Amidinato and triazenido complexes of ruthenium(II): X-ray crystal structure of the N,N′-diphenylformamidine fragmentation product [RuCl(NH2Ph) {PhNC(H)NPh} (Me2SO)2]

Article abstract of DOI:10.1016/S0277-5387(01)00769-0

N,N′-Diphenylamidines, PhNC(R)NHPh (R = H, Me, Et, Ph), and 1,3-diaryltriazenes, ArNNNHAr (Ar = p -C₆H₄X, X = H, Cl, Me, OMe) react with ruthenium(II) complexes, [RuCl₂(C₇H₈)]_n, [RuCl₂(CO)₂]_n and [RuCl₂(Me₂SO)₄] in the presence of a base (NEt₃ or Na₂CO₃) to afford a selection of bis(chelate) products [Ru{PhNC(R)NPh}₂L₂] and [Ru(ArNNNAr)₂L₂] (L = CO, Me₂SO; L₂ = C₇H₈). In contrast one particular combination - [RuCl₂(Me₂SO)₄]/PhNC(H)NHPh/NEt₃ - in refluxing dimethylformamide yields a novel amidine fragmentation product [RuCl(NH₂Ph){PhNC(H)NPh}(Me₂SO)₂] which has been characterised by X-ray diffraction methods.

Full text of DOI:10.1016/S0277-5387(01)00769-0

Polyhedron 20 (2001) 1875–1880
www.elsevier.com/locate/poly
Amidinato and triazenido complexes of ruthenium(II):
X-ray crystal structure of the N,N%-diphenylformamidine
fragmentation product [RuCl(NH2Ph){PhNC(H)NPh}(Me2SO)2]ꢀ
Terry Clark, James Cochrane, Stephen F. Colson, Kausar Z. Malik,
Stephen D. Robinson *, Jonathan W. Steed
Department of Chemistry, King’s College London, Strand, London, WC2R 2LS, UK
Received 18 December 2000; accepted 28 February 2001
Abstract
N,N%-Diphenylamidines, PhNC(R)NHPh (R=H, Me, Et, Ph), and 1,3-diaryltriazenes, ArNNNHAr (Ar=p-C6H4X, X=H,
Cl, Me, OMe) react with ruthenium(II) complexes, [RuCl2(C7H8)]n, [RuCl2(CO)2]n and [RuCl2(Me2SO)4] in the presence of a base
(NEt3 or Na2CO3) to afford a selection of bis(chelate) products [Ru{PhNC(R)NPh}2L2] and [Ru(ArNNNAr)2L2] (L=CO,
Me2SO; L2=C7H8). In contrast one particular combination — [RuCl2(Me2SO)4]/PhNC(H)NHPh/NEt3 — in refluxing dimethyl-
formamide yields a novel amidine fragmentation product [RuCl(NH2Ph){PhNC(H)NPh}(Me2SO)2] which has been characterised
by X-ray diffraction methods. © 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Ruthenium; Amidinate; Triazenide; X-ray crystal structure
reactions, and has been characterised by X-ray diffrac-
tion methods.
1. Introduction
The reactions of ruthenium(II) complexes — notably
[RuCl2(CO)2]n [2], [RuCl2(Me2SO)4] [3], [RuCl2(PPh3)3]
[4] and [RuCl2(diene)]n [5,6] — with weak organic
2. Experimental
acids, XꢀYH, in the presence of a suitable base (NEt3,
Hydrated ruthenium trichloride was obtained from
anhydrous Na2CO3) have been widely employed as a
Johnson Matthey; dichloro-tetrakis(dimethylsulphox-
general route to ruthenium(II) bis(chelate) complexes of
ide)ruthenium(II) [9] and catena-dichloro(norbornadi-
ene)ruthenium(II) [10] were prepared by the literature
procedures. All other reagents were purchased from
Avocado. Reactions were performed under nitrogen
the form [Ru(X-Y)2L2] (XꢀYH=acetylacetone, salicy-
laldehyde, 2-mercaptopyridine, etc.; L=CO, Me2SO,
PPh3: L2=diene). In the course of our work on the
synthesis and characterisation of triazenido [7] and
unless specified otherwise, but products were worked up
amidinato [8] complexes of the platinum metals we
in open vessels. Instrumentation was described in a
have now employed the same general technique to
previous paper [11]. Infrared and NMR data are given
generate new bis(triazenido) and bis(amidinato) com-
plexes of ruthenium(II). An unexpected aniline contain-
in Tables 1 and 2, respectively.
