Novel (η6-arene)-ruthenium(II) complexes containing bis(iminophosphorano)methanide and methandiide ligands

Article abstract of DOI:10.1016/j.jorganchem.2004.12.034

The novel bis(iminophosphorano)methanes CH₂[P{NP(S)(OR) ₂}Ph₂]₂ (R = Ph (1a), Et (1b)) have been obtained by oxydation of dppm with the corresponding thiophosphorylated azides (RO)₂P(S)N₃.

Full text of DOI:10.1016/j.jorganchem.2004.12.034

Journal of Organometallic Chemistry 690 (2005) 2087–2096
www.elsevier.com/locate/jorganchem
Novel (g6-arene)-ruthenium(II) complexes containing
bis(iminophosphorano)methanide and methandiide ligands
´
Victorio Cadierno , Josefina Dıez, Joaquın Garcıa-Alvarez, Jose Gimeno
*
*
´
´
´
´
´ ´ ´ ´ ´
Departamento de Quımica Organica e Inorganica, Instituto Universitario de Quımica Organometalica ‘‘Enrique Moles’’
´
(Unidad Asociada al CSIC), Facultad de Quımica, Universidad de Oviedo, E-33071 Oviedo, Spain
Received 20 December 2004; accepted 20 December 2004
Available online 5 February 2005
Abstract
The novel bis(iminophosphorano)methanes CH2[P{@NP(@S)(OR)2}Ph2]2 (R = Ph (1a), Et (1b)) have been obtained by oxyda-
tion of dppm with the corresponding thiophosphorylated azides (RO)2P(@S)N3. Deprotonation of 1a,b with KH generates the
methanide species KCH[P{@NP(@S)(OR)2}Ph2]2 (R = Ph (2a), Et (2b)). The ruthenium(II) dimer [{Ru(g6-p-cymene)(l-Cl)Cl}2]
reacts with 2a,b to afford the cationic complexes [Ru(g6-p-cymene)(j3-C,N,S-CH[P{@NP(@S)(OR)2}Ph2]2)]+ (R = Ph (3a), Et
(3b)), via selective j3-C,N,S-coordination of the bis(iminophosphorano)methanide anions to ruthenium. The structure of [Ru(g6-
p-cymene)(j3-C,N,S-CH[P{@NP(@S)(OEt)2}Ph2]2)][PF6] (3b) has been confirmed by single-crystal X-ray crystallography. Deproto-
nation of complexes 3a,b with NaH leads to the neutral carbene derivatives [Ru(g6-p-cymene)(j2-C,N-C[P{@NP(@S)(OR)2}Ph2]2)]
(R = Ph (4a), Et (4b)).
ꢀ 2005 Elsevier B.V. All rights reserved.
Keywords: Bis(iminophosphorano)methane; Bis(iminophosphorano)methanide; Bis(iminophosphorano)methandiide; Ruthenium; Carbene com-
plexes
1. Introduction
tion chemistry of these monoanions has been the subject
of several studies over the last few years due to their
topological similarity with the well-known b-diketimi-
nate ligands B [4]. As expected, bis(iminophosphor-
Oxidation of the two phosphorus atoms of bis(diph-
enylphosphino)methane (dppm) with organic azides
(RN3), by means of the Staudinger reaction [1], has been
successfully applied to the preparation of several bis
(iminophosphorano)methane derivatives CH2{P(@NR)-
Ph2}2 (see for example [2]). The presence of two highly
polarized P@N groups in these compounds results in
an enhanced acidity of the methylenic hydrogen atoms,
and consequently deprotonation reactions to afford the
corresponding bis(iminophosphorano)methanide anions
(A; see Chart 1) can easily take place [3]. The coordina-
ano)methanides
A
have proven to be versatile
chelating ligands being able to adopt j2-N,N (C; Zn,
Fe, Ge and group 13 complexes) (see for example [5]),
j2-C,N (D; Rh, Ir, Pd and Pt complexes) (see for exam-
ple [6]) or j3-N,C,N (E; V, Co, Rh, Ir, Ni, Mn, Fe, U, Y
and lanthanide complexes) (see for example [7]) coordi-
nation modes, depending on the nature of the metal
fragment (Chart 1).
In this context, the groups of Cavell [8] and Stephan [9]
have also reported the synthesis and structural
characterization of the dilithiomethandiide dimer [Li2C-
{P(@NSiMe3)Ph2}2]2, as the result of the double depro-
tonation of the PCH2P backbone of the bis(iminophos-
phorano)methane derivative CH2{P(@NSiMe3)Ph2}2.
*
Corresponding authors. Tel.: +34 985 103 461; fax: +34 985 103
446.
E-mail addresses: jgh@uniovi.es (J. Gimeno), vcm@uniovi.es (V.
Cadierno).
0022-328X/$ - see front matter ꢀ 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.12.034

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V. Cadierno et al. / Journal of Organometallic Chemistry 690 (2005) 2087–2096
H
4 metals [10], samarium [11], and molybdenum [12], while
H
R´
R
R´
R
bimetallic species G are known for chromium [13], alumi-
num [5b,14] and group 14 metals [15]. The synthesis
and reactivity of the platinum–carbene complex H [16]
and the bis(germavinylidene) I [5f,12,15] has been also
reported.
Ph2P
PPh2
N
R
N
R
N
N
A
B
In contrast, very few ruthenium complexes contain-
ing bis(iminophosphorano)methanide anions A have
been described in the literature (see Chart 3). Recently,
we and others have reported the only examples known
to date, namely: (i) the cationic complex [Ru(g6-p-cym-
ene)(j3-N,C,N-CH{P(@NPh)Ph2}2)][Cl] (J) in which the
H
H
Ph2
P
Ph2P
PPh2
Ph2P
PPh2
H
N
R
N
N
R
N
R
N
R
N
P
Ph2
R
[M]
[M]
C
[M]
E
R
D
bis(iminophosphorano)methanide ligand displays
a
symmetric j3-N,C,N-coordination mode [17] and (ii)
complexes of the type K and L (R = Ph, Et) in which
Chart 1. Structure of the anions A and B, and coordination modes
of A.
