Syntheses of complexes containing substituted 4-ethynylquinolines or 1-azabuta-1,3-dienes by addition of imines to a cationic butatrienylidene-ruthenium complex

Article abstract of DOI:10.1016/S0022-328X(99)00456-8

Reactions of [Ru(=C=C=C=CH₂)(PR₃)₂Cp]⁺ (R=Ph or OMe) with arylimines ArN=CH(C₆H₄R) afford either substituted quinolines, Ru{CCC₉H₄RN(Ar)}(PR₃)₂Cp, by attack of the terminal carbon of the butatrienylidene ligand at the imine carbon, followed by C-C bond formation between the ortho carbon of the N-aryl group and C_γ of the unsaturated carbene, or 1-azabuta-1,3-dienyl complexes, formed by cycloaddition of the N=CH group to C_γ=C_δ of the carbene, followed by opening of the resulting four-membered ring. Some product dependence on the nature of the substituents in the N- and C-aryl groups is found. The N atoms in the products are strongly basic, being readily protonated, methylated or aurated. The molecular structures of nine complexes are reported, together with that of a new modification of RuCl{P(OMe)₃}₂Cp.

Full text of DOI:10.1016/S0022-328X(99)00456-8

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Journal of Organometallic Chemistry 590 (1999) 184–201
Syntheses of complexes containing substituted 4-ethynylquinolines
or 1-azabuta-1,3-dienes by addition of imines to a cationic
butatrienylidene-ruthenium complex
Michael I. Bruce a,*, Mingzhe Ke a, Brian D. Kelly a, Paul J. Low a, Mark E. Smith a,
Brian W. Skelton b, Allan H. White b
a Department of Chemistry, Uni6ersity of Adelaide, Adelaide, SA 5005, Australia
b Department of Chemistry, Uni6ersity of Western Australia, Nedlands, WA 6907, Australia
Received 23 June 1999; accepted 28 July 1999
Abstract
Reactions of [Ru(ꢀCꢀCꢀCꢀCH2)(PR3)2Cp]+ (R=Ph or OMe) with arylimines ArNꢀCH(C6H4R) afford either substituted
quinolines, Ru{CꢁCC9H4RN(Ar)}(PR3)2Cp, by attack of the terminal carbon of the butatrienylidene ligand at the imine carbon,
followed by CꢂC bond formation between the ortho carbon of the N-aryl group and Ck of the unsaturated carbene, or
1-azabuta-1,3-dienyl complexes, formed by cycloaddition of the NꢀCH group to CkꢀCl of the carbene, followed by opening of
the resulting four-membered ring. Some product dependence on the nature of the substituents in the N- and C-aryl groups is
found. The N atoms in the products are strongly basic, being readily protonated, methylated or aurated. The molecular structures
of nine complexes are reported, together with that of a new modification of RuCl{P(OMe)3}2Cp. © 1999 Elsevier Science S.A. All
rights reserved.
Keywords: Ruthenium; Butatrienylidene; 4-Ethynylquinoline; 1-Azabuta-1,3-dienes
nations that are both electron rich and also have steri-
cally large ligands, such as PPh3, which give a measure
of steric protection to Ch, allowing a rich chemistry
derived from the nucleophilic properties of these com-
plexes. Examples of reaction sequences involving both
Ch and Ci are rare. The steric protection does not
extend beyond Ci, so that allenylidenes (n=1) and
higher members might be expected to enter into cy-
cloaddition reactions with suitable reagents. This has
been demonstrated recently with [Ru(ꢀCꢀCꢀCPh2)-
(CO)(PPri3)Cp]+ to give tetrahydronaphthofuranyl [4]
and pyrazolopyrazolyl [5] derivatives, and with cycload-
dition of alkynyl complexes to Group 6 diarylallenyli-
denes to give cyclobutenylidene complexes [6].
Recently, we described the reaction between buta-
1,3-diyne and [Ru(THF)(PPh3)2Cp]+, which at low
temperatures affords an intermediate which, on the
basis of its synthesis and chemistry, appears to be the
cationic butatrienylidene complex [Ru(ꢀCꢀCꢀCꢀCH2)-
(PPh3)2Cp]+ or a close relative [7]. Although we
have not yet managed to characterise this
1. Introduction
The synthesis and chemistry of transition metal com-
plexes containing unsaturated carbenes, M{ꢀC(ꢀC)nꢀ
CR2}Ln, continues to attract attention. Whereas the
reactions of the first member of the series (vinylidenes,
n=0) have been explored in some detail [1], those of
the next higher members of the series, allenylidenes
(n=1) and butatrienylidenes (n=2), have not received
so much attention [2]. Theoretical and experimental
evidence points to the alternating electron deficiency
and richness of the carbons of the unsaturated chain,
resulting in specific reactivities towards nucleophiles
(at odd-numbered carbons) and electrophiles (at
even-numbered carbons) [3]. Much of the chemistry of
vinylidene complexes has utilised metal–ligand combi-
* Corresponding author. Tel.: +61-8-83035939; fax: +61-8-
83034358.
E-mail address: michael.bruce@adelaide.edu.au (M.I. Bruce)
0022-328X/99/$ - see front matter © 1999 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00456-8

M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
185
species fully, we have observed and briefly reported its
reactions with imines to give products containing
quinoline or azabutadiene moieties, the formation of
which suggests that a sequence of electrophilic and
nucleophilic attack of the complex on the imine has
occurred [8]. This paper describes these reactions in
more detail, together with the crystal and molecular
structures of several of the products.
hydrogen-acceptor in the reaction. This was confirmed
by the identification of benzylaniline as also being
formed in the reaction. Consequently, improved (but
not high) yields were obtained when two equivalents of
imine were employed in this and subsequent reactions
(see Scheme 1). Difficulties in isolation of this and
related complexes arose from their extremely basic na-
ture, which led to their ready protonation, even by
water. This was accompanied by a colour change from
orange to claret red and was particularly evident during
attempted purification by TLC, for example. In part,
this is overcome by addition of KOBut to the reaction
mixture before work-up. The spectroscopic properties
of the complexes are summarised in Table 1.
2. Results and discussion
The formation of the cation [Ru(ꢀCꢀCꢀCꢀCH2)-
(PPh3)2Cp]+ has been described before [7]. In the
present work we have used this complex and the related
derivative containing P(OMe)3 ligands, which was pre-
pared similarly. The latter is also very reactive, but was
chosen to simplify the NMR assignments of the prod-
1
Assignments of the H-NMR spectra are based on
H,H-COSY and homonuclear decoupling experiments,
and are also listed in Table 1 (Scheme 2). The preferred
solvent for these studies was C6D6. Resonances of
hydrogen atoms that are on carbons adjacent to N are
generally somewhat broadened, which helps in the as-
signments. Similarly, H atoms close to NO2 groups are
found at relatively low field. In the benzoquinoline
derivative 10, the large downfield shift of H5 (l 12.25)
is probably the result of its close proximity to the CꢁC
triple bond.
Complex 1 was identified as the 4-substituted quino-
line by an X-ray study (see below). Its formulation as a
deprotonated 1/1 adduct between the imine and the
butatrienylidene cation was indicated by analysis and
its mass spectrum, which showed a parent ion at m/z
919. In the IR spectrum, a band at 2048 cm−1 was
assigned to a w(CꢁC) absorption, not unexpected if
addition of a nucleophile to Ck had occurred. After the
structure was established, detailed examination of the
1H-NMR spectrum, using COSY and other decoupling
techniques, allowed assignment of most of the reso-
nances as detailed in Table 1.
We have briefly examined the influence of a variety
of substituents on the course of this reaction. Similar
quinoline complexes were obtained when H or electron-
donating substituents were present on the N-aryl group,
or H or electron-withdrawing groups were in the C-aryl
group. Thus the reactions of RC6H4NꢀCHC6H4R%
(R=Me, R%=H; R=H, R%=NO2-4; R=OMe-4,
R%=NO2-4) afforded complexes 2, 3 and 7, respec-
tively. Using the P(OMe)3 precursor, we made similar
derivatives from imines with R=H, R%=NO2-4 (4),
CO2Me (6) and R=OMe-4, R%=NO2-4 (8). All com-
plexes were readily identified as the substituted
ethynylquinolines by elemental analysis, mass spec-
trometry and analyses of their 1H-NMR spectra. In
addition, X-ray structural studies were carried out on 2,
3, 6 and 8 (see below).
1
ucts. The H-NMR spectra of these complexes contain
characteristic doublets for the P(OMe)3 groups (separa-
tion ca. 12 Hz), while the region above l 5 contains
only aromatic protons for the ligands derived from the
imines. The Cp groups in the Ru(PPh3)2Cp complexes
give rise to singlet resonances between l 4.20 and 4.76,
values tending to higher fields for the azabutadiene
derivatives. In the P(OMe)3 complexes, the Cp reso-
nances are found between l 4.90 and 5.10; the quinoli-
nes show H–P coupling of ca. 1 Hz, whereas most of
the azabutadienes give only singlet resonances. As de-
scribed earlier, we have carried out these reactions by
generating the butatrienylidene complex in situ, from
the reaction of buta-1,3-diyne with [Ru(THF)(L)2Cp]+
[L=PPh3 or P(OMe)3], the latter obtained by addition
of AgPF6 to a solution of RuCl(L)2Cp in THF. Exper-
imentally, it is convenient to add a solution of buta-1,3-
diyne in THF to a mixture of the cation and the imine
in the same solvent kept between −100 and −78°C.
After warming to r.t., the now orange–red solution is
treated with KOBut and worked up to give the neutral
products, which form yellow–orange crystals.
The reactions may proceed to give either of two
products, namely the substituted 4-ethynylquinoline or
a 1-azabuta-1,3-dien-2-yl complex. The identities of
these were originally established by the X-ray structural
determinations but, as described in detail below, it has
also been possible to distinguish between them using
NMR spectroscopy.
2.1. Quinoline deri6ati6es
The reaction of [Ru(ꢀCꢀCꢀCꢀCH2)(PPh3)2Cp]+ with
benzylideneaniline proceeded to give the orange com-
plex 1 in moderate yield. Consideration of the stoi-
chiometry of the reaction, in which
a total of
(2H+H+) is lost from the combination (C4H+2 +
PhCHꢀNPh), suggested that the imine also acts as a
The product from 3-ClC6H4NꢀCHPh and the PPh3
complex was shown to be the corresponding quinoline