ing product [RuCl(NH2Ph){PhNC(H)NPh}(Me2SO)2],
formed by fragmentation of N,N%-diphenylfor-
mamidine, has also been isolated from one of these
2.1. Bis(N,N%-diphenylbenzamidinato)norborna-
dieneruthenium(II)
Catena-dichloro(norbornadiene)ruthenium(II) (0.40
g, 1.5 mmol) was added to a stirred solution of N,N%-
diphenylbenzamidine (1.68 g, 5.88 mmol) in dimethyl-
formamide (10 ml), anhydrous sodium carbonate (0.5
ꢀ Complexes of the platinum metals. Part 53 [1].
* Corresponding author. Fax: +44-207-8482810.
E-mail address: stephen.robinson@ukgateway.net (S.D. Robinson).
0277-5387/01/$ - see front matter © 2001 Elsevier Science Ltd. All rights reserved.
PII: S0277-5387(01)00769-0

1876
T. Clark et al. / Polyhedron 20 (2001) 1875–1880
g) was added and the mixture heated under reflux for
10 min. After cooling the mixture was filtered and the
residue (Na2CO3/NaCl) washed with acetone until
white. The filtrate and washings were combined and the
acetone removed under reduced pressure. The remain-
ing dimethylformamide solution was diluted with
methanol (10 ml) and kept at −10°C for 4 h. Filtration
followed by successive washings with methanol, water,
methanol and light petroleum (60–80°), and drying in
vacuo gave a yellow powder (0.74 g, 67%); m.p. 256–
257°C. Anal. Found: C, 73.05; H, 5.25; N, 7.55. Calc.
for C45H38N4Ru: C, 73.45; H, 5.20; N, 7.60%.
The following were similarly prepared on the same
scale.
2.2. Bis(N,N%-diphenylformamidinato)norborna-
dieneruthenium(II)
Table 1
Selected infrared data
Amidinato complexes [Ru{PhNC(R)NPh}2L2]
As a yellow powder (50%); m.p. 190–192°C. Anal.
Found: C, 67.40; H, 5.0; N, 9.50. Calc. for C33H30N4-
Ru: C, 67.90; H, 5.2; N, 9.6%.
L
R
Ph
H
w(NCN)
1592
w(CO)
1/2C7H8
1596
Me
Et
Ph
1591
1592
1589
2.3. Bis(N,N%-diphenylacetamidinato)norborna-
dieneruthenium(II)
CO
2030, 1958
Triazenido complexes [Ru(ArNNNAr)2L2]
As a yellow powder (69%); m.p. 170–171°C. Anal.
Found: C, 68.45; H, 4.6; N. 9.05. Calc. for C35H34N4-
Ru: C, 68.7; H, 5.6; N, 9.15%.
L
Ar
w(NNN)
w(CO)
CO
Ph
1481,1284
1499, 1281
1483, 1298
2066, 2007
2067, 1998
2068, 2013
p-C6H4Me
p-C6H4Cl
2.4. Bis(N,N%-diphenylpropionamidinato)norborna-
dieneruthenium(II)
Table 2
Selected NMR data a
As a yellow powder (55%); m.p. 192–195°C. Anal.
Found: C, 69.15; H, 5.95; N, 8.7. Calc. for C37H38N4-
Ru: C, 69.45; H, 6.0; N, 8.75%.
