Thiourea monoanion and dianion complexes of rhodium(III) and ruthenium(II)

Article abstract of DOI:10.1016/S0020-1693(02)01017-4

The versatility of deprotonated thioureas as ligands is shown by the synthesis and characterisation of a range of rhodium(III) complexes of substituted thioureas, with support from a ruthenium(II) analogue in one case. Reaction of the complexes [LMCl(μ-Cl)]₂ [M=Rh, L=η⁵-C₅Me₅ (Cp*); M=Ru, L=η⁶-p-cymene] with Na[MeNHC(S)NCN] and excess trimethylamine base gives the dinuclear complexes [LM{SC(=NCN)NMe}]₂ containing chelate-bridging thiourea dianion ligands. The Ru complex was characterised by an X-ray diffraction study. The mononuclear complexes [Cp*Rh{SC(=NCN)NMe}(PPh₃)] and [Cp*Rh{SC(=NPh)NPh}(PPh₃)], containing chelating thiourea dianion ligands, were prepared by analogous reactions in the presence of triphenylphosphine. Reaction of [Cp*Rh{SC(=NCN)NMe}(PPh₃)] with HCl, or [Cp*RhCl(μ-Cl)]₂ with 2 equiv. of PPh₃ and Na[MeNHC(S)NCN] (with no added base) gave the complex [Cp*RhCl{SC(=NCN)NHMe}(PPh₃)], containing a (monodentate) S-bonded thiourea monoanion ligand, which was characterised by an X-ray diffraction study. The AsPh₃ and SbPh₃ analogues of this complex were also prepared and characterised. Reaction of [Cp*RhCl(μ-Cl)]₂ with 2 equiv. of PPh₃ or SbPh₃ and PhNHC(S)NHPh or various trisubstituted thioureas PhNHC(S)NR₁R₂, triethylamine and NaBPh₄ gave a range of cationic complexes [Cp*Rh{SC(=NR¹R²)NPh}(EPh₃)] ⁺ (E=P, Sb), as their tetraphenylborate salts, in which the thiourea is bonded as a monoanion through the S and the NPh group. The corresponding reaction utilising 1,6-bis(diphenylphosphino)hexane (dpph) gave the dinuclear complex [Cp*Rh{SC(=N(CH₂CH₂)₂O)NPh}] ₂(μ-η²-dpph) (BPh₄)₂.

Full text of DOI:10.1016/S0020-1693(02)01017-4

Inorganica Chimica Acta 338 (2002) 210ꢂ218
/
www.elsevier.com/locate/ica
Thiourea monoanion and dianion complexes of rhodium(III) and
ruthenium(II)
William Henderson *, Brian K. Nicholson, Maarten B. Dinger, Rachel L. Bennett
Department of Chemistry, University of Waikato, Private Bag 3105, Hamilton, New Zealand
Received 22 February 2002; accepted 24 April 2002
Abstract
The versatility of deprotonated thioureas as ligands is shown by the synthesis and characterisation of a range of rhodium(III)
complexes of substituted thioureas, with support from a ruthenium(II) analogue in one case. Reaction of the complexes [LMCl(m-
Cl)]2 [Mꢀ
the dinuclear complexes [LM{SC(Ä
characterised by an X-ray diffraction study. The mononuclear complexes [Cp*Rh{SC(Ä
NPh)NPh}(PPh3)], containing chelating thiourea dianion ligands, were prepared by analogous reactions in the presence of
triphenylphosphine. Reaction of [Cp*Rh{SC(ÄNCN)NMe}(PPh3)] with HCl, or [Cp*RhCl(m-Cl)]2 with 2 equiv. of PPh3 and
NCN)NHMe}(PPh3)], containing a (monodentate) S-
/
Rh, Lꢀ
/
h5-C5Me5 (Cp*); Mꢀ
/
Ru, Lꢀ
NCN)NMe}]2 containing chelate-bridging thiourea dianion ligands. The Ru complex was
NCN)NMe}(PPh3)] and [Cp*Rh{SC(Ä
/
h6-p-cymene] with Na[MeNHC(S)NCN] and excess trimethylamine base gives
/
/
/
/
Na[MeNHC(S)NCN] (with no added base) gave the complex [Cp*RhCl{SC(Ä
/
bonded thiourea monoanion ligand, which was characterised by an X-ray diffraction study. The AsPh3 and SbPh3 analogues of this
complex were also prepared and characterised. Reaction of [Cp*RhCl(m-Cl)]2 with 2 equiv. of PPh3 or SbPh3 and PhNHC(S)NHPh
or various trisubstituted thioureas PhNHC(S)NR1R2, triethylamine and NaBPh4 gave a range of cationic complexes [Cp*Rh{SC(Ä
/
NR1R2)NPh}(EPh3)]ꢁ (Eꢀ
and the NPh group. The corresponding reaction utilising 1,6-bis(diphenylphosphino)hexane (dpph) gave the dinuclear complex
/P, Sb), as their tetraphenylborate salts, in which the thiourea is bonded as a monoanion through the S
[Cp*Rh{SC(Ä
N(CH2CH2)2O)NPh}]2(m-h2-dpph) (BPh4)2.
/
# 2002 Elsevier Science B.V. All rights reserved.
Keywords: Crystal structures; Rhodium complexes; Ruthenium complexes; Thiourea complexes
1. Introduction
bonding either as a monodentate ligand through sulfur,
or as a chelating ligand through sulfur and nitrogen [6].
We subsequently wished to investigate the reactions of
Thioureas are potentially very versatile ligands, able
to coordinate to a range of metal centres as either
neutral ligands [1], monoanions [2] or dianions [3,4]. In
addition, the hard nitrogen and soft sulfur donor atoms
provide a multitude of bonding possibilities. We have
been investigating the coordination chemistry of the
thiourea MeNHC(S)NH(CN), which is commercially
available as its monosodium salt. From this thiourea,
platinum(II) complexes have been prepared which con-
tain the thiourea bonding as a dianion through the S
and NMe groups [5] or containing the monoanion
thioureas with other transitionꢂmetal halide complexes.
/
In this paper, we report our studies of rhodium(III) and
ruthenium(II) complexes with the thiourea salt
Na[MeNHC(S)NCN] under different conditions. Some
complexes containing thiourea monoanion ligands of
both rhodium(III) and ruthenium(II) have been de-
scribed previously. Thus, the rhodium(III) complex
[Cp*RhCl{PhN(CÃ
ing a chelated thiourea monoanion, was prepared by
reaction of the complex [Cp*RhCl(CO)(TolNÃCHÄ
/
N(Tol)(CHÄ/NTol))S}] (1) contain-
/
/
NTol)] with PhNCS [7]. For ruthenium, reactions of
the complexes RuHCl(CO)(PPh3)3, RuH2(CO)(PPh3)3
or RuCl2(PPh3)3 with PhNHC(S)NHPh have been
reported to give complexes containing the chelating
PhNC(NHPh)S monoanion ligand [8].