N-phosphorylated
bis(iminophosphorano)methanide
Interestingly, the coordination of this dianionic unit to a
metal fragment leads to unique ‘‘pincer’’ (F) or bridged
(G) carbene complexes (see Chart 2). Thus, pincer-type
structures F have been found in some complexes of group
anions are acting as unsymmetrical j2-C,N (K) or j3-
C,N,O (L) chelate ligands [18]. Significantly, the latter
complexes have shown to be good precursors of nucleo-
philic carbenes M via deprotonation of the methinic
Ph2
P
[M]
PPh2
N
Ph2P
N
C
N
SiMe3
Me3Si
N
C
[M]
P
Ph2
[M]
Me3Si
SiMe3
F
G
Ph2
Me3Si
Ph2
P
Ph2
P
Me3Si
Me3Si
P
N
PPh2
N
N
C
C
SiMe3
N
N
Ge
Ge
Pt
SiMe3
C
Ph2P
N
SiMe3
P
Ph2
H
I
Chart 2. Structure of the carbenic species F–I.
[Cl]
Cl
Ru
P
O
P
H
Ph
Ph
Ru
C
N
N
(OR)
C
N
2
Ph2P
N
Ph2P
PPh2
Ph2
H
(RO)2P
O
J
K
[SbF6]
O
O
Ru
Ru
(RO)
2P
N
O
N
(OR)
P
O
2
P
C
N P
(OR)2
(RO)2
P
C
Ph2
PPh2
P
P
Ph2
N
H
Ph2
L
M
Chart 3. Ruthenium(II) complexes containing bis(iminophosphorano)methanide and methandiide ligands.

V. Cadierno et al. / Journal of Organometallic Chemistry 690 (2005) 2087–2096
2089
PCHP hydrogen atom [18]. To the best of our knowl-
edge, they are the sole examples of ruthenium complexes
containing bis(iminophosphorano)methandiide ligands.
As an extension of our previous studies, mainly
devoted to explore the scope of this synthetic approach
to ruthenium–carbene complexes, in this paper we
report: (i) the synthesis of the novel N-thiophosphory-
lated bis(iminophosphorano)methanes CH2[P{@NP(@S)-
(OR)2}Ph2]2 (R = Ph, Et), (ii) the reactions of their
methanide anions with the ruthenium(II) dimer [{Ru-
(g6-p-cymene)(l-Cl)Cl}2] giving rise to thiophosphory-
lated ruthenacarbobicycles, and (iii) the synthesis of
novel carbene derivatives of the type M.
the methylenic PCH2P group which appear as triplet sig-
nals at ca. 5 and 23 ppm, respectively, due to the cou-
pling with the two equivalent Ph2P@N phosphorus
1
atoms (ca.2JHP = 15 Hz and JCP = 56 Hz).
2.2. Synthesis of the anionic
bis(iminophosphorano)methanide species
KCH[P{@NP(@S)(OR)2}Ph2]2 (R = Ph (2a),
Et (2b))
The reaction of 1a,b with an excess of potassium hy-
dride, in THF at room temperature, consumes only
one equivalent of KH to give the moisture-sensitive
bis(iminophosphorano)methanide potassium salts KCH-
[P{@NP(@S)(OR)2}Ph2]2 (R = Ph (2a), Et (2b)) in
almost quantitative yields (see Scheme 2) [20]. No evi-
dence for further deprotonation of these ligands was ob-
served even when LDA or organolithium reagents were
used.
2. Results and discussion
2.1. Synthesis of the N-thiophosphorylated
bis(iminophosphorano)methane ligands
CH2[P{@NP(@S)(OR)2}Ph2]2 (R = Ph (1a), Et
(1b))
Compounds 2a,b have been characterized by multi-
nuclear NMR spectroscopic techniques (see Section 4
for details). As previously reported for other bis(imino-
phosphorano)methanides [3,18]: (i) The 31P resonances
of the Ph2P@N groups in 2a,b are downfield shifted
(Dd ca. 8 ppm) relative to their parent bis(iminophos-
phorano)methanes 1a,b (in contrast, slight high-field
shifts (Dd ca. ꢀ2 ppm) are observed for the thiophos-
phoryl units (RO)P@S). (ii) The methine PCHP proton
The novel N-thiophosphorylated bis(iminophosphor-
ano)methane ligands 1a,b have been readily prepared by
treating dppm with two equivalents of the correspond-
ing azides (RO)2P(@S)N3 in THF at room temperature
(see Scheme 1).
Compounds 1a,b have been isolated as air-stable
white solids in high yields (90% and 84%, respectively).
They are soluble in chlorinated solvents, THF and
diethyl ether, and are insoluble in apolar solvents such
n-pentane or hexanes. Characterization of 1a,b was
straightforward following their analytical and spectro-
scopic data (details are given in Section 4). The most
remarkable features of the NMR spectra are: (i)
(31P{1H} NMR) The presence of two multiplets with
equal relative intensities (1a: 10.95 (Ph2P@N) and
51.23 ((PhO)2P@S) ppm; 1b: 9.14 (Ph2P@N) and 59.07
((EtO)2P@S) ppm; AA0 XX0 spin system). These chemi-
cal shifts can be compared with those described in the
literature for related bis(iminophosphoranes) CH2{P-
(@NR)Ph2}2 [2] and thiophosphorylated species R3P@
NP(@S)(OR)2 (see for example [19]). And, (ii) (1H and
13C{1H} NMR) both proton and carbon resonances of
1
appears in the H NMR spectra as a broad signal at
1.42–2.02 ppm (instead of the expected triplet because
of coupling with the equivalent Ph2P@N phosphorus
nuclei). And, (iii) the methine carbon resonates in the
13C{1H} NMR spectra as a well-defined triplet (ca.