186
M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
9, but the 1H-NMR spectrum showed that it was
formed as a 4/1 mixture of isomers. Two Cp singlet
resonances at l 4.67 (major) and 4.58 (minor) were
present and detailed analysis allowed the structural
assignments shown in Scheme 1.
responding azabuta-1,3-dienyl derivative, 11 (Scheme
3). This was readily identified from its ES mass spec-
trum, which contained [M+H]+ at m/z 646, and from
1
its H-NMR spectrum, in which a resonance assigned
to the vinylic proton H4 at l 7.71 is characterised by a
15.8 Hz coupling to H3 trans to it (the H3 resonance is
contained within the multiplet at l 7.02–7.40). The
Use of imines containing naphthyl groups was inves-
tigated as a possible route to tricyclic systems. Cyclisa-
tion to the naphthyl group occurred with
(2-C10H7)NꢀCHPh, when the orange benzo[h]quinoline
complex 10 was obtained. The mass spectrum con-
tained M+ at m/z 969 and detailed examination of the
1H-NMR spectrum enabled assignment of individual
resonances to the eight protons of the benzoquinoline
ligand as shown. In particular, there is a low-field
resonance at l 12.25 which we suggest arises from
H(13), which from the X-ray structural study is found
in close proximity to the CꢁC triple bond [H(13)···C(13)
w(CꢁC) absorption is found at 2051 cm−1
.
Similarly, complexes 12, 14, 16–19 and 21 were
obtained from reactions between [Ru(ꢀCꢀCꢀCꢀCH2)-
(PPh3)2Cp]+ and RC6H4NꢀCHC6H4R% (R=R%=Me-4,
OMe-4; R=NO2-3, NO2-4, R%=H; R=H, R%=
CO2Me-4; R=NO2-4, R%=CO2Me-4), respectively.
The P(OMe)3 analogues 11, 13, 15 and 20 (with R=
R%=H, Me-4, OMe-4; R=NO2-4, R%=CO2Me-4)
were also prepared. The distinction from the quinoline
structure is readily made, the two trans vinylic protons
giving characteristic doublets with J(HH) ca. 16 Hz.
It is notable that similar complexes were obtained in
both series [PPh3 and P(OMe)3] from the bis-tolyl and
bis-anisyl imines, 4-RC6H4NꢀCHC6H4R-4 (R=Me,
OMe). These complexes (12–15) were identified from
,
separation is 2.3 A].
2.2. 1-Azabuta-1,3-dienyl complexes
In contrast to the product found with the PPh3
complex, the reaction between [Ru(THF){P(OMe)3}2-
Cp]+, buta-1,3-diyne and PhCHꢀNPh afforded the cor-
1
their H-NMR spectra and the molecular structure of
15 was confirmed by a single-crystal X-ray study. How-
Scheme 1.

M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
187
Table 1
Analytical and spectroscopic data
Compound and analysis
Spectroscopic data a
1 4-{Cp(PPh3)2Ru(CꢀC)}-2-PhC9H5N yellow; m.p.
136–138°C (dec.) Anal. Found: C, 73.99; H, 5.18; N,
IR: w(CꢁC) 2048s 1H-NMR: 4.60 (s, 5H, Cp), 7.00 (m, 18H, Hm+Hp of PPh3),
7.29 [t, J(HH) 7.5, 1H, H11], 7.44 [t, J(HH) 7.5, 2H, H10], 7.49 [t, J(HH) 7.5,
1.51. C58H45NP2Ru·0.2CH2Cl2·0.5Et2O calc.: C, 74.31; 1H, H6 or H7], 7.62 [t, J(HH) 7.5, 1H, H7 or H6], 7.78 (m, 12H, Ho of PPh3),
H, 5.22; N, 1.44; M (solvent-free), 919 (both solvate
molecules were detected by NMR)
8.05 (s, 1H, H3), 8.59 [d, J(HH) 7.5, 3H, H9 +H5 or H8], 9.03 [d, J(HH) 7.5,
1H, H8 or H5] 13C-NMR: 85.7 (s, Cp), 112.8 (s), 116.1 (s), 119.7 (s), 128.0 (s),
124.9 (s), 125.9 (s), 128.7 (t), 129.4 (s), 131.4 (s), 133.4 (t), 136.6 (s), 138.5 (m),
140.7 (s), 148.6 (s), 157.0 (s), 160.4 (s) ES MS: 919, M+; 657, [M−PPh3]+
2 4-{Cp(PPh3)2Ru(CꢁC)}-6-Me-2-PhC9H4N bright yellow; IR: w(CꢁC) 2051s 1H-NMR: 2.36 (s, 3H, Me), 4.33 (s, 5H, Cp), 7.1–8.3 (m,
m.p. 191–195°C Anal. Found: C, 74.50; H, 5.00; N,
1.48. C59H47NP2Ru calc.: C, 75.97; H, 5.04; N, 1.50;
M, 933
39H, aromatic H) FAB MS: 933, M+; 671, [M−PPh3]+; 428,
[Ru(PPh3)(C5H5)]+
3 4-{Cp(PPh3)2Ru(CꢁC)}-2-(4-NO2C6H4)C9H5N yellow;
IR: w(CꢁC) 2046s, w(NO) 1511s, 1343s, w(CN) 846m 1H-NMR: 4.38 (s, 5H, Cp),
m.p. 208–210°C (dec.) Anal. Found: C, 71.85; H, 4.63; 7.03 [t, J(HH) 7, 12H, Hm of PPh3], 7.16 [t, J(HH) 7, 6H, Hp of PPh3], 7.30 (s,
N, 2.86. C58H44N2O2P2Ru calc.: C, 72.26; H, 4.60; N,
2.91; M, 964
1H, H3), 7.35 [t, J(HH) 8, 1H, H6], 7.40 (m, 12H, Ho of PPh3), 7.59 [t, J(HH)
8, 1H, H7], 7.99 [d, J(HH) 8, 1H, H5], 8.16 [d, J(HH) 9, 2H, H9], 8.28 [d,
J(HH) 9, 2H, H10], 8.40 [d, J(HH) 8, 1H, H8] FAB MS: 965, [M+H]+; 702,
[M−PPh3]+; 625, [M−PPh3−Ph]+; 429, [Ru(PPh3)(C5H5)]+
4 4-{Cp[P(OMe)3]2Ru(CꢁC)}-2-(4-NO2C6H4)C9H5N
orange; m.p. 129–131°C Anal. Found: C, 47.22; H,
4.56; N, 4.07. C28H32N2O8P2Ru calc.: C, 48.90; H,
4.56; N, 4.07; M, 688
IR: w(CꢁC) 2062s, w(NO) 1525s, 1347s, w(PO) 1024vs (br) 1H-NMR: 3.68 [t,
J(HP) 11.7, 18H, OMe], 5.09 [t, J(HP) 0.9, 5H, Cp], 7.45 [t, J(HH) 8.1, 1H,
H7], 7.61 (s, 1H, H3), 7.64 [t, J(HH) 8.4, 1H, H6], 8.03 [d, J(HH) 9.0, 1H, H5],
8.25, 8.33 [2×d, J(HH) 9.0, 4H, H9,10], 8.58 [d, J(HH) 8.1, 1H, H8] ES MS:
689, [M+H]+
5 4-{Cp(PPh3)2Ru(CꢁC)}-2-(3-NO2C6H4)C9H5N yellow:
IR: w(CꢁC) 2054s, w(NO) 1529s, 1350s, w(CN) 808m 1H-NMR: 4.45 (s, 5H, Cp),
m.p. 202–204°C (dec.) Anal. Found: C, 71.09; H, 4.57; 7.03 [t, J(HH) 7, 13H, Hm of PPh3+H11], 7.10 [t, J(HH) 7, 6H, Hp of PPh3],
N, 2.86. C58H44N2O2P2Ru.0.2CH2Cl2 calc.: C, 71.26;
H, 4.56; N, 2.86; M (solvent-free), 964 (CH2Cl2
detected in NMR)
7.54 [td, J(HH) 8, 1.5, 1H, H6], 7.63 [td, J(HH) 8, 1.5, 1H, H7], 7.75 (m, 12H,
Ho of PPh3), 7.89 (s, 1H, H3), 7.96 [dt, J(HH) 8, 1.5, 1H, H9], 8.52 [d, J(HH)
8, 1H, H8], 8.81 [dt, J(HH) 8, 1.5, 1H, H10], 9.05 [t, J(HH) 1.5, 1H, H13], 9.15
[dd, J(HH) 8, 1.5, 1H, H5] ES MS: 965, [M+H]+; 703, [M+H−PPh3]+
6 4-{Cp[P(OMe)3]2Ru(CꢁC)}-2-(4-MeO2CC6H4)C9H5N
yellow; m.p. 155–156°C Anal. Found: C, 51.53; H,
IR: w(CꢁC) 2064s, w(CO) 1719s, w(PO) 1023vs(br) 1H-NMR: 3.69 [t, J(HP) 12.0,
18H, OMe], 3.95 (s, 3H, CO2Me), 5.10 (s, 5H, Cp), 7.43 [t, J(HH) 7.2, 1H, H7],
5.04; N, 1.98. C30H35NO8P2Ru calc.: C, 51.43; H, 5.04; 7.62 (s, 1H, H3), 7.63 [t, J(HH) 7.2, 1H, H6], 8.05 [d, J(HH) 8.0, 1H, H5], 8.16
N, 2.00; M, 701
[2×d, J(HH) 8.4, 4, 4H, H9,10], 8.51 [d, J(HH) 8.4, 1H, H8] ES MS: 702,
[M+H]+
7 4-{Cp(PPh3)2Ru(CꢁC)}-6-MeO-2-(4-NO2C6H4)C9H4N
yellow; m.p. 220–222°C (dec.) Anal. Found: C, 70.45;
IR: w(CꢁC) 2037s, w(NO) 1513s, 1339s, w(CN) 853m 1H-NMR: 3.43 (s, 3H,
OMe), 4.42 (s, 5H, Cp), 7.08 [t, J(HH) 7, 12H, Hm of PPh3], 7.21 [t, J(HH) 7,
H, 4.56; N, 2.87. C59H46N2O2P2Ru.0.2CH2Cl2 calc.: C, 6H, Hp of PPh3], 7.29 [dd, J(HH) 9, 3, 1H, H7], 7.40 (s, 1H, H3), 7.49 (m, 12H,
70.33; H, 4.63; N, 2.77; M (solvent-free), 994 (CH2Cl2
detected in NMR)
Ho of PPh3), 7.82 [d, J(HH) 3, 1H, H5], 7.96 [d, J(HH) 9, 1H, H8], 8.22 [d,
J(HH) 9, 2H, H9], 8.35 [d, J(HH) 9, 2H, H10] ES MS: 994, M+; 731,
[M−H−PPh3]+
8 4-{Cp[P(OMe)3]2Ru(CꢁC)}-6-MeO-2-(4-NO2C6H4)-
IR: w(CꢁC) 2061s, w(NO) 1524s, 1347s, w(PO) 1030vs(br) 1H-NMR: 3.68 [t,
C9H4N orange; m.p. 115–116°C Anal. Found: C, 48.38; J(HP) 12.0, 18H, OMe], 3.96 (s, 3H, OMe), 5.09 (s, 5H, Cp), 7.32 [dd, J(HH)
H, 4.73; N, 3.89. C29H34N2O9P2Ru calc.: C, 48.53; H,
4.77; N, 3.90; M, 740
9.3, 2.7, 1H, H7], 7.57 (s, 1H, H3), 7.87 [d, J(HH) 3.0, 1H, H5], 7.95 [d, J(HH)
9.3, 1H, H8], 8.23, 8.30 [2d, J(HH) 9.3, 4H, H9,10] ES MS: 741, [M+H]+
9 4-{Cp(PPh3)2Ru(CꢁC)}-(5/7)-Cl-2-PhC9H4N yellow;
IR: w(CꢁC) 2039s 1H-NMR: (9a, ꢁ80%) 4.67 (s, 5H, Cp), 7.01* (m, 18H, Hm
m.p. 154–156°C (dec.) Anal. Found: C, 70.91; H, 4.71; and Hp of PPh3), 7.20 [t, J(HH) 8, 1H, H7], 7.31* [t, J(HH) 7.5, 1H, H11], 7.41
N, 1.43. C58H44ClNP2Ru.0.4CH2Cl2.0.2Et2O calc.: C, [t, J(HH) 7.5, 2H, H10], 7.53 [d, J(HH) 8, 1H, H6 or H8], 7.77* (m, 12H, Ho of
70.94; H, 4.71; N, 1.40; M, 953 (both solvate molecules PPh3), 7.88 (s, 1H, H3), 8.35 [d, J(HH) 8, 1H, H8 or H6], 8.45 [d, J(HH) 7.5,
found in NMR)
2H, H9] (9b, ꢁ20%) 4.58 (s, 5H, Cp), 7.41 (m, 1H, H6), 8.00 (s, 1H, H3), 8.50
[d, J(HH) 7.5, 2H, H9], 8.58 (s, 1H, H8), 8.72 [td, J(HH) 8, 2H, H5] *
resonances so indicated are common to both isomers FAB MS: 953, M+; 691,
[M−PPh3]+; 614, [M−PPh3−Ph]+; 429, [M−2PPh3]+ or [Ru(PPh3)(C5H5)]+
10 4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC13H8N yellow; m.p.
133–134°C (dec.) Anal. Found: C, 76.88; H, 5.32; N,
1.46. C62H47NP2Ru calc.: C, 76.84; H, 4.89; N, 1.45;
M, 969
IR: w(CꢁC) 2038s 1H-NMR: 4.76 (s, 5H, Cp), 6.95 (m, 18H, Hm and Hp of
PPh3), 7.35 [t, J(HH) 7.5, 1H, H13], 7.48 [t, J(HH) 7.5, 2H, H12], 7.65 [t, J(HH)
7.5, 1H, H7], 7.77 (m, 12H, Ho of PPh3), 7.87 (m, 3H, H6,8+H9 or H10), 8.12
(s, 1H, H3), 8.52 [d, J(HH) 9, 1H, H10 or H9], 8.60 [d, J(HH) 7.5, 2H, H11],
12.25 d, J(HH) 9, 1H, H5] FAB MS: 969, M+; 707, [M−PPh3]+; 630,
[M−PPh3−Ph]+; 429, [Ru(PPh3)(C5H5)]+; 154, [Ph2]+