Amidinato complexes [Ru{PhNC(R)NPh}2L2]
R=Ph, L2=C7H8: 1H, l 1.12(s), 3.01 (br), 3.71 (br), 4.16 (br),
C7H8; l 6.61–7.11 (m) C6H5: 13C, l 167.56 (s) NC(Ph)N
R=H, L2=C7H8: 1H, l 1.23 (s), 3.38 (br), 3.62 (br), 4.45 (br),
C7H8; l 6.87–7.25 (m) C6H5; l 8.39 (s) NCHN: 13C, l 155.44
(s) NC(H)N
2.5. cis-Bis(N,N%-diphenylbenzamidinato)-
dicarbonylruthenium(II)
R=Me, L2=C7H8: 1H, l 1.02 (s), 3.11 (br), 3.48 (br), 3.64 (br)
C7H8; l 6.81–7.24 (m) C6H5; l 1.95 (s) CH3; 13C, l 165.56 (s)
NC(Me)N
A solution of hydrated ruthenium trichloride (0.15 g,
0.6 mmol) in ethanol (10 ml) was heated under reflux in
a stream of carbon monoxide for 5 h. The resulting red
solution was cooled then triethylamine (0.5 g, 0.5
mmol) and N,N%-diphenylbenzamidine (0.48 g, 1.8
mmol) were added, and the mixture heated under reflux
for a further 2 h. The solution was cooled, filtered and
then evaporated to dryness under reduced pressure.
Crystallisation of the residue from dichloromethane–
methanol followed by successive washing with
methanol, water, methanol and light petroleum (60–
80°), and drying in vacuo gave green micro crystals
(0.21 g, 33%); m.p. 238–239°C. Anal. Found: C, 67.95;
H, 4.15; N, 7.95. Calc. for C40H30N4O2Ru: C, 68.65; H,
4.3; N, 8.0%.
R=Et, L2=C7H8: 1H, l 1.04 (s), 3.13 (br), 3.46 (br), 3.55 (br)
C7H8; l 6.78–7.25 (m) C6H5; l 0.76 (t) 3JHH=7.5 Hz, CH3; l
2.19 (d of q) 2JHH=14, 3JHH=7.5 and l 2.43 (d of q)
2JHH=14, 3JHH=7.5 Hz, CH2: 13C, l 170.91 (s) NC(Et)N
R=Ph, L=CO: 13C, l 169.87 (s) NC(Ph)N; 197.04 (s) CO
Amidinato complex [RuCl(NH2Ph){PhNC(H)NPh}(Me2SO)2]
1H, l 2.85 (s), 3.30 (s), 3.34 (s), 3.36 (s) CH3; l 8.25 (s)
NC(H)N; l 8.00 (s) NH2; l 6.75–7.50 (m) C6H5
Triazenido compounds [Ru(ArNNNAr)2L2]
Ar=Ph, L=CO: 1H l 7.11 (m) C6H5
Ar=p-C6H4CH3, L=CO: 1H l 2.23 (s), 2.38 (s) CH3; l 6.96,
7.19 (AX pattern, JAXꢀ9 Hz) C6H4CH3
Ar=p-C6H4Cl, L=CO: 1H l 7.26 (m) C6H4Cl
Ar=Ph, L=Me2SO: 1H 3.10 (s), 3.20 (s) CH3; 6.8–7.8 (m) C6H5
Ar=p-C6H4CH3, L=Me2SO: 1H l 2.20 (s), 2.35 (s) C6H4CH3; l
3.09 (s), 3.14 (s) (CH3)2SO; l 6.90, 7.03 (AX pattern, JAX=9
Hz) 7.14, 7.64 (AX pattern JAX=9 Hz) C6H4CH3
2.6. cis/trans-Bis(N,N%-diphenylbenzamidinato)-
dicarbonylruthenium(II)
Ar=p-C6H4OCH3, L=Me2SO: 1H l 3.10 (s), 3.20 (s) (CH3)2SO:
l 3.70 (s), 3.85 (s) OCH3; l 6.65, 7.05 (AX pattern, JAX=9
Hz) l 6.90, 7.70 (AX pattern, JAX=9 Hz) C6H4OCH3
Ar=p-C6H4Cl; L=Me2SO: 1H l 3.10 (s), 3.15 (s) CH3; l 7.01,
7.10 (AX pattern, JAX=9 Hz) l 7.33, 7.70 (AX pattern,
Similar reactions with shorter reflux times (10 and 40
min) yielded cis/trans mixtures in modest yields (21 and
33%, respectively). Heating these mixtures in refluxing
benzene for approximately 2 h gave complete conver-
sion to the cis isomer.