1JCP = 140 Hz) at ca. 20 ppm.
2.3. Reactions of the bis(iminophosphorano)methanide
anions 2a,b with [{Ru(g6-p-cymene)(l-Cl)Cl}2]
The treatment of [{Ru(g6-p-cymene)(l-Cl)Cl}2] with
2a,b in refluxing THF affords selectively the catio-
nic derivatives [Ru(g6-p-cymene)(j3-C,N,S-CH[P{@NP-
(@S)(OR)2}Ph2]2)][Cl] (R = Ph (3a), Et (3b)) (see Scheme
3). These air-stable complexes have been isolated as the
corresponding hexafluorophosphate salts, in 54 (3a)
and 49% (3b) yield, via a classical Clꢀ=PF6ꢀ exchange
H
H
H
H
H
2 N2
H
H
S
H2
Ph2P
PPh2
Ph2P
N
PPh2
N
2 (RO)2P-N3
Ph2P
PPh2
KH
Ph2P
PPh2
N
N
THF / r.t.
THF / r.t.
N
N
(RO)2P
P(OR)2
K
P(OR)2
(RO)2P
P(OR)2
(RO)2P
S
S
S
S
S
S
R = Ph (2a), Et (2b)
R = Ph (1a), Et (1b)
R = Ph (1a), Et (1b)
Scheme 1. Synthesis of the N-thiophosphorylated bis(iminophosphor-
ano)methanes 1a,b.
Scheme 2. Synthesis of the N-thiophosphorylated bis(iminophosphor-
ano)methanides 2a,b.

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V. Cadierno et al. / Journal of Organometallic Chemistry 690 (2005) 2087–2096
using NaPF6 in a mixture CH2Cl2/MeOH at room
temperature.
Moreover, the structure of complex 3 b was unambig-
uously confirmed by a single-crystal X-ray diffraction
study (a RRuSC/SRuRC racemic mixture is present). An
ORTEP-type drawing of the molecular structure of the
Compounds 3a,b have been characterized by elemen-
tal analyses, conductance measurements (1:1 electro-
lytes; KM = 107 (3a) and 120 (3b) Xꢀ1 cm2 molꢀ1), and
IR and NMR spectroscopy (details are given in Section
4), the latter supporting the diastereoselective formation
of an unsymmetric metallabicycle (two stereogenic cen-
ters are formed, i.e. the ruthenium atom and the PCHP
carbon). The most relevant spectroscopic data concern
the methine PCHP resonances: (i) (1H NMR) A doublet
R
RuSC enantiomer is shown in Fig. 1, and selected bond
distances and angles are listed in the caption. The coor-
dination sphere around ruthenium consists of the g6-
p-cymene ring, the methinic PCHP carbon, the nitrogen
atom of one of the –P@N–P@S arms, and the sulphur
atom of the second one, disposed with a classical
three-legged piano-stool geometry. In accord, the values
of the interligand angles N(2)–Ru–C(27), C(27)–Ru–
S(1), and N(2)–Ru–S(1), and those between the centroid
of the p-cymene ring C* and the legs, are typical of a
pseudo-octahedron. In spite of the unsymmetrical
2
of doublets (3a; JHP = 11.8 and 7.9 Hz) or multiplet
(3b) at ca. 4.3 ppm. And, (ii) (13C{1H} NMR) a well-re-
solved dddd signal at ca. ꢀ8 ppm (1JCP = 55.7–62.4 Hz;
3JCP = 10.6–17.8 Hz).
[PF6]
1/2 [{Ru(η6-p-cymene)(µ-Cl)Cl}2]
1) THF / reflux
S
P
2) NaPF6 / CH2Cl2-MeOH / r.t.
Ru
C
+
N
(OR)
2
S
(RO)2P
KCH[P{=NP(=S)(OR)2}Ph2]2
PPh2
P
KCl, NaCl
N
H
Ph2
R = Ph (2a), Et (2b)
R = Ph (3a), Et (3b)
Scheme 3. Coordination of the bis(iminophosphorano)methanides 2a,b to a (g6-arene)-Ru(II) fragment.
Fig. 1. ORTEP-type view of the structure of 3b showing the crystallographic labeling scheme. Hexafluorophosphate anion, phenyl groups of the
ligand and hydrogen atoms (except that on the C(27) carbon) have been omitted for clarity. Thermal ellipsoids are drawn at the 20% probability level.
˚
Selected bond distances (A) and angles (ꢁ): Ru–N(2) = 2.163(11); Ru–C(27) = 2.160(13), Ru–S(1) = 2.445(4); Ru–C* = 1.6852(5); C(27)–
P(2) = 1.825(12); P(2)–N(1) = 1.547(9); N(1)–P(1) = 1.568(10); P(1)–S(1) = 1.998(5); P(1)–O(1) = 1.597(9); P(1)–O(2) = 1.586(9); C(27)–
P(3) = 1.756(12); P(3)–N(2) = 1.607(9); N(2)–P(4) = 1.632(11); P(4)–S(2) = 1.929(5); P(4)–O(3) = 1.599(9); P(4)–O(4) = 1.571(9); C*–Ru–N(2) =
130.82(2); C*–Ru–C(27) = 129.35(3); C*–Ru–S(1) = 125.71(2); N(2)–Ru–C(27) = 71.5(4); N(2)–Ru–S(1) = 85.5(3); C(27)–Ru–S(1) = 96.7(3); Ru–
C(27)–P(3) = 93.2(6); C(27)–P(3)–N(2) = 97.2(6); P(3)–N(2)–Ru = 97.6(5); P(3)–N(2)–P(4) = 132.4(7); N(2)–P(4)–S(2) = 117.1(4); Ru–N(2)–P(4) =
129.7(5); Ru–C(27)–P(2) = 120.5(6); C(27)–P(2)–N(1) = 115.8(6); P(2)–N(1)–P(1) = 136.4(6); N(1)–P(1)–S(1) = 118.4(4); P(1)–S(1)–Ru = 113.07(18).
