.; Skelton, B. W.; White, A. H. J. Chem. Soc., Dalton
Trans. 1999, 3719–3728. (h) Bruce, M. I.; Smith, M. E.; Skelton, B. W.;
White, A. H. J. Organomet. Chem. 2001, 637-639, 484–499. (i) Bruce,
M. I.; Low, P. J.; Ke, M.; Kelly, B. D.; Skelton, B. W.; Smith, M. E.;
White, A. H.; Witton, N. B. Aust. J. Chem. 2001, 54, 453–460. (j) Bruce,
M. I.; Low, P. J.; Hartl, F.; Humphrey, P. A.; de Montigny, F.; Jevric, M.;
Lapinte, C.; Perkins, G. J.; Roberts, R. L.; Skelton, B. W.; White, A. H.
Organometallics 2005, 24, 5241–5255.
While the mechanism of cyclobutene formation has not been
completely elucidated, the role of the metal-ligand fragment
is important. When electron-rich metal centers are present, these
result in an increase in electron density and consequently the
nucleophilicity of the alkynyl group. There is spectroscopic
evidence of radical formation in the initial stages of the reactions
of metal alkynyls, and highly colored solutions, thought to
contain charge-transfer complexes, are often observed. Other
electron-poor alkenes that react in this way include
(NC)2CdC(CF3)27 and (MeO2C)CHdC(CN)(CO2Me),8 the lat-
ter being used to confirm the usual electrocyclic ring-opening
of the cyclobutene to butadiene. Similar [2 + 2]-cycloadditions
between 1 and organic alkynes are rare, recent examples being
those of p-(dimethylamino)phenylethynes9 and ethynylfer-
(3) Kergoat, R.; Kubicki, M. M.; Comes de Lima, L. C.; Scordia, H.;
Guerchais, J. E.; L’Haridon, P. J. Organomet. Chem. 1989, 367, 143–160.
(4) Cambridge, J.; Choudhary, A.; Friend, J.; Garg, R.; Hill, G.; Hussain,
Z. I.; Lovett, S. M.; Whiteley, M. W. J. Organomet. Chem. 1999, 577,
249–256.
(5) Onitsuka, K.; Ose, N.; Ozawa, F.; Takahashi, S. J. Organomet. Chem.
1999, 578, 169–177.
(6) Cordiner, R. L.; Smith, M. E.; Batsanov, A. S.; Albesa-Jove´, D.;
Hartl, F.; Howard, J. A. K.; Low, P. J. Inorg. Chim. Acta 2006, 359, 946–
961.
(7) (a) Bruce, M. I.; Liddell, M. J.; Snow, M. R.; Tiekink, E. R. T.
Organometallics 1988, 7, 343–350. (b) Bruce, M. I.; Hambley, T. W.;
Liddell, M. J.; Snow, M. R.; Swincer, A. G.; Tiekink, E. R. T. Organo-
metallics 1990, 9, 96–104.
(8) Bruce, M. I.; Duffy, D. N.; Liddell, M. J.; Tiekink, E. R. T.;
Nicholson, B. K. Organometallics 1992, 11, 1527–1536.
(9) (a) Michinobu, T.; May, J. C.; Lim, J. H.; Boudon, C.; Gisselbrecht,
J.-P.; Seiler, P.; Gross, M.; Biaggio, I.; Diederich, F. Chem. Commun. 2005,
737–739. (b) Michinobu, T.; Boudon, C.; Gisselbrecht, J.-P.; Seiler, P.;
Frank, B.; Moonan, N. N. P.; Gross, M.; Diederich, F. Chem.-Eur. J. 2006,
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10.1021/om7011437 CCC: $40.75
2008 American Chemical Society
Publication on Web 07/02/2008

Reactions of Alkynyl-Ruthenium Complexes
Organometallics, Vol. 27, No. 14, 2008 3557
Scheme 2
rocenes;10 tetrathiofulvene has also been reported to enter into
similar reactions.11
Ketene dithiodiacetals are extremely useful as synthons and
have multiple reactivity, often as precursors to various hetero-
cycles.12 We considered that the highly polarized CdC double
bond in (MeS)2CdC(CN)2 (2)13 would be an ideal coupling
partner in dipolar two-step cycloaddition reactions with σ-alky-
nylmetal complexes, and with a view to extending the range of
these reactions, we have studied some reactions of 2 with
Ru(Ct CPh)(PPh3)2Cp and related complexes. A related reaction
of dimethyl 2,3-dicyanofumarate (3) is also reported.
Figure 1. Plot of
a molecule of Ru{CdCRC(SMe)dC-
(CN)CdN(SMe)}(PPh3)Cp (5a).
1.741(1) Å found for 5a. Within the C5 ring of 5a, C(1)-C(2)
and C(3)-C(4) are 1.378(2) and 1.377(2) Å, with values for
C(2)-C(3), C(1)-C(5), and C(4-5) being 1.485(2), 1.512(2), and
1.461(2) Å, respectively [cf. analogous separations in 6: C(1)-C(5)
1.379(14), C(3)-C(4) 1.398(14), C(4)-C(5) 1.440(14), C(1)-C(2)
1.482(13), and C(2)-C(3) 1.447(14) Å].
Results and Discussion
When a mixture of Ru(Ct CPh)(PPh3)2Cp (4a) with a slight
excess of (MeS)2CdC(CN)2 (2) was heated in refluxing
benzene, the color gradually changed from yellow-orange to
deep red over a period of 24 h. Column chromatography (basic
alumina) gave the novel 6-methylthio-6-azafulvene complex 5a
in 26% yield after recrystallization, along with extensive
recovery of the reactants (Scheme 2).
The structure of 5a, which is the first reported complex
containing this type of ligand, was determined by X-ray
crystallography (Figure 1). Selected bond lengths and angles
for complexes 5a, 8, 9, and 11 are summarized in Table 1.
In 5a, the ruthenium center adopts the usual pseudo-octahedral
geometry, with < Ru-C(cp)> 2.24(2) and Ru-P 2.2944(4) Å
and angles S(5)-Ru-P 101.19(2)°, S(5)-Ru-C(1) 80.93(4)°, and
P-Ru-C(1) 91.68(4)°. The organic ligand appears to be unprec-
edented and chelates the metal via C(1) and S(5). The Ru-C(1)
bond length [2.025(1) Å] is similar to those found in other
compounds containing Ru-C(sp2) bonds,2 while the Ru-S bond
[2.2589(4) Å] is somewhat shorter than found in other ruthenium
complexes with pendant MeS ligands (2.309-2.401 Å).14 The
closest structural analogue to the organic ligand is the cyclopen-
tadithiazole 6, which has N(1)dC(2) and N(1)-S(2) bonds of
1.306(12) and 1.632(9) Å, respectively,15 compared with values
for C(5)-N(5) and the longer N(5)-S(5) bonds of 1.290(2) and
Spectroscopic data for 5a are consistent with the molecular
structure; a molecular ion at m/z 700 was observed in the
electrospray mass spectrum (ES-MS), while an IR absorption band
at 2192 cm-1 is assigned to ν(CN). The relative intensities of the
aromatic (δ 7.29-7.46), cyclopentadienyl (δ 4.74), and methyl
1
peaks (δ 1.65, 2.67) in the H NMR spectrum indicated the loss
of one PPh3 ligand from the metal center of the precursor. However,
the methyl signal at δ 2.67 was very broad, possibly signifying
slow dissociation and recoordination of the MeS ligand in solution
on the NMR time scale at 294 K. At 323 K, the methyl signal
became noticeably sharper, while a second set of phenyl, cyclo-
pentadienyl, and methyl peaks appeared at δ 6.77-6.91, 4.46, 2.80,
and 2.17 in a ca. 1:1 ratio with the original peaks, possibly due to
a presently uncharacterised isomer.