* Corresponding author. Tel.: ꢁ
4219
E-mail address: w.henderson@waikato.ac.nz (W. Henderson).
/
64-7-856 4656; fax: ꢁ64-7-838
/
0020-1693/02/$ - see front matter # 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 0 - 1 6 9 3 ( 0 2 ) 0 1 0 1 7 - 4

W. Henderson et al. / Inorganica Chimica Acta 338 (2002) 210ꢂ
/218
211
dimeric nature of the complex, with two h6-p-cymene
ruthenium groups linked by two thiourea dianion
ligands. Selected bond lengths and angles for the
structure are given in Table 1. The thiourea chelates to
one ruthenium through the sulfur and N-methyl groups,
with the sulfurs then bridging to the second ruthenium
atom, forming a four-membered RuÃ
/
SÃ
/
RuÃ
/
S ring
system. The structure bears a strong resemblance to
that of related compounds such as [Cp*Rh(4-methyl-
2ꢁ
pyrimidine-2-thionate)]2
CÃ
which contains a [RhÃ
/
NÃ
/
/
S]2 sulfur-bridged dinuclear unit [9].
The Ru2S2 ring of 3 is puckered, with the two sulfur
atoms defining an angle of 1598 about the RuÁ Á ÁRu
vector. This contrasts with related dinuclear sulfur-
bridged structures such as [(h6-C6H3Me3)Ru{SC-
Me2CH(CO2H)NH2}2]2 [10], where the central Ru2S2
core is essentially planar. The cymene ligands adopt a
cis arrangement about the Ru2S2 core, similar to the
2. Results and discussion
arrangement
2ꢁ
in
[9] and [(h6-C6H3Me3)Ru{SCMe2CH-
S distances of 3
[Cp*Rh(4-methylpyrimidine-2-
2.1. Thiourea dianion-bridged dinuclear complexes
thionate)]2
(CO2H)NH2}2]2 [10]. All of the RuÃ
/
The reaction of the dimeric rhodium complex
[Cp*RhCl(m-Cl)]2 with 2 equiv. of the thiourea salt
Na[MeNHC(S)NCN] and excess trimethylamine in hot
methanol, followed by addition of water and slow
are essentially equal in length [range 2.3985(10)ꢂ
/
˚
2.4285(10) A], indicating symmetrical bridging of the
sulfur atoms. Bond distances within the two thiourea
ligands of 3 are very comparable to those in the related
mononuclear platinum(II) complex [Pt{SC(NCN)-
evaporation gives [Cp*Rh{SC(Ä/NCN)NMe}]2 (2) as a
red crystalline solid. In an analogous manner, the
dinuclear ruthenium complex [(h6-p-cymene)RuCl(m-
NMe}(cod)] (codꢀ
/1,5-cyclo-octadiene), which also
Cl)]2 gave the complex [(h6-p-cymene)Ru{SC(Ä
/
Table 1
Selected bond lengths (A) and angles (8) for [(h6-p-cymene)-
Ru{SC(ÄNCN)NMe}]2 (3)
NCN)NMe}]2 (3) as an orange crystalline solid. The
complexes give ions at m/z 703 (Rh) and 699 (Ru) in
their positive-ion electrospray ionisation (ES) mass
˚
spectra, assigned to the [Mꢁ
H]ꢁ ions of the dimeric
species. At higher cone voltages, fragmentation of the
dimer to monomer occurs. Thus, for example, the ion
/
Bond lengths
Ru(1)ÃN(21)
Ru(1)ÃS(1)
Ru(2)ÃS(1)
S(1)ÃC(11)
N(11)ÃC(11)
N(12)ÃC(13)
N(13)ÃC(13)
N(21)ÃC(22)
N(22)ÃC(21)
RuÃCring
2.067(3)
2.4164(11)
2.3985(10)
1.797(3)
1.309(4)
1.335(5)
1.160(5)
1.474(4)
1.335(4)
Ru(2)ÃN(11)
Ru(1)ÃS(2)
Ru(2)ÃS(2)
S(2)ÃC(21)
N(11)ÃC(12)
N(12)ÃC(11)
N(21)ÃC(21)
N(22)ÃC(23)
N(23)ÃC(23)
2.084(3)
2.4285(10)
2.4263(10)
1.800(3)
1.458(4)
1.343(4)
1.301(4)
1.322(5)
1.162(5)
[Cp*Rh{SC(Ä
/
NCN)NMe}ꢁ
H]ꢁ (m/z 352) is observed
with increasing intensity at higher cone voltages (70%
relative intensity at a cone voltage of 70 V).
/
In one preparation of the ruthenium complex, single
crystals suitable for an X-ray diffraction study were
obtained. The molecular structure (Fig. 1) confirms the
2.167(3)ꢂ
/
2.238(3)
Bond angles
N(21)ÃRu(1)ÃS(1)
S(1)ÃRu(1)ÃS(2)
N(11)ÃRu(2)ÃS(2)
C(11)ÃS(1)ÃRu(2)
Ru(2)ÃS(1)ÃRu(1)
C(21)ÃS(2)ÃRu(1)
C(11)ÃN(11)ÃC(12) 121.6(3)
C(12)ÃN(11)ÃRu(2) 132.1(2)
C(21)ÃN(21)ÃC(22) 121.9(3)
C(22)ÃN(21)ÃRu(1) 131.4(2)
N(11)ÃC(11)ÃN(12) 128.5(3)
90.49(8)
80.14(3)
91.04(8)
80.64(11)
98.53(3)
79.26(11)
N(21)ÃRu(1)ÃS(2)
N(11)ÃRu(2)ÃS(1)
S(1)ÃRu(2)ÃS(2)
C(11)ÃS(1)ÃRu(1)
C(21)ÃS(2)ÃRu(2)
Ru(2)ÃS(2)ÃRu(1)
C(11)ÃN(11)ÃRu(2) 106.2(2)
C(13)ÃN(12)ÃC(11) 115.2(3)
C(21)ÃN(21)ÃRu(1) 106.6(2)
C(23)ÃN(22)ÃC(21) 118.3(3)
N(11)ÃC(11)ÃS(1)
N(13)ÃC(13)ÃN(12) 176.3(4)
N(21)ÃC(21)ÃS(2) 106.8(2)
N(23)ÃC(23)ÃN(22) 172.5(4)
67.23(8)
67.19(8)
80.54(3)
107.96(11)
107.96(11)
97.44(3)
105.8(2)
N(12)ÃC(11)ÃS(1)
N(21)ÃC(21)ÃN(22) 126.3(3)
N(22)ÃC(21)ÃS(2) 126.8(3)
125.6(3)
Fig. 1. Molecular structure and atom numbering scheme of [(h6-p-
cymene)Ru{SC(ÄNCN)NMe}]2 (3).