C* = centroid of the p-cymene ring (C(1), C(2), C(3), C(4), C(5) and C(6)).

V. Cadierno et al. / Journal of Organometallic Chemistry 690 (2005) 2087–2096
2091
j3-C,N,S-coordination of the bis(iminophospho-
rane)methanide ligand, only slight differences in the
bond distances within the two APh2P@NAP(@S)(OEt)2
frameworks are observed (ca. 0.07 A). This fact, along
with the similarity between the formal single and double
room temperature, generates the novel carbene deriva-
tives [Ru(g6-p-cymene)(j2-C,N-C[P{@NP(@S)(OR)2}-
Ph2]2)] (R = Ph (4a), Et (4b)) (see Scheme 4). They have
been isolated as air-stable violet solids in good yields
(80–83%).
˚
˚
PN bonds (from 1.547(9) to 1.632(11) A), is indicative of
Analytical and spectroscopic data (IR, and 1H,
31P{1H} and 13C{1H} NMR) of complexes 4a,b sup-
port the proposed formulation. In particular, the
31P{1H} NMR spectra show the presence of four
chemically inequivalent phosphorus nuclei. The down-
field chemical shift observed for one of the two
Ph2P@N phosphorus resonances (4a: 66.02 ppm (dd,
2JPP = 96.7 and 23.0 Hz); 4b: 60.49 ppm (dd,
2JPP = 84.7 and 14.1 Hz)) confirms its coordination to
the metal center forming part of the four-membered
ruthenacarbocycle (the uncoordinated Ph2P@N units
an extensive p-electronic delocalization within both
Ph2P@N-P(@S)(OEt)2 arms of the ligand. A similar
trend was previously observed in the X-ray structure
of the related N-phosphorylated complex [Ru(g6-p-cym-
ene)(j3-C,N,O-CH[P{@NP(@O)(OPh)2}Ph2]2)][SbF6]
˚
[18]. The Ru–C(27) bond length (2.160(13) A) shows the
expected value for a ruthenium–carbon single bond [21].
The formation of complexes 3a,b, containing two
fused six- and four-membered ruthenacarbocycles,
contrast with our previous results using the closely
related N-phosphorylated sodium salts NaCH[P{@NP-
(@O)(OR)2}Ph2]2 [18] which lead instead to neutral
1
resonate at ca. 12 ppm). The H and 13C{1H} NMR
spectra clearly confirm the deprotonation of bis(imino-
phosphorano)methanide ligands by the disappearance
of the characteristic methinic PCHP signals. As previ-
ously observed for the related compounds [Ru(g6-p-
cymene)(j2-C,N-C[P{@NP(@O)(OR)2}Ph2]2)] (M) [18],
the carbenic Ru@C carbon resonances of complexes
4a,b fall within the aromatic signals region being over-
lapped. Only in the case of 4b this resonance could be
identified by using 13C{1H} APT experiments (dC
128.59 ppm).
complexes
[RuCl(g6-p-cymene)(j2-C,N-CH[P{@NP-
(@O)OR)2} Ph2]2)] (K in Chart 3). Nevertheless, the
corresponding cationic derivatives [Ru(g6-p-cymene)-
(j3-C,N,O-CH[P{@NP(@O)(OPh)2}Ph2]2)][SbF6] (L in
Chart 3) were prepared via coordination of the phos-
phoryl group after chloride abstraction. All attempts
to isolate or detect the analogous j2-C,N-thiophospho-
ryl derivatives containing the four-membered ruthena-
carbocycle of the type K have been unsuccessful. All
these results indicate how the nature of the P@N substit-
uents can modify the binding preferences of this type of
ligands. This is also assessed by the formation of com-
plex [Ru(g6-p-cymene)(j3-N,C,N-CH{P(@NPh)Ph2}2)]-
[Cl] (J in Chart 3), recently reported by Caulton and
co-workers [17], in which the analogous methanide
anion [CH{P(@NPh)Ph2}2]ꢀ shows a symmetric j3-N,
C,N-coordination mode forming a fused two four-
membered ruthenacarbocycle.
3. Concluding remarks
In this paper, we have shown that the sequential
double deprotonation of the methylenic backbone of
the readily available bis(iminophosphorano)methanes
CH2{P(@NR)Ph2}2 [2] is a general route for the prepa-
ration of metallacyclic ruthenium–carbene complexes. It
is also shown the versatile coordination ability of the
methanide species {CH[P{@NP(@X)(OR)2}Ph2]2}ꢀ (X =
O,S), which display j2-C,N- or j3-C,N,X-coordination
modes depending on the presence of both P@O or
P@S groups in the partner iminophosphorane. Cur-
rent studies aimed at exploring the reactivity and syn-
thetic applications of the unusual metallacyclic carbene
2.4. Synthesis of ruthenium(II) carbene complexes
[Ru(g6-p-cymene)(j2- C,N-C[P{@NP(@S)-
(OR)2}Ph2]2)] (R = Ph (4a), Et (4b))
Following the synthetic route for the preparation of
carbene complexes M (see Chart 3) [18], the treatment
of the cationic complexes [Ru(g6-p-cymene)(j3-C,N,S-
CH[P{@NP(@S)(OR)2}Ph2]2)][Cl] (R = Ph (3a), Et
(3b)) with an excess of NaH (ca. 10 equiv.), in THF at
complexes
progress.
are now in
[Ru]=C{P(=NR)Ph2}P(=NR)Ph2
[PF6]
H2
S
NaH
THF / r.t.
