Coordination chemistry of o-Ph2PNHC6H4P(S)Ph2 a P,S-donor ligand: Synthesis of new Ru, Rh and Ir complexes

Article abstract of DOI:10.1016/S0277-5387(02)01357-8

The late transition metal complexes [(Ar)RuCl₂(PS)] (Ar = C₆H₆, o-MeC₆H₄(ⁱPr) and C₆Me₆), [RuCl₂(η³:η³- C₁₀H₁₆)(PS)], [RhCl(cod)(PS)] (cod = 1,5-cyclooctadiene) and [(Cp*)MCl₂(PS)] (Cp* = pentamethylcyclopentadienyl, M = Rh or Ir) (where PS = Ph₂PNHC₆H₄P(S)Ph₂) have been synthesised by the reaction of Ph₂PNHC₆H₄P(S)Ph₂ with the appropriate chloride bridged transition metal dimers. In all of these complexes the ligand is monodentate P-bound. Chloride abstraction from representative complexes, using Ag[ClO₄], gave the cationic compounds [(o-MeC₆H₄{ⁱPr})RuCl(PS)][ClO₄], [Rh(cod)(PS)][ClO₄] and [(Cp*)RhCl(PS)][ClO₄] in which the ligand is k²-P,S bound. All new compounds were characterised by a combination of ³¹P{¹H} and ¹H NMR spectroscopy, microanalysis, FAB mass spectrometry and IR spectroscopy. The molecular structures of five complexes have been determined by single-crystal X-ray diffraction - both monodentate and chelate coordination has been characterised. The P-monodentate compounds all display intramolecular N-H?S hydrogen bonding.

Full text of DOI:10.1016/S0277-5387(02)01357-8

Polyhedron 22 (2003) 361ꢂ368
/
www.elsevier.com/locate/poly
Coordination chemistry of o-Ph2PNHC6H4P(S)Ph2 a P,S-donor
ligand: synthesis of new Ru, Rh and Ir complexes
Stephen M. Aucott, Alexandra M.Z. Slawin, J. Derek Woollins ꢀ
Department of Chemistry, University of St. Andrews, Fife, Scotland KY16 9ST, UK
Received 30 August 2002; accepted 1 November 2002
Abstract
The late transition metal complexes [(Ar)RuCl2(PS)] (Arꢁ
/
C6H6, o-MeC6H4(i Pr) and C6Me6), [RuCl2(h3:h3-C10H16)(PS)],
pentamethylcyclopentadienyl, MꢁRh or Ir) (where PSꢁ
[RhCl(cod)(PS)] (codꢁ1,5-cyclooctadiene) and [(Cpꢀ)MCl2(PS)] (Cpꢀꢁ
/
/
/
/
Ph2PNHC6H4P(S)Ph2) have been synthesised by the reaction of Ph2PNHC6H4P(S)Ph2 with the appropriate chloride bridged
transition metal dimers. In all of these complexes the ligand is monodentate P-bound. Chloride abstraction from representative
complexes, using Ag[ClO4], gave the cationic compounds [(o-MeC6H4{i Pr})RuCl(PS)][ClO4], [Rh(cod)(PS)][ClO4] and
[(Cpꢀ)RhCl(PS)][ClO4] in which the ligand is k2-P,S bound. All new compounds were characterised by a combination of
31P{1H} and 1H NMR spectroscopy, microanalysis, FAB mass spectrometry and IR spectroscopy. The molecular structures of five
complexes have been determined by single-crystal X-ray diffraction*
characterised. The P-monodentate compounds all display intramolecular NÃ
# 2002 Elsevier Science Ltd. All rights reserved.
/
both monodentate and chelate coordination has been
/
HÁ Á ÁS hydrogen bonding.
Keywords: Phosphorus sulfur ligand; Monodentate bidentate; Transition metal complexes; Crystal structures
1. Introduction
Ph2PNHP(S)Ph2 [26] and Ph2PNPhP(S)Ph2 [27]. We
recently reported the synthesis and coordination chem-
istry of the unsymmetrical diphosphine ligand
Ph2PNHC6H4PPh2 [28,29] and also the preparation of
the monosulfide Ph2PNHC6H4P(S)Ph2 [30] and its
reactivity towards platinum palladium and gold pre-
cursors. Here we report on the coordination chemistry
of ruthenium, rhodium and iridium with the
The coordination chemistry of unsymmetrical poten-
tially polydentate ligands containing different donor
atoms is well documented. Particular attention has been
paid to ligands bearing PO [1], PN [2ꢂ4] and PS [5]
/
donor sets in part because of the potential hemilability
[6] displayed by these type of ligand. The chemistry of
phosphorus sulfur ligands is particularly rich due to the
large number of sulfur containing functionalities that
can be utilised in the preparation of these molecules
mixed
Ph2PNHC6H4P(S)Ph2
phosphine-aminophosphinesulfide
ligand
examples include phosphine-thioethers [7ꢂ
phine-thiolate [12ꢂ16], phosphine-thioformamide [17],
phosphine-thiophene [18ꢂ20], phosphine-sulfoxide [21],
the methyl [22,23] Ph2PCH2P(S)Ph2, ethyl [23,24]
Ph2PCH2CH2P(S)Ph2 and the propyl [25]
/
11], phos-
2. Results and discussion
/
/
2.1. Monodentate coordination chemistry of
Ph2PNHC6H4P(S)Ph2
Ph2P(CH2)3P(S)Ph2 backboned bis(phosphine)monosul-
fides as well as the bis(phosphino)amine monosulfides
We have previously demonstrated [30] that the direct
reaction of the heterofunctional phosphine
Ph2PNHC6H4P(S)Ph2 with dinuclear [Pd(m-Cl)(h3-
C3H5)]2, [{PtCl(m-Cl)(PMe2Ph)}2] and tetranuclear sys-
tems such as [Pt(m-Cl)(m-h2:h1-C3H5)]4 is an excellent
preparative technique for the preparation of neutral
ꢀ Corresponding author. Tel.: ꢃ
463384
E-mail address: jdw3@st-and.ac.uk (J.D. Woollins).