JAX=9 Hz) C6H4Cl
a s=singlet, d=doublet, t=triplet, q=quartet, m=multiplet,
br=broad ill-resolved pattern.

T. Clark et al. / Polyhedron 20 (2001) 1875–1880
1877
2.7. Bis(1,3-diphenyltriazenido)dicarbonylruthenium(II)
2.12. Bis(di-p-methoxyphenyltriazenido)-
bis(dimethylsulphoxide)ruthenium(II)
A solution of hydrated ruthenium trichloride (0.3 g,
1.2 mmol) in ethanol (15 ml) was heated under reflux in
a stream of carbon monoxide for 5 h. After cooling to
50°C, triethylamine (1 g, 10 mmol) was added, followed
by 1,3-diphenyltriazene (0.71 g, 3.6 mmol), and the
mixture was then heated under reflux in a carbon
monoxide atmosphere for a further 30 min. The
product which deposited over a period of 12 h, was
filtered off, washed with ice-cold ethanol and light
petroleum (60–80°) then dried in vacuo as red–brown
crystals (0.185 g, 28%); m.p. 197–199°C. Anal. Found:
C, 56.85; H, 3.65; N, 15.2. Calc. for C26H20N6O2Ru: C,
56.8; H, 3.65; N, 15.3%.
As yellow micro crystals (17%) Anal. Found: C, 49.7;
H, 5.1; N, 10.7. Calc. for C32H40N6O6RuS2: C, 49.95;
H, 5.25; N, 10.9%.
2.13. Anilinechloro(1,3-diphenylformamidinato)-
bis(dimethylsulphoxide)ruthenium(II)
Dichlorotetrakis(dimethylsulphoxide)ruthenium(II)
(0.36 g, 0.74 mmol), 1,3-diphenylformamidine (0.33 g,
1.68 mmol) and triethylamine (1 ml) were added to
dimethylformamide (10 ml). The mixture was heated
under reflux for 10 min, cooled and then evaporated to
dryness under reduced pressure. Crystallisation of the
residue from methanol–diethyl ether afforded yellow
crystals (0.11 g, 26%). Anal. Found: C, 47.2; H, 5.15; N,
7.0. Calc. for C23H30ClN3O2RuS2: C, 47.55; H, 5.2; N,
7.25%.
The following were similarly prepared on the same
scale.
2.8. Bis(1,3-di-p-tolyltriazenido)dicarbonylruthenium(II)
As orange–brown crystals (16.5%); m.p. 178–182°C.
Anal. Found: C, 59.4; H, 4.7; N, 13.75. Calc. for
C30H28N6O2Ru: C, 59.5; H, 4.65; N, 13.85%.