S
P
Ru
Ru
C
(RO)
2P
N
S
N
(OR)
2
S
P
C
N
P
(OR)2
(RO)2P
Ph2
NaPF6
PPh2
P
P
Ph2
N
H
Ph2
R = Ph (4a), Et (4b)
R = Ph (3a), Et (3b)
Scheme 4. Synthesis of the novel carbene-ruthenium(II) complexes 4a,b.

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V. Cadierno et al. / Journal of Organometallic Chemistry 690 (2005) 2087–2096
4. Experimental
4.1. General information
(w) cmꢀ1 31P{1H} NMR (CDCl3) d = 9.14 (m,
;
Ph2P@N), 59.07 (m, (EtO)2P@S) ppm (AA0 XX0 spin
system); 1H NMR (CDCl3) d = 1.18 (t, 12H,
3JHH = 7.1 Hz, OCH2CH3), 3.90 (m, 8H, OCH2CH3),
2
The manipulations were performed under an atmo-
sphere of dry nitrogen using vacuum-line and standard
Schlenk techniques. Solvents were dried by standard
methods and distilled under nitrogen before use. All re-
agents were obtained from commercial suppliers with
the exception of compounds (RO)2P(@S)N3 (R = Et,
Ph) [22] and [{Ru(g6-p-cymene)(l-Cl)Cl}2] [23] which
were prepared by following the methods reported in
the literature. Infrared spectra were recorded on a Per-
kin–Elmer 1720-XFT spectrometer. The conductivities
were measured at room temperature, in ca. 10ꢀ3 mol
dmꢀ3 acetone solutions, with a Jenway PCM3 conduc-
timeter. Mass spectra (FAB) were recorded using a
VG Autospec spectrometer, operating in the positive
mode; 3-nitrobenzyl alcohol was used as the matrix.
The C, H, and N analyses were carried out with a Per-
kin-Elmer 2400 microanalyzer. NMR spectra were re-
corded on a Bruker DPX-300 instrument at 300 MHz
(1H), 121.5 MHz (31P) or 75.4 MHz (13C) using SiMe4
or 85% H3PO4 as standards. DEPT experiments have
been carried out for all the compounds reported.
5.31 (t, 2H, JHP = 15.4 Hz, PCH2P), 7.26–7.49 (m,
12H, Ph), 7.78–7.85 (m, 8H, Ph) ppm; 13C{1H} NMR
3
(CDCl3) d = 15.95 (d, JCP = 8.7 Hz, OCH2CH3), 22.59
1
2
(t, JCP = 55.3 Hz, PCH2P), 61.82 (d, JCP = 5.8 Hz,
OCH2CH3), 128.18–131.99 (m, Ph) ppm.
4.3. Synthesis of KCH[P{@NP(@S)(OR)2}Ph2]2
(R = Ph (2a), Et (2b))
A solution of the corresponding bis(iminophosphor-
ano)methane 1a,b (0.45 mmol) in THF (30 ml) was trea-
ted, at room temperature, with KH (0.180 g, 4.5 mmol)
for 30 min. The resulting suspension was filtered
through Kieselguhr and the filtrate evaporated to dry-
ness giving 2a,b as colorless oils in almost quantitative
yield. (2a): 31P{1H} NMR (C6D6) d = 18.83 (m,
Ph2P@N), 48.31 (m, (PhO)2P@S) ppm (AA0 XX0 spin
system); 1H NMR (C6D6) d = 2.02 (br, 1H, PCHP),
6.87–7.35 (m, 28H, Ph), 8.04 (m, 12H, Ph) ppm;
1
13C{1H} NMR (C6D6) d = 17.78 (t, JCP = 138.3 Hz,
2
PCHP), 122.06–138.19 (m, Ph), 152.88 (d, JCP
=
9.3 Hz, Cipso of OPh) ppm. (2b): 31P{1H} NMR
(C6D6) d = 17.65 (m, Ph2P@N), 57.55 (m, (EtO)2P@S)
ppm (AA0 XX0 spin system); 1H NMR (C6D6)
d = 0.94 (t, 12H, JHH = 7.0 Hz, OCH2CH3), 1.42 (br,
1H, PCHP), 3.72 (m, 8H, OCH2CH3), 7.00–7.19 (m,
12H, Ph), 8.03–8.10 (m, 8H, Ph) ppm; 13C{1H} NMR
4.2. Synthesis of CH2[P{@NP(@S)(OR)2}Ph2]2
(R = Ph (1a), Et (1b))
3
A
solution of bis(diphenylphosphino)methane
(0.384 g; 1 mmol) in THF (40 ml) was treated with the
corresponding azide (RO)2P(@S)N3 (2.2 mmol) for
10 h at room temperature. The solvent was then re-
moved under reduced pressure to give a colorless oil
which was washed with n-pentane (3 · 20 ml) and dried
in vacuo to afford compounds 1a,b as white solids. (1a):
Yield: 90% (0.820 g); Anal. Calcd for C49H42O4P4N2S2
(910.90 g molꢀ1): C, 64.61; H, 4.65; N, 3.07. Found:
C, 64.59; H, 4.58; N, 3.19%; IR (KBr) m = 468 (w), 501
(s), 517 (w), 548 (w), 605 (w), 625 (m), 691 (s), 736 (s),
759 (m), 775 (m), 834 (s), 890 (vs), 910 (vs), 1027 (m),
1108 (m), 1195 (vs), 1269 (s), 1440 (m), 1459 (w), 1485
3
(C6D6) d = 18.22 (d, JCP = 8.7 Hz, OCH2CH3), 20.31
1
2
(t, JCP = 140.9 Hz, PCHP), 63.91 (d, JCP = 7.0 Hz,
OCH2CH3), 132.39–140.70 (m, Ph) ppm. Compounds
2a,b were too sensitive to moisture to give satisfactory
elemental analyses.
