Reactions of cyano(alkynyl)ethenes with some alkynyl- and diynyl-ruthenium complexes

Article abstract of DOI:10.1016/j.jorganchem.2008.07.006

Reactions of Ru(C{triple bond, long}CPh)(PPh₃)₂Cp with (NC)₂C{double bond, long}CR¹R² (R¹ = H, R² = C{triple bond, long}CSiPrⁱ₃ 8; R¹ = R² = C{triple bond, long}CPh 9) have given η³-butadienyl complexes Ru{η³-C[{double bond, long}C(CN)₂]CPh{double bond, long}CR¹R²}(PPh₃)Cp (11, 12), respectively, by formal [2 + 2]-cycloaddition of the alkynyl and alkene, followed by ring-opening of the resulting cyclobutenyl (not detected) and displacement of a PPh₃ ligand. Deprotection (tbaf) of 11 and subsequent reactions with RuCl(dppe)Cp and AuCl(PPh₃) afforded binuclear derivatives Ru{η³-C[{double bond, long}C(CN)₂]CPh{double bond, long}CHC{triple bond, long}C[ML_n]}(PPh₃)Cp [ML_n = Ru(dppe)Cp 19, Au(PPh₃) 20]. Reactions between 8 and Ru(C{triple bond, long}CC{triple bond, long}CR)(PP)Cp [PP = (PPh₃)₂, R = Ph, SiMe₃, SiPrⁱ₃; PP = dppe, R = Ph] gave η¹-dienynyl complexes Ru{C{triple bond, long}CC[{double bond, long}C(CN)₂]CR{double bond, long}CH[C{triple bond, long}C(SiPrⁱ₃)]}(PP)Cp (15-18), respectively, in reactions not involving phosphine ligand displacement. The phthalodinitrile C₆H(C{triple bond, long}CSiMe₃)(CN)₂(NH₂)(SiMe₃) 10 was obtained serendipitously from (Me₃SiC{triple bond, long}C)₂CO and CH₂(CN)₂, as shown by an XRD structure determination. The XRD structures of precursor 7 and adducts 11, 12 and 17 are also reported.

Full text of DOI:10.1016/j.jorganchem.2008.07.006

Journal of Organometallic Chemistry 693 (2008) 3571–3581
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Journal of Organometallic Chemistry
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Reactions of cyano(alkynyl)ethenes with some alkynyl- and
diynyl-ruthenium complexes
b
b
David J. Armitt a, Michael I. Bruce a, , Brian W. Skelton , Allan H. White
*
a School of Chemistry and Physics, University of Adelaide, Adelaide, South Australia 5005, Australia
b Chemistry M313, SBBCS, University of Western Australia, Crawley, Western Australia 6009, Australia
a r t i c l e i n f o
a b s t r a c t
Reactions of Ru(C„CPh)(PPh3)2Cp with (NC)2C@CR1R2 (R1 = H, R2 = C„CSiPr3i 8; R1 = R2 = C„CPh 9) have
given
3-butadienyl complexes Ru{ 3-C[@C(CN)2]CPh@CR1R2}(PPh3)Cp (11, 12), respectively, by formal
[2 + 2]-cycloaddition of the alkynyl and alkene, followed by ring-opening of the resulting cyclobutenyl
Article history:
Received 4 June 2008
Received in revised form 11 July 2008
Accepted 12 July 2008
Available online 18 July 2008
g
g
(not detected) and displacement of a PPh3 ligand. Deprotection (tbaf) of 11 and subsequent reactions with
RuCl(dppe)Cp and AuCl(PPh3) afforded binuclear derivatives Ru{
(PPh3)Cp [MLn = Ru(dppe)Cp 19, Au(PPh3) 20]. Reactions between 8 and Ru(C„CC„CR)(PP)Cp [PP = (PPh3)2,
g
3-C[@C(CN)2]CPh@CHC„C[MLn]}-
Keywords:
R = Ph, SiMe3, SiPr3i ; PP = dppe, R = Ph] gave
g
1-dienynyl complexes Ru{C„CC[@C(CN)2]CR@CH[C„C(Si-
Cyanocarbon
Ruthenium
Cyclo-addition
Alkynyl
Pri3)]}(PP)Cp (15–18), respectively, in reactions not involving phosphine ligand displacement. The phthalod-
initrile C6H(C„CSiMe3)(CN)2(NH2)(SiMe3) 10 was obtained serendipitously from (Me3SiC„C)2CO and
CH2(CN)2, as shown by an XRD structure determination. The XRD structures of precursor 7 and adducts
11, 12 and 17 are also reported.
Diynyl
XRD structure
Ó 2008 Elsevier B.V. All rights reserved.
1. Introduction
Donor-substituted 1,1,4,4-tetracyanobutadienes [6] and cyano-
(alkynyl)ethenes [7,8] are of considerable contemporary interest
Reactions of transition metal
r
-alkynyl complexes with a vari-
on account of their reactivity, showing strong intra-molecular
charge-transfer effects and non-linear optical properties. Some
examples of cyano(alkynyl)ethenes undergo similar [2 + 2]-cyclo-
addition and ring-opening reactions to those mentioned above
[9–11]. These compounds fall between tetracyanoethene on the
one hand and the recently described tetra-alkynylethenes [12–14]
on the other. Some of the latter have been shown to form interest-
ing transition metal complexes, including the tetra-cluster com-
ety of electron-deficient alkenes have been described, among
which cyano-alkenes such as tetracyanoethene (tcne) [1,2],
R2C@C(CN)2 (R = CF3 [3], SMe [4]) and dimethyl dicyanofumarate
[4], predominate. The products are generally formed by [2 + 2]-
cycloaddition reactions to give substituted cyclobutenyl-metal
complexes A (Chart 1), often proceeding via initial highly coloured
charge transfer complexes or radical intermediates. In turn, the
cyclobutenyls obtained from the alkenes undergo electrocyclic
ring-openings to the butadienyl derivatives B, and further interac-
tion of a C@C double bond with the metal centre may occur if eas-
plex
{[(OC)9Co3]2[l3-(„CC„C)]}2C@C{C„C-l3-C„[Co3(CO)9]}2
[15]. Consequently, it is of interest to examine the reactions of sev-
eral bis(alkynyl)dicyanoethenes with transition metal substrates.
This paper describes the results of a brief study of the reactions
of several ruthenium complexes Ru(C„CR)(PP)Cp [PP = (PPh3)2,
R = Ph 1, SiPri3 2; PP = dppe, R = Ph 3] and Ru(C„CC„CR)(PP)Cp
[PP = (PPh3)2, R = Ph 4, SiMe3 5, SiPri3 6; PP = dppe, R = Ph 7] (Chart
1) with selected 1,1-dicyanobis(alkynyl)ethenes.
ily displaced ligands are present to give 1,2,3-g
3-butadienyl
complexes C (Scheme 1).
In the case of poly-ynyl complexes, several sites of addition are
available. Previous studies have described the addition of tcne to
complexes Ru{(C„C)nR}(PP)Cp0 [n = 2,3; R = Ph, Fc; PP = (PPh3)2,
dppe; Cp0 = Cp, Cp*] [5]. Isomeric products formed by cycloaddi-
tion/ring-opening involve either of the C„C triple bonds adjacent
to or one removed from the metal centre. Of some interest in these
complexes is the extensive delocalisation found in the Ru–C„C–C-
2. Ruthenium complexes
For the purposes of this study, we also required some ruthe-
nium complexes which have not been described previously. The
reaction between RuCl(PPh3)2Cp and HC„C(SiPri3) in the presence
of NaOMe afforded Ru(C„CSiPri3)(PPh3)2Cp (2) in a reaction analo-
gous to that already described for the preparation of the related
Me3SiC„C complex [16]. The complex was obtained as a yellow
{@C(CN)2}CR@C(CN)2 fragment, in which the Ru–C bond has con-
siderable multiple bond character.
a
* Corresponding author. Fax: +61 8 8303 4358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce).
0022-328X/$ - see front matter Ó 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2008.07.006

3572
D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
diynyl C at dC 63.9, 80.4, 82.4, 83.9; dppe at dP 85.9. The ES-MS
spectrum contained [M + H]+ and [Ru(dppe)Cp]+ ions at m/z 691
and 565, respectively.
Ru
Ph
Ru
R
Ph2P
Ph3P
PPh2
PPh3
The XRD structure of 7 was determined and a molecule is de-
picted in Fig. 1; selected bond parameters are listed in the caption.