/

212
W. Henderson et al. / Inorganica Chimica Acta 338 (2002) 210ꢂ218
/
contains the same thiourea dianion ligand [5]. The
cyanide group lies on the same side of the ligand as
the sulfur, as observed in all other structurally char-
acterised complexes of this ligand [5,6].
The 1H NMR spectrum of 2 shows a single Cp*
resonance at d 1.76 together with an NMe resonance at
d 2.96. For the ruthenium complex 3, the two isopropyl
methyl resonances of the p-cymene ligand are inequi-
valent (d 1.28 and 1.24) as a result of metal-centred
chirality. The four aromatic protons of this ligand also
appear as four separate resonances (at d 5.56, 5.34, 5.31
and 5.20) for the same reason.
slightly low C analyses for several independent prepara-
tions of the complex. However, additional supporting
characterisation data provide strong support to the
formulation of this complex. It is assumed that complex
4 has a coordinated NMe group, analogous to 3, and
previously prepared platinum analogues [5].
Complexes 4 and 5 give the expected [Mꢁ
their positive-ion ES mass spectra at low cone voltages.
NPh)NPh}(PPh3)]
/
H]ꢁ ions in
The ES spectrum of [Cp*Rh{SC(Ä
/
(5) is highly dependent on the cone voltage, as illustrated
in Fig. 2. At a low cone voltage (20 V, Fig. 2(a)) the
[Mꢁ
cone voltage to 40 V, Fig. 2(b), results in loss of the
labile PPh3 ligand giving [MꢁHꢃ
PPh3]ꢁ, while a
further increase to 80 V, Fig. 2(c), results in fragmenta-
/
H]ꢁ ion is observed exclusively. Increasing the
/
/
2.2. Mononuclear complexes with chelating thiourea
dianions
tion of the thiourea ligand giving [Mꢁ
/
Hꢃ
/
PPh3ꢃ
/
PhNCS]ꢁ, i.e. [Cp*RhNHPh]ꢁ. Similar loss of phos-
phine ligands from related rhodium(III) dioxolene
complexes, which also contain Cp* ligands, has been
noted previously [11].
Reaction of [Cp*RhCl(m-Cl)]2 with 2 equiv. of each of
triphenylphosphine and Na[MeNHC(S)NCN] or
PhNHC(S)NHPh with added triethylamine base gives
the mononuclear complexes 4 and 5, respectively, which
contain chelated thiourea dianion ligands. Complex 4 is
isolated as a yellow solid, while 5 is red-brown.
Satisfactory microanalytical data were obtained for 5;
however complex 4 gave good H and N analyses, but
The 31P NMR spectral features of these complexes are
as expected, with single resonances showing the expected
1
coupling to 103Rh (complex 4, d 40.4, J(RhP) 153 Hz;
1
complex 5, d 40.6, J(RhP) 158 Hz).
2.3. Mononuclear complexes with the monodentate S-
bonded thiourea monoanion [MeNHC(S)NCN]ꢃ
Reaction of a CDCl3 solution of 4 with 2 M aqueous
hydrochloric acid in an NMR tube, and monitored by
31P{1H} NMR spectroscopy, resulted in conversion of
the yellowꢂorange starting material to a new orange
/
1
species [d 31P 33.2, J(RhP) 140.1], which was subse-
quently shown to be the monodentate S-bonded
thiourea
monoanion
complex
[Cp*RhCl{SC(Ä
/
NCN)NHMe}(PPh3)] (6), which also contains a chloride
ligand. Under these conditions, there was no evidence
for complete loss of the thiourea ligand, by the absence
of a doublet at d 30.8 with 1J(RhP) 144.2 for
Cp*RhCl2(PPh3). Treatment of a CDCl3 solution of 6
with excess triethylamine resulted in regeneration of 4.
Complex 6 was also serendipitously obtained by at-
tempted recrystallisation of a sample of 4 from dichlor-
omethane that had not been distilled prior to use (and
therefore which presumably contained some HCl im-
Fig. 2. Positive-ion electrospray mass spectra (MeCNÃ
of [Cp*Rh{SC(ÄNPh)NPh}(PPh3)] (5) at cone voltages of (a) 20; (b)
40; and (c) 80 V.
/
H2O solvent)
/

W. Henderson et al. / Inorganica Chimica Acta 338 (2002) 210ꢂ
/
218
213
for
purity). Red single crystals of complex 6 suitable for an
X-ray diffraction study were thus obtained.
Table 2
Selected
˚
(A)
bond
lengths
and
angles
(8)
[Cp*RhCl{SC(ÄNCN)NHMe}(PPh3)] 6.CH2Cl2
The molecular structure of 6 is shown in Fig. 3
together with the atom numbering scheme; selected
bond lengths and angles are given in Table 2. The
complex has, in addition to a chloride ligand, a
triphenylphosphine, an h5-pentamethylcyclopentadienyl
ligand, and a thiourea monoanion bonded through the
Bond lengths
Rh(1)ÃC(4)
Rh(1)ÃC(6)
Rh(1)ÃC(8)
P(1)ÃC(21)
P(1)ÃC(41)
Rh(1)ÃCl(1)
N(1)ÃC(1)
N(2)ÃC(3)
N(3)ÃC(3)
2.225(2)
2.240(2)
2.178(2)
1.833(2)
1.842(2)
2.4281(6)
1.332(3)
1.332(4)
1.157(4)
Rh(1)Ã-C(5)
Rh(1)ÃC(7)
Rh(1)ÃP(1)
P(1)ÃC(31)
Rh(1)ÃS(1)
S(1)ÃC(1)
2.228(2)
2.237(2)
2.3434(6)
1.832(2)
2.3884(6)
1.748(2)
1.466(4)
1.334(3)
sulfur, i.e. RhÃ
/
SÃ
/
C(Ä
/
NÃ
/
CN)NHMe, giving the usual
N(1)ÃC(2)
N(2)ÃC(1)
piano-stool arrangement. The bond distances in the
thiourea ligand are comparable to those in the corre-
sponding platinum complex trans-[Pt{SÃ
CN)NHMe}2(PPh3)2] [6] and it is noteworthy that in
both 6 and trans-[Pt{SÃC(ÄNÃCN)NHMe}2(PPh3)2]
/
C(Ä
/
NÃ
/
Bond angles
P(1)ÃRh(1)ÃS(1)
S(1)ÃRh(1)ÃCl(1)
C(1)ÃN(1)ÃC(2)
N(1)ÃC(1)ÃN(2)
N(2)ÃC(1)ÃS(1)
86.310(19) P(1)ÃRh(1)ÃCl(1)
90.11(2)
109.69(9)
119.0(2)
/
/
/
97.47(2)
123.5(3)
117.9(2)
121.7(2)
C(1)ÃS(1)ÃRh(1)
C(3)ÃN(2)ÃC(1)
N(1)ÃC(1)ÃS(1)
N(3)ÃC(3)ÃN(2)
the hydrogen is on the NMe group (as opposed to the
alternative which would have an NH(CN) group), and
the geometry of the thiourea ligand is the same in all
120.39(19)
173.1(3)
cases, with the NÃ
/
CÅ
/
N group on the same side of the
S bond of 6 [1.748(2)
A] is notably shorter than those of 3 [1.797(3) and
ligand as the sulfur atom. The CÃ
/
complex 4. Using the same method, the corresponding
orange triphenylarsine 7 and triphenylstibine 8 com-
plexes were obtained in good yields and purities.