4.4. Synthesis of [Ru(g6-p-cymene)(j3- C,N,S-
CH[P{@NP(@S)(OR)2}Ph2]2)][PF6] (R = Ph (3a),
Et (3b))
To
a
solution of [{Ru(g6-p-cymene)(l-Cl)Cl}2]
(s), 1591 (m), 2857 (w), 2885 (w), 3056 (w) cmꢀ1
;
(0.092 g, 0.15 mmol) in 30 ml of THF was added, at
room temperature, the corresponding bis(iminophos-
phorano)methanide compound 2a,b (0.45 mmol), and
the reaction mixture refluxed for 1 h. The solvent was
then removed under vacuum, the crude product
extracted with dichloromethane (ca. 20 ml), and the
extract filtered. The resulting solution was treated, at
room temperature, with a solution of NaPF6 (0.252 g,
1.5 mmol) in 10 ml of methanol for 3 h. The solvents
were then removed under vacuum, the crude product ex-
tracted with dichloromethane (ca. 20 ml), and the ex-
tract filtered. Concentration of the resulting solution
(ca. 5 ml) followed by the addition of a mixture diethyl
ether/hexanes (ca. 50 ml; 1:1 v/v) precipitated an orange
31P{1H} NMR (CDCl3) d = 10.95 (m, Ph2P@N), 51.23
(m, (PhO)2P@S) ppm (AA0 XX0 spin system); 1H
NMR (CDCl3) d = 5.02 (t, 2H, 2JHP = 15.1 Hz, PCH2P),
7.11–7.44 (m, 28H, Ph), 7.68–7.79 (m, 12H, Ph) ppm;
13C{1H} NMR (CDCl3) d = 23.85 (t, JCP = 57.1
1
Hz, PCH2P), 121.28–132.30 (m, Ph), 151.80 (d,
2JCP = 9.3 Hz, Cipso of OPh) ppm. (1b): Yield: 84%
(0.604 g); Anal. Calcd for C33H42O4P4N2S2 (718.72 g
molꢀ1): C, 55.15; H, 5.89; N, 3.90. Found: C, 55.20;
H, 5.86; N, 3.89%; IR (KBr) m = 498 (s), 517 (w), 551
(w), 590 (w), 691 (m), 721 (m), 757 (m), 810 (m), 959
(s), 1037 (s), 1109 (m), 1174 (w), 1231 (vs), 1386 (w),
1437 (m), 1486 (w), 1591 (w), 2981 (m), 2979 (m), 3053

V. Cadierno et al. / Journal of Organometallic Chemistry 690 (2005) 2087–2096
2093
2
solid, which was washed with a mixture diethyl ether/
hexanes (3 · 30 ml; 1:1 v/v) and dried in vacuo. (3a):
Yield: 54% (0.209 g); Anal. Calcd for RuC59H55F6-
P5O4N2S2 Æ 1/5CH2Cl2 (1307.13 g molꢀ1): C, 54.40; H,
4.27; N, 2.14. Found: C, 54.48; H, 4.18; N, 2.17%; Con-
ductivity (acetone, 20 ꢁC) 107 Xꢀ1 cm2 molꢀ1; IR (KBr)
m = 557 (m), 689 (m), 729 (w), 768 (w), 842 (s), 919 (s),
1024 (w), 1111 (m), 1130 (m), 1161 (m), 1191 (s), 1287
(w), 1438 (m), 1488 (s), 1570 (m), 2860 (w), 2960 (w)
Hz, OCH2CH3), 64.24 (d, JCP = 7.5 Hz, OCH2CH3),
79.09, 82.18, 83.32 and 84.19 (s, CH of p-cymene),
99.60 and 110.67 (s, C of p-cymene), 125.25–135.56
(m, Ph) ppm.
4.5. Synthesis of [Ru(g6-p-cymene)(j2-C,N-
C[P{@NP(@S)(OR)2}Ph2]2)] (R = Ph (4a),
Et (4b))
cmꢀ1
;
31P{1H} NMR (CD2Cl2) d = 28.49 (ddd,
A solution of the corresponding cationic complex
[Ru(g6-p-cymene)(j3-C,N,S-CH[P{@NP(@S)(OR)2}-
Ph2]2)][PF6] 3a,b (0.1 mmol) in 30 ml of THF was trea-
ted, at room temperature, with NaH (0.024 g, 1 mmol)
for 3 h. The solvent was then removed under vacuum,
the crude product extracted with diethyl ether (ca.