The Ru(dppe)Cp fragment has the usual pseudo-octahedrally coor-
dinated ruthenium centre. The diynyl is attached by C(1) [Ru–C(1)
1.988(2) Å] and contains alternating C„C and C–C separations
along the C4 chain from the metal [C(n)–C(n + 1) 1.227(3),
1.367(3), 1.147(7) Å with angles at C(n) of 174.5(2)°, 172.5(2)°,
167.5(3)°, 172.4(6)°, respectively]. Overall, the molecular structure
closely resembles those recently described for Ru(C„CC„CX)(dp-
1 R = Ph; 2 R = SiPri3
3
Ru
Ph
Ru
R
Ph2P
PPh2
Ph3P
PPh3
4 R = Ph; 5 R = SiMe3; 6 R = SiPri3
7
pe)Cp* [X = H, SiMe3, Au(PPh3), Hg, CCo3(
l-dppm)(CO)7] [17–19].
Chart 1.
3. Synthesis of cyano(alkynyl)ethenes
We prepared ðNCÞ2C@CHfCBCðSiPri3Þg (8) as a pale yellow oil in
83% yield by condensation of SiPri3(C„CCHO) with malononitrile in
the presence of basic alumina; the compound (NC)2C@C(C„CPh)2
(9) is known [20] (Chart 2).
An attempted synthesis of (NC)2C@C{C„C(SiMe3)}2 from
bis(trimethylsilylethynyl) ketone gave instead the white 2,6-di-
solid, with characteristic aromatic (dH 7.52–7.58, 7.03–7.20, dC
127.1–139.5), Cp (dH 4.27, dC 97.8), alkynyl (dC 113.5, 215.9), SiPr3i
(dH 0.98–1.12, dC 12.2, 19.3) and PPh3 resonances (dP 49.9), m(C„C)
at 1987 cmꢀ1 and [M + Na]+ and [Ru(PPh3)nCp]+ at m/z 895 and
691 (n = 2), 429 (n = 1), respectively.
Diynyl-ruthenium complexes Ru(C„CC„CR)(PP)2Cp [PP =
(PPh3)2, R = SiPri3 6; PP = dppe, R = Ph 7] were obtained from similar
reactions between the corresponding chloro-ruthenium complexes
and HC„CC„CSiPri3 (quantitative) or PhC„CC„CSiMe3 (18%),
respectively [17]. Both complexes were yellow solids, readily identi-
fied from characteristic features in their NMR spectra. For 6, these
include Cp at dC 4.31, dC 96.7, SiPri3 at dH 1.08–1.12, dC at 11.8,
18.9, and PPh3 at dH 7.18–7.23, 7.38–7.44, dC 127.3–138.8; diynyl
carbons were found at dC 63.8, 81.4, 85.5, 118.5. The ES-MS spectrum
contained [M + Na]+, [M + H]+ and [Ru(PPh3)nCp]+ ions at m/z 919,
897, 691 (n = 2) and 429 (n = 1), respectively. For 7, corresponding
data are Cp at dH 4.67, dC 95.2; Ph at dH 6.81–7.98, dC 126.3–132.9;
Ph
Ph
TIPS
NC
NC
NC
NC
H
8
9
Chart 2.
NC
CN
NC
CN
R
NC
NC
CN
CN
NC CN
CN
- L
NC
R
LnM
L
n-1M
+
LnM
R
CN
NC
NC
CN
LnM
R
A
B
C
Scheme 1.
Fig. 1. Plot of a molecule of Ru(C„CC„CPh)(dppe)Cp (7). Bond distances: Ru–P(1,2) 2.2515(5), 2.2577(6), Ru–C(cp) 2.238–2.251(2), av. 2.244(6), Ru–C(1) 1.988(2), C(1)–C(2)
1.227(3), C(2)–C(3) 1.367(3), C(3)–C(4) 1.147(7), C(4)–C(41) 1.438(7) Å. Bond angles: P(1)–Ru–P(2) 82.80(2)°, P(1,2)–Ru–C(1) 84.91(6)°, 88.75(5), Ru–C(1)–C(2) 174.5(2)°,
C(1)–C(2)–C(3) 172.5(2)°, C(2)–C(3)–C(4) 167.5(3)°, C(3)–C(4)–C(41) 172.4(6)°.

D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
3573
Fig. 2. Plot of
a molecule of the 2,6-dicyanoaniline (10). Bond distances: C(1)–C(11) 1.433(1), C(11)–C(12) 1.214(2), C(12)–Si(12) 1.847(1), C(n)–C(n1) (n = 2,4)
1.433(2), 1.438(1), C(3)–N(3) 1.359(1), C(5)–Si(5) 1.907(1) Å. Bond angles: C(1)–C(11)–C(12) 176.7(1)°, C(11)–C(12)–Si(12) 176.1(1)°, C(n)–C(n1)–N(n1) (n = 2,4) 175.5(1)°,
178.7(1)°.
cyanoaniline 10 (2-amino-4-trimethylsilyl-6-trimethylsilylethy-
nylisophthalonitrile) (44%), characterised by an XRD structure
determination (Fig. 2). The 1H NMR spectrum contains resonances
from two non-equivalent SiMe3 groups (d 0.30, 0.40), the NH2
group (d 5.16) and a single C(sp2)-H (d 6.96). In the 13C NMR spec-
trum, the two CN groups appeared at d 114.8, 116.7 and the C„C
4. Cycloaddition/ring opening reactions of
cyano(alkynyl)ethenes with alkynyl-Ru complexes
Reactions between the alkynyl- or diynyl-ruthenium complexes
and the dicyanobis(alkynyl)ethenes afforded several complexes,
the identities of which were deduced largely from their spectro-
scopic properties, backed up by a selection of XRD structural
studies.
carbons at d 100.4, 100.5. The IR spectrum contained
m(C„C) at
2163 cmꢀ1 and (CN) at 2215 cmꢀ1
m
.
A molecule of 10 is depicted in Fig. 2, with selected bond
parameters being listed in the caption thereto. The structure itself
is unremarkable, except that there is a slight bending of the ethy-
nyl group from absolute linearity, and that the SiMe3 substituent
deviates a small amount from the plane of the benzene ring. Both
of these effects could be due to crystal packing constraints; inver-
sion-related molecules pack in columns up crystallographic a. Dur-
4.1. Ru(C„CPh)(PPh3)2Cp and ðNCÞ C@CHfCBCðSiPri Þg
2
3
The reaction between Ru(C„CPh)(PPh3)2Cp (1) and
ðNCÞ2C@CHfCBCðSiPri3Þg (8) was carried out in refluxing benzene
for 24 h and the products separated to give
g
3-dienyl complex
11 as a yellow solid (32%) (Scheme 2). A larger yield (86%) was ob-
tained by irradiation of the mixture with a 300 W sunlamp. Loss of
one PPh3 ligand during the reaction is indicated by microanalyes,
ES-MS ([M + Na]+ at m/z 811) and the NMR spectra. In the latter
ing the course of preparation of this paper,
a generalised
conversion of dicyanoanilines, including 10, from ynones and mal-
ononitrile by a similar route was reported [21].
NC
CN
NC
CN
Ru
Ru
H
Ru
Ph
9
8
Ph3P
Ph3P
Ph3P
Ph
Ph
PPh3
Ph
1
NC
R1
R2
R2
Ph
13
11 R2 = SiPri3
[NBu4]F
MClLn
NC
12 R2 = H
8 R1 = H; R2 = CCSiPri3
9 R1 = R2 = CCPh
19 R2 = Ru(dppe)Cp
20 R2 = Au(PPh3)
Scheme 2.