188
M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
Table 1 (Continued)
Compound and analysis
Spectroscopic data a
11 Ru{CꢁCC(ꢀNPh)CHꢀCHPh}{P(OMe)3}2Cp
IR: w(CꢁC) 2051s, w(PO) 1041vs(br) 1H-NMR: 3.52 [t, J(HP) 12.0, 18H, OMe],
pale yellow, m.p. 152–154°C Anal. Found: C, 52.59; H, 4.89 [t, J(HP) 1.0, 5H, C5H5], 7.02–7.40 (m, 9H, H1,2,3,5,7,8), 7.51 [d, J(HH) 6.9,
5.40; N, 2.16. C28H35NO6P2Ru calc.: C, 52.16; H, 5.47; 2H, H6], 7.71 [d, J(HH) 15.8, 1H, H4] ES MS: 646, [M+H]+
N, 2.17; M, 645
12 Ru{CꢁCC[ꢀN(C6H4Me-4)]CHꢀCH(C6H4Me-4)}-
(PPh3)2Cp yellow Anal. Found: C, 75.22; H, 5.98; N,
1.72. C60H51NP2Ru calc.: C, 75.93; H, 5.42; N, 1.48;
M, 949
IR: w(CꢁC) 2022s 1H-NMR: 2.26 (s, 3H, Me), 2.35 (s, 3H, Me), 4.21 (s, 5H, Cp),
6.90–7.43 (m, 40H, aromatic H) ES MS: 950, [M+H]+; 688,
[Ru(PPh3)2(C5H5)−2H]+
13 Ru{CꢁCC[ꢀN(C6H4Me-4)]CHꢀCH(C6H4Me-4)}-
{P(OMe)3}2Cp orange; m.p. 119–120°C Anal.
Found: C, 53.59; H, 5.83; N, 2.05. C30H39NO6P2Ru
calc.: C, 53.57; H, 5.84; N, 2.08; M, 673
IR: w(CꢁC) 2049s, w(PO) 1024vs(br) 1H-NMR: 2.33, 2.35 (2×s, 6H, Me), 3.52 [t,
J(HP) 12.0, 18H, OMe], 4.91 (s, 5H, Cp), 7.01 [d(br), J(HH) 15.9, 1H, H5], 7.07,
7.14 [2×d, J(HH) 7.9, 4H, H2,3], 7.16, 7.40 [2d, J(HH) 7.8, 4H, H6,7], 7.67 [d,
J(HH) 15.8, 1H, H4] ES MS: 674, [M+H]+
14 Ru{CꢀCC[ꢀN(C6H4OMe-4)]CHꢀCH(C6H4OMe-4)}-
(PPh3)2Cp orange M, 981
IR: w(CꢀC) 2024s 1H-NMR: 3.74, 3.77 (2×s, 6H, OMe), 4.29 (s, 5H, Cp), 6.58
[d, J(HH) 9.0, 2H, H7], 6.75 [d, J(HH) 8.8, 2H, H2], 6.97 [t, J(HP) 7, 12H, Hm
of PPh3], 7.11 [t, J(HP) 7, 6H, Hp of PPh3], 7.25 (m, 17H, 12 o-H of PPh3+H2,
H4 or 5, H6), 7.32 [d, J(HH) 16, 1H, H4 or 5] ES MS: 982, [M+H]+; 720,
[M+H−PPh3]+
15 Ru{CꢀCC[ꢀN(C6H4OMe-4)]CHꢀCH(C6H4OMe-4)}-
IR: w(CꢀC) 2046s, w(PO) 1033vs(br) 1H-NMR: 3.53 [t, J(HP) 12.0, 18H,
{P(OMe)3}2Cp orange; m.p. 90–91°C Anal. Found: C, P-OMe], 3.79, 3.80 (2×s, 6H, OMe), 4.97 (s, 5H, Cp), 6.84, 6.86 [2×d, J(HH)
51.88; H, 5.90; N, 1.97. C30H39NO8P2Ru calc.:
C, 51.13; H, 5.58; N, 1.99; M, 705
9.0, 4H, H2,3], 7.14 [d, J(HH) 15.8, 1H, H5], 7.50 (m, 4H, H6,7), 7.67 [d, J(HH)
15.8, 1H, H4] ES MS: 706, [M+H]+
16 Ru{CꢁCC[ꢀN(C6H4NO2-4)]CHꢀCHPh}(PPh3)2Cp
yellow; m.p. 101–104°C (dec.) Anal. Found: C, 71.38;
IR: w(CꢁC) 2016s, w(NO) 1502s, 1329s, w(CN) 846m 1H-NMR: 4.38 (s, 5H, Cp),
6.97 (m, 18H, Hm+Hp of PPh3), 7.15 (m, 3H, H1+H2 or H3), 7.30 [d, J(HH) 9,
H, 5.32; N, 2.84. C58H46N2O2P2Ru.0.2CH2Cl2.0.2C6H14 2H, H6 or H7], 7.46 (m, 14H, Ho of PPh3+H3 or H2), 7.62 [d, J(HH) 16, 1H, H4
calc.: C, 71.33; H, 4.96; N, 2.80; M, 966 (both solvate
molecules found in NMR)
or H5], 8.07 [d, J(HH) 16, 1H, H5 or H4], 8.09 [d, J(HH) 9, 2H, H7 or H6] ES
MS: 966, M+; 703, [M−H−PPh3]+
17 Ru{CꢁCC[ꢀN(C6H4NO2-3)]CHꢀCHPh}(PPh3)2Cp
yellow; m.p. 171–172°C Anal. Found: C, 71.89; H,
4.91; N, 2.87. C58H46N2O2P2Ru calc.: C, 72.11; H,
4.80; N, 2.90; M, 966
IR: w(CꢁC) 2048s, w(NO) 1530s, 1351s, w(CN) 831m 1H-NMR: 4.56 (s, 5H, Cp),
7.08 [t, J(HH) 7.5, 12H, Hm of PPh3], 7.21 [t, J(HH) 7.5, 6H, Hp of PPh3],
7.3–7.6 (m, 12H, Ho of PPh3+H1, H2, H6, H8, H9), 7.62 [t, J(HH) 16, 1H, H4 or
H5], 8.04 [d, J(HH) 7.5, 2H, H3], 8.21 [d, J(HH) 7.5, 1H, H7 or H9] FAB MS:
966, M+; 702, [M−2H−PPh3]+; 427, [Ru(PPh3)(C5H5)−2H]+
18 Ru{CꢁCC(ꢀNPh)CHꢀCH(C6H4CO2Me -4)}(PPh3)2Cp
orange Anal. Found: C, 72.87; H, 5.30; N, 2.16.
C60H49NO2P2Ru calc.: C, 73.65; H, 5.04; N, 1.43; M,
980
IR: w(CꢁC) 2033s, w(CO) 1715s 1H-NMR: 3.88 (s, 3H, OMe), 4.38 (s, 5H, Cp),
6.71 [d, J(HH) 16.6, 1H, H4 or H5], 7.02 [t, J(HP) 7, 12H, Hm of PPh3], 7.19 [t,
J(HP) 7, 6H, Hp of PPh3], 7.33–7.46 (m, 13H, 12 o-H of PPh3+H4 or H5), 7.58
[t, J(HH) 8.6, 1H, H8], 7.90 [d, J(HH) 8.4, 2H, H3], 8.00 [d, J(HH) 8.4, 2H, H7],
8.07 [d, J(HH) 8.0, 2H, H6], 8.40 [d, J(HH) 8.6, 1H, H2] ES MS: 980, [M+H]+
718, [M+H−PPh3]+
;
19 Ru{CꢁCC[ꢀN(C6H4NO2-4)]CHꢀCH(C6H4CO2Me-4)}-
IR: w(CꢁC) 2017s, w(CO) 1718, w(NO) 1505, 1331 1H-NMR: 3.90 (s, 3H, OMe),
(PPh3)2Cp red Anal. Found: C, 70.36; H, 5.32; N, 2.70. 4.22 (s, 5H, Cp), 6.55 (m, 2H, H6), 6.98 [t, J(HP) 7, 12H, Hm of PPh3], 7.15 (m,
C60H48N2O4P2Ru calc.: C, 70.37; H, 4.72; N, 2.74; M, 18H, Ho+Hp of PPh3), 7.28 [d, J(HH) 8.6, 2H, H2], 7.43 [d, J(HH) 15, 1H, H4
1025
or H5], 7.90 [dd, J(HH) 8.6, 5.8, 2H, H3], 8.04 [d, J(HH) 15, 1H, H5 or H4], 8.14
[d, J(HH) 8.6, 2H, H7] ES MS: 1025, [M+H]+; 763, [M+H−PPh3]+
20 Ru{CꢁCC[ꢀN(C6H4NO2-4)]CHꢀCH(C6H4CO2Me-4)}-
{P(OMe)3}2Cp bright orange, m.p. 158–159°C Anal.
Found: C, 48.15; H, 4.35; N, 3.79. C30H36N2O10P2Ru
calc.: C, 48.19; H, 4.85; N, 3.75; M, 748
IR: w(CꢁC) 2048s, w(CO) 1718s, w(NO) 1519s, 1340s, w(PO) 1025vs(br) 1H-NMR:
3.51 [t, J(HP) 12.0, 18H, OMe], 3.92 (s, 3H, CO2Me), 4.90 (s, 5H, Cp), 7.07 [d,
J(HH) 15.8, 1H, H4], 7.26 [d, J(HH) 9.0, 2H, H6], 7.56 [d, J(HH) 8.2, 2H, H3],
7.77 [d, J(HH) 15.8, 1H, H5], 8.04 [d, J(HH) 8.2, 2H, H2], 8.17 [d, J(HH) 9.0,
2H, H7]; ES MS: 749, [M+H]+
21 Ru{CꢁCC[ꢀN(C6H4CO2Et-4)]CHꢀCHPh}(PPh3)2Cp
yellow; m.p. 191–193°C (dec.) Anal. Found: C, 72.96;
H, 5.13; N, 1.43. C61H49NO2P2Ru.0.2CH2Cl2 calc.: C,
72.77; H, 5.13; N, 1.39; M, 993 (solvate molecule
observed in NMR)
IR: w(CꢁC) 2027s, w(CO) 1702s 1H-NMR: 1.11 [t, J(HH) 7, 3H, Me], 4.24 [q,
J(HH) 7, 2H, CH2], 4.37 (s, 5H, Cp), 7.00 (m, 18H, Hm+Hp of PPh3), 7.14 (m,
3H, H1+H2), 7.41 [d, J(HH) 6.5, 2H, H3], 7.54 (m, 12H, Ho of PPh3), 7.63 [d,
J(HH) 8.5, 2H, H6 or H7], 7.64 [d, J(HH) 16, 1H, H4 or H5], 7.92 [d, J(HH) 16,
1H, H5 or H4], 8.39 [d, J(HH) 8.5, 2H, H7 or H6] ES MS: 993, M+; 731,
[M−PPh3]+