2.14. X-ray crystallography
The X-ray crystal structure of [RuCl(NH2Ph)-
{PhNC(H)NPh}(Me2SO)2] has been determined. Yel-
low crystals suitable for X-ray diffraction study were
grown from methanol–diethyl ether solution and were
mounted on thin glass fibres using a fast setting epoxy
resin. A total of 180 oscillation frames of 90 s exposure
time with 1° in ¥ were recorded using a Nonius Kappa
CCD diffractometer, with a detector to crystal distance
of 35 mm. The crystals were indexed for the first ten
frames using a DENZO package [12] and positional data
were refined along with diffractometer constants to give
the final unit cell parameters. Integration and scaling of
the whole data set resulted in a total of 8828 data (4893
unique) which were corrected for Lorentz and polarisa-
tion effects. The structure was solved using the direct
methods option of SHELXS-86 [13] and developed via
alternating least-squares cycles and difference Fourier
synthesis [SHELXL-97] [14] with the aid of the program
2.9. Bis(1,3-di-p-chlorophenyltriazenido)-
dicarbonylruthenium(II)
As orange–yellow micro crystals (37%); m.p. 193–
196°C. Anal. Found: C, 44.75; H, 2.0; N, 11.2. Calc for
C26H16Cl4N6O2Ru: C, 45.45; H, 2.35; N, 12.25%.
2.10. Bis(1,3-diphenyltriazenido)bis(dimethylsulphoxide)-
ruthenium(II)
Dichlorotetrakis(dimethylsulphoxide)ruthenium (0.30
g, 0.62 mmol), 1,3-diphenyltriazene (0.29 g, 1.47 mmol)
and triethylamine (1 ml) were added to dimethylfor-
mamide (10 ml). The mixture was heated under reflux
for 10 min, then filtered while hot, diluted with
methanol (10 ml) and set aside for 48 h at 0°C to
crystallise. Recrystallisation from dichloromethane–
methanol afforded brown crystals (0.28 g, 84%). Anal.
Found: C, 50.8; H, 5.15; N, 12.85. Calc. for
C28H32N6O2RuS2; C, 51.75; H, 4.95; N, 12.95%.
The following were similarly prepared on the same
scale.
RES2INS [15]. All non-hydrogen atoms were modelled
anisotropically, while hydrogen atoms were assigned an
isotropic parameter 1.2 times (1.5 times for CH3
groups) that of the parent atom and allowed to ride.
Crystal data and structural refinement details are given
in Table 3.
2.11. Bis(di-p-tolyltriazenido)bis(dimethylsulphoxide)-
ruthenium(II)
3. Results and discussion
Catena-Dichloro(norbornadiene)ruthenium(II) reacts
with N,N%-diphenylamidines and anhydrous sodium
carbonate in refluxing dimethylformamide to afford the
yellow air-stable complexes [Ru{PhNC(R)NPh}2-
As yellow felted needles (75%). Anal. Found: C,
54.45; H, 5.65; N, 11.9. Calc. for C32H40N6O2RuS2; C,
54.45; H, 5.7; N, 11.9%.

1878
T. Clark et al. / Polyhedron 20 (2001) 1875–1880
Table 3
ppm. Norbornadiene is known to be a strong chelating
ligand and all attempts to dislodge it from the amidi-
nato complexes using molten triphenylphosphine and
bis(diphenyl-phosphino)ethane in boiling toluene were
unsuccessful.
Crystal data and structure refinement for [RuCl(NH2Ph){PhNC-
(H)NPh}(Me2SO)2]
Empirical formula
Formula weight
Temperature (K)
Wavelength (A)
Crystal system
Space group
C23H30ClN3O2RuS2
581.14
173 (2)
0.71070
monoclinic
P21/n
The red solution obtained by carbonylating ruthe-
nium trichloride in ethanol [19] reacted with N,N-
diphenylbenzamidine and triethylamine in boiling
ethanol over a period of 2 h to yield cis-[Ru{PhNC-
(Ph)NPh}2(CO)2]. When a shorter reaction time was
employed (10–40 min) mixtures of cis and trans isomers
were obtained. The infrared spectrum of the cis isomer
displayed bands at 2030, 1958 and 1589 cm−1 at-
tributable to w(CO)asym, wCOsym and w(NCN), respec-
tively. The proton NMR spectrum contained three sets
of phenyl resonances consistent with the presence of
asymmetrically coordinated N,N%-diphenylbenzamidi-
nato ligands (see above). The 13C NMR spectrum in-
cluded resonances at 197.04 and 169.87 ppm
attributable to CO and NCN carbon atoms, respec-
tively. The cis/trans isomer mixture displayed an extra
infrared band at 1902 cm−1 [w(CO)] and additional 13C
NMR resonances at 203.30 (CO) and 169.77 ppm
(NCN).