˚
˚
1.800(3) A], indicating a greater degree of CÃ
bond character in 6, while the CÃNHMe bond of 6
[1.332(3) A] is longer than those of 3 [1.309(4) and
/
S multiple
/
It is noteworthy that the positive-ion ES mass
spectrum of the chloride complex 6 pays a strong
resemblance to that of the dianion complex 4, with
chloride loss from 6 producing an ion with the same m/z
value as the ion formed by protonation of 4. In a study
of the ES behaviour of a wide range of platinum group
metal halide complexes we found that loss of halide is
the dominant ionisation pathway for this type of
complex [12]. Furthermore, under gentle ionisation
conditions, solvated ions are typically observed, with
the neutral solvent molecule replacing the anionic
halide, producing a cationic solvated ion detectable by
the mass spectrometer. However, in the case of the
˚
˚
1.301(4) A]. A dichloromethane of crystallisation was
present in the structure of 6, weakly hydrogen bonded to
˚
N(3) [HÁ Á ÁN(3) 2.66 A], and the hydrogen on N(1) is
˚
weakly hydrogen bonded to Cl(1) [HÁ Á ÁCl(1) 2.4 A],
forming a six-membered metallacycle with six different
atoms (Rh, S, C, N, H, Cl).
A more systematic route for the synthesis of complex
6 involves the reaction of [Cp*RhCl(m-Cl)]2 with 2
equiv.
of
each
of
triphenylphosphine
and
Na[MeNHC(S)NCN] in methanol, which gives 6 in
good yield as an orange solid, which is less soluble in
methanol than the corresponding thiourea dianion
current rhodium halideꢂ
6ꢂ8 no such solvated ions were seen. Additionally, the
aggregate ion [2Mꢁ
H]ꢁ was observed with greater
/
thiourea monoanion complexes
/
/
intensity for the thiourea dianion complex 4 than for the
chloride complex 6. These observations suggest that
intramolecular cyclisation of the thiourea ligand occurs
to block solvent coordination.
The N-methyl group shows a distinct shift, from d
34.7 in the 13C NMR spectrum of the thiourea dianion
complex 4 to d 29.7 in 6, though interestingly there is an
insignificant change in the CÄ
/
N carbon chemical shift.
2.4. Mononuclear complexes with bidentate chelating
thiourea monoanions
Reaction of [Cp*RhCl(m-Cl)]2 with 2 equiv. of each of
triphenylphosphine and PhNHC(S)NHPh or the trisub-
stituted
PhNHC(S)NMe(CH2Anth) (Anthꢀ
PhNHC(S)NBz2 (BzꢀCH2Ph) in refluxing methanol
with added triethylamine base gives clear solutions,
thioureas
PhNHC(S)N(CH2CH2)2O,
/9-anthracenyl) or
Fig. 3. Molecular structure and atom numbering scheme of
/
[Cp*RhCl{SC(Ä
/
NCN)NHMe}(PPh3)] (6). The dichloromethane of
crystallisation is omitted for clarity.

214
W. Henderson et al. / Inorganica Chimica Acta 338 (2002) 210ꢂ218
/
from which the salts 9ꢂ/12 can be obtained by addition
positive-ion mode, using MeOH as the solvent and
mobile phase, unless otherwise stated. Assignment of
ions was assisted by comparison of experimental and
calculated isotope patterns, the latter obtained by means
of the Isotope program [13].
of NaBPh4 to the hot methanol solution. In the same
manner, the triphenylstibine complex 13, and the di-
nuclear complex 14 containing a bridging 1,6-bis(diphe-
nylphosphino)hexane (dpph) ligand can be obtained.
These complexes are analogous to those previously
reported for platinum(II) [6].
The complexes [Cp*RhCl(m-Cl)]2 [14] and [(h6-p-
cymene)RuCl(m-Cl)]2 [15] were prepared by the litera-
ture
procedures.
PhNHC(S)N(CH2CH2)2O,
PhNHC(S)NMe(CH2Anth) and PhNHC(S)NBz2 were
prepared by reaction of the appropriate secondary
amine with phenylisothiocyanate in Et2O [6].
Na[MeNHC(S)NCN] (N-methyl N?-cyanoisothiourea
sodium salt) (Aldrich), N,N?-diphenylthiourea (BDH),
NaBPh4 (BDH), Me3N (BDH) and aq. trimethylamine
solution (BDH, 25ꢂ30%) were used as supplied. Tri-
/
phenylphosphine (BDH), triphenylarsine (Fluka), tri-
phenylstibine (Aldrich) and 1,6-bis(diphenylphosphino)-
hexane (dpph) (Aldrich) were used as supplied. Reac-
tions were carried out in LR grade solvents with no
precautions to exclude air or moisture.
The complexes give excellent microanalytical data.
The 31P{1H} NMR spectrum for the diphenylthiourea
monoanion complex 12 gives a doublet at d 38.5
3.1. Synthesis of [Cp*Rh{SC(Ä
/
NCN)NMe}]2 (2)
1
showing a J(RhP) coupling constant of 149 Hz, these
values being significantly different to the corresponding
[Cp*RhCl(m-Cl)]2 (400 mg,
0.647 mmol),
1
thiourea dianion complex 5 [d 31P 40.6, J(RhP) 158
Hz]. Only a single isomer was observed for each complex
Na[MeNHC(S)NCN] (185 mg, 1.349 mmol) and aq.
Me3N (4 ml, excess) in MeOH (20 ml) were refluxed for
10 min giving a clear, deep red solution. Water (50 ml)
was added and the resulting clear solution allowed to
slowly evaporate at room temperature (r.t.), giving deep
red crystals of 2, which were filtered, washed with water
in their 31P NMR spectra. All of the cationic thiourea
complexes 9ꢂ
13 give the expected [M]ꢁ cations in their
positive-ion ES mass spectra at low cone voltages (e.g.