M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
189
Table 1 (Continued)
Compound and analysis
Spectroscopic data a
22 Ru{CꢁCC(ꢀNPh)CHꢀCH(C10H7-1)}(PPh3)2Cp yellow; IR: w(CꢁC) 2011s[1H-NMR: 4.45 (s, 5H, Cp), 6.96 (m, 18H, Hm+Hp of PPh3),
m.p. 177–179°C (dec.) Anal. Found: C, 76.61; H, 5.15; 7.15 (m, 2H, H2+H12), 7.25 (m, H1 or H3, H5+H6; resonance coincides with
N, 1.44. C62H49NP2Ru calc.: C, 76.68; H, 5.09; N, 1.44; C6H6), 7.41 [t, J(HH) 7.5, 2H, H11], 7.60 (m, 12H, Ho of PPh3), 7.70 [d, J(HH)
M, 971
7, 2H, H4 or H7], 7.72 [d, J(HH) 16, 1H, H8 or H9], 7.73 [d, J(HH) 7, 1H, H7
or H4], 7.80 [d, J(HH) 7.5, 2H, H10], 8.02 [d, J(HH) 8.5, 1H, H3 or H1], 8.72 [d,
J(HH) 16, 1H, H9 or H8] FAB MS: 972, [M+H]+; 709, [M−PPh3]+; 633,
[M+H−PPh3−Ph]+; 429, Ru(PPh3)(C5H5)]+; 154, [Ph2]+
23 [4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC9H5NH][BF4] red; m.p.
177°C (dec.)
IR: w(CꢁC) 2009s, w(BF) 1092vs(br) 1H-NMR: 4.56 (s, 5H, Cp), 7.1–8.5 (m, 40H,
aromatic H) (NH not observed) FAB MS: 922, [M+2H−BF4]+; 659,
[M+H−BF4−PPh3]+; 428, [Ru(PPh3)(C5H5)]+
24 [4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC13H8NH][PF6] black
Anal. Found: C, 65.23; H, 4.30; N, 1.2.
C62H48F6NP3Ru.0.4CH2Cl2 calc.: C, 65.23; H, 4.28;
N, 1.22; M, 933 (solvate observed in NMR)
IR: w(CꢁC) 1988s, w(PF) 841vs(br) 1H-NMR: 4.65 (s, 5H, Cp), 7.0–8.4 (m, 42H,
aromatic H), 11.55 (d, 1H, aromatic H) FAB MS: 969, [M−H−PF6]+; 708,
[M−PF6−PPh3}+; 446, [M−H−PF6−2PPh3]+; 154, [Ph2]+
25 [Ru{CꢁCC(ꢀNHPh)CHꢀCH(C10H7-1)}(PPh3)2Cp][PF6] IR: w(CꢁC) 1985s, w(PF) 846vs(br) 1H-NMR: 4.58 (s, 5H, Cp), 6.9-8.4 (m, 42H,
red; m.p. 210–212°C (dec.) Anal. Found: C, 67.97; H,
aromatic H), 10.86 [s(br), 1H, NH] FAB MS: 972, [MꢂPF6]+; 710,
4.77; N, 1.32. C62H50F6NP3Ru calc.: C, 67.82; H, 4.58; [M−PF6−PPh3]+; 429, [Ru(PPh3)(C5H5)]+; 154, [Ph2]+
N, 1.28; M, 972 (for material containing ꢁ15% 22, as
shown by NMR)
26-OTf [4-{Cp(PPh3)2Ru(CꢀC)}-2-PhC9H5NMe][OTf]
IR: w(CꢁC) 2003s 1H-NMR: 4.12 (s, 3H, Me), 4.55 (s, 5H, Cp), 6.7–8.5 (m, 40H,
dark red; m.p. 134–135°C (dec.) Anal. Found: C, 64.21; aromatic H) FAB MS: 934, [M−SO3CF3]+; 672, [M−SO3CF3−PPh3]+; 154,
H, 4.32; N, 1.24. C60H48F3NO3P2RuS.0.5CH2Cl2 calc.: [Ph2]+
C, 64.56; H, 4.39; N, 1.24; M, 934 (CH2Cl2 solvate
found in NMR)
26-PF6 [4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC9H5NMe][PF6] red
IR: w(CꢁC) 1997s; w(PF) 841vs(br) 1H-NMR: 4.07 (s, 3H, Me), 4.55 (s, 5H, Cp),
6.7–8.5 (m, 40H, aromatic H) FAB MS: 934, [M−PF6]+; 672, [M−PF6−PPh3]+
154, [Ph2]+
;
27 [Ru{CꢁCC[ꢀN(C6H4Me-4){Au(PPh3)}]CHꢀCH-
IR: w(CꢁC) 2050s 1H-NMR: 2.20, 2.22 (2×s, 6H, Me), 4.38 (s, 5H, Cp),
(C6H4Me-4)}(PPh3)2Cp][PF6] dark red Anal. Found: C, 6.95–7.46 (m, 56H, aromatic H) ES MS: 1408, M+; 1144, [M−PPh3]+; 950,
59.61; H, 4.05; N, 1.19. C78H67AuF6NP3Ru calc.: C,
60.31; H, 4.28; N, 0.90; M, 1408
[M−Au(PPh3)]+; 844, [M−2PPh3]+; 684, [M−Au−2PPh3]+
a IR (cm−1); NMR: l, J (Hz); MS (m/z). See Scheme 2 for NMR numbering schemes.
complex (Scheme 4). In this regard, there is a similarity
with the equilibrium that can be established between
alkynyl and vinylidene complexes, e.g. the pKa of
Fe(CꢁCMe)(PMe3)2Cp is 7.78 [9]. Given the presence of
the alkynyl group in the present complexes, we were
interested to determine whether C(2) or the N atom is
the more basic centre. Protonation of complexes 1, 10
or 22 with HBF4 or HPF6 afforded cationic complexes
23–25, of which the latter exhibited an NH resonance
at l 10.86. In addition, the site of protonation as the N
atom was further suggested by the presence of w(CꢁC)
bands in the IR spectra near 1990 cm−1. The lower
frequency, compared with the absorption in 1, suggests
some contribution from the allenylidene mesomer de-
picted. However, the X-ray structural data gives little
support for this idea, the distances within the
RuꢂC(12)ꢂC(11)ꢂC(1) fragment (albeit imprecisely) be-
ing consistent with those found in the neutral ana-
logues. In no case is there any evidence for electrophilic
addition to Cb of the alkynyl group.
ever, with PhNꢀCHC6H4CO2Me-4, the PPh3 complex
18 was identified as the quinoline, while the P(OMe)3
derivative 11 is the azabutadienyl, as confirmed by an
X-ray structure after provisional identification from the
1H-NMR spectrum.
The reaction with PhNꢀCH(1-C10H7) afforded com-
plex 22, which was assigned the azabutadienyl structure
on the basis of the [M+H]+ ion at m/z 972 in the ES
1
mass spectrum and by analysis of the H-NMR spec-
trum which contains trans vinylic H atoms at l 7.72
and 8.72, showing a typical J(HH) of 16 Hz.
2.3. Reactions with electrophiles
As mentioned above, these complexes are quite basic,
even traces of water being sufficient to result in a colour
change from yellow or orange to deep red. This colour
change can be reversed by addition of a base and is
consistent with a reversible protonation of the neutral