(10) Mochida, T.; Yamazaki, S. J. Chem. Soc., Dalton Trans. 2002,
3559–3564.
(11) Hopf, H.; Kreutzer, M.; Jones, P. G. Angew. Chem., Int. Ed. Engl.
1991, 30, 1127–1128.
(12) (a) Borrman, D. Houben-Weyl Methoden der Organischen Chemie;
Thieme: Stuttgart, 1968; Vol. VII/4, pp 404-441. (b) Schaumann, E.
Houben-Weyl Methoden der Organischen Chemie; Thieme: Stuttgart, 1985;
Vol. E11/4, pp 260-324. (c) Dieter, R. K. Tetrahedron 1986, 42, 3029–
3096. (d) Junjappa, H.; Ila, H.; Asokan, C. V. Tetrahedron 1990, 46, 5423–
5506.
(13) (a) Sandstro¨m, J.; Wannerbeck, I. Acta Chem. Scand. 1970, 24,
1191–1201. (b) Ericsson, E.; Marnung, T.; Sandstro¨m, J.; Wannerbeck, I.
J. Mol. Struct. 1975, 24, 373–387. (c) Kleinpeter, E.; Klod, S.; Rudorf,
W.-D. J. Org. Chem. 2004, 69, 4317–4329. (d) Kleinpeter, E.; Schulenburg,
A. Tetrahedron Lett. 2005, 46, 5995–5997.
Formally, 5a arises from the [3 + 2]-cycloaddition of the
metalated alkyne to the acrylonitrile subunit of 2, with con-
(14) (a) Hossain, M.; Maji, M.; Chattopadhyay, S. K.; Ghosh, S.; Blake,
A. J. Polyhedron 1998, 17, 1897–1906. (b) Maji, M.; Hossain, M.;
Chatterjee, M.; Chattopadhyay, S. K.; Puranik, V. G.; Chakrabarti, P.;
Ghosh, S. Polyhedron 1999, 18, 3735–3739. (c) Moreno, M. A.; Haukka,
M.; Ja¨a¨skela¨inen, S.; Vuoti, S.; Pursiainen, J.; Pakkanen, T. A. J. Organomet.
Chem. 2005, 690, 3803–3814.

3558 Organometallics, Vol. 27, No. 14, 2008
Armitt et al.
Table 1. Selected Bond Distances and Anglesa
5a
8
9;9′
11
Bond Distances (Å)
Ru-P/C(CO)
Ru-S/C(CO)
Ru-C(0) (cp)
Ru-C(cp)
<>
2.2944(4)
2.2589(4)
1.875
2.222-2.266(2)
2.24(2)
2.3229(4)
1.845(2) [C]
1.925
2.261-2.280(2)
2.271(8)
2.099(2)
1.387(2)
1.756(2)
1.813(2)
1.490(2)
1.463(2)
1.743(2)
1.794(2)
1.383(2)
1.428, 1.432(3)
1.871(2); 1.865(2) [C]
2.3132(5); 2.2881(6)
1.894; 1.896
2.235-2.258(2); 2.230-2.266(2)
2.246(9); 2.25(1)
2.058(2); 2.049(2)
1.412(3); 1.412(2)
1.740(2); 1.732(2)
1.798(3); 1.802(2)
1.498(3); 1.500(2)
1.403(3); 1.403(3)
1.805(2); 1.801(2)
1.814(2); 1.814(2)
1.399(3); 1.392(3)
1.432, 1.429(3); 1.428, 1.431(3)
2.311(3)
2.305(4)
1.883
2.219-2.247(11)
2.235(12)
1.991(9) [C(4)]
1.43(2)
1.75(1)
1.81(1)
1.39(1)
1.38(2)
Ru-C(1)
2.025(1)
1.378(2)
C(1)-C(2)
C(1)-S(1)
C(11)-S(1)
C(2)-C(21)
C(2)-C(3)
C(3)-S(3)
C(31)-S(3)
C(3)-C(4)
C(4)-C(41,42)
1.475(2)
1.485(2)
1.721(2)
1.786(2)
1.377(2)
1.424(2), -
1.815(9)
1.82(1)
1.39(2)
1.42, 1.43(2)
Bond Angles (deg)
C(1)-Ru-S/C(01)
P-Ru-S
80.93(4)
101.19(2)
91.68(4)
89.72(7)
81.44(5); 81.16(5) [S(3)]
81.8(4)
89.8(1)
91.3(4)
129.0(7)
118.8(9)
122.7(12)
130.9(9)
P-Ru-C(1)
94.86(4)
109.61(6)
120.3(2)
125.0(1)
119.6(2)
91.57(8); 92.31(8)
126.8(1); 126.42(9)
119.2(2); 118.0(1)
121.6(2); 122.3(2)
129.2(2); 130.3(2)
Ru-C(1)-S
C(1)-C(2)-C(3)
C(1)-C(2)-C(21)
C(2)-C(3)-C(4)
C(2)-C(3)-S(3)
C(3)-C(4)-C(41,42)
110.0(1)
129.1(1)
110.1(1)
117.4(1)
130.8(2), -
124.6(1)
121.3, 122.6(2)
114.0(1); 114.0(1)
125.4(2), 121.0(2); 125.7(2), 120.2(2)
124.9, 123.5(12)
a For 5a: C(1)-C(5) 1.512(2), C(4)-C(5) 1.461(2), C(5)-N(5) 1.290(2), C(51)-S(5) 1.806(2), N(5)-S(5) 1.741(1) Å, N(5)-S(5)-Ru 107.67(5)°,
N(5)-S(5)-C(51) 96.93(7)°, S(5)-N(5)-C(5) 109.6(1)°, C(2)-C(1)-C(5) 104.4(1)°, C(1)-C(5)-C(4) 109.6(1)°, C(1)-C(5)-N(5) 125.4(1)°,
C(4)-C(5)-N(5) 124.9(1)°. For 8: P-Ru-C(01) 87.75(5)°, C(3)-S(3)-C(31) 105.27(8)°, Ru-C(1)-C(2) 131.3(1)°. For 9; 9′: S(3)-Ru-C(01)
96.45(6)°; 95.70(7)°, Ru-S(3)-C(3) 102.06(6)°; 101.82(6)°, C(2)-C(1)-S(1) 111.6(1)°; 112.7(1)°, C(4)-C(3)-S(3) 116.8(1)°; 115.7(1)°. For 11:
C(21)-C(22) 1.22(1), C(22)-C(23) 1.45(1) Å, C(1)-S(1)-C(11) 109.1(5)°, Ru-S(3)-C(3) 102.5(5)°, Ru-S(3)-C(31) 108.3(5)°, Ru-C(1)-C(2)
123.4(9)°, C(2)-C(1)-S(1) 107.6(7)°, C(3)-C(2)-C(21) 118.5(11)°, S(3)-C(3)-C(4) 115.8(9)°, C(2)-C(21)-C(22) 173.6(15)°, C(21)-C(22)-C(23)
176.6(14)°, S(3)-C(3)-C(2) 113.3(9)°.