3574
D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
Ph (dH 7.24–7.69, dC 128.1–137.0), Cp (dH 4.58, dC 88.8), CN (dC
111.3, 112.8), SiPri3 (dH 1.07, dC 11.4, 18.7) and PPh3 (dP 49.8) reso-
nances are accompanied by signals for five carbons of the unsatu-
rated C6 chain at dC 28.4, 69.5, 79.4, 86.9 and 111.3. The proton
attached to C(4) is found at dH 2.60 as a doublet with J(HP) = 13.0 Hz.
scopic data, was confirmed by an XRD structural determination. In
the NMR spectra, the signals for the Ph (dH 7.27–7.66, dC 128.1–
137.0), Cp (dH 4.59, dC 89.0) and the protons attached to C(4) and
C(6) (dH 2.63 d, J = 2.2 Hz) and 2.42 (dd, J = 2.2, 13.5 Hz), respectively,
and PPh3 (dP 49.8) also contained signals which we have assigned to
CN (dC 112.7, 118.0) and some of the carbon chain atoms (dC 26.8,
69.2, 73.4, 87.6, 89.0). The ES-MS contained [2M + Na]+ and
[M + Na]+ at m/z 1287 and 655, respectively, while bands in the IR
The IR spectrum contains bands assigned to
(CN) at 2213, 2250 cmꢀ1
Removal of the SiPri3 group from complex 11 was readily achieved
m(C„C) at 2129 and
m
.
by treatment with [NBu4]F at 0 °C for 40 min. Conventional work-up
afforded 12 as a yellow solid in quantitative yield. The molecular
structure, initially established from microanalytical and spectro-
spectrum were assigned to m(CN) at 2214 and m .
(CC) at 2088 cmꢀ1
The very similar XRD molecular structures of 11 and 12 are
shown in Figs. 3 and 4, with selected bond parameters in Table 1,
Fig. 3. Plot of a molecule of Ru{g3 ꢀ C[@C(CN)2]CPhCC„C(SiPr3i )}(PPh3)Cp (11).
Fig. 4. Plot of a molecule of Ru{g3 ꢀ C[@C(CN)2]CPhCC„CH}(PPh3)Cp (12).

D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
3575
Table 1
Selected bond distances (Å) and angles (°) for 11, 12 and 17
Complex
11 (molecules 1; 2)
12
17 (molecules 1; 2)
Bond distances (Å)
Ru–P(1)
Ru–P(2)
2.3280; 2.3272(7)
2.3215(5)
2.298; 2.312(1)
2.319; 2.300(1)
Ru–C(cp)
(av.)
2.225–2.258(3); 2.218–2.259(3)
2.232(15);2.231(15)
2.217–2.258(2)
2.234(15)
2.226–2.249(4); 2.222–2.241(4)
2.239;2.234(9)
Ru–C(1)
1.976; 1.981(5)
Ru–C(2)
Ru–C(3)
Ru–C(4)
C(1)–C(2)
C(1)–C(1A,1B)
1.970; 1.977(3)
2.146; 2.147(3)
2.202; 2.204(3)
1.352; 1.353(4)
1.433, 1.444(4);
1.435, 1.433(4)
1.986(2)
2.151(2)
2.203(2)
1.363(3)
1.439, 1.435(3)
[C(11, 12)]
1.221; 1.226(6)
C(2)–C(3)
C(3)–C(4)
C(3)–C(5)
C(3)–C(31)
1.439; 1.439(4)
1.444; 1.438(4)
1.443(3)
1.439(3)
1.400; 1.399(6)
1.380; 1.382(5)
1.501; 1.486(6)
1.492; 1.483(4)
[C(41)]
1.489(3)
C(4)–C(41,42)
C(4)–C(5)
C(5)–C(6)
C(6)–C(7)
C(7)–C(8)
C(5)–Si(1)
C(6)–Si
1.424, 1.438(6); 1.434, 1.427(6)
1.446; 1.447(4)
1.202; 1.205(4)
1.445(3)
1.173(3)
1.349; 1.341(6)
1.428; 1.427(6)
1.210; 1.187(6)
1.884; 1.894(4)
1.838; 1.836(3)
Bond angles (°)
P(1)–Ru–P(2)
P(1)–Ru–C(1)
P(2)–Ru–C(1)
P–Ru–C(2)
99.48; 99.72(4)
92.8; 93.1(1)
96.0; 95.4(1)
91.03; 90.04(8)
87.48; 86.92(7)
70.01; 69.67(11)
90.71(5)
87.31(5)
69.37(7)
P–Ru–C(4)
C(2)–Ru–C(4)
Ru–C(1)–C(2)
C(1)–C(2)–C(3)
C(2)–C(3)–C(4)
C(2)–C(3)–C(5)
C(3)–C(4)–C(5)
C(3)–C(5)–C(6)
C(4)–C(5)–C(6)
C(5)–C(6)–C(7)
C(6)–C(7)–C(8)
C(3)–C(5)–Si(1)
C(7)–C(8)–Si(2)
C(5)–C(6)–Si
167.0; 164.0(4)
167.6; 162.8(4)
120.2; 120.3(4)
121.1; 119.3(4)
136.8; 134.6(3)
112.7; 112.8(2)
130.1(2)
112.1(2)
122.1; 121.3(2)
177.7; 179.4(3)
123.7(2)
175.4(2)
117.1; 118.1(4)
125.5; 125.7(4)
176.4; 175.9(5)
123.6; 121.6(3)
176.4; 163.6/171.7(6)
171.5; 173.5(2)
and confirm that the outer dienyl C@C double bond displaces a
PPh3 ligand with formation of a
3-butadienyl complex. In both
4.2. Ru(C„CPh)(PPh3)2Cp and (NC)2C@C(C„CPh)2
g
compounds, the ruthenium atom, which is a chiral centre, is at-
tached to the Cp [Ru–C(cp) 2.225–2.258(3), 2.218–2.259(3) (mole-
cules 1, 2); h i 2.232, 2.231 11; 2.217–2.258(2), av. 2.234(15) Å 12]
and PPh3 ligands [Ru–P 2.3280, 2.3272(7); 2.3215(5) Å, respec-
tively]. The organic ligand is bonded to Ru by C(2) [1.970,
1.977(3); 1.986(2) Å] and C(3)–C(4) [Ru–C(3,4) 2.146, 2.147(3);
2.202, 2.204(3) 11; 2.151, 2.203(2) Å 12], the short former bond
indicating a degree of multiple bond character. Within the carbon
chain, similar C(2)–C(3) and C(3)–C(4) distances [1.439, 1.439,
1.434, 1.438(4) 11; 1.443, 1.439(3) Å 12] indicate a degree of con-
jugation within the dienyl ligand, while C(1)@C(2) [1.352(5),
1.353(4); 1.363(3) Å] and C(5)–C(6) [1.202, 1.205(4); 1.173(3) Å]
have the usual dimensions for unperturbed C@C and C„C triple
bonds. Other dimensions are also similar, with the exception of a
slight contraction in angle C(1)–C(2)–C(3) for 12 [130.1(2)°; cf.
136.8°, 134.6(3)° for 11]. With respect to the plane defined by
C(2,3,4), C(1) lies out of plane to one side by ꢀ0.676, ꢀ0.717(6);
ꢀ0.771(4) Å [11 (molecules 1, 2); 12], with Ru [1.566, 1.582(5);
1.595(3) Å] and C(5) [0.426, 0.395(6); 0.401(4) Å] to the other side.
The C(2,3,4) planes are quasi-parallel to their companion C5 planes
[dihedrals: 8.4°, 7.7(3)°; 9.6(2)°].
The reaction between Ru(C„CPh)(PPh3)2Cp (1) and (NC)2C@C-
(C„CPh)2 (9) is similar to that with 8, giving orange solid 13 in
54% yield. Microanalytical and ES-MS data established the g3
-
butadienyl formulation, with [M + H]+ at m/z 809 in the ES-MS.
The NMR spectra were not well resolved as a result of low solubil-
ity, the characteristic resonances for the Ph (dH 6.88–7.76, dC
126.0–134.9), Cp (dH 5.11, dC 86.0) and PPh3 (dP 52.1) groups being
accompanied by signals at dC 29.3, 29.7, 87.9, 89.1 and 101.3 which
we assign to some of the chain carbons, and one at dC 117.4,
assigned to CN.
4.3. Ru(C„CPh)(dppe)Cp and ðNCÞ2C@CHfCBCðSiPri3Þg
The reaction between Ru(C„CPh)(dppe)Cp (3) and (NC)2C@CH-
{C„C(SiPri3)} (8) afforded 14 (Scheme 3) as a yellow solid in 95%
yield. In this case, the microanalysis, ES-MS ([M + Na]+ and [M + H]+
at m/z 947, 925, respectively) and NMR spectra confirmed that the
dppe ligand remained, and that the alkynyldiynyl ligand was at-
tached to the Ru centre by a
r-bond alone. The NMR parameters
are similar to those of 13 (with the exception of the relative intensi-
ties of the aromatic protons), with the proton attached to C(4) now

3576
D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
NC
CN
Ph
Ru
8
Ph2P
Ru
PPh2
Ph
PPh2
Ph2P
H
SiPri3
14
Scheme 3.
appearing at dH 4.92. The 31P resonances of the dppe ligand are
18.5 Hz doublets at dP 70.6 and 81.4, indicating the magnetic inequiv-
alence induced by the asymmetric organic ligand. Some of the chain
carbons are found at dC 28.3, 85.5, 86.0, 95.1, 105.0 and 119.8, while
the SiPri3 group gives rise to resonances at dH 1.08 and dC 11.4, 18.7.