/
44-1334-463861; fax: ꢃ44-1334-
/
0277-5387/02/$ - see front matter # 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 2 ) 0 1 3 5 7 - 8

362
S.M. Aucott et al. / Polyhedron 22 (2003) 361ꢂ368
/
mononuclear complexes bearing a pendent or dangling
P(S)Ph2 group. The same preparative method has been
extended successfully to obtain neutral mononuclear
complexes of Groups and bearing the
Table 1
31P{1H} NMR spectral parameters for compounds 1ꢂ
{(PA)ꢁ ÃP(S)Ph2 group and (PX)ꢁPh2PNHÃ group}
/
10 inclusive
Ã
/
8
9
Compound
d(PA)
Chemical shifts (ppm)
Ph2PNHC6H4P(S)Ph2 ligand. Thus the reaction of the
dinuclear chloride complexes [{RuCl(m-Cl)(h6-C6H6)}2],
d(PX)
[{RuCl(m-Cl)(h6-p-MeC6H4i Pr)}2],
[{RuCl(m-Cl)(h6-
a
1
2
3
4
5
6
7
8
9
[{(h6-C6H6){RuCl2(PS)-P}]
[{(h6-p-MeC6H4i Pr)RuCl2{PS}-P}]
[{(h6-C6Me6)RhCl2{PS}-P}]
[{(h3:h3-C10H16)RuCl2{PS}-P}]
[{(cod)RhCl{PS}-P}]
39.5
40.9
39.5
40.6
40.5
39.4
39.4
58.2
57.7
C6Me6)}2], [{RuCl(m-Cl)(h3:h3-C10H16)}2], [{Rh(m-
a
a
Cl)(cod)}2] and [{MCl(m-Cl)(h5-C5Me5)}2] (Mꢁ
/
Rh or
55.6
46.3
b
b
a
Ir), with 2 equiv. of Ph2PNHC6H4P(S)Ph2 at room
temperature leads to the formation of the mononuclear
complexes [{(h6-C6H6)RuCl2{PS}-P}] (1), [{(h6-p-Me-
C6Hi4Pr)RuCl2{PS}-P}] (2), [{(h6-C6Me6)RhCl2{PS}-
c
c
59.6(164)
62.0(163)
27.1
[{(h5-C5Me5)RhCl2{PS}-P}]
a
[{(h5-C5Me5)IrCl2{PS}-P}]
b
b,e
[{(h6-p-MeC6Hi4Pr)RuCl{PS}-P,S}] 49.6
76.7
67.0(158)
85.9(155)
d
d
c
c
[{(h3:h3-C10H16)RuCl2{PS}-P}]
(4),
[{(cod)Rh{PS}-P,S}]
[{(h5-C5Me5)RhCl{PS}-P,S}]
42.7(2)
47.4(3)
P}]
(3),
a,f
10
[{(cod)RhCl{PS}-P}] (5), [{(h5-C5Me5)RhCl2{PS}-P}]
(6), [{(h5-C5Me5)IrCl2{PS}-P}] (7), in good to excellent
a
b
c
d
e
f
Spectra (101.3 MHz) measured in CDCl3.
Spectra (109.4 MHz) measured in CD2Cl2.
yield (76ꢂ
display the anticipated 31P{1H} NMR resonances (Ta-
ble 1). The spectra of compounds 1ꢂ7 are of the AX
type with no observable 4J(31PAꢂ31
PX) coupling be-
/
90%) (Scheme 1). All of the neutral complexes
Values in parentheses denote 1J(103Rhꢂ31
/
P)/Hz.
P)/Hz.
Values in parentheses denote 2J(103Rhꢂ31
/
/
Other 31P{1H} spectral parameters for 9 3J(31PA ꢂ31
/
PX) 7 Hz.
Other 31P{1H} spectral parameters for 10 3J(31PA ꢂ31
PX) 5 Hz.
/
/
tween the two phosphorus environments. The pendant
thiophosphoryl group typically occurs at around dP 40
ppm which is concordant with non-coordinating beha-
viour and is comparable to that of the ‘free’ ligand (dP
39.6 ppm) [30]. The chemical shift of the phosphor-
us(III) moiety is dependent on the metal it is coordi-
nated to and can be observed between the values dP 27.1
group resonances of the rhodium complexes 5 and 6
1
appear as doublets with J(103Rhꢂ31P(III)) couplings of
/
164 and 163 Hz, respectively. In complexes 1, 3, 4, 6, and
7 the ligand amine proton resonance is displayed as a
broad doublet at approximately dH 8.1 ppm with an
average 2J(31Pꢂ1
H) coupling constant of 5 Hz. The
/
ppm for 7 and dP 62.0 ppm for 6. The bound Ã
/
HNPPh2
Scheme 1. (i) [{RuCl(m-Cl)(h6-C6H6)}2]; (ii) [{RuCl(m-Cl)(h6-MeC6Hi4Pr)}2]; (iii) [{RuCl(m-Cl)(h6-C6Me6)}2]; (iv) [{RuCl(m-Cl)(h3:h3-C10H16)}2];
(v) [{Rh(m-Cl)(cod)}2]; (vi) [{MCl(m-Cl)(h5-C5Me5)}2].