Scheme 3
comitant 1,4-migration of a methylthio group. It is unlikely,
however, that the reaction proceeds in a concerted fashion. While
addition of the radical initiator AIBN resulted in only a modest
increase in the yield of 5a to 42%, irradiation with a broad-
spectrum sun lamp gave a dramatic increase in yield to 71%.
These results may implicate the participation of radical species
in the mechanistic pathway leading to 5a.
Treatment of the more electron-rich acetylide
Ru(Ct CFc)(PPh3)2Cp (4b) with 2 resulted in the formation of
the corresponding 6-azafulvene 5b in 28% yield. The dark red
product was characterized by comparison of its spectroscopic
data with those of 5a; in particular, the broadened methyl signal
in its 1H NMR spectrum is a useful diagnostic tool. Other
spectral data include resonances for Ph (δH 7.16-7.33, δC
128.3-133.3), RuCp (δH 4.85, δC 85.4), FeCp (δH 4.11, δC
83.6), Fe(C5H4) (δH 4.27, 4.44, 4.66, δC 69.1, 69.6, 71.5, 72.2),
and PPh3 (δP 48.5), with carbon chain atoms at δC 26.3, 29.7.
The IR band at 2192 cm-1 is assigned to ν(CN). The ES-MS
contains M+ and [M + Na]+ at m/z 808 and 831, respectively.
The reaction between 2 and Ru(Ct CPh)(CO)(PPh3)Cp (7)
takes a different course, affording the butadienyl complexes 8
and 9 in 31% and 11% yields, respectively (Scheme 3). The
structures of 8 and 9 were deduced by a combination of
spectroscopic and crystallographic methods.
The ES-MS of 8 contained an ion at m/z 751, corresponding
to [M + Na]+, IR absorptions were observed at 2251, 2210
[ν(CN)] and 1940 cm-1 [ν(CO)], and the 31P{1H} NMR
spectrum confirmed the presence of the PPh3 ligand (δP 50.1).
The 13C{1H} NMR spectrum contained three signals between
δ 112.7 and 117.1 attributed to two CN resonances and one
carbon from the 1,3-butadienyl backbone. Other resonances
arising from the Me (δH 1.50, 2.25; δC 17.7, 26.7), Cp (δH 5.18,
δC 90.5), and phenyl groups (δH 7.33-7.53, δC 126.0-138.2)
were present. The Ru-CO ligand gives a doublet at δ 204.8
[J(CP) ) 20.3 Hz], while C(1) is found at δ 189.5.
The XRD molecular structure obtained from deep red, rod-like
crystals of 8 · CH2Cl2 is shown in Figure 2. The ruthenium center
has the usual distorted octahedral geometry [Ru-CO 1.845(2),
Ru-P 2.3229(4),<Ru-C(cp)> 2.271(8) Å; P-Ru-C(1,01)
94.86(4), 87.75(5), C(1)-Ru-C(01) 89.72(7)°]. With four different
substituents, the Ru center is chiral, and the centrosymmetric crystal
contains equal amounts of both enantiomers. In the organic ligand,
sequential C(1)-C(2)-C(3)-C(4) bond lengths [1.387(2), 1.463(2),
1.383(2) Å] are consistent with alternating CdC double and C-C
single bonds in the butadienyl group, while the Ru-C(1) distance
(15) Go´mez, T.; Macho, S.; Miguel, D.; Neo, A. G.; Rodr´ıguez, T.;
Torroba, T. Eur. J. Org. Chem. 2005, 5055–5066.

Reactions of Alkynyl-Ruthenium Complexes
Organometallics, Vol. 27, No. 14, 2008 3559
[2.099(2) Å] lies in the range typical for an Ru-C(sp2) bond.2
The diene has the s-trans conformation found previously for most
analogous complexes. An angle of 55.6° is subtended by the two
halves of the 1,3-butadien-1-yl ligand, similar to those reported
previously for related complexes.2 There is also some twisting of
the C(1)-C(2) double bond, as shown by the Ru-C(1)-C(2)-C(3)
and S(1)-C(1)-C(2)-C(21) torsion angles of 26.4(3)° and
24.0(2)°, respectively.
Å], while the coordination of the SMe group to the metal is
reflected in the increased length of the C(3)-S(3) bond [1.801(2)
Å].
The reaction of Ru(Ct CCt CPh)(PPh3)2Cp (10) with 2 also
afforded two major adducts, to which we assign structures 11
and 12, i.e., the products of addition of 2 to each of the Ct C
systems in 10 (Scheme 4).
In the case of 11, the molecular structure has been confirmed
by an XRD structure determination (Figure 4), which showed that
a formal insertion of the Ct C triple bond adjacent to the metal
center into one of the C-SMe bonds of 2 had occurred. The
formulation is consistent with the observation of [M + Na]+ at
m/z 747 in the ES-MS and the 1H NMR spectrum, which confirmed
that only one PPh3 ligand was present. The usual Ru(PPh3)Cp
fragment [Ru-P 2.311(3), <Ru-C(cp)> 2.235(12) Å] also bears
a chelating vinyl-thiolate ligand [Ru-S(1) 2.305(4), Ru-C(4)
1.991(9) Å; S(3)-Ru-P 89.8(1)°, S-Ru-C(1) 81.8(4)°, P-Ru-C(1)
91.3(4)°] resembling that in 9. The butadienyl ligand in 11 differs
slightly from that in 9; the somewhat shorter Ru-C(1) bond
[1.991(9) 11, cf. 2.058(2) Å in 9] and the C(1)-C(2)-C(3)
separations [1.43(2), 1.38(2) Å] suggest that electronic reorganiza-
tion within the ring results in some multiple bond character in the
Ru-C(1) bond, reflecting the more electron-rich metal center.