190
M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
Methylation of 1 was achieved either with methyl
cussed here for completeness, atoms being renumbered
for consistency. Figs. 1–4 contain plots of molecules of
the quinolines 1–3, 6 and 8, benzoquinoline 10, azabu-
tadiene complexes 15 and 17 and the cation of 23. The
structural parameters for all complexes determined are
collected in Table 2. The metal–ligand fragment
Ru(CꢁCꢂ)(PR3)2Cp (R=Ph or OMe) is common to all
complexes and is similar to those found to a host of
similar complexes. Thus, the familiar distorted octahe-
dral geometry of the Ru atom is achieved by the
tridentate Cp ligand [RuꢂC(Cp) ranges between 2.20(1)
triflate or with MeI in the presence of NH4PF6, from
which reactions the OTf and PF6 salts, respectively, of
the N-methylquinolinium cation 26 were obtained. The
retention of the w(CꢁC) absorption at 2003 cm−1 serves
to indicate that the N atom is the site of methylation in
this case also.
Finally, auration of azabutadiene 12 was achieved by
addition of AuCl(PPh3)/TlPF6 to the neutral complex.
A rapid reaction ensued, with precipitation of TlCl.
From the resulting solution, dark red 27 was isolated,
the IR spectrum of which contained w(CꢁC) at 2050
cm−1, again suggesting that the N atom is the site of
addition of the [Au(PPh3)]+ fragment.
,
,
and 2.265(3) A, average for all structures 2.23 A, with
no significant differences between the PPh3 and
P(OMe)3 complexes], the two PR3 ligands and C(12) of
the alkynyl groups. The RuꢂPPh3 distances are between
,
,
(average 2.30 A), the
2.4. Molecular structures of quinoline and azabutadiene
complexes
2.28(1) and 2.319(2)
A
RuꢂP(OMe)3 distances being appreciably shorter at
,
2.2113–2.2301(9) A, while the RuꢂC(12) separations
,
[ignoring one imprecise value of 1.97(3) A] are found
The crystal and molecular structures of complexes
1–3, 6, 8, 10, 15, 17 and 23 have been determined by
single-crystal X-ray methods; those of 2 and 17 were
reported in our original communication, but are dis-
,
between 1.978(8) and 2.015(3) A. The C(12)ꢂC(11)
,
triple bond length lies between 1.197(4) and 1.220(3) A.
Angles at Ru range between 97.25(8)–102.3(4)° (PPh3)
Scheme 2.

Table 2
Selected structural parameters
Complex
1
2
3
6
8
10
15
17
23
28 P21/c
form (2
molecules)
28 Pna21
form (Ref.
[12])
Q or A
R
R%
Q
Q
Me-6
H
Q
H
NO2-4
Ph
Q
H
Q
Q
Benzo
H
A
A
NO2-3
H
Q
(Cl)
–
–
(Cl)
–
–
H
H
Ph
OMe-6
NO2-4
OMe
OMe-4
OMe-4
Ph
H
H
Ph
CO2Me-4
OMe
R%% in PR%3%
Ph
Ph
Ph
OMe
OMe
,
Bond distances (A)
RuꢂP(1)
/
2.2954(5)
2.3030(6)
2.2966(7)
2.3079(2)
2.2971(8)
2.2945(8)
2.2113(8)
2.2287(8)
2.2199(7)
2.2114(8)
2.293(1)
2.295(1)
2.215(1)
2.293(2)
2.319(2)
2.30(1)
2.28(1)
2.225(1)
2.2301(9)
2.2285(7)
2.2230(8)
2.176(3)–
2.241(3)
2.217
2.4307(8),
2.434(1) a
–
2.234(2)
2.199(3)
RuꢂP(2)
2.2133(7)
RuꢂC(cp)
2.235–
2.252(2)
2.242
2.224(3)–
2.259(4)
2.241
2.219(4)–
2.253(3)
2.237
2.229–
2.261(4)
2.247
2.221–
2.253(3)
2.238
2.223–
2.251(4)
2.238
2.238(5)–
2.265(3)
2.250
2.21(1)–
2.240(7)
2.226
2.20–
2.24(2)
2.22
(av.)
RuꢂC(12)
2.282
2.393(3)
a
1.995(2)
1.997(3)
1.990(2)
2.012(3)
2.015(2)
2.004(4)
2.001(3)
1.978(8)
1.97(3)
C(12)ꢂC(11)
C(11)ꢂC(1)
C(1)ꢂC(2)
C(1)ꢂN(4)
C(2)–C(3)
1.220(3)
1.422(2)
–
–
–
1.197(4)
1.431(4)
–
–
–
1.219(4)
1.428(4)
–
–
–
1.203(4)
1.432(4)
–
–
–
1.197(3)
1.436(3)
–
–
–
1.202(5)
1.431(5)
–
–
–
1.220(4)
1.436(4)
1.469(3)
1.295(3)
1.320(4)
1.22(1)
1.43(1)
1.48(1)
1.280(9)
1.32(1)
1.21(4)
1.41(4)
–
–
–
–
–
–
–
590
Bond angles (°)
P(1)ꢂRuꢂP(2)
(
101.19(2)
91.06(6)
87.65(6)
99.00(3)
90.30(8)
88.78(7)
100.30(3)
89.72(9)
89.50(8)
94.10(3)
87.05(8)
91.11(8)
95.79(2)
91.36(6)
89.13(6)
101.44(4)
87.5(1)
93.89(3)
89.55(9)
90.22(7)
97.25(8)
89.7(2)
96.0(2)
102.3(4)
87(1)
94.03(3),
93.96(3)
91.2(1)
184
P(1)ꢂRuꢂC(12)
P(2)ꢂRuꢂC(12)
92.28(3),
91.8(1) a
95.0(1) a
89.85(4) a
201
89.1(1)
88(1)
93.14(3),
90.92(3) a
RuꢂC(12)ꢂC(11)
C(12)ꢂC(11)ꢂC(1)
C(11)ꢂC(1)ꢂC(2)
C(11)ꢂC(1)ꢂN(4)
C(2)ꢂC(1)ꢂN(4)
173.9(2)
171.0(2)
–
–
–
175.9(3)
169.4(3)
–
–
–
174.0(2)
170.7(3)
–
–
–
176.8(2)
176.9(3)
–
–
–
173.2(2)
174.6(2)
–
–
–
174.3(3)
173.8(4)
–
–
–
173.9(2)
178.6(3)
118.5(2)
125.2(2)
116.2(2)
171.2(6)
176.9(6)
119.6(6)
124.2(7)
116.0(8)
175(3)
174(3)
–
–
–
–
–
–
–
–
a For C(12), read Cl.+Ref. [12]. For 15 and 17: angles at N(4) are 120.3(2), 119.4(7)°; angles at C(2) are 125.6(2), 124.1(8)°; angles at C(3) are 126.12(3), 127.2(8)°.