,
Unit cell dimensions
,
a (A)
11.0654 (5)
14.4607 (4)
16.3889 (9)
109.558 (2)
2471.14 (19)
4
1.562
0.937
1192
0.30×0.25×0.20
3.43–27.49
−14BhB14, −16BkB16,
−20BlB20
8828
4893 [Rint=0.0301]
full-matrix, least-squares on F2
4893/0/296
,
b (A)
,
c (A)
i (°)
3
,
V (A )
Z
Dcalc (Mg m−3
)
Absorption coefficient (mm−1
F(000)
)
Crystal size (mm)
q Range (°)
Index ranges
Reflections collected
Independent reflections
Refinement method
Data/restraints/parameters
Goodness-of-fit on F2
Final R indices [I\2|(I)]
R indices (all data)
1.037
R1=0.0293, wR2=0.0676
R1=0.0360, wR2=0.0705
0.0029(4)
Similar reactions of the red carbonylated ruthenium
trichloride solution with 1,3-diaryltriazenes in the pres-
ence of triethylamine afforded the triazenido complexes
cis-[Ru(ArNNNAr)2(CO)2] in modest yield as air stable
orange–brown crystalline solids. Confirmation of the
cis stereochemistry is provided by infrared bands at
approximately 2067 and approximately 2000 cm−1 at-
tributable to w(CO)asym and w(CO)sym, respectively. Also
Extinction coefficient
Largest difference peak and hole 0.506 and −0.802
−3
,
(e A
)
(C7H8)] (R=H, Me, Et, Ph) in fair yield. Their infrared
spectra (Table 1) show the absorptions expected for
coordinated norbornadiene and amidinate ligands. In
particular the w(NH) absorption of the free amidines at
approximately 3200 cm−1 is absent and the absorption
attributed to w(NCN) [16] is shifted from approximately
1620 to approximately 1590 cm−1. The 1H and 13C
NMR data (Table 2) are consistent with the cis stereo-
chemistry imposed by the chelate norbornadiene lig-
ands. The two amidinate ligands in each complex are
equivalent; however, they are bound in asymmetric
environments and consequently display two sets of
phenyl resonances in each case. The formamidinato and
1
the presence of two singlets of equal intensity in the H
NMR spectrum of the di-p-tolyltriazenido complex,
attributable to methyl groups in two different environ-
ments, is indicative of cis rather than trans
stereochemistry.
Mixtures of [RuCl2(Me2SO)4], 1,3-diaryltriazene and
triethylamine when heated briefly in refluxing dimethyl-
formamide afford solutions from which the complexes
[Ru(ArNNNAr)2(Me2SO)2] can be isolated in good
yield as air-stable yellow-brown crystalline solids. For
each complex the proton NMR spectra reveal the pres-
ence of non-equivalent aryl and methyl groups, thereby
establishing cis-stereochemistry rather than the trans
alternative. Thus all three complexes display a pair of
equal intensity singlets arising from non-equivalent
methyl groups in each dimethylsulphoxide ligand. In
addition the 1,3-di-p-tolyltriazenido complex shows a
second pair of equal intensity singlets arising from the
non-equivalent methyl groups of each triazenide ligand.
Likewise the aromatic protons in each complex give rise
to two sets of signals of equal intensity.