Internal angles at Ru-S(3)-C(3)-C(2)-C(1) are 81.8(4)°,
102.5(5)°, 113.3(9)°, 118.8(9)°, and 123.4(9)°, respectively. Also
noteworthy is the syn-arrangement of the angular methyl group
attached to sulfur and the cyclopentadienyl ligand of the
metallocycle; in compounds 5a and 9 these groups have an anti-
orientation. The presence of the C(21)t C(22)-Ph fragment
[C(21)-C(22) 1.22(1), C(22)-C(23) 1.45(1) Å] confirms that
reaction of the cyano-ketal has occurred at the inner Ct C triple
bond.
The ion at m/z 489 observed in the ES-MS of 9 is assigned
to [M + Na]+ and indicates that PPh3 is no longer present. This
was confirmed by the ratio of the aromatic, cyclopentadienyl,
and methyl signals in its 1H NMR spectrum and the absence of
any 31P signal. As a consequence, the 13C{1H} NMR spectrum
is greatly simplified, with characteristic signals for the CO ligand
(δC 201.1), CN (δC 112.5, 117.6), Cp (δH 5.21, δC 86.0), and
two MeS groups (δH 2.51, 2.83, δC 29.7). Resonances at δC
32.8, 89.5, 137.5, 144.1, and 170.5 are assigned to the carbon
skeleton of the thiolate ligand. As for 8, the IR spectrum of 9
contained absorptions at 2200 [ν(CN)] and 1953 cm-1 [ν(CO)].
Recrystallization of 9 from CH2Cl2/MeOH afforded yellow-
brown crystals with two distinct morphologies, plates and rods.
Samples of each were examined by X-ray crystallography
(Figure 3), and it was found that the difference lay entirely in
the molecular dispositions within their unit cells, both of which
have the common feature of centrosymmetrically related mo-
lecular pairs in similar alignments. Comparison of the bond
parameters for the two forms showed only minor differences.
The following discussion therefore cites the values found for
the rod form.
Coordination about the pseudo-octahedral Ru atom is achieved
by the Cp [<Ru-C(cp)> 2.25(1) Å], CO [1.865(2) Å]. and
the chelating vinyl-thio ligands [Ru-C(1) 2.049(2), Ru-S(3)
2.2881(6)Å;S(3)-Ru-C(1,01)81.16(5),95.70(7),C(1)-Ru-C(01)
92.31(8)°]. In stark contrast to 8, an almost planar butadienyl
ligandispresentin9[internalanglesatRu-C(1)-C(2)-C(3)-S(3)
are 81.16(5)°, 120.7(1)°, 118.0(1)°, 114.0(1)°, and 101.82(6)°
(∑ ) 535.7°)]. Extensive delocalization of the π-system is
indicated by the nearly equal bond lengths along the butadienyl
backbone [C(1)-C(2)-C(3)-C(4) 1.412(2), 1.403(3), 1.392(3)
Unfortunately, crystals of 12 suitable for X-ray crystal-
lography could not be obtained. The structural assignment is
therefore based on the spectroscopic similarities between 8 and
12, particularly in their IR spectra. The broad intense ν(Ct C)
absorption at 2017 cm-1 is similar to that observed at 1993
cm-1 in Ru{Ct CC[dC(CN)2]CdC(CN)2}(dppe)Cp, for ex-
ample, albeit shifted by 20-30 cm-1 to higher frequency;2f,g
Figure 2. Plot of a molecule of Ru{C(SMe)dCPhC(SMe)dC-
(CN)2}(CO)(PPh3)Cp (8).
Figure 3. Plot of a molecule of Ru{C(SMe)dCPhC(SMe)dC-
(CN)2}(CO)Cp (9).

3560 Organometallics, Vol. 27, No. 14, 2008
Armitt et al.
Scheme 4
in comparison, the ν(Ct C) absorptions for organic alkynes
generally lie between 2100 and 2200 cm-1. Ions at m/z 1009
and 987 in the ES-MS correspond to [M + Na]+ and [M +
H]+, respectively, and confirm the retention of both phosphine
ligands in this derivative. The NMR spectra of 12 contain two
sets of signals of relative intensities 3:2, although it is not clear
whether these result from the presence of two inseparable
isomeric forms (e.g., 12a and 12b) or from two rotamers. Thus,
resonances for the Me (δH 1.73 and 2.237, δC 15.9 and 29.7)
and Cp (δH 4.46, δC 86.4) for the major isomer are accompanied
by others at δH 2.19, 2.242, δC 16.7 (Me), and δH 4.33, δC 86.1
(Cp) from the minor component. The relatively large difference
in the Me chemical shifts suggests that one Me group of the
major component lies in close proximity to an aromatic ring,
most likely that of a PPh3 ligand.
The formation of compounds 8, 9, 11, and 12 occurs via a
formal trans-insertion of the alkynyl or butadiynyl ligand of
4a into one carbon-sulfur bond of the ketene dithioacetal. To
date, there have been very few reported examples of insertions
of alkynes into carbon-sulfur bonds of any type,16 the majority
involving reactions of the coordinated bond of η2-complexes
of carbon disulfide or dithioformate with electron-deficient
alkynes. There are also examples of additions of metal thiolates
to alkynes to give complexes with structures similar to those
found in 9 and 11.2b,17
cis and trans isomers, are obtained.18 Thus it is likely that the
insertion reactions observed here also follow a cis-addition
pathway. We suggest that the polar CdC double bond of the
ketene dithioacetal and the nucleophilic alkynyl Cꢀ atom (and
by extension, the δ-position of butadiynyl ligands)19 initially
form zwitterionic intermediate D (Scheme 5), which then
undergoes a 1,3-shift of a methylthio group, in a process that
may be either concerted or stepwise.20 The trans-adduct E (cf.
8, R ) Ph) may thus be formed directly, or via an intermediate
cis-adduct F followed by isomerization. Loss of PPh3 or CO
from E then gives 9 or 11, respectively.
Triphenylphosphine liberated during the reaction could
catalyze the isomerization; alternatively, it is possible that
ambient light promotes biradical formation in which both radical
centers are further stabilized by delocalization. Such a relatively
long-lived radical species may undergo internal rotation prior
to recombination, as established for stilbenes, to form E. On
the other hand, intramolecular addition of the R-carbon-centered
radical to a nitrile group might give a 6-azafulvene biradical as
an advanced intermediate in the formation of 5, although no
products of type E were detected during the reactions leading
to 5.
Reaction of Ru(Ct CPh)(PPh3)2Cp with Dimethyl Dicy-
anofumarate. Treatment of 4a with dimethyl dicyanofumarate
(3) under the same conditions described for the cycloaddition
of 1 afforded the 1,2,3-η3-butadienyl complex 13 in 21% yield
(Scheme 6). The reaction mixture became deep claret, then
intense violet after a few minutes, possibly as a result of the
formation of an intermediate charge-transfer complex(es).