192
M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
line, and the formation of the tricyclic benzo[h]-
quinoline nucleus in 10. The close proximity of H(13)
to the CꢁC triple bond, mentioned above, also affects
the intra-ring angles, C(11)ꢂC(1)ꢂC(2, 10) being
117.7(3) and 125.0(3)°, respectively. As can be seen
from Fig. 2, the benzoquinoline nucleus is non-planar.
The peripheral planes have dihedrals of 8.5(1), 7.2(1)°
to the central plane, with a dihedral between them of
15.2(1)°, the bulk of the distortion being in the periph-
eral plane pendant to the acetylide and the central
2
plane ( 433, 422, cf. the outer plane 78.5°). The
,
pendant acetylide atom lies 0.254(6) A out of the
attached ring plane.
In contrast, complexes 15 and 17 (Fig. 3) contain the
Ru(CꢁCꢂ)(PR3)2Cp fragment attached to C(2) of an
NꢀCCꢀC chain that has a direct relationship to the
parent imine. In the two structures, the substitution
pattern of the imine is preserved and for 15, at least, all
H atoms have also been resolved. The CꢀN and CꢀC
bonds are within the expected ranges and angles at the
atoms of the chains are 119.4(7)° or greater, consistent
with the expected sp2 hybridisation of these atoms.
The imprecisely determined structure of the proto-
nated complex 23 (Fig. 4) shows a similar metal frag-
ment to those found in the neutral complexes: the
presence of the charge does not affect the bond parame-
ters which are consistent with the site of protonation
being the N atom of the quinoline, the protonic hydro-
gen not being directly located in the structural determi-
nation; the crystal lattice contains the BF4 anion.
In the course of these studies, the structure of a new
modification of RuCl{P(OMe)3}2Cp, a precursor of the
related butatrienylidene cation, was also determined
(Fig. 5). In comparison with that of the present mono-
clinic (P21/c) form, it shows a significant difference in
Scheme 3.
and 94.10(3)–95.79(2)° [P(OMe)3] [PꢂRuꢂP], paralleling
the diminution in RuꢂP distances, and 87.05(8)–
96.0(2)° [PꢂRuꢂC(12)]. The RuꢂC(12)ꢂC(11) group
is close to linear with angles at C(12) and C(11)
of between 173.2(2)–176.8(2) and 169.4–178.6(3)°, re-
spectively. Comparison with the structure of
Ru(CꢁCPh)(PPh3)2Cp [10] shows that the structural
parameters of the present complexes do not differ sig-
nificantly, similar conclusions being drawn from a study
of other ethynyl–ruthenium complexes containing ex-
tended unsaturated substituents of relevance to their
non-linear optical behaviour [11]. Further detailed dis-
cussion is unwarranted as a result of the differing
precisions of the various structural determinations.
The presence of the quinoline nucleus is quite evident
in 1–3, 6, 8 and 10, with the location of the nitrogen
atom consistent with that expected from the precursor
imines. The structural determinations also confirm that
the C-aryl substituent is in the 2-position in the quino-
,
the average RuꢂP distance (2.217 A compared with
,
2.282 A found for the orthorhombic (Pna21) form
previously reported [12]). The latter study was recorded
using Cu–Ka radiation, resulting in very large absorp-
tion effects that may account for the anomaly. The
RuꢂCl distance is substantially longer in the present
,
form [2.4307(8) vs. 2.393(3) A]. Significant differences
in the angles subtended at Ru by the Cl and P atoms
[92.28(3), 93.15(3), 94.02(3) vs. 91.8(1), 95.0(1), 91.2(1)°]
are also found.
3. Discussion
The chemistry described above is consistent with the
intermediacy of the butatrienylidene complex in these
reactions; separate experiments demonstrated that the
performed complex, obtained from buta-1,3-diyne and
[Ru(THF)(PPh3)2Cp]+, reacts with the imines to afford
the same products. The formation of the quinoline or
azabutadiene appears to be a function of the sub-
Scheme 4.

M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
193
Fig. 1. Plot of
a molecule of (a) 4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC9H5N (1); (b) 4-{Cp(PPh3)2Ru(CꢁC)}-6-Me-2-PhC9H4N (2); (c) 4-
{Cp(PPh3)2Ru(CꢁC)}-2-(4-NO2C6H4)C9H5N (3); (d) 4-{Cp[P(OMe)3]2Ru(CꢁC)}-2-(4-MeO2CC6H4)C9H5N (6) and (e) 4-{Cp[P(OMe)3]2-
Ru(CꢁC)}-6-MeO-2-(4-NO2C6H4)C9H4N (8), showing the atom numbering schemes. In this and subsequent Figures, non-hydrogen atoms are
,
shown with 20% thermal envelopes; hydrogen atoms have arbitrary radii of 0.1 A. Settings of the figures correspond to Scheme 2.
stituents present on the imine and the metal-bonded
P-ligand, rather than whether or not the reaction is
carried out with performed butatrienylidene complex.
The formation of the products can be understood in
terms of reaction of the imine with carbons of differing
electronic character, although at this stage we are not
able to determine the sequence of bond formation.
Thus, Cl of the butatrienylidene ligand is electron rich
and would be expected to attack the imine at the
methine carbon. Subsequent reaction of Ck, which is
electron deficient, might occur at the electron-rich ortho
carbon of the N-aryl group or with the imine N atom.

194
M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
Fig. 1. (Continued)

M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
195
would be that Ci and Cl of the unsaturated carbon
chain would have more nucleophilic character. That
this is not the whole story, however, can be seen by
comparing these results with those obtained with 4-
RC6H4NꢀCHC6H4R-4 (R=Me, OMe), which uni-
formly produce the azabutadienes. Further work is
necessary to understand fully the course of these inter-
esting reactions and also to devise suitable methods for
removal of the metal-containing fragment.
Related chemistry has been described. The reactions
between M(ꢀCꢀCR2)Ln (MLn=W(CO)5, R=Ph [15];
Mn(CO)2Cp, R2ꢀH2, HMe, HPh [16]; Re(CO)2Cp,
RꢀH [16]; [Fe(CO)(L)Cp]+, L=PPh3, P(OMe)3; R=
H, Me [17]) and RNꢀCHPh (R=Me, Ph) resulted in
cycloaddition of the imine to the ChꢀCi double bond to
give the corresponding [2+2] cycloaddition products.
The likely pathway is via initial addition of Ch to the N
atom, followed by ring closure. h4-Isoquinolinium
derivatives have been obtained from alkynes and cy-
cloruthenated complexes derived from dimethy-
laminomethylbenzenes [18]. Quinoline-2-thiolates have
been constructed by cycloaddition of electron deficient
alkynes to isothiocyanates [19].
In the former case, formation of a new CꢂC bond
results in formation of the bicyclic N-heterocycle, dihy-
droquinoline, aromatisation of which drives the formal
elimination of 2H (Scheme 1). By virtue of the C-aryl
group, substituents on the N-aryl group and the metal–
ligand fragment which becomes attached to C(6), a
variety of polysubstituted quinolines may be formed by
this reaction.
The alternative route is followed when electron-with-
drawing substituents are present at the meta position of
the N-aryl group. These reduce the nucleophilic charac-
ter of the ortho carbon, resulting in cycloaddition of the
CkꢀCl unit of the butatrienylidene to the NꢀCH system
of the imine and generating a four-membered ring
(Scheme 2). The observed product is formed by a
subsequent ring-opening reaction, which is reminiscent
of and no doubt related to the similar reactions found
between alkynyl–metal complexes and electron-defi-
cient olefins [12–14]. The reaction can be directed along
this pathway if the electron density in the N-aryl group
is reduced, for example, by the presence of electron-
withdrawing groups such as NO2 or CO2Me. However,
this is not an exclusive condition, since formation of
azabutadienes was also found for methyl- and methoxy-
substituted systems.
4. Conclusions
The formation of a quinoline with PhNꢀCHPh in the
PPh3 system, but the azabutadiene with the P(OMe)3
system, may be related to the degree of electron rich-
ness of the metal fragment and thereby to the degree of
transfer of electron density along the chain. It is gener-
ally accepted that PPh3 is a much more basic ligand
that P(OMe)3, so that in the former case, the metal
centre is more electron rich. In turn, the expectation
The possible intermediacy of cationic butatrienyli-
dene complexes as the products from buta-1,3-diyne
and [Ru(THF)(PR3)2Cp]+ is further shown in their
subsequent reactions with arylimines which, according
to substituent, afford either quinoline or azabutadiene
derivatives. The formation of these products can be
partially rationalised in terms of cycloaddition of Ck
Fig. 2. Plot of a molecule of 4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC13H8N (10), showing atom numbering scheme.