1
acetamidinato complexes display singlet H resonances
at l 8.39 and 1.95 attributable to the NC(H)N [17] and
NC(CH3)N protons, respectively. For the propionamid-
inato complexes an ABX3 pattern characteristic of
NC(CH2CH3)N groups containing diastereotrophic
methylene protons is observed. A third set of phenyl
proton resonances arising from the NC(C6H5)N group
is seen in the spectrum of the benzamidinato complex.
Three of the four complexes display 13C resonances in
the range 165–171 ppm attributable to the central
carbon atoms in the NC(R)N groups [18], the for-
mamidinato complex has a similar resonance at 155
The reaction of N,N%-diphenylformamidine with
[RuCl2(Me2SO)4] in the presence of triethylamine took
a very different course to that involving 1,3-diphenyltri-

T. Clark et al. / Polyhedron 20 (2001) 1875–1880
1879
azene (see above). The yellow air-stable product iso-
lated in modest yield had spectroscopic properties
which did not conform to those expected for a
bis(N,N%-diphenylformamidinato) formulation. In addi-
tion to bands characteristic of N,N%-diphenylformamid-
inate and dimethylsulphoxide ligands, the infrared
spectrum displayed a w(NH2) absorption at approxi-
mately 3400 cm−1. The proton NMR spectrum con-
tained singlet resonances attributable to four different
methyl groups and, in addition to the expected singlet
resonance for NCHN at l 8.25, another singlet at l
8.00 tentatively assigned to NH2 protons. In order to
firmly establish the structure and stereochemistry of this
complex an X-ray diffraction study was undertaken.
This revealed octahedral coordination geometry about
ruthenium(II) (Fig. 1) with a chelate N,N%-diphenylfor-
mamidinate trans to chloride and dimethylsulphoxide
ligands, and an aniline moiety trans to a second
dimethylsulphoxide ligand. This structure with two dis-
similar dimethylsulphoxide ligands each with a pair of
non-equivalent methyl groups is fully in accord with the
NMR data. Bond length and bond angle data are given
in Table 4. Metal–ligand bond lengths found are within
the range expected for octahedral ruthenium(II). As
expected the major deviation from regular octahedral
coordination is enforced by the small bite angle
[61.74(7)°] of the formamidinate ligand. The formation
of an aniline-containing product in the above reaction
merits some comment. Cleavage of N,N%-diphenylfor-
mamidine and coordination of the resulting fragments
is a well-established phenomenon [20]. However to the
best of our knowledge no such reaction leading to
generation of coordinated aniline has previously been
reported. Formation of aniline in the present reaction
was particularly unexpected since the corresponding
reaction involving 1,3-diaryltriazenes, molecules known
to cleave off arylamines rather readily [21], afforded
simple bis(1,3-diaryltriazenido) complexes in good
yield.
4. Supplementary material
Crystallographic data for the structural analysis has
been deposited with the Cambridge Crystallographic
Data Centre, CCDC No. 153620. Copies of this infor-
mation may be obtained free of charge from The
Director, CCDC, 12 Union Road, Cambridge CB2
1EZ, UK. (fax: +44-1223-336033; e-mail: deposit@
ccdc.cam.ac.uk or www: http://www.ccdc.cam.ac.uk.
Fig. 1. Molecular structure of [RuCl(NH2Ph){PhNC(H)NPh}-
(Me2SO)2] showing atom numbering scheme.
Table 4
,
Selected bond length (A) and bond angles (°) data for
{RuCl(NH2Ph){PhNC(H)NPh}(Me2SO)2]
References
Bond lengths
[1] S.D. Robinson, A. Sahajpal, J.W. Steed, Inorg. Chim. Acta 306
(2000) 205.
[2] J.V. Kingston, T.W.S. Jamieson, G. Wilkinson, J. Inorg. Nucl.
Chem. 29 (1967) 133.
[3] V. Ravindar, P. Lingaiah, K.V. Reddy, Inorg. Chim. Acta 87
(1984) 35.
[4] F.H. Jardine, Prog. Inorg. Chem. 31 (1984) 265 (and references
therein).