2211 cmꢀ1 (CC) between 1981 and 2002 cmꢀ1 in their IR spectra;
, m
Cp resonances between dH 4.47–4.56 (4.87 for 17), dC 85.5–89.7,
vinylic proton signals between dH 5.52 and 6.10, and PPh3 reso-
nances between dP 46.3 and 50.8, with the dppe at dP 83.2 in 18.
In 17, the bulky PPh3 groups give rise to an AB quartet at dP 46.6
(J = 34 Hz), possibly because of restricted rotation of the alkynyl li-
gand, although this is not found in any of the other complexes. Res-
onances for the CN groups occurred at dC 110.1–118.2. The ES-MS
of solutions containing NaOMe all contained [M + Na]+ and M+
ions. The SiPri3 groups give characteristic resonances at dH ca.
1.03–1.12 and dC ca. 11.0 and 18.0. Complex 16 showed SiMe3 reso-
nances at dH 0.16 and dC ꢀ1.0.
4.4. Reactions between ðNCÞ2C@CHfCBCðSiPri3Þg (8) and diynyl
complexes
The diynyl complexes Ru(C„CC„CR)(PP)Cp [PP = (PPh3)2 R = Ph
4, SiMe3 5, SiPri3 6; PP = dppe, R = Ph 7] all react with 8 to give com-
plexes in which the cyano(alkynyl)ethene has added to the outer
C„C triple bond, namely Ru{C„CC[@C(CN)2]CR@CH[C„C(Si-
Pri3)]}(PP)Cp (15–18, respectively; Scheme 4), as confirmed by the
XRD structure determination for 17 (Fig. 5, Table 1). The usual
Ru(PPh3)2Cp fragment [Ru–P 2.298–2.319(1); Ru–C(cp) 2.222–
2.249(4), av. 2.239; 2.234(9) Å (molecules 1, 2)] is attached to the or-
ganic ligand by Ru–C(1) [1.976(3); 1.981(5) Å]. Bond lengths along
the carbon chain confirm triple bonds between C(1)–C(2) and C(7)–
C(8) [1.221, 1.226(6); 1.210, 1.187(6) Å] and double bonds between
C(3)–C(4) and C(5)–C(6) [1.380, 1.382(5) and 1.349, 1.341(6) Å].
The differences in formal single bond lengths between C(2)–C(3),
C(3)–C(5) and C(6)–C(7) [1.400; 1.399(6) and 1.501; 1.486(6) and
1.428, 1.427(6) Å] reflect the differing hybridisation [C(sp) vs.
C(sp2)] and partial delocalisation along the C(1)–C(4) fragment, as
found earlier in the structure of Ru{C„CC[@C(CN)2]CFc@C(CN)2}(dp-
pe)Cp* [5c]. Deviations in angles at individual carbon atoms [164.0–
176.4(4) for C(sp), 117.1–125.7(4) for C(sp2)] probably result from
‘‘crystal packing effects”.
5. Further reactions of g
3-butadienyl complexes
5.1. Addition of other metals
After deprotection of complex 11 in situ with [NBu4]F (as in (a)
above), the resulting ethynyl derivative 12 reacts with RuCl(dp-
pe)Cp in the presence of Na[BPh4] to give the binuclear derivative
19 (Scheme 2). The entering Ru(dppe)Cp group becomes
r-bonded
to the alkynyl function of the butadienyl in 12 as indicated by the
usual microanalytical and spectroscopic data. In the 31P NMR spec-
trum, signals at dP 49.8 and 78.1 with intensity ratio 1/2 are as-
signed to the PPh3 and dppe ligands, respectively. The other
groups present give rise to resonances at dH 4.52 and 4.59, dC
87.3 and 87.5 (2 ꢁ Cp), dH 2.17 and 2.41, dC 26.8, 29.3 (CH2 of dppe)
and dH 7.15–7.86, dC 127.8-137.0 (Ph). The proton attached to C(4)
appears as a doublet at dH 2.41, while carbons of CN (dC 112.7,
117.9) and the C6 chain appear at dC 26.6, 87.5, 141.0, 141.7 and
210.6. The ES-MS contains [M + H]+ at m/z 1197, together with
All compounds have similar spectroscopic properties (see Sec-
tion 7 for details), which include
m
(CN) between 2208 and
NC
CN
Ru
8
P
Ru
P
R
Ph
P
H
P
PP = (PPh3)2; R = Ph 4, SiMe3 5, SiPri3
PP = dppe; R = Ph 7
6
SiPri3
PP = (PPh3)2; R = Ph 15, SiMe3 16, SiPri3 17
PP = dppe; R = Ph 18
Scheme 4.

D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
3577
Fig. 5. Plot of a molecule of Ru{C„CC[@C(CN)2]C(SiPri3)@CHC„C(SiPri3)}(PPh3)2Cp (17).
[Ru(dppe)Cp]+ at m/z 565. In the IR spectrum,
2213 cmꢀ1
m
(CN) occurs at
nitrogen and degassed before use. Separations were carried out
by preparative thin-layer chromatography on glass plates
(20 ꢁ 20 cm2) coated with silica gel (Merck, 0.5 mm thick).
.
Addition of [NBu4]F to a mixture of 11 and AuCl(PPh3) afforded
a yellow solid in 90% yield, identified as the gold–ruthenium com-
plex 20. The ES-MS contains aggregate ions at m/z 1549
([M + Au(PPh3)]+) and 1113 ([M + Na]+), together with [Au(PPh3)]+
and [Au(PPh3)(MeOH)]+ at m/z 721 and 500, respectively. In the
NMR spectra, characteristic resonances for Ph (dH 7.19–7.88, dC
127.7–137.9), Cp (dH 4.55, dC 88.9), PPh3 [dP 40.7 (Au–P) and 50.3
(Ru–P)] and the proton attached to C(4) (dH 2.70) were accompa-
nied by signals for CN (dC 113.2, 118.5) and the chain carbons (dC
31.4, 68.3, 78.3).
7.2. Instruments
IR spectra were obtained on a Bruker IFS28 FT-IR spectrometer.
Nujol mull spectra were obtained from samples mounted between
NaCl discs. NMR spectra were recorded on a Varian 2000 instru-
ment (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 tetramethylsilane for
1H and 13C NMR spectra and external H3PO4 for 31P NMR spectra.
Electrospray mass spectra (ES-MS) were obtained from samples
dissolved in MeOH, containing NaOMe to aid ionisation [22]. Solu-
tions were injected into a Fisons VG Platform II spectrometer via a
10 mL injection loop. Nitrogen was used as the drying and nebulis-
ing gas. Ions listed are the most intense in the isotopic patterns.
Elemental analyses were by CMAS, Belmont, Vic., Australia.
6. Conclusions
This study has shown that cyano(alkynyl)ethenes, such as
ðNCÞ2C@CHfCBCðSiPri3Þg, enter into the cycloaddition/ring-open-
ing reactions with ruthenium alkynyl and diynyl complexes which
are analogous to those found earlier with tcne and other related
electron-deficient alkenes. In one instance, we have demonstrated
the ready deprotection of the alkynyl group and subsequent reac-
tions of the terminal alkyne to incorporate Ru(dppe)Cp and
Au(PPh3) groups in the resulting binuclear complexes. Inclusion
of the C„C triple bond gives an extra functionality for construction
of further examples of polynuclear complexes which may have
exciting unusual optical and electronic properties.
In the course of preparing substrates for the cycloaddition reac-
tions, we have also made and characterised ðNCÞ2C@CHfCBC
ðSiPri3Þg, while, during an attempted synthesis of 1,1-dicyano-2,2-
bis(trimethylsilyethynyl)ethene, the obtained product was shown
crystallographically to be 2-amino-4-trimethylsilyl-6-(trimethyl-
silylethynyl)isophthalonitrile (10).