S.M. Aucott et al. / Polyhedron 22 (2003) 361ꢂ
/368
363
amine protons of complexes 2 and 5 appear as a broad
singlet and a broad pseudo triplet, respectively. The
remaining proton data for compounds 1ꢂ7 is consistent
/
with the structural assignments (see Section 3). Further
evidence in support of the monodentate phosphorus-
bound coordination mode is provided by the IR spectra
of the complexes which all display distinct n(PÄ
at 631ꢂ
635 cmꢄ1 which are very similar to those of the
free ligand value [n(PÄ
S) 634 cmꢄ1] and characteristic
of no interaction between the ÃP(S)Ph2 and the metal
/S) bands
/
/
/
centre. Additional data for the neutral mononuclear
complexes include bands at around 634 cmꢄ1 which we
have assigned as n(PÃ
n(NÃ
H) at between 3103 and 3293 cmꢄ1. In most cases
the observed frequency of the n(NÃH) band of the
complexes is significantly lower than that of the ‘free’
ligand [n(NÃH)ꢁ
3223 cmꢄ1] [30]. We have previously
observed this phenomenon in Ph2PNHC6H4P(S)Ph2
complexes of platinum, palladium and gold and it is
suggestive of intramolecular hydrogen bonding interac-
tions between the amine proton and the sulfur atom of
the ligand which we observed in the solid state structure
of [AuClPh2PNHC6H4P(S)Ph2] [30]. Single crystals of
/
N) and also a band assigned to
Fig. 2. Crystal structure of [(h5-C5Me5)IrCl2{Ph2PNHC6H4P(S)Ph2-
P}] (7) showing the intra-molecular amine-proton sulfur hydrogen-
bonding interaction.
/
/
/
/
the Ph2PNHC6H4P(S)Ph2 ligand. The P(1)Ã
C(2)ÃP(2) ligand backbone of complex 7 is essentially
planar whilst the P(1) atoms of 1, 2 and 3 lie 0.11 A
/
N(1)Ã
/
C(1)Ã
/
/
˚
˚
˚
below, 0.1 A below and 0.22 A above their P(1)Ã
/
N(1)Ã
/
C(1)ÃC(2)ÃP(2) mean planes, respectively. The molecu-
/
/
lar structures of complexes 1, 2 and 3 reveal, as
suggested by the n(NH) stretching frequencies in their
IR spectra, intramolecular hydrogen-bond between the
compounds [{(h6-C6H6)RuCl2{PS}-P}]×
[{(h6-p-MeC6H4i Pr)RuCl2{PS}-P}]×
1.5CHCl3
[{(h6-C6Me6)RhCl2{PS}-P}]×
0.5C2H5OH (3)
[{(h5-C5Me5)IrCl2{PS}-P}]×
/
0.5C4H10 (1),
/
(2),
and
amine hydrogen H(1n) and the S(2) atom [in 1ꢂ3
/
/
˚
H(1n)Á Á ÁS(2) approximately 2.45 A, S(2)Á Á ÁN(1) ap-
/
CHCl3 (7) suitable for X-
˚
proximately 3.30 A, N(1)Ã
/
H(1n)Á Á ÁS(2) approximately
ray diffraction studies were grown by the slow diffusion
of petroleum ether 1, 2 and 7 or ethanol 3 into
concentrated chloroform or dichloromethane solutions
of the complexes. Those of 3 (Fig. 1) and 7 (Fig. 2) are
pictured here (solvent molecules omitted for the sake of
clarity) along with selected bond lengths and angles
(Table 3) for all four complexes. The predicted intra-
molecular amine proton sulfur hydrogen-bonding inter-
action is corroborated by the X-ray crystallographic
evidence. The molecules all display very similar bond
lengths, angles and geometries. All possess the expected
three-legged ‘piano stool’ structures and the metal in all
cases is coordinated to an arene or Cpꢀ group, two
chlorine atoms and the phosphorus(III) centre, P(1), of
1408] though this is somewhat longer in 7. In addition a
‘syn’ type arrangement of the P(1) and P(2) atoms is
common to all four complexes (Table 2 and Figs. 1 and
2).