50 ml), and the extract filtered. Concentration of the
resulting solution (ca. 2 ml) followed by the addition
of hexanes (ca. 50 ml) precipitated a violet solid, which
was filtered, washed with hexanes (3 · 20 ml) and dried
in vacuo. (4a): Yield: 80% (0.092 g); Anal. Calcd for Ru-
C59H54O4P4N2S2 (1144.17 g molꢀ1): C, 61.93; H, 4.76;
N, 2.45. Found: C, 62.00; H, 4.48; N, 2.20%; IR (KBr)
m = 498 (w), 531 (w), 617 (w), 688 (s), 768 (m), 804 (s),
909 (m), 1024 (s), 1101 (s), 1159 (m), 1195 (s), 1261
(s), 1434 (m), 1488 (s), 1590 (m), 2924 (w), 2962 (w),
2JPP = 18.6 and 4.7 Hz, JPP = 3.1 Hz, Ph2P@N), 43.08
(d, 2JPP = 18.6 Hz, (PhO)2P@SARu), 60.65 (dd,
2JPP = 27.6 and 4.7 Hz, Ru–N@PPh2), 66.89 (dd,
4
2JPP = 27.6 Hz, 4JPP = 3.1 Hz, Ru–NP(@S)(OPh)2)
ppm; 1H NMR (CD2Cl2) d = 0.83 (d, 3H, JHH
=
3
3
6.9 Hz, CH(CH3)2), 1.04 (d, 3H, JHH = 6.7 Hz, CH-
(CH3)2), 1.90 (s, 3H, CH3), 2.16 (m, 1H, CH(CH3)2),
2
4.21 (dd, 1H, JHP = 11.8 and 7.9 Hz, PCHP), 4.31
3
and 4.59 (d, 1H each, JHH = 5.8 Hz, CH of p-cymene),
5.40 (br, 2H, CH of p-cymene), 6.70–8.32 (m, 40H, Ph)
1
ppm; 13C{1H} NMR (CD2Cl2) d = ꢀ8.16 (dddd, JCP
=
3
55.7 and 55.7 Hz, JCP = 17.8 and 10.9 Hz, PCHP),
18.24 (s, CH3), 19.93 and 23.26 (s, CH(CH3)2), 30.45
(s, CH(CH3)2), 77.43, 82.17, 83.24 and 84.45 (s, CH of
p-cymene), 98.14 and 113.84 (s, C of p-cymene),
2
120.02–135.22 (m, Ph), 151.05 (d, JCP = 12.1 Hz, Cipso
2
of OPh), 151.12 (d, JCP = 7.6 Hz, Cipso of OPh),
3047 (w) cmꢀ1
;
31P{1H} NMR (C6D6) d = 12.72 (ddd,
2JPP = 96.7 and 27.0 Hz, JPP = 9.8 Hz, Ph2P@N),
4
2
2
151.34 (d, JCP = 6.8 Hz, Cipso of OPh), 152.10 (d,
47.71 (d, JPP = 27.0 Hz, (PhO)2P@S), 61.00 (dd,
2JCP = 8.3 Hz, Cipso of OPh) ppm. (3b): Yield: 49%
(0.161 g); Anal. Calcd for RuC43H55F6P5O4N2S2
(1097.98 g molꢀ1): C, 47.04; H, 5.05; N, 2.55. Found:
C, 47.33; H, 5.21; N, 2.53%; Conductivity (acetone,
20 ꢁC) 120 Xꢀ1 cm2 molꢀ1; IR (KBr) m = 487 (w), 531
(w), 557 (s), 596 (w), 655 (w), 691 (m), 752 (s), 840 (s),
912 (m), 958 (s), 1026 (s), 1110 (s), 1159 (m), 1264 (m),
1285 (m), 1388 (w), 1438 (s), 1473 (w), 1588 (w), 2901
2JPP = 23.0 Hz, 4JPP = 9.8 Hz, Ru–NP(@S)(OPh)2),
2
66.02 (dd, JPP = 96.7 and 23.0 Hz, Ru–N@PPh2)
ppm; 1H NMR (C6D6) d = 1.11 (d, 6 H, JHH = 6.9
3
Hz, CH(CH3)2), 1.96 (s, 3H, CH3), 2.24 (sept, 1H,
3JHH = 6.9 Hz, CH(CH3)2), 5.48 and 5.59 (d, 2H each,
3JHH = 5.9 Hz, CH of p-cymene), 6.85–7.90 (m, 40H,
Ph) ppm; 13C{1H} NMR (C6D6) d = 19.33 (s, CH3),
23.46 (s, CH(CH3)2), 31.34 (s, CH(CH3)2), 79.11 and
81.97 (s, CH of p-cymene), 87.17 and 98.69 (s, C of p-
cymene), 121.61–136.44 (m, Ph and PCP), 153.32 (d,
2JCP = 9.3 Hz, Cipso of OPh) ppm. (4b): Yield: 83%
(0.079 g); Anal. Calcd for RuC43H54O4P4N2S2 (952.00
g molꢀ1): C, 54.25; H, 5.72; N, 2.94. Found: C, 54.01;
H, 5.61; N, 2.89%; IR (KBr) m = 479 (w), 531 (w), 556
(w), 690 (m), 748 (m), 801 (s), 911 (w), 948 (m), 1024
(s), 1102 (s), 1152 (m), 1261 (s), 1387 (w), 1436 (m),
(w), 2928 (w), 2978 (m), 3059 (w) cmꢀ1
;
31P{1H}
2
NMR ((CD3)2CO) d = 26.27 (ddd, JPP = 17.8 and
4
2
3.4 Hz, JPP = 5.1 Hz, Ph2P@N), 51.29 (d, JPP
=
2
17.8 Hz, (EtO)2P@SARu), 64.68 (dd, JPP = 23.8 and
2
3.4 Hz, Ru–N@PPh2), 69.80 (dd, JPP = 23.8 Hz,
4JPP = 5.1 Hz, Ru–NP(@S)(OEt)2) ppm; 1H NMR
3
((CD3)2CO) d = 1.15 and 1.50 (t, 3H each, JHH
=
7.0 Hz, OCH2CH3), 1.21–1.28 (m, 12H, CH(CH3)2 and
OCH2CH3), 2.15 (s, 3H, CH3), 3.06 (m, 1H, CH(CH3)2),
3.65, 3.87 and 4.03 (m, 2H each, OCH2CH3), 4.30 (m,
3H, OCH2CH3 and PCHP), 4.64 and 5.39 (d, 1H each,
3JHH = 5.6 Hz, CH of p-cymene), 5.06 (br, 2H, CH of p-
cymene), 7.17–8.44 (m, 20H, Ph) ppm; 13C{1H} NMR
1460 (w), 2855 (w), 2931 (w), 2951 (w) cmꢀ1
;
31P{1H}
2
NMR (C6D6) d = 11.59 (ddd, JPP = 84.7 and 29.3 Hz,