/
20 V). At higher cone voltages (e.g. 50 V) the neutral
EPh3 ligand is relatively easily lost, giving [Mꢃ
EPh3]ꢁ
ions. The dinuclear complex 14 behaved similarly, giving
/
(2ꢄ10 ml) and vacuum dried (205 mg, 45%). Further
/
concentration of the filtrate gave an additional 116 mg
of product which was spectroscopically identical to the
the [M]2ꢁ ion at low cone voltages (approximately 20
V) and at 40
V
the ions [Cp*Rh{SC(Ä
/
first crop, giving a total yield of 71%. M.p. ꢀ
(dec.), ꢀ300 8C. Anal. Found: C, 44.4; H, 5.25; N,
11.9. Calc. for C26H36N6Rh2S2: C, 44.45; H, 5.2; N,
/
140 8C
N(CH2CH2)2O)NPh}]ꢁ (m/z 459) and [Cp*Rh{SC(Ä
/
/
N(CH2CH2)2O)NPh}(PPh3)](dpph)]ꢁ (m/z 913).
3. Experimental
12.0%. ESMS: (cone voltage 20 V) [Mꢁ
100%), [2Mꢁ
H]ꢁ (m/z 1406, 30%); cone voltage 70 V,
[Cp*Rh{SC(ÄNCN)NMe}ꢁ
H]ꢁ (m/z 352, 70%), [Mꢁ
H]ꢁ (m/z 703, 100%), [2Mꢁ
NMR: d 2.96 (s, 3H, NMe) and 1.76 (s, 15H, Cp*).
/
H]ꢁ (m/z 703,
/
General experimental procedures were as described
previously [6]. NMR spectra were recorded in CDCl3
solution. Electrospray mass spectra were recorded in
/
/
/
1
/
H]ꢁ (m/z 1406, 55%). H

W. Henderson et al. / Inorganica Chimica Acta 338 (2002) 210ꢂ
/218
215
13C{1H} NMR: d 166.9 (s, br, CÅ
/
N), 118.7 (s, br, CÄ
/
petroleum spirits (5 ml) and dried under vacuum to give
5 as a redꢂbrown solid (90 mg, 71%). The complex
shows some solubility in Et2O. M.p. ꢀ180 8C (dec.).
N), 95.9 [d, Cp* C, 1J(RhC) 7.2], 34.8 (s, NMe) and 9.6
/
(s, Cp* Me).
/
Anal. Found: C, 67.5; H, 5.5; N, 3.85. Calc. for
C41H40N2PRhS: C, 67.8; H, 5.55; N, 3.85%. 31P{1H}
3.2. Synthesis of [(h6-p-cymene)Ru{SC(Ä
NCN)NMe}]2 (3)
/
1
1
NMR: d 40.6 [d, J(RhP) 158]. H NMR: d 7.44ꢂ
(m, Ph), 1.50 (d, Me, J 3). ESMS: (MeCNÃH2O), cone
voltage 20 V, [Mꢁ
H]ꢁ (m/z 727, 100%); cone voltage
40 V, [MꢁHꢃ
PPh3]ꢁ (m/z 465, 100%), [MꢁH]ꢁ (m/z
727, 80%); cone voltage 80 V, [Cp*RhNHPh]ꢁ (m/z
330, 100%), [MꢁHꢃ
PPh3]ꢁ (m/z 465, 90%), refer Fig.
2.
/7.13
/
[(h6-p-Cymene)RuCl(m-Cl)]2 (400 mg, 0.652 mmol)
was suspended in MeOH (25 ml), Na[MeNHC(S)NCN]
(200 mg, 1.46 mmol) and aq. Me3N (3 ml, excess) added,
and the mixture refluxed for 30 min giving a clear
/
/
/
/
/
/
orangeꢂbrown solution. Water (70 ml) was added and
/
the mixture cooled, giving an orange microcrystalline
precipitate, which was filtered, washed with water, and
3.5. Synthesis of [Cp*RhCl{SC(Ä
/
dried under vacuum to give 3 (410 mg, 90%). M.p. ꢀ
/
NCN)NHMe}(PPh3)] (6)
180 8C (dec.). Anal. Found: C, 44.2; H, 4.7; N, 12.1.
Calc for C26H34N6Ru2S2: C, 44.8; H, 4.9; N, 12.1%. IR
[Cp*RhCl(m-Cl)]2 (200 mg, 0.324 mmol) and triphe-
nylphosphine (169 mg, 0.645 mmol) were stirred in
MeOH (20 ml) for 5 min giving an orange suspension.
Na[MeNHC(S)NCN] (89 mg, 0.649 mmol) was added
and the mixture stirred for 24 h giving an orange
suspension. Water (30 ml) was added and the product
filtered, washed with water (10 ml) and Et2O (10 ml) and
dried under vacuum to give 6 as an orange microcrystal-
(KBr disk): 2153 (s, nCÅ
/
N), 1592 (vs, nCÄ
H]ꢁ (m/z 699, 100%),
H]ꢁ (m/z 1395, 60%). H NMR: d 5.56 [d, 1H,
/
N) cmꢃ1
.
ESMS: (cone voltage 40 V), [Mꢁ
/
1
[2Mꢁ
/
cymene, J(HH) 6], 5.34 [d, AB, 1H, cymene, J(HH) 6.3],
5.31 [d, AB, 1H, cymene, J(HH) 5.3], 5.20 [d, 1H,
cymene, J(HH) 5.4], 3.13 (s, NMe), 2.74 [m, CHMe2,
J(HH) 7], 2.29 (s, cymene Me), 1.28 [d, CHMeA, J(HH)
6.9] and 1.24 [d, CHMeB, J(HH) 6.9].
line solid (300 mg, 71%). M.p. 219ꢂ221 8C. Anal.
/
Found: C, 56.4; H, 5.2; N, 6.4. Calc. for
C31H34ClN3PRhS: C, 57.3; H, 5.3; N, 6.5%. The
complex is only slightly soluble in MeOH, in contrast
to the related metallacyclic complex 4. ESMS: cone
3.3. Synthesis of [Cp*Rh{SC(Ä
/
NCN)NMe}(PPh3)]
(4)
[Cp*RhCl(m-Cl)]2 (100 mg, 0.161 mmol) and triphe-
nylphosphine (85 mg, 0.324 mmol) were stirred in
MeOH (20 ml) for 5 min giving an orange suspension.
Na[MeNHC(S)NCN] (49 mg, 0.357 mmol) and Et3N (1
ml, excess) were added and the mixture refluxed for 70
min giving a clear orange solution. Water (70 ml) was
voltage 20 V, [Mꢃ
50 V, [MꢃClꢃ
PPh3]ꢁ (m/z 352, 100%), [Mꢃ
z 614, 30%). 31P{1H} NMR: d 33.2 [s, 1J(RhP) 140]. 1H
NMR: d 8.0 (m, br, NH), 7.59ꢂ7.33 (m, 15H, Ph), 2.70
[d, NMe, J(HH) 4.6] and 1.45 [d, 15H, Cp*, J 3.4].