2.2. Bidentate coordination chemistry of
Ph2PNHC6H4P(S)Ph2
We have previously reported that chelation of the
potentially bidentate P,N 2-(Ph2PNH)py [31] and P,P
ligands
Ph2PNHC6H4PPh2
[28]
as
well
as
Ph2PNHC6H4P(S)Ph2 [30] can be induced by the use
of halide abstraction using Ag[BF4] or Ag[ClO4]. Here
we have used this preparative technique to bring about
the chelation of the monodentate Ph2PNHC6H4P(S)Ph2
ligand in representative complexes of Groups 8 and 9
resulting in the formation of cationic species containing
seven-membered PÃ
/
NÃ
/
CÃ
/
CÃ
/
PÃ
/
SÃ
/
M rings. Halide ab-
straction from the neutral complexes [{(h6-p-Me-
C6Hi4Pr)RuCl2{PS}-P}] (2), [{(cod)RhCl{PS}-P}] (5)
and [{(h5-C5Me5)RhCl2{PS}-P}] (6) with 1 equiv. of
Ag[ClO4] in dichloromethane gave the cationic com-
pounds [{(h6-p-MeC6H4i Pr)RuCl{PS}-k2-P,S}][ClO4]
(8), [{(cod)RhCl{PS}-k2-P,S}][ClO4] (9) and [{(h5-
C5Me5)RhCl2{PS}-k2-P,S}][ClO4] (10)
.
Fig. 1. Crystal structure of [(h6-C6Me6)RuCl2{Ph2PNHC6H4P(S)Ph2-
P}] (3) showing the intra-molecular amine-proton sulfur hydrogen-
bonding interaction.
The cationic complexes display the anticipated analy-
tic and spectral properties. Their 31P{1H} NMR spectra

364
S.M. Aucott et al. / Polyhedron 22 (2003) 361ꢂ368
/
Table 3
˚
Selected bond lengths (A) and angles (8) for complexes 1, 2, 3, 7 and 10 (where MꢁRu, Rh or Ir)
Complex
1
2
3
7
10
Bond lengths
P(2)ÃS(2)
P(2)ÃC(2)
1.968(2)
1.813(6)
1.419(7)
1.418(7)
1.697(4)
2.347(2)
2.408(2)
2.410(2)
1.961(4)
1.816(8)
1.429(10)
1.402(9)
1.688(6)
2.338(3)
2.405(3)
2.415(3)
1.966(2)
1.816(5)
1.420(7)
1.402(7)
1.715(4)
2.3415(14)
2.408(2)
2.418(14)
1.9538(18)
1.809(5)
1.410(6)
2.008(3)
1.808(12)
1.375(12)
1.441(12)
1.684(8)
2.309(3)
2.401(3)
C(2)ÃC(1)
C(1)ÃN(1)
N(1)ÃP(1)
P(1)ÃM(1)
M(1)ÃCl(1)
M(1)ÃCl(2)
M(1)ÃS(2)
M(1)ÃC range
1.405(5)
1.705(4)
2.3029(12)
2.3875(12)
2.422(13)
2.402(3)
2.153ꢂ
/
2.203
2.154ꢂ
/
2.248
2.214ꢂ
/
2.293
2.168ꢂ/2.240
2.173ꢂ2.241
/
Bond angles
S(2)ÃP(2)ÃC(2)
P(2)ÃC(2)ÃC(1)
C(2)ÃC(1)ÃN(1)
C(1)ÃN(1)ÃP(1)
N(1)ÃP(1)ÃM(1)
P(1)ÃM(1)ÃCl(1)
P(1)ÃM(1)ÃCl(2)
P(1)ÃM(1)ÃS(2)
HÁ Á ÁS(2)
112.7(2)
120.8(4)
118.8(5)
126.3(4)
115.5(2)
90.59(8)
85.06(6)
113.0(4)
121.1(6)
120.3(8)
126.3(6)
114.1(3)
90.31(9)
89.37(8)
114.6(2)
121.2(4)
120.4(4)
127.9(4)
117.6(2)
89.66(5)
88.58(5)
113.9(2)
121.3(3)
120.2(4)
129.5(3)
116.89(14)
91.00(4)
91.72(5)
118.1(3)
120.2(7)
117.7(8)
122.9(7)
116.2(3)
92.71(10)
89.16(11)
2.50
3.30
2.45
3.24
2.48
3.33
2.60
3.42
N(1)Á Á ÁS(2)
N(1)ÃHÁ Á ÁS
139
138
142
142
Table 2
Microanalytical data for complexes 1ꢂ/10 inclusive
Complex
C
H
N
1
2
3
4
5
6
7
8
9
[{(h6-C6H6)RuCl2(L)}]
58.5 (58.1) 4.3 (4.2) 1.9 (1.9)
60.0 (60.1) 4.6 (4.9) 2.2 (1.7)
60.5 (60.9) 4.9 (5.2) 1.6 (1.7)
59.8 (59.9) 5.1 (5.1) 1.7 (1.7)
61.4 (61.7) 4.7 (5.0) 1.8 (1.9)
60.0 (59.9) 5.0 (5.0) 1.5 (1.7)
54.1 (53.9) 4.8 (4.5) 1.3 (1.6)
55.4 (55.8) 4.3 (4.4) 1.4 (1.6)
56.0 (56.8) 4.6 (4.6) 1.7 (1.7)
55.4 (55.4) 4.1 (4.6) 1.3 (1.6)
[{(h6-p-Cy)RuCl2(L)}]
[{(h6-C6Me6)RuCl2(L)}]
[{(h3:h3-C10H16)RuCl2(L)}]
[{(cod)RhCl(L)}]
[{(h5-C5Me5)RhCl2(L)}]
[{(h5-C5Me5)IrCl2(L)}]
[{(h6-p-Cy)RuCl(L)}][ClO4]
[{(cod)Rh(L)}][ClO4]
10 [{(h5-C5Me5)RhCl2(L)}]
Calculated values in parentheses. LꢁPh2PNHC6H4P(S)Ph2.