7.3. Reagents
The following compounds were obtained by the cited literature
methods: Ru(C„CPh)(PP)Cp [PP = (PPh3)2 1, dppe
3 [23]],
Ru(C„CC„CR)(PPh3)2Cp (R = Ph 4 [24], SiMe3 5 [17]), SiPri3(C„C-
CHO) [25], Br2C = CHC„C(SiPri3) [25], (NC)2C@C(C„CPh)2 (9) [20].
Previously unknown materials were prepared as described below.
7.4. Ruthenium complexes
7.4.1. Ru{C„C(SiPri3)}(PPh3)2Cp (2)
A mixture of RuCl(PPh3)2Cp (0.70 g, 0.96 mmol) and HC„C(Si-
Pri3) (0.24 mL, 1.05 mmol) was heated in refluxing MeOH (30 mL)
for 2 h. After cooling, NaOMe (1 M in MeOH, 3.00 mL, 3.00 mmol)
was added, the solution was stirred at r.t. for 30 min, then concen-
trated to ca. 10 mL under reduced pressure. The resulting precipitate
was collected by filtration, washed with cold MeOH (5 mL) and dried
to afford Ru{C„C(SiPri3)}(PPh3)2Cp (2) as a yellow solid (312 mg,
37%). Anal. Calc. for C52H56P2RuSi: C, 71.61; H, 6.47; M, 872. Found:
7. Experimental
7.1. General
All reactions were carried out under dry nitrogen, although nor-
mally no special precautions to exclude air were taken during sub-
sequent work-up. Common solvents were dried, distilled under
C, 71.58; H, 6.39%. IR (cmꢀ1):
803m, 756m, 737m, 703m, 693m. 1H NMR: d 7.52–7.58 (12H, m),
m(CC) 1987m; other bands at 1432s,

3578
D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
Table 2
Crystal data and refinement details
Complex qc (g cmꢀ3
)
7
10
11
12
17
Formula
C41H34P2Ru
689.69
Monoclinic
C2/c
29.6151(5)
9.3742(3)
27.6709(9)
C16H21N3Si2
311.54
C46H47N2PRuSi
788.03
C37H27N2PRu
631.65
Monoclinic
C2/c
17.7791(8)
9.5073(4)
36.2525(4)
C69H78N2P2RuSi2 ꢂ 0.25CH2Cl2
1175.76
Monoclinic
I2/a
46.512(6)
13.6207(7)
40.653(2)
Molecular weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Triclinic
Triclinic
ꢀ
ꢀ
P1
P1
9.8992(6)
10.0452(7)
11.0297(7)
69.694(1)
63.369(1)
80.071(1)
919.3
13.271(1)
15.851(1)
20.848(2)
74.294(2)
84.871(2)
80.912(2)
4164
a
(°)
b (°)
124.885(2)
104.358(3)
101.796(7)
c
(°)
V (Å3)
6301
5936
25211
qc
1.454
1.125
1.257
1.413
1.239
Z
8
2
4
8
16
2hmax (°)
65
0.63
74
0.19
70
0.48
62
0.61
53
0.40
l
(Mo-K ) (mmꢀ1
)
a
Tmin/max
0.93
0.89
0.77
0.88
0.98
Crystal dimensions (mm)
Ntot
0.40 ꢁ 0.19 ꢁ 0.04
0.60 ꢁ 0.40 ꢁ 0.35
0.25 ꢁ 0.25 ꢁ 0.10
0.35 ꢁ 0.12 ꢁ 0.06
0.23 ꢁ 0.18 ꢁ 0.11
101590
24229(0.061)
12374
43507
16722
68613
44119
N (Rint
)
11204 (0.054)
7201
0.040
8819 (0.020)
5971
0.052
35719 (0.051)
21678
0.066
9393 (0.037)
6284
0.033
No
R
0.049
Rw (a, b)
T (K)
0.083 (0.040, ꢀ)
0.16 (0.089, 0.039)
150
0.16 (0.061, 3.99)
150
0.077 (0.036, ꢀ)
0.14 (0.067, ꢀ)
100
100
100
7.03–7.20 (18H, m), 4.27 (5H, s), 0.98–1.12 (21H, m). 13C NMR: d
215.9, 139.5, 139.1, 138.7, 133.9 [t, J(CP) = 5.3 Hz], 132.1 [d,
J(CP) = 9.9], 128.3, 127.1 [t, J(CP) = 4.6 Hz], 113.5, 97.8, 85.9 [t,
J(CP) = 2.3 Hz], 19.3, 12.8. 31P NMR: d 49.9. ES-MS (m/z): 895,
[M + Na]+; 691, [Ru(PPh3)2Cp]+; 429, [Ru(PPh3)Cp]+.
1097m, 791m, 744m, 693m. 1H NMR: d 7.92–7.98 (4H, m), 7.37–
7.40 (2H, m), 7.23–7.28 (4H, m), 7.07–7.13 (6H, m), 6.81–7.00
(9H, m), 4.67 (5H, s), 2.47–2.59 (2H, m), 1.93–2.08 (2H, m). 13C
NMR: d 142.8 (m), 137.6 (m), 134.6 [t, J(CP) = 5.3 Hz], 132.9,
132.3 [t, J(CP) = 5.3 Hz], 130.2, 129.3, 128.7, 128.5, 126.3, 95.2,
83.9 [t, J(CP) = 1.9 Hz], 82.4, 80.4, 63.9, 28.9 [1:1:1 t,
J(CP) = 22.9 Hz]. 31P NMR: d 85.9. ES-MS (m/z): 691, [M + H]+;
565, [Ru(dppe)Cp]+.
7.4.2. Ru(C„CC„CSiPri3)(PPh3)2Cp (6)
BuLi (2.30 M in hexanes, 2.41 mL, 5.54 mmol) was added drop-
wise to a solution of NHPri2 (0.78 mL, 5.54 mL) in thf (4 mL) at 0 °C.
The solution was stirred for 15 min at 0 °C, then added dropwise to a
solution of Br2C@CHC„C(SiPr3i ) (0.61 g, 1.68 mmol) in thf (4 mL) at
ꢀ78 °C. The mixture was stirred at ꢀ78 °C for 2 h, 1 M HCl (6 mL)
was added and the mixture was stirred at r.t. for a further 30 min.
The organic layer was separated, washed with brine (5 mL) and
water (5 mL), dried (MgSO4), and filtered. This solution of Pr3i -
SiC„CC„CH was added to a suspension of RuCl(PPh3)2Cp (0.61 g,
0.84 mmol) and Na[BPh4] (0.32 g, 0.92 mmol) in 1/1 NEt3-thf
(18 mL) and the mixture was stirred at 50 °C for 18 h. After cooling,
the mixture was concentrated under reduced pressure. Flash chro-
matography of the residue (acetone–hexane, 1/3) afforded
Ru(C„CC„CSiPri3)(PPh3)2Cp (6) as a yellow solid (0.75 g, 100%).
Anal. Calc. for C54H56P2RuSi: C, 72.38; H, 6.30; M, 896. Found: C,
7.5. 1,1-Dicyano-4-(triisopropylsilyl)but-1-en-3-yne,
ðNCÞ2C@CHfCBCðSiPri3Þg (8)
A
mixture of 3-(triisopropylsilyl)propargaldehyde (1.15 g,
5.48 mmol), malononitrile (0.52 mL, 8.22 mmol), basic alumina
(1.50 g, activity II) was heated in refluxing CH2Cl2 (25 mL) for
40 min. After cooling the alumina was filtered off and extracted with
CH2Cl2 (3 ꢁ 10 mL). The combined filtrate and extracts were con-
centrated under reduced pressure. Short column chromatography
of the residue (silica; CH2Cl2-hexane, 1/1) afforded ðNCÞ2C@
CHfCBCð SiPri3Þg (8) as a pale yellow oil (1.17 g, 83%). Anal. Calc.
(C15H22N2Si): C, 69.71; H, 8.58; N, 10.84; M, 259. Found: C, 69.73;
H, 8.52; N, 10.85%. IR (Nujol, cmꢀ1): mmax 3026w, 2234m, 2178s,
2127w, 2030w, 1561m, 1368s, 1244m, 1165m, 1106m, 1086m,
71.70; H, 6.17%. IR (cmꢀ1):
m(CC) 2162w, 2101m, 1993w; other
bands at 740m, 723m, 696m. 1H NMR: d 7.38–7.44 (12H, m), 7.18–
7.23 (6H, m), 7.08–7.13 (12H, m), 4.31 (5H, s), 1.08–1.12 (21H, m).