13C{1H} NMR: d 178.8 [d, CÄ
N, J 5.9], 134.8ꢂ128.3
(m, PPh3), 120.0 (s, CÅN), 101.6 (m, Cp* C), 29.7 (s,
NMe) and 8.8 (s, Cp* Me).
/
Cl]ꢁ (m/z 614, 100%); cone voltage
Cl]ꢁ (m/
/
/
/
/
/
/
added giving a yellowꢂ
in ice, the solid was filtered, washed with water (2ꢄ
ml), and Et2O (10 ml) and dried under vacuum to give 4
as a yellow powder (125 mg, 63%). M.p. 188ꢂ190 8C.
/
orange precipitate. After cooling
/
/
20
/
3.6. Synthesis of [Cp*RhCl{SC(Ä
/
Anal. Found: C, 59.1; H, 5.5; N, 6.8. Calc. for
C31H33N3PRhS: C, 60.7; H, 5.4; N, 6.85%. ESMS:
NCN)NHMe}(AsPh3)] (7)
(cone voltage 20 V): [Mꢁ
[2Mꢁ
H]ꢁ (m/z 1227, 20%). 31P{1H} NMR: d 40.4 [d,
1J(RhP) 153]. 13C{1H} NMR: d 178.9 (s, CÄ
N), 134.1ꢂ
128.3 (m, Ph), 119.2 (s, CÅN), 99.2 (dd, Cp* C), 34.7 (s,
NMe) and 9.5 (s, Cp* Me).
/
H]ꢁ (m/z 614, 100%),
As for the synthesis of 6, [Cp*RhCl(m-Cl)]2 (200 mg,
0.324 mmol), triphenylarsine (197 mg, 0.644 mmol) and
Na[MeNHC(S)NCN] (89 mg, 0.650 mmol) in MeOH
(20 ml) gave an orange solution. Addition of water (30
ml) gave a milky orange precipitate which was stirred
for 24 h, filtered and the product washed with water (10
ml) and Et2O (10 ml) and vacuum dried to give 7 as an
/
/
/
/
3.4. Synthesis of [Cp*Rh{SC(Ä
/
NPh)NPh}(PPh3)]
(5)
orange powder (365 mg, 82%). M.p. 178ꢂ182 8C (dec.).
/
Anal. Found: C, 53.2; H, 4.9; N, 6.4. Calc. for
C31H34AsClN3RhS: C, 53.65; H, 4.9; N, 6.1%. 1H
A mixture of [Cp*RhCl(m-Cl)]2 (54 mg, 0.087 mmol),
triphenylphosphine (46 mg, 0.176 mmol) and N,N?-
diphenylthiourea (40 mg, 0.175 mmol) in MeOH (10 ml)
was refluxed for 5 min, cooled to r.t. and water (25 ml)
NMR: d 8.30ꢂ
and 1.26 (s, 15H, Cp*). ESMS: cone voltage 20 V, [Mꢃ
Cl]ꢁ (m/z 658, 100%); cone voltage 50 V, [Mꢃ
Clꢃ
AsPh3]ꢁ (m/z 352, 100%), [MꢃCl]ꢁ (m/z 658, 10%).
13C{1H} NMR: d 178.9 (s, CÄ
N), 139.7ꢂ128.5 (m, Ph),
/
7.15 (s, 15H, AsPh3), 1.65 (s, NMe),
/
/
/
added. The mixture was stirred for 16 h, and the redꢂ
/
/
brown precipitate filtered, washed with water (5 ml) and
/
/

216
W. Henderson et al. / Inorganica Chimica Acta 338 (2002) 210ꢂ218
/
120.1 (s, CÅ
/
N), 99.9 [d, 1J(RhC) 6.2], 29.8 (s, NMe) and
cooling to r.t. the solid was filtered, washed with cold
MeOH (5 ml) and dried under vacuum to give 375 mg
1
8.9 (s, Cp* Me). H NMR: d 8.0 (s, br, NH), 7.58ꢂ7.32
(m, Ph), 2.69 [d, NMe, J(HH) 4.7] and 1.44 (s, Cp* Me).
/
(97%) of 10. M.p. 186ꢂ188 8C. Anal. Found: 76.4; H,
/
6.0; N, 2.5. Calc. for C75H69BN2PRhS: C, 76.7; H, 5.9;
N, 2.4%. ESMS: (cone voltage 20 V), [M]ꢁ (m/z 855,
3.7. Synthesis of [Cp*RhCl{SC(Ä
/
NCN)NHMe}(SbPh3)] (8)
100%), (cone voltage 50 V), [Mꢃ
PPh3]ꢁ (m/z 593,
/
1
100%). 31P{1H} NMR: d 40.9 [d, J(RhP) 149]. Only a
As for the synthesis of 6, [Cp*RhCl(m-Cl)]2 (100 mg,
0.161 mmol), triphenylstibine (114 mg, 0.323 mmol) and
Na[MeNHC(S)NCN] (45 mg, 0.328 mmol) in MeOH
(15 ml) gave an orange solution. Addition of water (30
ml) gave a milky orange precipitate which was stirred
for 24 h, filtered and the product washed with water (10
ml) and Et2O (5 ml) and vacuum dried to give 8 as an
orange powder (170 mg, 71%), which is slightly soluble
single isomer was observed by 31P NMR. 13C{1H}
NMR: d 173.9 (s, CÄ
/
N), 164.4 (m, BPh4), 144.1ꢂ
/
121.6 (m, Ph), 100.4 (dd, Cp* C), 44.7 (CH2N), 37.3
(NMe), and 9.2 (s, Cp* Me). NCH2 and NCH3 signals
were identified from the DEPT90 spectrum.
3.10. Synthesis of [Cp*Rh{SC(Ä
/NBz2)NPh}(PPh3)]
BPh4 (11)
in ether. M.p. 182ꢂ
H, 4.6; N, 5.5. Calc. for C31H34ClN3RhSSb: C, 50.3; H,
4.6; N, 5.7%. ESMS: cone voltage 20 V, [Mꢃ
Cl]ꢁ (m/z
704, 100%). 13C{1H} NMR: d 178.7 (s, CÄ
N), 136.3ꢂ
128.7 (m, Ph), 120.0 (s, CÅN), 99.5 [d, Cp* C, J(RhC)
6.1], 29.8 (s, NMe) and 9.2 (s, Cp* Me). 1H NMR: d 7.9
(s, br, NH), 7.62ꢂ7.32 (m, Ph), 2.67 [d, NMe, J(HH)
4.6] and 1.55 (s, Cp* Me).