Complex 13, obtained as an orange solid, was characterized as
In general, most mechanisms accounting for the insertion of
unsaturated hydrocarbons into σ-bonds invoke a cis-addition
process, even when exclusively trans-adducts, or mixtures of
(16) Bruce, M. I.; Swincer, A. G. Aust. J. Chem. 1980, 33, 1471–1483.
(17) (a) Kubicki, M. M.; Kergoat, R.; Scordia, H.; Gomes de Lima,
L. C.; Guerchais, J. E.; L’Haridon, P. J. Organomet. Chem. 1988, 340,
41–49. (b) Petillon, F. Y.; Le Floch-Perennou, F.; Guerchais, J. E.; Sharp,
D. W. A. J. Organomet. Chem. 1979, 173, 89–106. (c) Guerchais, J. E.; Le
Floch-Perennou, F.; Petillon, F. Y.; Keith, A. N.; Manojlovic-Muir, L.; Muir,
K. W.; Sharp, D. W. A. J. Chem. Soc., Chem. Commun. 1979, 410–411.
(18) Cross, R. J.; Davidson, M. F. J. Chem. Soc., Dalton Trans. 1986,
411–414.
(19) (a) Le Bozec, H.; Gorgues, A.; Dixneuf, P. H. Inorg. Chem. 1981,
20, 2486–2489. (b) Touchard, D.; Dixneuf, P. H.; Adams, R. A.; Segmu¨ller,
B. E. Organometallics 1984, 3, 640–642. (c) Fischer, H.; Gerbing, U.;
Tiriliomis, A. J. Organomet. Chem. 1987, 332, 105–114. (d) Fischer, H.;
Hofmann, J.; Gerbing, U.; Tiriliomis, A. J. Organomet. Chem. 1988, 358,
229–244. (e) Touchard, D.; Fillaut, J.-L.; Dixneuf, P. H.; Adams, R. A.;
Segmu¨ller, B. E. J. Organomet. Chem. 1990, 386, 95–109. (f) Khasnis,
D. V.; Pirio, N.; Touchard, D.; Toupet, L.; Dixneuf, P. H. Inorg. Chim.
Acta 1992, 198-200, 193–201. (g) Hogarth, G.; Skordalakis, E. J.
Organomet. Chem. 1993, 458, C8-C9. (h) Forster, G. D.; Hogarth, G.
J. Chem. Soc., Dalton Trans. 1997, 2305–2307.
Figure 4. Plot of a molecule of Ru{C(SMe)dCCt CPh)C-
(SMe)dC(CN)2}(PPh3)Cp (11).
(20) Davidson, J. L.; Shiralian, M.; Manojlovic-Muir, L.; Muir, K. W.
J. Chem. Soc., Dalton Trans. 1984, 2167–2176.

Reactions of Alkynyl-Ruthenium Complexes
Organometallics, Vol. 27, No. 14, 2008 3561
Scheme 5
Figure 5. Plot of
a
molecule of Ru{η3-C(CN)(CO2Me)-
CPhCdC(CN)(CO2Me)}(PPh3)Cp (13). Selected bond distances (Å)
and angles (deg): Ru-P 2.3785(7), <Ru-C(cp)> 2.22(2), centroid
1.87, Ru-C(2,3,4) 2.218(3), 2.128(3), 1.998(3), C(2)-C(3) 1.458(4),
C(3)-C(4) 1.430(4), C(4)-C(5) 1.347(5); P-Ru-C(2) 98.12(7),
P-Ru-C(3)114.06(8),P-Ru-C(4)89.02(8),C(cpcentroid)-Ru-C(2,3,4)
are: 128.4, 126.5, 137.5, C(2)-C(3)-C(4) 115.1(2), C(3)-C(4)-C(5)
136.2(3).
Scheme 6
Chart 1
the 1:1 adduct by NMR, IR, ES-MS, and elemental analysis
and contains only one PPh3 ligand, while the presence of two
ν(CN) (2250, 2212 cm-1) and two ν(ester CO) absorptions
(1715, 1615 cm-1) in the IR spectrum is consistent with the
desymmetrization of the original alkene unit.
azafulvenes 5 or 1,3-butadien-1-yl complexes 8, 9, 11, and
12, depending on the nature of metal alkynyl. Increases in
yields found under appropriate conditions suggest the in-
volvement of radical species. The presence of two different
labile ligands in complexes 5 may result in useful catalytic
activity, particularly if one of the ligands is tethered. A further
example of an η3-butadienyl complex (13) was obtained in
low yield from the reaction between Ru(Ct CPh)(PPh3)2Cp
and dimethyl dicyanofumarate.
The NMR spectra of 13 contain two sets of resonances, with
intensity ratio approximately 3:2, indicating the presence of two
isomers. At this time it is not clear whether this is a consequence
of differing orientations of 3 with respect to the metal acetylide
during the presumed initial cycloaddition step, of isomerization
of the reactant 3 (unlikely), or of internal rotation of an
intermediate zwitterion or biradical adduct. The XRD structure
determination of 13 shows that only one enantiomer is present
in the unit cell, along with its mirror image; however, NMR
analysis of a recrystallized sample again showed the same ratio
of isomers, making it impossible to determine if the structure
obtained was the minor or major enantiomer. The molecular
structure of 13 (Figure 5) is similar to those of other η3-dienyl
complexes 14,2j 15,21 and 16 (Chart 1).8
The Ru(PPh3)Cp fragment [Ru-P 2.3785(7), <Ru-C(cp)>
2.22(2) Å] is bonded to the η3-dienyl ligand [Ru-C(2,3,4)
2.218, 2.128, 1.998(3) Å; P-Ru-C(2) 98.12(7)°], which bears
CN and CO2Me substituents on C(2), Ph on C(3), and
dC(CN)(CO2Me) on C(4). Overall, this ligand is similar to
several others that have been obtained from addition of electron-
deficient alkenes to alkynyl-metal complexes containing an
easily displaceable ligand.2
Experimental Section
General Procedures. All reactions were performed in oven-
dried glassware under a dry N2 atmosphere, although normally no
special precautions to exclude air were taken during subsequent
workup. Common solvents were dried, distilled under argon, and
degassed with a stream of dry N2 before use; CH2Cl2 was distilled
from CaH2 prior to use, and benzene was used as supplied.
Separations were carried out by preparative thin-layer chromatog-
raphy on glass plates (20 × 20 cm2) coated with silica gel (Merck,
0.5 mm thick).
Instruments. IR spectra were obtained on a Bruker IFS28 FT-
IR spectrometer. Spectra in CH2Cl2 were obtained using a 0.5 mm
path-length solution cell with NaCl windows. Nujol mull spectra
were obtained from samples mounted between NaCl discs. NMR
spectra were recorded on a Varian 2000 instrument (1H at 300.13
MHz, 13C at 75.47 MHz, 31P at 121.503 MHz). Samples were
dissolved in CDCl3 contained in 5 mm sample tubes. Chemical
shifts are given in ppm relative to internal tetramethylsilane for 1H
and 13C NMR spectra and external H3PO4 for 31P NMR spectra.