13C NMR: d 138.8, 138.5, 138.2, 137.9, 137.7, 133.7 [t, J(CP) = 4.9 Hz],
132.1 [d, J(CP) = 9.7 Hz], 128.5, 127.3 [t, J(CP) = 4.6 Hz], 118.5 [t,
J(CP) = 24.6 Hz], 96.7, 85.5, 81.4, 63.8, 18.9, 11.8. 31P NMR: d 47.9.
ES-MS (m/z): 919, [M + Na]+; 897, [M + H]+; 691, [Ru(PPh3)2Cp]+;
429, [Ru(PPh3)Cp]+.
1018m, 882s, 665s, 611s. 1H NMR:
d
6.95 (1H, s),
1.10–1.14 (21H, m). 13C NMR: d 140.9, 122.7, 112.1, 110.9, 99.7,
96.3, 18.4, 11.0. ES-MS (m/z): 313, [M + Na + MeOH]+; 291,
[M + MeOH]+.
7.6. 2-Amino-4-trimethylsilyl-6-(trimethylsilylethynyl)-
isophthalonitrile (10)
7.4.3. Ru(C„CC„CPh)(dppe)Cp (7)
A mixture of malononitrile (0.10 mL, 1.62 mmol), (Me3SiC„C)2-
CO (0.24 g, 1.08 mmol), basic alumina (0.30 g, activity II) was
heated in refluxing CH2Cl2 (5 mL) for 2 h, with addition of further
portions of basic alumina every 30 min. After cooling, the alumina
was filtered off and extracted with CH2Cl2 (3 ꢁ 10 mL). The com-
bined filtrate and extracts were concentrated under reduced pres-
sure. Flash chromatography of the residue (CH2Cl2–hexane, 2/1,
then 4/1) afforded recovered ketone (84 mg, 35%) and the 2,6-di-
cyanoaniline (10) as a colourless solid (148 mg, 44%), m.p. 123–
125 °C. Crystals for X-ray analysis were grown by slow evaporation
A mixture of RuCl(dppe)Cp (0.85 g, 1.42 mmol), PhC„CC„
CSiMe3 (0.28 g, 1.42 mmol) and KF (82 mg, 1.42 mmol) was heated
in refluxing MeOH (50 mL) for 1 h. After cooling, the yellow-green
precipitate was filtered from the dark blue-green solution, rinsed
with cold MeOH (10 mL) and dried. Chromatography of the crude
product (basic alumina; acetone–hexane, 1/1) afforded
Ru(C„CC„CPh)(dppe)Cp (7) as a yellow solid (176 mg, 18%). Anal.
Calc. for C41H34P2Ru: C, 71.40; H, 4.97; M, 690. Found: C, 71.49; H,
4.97%. IR (cmꢀ1):
m(CC) 2156m, 2017w; other bands at 1435m,

D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
3579
of
a
CH2Cl2 solution layered with hexane. Anal. Calc. for
the mixture was concentrated under vacuum and the residue was
purified on a column of basic alumina. Elution with CH2Cl2 gave
an orange band which was further purified by preparative t.l.c. to
afford Ru{C„CC[@C(CN)2]C(SiMe3)@CHC„C(SiPri3)}(PPh3)2Cp (16)
as a dark orange oil (182 mg, 71%) as a mixture of isomers by NMR.
Anal. Calc. for C63H66N2P2RuSi2: C, 70.69; H, 6.21; N, 2.62; M, 1070.
Found: C, 71.37; H, 6.71; N, 2.04%. IR (cmꢀ1): mmax 3053w, 2210m,
1995vs, 1434m, 1090m, 844m, 742m, 694s. 1H NMR: d 7.12–7.32
(30H, m), 6.10 (1H, s), 4.52 (5H, s), 1.12 (21H, s), 0.16 (9H, s). 13C
NMR: d 210.6, 195.8, 190.0, 189.6, 161.7, 157.1, 138.3, 138.0, 137.5,
137.1, 136.7, 133.5 (t, J = 5.3 Hz), 132.0 (d, J = 9.9 Hz), 129.0, 128.6,
128.3, 128.2, 128.0, 127.6 (t, J = 4.6 Hz), 125.5, 122.4, 117.3, 116.7,
104.9, 100.3, 87.8, 87.6, 69.4, 53.9, 31.6, 29.2, 18.6, 11.4, ꢀ1.0. 31P
NMR: d 48.0. ES-MS (m/z): 1093, [M + Na]+; 1071, [M + H]+; 691
[Ru(PPh3)2Cp]+; 429, [Ru(PPh3)Cp]+.
C16H21N3Si2: C, 61.69; H, 6.79; N, 13.49; M, 311. Found: C, 61.36;
H, 8.17; N, 12.70%. IR (cmꢀ1): mmax 3478m, 3359s, 3244m, 2215s,
2163w, 1643s, 1633s, 1563m, 1557m, 1538s, 1404m, 1267s,
1252s, 1064m, 948m, 843vs, 759m, 673m. 1H NMR: d 6.96 (1H,
s), 5.16 (2H, br s), 0.40 (9H, s), 0.30 (9H, s). 13C NMR: d 151.3,
151.2, 130.1, 126.4, 116.7, 114.8, 105.6, 100.6, 100.5, 100.4, ꢀ0.5,
ꢀ1.7. EI-MS (m/z): 311, M+Å; 296, [M ꢀ MeÅ]+; 73, [SiMe3]+.
7.7. Reactions of ðNCÞ2C@CHfCBCðSiPri3Þg (8)
7.7.1. With Ru(C„CPh)(PPh3)2Cp
(i) A mixture of Ru(C„CPh)(PPh3)2Cp (1) (200 mg, 0.25 mmol)
and ðNCÞ2C@CHfCBCðSiPri3Þg (8) (80 mg, 0.31 mmol) was
heated in refluxing benzene (10 mL) for 24 h. After cooling,
the mixture was concentrated under reduced pressure and the
residue was purified on a column of basic alumina. Elution with
CH2Cl2 firstly gave an orange band containing unreacted start-
ing materials (166 mg); further elution with CH2Cl2 gave a yel-
7.7.4. With Ru{C„CC„C(SiPri3)}(PPh3)2Cp
A mixture of Ru{C„CC„C(SiPri3)}(PPh3)2Cp (6) (90 mg, 0.10
i
mmol) and ðNCÞ2C@CHfCBCðSiPr3 Þg (8) (31 mg, 0.12 mmol) in thf
(4 mL) was irradiated with a 300 W sunlamp for 24 h. The mixture
began to reflux after ca. 15 min. After cooling, the mixture was con-
centrated under reduced pressure. Preparative t.l.c. of the residue
(silica, acetone–toluene–hexane, 1/29/30) afforded Ru{C„CC[@C-
(CN)2]C(SiPri3)@CHC„C(SiPr3i )}(PPh3)2Cp (17) as an orange solid
(46 mg, 40%). Crystals suitable for X-ray were grown by slow evapo-
ration of a CH2Cl2 solution. Anal. Calc. for C69H78N2P2RuSi2: C, 71.78;
H, 6.81; N, 2.43; M, 1154. Found: C, 71.73; H, 6.76; N, 2.49%. IR
(cmꢀ1): mmax 3053w, 2211m, 1981vs, 1436s, 881m, 695s. 1H NMR:
d 7.09–7.71 (30H, m), 6.08 (1H, s), 4.47 (5H, s), 0.99–1.13 (42H, s).
13C NMR: d 221.1 [d, J(CP) = 14.9 Hz], 134.2, 134.1 [d, J(CP) = 10.6 Hz],
133.6, 132.4 [d, J(CP) = 9.7 Hz], 130.9, 128.7 [d, J(CP) = 10.3 Hz],
117.8, 112.4, 110.1, 104.0, 91.2, 89.7, 86.7, 50.7, 35.7, 31.2, 19.1,
19.0, 11.6, 11.5. 31P NMR: d 46.8 (1P, d, J = 34 Hz), 46.3 (1P, d,
J = 34 Hz). ES-MS (m/z): 1177, [M + Na]+; 1154, M+.
low band which afforded
g
3-dienyl complex 11 as a yellow
solid (63 mg, 32%). Crystals suitable for X-ray analysis were
grown by slow evaporation of a CH2Cl2 solution layered with
MeOH. Anal. Calc. for C46H47N2PRuSi: C, 70.11; H, 6.01; N,
3.55; M, 788. Found C, 70.20; H, 6.07; N, 3.48%. IR (cmꢀ1): mmax
3061w, 2250m, 2213s, 2129m, 1579s, 1494m, 1460s, 1435s,
1092s, 1011m, 998m, 881m, 812m, 765m, 732s, 694s, 660s.