/
184 8C (dec.). Anal. Found: C, 49.8;
A mixture of [Cp*RhCl(m-Cl)]2 (100 mg, 0.161 mmol),
triphenylphosphine (85 mg, 0.324 mmol),
/
/
/
PhNHC(S)NBz2 (108 mg, 0.348 mmol) and Et3N (1
ml, excess) were refluxed in MeOH (20 ml) for 5 min
giving a clear orange solution. Solid NaBPh4 (120 mg,
0.351 mmol) was added to the refluxing mixture,
resulting in the formation of an orange solid on cooling.
The solid was filtered, washed with cold MeOH (5 ml)
and dried under vacuum to give 210 mg (57%) of 11 as
1
/
/
3.8. Synthesis of [Cp*Rh{SC(Ä
/
N(CH2CH2)2O)NPh}(PPh3)] BPh4 (9)
orange microcrystals. M.p. 90ꢂ92 8C. Anal. Found: C,
/
75.9; H, 6.0; N, 2.6. Calc. for C71H69BN2PRhS: C, 75.6;
H, 6.2; N, 2.5%. ESMS: (cone voltage 20 V), [M]ꢁ (m/z
A mixture of [Cp*RhCl(m-Cl)]2 (100 mg, 0.161 mmol),
triphenylphosphine
(85
mg,
0.324
mmol),
831, 100%); (cone voltage 50 V), [Mꢃ
100%). 31P{1H} NMR: d 38.6 [s, 1J(RhP) 152]. 13C{1H}
N), 164.6 (m, BPh4), 144.5ꢂ121.6
/
PPh3]ꢁ (m/z 569,
PhNHC(S)N(CH2CH2)2O (72 mg, 0.324 mmol) and
Et3N (1 ml, excess) were refluxed in MeOH (20 ml)
for 5 min giving a clear orange solution. Solid NaBPh4
(120 mg, 0.351 mmol) was added to the refluxing
mixture, resulting in the formation of an orange
microcrystalline solid. After cooling to r.t. the solid
was filtered, washed with cold MeOH (5 ml) and dried
NMR: d 177.0 (s, CÄ
/
/
(m, Ph), 101.0 (dd, Cp* C), 52.3 (s, CH2) and 9.4 (Cp*
Me).
3.11. Synthesis of [Cp*Rh{SC(Ä
/NHPh)NPh}(PPh3)]
under vacuum to give 328 mg (98%) of 9. M.p. ꢀ
/
BPh4 (12)
220 8C (dec.). Anal. Found: C, 72.6; H, 6.1; N, 2.8.
Calc. for C63H63BN2OPRhS: C, 72.7; H, 6.1; N, 2.7%.
ESMS: (cone voltage 20 V), [M]ꢁ (m/z 721, 100%);
A mixture of [Cp*RhCl(m-Cl)]2 (50 mg, 0.081 mmol),
triphenylphosphine (43 mg, 0.164 mmol), N,N?-diphe-
nylthiourea (37 mg, 0.162 mmol) and Et3N (1 ml, excess)
were refluxed in MeOH (20 ml) for 5 min giving a clear
orange solution. Solid NaBPh4 (70 mg, 0.205 mmol) was
added to the refluxing mixture, giving an orange
microcrystalline solid. After cooling to r.t. the solid
was filtered, washed with MeOH (10 ml) and Et2O (10
ml) and dried under vacuum to give 12 as bright orange
cone voltage 50 V, [Mꢃ
31P{1H} NMR: d 41.17 [d, 1J(RhP) 149]. 13C{1H}
N), 164.4 (m, BPh4), 144.4ꢂ
/
PPh3]ꢁ (m/z 459, 100%).
NMR: d 174.5 (s, CÄ
/
/
121.6 (m, Ph), 100.5 (dd, Cp* C), 65.2 (s, CH2O), 46.2
(s, CH2N) and 9.1 (s, Cp* Me).
3.9. Synthesis of [Cp*Rh{SC(Ä
/
NMe(CH2Anth))NPh}(PPh3)] BPh4 (10)
microcrystals (137 mg, 81%). M.p. ꢀ230 8C (dec.).
/
Anal. Found: C, 74.5; H, 5.9; N, 2.8. Calc. for
C65H61BN2PRhS: C, 74.5; H, 5.9; N, 2.7%. ESMS:
(cone voltage 20 V), [M]ꢁ (m/z 727, 100%): (cone
A mixture of [Cp*RhCl(m-Cl)]2 (100 mg, 0.161 mmol),
triphenylphosphine
(85
mg,
0.324
mmol),
PhNHC(S)NMe(CH2Anth) (115 mg, 0.323 mmol) and
Et3N (1 ml, excess) were refluxed in MeOH (20 ml) for 5
min giving a clear orange solution. Solid NaBPh4 (120
mg, 0.351 mmol) was added to the refluxing mixture,
resulting in the formation of an orange solid. After
voltage 50 V), [Mꢃ
PPh3]ꢁ (m/z 465, 100%). Negative
/
ion ESMS, cone voltage 20 V [BPh4]ꢃ (m/z 320).
31P{1H} NMR: d 38.5 [d, 1J(RhP) 149]. 13C{1H}
NMR: d 172.5 (s, br, CÄ
/
N), 164.6 (m, BPh4), 140.4ꢂ
/
121.6 (m, Ph), 100.6 (dd, Cp* C), and 9.4 (s, Cp* Me).

W. Henderson et al. / Inorganica Chimica Acta 338 (2002) 210ꢂ
/218
217
1H NMR: d 7.41 (m, Ph) and 1.23 [d, Cp* Me, J(PH)
3.1].
Table 3
Crystal data and refinement details for [(h6-p-cymene)-
Ru{SC(ÄNCN)NMe}]2 (3) and [Cp*RhCl{SC(ÄNCN)NHMe}-
(PPh3)]6×CH2Cl2
3
6×CH2Cl2
3.12. Synthesis of [Cp*Rh{SC(Ä
/
N(CH2CH2)2O)NPh}(SbPh3)] BPh4 (13)
Empirical formula
Formula weight
Temperature (K)
C26H34N6Ru2S2 C32H36Cl3N3PRhS
734.93
203(2)
696.86
168(2)
A mixture of [Cp*RhCl(m-Cl)]2 (50 mg, 0.081 mmol),
˚
Wavelength (A)
0.71073
monoclinic
P21/n
0.71073
triclinic
¯
P1/
triphenylstibine
(57
mg,
0.162
mmol),
Crystal system
Space group
Unit cell dimensions
PhNHC(S)N(CH2CH2)2O (36 mg, 0.162 mmol) and
Et3N (1 ml, excess) were refluxed in MeOH (20 ml)
for 5 min giving a clear orange solution. Solid NaBPh4
(70 mg, 0.205 mmol) was added to the refluxing mixture,
resulting in the formation of an orange microcrystalline
solid. After cooling to r.t. the solid was filtered, washed
with cold MeOH (10 ml) and Et2O (10 ml) and vacuum
/
˚
a (A)
13.882(4)
14.222(4)
15.025(5)
90
8.6275(1)
11.1409(2)
17.8419(1)
82.834(1)
82.092(1)
85.897(1)
1682.77(4)
2
˚
b (A)
˚
c (A)
a (8)
b (8)
g (8)
107.813(4)
90
3
˚
V (A )
Z
2824.1(15)
4
1.639
dried to give 13 (154 mg, 84%). M.p. ꢀ220 8C (dec.).