196
M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
Fig. 3. Plots of a molecule of (a) Ru{CꢁCC[ꢀN(C6H4OMe-4)]CHꢀCH(C6H4OMe-4)}{P(OMe)3}2Cp (15) and (b) Ru{CꢁCC[ꢀN(C6H4NO2-
3)]CHꢀCHPh}(PPh3)2Cp (17), showing atom numbering schemes.
and Cl of the unsaturated carbene to either the unsatu-
rated NꢀCH group followed by ring-opening, or by
attack at the imine carbon and addition to the ortho
carbon of the N-aryl group. These reactions extend the
range of reactions reported for this unsaturated carbene
ligand, which also include addition of nucleophiles to
Ck to give alkenylvinylidenes that may rearrange to
allenylidenes [7]. More work is required, however, to
delineate the precise effects of substituents and nature
of the metal centre on the course of these reactions.
beam, NaCl optics; NMR: Gemini 200 (1H-NMR at
199.975 MHz, 13C-NMR at 50.289 MHz; Bruker
ACP300 (1H-NMR at 300.13 MHz, 13C-NMR at 75.47
MHz). FAB MS: VG ZAB 2HF, using 3-nitrobenzyl
alcohol as matrix, exciting gas Ar, FAB gun voltage 7.5
kV, current 1 mA, accelerating potential 7 kV. Electro-
spray (ES) MS: The samples were dissolved in
methanol, unless otherwise indicated, and injected into
a 10 ml injection loop attached to a VG Platform II
instrument or directly infused, using a syringe pump,
into a Finnegan LCQ spectrometer. Nitrogen was used
as the drying and nebulising gas. Samples were exam-
ined over a range of cone voltages (20–90 V) to find the
best conditions in the former. Chemical aids to ionisa-
tion are indicated where used [20].
5. Experimental
5.1. General reaction conditions
All reactions were carried out under dry, high-purity
nitrogen using standard Schlenk techniques. Solvents
were dried, distilled and degassed before use. Light
petroleum refers to a fraction of b.p. 60–80°C. Elemen-
tal analyses were by the Canadian Microanalytical Ser-
vice, Delta, B.C. Preparative TLC was carried out on
glass plates (20×20 cm) coated with silica gel (Merck
60 GF254, 0.5 mm thick).
5.3. Reagents
AgPF6 (Pennwalt) and KOtBu (Merck) were used
as received. The compounds RuCl(PPh3)2Cp [21],
[Ru(NCMe)(PPh3)2Cp][PF6] [22], AuCl(PPh3) [23],
HCꢁCCꢁCH [24] and the imines ArNꢀCHAr% [25] were
prepared using the cited literature methods.
5.2. Instrumentation
5.4. General method of preparation
Analytical and spectroscopic data are collected in
Table 1. IR: Perkin–Elmer 1700X FT-IR; 683 double
The complexes RuCl(PPh3)2Cp (200 mg, 0.28 mmol)
or RuCl{P(OMe)3}2Cp (125 mg, 0.28 mmol) in THF

M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
197
(50 ml) was treated with AgPF6 (70 mg, 0.28 mmol)
and stirred at room temperature (r.t.) for 5 min. The
resulting orange solution was cooled to −94°C
(MeOH slush bath), then filtered (from precipitated
AgCl; however, the reaction proceeds in similar yield if
the AgCl is not removed) into a second flask containing
buta-1,3-diyne (0.3 ml of 1.1 M solution in THF, large
excess) and the imine (0.56 mmol) in THF (5 ml) at the
same temperature. The cold bath was removed and the
mixture allowed to warm to r.t. During this time the
colour of the solution changed from orange to deep
red. The solution was then treated with KOBut (40 mg);
after 30 min, the solvent was removed. A CH2Cl2
extract of the residue was purified by column chro-
matography on Al2O3, elution with Et2O giving a deep
yellow band, which afforded the pure product after
crystallisation (Et2O–pentane). In some cases, further
purification could be achieved by TLC (silica gel; 3:2
hexane–CH2Cl2).
3. 4-{Cp(PPh3)2Ru(CꢁC)}-2-(4-NO2C6H4)C9H5N (3),
from CH2Cl2–hexane (54%). If a solution of 3 in
benzene (10 mg/2 ml) was left under sunlight for 30
min, the complex is partly decomposed, to give a
black solid.
4. 4-{Cp[P(OMe)3]2Ru(CꢁC)}-2-(4-NO2C6H4)C9H5N
(4) (31%).
5. 4-{Cp(PPh3)2Ru(CꢁC)}-2-(3-NO2C6H4)C9H5N (5),
from CH2Cl2–hexane (40%). This complex re-
quired further purification by chromatography on
Al2O3.
6. 4-{Cp[P(OMe)3]2Ru(CꢁC)}-2-(4-MeO2CC6H4)C9-
H5N (6), from THF–pentane (22 mg, 6%; in this
case, difficulties in separation from residual imine
were experienced).
7. 4-{Cp(PPh3)2Ru(CꢁC)}-6-MeO-2-(4-NO2C6H4)C9-
H4N (7), from CH2Cl2–hexane after rechromatog-
raphy (41%).
8. 4-{Cp[P(OMe)3]2Ru(CꢁC)}-6-MeO-2-(4-NO2C6-
H4)C9H4N (8), from CH2Cl2–hexane (28%).
9. 4-{Cp(PPh3)2Ru(CꢁC)}-(5/7)-Cl-2-PhC9H4N (9),
In this manner were prepared:
1. 4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC9H5N (1), from pen-
tane–Et2O (41%). In this case, extraction of the
residue (after removal of solvent) with hexane (2
ml) and evaporation gave a pale yellow solid. A
THF solution (0.5 ml) of this residue was analysed
by GLC (Pye Series 104 Chromatograph, 15%
FFAP column, 200°C, FID detector), both
NHPh(CH2Ph) and unreacted PhNꢀCHPh being
confirmed by comparison of retention times with
those of standard samples.
1
from Et2O–hexane (39%). The H-NMR spectrum
(C6D6) showed the presence of two isomers (9a and
9b) in ꢁ4:1 ratio which could not be separated by
chromatography or by recrystallization. Attempts
to grow single crystals were unsuccessful. The sam-
ple decomposes slowly in solution, even in the
dark.
10. 4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC13H8N (10), from
THF–hexane (30%).
11. Ru{CꢁCC(ꢀNPh)CHꢀCHPh}{P(OMe)3}2Cp (11),
from CH2Cl2–hexane (22%).
2. 4-{Cp(PPh3)2Ru(CꢁC)}-6-Me-2-PhC9H4N
(2),
from pentane–Et2O (26%).
Fig. 4. Plot of the cation of [4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC9H5NH][BF4] (23), showing atom numbering scheme.

198
M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
14. Ru{CꢁCC[=N(C6H4OMe-4)]CHꢀCH(C6H4OMe-
4)}(PPh3)2Cp (14), from CH2Cl2–MeOH (39%).
15. Ru{CꢁCC[ꢀN(C6H4OMe - 4)]CHꢀCH(C6H4OMe -
4)}{P(OMe)3}2Cp (15) from CH2Cl2–hexane
(25%).
16. Ru{CꢁCC[ꢀN(C6H4NO2 - 4)]CHꢀCHPh}(PPh3)2Cp
(16), from CH2Cl2–hexane (34%).
17. Ru{CꢁCC[ꢀN(C6H4NO2 - 3)]CHꢀCHPh}(PPh3)2Cp
(17), from Et2O–hexane in the dark (29%). This
compound is sunlight/UV-light sensitive, changing
to an unidentified blue species after photolysis.
18. Ru{CꢁCC(ꢀNPh)CHꢀCH(C6H4CO2Me - 4)}(PP -
h3)2Cp (18), from CH2Cl2–hexane (70%).
19. Ru{CꢁCC[ꢀN(C6H4NO2-4)]CHꢀCH(C6H4CO2Me-
4)}(PPh3)2Cp (19), from CH2Cl2–hexane (32%).
20. Ru{CꢁCC[ꢀN(C6H4NO2-4)]CHꢀCH(C6H4CO2Me-
4)}{P(OMe)3}2Cp (20), from CH2Cl2–hexane
(24%).
21. Ru{CꢁCC[ꢀN(C6H4CO2Et-4)]CHꢀCHPh}(PPh3)2 -
Cp (21), from CH2Cl2–hexane after rechromatog-
raphy (37%).
22. Ru{CꢁCC(ꢀNPh)CHꢀCH(C10H7-1)}(PPh3)2C (22),
precipitated from Et2O with C6H6 (34%).
5.5. Protonation
5.5.1. [4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC9H5NH][BF4] (23)
A solution of HBF4 (5 mg, 0.057 mmol) in THF (4
ml) was added to a solution of 1 (50 mg, 0.054 mmol)
in THF (5 ml). The solution turned red and the solvent
was evaporated to give [4-{Cp(PPh3)2Ru(CꢁC)}-2-
PhC9H5NH][BF4] (23) (50 mg, 84%) as a red solid after
washing the solid residue three times with Et2O.
5.5.2. [4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC13H8NH][PF6]
(24)
Two drops of HPF6 in Et2O were added to a solution
of 4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC13H8N (10) (50 mg,
0.052 mmol) in benzene (10 ml). The solution became
red immediately, and a precipitate formed. After evapo-
ration, dissolution in CH2Cl2 and precipitation with
hexane, [4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC13H8NH][PF6]
(24) (90%) was obtained as a black solid.
Fig. 5. Plots of the two independent molecules of RuCl{P-
(OMe)3}2Cp (28), showing atom numbering scheme.
5.5.3. [Ru{CꢁCC(ꢀNHPh)CHꢀCH(C10H7-1)}-
(PPh3)2Cp][PF6] (25)
12. Ru{CꢁCC[ꢀN(C6H4Me - 4)]CHꢀCH(C6H4Me - 4)} -
(PPh3)2Cp (12), from CH2Cl2–hexane (29%).
13. Ru{CꢁCC[ꢀN(C6H4Me - 4)]CHꢀCH(C6H4Me - 4)} -
{P(OMe)3}2Cp (13), from light petroleum–CH2Cl2
(28%).
This complex was prepared in 73% yield from
Ru{CꢁCC(ꢀNPh)CHꢀCH(C10H7-1)}(PPh3)2Cp (22) by
the method described above for 24. Analytical and
NMR data are consistent with the presence of some
neutral 22 in the product.