1H NMR: d 7.66–7.69 (2H, m), 7.40–7.52 (15H, m), 7.24–7.27
(3H, m), 4.58 (5H, s), 2.60 (1H, d, J 13.0), 1.07 (21H, s). 13C
NMR: d 137.0, 133.94, 133.93 [d, J(CP) = 10.3 Hz], 133.0, 130.6
[d, J(CP) = 2.3 Hz], 129.9, 128.3 [d, J(CP) = 9.9 Hz], 128.1, 118.0
[d, J(CP) = 3.1 Hz], 112.8 [d, J(CP) = 3.1 Hz], 111.3, 88.8 [d,
J(CP) = 1.1 Hz], 86.9, 79.4 [d, J(CP) = 8.0 Hz], 69.5, 28.4 [d,
J(CP) = 2.7 Hz], 18.7, 11.4. 31P NMR: 49.8. ES-MS (m/z): 811,
[M + Na]+.
(ii) A mixture of 1 (200 mg, 0.25 mmol), 8 (80 mg, 0.31 mmol)
and benzene (10 mL) was irradiated with a 300 W sunlamp
for 24 h. The mixture began to reflux after ca. 15 min. Work-
up and purification as above afforded starting materials
(57 mg) and 11 (170 mg, 86%).
7.7.5. With Ru(C„CPh)(dppe)Cp
A mixture of Ru(C„CPh)(dppe)Cp 3 (173 mg, 0.26 mmol) and
i
ðNCÞ2C@CHfCBCðSiPr3 Þg (8) (83 mg, 0.32 mmol) was heated in
refluxing benzene (10 mL) for 24 h. After cooling, the mixture
was concentrated under reduced pressure and the residue was
purified on a column of basic alumina. Elution with CH2Cl2 affor-
ded Ru{C[@C(CN)2]CPh@CHC„C(SiPri3)}(dppe)Cp (14) as a yellow
solid (228 mg, 95%). Anal. Calc. for C54H56N2P2RuSi: C, 70.18; H,
6.11; N, 3.03; M, 902. Found: C, 70.15; H, 6.19; N, 3.03%. IR
(cmꢀ1): mmax 3055m, 2202s, 2117m, 1484m, 1462m, 1434vs,
1096s, 1073m, 1015m, 999m, 881s, 804s, 743s, 696vs, 675s. 1H
NMR: d 6.63–7.43 (25H, m), 4.92 (1H, br s), 4.61 (5H, br s), 2.17–
2.62 (4H, m), 1.08 (21H, s). 13C NMR: d 135.8, 135.0, 132.2, 132.0,
129.6 [d, J(CP) = 9.9 Hz], 128.4, 128.3, 128.2, 128.1, 127.9, 127.4,
127.0, 119.8, 105.0, 95.1, 86.0, 85.5, 28.3, 18.7, 11.4. 31P NMR: d
81.4 (d, J = 18.5 Hz), 70.6 (d, J = 18.5 Hz). ES-MS (m/z): 947,
[M + Na]+; 925, [M + H]+.
7.7.2. With Ru(C„CC„CPh)(PPh3)2Cp
A
mixture of Ru(C„CC„CPh)(PPh3)2Cp (4) (119 mg, 0.15
mmol) and ðNCÞ2C@CHfCBCðSiPri3Þg (8) (47 mg, 0.18 mmol) was
heated in refluxing benzene (6 mL) for 24 h. After cooling, the mix-
ture was concentrated under reduced pressure and the residue was
purified on a column of basic alumina. Elution with CH2Cl2 affor-
ded Ru{C„CC[@C(CN)2]CPh@CHC„C(SiPri3)}(PPh3)2Cp (15) as a
dark orange oil (102 mg, 63%) as a mixture of isomers by NMR. Anal.
Calc. for C66H62N2P2RuSi: C, 73.79; H, 5.82; N, 2.61; M, 1074. Found:
C, 73.91; H, 5.89; N, 2.57%. IR (cmꢀ1): mmax 3057w, 2210m, 2125w,
1995vs, 1562m, 1434s, 1089s, 998m, 882m, 812m, 743m, 696s,
682s. 1H NMR: d 7.00–7.47 (35H, m), 6.95 (1H, s), 5.95 (1H, s),
4.56 (5H, s), 1.04 (21H, s). 13C NMR: d 155.3, 149.2, 138.0, 137.6,
137.1, 136.8, 136.1, 133.6, 133.5, 133.4, 132.2, 132.0, 131.9, 129.3,
129.1, 128.6, 128.4, 128.0, 127.9, 127.8, 127.7, 127.6, 127.4, 118.2,
115.3, 113.4, 112.1, 104.5, 101.9, 99.7, 88.0, 87.8, 79.4, 18.82,
18.76, 18.6, 18.4, 11.3, 11.0. 31P NMR: d 50.8. ES-MS (m/z): 1097,
[M + Na]+; 1074, [M]+.
7.7.6. With Ru(C„CC„CPh)(dppe)Cp
A mixture of Ru(C„CC„CPh)(dppe)Cp (7) (69 mg, 0.10 mmol)
and ðNCÞ2C@CHfCBCðSiPri3Þg (8) (31 mg, 0.12 mmol) was heated
in refluxing benzene (4 mL) for 18 h. After cooling, the mixture
was concentrated under reduced pressure. Preparative t.l.c. of the
residue (silica, 1/19/20 acetone–toluene–hexanes) afforded
Ru{C„CC[@C(CN)2]CPh@CHC„CSiPri3}(dppe)Cp 18 as a dark red
solid (54 mg, 57%). Anal. Calc. for C56H56N2P2RuSi: C, 70.94; H,
5.95; N, 2.95; M, 948. Found C, 70.86; H, 6.03; N 3.01%. IR (cmꢀ1):
mmax 3055w, 2208m, 2002vs, 1434s, 1096m, 806m, 744m, 695s,
677s. 1H NMR: d 7.64–7.71 (4H, m), 7.42–7.47 (6H, m), 7.14–7.36
(11H, m), 6.94–7.06 (4H, m), 5.52 (1H, s), 4.87 (5H, s), 2.19–2.30
7.7.3. With Ru{C„CC„C(SiMe3)}(PPh3)2Cp
A
mixture of Ru{C„CC„C(SiMe3)}(PPh3)2Cp (5) (200 mg,
0.24 mmol) and ðNCÞ2C@CHfCBCðSiPri3Þg (8) (77 mg, 0.30 mmol)
in benzene (10 mL) was irradiated with a 300 W sunlamp for
24 h. The mixture began to reflux after ca. 15 min. After cooling,

3580
D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
(4H, m), 1.03 (21H, s). 31P NMR: d 83.2. ES-MS m/z 1919, [2M + Na]+;
7.11. Reaction of 11 with AuCl(PPh3)/TBAF
949, [M + H]+; 565, [Ru(dppe)Cp]+.
A solution of 11 (79 mg, 0.10 mmol) and AuCl(PPh3) in thf
(10 mL) was cooled to 0 °C under N2. TBAF (1 M in thf, 0.10 mL,
0.10 mmol) was added dropwise, and the mixture was stirred at
0 °C for 30 min, then at room temperature for 1 h. The mixture
was concentrated under vacuum, and preparative t.l.c. of the resi-
due (acetone–hexane, 1/2) afforded ruthenium–gold complex 20
as a yellow solid (98 mg, 90%). Anal. Calc. for C55H41N2AuP2Ru: C,
60.61; H, 3.79; N, 2.57; M, 1090. Found: C, 60.54; H, 3.81; N,
2.60%. IR (cmꢀ1): mmax 3056w, 2249w, 2213vs, 1568s, 1436vs,
1184m, 1101s, 1091s, 998m, 910s, 814m, 732vs, 694vs, 644m,
625m, 615m. 1H NMR: d 7.85–7.88 (2H, m), 7.19–7.66 (33H, m),
4.55 (5H, s), 2.70 (1H, d, J = 13.5 Hz); 13C NMR: d 137.9, 134.2 [d,
J(CP)= 13.7 Hz], 134.0, 131.6, 130.2 [d, J(CP) = 2.3 Hz], 129.7,
129.1 [d, J(CP) = 11.5 Hz], 128.1 [d, J(CP) = 10.0 Hz], 127.9, 127.7,
118.5 [d, J(CP) = 2.9 Hz], 113.2 [d, J(CP) = 2.9 Hz], 88.9 [d,
J(CP) = 1.1 Hz], 78.3 [d, J(CP) = 8.0 Hz], 68.3, 31.4. 31P NMR: d 50.3
(1P, s), 40.7 (1P, br s). ES-MS (MeOH, m/z): 1549, [M + Au(PPh3)]+;
1113, [M + Na]+; 721, [Au(PPh3)2]+; 500, [Au(PPh3)(MeOH)]+.