[5] P. Powell, J. Organomet. Chem. 65 (1974) 89.
[6] E.C. Constable, J. Lewis, J. Organomet. Chem. 254 (1983) 105.
[7] S.F. Colson, S.D. Robinson, Polyhedron 9 (1990) 1737.
[8] T. Clark, S.D. Robinson, M.A. Mazid, M.B. Hursthouse, Poly-
hedron 12 (1994) 175.
[9] I.P. Evans, A. Spencer, G. Wilkinson, J. Chem. Soc., Dalton
Trans. (1973) 204.
[10] E.W. Abel, M.A. Bennett, G. Wilkinson, Chem. Ind. (1959)
1516.
RuꢀN(1)
RuꢀN(2)
RuꢀN(3)
RuꢀS(1)
RuꢀS(2)
RuꢀCl
S(1)ꢀO(1)
S(1)ꢀC(2)
S(1)ꢀC(1)
2.1588(18)
2.107(2)
S(2)ꢀO(2)
S(2)ꢀC(3)
S(2)ꢀC(4)
N(1)ꢀC(5)
N(1)ꢀC(12)
N(2)ꢀC(5)
N(2)ꢀC(6)
N(3)ꢀC(18)
1.4887(16)
1.782(3)
1.788(2)
1.326(3)
1.404(3)
1.324(3)
1.410(3)
1.446(3)
2.1907(19)
2.2282(5)
2.2144(6)
2.4147(6)
1.4908(17)
1.788(2)
1.792(2)
bond angles
N(2)ꢀRuꢀN(1)
N(2)ꢀRuꢀN(3)
N(1)ꢀRuꢀN(3)
N(2)ꢀRuꢀS(2)
N(1)ꢀRuꢀS(2)
N(3)ꢀRuꢀS(2)
N(2)ꢀRuꢀS(1)
N(1)ꢀRuꢀS(1)
61.95(7)
88.12(8)
90.13(7)
93.95(5)
89.10(5)
177.13(5)
105.53(5)
167.36(6)
N(3)ꢀRuꢀS(1)
S(2)ꢀRuꢀS(1)
N(2)ꢀRuꢀCl
N(1)ꢀRuꢀCl
N(3)ꢀRuꢀCl
S(2)ꢀRuꢀCl
S(1)ꢀRuꢀCl
87.60(5)
93.75(2)
163.60(5)
102.91(6)
85.51(6)
91.96(2)
89.31(2)
[11] S.D. Robinson, A. Sahajpal, D.A. Tocher, J. Chem. Soc., Dal-
ton Trans. (1995) 3497.
[12] Z. Otwinowski, W. Minor, Methods Enzymol. 276 (1996) 307.

1880
T. Clark et al. / Polyhedron 20 (2001) 1875–1880
[13] G.M. Sheldrick, SHELXS-86, Program for the solution of crystal
structure, University of Go¨ttengen, 1986.
[18] J. Barker, M. Kilner, R.O. Gould, J. Chem. Soc., Dalton Trans.
(1987) 2687.
[14] G.M. Sheldrick, SHELXL-97, Program for the refinement of
crystal structure, University of Go¨ttengen, 1997.
[19] J. Chatt, B.L. Shaw, A.E. Field, J. Chem. Soc. (1964)
3466.
[15] L.J. Barbour, RES
2
INS, University of Missouri-Columbia, 1995.
[20] F.A. Cotton, L.M. Daniels, J.H. Matonic, X. Wang, C.A.
Murillo, Polyhedron 16 (1997) 1177.
[21] S.F. Colson, S.D. Robinson, M. Motevalli, M.B. Hursthouse,
Polyhedron 7 (1988) 1919.
[16] J. Barker, M. Kilner, Cord. Chem. Rev. 133 (1994) 219.
[17] L.D. Brown, S.D. Robinson, A. Sahajpal, J.A. Ibers, Inorg.
Chem. 16 (1977) 2728.
.