Table 3
Crystal data and refinement details for complexes
Compound
1
2
3
6
8
10
15
17
23
28
Diffractometer a
Formula
AXS
C58H45NP2Ru
AXS
C59H47NP2Ru
AXS
AXS
AXS
CAD4
AXS
CAD4
CAD4
AXS
C11H23ClO6P2Ru
C58H44N2O2P2Ru C30H35NO8P2Ru C29H34N2O9P2Ru C62H47NP2Ru·
C4H8O
964.0
C30H39NO8P2Ru
·0.5CH2Cl2
747.1
C58H46N2O2P2Ru C58H46NP2Ru+
·BF−4 ·Et2O
/
Mw
919.0
933.1
700.6
717.6
1041.2
966.0
1081.0
449.8
Crystal system
Space group
Monoclinic
P21/n
15.958(1)
16.980(1)
16.553(1)
Triclinic
Triclinic
Triclinic
Monoclinic
P21/n
19.947(4)
7.867(2)
20.598(4)
Monoclinic
P21/c
11.934(3)
14.724(3)
31.157(6)
Triclinic
Triclinic
Monoclinic
P21/c
13.697(11)
23.764(20)
17.038(9)
Monoclinic
P21/c
22.433(1)
9.3819(7)
18.411(1)
(
(
(
(
(
P1
P1
P1
P1
P1
,
a (A)
11.242(1)
11.402(1)
17.899(2)
87.703(2)
82.419(2)
86.529(2)
2269
13.023(2)
13.263(2)
14.554(2)
80.841(2)
81.407(2)
69.541(2)
2313
8.216(1)
12.516(2)
15.741(3)
78.169(3)
88.641(3)
77.320(3)
1545
10.0633(8)
12.1873(9)
14.9825(10)
90.796(1)
108.182(1)
102.009(1)
1701
19.787(8)
11.684(3)
10.688(3)
98.26(2)
101.18(3)
101.39(3)
2333
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
96.681(1)
100.875(3)
106.03(2)
100.37(6)
110.568(1)
3
,
V (A )
Z
4455
4
1.370
3174
4
1.501
5262
4
1.314
5455
4
1.315
3628
8
1.647
2
2
1.38
2
2
2
Dcalc. (g cm−3
)
1.366
1.506
1.458
1.375
Crystal size (mm) 0.20×0.15×0.12 0.24×0.20×0.07 0.30×0.18×0.12
0.25×0.17×0.10 0.33×0.25×0.11 0.75×0.52×0.20 0.61×0.51×0.30
0.40×0.12×0.24
0.87, 0.94
4.5
0.08×0.16×0.14 0.55×0.18×0.07
a
T
(min, max)
0.71, 0.86
4.6
0.93, 0.98
4.6
0.81, 0.91
4.5
0.43, 0.56
6.6
0.80, 0.89
6.5
0.82, 0.93
4.0
0.69, 0.83
6.8
0.96, 0.97
4.0
0.61, 0.89
12.2
590
v (cm−1
)
)
Ntotal
52798
27145
26193
17940
36843
18939
42311
N (Rint
N0
R
Rw
)
11440 (0.034)
9171
0.034
11314 (0.036)
8372
0.041
11268 (0.025)
7560
0.037
7507 (0.026)
5648
0.036
8004 (0.017)
6570
0.031
11792
8421
0.044
0.048
8285 (0.014)
7206
0.041
8225
4544
0.059
0.058
6436
1315
0.088
0.076
9070 (0.023)
7389
0.031
184
0.040
0.041
0.037
0.040
0.043
0.058
0.040
201
a CAD4: single-counter instrument data (Tꢁ295 K; Gaussian absorption correction). AXS: CCD instrument data (Tꢁ300 K, 2qmax=58°; empirical absorption correction (SADABS).

200
M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
5.6. Methylation
ventional residuals R, Rw (statistical weights) on ꢀFꢀ are
quoted at convergence; neutral atom complex scattering
factors were employed, as was the XTAL 3.4 program
system [26]. Pertinent results are given in the figures
and tables, full crystallographic data being deposited.
Individual variations/idiosyncrasies are cited in Section
5.9 below (Table 3).
5.6.1. [4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC9H5NMe][OTf]
(26-OTf)
An excess of MeOTf (50 ml, 0.44 mmol) was added to
a solution of 1 (20 mg, 0.022 mmol) in CH2Cl2 (5 ml).
The solution turned red and was stirred for 10 min
before the solvent was evaporated. Reprecipitation
from CH2Cl2–hexane gave [4-{Cp(PPh3)2Ru(CꢁC)}-2-
PhC9H5NMe][OTf] (26-OTf) as a dark red solid (20 mg,
85%).
5.9. Variata
1, 2. Data were measured at ca. 153 K. (x, y, z, Uiso)H
were refined for all hydrogen atoms.
3. (x, y, z, Uiso)H were refined for all hydrogen atoms.
6. Methoxy groups of ligand 1 were modelled with
the oxygen atoms each disordered over pairs of sites,
5.6.2. [4-{Cp(PPh3)2Ru(CꢁC)}-2-PhC9H5NMe][PF6]
(26-PF6)
MeI (0.5 ml, freshly passed through Al2O3) was
added to a solution of 1 (100 mg, 0.11 mmol) in THF
(20 ml) and the mixture was degassed. The solution was
then refluxed for 8 h, the colour becoming deep red–
purple. NH4PF6 (20 mg, 0.12 mmol) was added to the
mixture which was then stirred for 30 min before
removing solvent. The residue was extracted with
CH2Cl2, addition of hexane giving [4-{Cp(PPh3)2-
Ru(CꢁC)}-2-PhC9H5NMe][PF6] (26-PF6) as a red solid.
Attempts to purify it by reprecipitation were unsuccess-
ful.
,
separations 0.95(2), 0.68(1), 1.07(1) A, site occupancies
of the two sets of components constrained as equal
after trial refinement, occupancy 0.69(1) and com-
plement.
10. Difference-map residues were modelled as solvent
THF, refining to an occupancy of unity, albeit with
very high thermal motion.
15. Difference-map residues were modelled as
dichloromethane, disposed close to an inversion image,
site occupancy set at 0.5 after trial refinement.
17. Data were measured rapidly as the crystal was
photosensitive.
23. Available material offered only very small speci-
mens, enabling assignment of broad structural features
only via single counter data (the material had deterio-
rated by the arrival of the CCD facility). Only Ru, P, F
were refined with anisotropic thermal parameter forms,
difference map residues being modelled as diethyl ether
of solvation, site occupancy set at unity after trial
refinement, albeit with high thermal motion. The struc-
ture determination does not definitively locate the pro-
tonating hydrogen atom at N(4), although the
remainder of the geometry is consistent with that.
A new phase of RuCl{P(OMe)3}2Cp (28). From one
fraction obtained during the purification of 6, crystals
of 28 were obtained by vapour diffusion of pentane into
a THF solution.
5.7. Auration of [Ru{CꢁCC[ꢀN(C6H4Me-4)-
{Au(PPh3)}]CHꢀCH(C6H4Me-4)}(PPh3)2Cp][PF6] (27)
A mixture of AuCl(PPh3) (54 mg, 0.11 mmol),
Ru{CꢁCC[ꢀN(C6H4Me-4)]CHꢀCH(C6H4Me-4)}(PPh3)2-
Cp (12) (100 mg, 0.11 mmol) and TlPF6 (38 mg, 0.11
mmol) was heated in refluxing THF (20 ml) for 1.5 h.
The solution was filtered to remove TlCl and the
solvent was removed. Precipitation of the product
from CH2Cl2 with hexane gave [Ru{CꢁCC[ꢀN(C6H4-
Me-4){Au(PPh3)}]CHꢀCH(C6H4Me-4)}(PPh3)2Cp][PF6]
(27) (155 mg, 91%) as a dark red solid.
5.8. Structure determinations
Diffraction data were measured in two ways, all
instruments being fitted with monochromatic Mo–Ka
,
radiation sources (u=0.71073 A). (a) Using a single
counter/four-circle instrument at ca. 295 K, N unique
data were measured, N0 with I\3|(I) being used in
the refinement after analytical absorption correction.
(b) Using a Bruker AXS CCD/area detector instrument
at ca. 300 K, Ntotal reflections were measured, merging,
after empirical absorption correction (Rint quoted) to N
6. Supplementary material
Crystallographic data for the structural analyses have
been deposited with the Cambridge Crystallographic
Data Centre as CCDC nos. 127434–127443 for com-
pounds 1 (127435), 2 (127436), 3 (127439), 6 (127441),
8 (127442), 10 (127437), 15 (127443), 17 (127438), 23
(127434) and 28 (127440; P21/c form). Copies of the
information can be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, England (Fax: +44-1223-336-033; e-mail: de-
posit@ccdc.cam.ac.uk or www: http://www.ccdc.ac.uk).
unique data using the proprietary software SMART
/
SAINT/SADABS/
XPREP, N0 with F\4|(F) being consid-
ered observed and used in the refinement. In all
structures an isotropic thermal parameter form was
refined for the non-hydrogen atoms, (x, y, z, Uiso)H
being included, constrained at estimated values. Con-

M.I. Bruce et al. / Journal of Organometallic Chemistry 590 (1999) 184–201
201
Skelton, A.H. White, Organometallics 14 (1995) 3970. (b) I.R.
Whittall, M.G. Humphrey, A. Persoons, S. Houbrechts,
Organometallics 15 (1996) 1935. (c) I.R. Whittall, M.P. Ci-
fuentes, M.G. Humphrey, B. Luther-Davies, M. Samoc, S. Hou-
brechts, A. Persoons, G.A. Heath, D.C.R. Hockless, J.
Organomet. Chem. 549 (1997) 127.
Acknowledgements
We acknowledge preliminary studies of these reac-
tions by Dr Peter Hinterding. Support of this work by
the Australian Research Council is gratefully acknowl-
edged. P.J.L. and M.E.S. were the holders of Australian
Post-graduate Awards. We thank Professor Brian
Nicholson (University of Waikato, Hamilton, New
Zealand) for most of the electrospray mass spectra.
Johnson Matthey Technology plc, Reading, UK, gener-
ously loaned the RuCl3·nH2O.
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