Fig. 3. Crystal structure of [(h5-C5Me5)RhCl{Ph2PNHC6H4P(S)Ph2-
k2-P,S}][ClO4] (10) ClO4 (counterion omitted for clarity).
show that upon chelation the chemical shift of both the
phosphorus centres occur at significantly higher fre-
quencies than their neutral monodentate P bound parent
compounds (Table 1). The shift to higher frequency is a

S.M. Aucott et al. / Polyhedron 22 (2003) 361ꢂ
/368
365
consequence of the chelate ring effect [32] and has been
previously observed in the cationic allyl complexes
[M(h3-C3H5)(Ph2PNHC6H4P(S)Ph2-k2-P,S)][ClO4]
Precious metal salts were provided on loan by
Johnson Matthey plc.
(where Mꢁ
ligand behaviour are the small 2J(103Rhꢂ31
Hz (for 9 and 10) and 3J(31P(III)ꢂ31P(V)) 7 and 5 Hz (for
/Pt and Pd) [30]. Also indicative of chelating
3.2. Preparations
/
P(V)) 2 and 3
/
3.2.1. [(h6-C6H6)RuCl2{Ph2PNHC6H4P(S)Ph2-P}]
(1)
9 and 10) couplings observed in the rhodium complexes.
Proton NMR assignments are consistent with the
proposed structures. The X-ray structure of 10 confirms
To a thf (2.5 cm3) suspension of [{RuCl(m-Cl)(h6-
C6H6)}2] (0.133 g, 0.266 mmol) was added as a solid in
one portion o-Ph2PNHC6H4P(S)Ph2 (0.263 g, 0.532
mmol). After stirring for 40 min the red/brown solid
was further precipitated by the addition of light
the formation of a seven-membered RhÃ
PÃS ring (Fig. 3). Upon chelation the PÃ
enlarged. The PÃRhÃS bite angle is 89.1(1)8 whilst the
rest of the internal angles in the seven-membered ring
are close to trigonal angles*the most distorted being
the N(1)ÃP(1)ÃRh [116.1(3)8] with the C(1)ÃN(1)ÃP(1)
being significantly reduced in 10 compared to the
monodentate systems. The N(1)ÃC(1)ÃC(2)ÃP(2) back-
S(2)ÃN(1)ÃP(1)
/
PÃ
/
NÃ
/
CÃ
/
CÃ
/
/
/
S distance is
/
/
petroleum (b.p. 40ꢂ
60 8C) (15 cm3) and collected by
/
/
suction filtration. The crude material was re-dissolved in
CH2Cl2 (5 cm3) and filtered through a small Celite plug
to remove a small amount of insoluble material. The
solution was concentrated under reduced pressure to
/
/
/
/
/
/
/
bone of the ring is planar and the P(2)Ã
/
/
/
approximately 1ꢂ
(b.p. 40ꢂ
60 8C) (20 cm3) gave the product as a dark red/
brown solid which was collected by suction filtration,
washed with Et2O (2ꢅ
10 cm3) and dried in vacuo.
Yield: 0.301 g, 76%. H NMR (CDCl3): d 8.06 (br d,
2J(31Pꢂ1
H) 4 Hz, 1H, NH), 7.85 (m, 4H, aromatics),
7.69ꢂ7.52 (m, 12H, aromatics), 7.38ꢂ7.20 (m, 6H,
aromatics), 6.85ꢂ6.76 (m, 2H, aromatics) and 5.39 (s,
6H, C6H6). FABꢃ MS: m/z 744 [M]ꢃ, 709 [MꢄCl]ꢃ
and 673 [Mꢄ
2Cl]2ꢃ. Selected IR data (KBr): 3129m
[n(NÃH)], 907s [n(PÃ S)].
N)], 635s cmꢄ1 [n(PÄ
/
2 cm3 and addition of light petroleum
portion of the ring is distorted planar with the seven-
/
membered ring adopting a boatlike conformation. The
C(2) bond
Cl(1) atom sits approximately over the C(1)Ã
/
/
1
˚
[Cl(1)Á Á ÁC(1) 3.33, Cl(1)Á Á ÁC(2) 3.19 A).
This work clearly demonstrates the utility of
Ph2PNHC6H4P(S)Ph2 to form monodentate and chelate
/
/
/
complexes*/the seven-membered ring is readily ob-
/
tained and appears to be quite stable.