/
Anal. Found: C, 66.7; H, 5.7; N, 2.6. Calc. for
C63H63BN2ORhSSb: C, 66.9; H, 5.6; N, 2.5%. ESMS:
(cone voltage 20 V), [M]ꢁ (m/z 811, 100%): (cone
Dcalc (g cmꢃ3
)
1.450
0.881
752
m(Mo Ka) (mmꢃ1
F(000)
Crystal size (mm)
)
1.244
1408
voltage 50 V), [Mꢃ
/
SbPh3]ꢁ (m/z 459, 100%). 13C{1H}
0.6ꢄ0.2ꢄ0.04 0.38ꢄ0.18ꢄ0.09
26.39 1.85ꢂ28.17
34 844
u Range for data collection (8) 2.02ꢂ
/
/
NMR: d 171.9 [d, CÄ
/
N, J 4.4], 164.3 (m, BPh4), 144.3ꢂ
/
Reflections collected
Independent reflections
Rint
15 876
121.6 (m, Ph), 98.7 [d, Cp* C, J(RhC) 6.5], 65.1 (s,
1
CH2O), 46.0 (s, CH2N) and 9.6 (s, Cp* Me). H NMR:
5715
0.0377
7375
0.0166
d 7.52ꢂ/6.83 (m, Ph), 3.2 (m, CH2O), 2.6 (m, CH2N) and
Max./min. transmission
Data/restraints/parameters
1.00 and 0.857
5715/0/327
0.958 and 0.802
7375/0/379
0.0301
1.32 (s, Cp*).
Final R indices R1 [I ꢀ2s(I)] 0.0305
R1 (all data)
wR2 (all data)
0.0428
0.0739
0.0351
0.0788
Goodness-of-fit on F2
Largest difference peak and
1.037
1.059 and
ꢃ1.042
1.036
1.287 and ꢃ1.127
3.13. Synthesis of [Cp*Rh{SC(Ä
/
N(CH2CH2)2O)NPh}(PPh3)]2(m-h2-dpph) (BPh4)2
(14)
ꢃ3
˚
hole (e A
)
3.14. X-ray structure determinations
A mixture of [Cp*RhCl(m-Cl)]2 (75 mg, 0.121 mmol),
dpph (55 mg, 0.121 mmol), PhNHC(S)N(CH2CH2)2O
(54 mg, 0.243 mmol) and Et3N (1 ml, excess) were
refluxed in MeOH (20 ml) for 5 min giving a clear
orange solution. Solid NaBPh4 (100 mg, 0.292 mmol)
was added to the refluxing mixture, giving a red oil,
which gave an orange precipitate on cooling and
stirring. The solid was filtered, washed with cold
MeOH (10 ml), water (10 ml), MeOH (10 ml) and
Et2O (10 ml) and dried under vacuum to give 220 mg
Crystal data, collection and refinement details for the
structures of 3 and 6 are given in Table 3. All
calculations used the SHELX-97 suite of programs [16].
3.15. [(h6-p-cymene)Ru{SC(Ä
/
NCN)NMe}]2 (3)
Crystals were obtained from one preparation of the
complex in MeOHꢂwater solution. The structure was
/
solved by direct methods and refined routinely by full-
matrix least-squares refinement on F2. The largest
residual electron density was adjacent to the iso-propyl
group on one of the cymene rings, associated with
partial disorder for this ligand as shown by large Uiso
values for these atoms.
(91%) of 14 as an orange powder. M.p. 208ꢂ
Anal. Found: C, 71.5; H, 6.5; N, 2.95. Calc. for
120H128B2N4O2P2Rh2S2: C, 71.6; H, 6.4; N, 2.8%.
ESMS: (cone voltage 20 V): [M]2ꢁ (m/z 686, 100%):
N(CH2CH2)2-
/
210 8C.
C
(cone voltage 40 V), [Cp*Rh{SC(Ä
O)NPh}]ꢁ (m/z 459, 100%), [Cp*Rh{SC(Ä
CH2)2O)NPh}(PPh3)](dpph)]ꢁ
(m/z 913,
/
/
N(CH2-
25%).
31P{1H} NMR: d 32.6 [d, 1J(RhP) 149]. 13C{1H}
3.16. [Cp*RhCl{SC(Ä
/
NCN)NHMe}(PPh3)]6×
/
NMR: d 174.8 (s, CÄ
/
N), 164.4 (m, BPh4), 144.2ꢂ
/
CH2Cl2
121.6 (m, Ph), 100.0 (d, br, Cp* C), 65.7 (s, CH2O),
46.7 (s, CH2N), 31.5 [d, dpph CH2, J(PC) 10.9], 25.5 [d,
dpph CH2, J(PC) 25.1], 24.3 [d, dpph CH2, J(PC) 7.6]
and 8.9 (s, Cp* Me).
Red crystals of the complex were serendipitously
obtained by diffusion of Et2O into a sample of 6 in
CH2Cl2 that had not been purified (and presumably

218
W. Henderson et al. / Inorganica Chimica Acta 338 (2002) 210ꢂ218
/
contained some HCl). Anal. Found: C, 52.2; H, 4.9; N,
5.65. Calc. for C31H34ClN3PRhS×CH2Cl2: C, 52.3; H,
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included in calculated positions, except for the hydrogen
on N(1) which was located in a penultimate difference
map and refined with a fixed temperature factor.
Residual electron density was close to the Cl atoms of
the solvent molecule, which was not tightly defined.
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Crystallographic data (excluding structure factors) for
the structures described in this paper have been depos-
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CCDC Numbers 183843 and 183844 for compounds 3
and 6, respectively. Copies of this information may be
obtained free of charge from The Director, CCDC, 12
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Acknowledgements
[11] W. Henderson, J. Fawcett, R.D.W. Kemmitt, D.R. Russell, J.
Chem. Soc., Dalton Trans. (1995) 3007.
We thank the University of Waikato for financial
support of this work. X-ray data sets were collected by
Jan Wikaira/Ward Robinson (University of Canter-
bury), and Allen Oliver/Cliff Rickard (University of
Auckland). A grant from the New Zealand Lottery
Grants Board for the purchase of precious metals and
the electrospray mass spectrometer is acknowledged.
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