7.8. Reaction of Ru(C„CPh)(PPh3)2Cp with (NC)2C@C(C„CPh)2
A mixture of Ru(C„CPh)(PPh3)2Cp (1) (79 mg, 0.10 mmol),
(NC)2C@C(C„CPh)2 9 (33 mg, 0.12 mmol) in thf (4 mL) was irradi-
ated with a 300 W sunlamp for 24 h. The mixture began to reflux
after ca. 15 min. After cooling, the mixture was concentrated under
reduced pressure. Preparative t.l.c. of the residue (acetone-hexane,
1/3) afforded
g
3-dienyl complex 13 as an orange solid (44 mg,
54%). Anal. Calc. for C51H35N2PRu: C, 75.82; H, 4.37; N, 3.47; M,
808. Found C, 73.65; H, 3.80; N, 2.90%. IR (cmꢀ1): mmax 3055w,
2240w, 1952w, 1705s, 1608m, 1482m, 1436m, 1213m, 1091m,
909m, 730m, 693vs. 1H NMR: d 6.88–7.76 (30H, m), 5.11 (5H, s).
13C NMR: d 126.0–134.9 (m), 117.4, 101.3, 89.1, 87.9, 86.0 [d,
J(CP) = 2.3 Hz], 29.7, 29.3. 31P NMR: d 52.1. ES-MS (m/z): 809,
[M + H]+.
7.9. Deprotection of 11 with TBAF
TBAF (1 M in thf, 0.11 mL, 0.11 mmol) was added dropwise to
a solution of 11 (86 mg, 0.11 mmol) in thf (11 mL) cooled to 0 °C
and the mixture was stirred at 0 °C for 40 min, then concentrated
under reduced pressure. The residue was chromatographed on a
7.12. Structure determinations
Full spheres of diffraction data were measured using CCD area-
detector instruments. Ntot reflections were merged to N unique
(Rint cited) after ‘‘empirical”/ multiscan absorption correction
(proprietary software) and used in the full matrix least squares
short column (silica; acetone–hexane, 1/3) to afford
g
3-dienyl
complex 12 as a yellow solid (69 mg, 100%). Anal. Calc. for
C37H27N2PRu: C, 70.35; H, 4.31; N, 4.43; M, 632. Found: C,
67.25; H, 4.11; N, 3.92%. IR (cmꢀ1): mmax 3299s, 3055s, 2214vs,
2088w, 1970w, 1578vs, 1573vs, 1446s, 1433vs, 1408m, 1310m,
1265s, 1184s, 1158m, 1091vs, 1071s, 1028m, 1012m, 998m,
911m, 832s, 814vs, 769vs, 736vs, 697vs, 640vs, 626vs, 613s. 1H
NMR: d 7.62–7.66 (2H, m), 7.40–7.54 (15H, m), 7.27–7.34 (3H,
m), 4.59 (5H, s), 2.63 (1H, d, J = 2.2 Hz), 2.42 (1H, dd, J = 2.2,
13.5 Hz). 13C NMR: d 137.0, 134.0 [d, J(CP) = 10.7 Hz], 133.8,
132.9, 130.6 [d, J(CP) = 2.3 Hz], 129.7, 128.35 [d, J(CP) = 10.3 Hz],
128.3, 128.1, 118.0 [d, J(CP) = 3.1 Hz], 112.7 [d, J(CP) = 3.1 Hz],
89.0 [d, J(CP) = 1.1 Hz], 87.6, 73.4, 69.2, 26.8 [d, J(CP) = 3.1 Hz].
refinements on F2; No with I > 2
r
(I) were considered ‘observed’.
All data were measured using monochromatic Mo K radiation,
k = 0.71073 Å. Anisotropic displacement parameter forms were re-
fined for the non-hydrogen atoms, (x, y, z, Uiso H being included fol-
lowing a riding model [reflection weights: (
2(F2) + (aP)2 + (bP))ꢀ1
a
)
r
,
P ¼ ðF2o þ 2F2c Þ=3ꢃ. Neutral atom complex scattering factors were
used; computation used the SHELXL-97 program [26]. Pertinent re-
sults 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.
Variata. 7. The CPh group and one phenyl ring of the dppe are
disordered over pairs of sites, seemingly concerted; occupancies
set at 0.5 after trial refinement.
31P NMR:
[M + Na]+.
d
49.8. ES-MS (m/z): 1287, [2M + Na]+; 655,
17. In molecule 2, the SiPri3 group was modelled as disordered
over a pair of sites, occupancies refining to 0.645(5) and comple-
ment. The dichloromethane solvent lies close to an inversion centre
and was modelled in terms of a pair of components, occupancies
0.25; geometries of the minor substrate component and solvent
were constrained in the refinement.
7.10. Reaction of 11 with RuCl(dppe)Cp/TBAF
A solution of 11 (50 mg, 0.06 mmol) in thf (6 mL) was cooled to
0 °C under N2. TBAF (1 M in thf, 0.06 mL, 0.06 mmol) was added
dropwise and the solution was stirred at 0 °C for 40 min, at which
point t.l.c. indicated complete desilylation. RuCl(dppe)Cp (38 mg,
0.06 mmol) and NaBPh4 (24 mg, 0.07 mmol) were added, the solu-
tion was warmed to 50 °C and stirred for 21 h. After cooling, the
mixture was concentrated under vacuum. Preparative TLC (silica;
acetone–hexane, 1/3) afforded binuclear complex 19 as a yellow–
orange solid (46 mg, 61%). Anal. Calc. for C68H55N2P3Ru2: C,
68.33; H, 4.64; N, 2.34; M, 1196. Found: C, 68.27; H, 4.69; N,
2.35%. IR (Nujol, cmꢀ1): mmax 3296w, 3053w, 2213s, 1578s,
1571s, 1433s, 1091s, 814m, 744s, 696vs. 1H NMR: d 7.15–7.86
(40H, m), 4.59 (5H, s), 4.52 (2H, s), 3.79 (1H, br s), 2.63 (3H, s),
2.41 (2H, dd, J = 2.2, 13.5 Hz), 2.17 (3H, s), 1.67 (1H, br s). 13C
NMR: d 210.6, 141.7, 141.0 [d, J(CP) = 20.2 Hz], 137.0, 135.3,
134.8, 134.4, 133.9, 133.8, 133.7, 132.8, 131.5, 131.4, 131.3, 130.6
[d, J(CP) = 2.3 Hz], 129.7, 129.5, 129.0, 128.4, 128.2, 128.1, 128.0,
127.9, 127.8, 117.9 [d, J(CP) = 3.1 Hz], 112.7 [d, J(CP) = 3.1 Hz],
89.0 [d, J(CP) = 1.1 Hz], 87.5, 87.3, 79.6 [t, J(CP) = 2.3 Hz], 73.4,
69.5, 69.1, 53.9, 31.7, 29.3, 27.5, 27.1, 26.8, 26.7, 26.6. 31P NMR: d
78.1 (s, 2P), 49.8 (s, 1P); ES-MS m/z 1197, [M + H]+; 565,
[CpRu(dppe)]+.
Acknowledgements
We thank Professor Brian Nicholson (University of Waikato,
Hamilton, New Zealand) for providing some of the mass spectra,
the ARC for support of this work and Johnson Matthey plc, Reading,
for a generous loan of RuCl3 ꢂ nH2O.
Appendix A. Supplementary material
CCDC 687316, 687317, 687318, 687319 and 687320 contain
the supplementary crystallographic data for this paper. These
data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_re-
quest/cif. Supplementary data associated with this article can
be
found,
in
the
online
version,
at
doi:10.1016/
j.jorganchem.2008.07.006.

D.J. Armitt et al. / Journal of Organometallic Chemistry 693 (2008) 3571–3581
3581
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