/
/
/
/
/
3. Experimental
3.2.2. [(h6-MeC6H4i Pr)RuCl2{Ph2PNHC6H4P(S)Ph2-
P}] (2)
3.1. General
To a thf (2 cm3) suspension of [{RuCl(m-Cl)(h6-
MeC6Hi4Pr)}2] (0.141 g, 0.230 mmol) was added as a
solid in one portion o-Ph2PNHC6H4P(S)Ph2 (0.230 g,
0.466 mmol). The mixture was stirred for 90 min and the
resulting red/brown microcrystalline solid was collected
by suction filtration, washed with ice cold thf (2 cm3)
Unless otherwise stated, manipulations were per-
formed under an oxygen-free nitrogen atmosphere using
predried solvents and standard Schlenk techniques. The
complexes [{RuCl(m-Cl)(h6-C6H6)}2] [33], [{RuCl(m-
Cl)(h6-p-MeC6H4i Pr)}2]
[34],
[{RuCl(m-Cl)(h6-
C6Me6)}2] [34], [{RuCl(m-Cl)(h3:h3-C10H16)}2] [35],
and Et2O (2ꢅ
/
10 cm3) and dried in vacuo. Yield: 0.309
g, 84%. H NMR (CDCl3): d 8.11 (br s, 1H, NH), 7.95
(m, 4H, aromatics), 7.75ꢂ7.56 (m, 12H, aromatics),
7.41ꢂ7.21 (m, 6H, aromatics), 6.87ꢂ6.77 (m, 2H, aro-
matics), 5.19ꢂ5.09 (m, 4H, aromatics), 2.41 (hept,
3J(1Hꢂ1
H) 6 Hz, 1H, CH), 1.56 (s, 3H, Me) and 0.87
(d, 3J(1Hꢂ1H) 7 Hz, 6H, Me). FABꢃ MS: m/z 800
[M]ꢃ, 764 [MꢄCl]ꢃ and 729 [Mꢄ2Cl]2ꢃ. Selected IR
data (KBr): 3179m(br) [n(NÃH)], 899s, [n(PÃN)], 633s
cmꢄ1[n(PÄ
S)].
1
[{Rh(m-Cl)(cod)}2] [36] and [{MCl(m-Cl)(h5-C5Me5)}2]
(Mꢁ/Rh or Ir) [37] were prepared according to litera-
/
ture procedures. Ag[ClO4] (Aldrich 99% purity) was
obtained commercially and used without further pur-
ification.
/
/
/
/
IR spectra were recorded as KBr pellets in the range
220 cmꢄ1 on a Perkinꢂ
/
4000ꢂ
/
/Elmer system 2000 Four-
/
/
1
ier transform spectrometer, H NMR spectra (250 or
270 MHz) either on a Bruker AC250 FT or a JEOL
GSX270 spectrometer with d referenced to external
SiMe4 and 31P{1H} NMR spectra (101.3 or 109.4 MHz)
either on a JEOL GSX270 or a Bruker AC250 FT
spectrometer with d referenced to external H3PO4.
Elemental analyses were performed by the St. Andrews
University Analytical Service within the School of
Chemistry Service. Fast atom bombardment (FAB)
mass spectra were run by the EPSRC mass spectrometry
service at Swansea.
/
/
/
3.2.3. [(h6-C6Me6)RuCl2{Ph2PNHC6H4P(S)Ph2-P}]
(3)
This was prepared in the same way as complex 2 using
[{RuCl(m-Cl)(h6-C6Me6)}2] (0.145 g, 0.217 mmol) in thf
(2.5 cm3) and o-Ph2PNHC6H4P(S)Ph2 (0.218 g, 0.442
mmol). After stirring for approximately 18 h the dark
red microcrystalline solid was collected by suction
filtration washed with ice cold thf (2 cm3) and Et2O

366
S.M. Aucott et al. / Polyhedron 22 (2003) 361ꢂ368
/
1
(2ꢅ
NMR (CDCl3): d 8.05 (br d, 2J(31Pꢂ1
NH), 7.88 (m, 4H, aromatics), 7.73ꢂ
aromatics), 7.27ꢂ
(m, 2H, aromatics) and 1.86 (s, 18H, Me). FABꢃ MS:
m/z 828 [M]ꢃ, 793 [MꢄCl]ꢃ and 757 [Mꢄ2Cl]2ꢃ
Selected IR data (KBr): 3103w [n(NÃH)], 910m [n(PÃ
N)], 634m cmꢄ1 [n(PÄ
S)].
/
5 cm3) and dried in vacuo. Yield: 0.320 g, 89%. H
followed by Et2O (2ꢅ
0.262 g, 90%. 1H NMR (CDCl3): d 8.20 (br d,
2J(31Pꢂ1
H) 5 Hz, 1H, NH), 7.94ꢂ7.12 (m, 22H,
aromatics), 6.79ꢂ
/
5 cm3) and dried in vacuo. Yield:
/
H) 6 Hz, 1H,
7.55 (m, 12H,
/
/
/
/
7.02 (m, 6H, aromatics), 6.80ꢂ
/
6.72
/
6.71 (m, 2H, aromatics) and 1.40 (d,
15H, J(31Pꢂ1
[M]ꢃ, 767 [Mꢄ
data (KBr): 3145w [n(NÃ
cmꢄ1 [n(PÄ
S)].
/
H) 4 Hz, C5Me5). FABꢃ MS: m/z 803
4
/
/
.