Electrospray mass spectra in positive-ion mode (ES-MS) were
obtained from samples dissolved in MeOH unless otherwise
Conclusions
The reactions of transition metal alkynyls with the ketene
S,S-diacetal 2 have given novel metalated 6-alkylthio-6-
(21) Bruce, M. I.; Liddell, M. J.; Snow, M. R.; Tiekink, E. R. T.
Organometallics 1988, 7, 343–350.

3562 Organometallics, Vol. 27, No. 14, 2008
Armitt et al.
indicated. NaOMe was used as an aid to ionization.22 Solutions
were injected into a Varian Platform II spectrometer via a 10 mL
injection loop. Nitrogen was used as the drying and nebulizing gas.
Ions listed are the most intense in the isotope envelopes. Elemental
analyses were by CMAS, Belmont, Vic., Australia.
J(CP) ) 10.6 Hz], 132.1 [d, J(CP) ) 10.0 Hz], 130.5, 128.3 [d,
J(CP) ) 9.7 Hz], 93.6, 85.4, 83.6, 72.2, 71.5, 69.6, 69.1, 66.3,
29.7, 26.3. 31P NMR: δ 48.5. ES-MS (m/z): 831, [M + Na]+; 808,
M+.
Reaction of Ru(Ct CPh)(CO)(PPh3)Cp with (NC)2CdC-
(SMe)2. Ru(Ct CPh)(CO)(PPh3)Cp (7) (139 mg, 0.25 mmol) and
2 (53 mg, 0.31 mmol) were added to benzene (10 mL), and the
mixture was heated to reflux under N2 for 48 h. The pale yellow
solution gradually became deep claret. After cooling, the solution
was concentrated under reduced pressure and the residue was
purified by column chromatography (basic alumina). Elution with
CH2Cl2 gave a yellow band containing unreacted starting materials
(95 mg); further elution with 1:9 acetone/CH2Cl2 gave a maroon
band, which was further purified by recrystallization from CH2Cl2/
MeOH to afford Ru{C(SMe)dCPhC(SMe)dC(CN)2}(CO)(PPh3)-
Cp (8) as dark red needles (56 mg, 31%). Crystals for X-ray analysis
were grown by slow evaporation of a CH2Cl2 solution layered with
MeOH. Anal. Calcd (C38H31N2OPRuS2): C, 62.71; H, 4.29; N, 3.85;
M, 728. Found: C, 62.79; H, 3.90; N, 4.23. IR (Nujol, cm-1): νmax
3057w, 2251w, 2210s, 2098w, 1940vs, 1479s, 1434vs, 1315m,
1234m, 1091s, 1027m, 998m, 910s, 838s, 812s, 732s, 695s. 1H
NMR: δ 7.33-7.53 (20H, m), 5.18 (5H, s), 2.25 (3H, s), 1.50 (3H,
s). 13C NMR: δ 204.8 [d, J(CP) ) 20.3 Hz], 189.5, 188.3, 142.9,
138.2, 135.5 [d, J(CP) ) 48.1 Hz], 133.7 [d, J(CP) ) 10.6 Hz],
130.1, 128.5 [d, J(CP) ) 3.8 Hz], 128.3 [d, J(CP) ) 10.0 Hz],
127.9, 126.0, 117.1, 114.8, 112.7, 90.5, 26.7, 17.7. 31P NMR: δ
50.1. ES-MS (m/z): 751, [M + Na]+.
Reagents. The compounds (MeS)2CdC(CN)2 (2),23 trans-
(NC)(MeO2C)CdC(CN)(CO2Me) (3),24 Ru(Ct CR)(PPh3)2Cp (R
) Ph 4a,25 Fc 4b,2j Ct CPh 102g), and Ru(Ct CPh)(CO)(PPh3)Cp
(7)16,26 were synthesized by the cited literature procedures.
Reactions of Ru(Ct CPh)(PPh3)2Cp with (MeS)2CdC(CN)2.
(a) Complex 4a (0.50 g, 0.63 mmol) and 2 (0.13 g, 0.78 mmol)
were added to benzene (25 mL), and the mixture was heated at
reflux point under N2 for 24 h. The initially yellow solution
gradually became deep claret in color. After cooling, the solution
was concentrated under reduced pressure, and the residue was
separated on a column of basic alumina. Elution with CH2Cl2 gave
a yellow band, which contained a mixture of starting materials (0.43
g); further elution with acetone/CH2Cl2 (1:9) gave a maroon band,
which was further purified by recrystallization (CH2Cl2/MeOH) to
afford Ru{C5Ph(SMe)(CN)dN(SMe)}(PPh3)Cp (5a) as dark red
blocks (115 mg, 26%). Crystals for X-ray analysis were grown by
slow evaporation of a CH2Cl2 solution layered with MeOH. Anal.
Calcd (C37H31N2PRuS2): C, 63.50; H, 4.46; N, 4.00; M, 700. Found:
C, 63.59; H, 4.41; N, 3.90. IR (Nujol, cm-1): νmax 3054w, 2192vs,
1463vs, 1432m, 1346m, 1289s, 1106m, 1090m, 695s. 1H NMR: δ
7.29-7.46 (20H, m), 4.74 (5H, s), 2.67 (3H, br s), 1.65 (3H, s).
13C NMR: δ 126.8-138.8 (m), 84.6 [d, J(CP) ) 1.9 Hz), 82.6 [d,
J(CP) ) 2.0 Hz], 60.3, 26.1. 31P NMR: δ 51.5. ES-MS (m/z): 723,
[M + Na]+; 718, [M + NH4]+; 700, M+.
Further elution with acetone/CH2Cl2 (1:9) gave a yellow band,
which was further purified by slow recrystallization from CH2Cl2/
MeOH to afford Ru{C(SMe)dCPhC(SMe)dC(CN)2}(PPh3)Cp (9)
as dark yellow rods and plates (13 mg, 11%), suitable for X-ray
analysis. Anal. Calcd (C20H16N2ORuS2): C, 51.60; H, 3.46; N, 6.02;
M, 466. Found: C, 51.47; H, 3.54; N, 6.13. IR (Nujol, cm-1): νmax
(b) Complex 4a (200 mg, 0.25 mmol), 2 (53 mg, 0.31 mmol),
and AIBN (20 mg) were added to benzene (10 mL), and the mixture
was heated to reflux under N2 for 24 h. A second portion of AIBN
(20 mg) was added after 5 h. The initially yellow solution gradually
became a deep claret color. Workup and purification as above
afforded 5a (73 mg, 42%).
(c) Complex 4a (200 mg, 0.25 mmol) and 2 (53 mg, 0.31 mmol)
were added to benzene (10 mL), and the mixture was illuminated
with a 300 W sun lamp under N2 for 24 h. The initially yellow
solution became a deep claret color after a few minutes and began
to reflux after ca. 30 min. Workup and purification as above afforded
5a (124 mg, 71%).
1
2200s, 1953vs, 1470vs, 1351m, 1323s, 1303s, 698s. H NMR: δ
7.33-7.46 (5H, m), 5.21 (5H, s), 2.83 (3H, s), 2.51 (3H, s). 13C
NMR: δ 201.1, 170.5, 144.1, 137.5, 128.0-133.8 (m), 117.6, 112.5,
89.5, 86.0, 32.8, 29.7, 26.4. ES-MS (m/z): 489, [M + Na]+.
Reaction of Ru(Ct CCt CPh)(PPh3)2Cp with (MeS)2CdC-
(CN)2. Ru(Ct CCt CPh)(PPh3)2Cp (10) (160 mg, 0.20 mmol) and
2 (41 mg, 0.24 mmol) were added to benzene (10 mL), and the
mixture was heated at reflux point for 48 h. The pale yellow solution
gradually became deep claret. After cooling, the solution was
concentrated under reduced pressure and the residue was purified
on a column of basic alumina. Elution with CH2Cl2 gave a mixture
of yellow and purple bands (fraction A); further elution with 1:9
acetone/CH2Cl2 gave a mixture of purple and blue-green bands
(fraction B). Fraction A was further purified by preparative TLC
(silica, CH2Cl2) to afford Ru{Ct CC(SMe)dCPhC(SMe)dC-
(CN)2}(PPh3)2Cp (12) as a dark red solid (26 mg, 13%), which
was found to exist in CDCl3 solution as a ca. 3:2 mixture of isomers
or rotamers by NMR. Anal. Calcd (C57H46N2P2RuS2): C, 69.42;
H, 4.70; N, 2.84; M, 986. Found: C, 70.89; H, 5.38; N, 1.57. IR
(Nujol, cm-1): νmax 3053m, 2218m, 2017vs, 1497m, 1479s, 1434vs,
Reaction of Ru(Ct CFc)(PPh3)2Cp with (MeS)2CdC(CN)2.
Ru(Ct CFc)(PPh3)2Cp (4b) (200 mg, 0.22 mmol) and 2 (47 mg,
0.28 mmol) were added to benzene (10 mL), and the mixture was
heated to reflux under N2 for 48 h. The pale yellow solution
gradually acquired a deep claret color. After cooling, the solution
was concentrated under reduced pressure and the residue was
purified by column chromatography (basic alumina). Elution with
CH2Cl2 gave a yellow band containing a mixture of unreacted
starting materials (176 mg); further elution with 1:9 acetone/CH2Cl2
gave a maroon band, which was further purified by recrystallization
fromCH2Cl2/MeOHtoaffordRu{C5Fc(SMe)(CN)dN(SMe)}(PPh3)-
Cp (5b) as dark red prisms (50 mg, 28%). Crystals for X-ray
analysis were grown by slow evaporation of a CH2Cl2 solution
layered with MeOH. Anal. Calcd (C41H35FeN2PRuS2): C, 60.96;
H, 4.37; N, 3.47; M, 808. Found: C, 59.96; H, 4.47; N, 3.35. IR
(Nujol, cm-1): νmax 2192s, 1467s, 1433vs, 1269s, 1189m, 1133m,
1
1089m, 741m, 695vs H NMR: δ 7.02-7.42 (35H, m), 4.46 (5H,
s, major), 4.33 (5H, s, minor), 2.242 (3H, s, minor), 2.237 (3H, s,
major), 2.19 (3H, s, minor), 1.73 (3H, s, major). 13C NMR: δ 186.6,
185.9, 124.4-138.9 (m), 114.4, 114.1, 113.6, 112.1, 96.6, 94.3,
91.0, 89.9, 86.4, 86.1, 81.4, 79.9, 29.7, 16.7, 16.1, 15.9. 31P NMR:
δ 47.4 (major), 47.1 (minor). ES-MS (m/z): 1009, [M + Na]+;
987, [M + H]+.
1
1105m, 1090m, 910m, 729s, 694s. H NMR: δ 7.16-7.38 (15H,
m), 4.85 (5H, s), 4.66 (1H, br s), 4.44 (1H, br s), 4.27 (2H, m),
4.11 (5H, s), 2.16 (3H, br s), 1.25 (3H, s). 13C NMR: δ 133.3 [d,
A second dark red band yielded a small amount of 11, which
was added to that obtained from fraction B (see below). Extensive
decomposition of the initially yellow band was observed, charac-
teristic of the behavior of 10 on silica.
Fraction B was further purified by preparative TLC (silica,
CH2Cl2) to afford Ru{C(SMe)dC(Ct CPh)C(SMe)dC(CN)2}(PPh3-
Cp (11) as a dark red solid (total yield 27 mg, 19%). Dark red
(22) Henderson, W.; McIndoe, J. S.; Nicholson, B. K.; Dyson, P. J.
J. Chem. Soc., Dalton Trans. 1998, 519.
(23) Gompper, R.; To¨pfl, W. Chem. Ber. 1962, 95, 2861–2870.
(24) Ireland, C. J.; Jones, K.; Pizey, J. S. Synth. Commun. 1976, 6, 185–
191.
(25) Bruce, M. I.; Hameister, C.; Swincer, A. G.; Wallis, R. C. Inorg.
Synth. 1982, 21, 82.
(26) Bruce, M. I.; Wallis, R. C. Aust. J. Chem. 1979, 32, 1471–1485.