/
Cl]ꢃ and 732 [Mꢄ2Cl]2ꢃ. Selected IR
/
/
/
/
H)], 902m [n(PÃ/N)], 634m
/
/
3.2.4. [(h3:h3-C10H16)RuCl2{Ph2PNHC6H4P(S)Ph2-
P}] (4)
3.2.7. [(h5-C5Me5)IrCl2{Ph2PNHC6H4P(S)Ph2-P}]
(7)
This was prepared in a similar manner to complex 2
by adding solid o-Ph2PNHC6H4P(S)Ph2 (0.254 g, 0.515
mmol) to a thf (5 cm3) suspension of [{RuCl(m-
Cl)(h3:h3-C10H16)}2] (0.158 g, 0.256 mmol). The dark
yellow/brown solution deposited a dark yellow solid
upon further stirring and to this was added Et2O (15
cm3) to further precipitate the product which was
This was prepared in the same way as complex 2 using
[{IrCl(m-Cl)(h5-C5Me5)}2] (0.80 g, 0.100 mmol) in thf (1
cm3) and solid o-Ph2PNHC6H4P(S)Ph2 (0.100 g, 0.203
mmol). The bright orange microcrystalline solid was
collected by suction filtration washed with ice cold thf (1
cm3) and Et2O (2ꢅ
0.158 g, 88%. 1H NMR (CDCl3): d 8.08 (br d,
2J(31Pꢂ1
H) 6 Hz, 1H, NH), 7.90ꢂ7.54 (m, 16H,
aromatics), 7.29ꢂ7.15 (m, 6H, aromatics), 6.79ꢂ
(m, 2H, aromatics) and 1.41 (d, J(31Pꢂ1
/
5 cm3) and dried in vacuo. Yield:
collected by suction filtration, washed with Et2O (2ꢅ
/
5
/
/
cm3) and dried in vacuo. Yield: 0.325 g, 79%. H NMR
(CD2Cl2): d 8.11 (br d, 2J(31Pꢂ1
H) 5 Hz, 1H, NH),
7.90ꢂ7.31 (m, 20H, aromatics), 6.73ꢂ6.51 (m, 3H,
aromatics), 6.23 (m, 1H, aromatic), 4.72 (m, 2H, CH),
3.79 (d, J(1Hꢂ1H) 9 Hz, 4H, CH2), 2.54 (dd, J(1Hꢂ1
H)
1 and 5 Hz, 4H, CH2) and 2.03 (s, 6H, Me). FABꢃ MS:
m/z 801/2 [M]ꢃ, 766 [MꢄCl]ꢃ and 730/1 [Mꢄ2Cl]2ꢃ
Selected IR data (KBr): 3293w [n(NÃH)], 900m [n(PÃ
N)], 637m cmꢄ1 [n(PÄ
S)].
/
/
6.70
1
4
/
/
H) 3 Hz, 15H,
/
/
C5Me5). FABꢃ MS: m/z 892 [M]ꢃ, 856 [MꢄCl]ꢃ and
/
821 [Mꢄ
H)], 903w [n(PÃ
/
2Cl]2ꢃ. Selected IR data (KBr): 3146w [n(NÃ
N)], 635m cmꢄ1 [n(PÄ
S)].
/
/
/
/
/
/
/
.
3.2.8. [(h6-MeC6H4i Pr)RuCl{Ph2PNHC6H4P(S)Ph2-
k2-P,S}][ClO4] (8)
/
/
/
To
a
CH2Cl2 (10 cm3) solution of [(h6-Me-
C6Hi4Pr)RuCl2{Ph2PNHC6H4P(S)Ph2-P}] (2) (0.155 g,
0.194 mmol) was added solid Ag[ClO4] (0.040 g, 0.193
mmol). The reaction mixture was stirred in the dark for
approximately 17 h and then filtered through a small
plug of Celite to remove precipitated AgCl. The dark
red/brown filtrate was concentrated in vacuo to approxi-
mately 4 cm3 to which was added with stirring Et2O (20
cm3) to give a dark red micro-crystalline solid. The
product was collected by suction filtration, washed with
3.2.5. [(cod)RhCl{Ph2PNHC6H4P(S)Ph2-P}] (5)
To a CH2Cl2 (4 cm3) solution of [{Rh(m-Cl)(cod)}2]
(0.131 g, 0.266 mmol) was added dropwise a solution (4
cm3) of o-Ph2PNHC6H4P(S)Ph2 (0.263 g, 0.533 mmol)
in the same solvent. The deep yellow solution was stirred
for 15 min and Et2O (40 cm3) was added to give 5 as a
yellow powder. The product was collected by suction
filtration, washed with Et2O (2ꢅ
/
5 cm3) and dried in
vacuo. Yield: 0.334 g, 85%. H NMR (CDCl3): d 8.19
1
Et2O (2ꢅ
/
10 cm3) and dried overnight in vacuo. Yield:
2
1
(br t, J(31Pꢂ1
/
H) 7 Hz, 1H, NH), 7.76ꢂ/7.23 (m, 22H,
0.132 g, 79%. H NMR (CDCl3): d 7.83ꢂ
/
7.35 (m, 16H,
7.07 (m, 6H, aromatics), 6.67 (m, 2H,
aromatics), 6.32 (br t, 2J(31Pꢂ1
H) 8 Hz, 1H, NH), 5.31ꢂ
5.30 (m, 4H, aromatics), 2.43 (hept, J(1Hꢂ1
1H, CH) and 1.55 (s, 3H, Me) and 0.87 (d, 3J(1Hꢂ1
Hz, 6H, Me). FABꢃ MS: m/z 764 [MꢄClO4]ꢃ and 729
[MꢄClO4ꢄ
Cl]ꢃ. Selected IR data (KBr): 3186w [n(NÃ
H)], 1101 [n(ClO4)], 901m [n(PÃ
N)], 620m cmꢄ1 [n(PÄ
S)].
aromatics), 6.80ꢂ/6.63 (m, 2H, aromatics), 5.52 (br m,
aromatics), 7.30ꢂ
/
2H, olefinic CH), 3.12 (br m, 2H, olefinic CH), 2.31 (br
m, 4H, CH2), 2.05 (br m, 2H, CH2) and 1.91 (br, m, 2H,
/
/
3
/
H) 7 Hz,
H) 7
CH2). FABꢃ MS: m/z 704/5 [Mꢄ
/
Cl]ꢃ and 596/7 [Mꢄ
/
/
Clꢄ
/
(C8H12)]ꢃ. Selected IR data (KBr): 3130w [n(NÃ
N)], 633m cmꢄ1 [n(PÄ
S)].