Reactions of Alkynyl-Ruthenium Complexes
Organometallics, Vol. 27, No. 14, 2008 3563
Table 2. Crystal Data and Refinement Details
5a
8 · CH2Cl2
9
9′
11
13
formula
MW
C37H31N2PRuS2
699.80
C38H31N2OPRuS2. CH2Cl2 C20H16N2ORuS2
C20H16N2ORuS2
465.56
C39H31N2PRuS2
723.87
C39H31N2O4PRu
723.73
812.79
465.56
cryst syst
space group
a/Å
b/Å
c/Å
triclinic
P1
triclinic
P1
monoclinic
P21/c
11.2373(7)
14.7510(6)
11.6038(5)
monoclinic
P21/c
10.481(2)
17.294(2)
10.778(1)
triclinic
P1
monoclinic
P21/n
14.400(1)
10.7480(9)
22.054(2)
j
j
j
10.360(2)
11.557(1)
13.634(1)
88.422(8)
80.42(1)
78.75(1)
1579
11.0170(9)
12.958(1)
13.858(1)
113.835(1)
91.729(2)
96.604(1)
1791
9.720(2)
13.312(2)
13.636(3)
97.32(2)
100.57(2)
108.64(2)
1610
R/deg
ꢀ/deg
95.161(4)
103.730(4)
103.395(2)
γ/deg
V/Å3
1916
1.614
4
1898
1.629
4
3320
1.448
4
Fc/g cm-3
Z
1.472
2
1.507
2
1.493
2
2θmax/deg
70
66
0.78
0.88
74
1.047
0.82
67
1.057
0.75
50
0.70
0.86
75
0.57
0.87
µ(Mo KR)/mm-1 0.71
Tmin/max
0.89
cryst dimens/mm3 0.31 × 0.23 × 0.10 0.48 × 0.21 × 0.18
0.46 × 0.35 × 0.10 0.43 × 0.15 × 0.12 0.28 × 0.13 × 0.015 0.42 × 0.36 × 0.14
Ntot
71 485
13 639 (0.032)
9943
26 771
12 879 (0.015)
11480
90 519
9440 (0.023)
7877
31 882
7136 (0.032)
6231
10 883
5525 (0.050)
2550
65 402
17 252 (0.050)
11506
N (Rint
No
)
R [I > 2σ(I)]
0.032
0.031
0.066 (4)
1.00
1.12
150
0.047
0.095 (8)
1.06
2.14
100
0.027
0.056 (5)
0.93
0.84
150
0.061
0.135 (40)
0.90
3.4
100
0.051
0.102 (20)
0.98
4.0
170
Rw [I > 2σ(I)] (nw) 0.088 (–)
S
1.04
1.68
100
|∆Fmax|/e Å-3
T/K
needles suitable for X-ray analysis were grown by slow evaporation
of CH2Cl2 solution layered with MeOH. Anal. Calcd
considered “observed”; all data were used in the full-matrix least-
squares refinements on F2. All data were measured using monochro-
matic Mo KR radiation, λ ) 0.71073 Å. Anisotropic displacement
parameter forms were refined for the non-hydrogen atoms, (x, y, z,
Uiso)H being included following a riding model. Conventional residuals
R, Rw on |F2| are quoted [weights: (σ2(F2) + 0.00nwF2)-1]. Neutral
atom complex scattering factors were used; computation used the
XTAL 3.7 program system.27 Pertinent results are given in the figures
(which show non-hydrogen atoms with 50% probability amplitude
displacement ellipsoids and hydrogen atoms with arbitrary radii of 0.1
Å) and in Tables 1 and 2.
a
(C39H31N2PRuS2): C, 64.71; H, 4.32; N, 3.87; M, 724. Found: C,
65.13; H, 4.41; N, 3.88. IR (Nujol, cm-1): νmax 3055w, 2195vs,
1466vs, 1433vs, 1277vs, 1221m, 1165m, 1091s, 909m, 731vs,
1
694vs. H NMR: δ 7.21-7.63 (20H, m), 4.84 (5H, s), 2.70 (3H,
br s), 2.50 (3H, s). 13C NMR: δ 198.2, 127.7-133.6 (m), 115.6,
102.1, 85.7, 84.8, 84.1, 29.7, 26.0. 31P NMR: δ 50.4. ES-MS (m/
z): 747, [M + Na]+; 719, [Ru(CO)(PPh3)2Cp]+.
Reaction of Ru(Ct CPh)(PPh3)2Cp with Dimethyl 2,3-Dicy-
anofumarate. Complex 4a (0.50 g, 0.63 mmol) and 3 (0.15 g, 0.78
mmol) were added to benzene (25 mL), and the mixture was heated
at reflux point for 2 h. The yellow-green solution became deep
claret after a few minutes and eventually turned intense violet. After
cooling, the solution was concentrated under reduced pressure and
the residue was purified by column chromatography (basic alumina).
Elution with CH2Cl2 gave a yellow band (49 mg), which contained
recovered 4a; further elution with 1:9 EtOAc/CH2Cl2 afforded a
yellow-orange band, which was further purified by preparative TLC
(silica, 1:49 acetone/CH2Cl2) to afford Ru{C[dC(CN)2]-
CPhdC(CN)(CO2Me)}(PPh3)Cp (13) as an orange microcrystalline
solid (88 mg, 21% based on recovered starting material) as an
approximately 3:2 mixture of isomers. Crystals for X-ray analysis
were grown by slow evaporation of a CH2Cl2 solution layered with
MeOH. Anal. Calcd (C39H31N2O4PRu): C, 64.63; H, 4.31; N, 3.87;
M, 722. Found: C, 64.70; H, 4.27; N, 3.89. IR (Nujol, cm-1): νmax
3058m, 2250w, 2212s, 1974m, 1916m, 1715vs, 1615s, 1482m,
1434vs, 1324m, 1282s, 1237vs, 1190m, 1122m, 1090s, 912m, 729s,
697vs. 1H NMR: δ 7.32-7.50 (20H, m), 4.69 (5H, s, minor), 4.61
(5H, s, major), 3.77 (3H, s, minor), 3.44 (3H, s, major), 3.39 (3H,
s, minor), 2.63 (3H, s, major). 13C NMR: δ 170.2, 170.1, 159.1,
159.0, 127.8-137.7 (m), 122.1, 119.4, 105.7, 91.2, 90.4, 69.8, 52.2,
51.9, 51.7. 31P NMR: δ 44.6 (minor), 37.3 (major). ES-MS (m/z):
748, [M + Na]+; 723, [M + H]+.
Variata. 5a. Refinement was executed using the SHELXL-97
2
program;28 reflection weights were [σ2(F2) + (0.50P)2]-1 [P ) (Fo
+ 2Fc2)/3]. Residuals cited are R1 and wR2.
9. As presented, the sample comprised crystals with two different
morphologies, both determined and found to be polymorphs, both
monoclinic P21/c, the “plate” form denoted 9 and the “rod” form as
9′.
Final atomic positional coordinates, with estimated standard
deviations, and bond lengths and angles have been deposited at
the Cambridge Crystallographic Data Centre under deposition
numbers 655563-655568.
Acknowledgment. We thank Professor Brian Nicholson
(University of Waikato, Hamilton, New Zealand) for provid-
ing the mass spectra, Dr. Simon Pyke for helpful discussions
on NMR, the ARC for support of this work, and Johnson
Matthey plc, Reading, for a generous loan of RuCl3 · nH2O.
Supporting Information Available: CIF files for the X-ray
structures. This material is available free of charge via the Internet
at http://pubs.acs.org.
OM7011437
Structure Determinations. Full spheres of diffraction data were
measured using CCD area-detector instrumentation. Ntot reflections
were merged to N unique (Rint cited) after “empirical”/multiscan
absorption correction (proprietary software), No with F > 4σ(F) being
(27) Hall, S. R., du Boulay, D. J., Olthof-Hazekamp, R., Eds. The XTAL
3.7 System; University of Western: Australia, 2000.
(28) Sheldrick, G. M. SHELXL-97, A Program for Crystal Structure
Refinement; University of Go¨ttingen, 1997.