/
/
H)], 902m [n(PÃ
/
/
/
/
/
/
/
3.2.6. [(h5-C5Me5)RhCl2{Ph2PNHC6H4P(S)Ph2-P}]
(6)
This was prepared in a similar fashion to complex 2
by adding solid o-Ph2PNHC6H4P(S)Ph2 (0.180 g, 0.365
mmol) to a thf (1.5 cm3) suspension of [{RhCl(m-Cl)(h5-
C5Me5)}2] (0.112 g, 0.181 mmol). The suspension was
dissolved and after a few minutes stirring the product 6
precipitated. After stirring for approximately 90 min,
the dark red micro-crystalline solid was collected by
suction filtration and washed with ice cold thf (3 cm3)
3.2.9. [(cod)Rh{Ph2PNHC6H4P(S)Ph2-k2-
P,S}][ClO4] (9)
This was prepared in the same way as complex 8 using
[(cod)RhCl{Ph2PNHC6H4P(S)Ph2-P}] (5) (0.158 g,
0.213 mmol) and Ag[ClO4] (0.045 g, 0.217 mmol) to
give a dark yellow powder. Yield: 0.165 g, 96%. 1H
NMR (CDCl3): d 8.08 (br t, 2J(31Pꢂ1
7.81ꢂ7.25 (m, 22H, aromatics), 6.79 (m, 1H, aromatics),
/
H) 7 Hz, 1H, NH),
/

S.M. Aucott et al. / Polyhedron 22 (2003) 361ꢂ
/368
367
6.50 (m, 1H, aromatics), 5.41 (br m, 2H, olefinic CH),
3.34 (br m, 2H, olefinic CH), 2.13 (br m, 4H, CH2) and
1.94 (br m, 4H, CH2). FABꢃ MS: m/z 704/5 [Mꢄ
/
ClO4]ꢃ and 596/7 [Mꢄ
data (KBr): 3237w [n(NÃ
907w [n(PÃ
N)], 623s cmꢄ1 [n(PÄ
/
ClO4ꢄ
H)], 1101vs(br) [n(ClO4)],
S)].
/
(C8H12)]ꢃ. Selected IR
/
/
/
3.2.10. [(h5-C5Me5)RhCl{Ph2PNHC6H4P(S)Ph2-k2-
P,S}][ClO4] (10)
This was prepared in an identical manner to complex
8 using [(h5-C5Me5)RhCl2{Ph2PNHC6H4P(S)Ph2-P}]
(6) (0.140 g, 0.174 mmol) and Ag[ClO4] (0.036 g, 0.174
mmol). The dark red microcrystalline product was
collected by suction filtration, washed with Et2O (2ꢅ5
/
1
cm3) and dried in vacuo. Yield: 0.138 g, 91%. H NMR
(CDCl3): d 7.94 (m, 4H, aromatics), 7.76ꢂ7.20 (m, 17H,
/
aromatics), 7.01 (m, 1H, aromatic), 6.61 (m, 1H,
aromatic), 6.38 (m, 1H, aromatic), 5.12 (br d, 1H,
4
2J(31Pꢂ1
/
H) 8 Hz, NH) and 1.33 (d, J(31Pꢂ1
/
H) 4 Hz,
ClO4]ꢃ and 731
Cl]ꢃ2)]ꢃ. Selected IR data (KBr): 3202br
H)], 1099vs(br) [n(ClO4)], 904w [n(PÃN)], 622s
cmꢄ1 [n(PÄ
S)].
15H, C5Me5). FABꢃ MS: m/z 767 [Mꢄ
[MꢄClO4ꢄ
[n(NÃ
/
/
/
/
/
/
3.3. X-ray crystallography
Details of the structure determination are given in
Table 4. X-ray diffraction measurements were made
with graphite-monochromated Mo Ka X-radiation (lꢁ
/
˚
0.71073 A) using a Siemens SMART diffractometer,
intensity data were collected using 0.3 or 0.158 width v
steps accumulating area detector frames spanning a
hemisphere of reciprocal space for all structures (data
were integrated using the SAINT program). All data were
corrected for Lp and long-term intensity fluctuations.
Absorption effects were corrected on the basis of
multiple equivalent reflections or by semi-empirical
methods. Structures were solved by direct methods
and refined by full-matrix least-squares against F2
(
SHELXTL). CÃ/H hydrogen atoms were assigned iso-
tropic displacement parameters and were constrained to
idealised geometries. The perchlorate counterions in 10
were refined in idealised geometries. All calculations
were made with SHELXTL [38].
4. Supplementary material
Atomic coordinates, thermal parameters and bond
lengths and angles have been deposited with the Cam-
bridge Crystallographic Data Centre, CCDC Nos.
189511ꢂ
obtained free of charge from The Director, CCDC, 12
Union Road, Cambridge, CB2 1EZ, UK (fax: ꢃ44-
/
189516. Copies of this information may be
/

368
S.M. Aucott et al. / Polyhedron 22 (2003) 361ꢂ368
/
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