4JPP = 9.8 Hz, Ph2P@N), 55.44 (d, JPP = 29.3 Hz,
2
2
(EtO)2P@S), 60.49 (dd, JPP = 84.7 and 14.7 Hz, Ru–
2
4
N@PPh2), 70.23 (dd, JPP = 14.7 Hz, JPP = 9.8 Hz,
1
((CD3)2CO) d = ꢀ8.09 (dddd, JCP = 62.4 and 62.4 Hz,
Ru–NP(@S)(OEt)2) ppm; 1H NMR (C6D6) d = 1.01
and 1.21 (t, 6H each, JHH = 6.9 Hz, OCH2CH3), 1.16
3
3
3JCP = 17.2 and 10.6 Hz, PCHP), 15.96 (d, JCP = 5.2
3
Hz, OCH2CH3), 16.01 (d, JCP = 6.0 Hz, OCH2CH3),
3
(d, 6H, JHH = 6.9 Hz, CH(CH3)2), 2.10 (s, 3H, CH3),
3
16.07 and 16.12 (d, JCP = 4.8 Hz, OCH2CH3), 18.21
(s, CH3), 21.25 and 22.33 (s, CH(CH3)2), 30.62 (s,
3
2.61 (sept, 1H, JHH = 6.9 Hz, CH(CH3)2), 4.04 (m,
3
8H, OCH2CH3), 5.41 and 5.47 (d, 2H each, JHH = 5.4
2
CH(CH3)2), 63.51 (d, JCP = 8.5 Hz, OCH2CH3), 63.60
Hz, CH of p-cymene), 6.94–7.94 (m, 20H, Ph) ppm;
13C{1H} NMR (C6D6) d = 15.98 and 16.29 (d,
2
(d, JCP = 10.0 Hz, OCH2CH3), 63.65 (d, JCP = 5.2
2

2094
V. Cadierno et al. / Journal of Organometallic Chemistry 690 (2005) 2087–2096
3JCP = 8.8 Hz, OCH2CH3), 19.35 (s, CH3), 23.41 (s,
Table 1
Crystal data and structure refinement for 3b
2
CH(CH3)2), 31.07 (s, CH(CH3)2), 61.43 (d, JCP = 5.6
2
Hz, OCH2CH3), 61.93 (d, JCP = 4.8 Hz, OCH2CH3),
Empirical formula
Formula weight
Temperature (K)
RuC43H55F6P5O4N2S2
1097.93
200(2)
79.10 and 81.80 (s, CH of p-cymene), 89.01 and 99.89
(s, C of p-cymene), 127.21–138.14 (m, Ph), 128.59 (m,
PCP) ppm.
˚
Wavelength (A)
1.5418
Monoclinic
Cc
Crystal system
Space group
Unit cell dimensions
4.6. X-ray crystal structure determination of
[Ru(g6-p-cymene)(j3- C,N,S-CH[P{@NP(@S)-
(OEt)2}Ph2]2)] [PF6] (3b)
˚
a (A)
15.339(5)
18.192(7)
18.931(7)
90
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
Crystals suitable for X-ray diffraction analysis were
obtained by slow diffusion of hexane into a saturated
solution of the complex in dichloromethane. Data col-
lection, crystal and refinement parameters are collected
in Table 1. Diffraction data were recorded at 200 K on
a Nonius Kappa CCD single-crystal diffractometer
using Cu Ka radiation. Crystal-detector distance was
fixed at 29 mm and a total of 1365 frames were col-
lected using the oscillation method, with 2ꢁ oscillation
and 45 s exposure time per frame. Data collection
strategy was calculated with the program Collect
[24]. Data reduction and cell refinement were
performed using the programs HKL Denzo and Scale-
pack [25].
106.18(2)
90
3
˚
Volume (A )
5073(3)
4
1.437
Z
Density (calculated) (g cmꢀ3
)
Absorption coefficient (mmꢀ1
F (0 0 0)
Crystal size (mm)
)
5.305
2256
0.1 · 0.075 · 0.025
3.86–67.98
Theta range for data collection (ꢁ)
Index ranges
ꢀ16 6 h 6 17
ꢀ20 6 k 6 20
ꢀ21 6 l 6 21
Reflections collected/unique
Completeness to theta = 67.98ꢁ
Refinement method
27372/6077 [R(int) = 0.110]
73.5%
Full-matrix least-squares on F2
Data/restraints/parameters
Goodness-of-fit on F2
6077/0/569
1.003
0.0585
The software package WINGX was used for space
group determination, structure solution and refinement
[26]. The structure was solved by Patterson methods
using the program DIRDIF [27]. Absorption correction
was applied by means of SORTAV [28]. Full-matrix
least-squares refinement on F2 was carried out with
SHELXL-97 [29]. All non-H atoms were anisotropically re-
fined. The H atoms were geometrically placed and their
coordinates were refined riding on their parent atoms.
The final cycle of full-matrix least-squares refinement
based on 6077 reflections and 569 parameters converged
to a final value of R1 (F2 > 2r (F2)) = 0.0585. The func-
a
R1 [I > rI]
a
wR2 [I > rI)]
R1 (all data)
0.1213
0.1181
wR2 (all data)
Largest difference peak
0.1457
0.383 and ꢀ0.517
ꢀ3
˚
and hole (e A
)
P
P
P
P
2
2
1=2
a
R1 ¼ ðjF ojꢀjF cjÞ= jF oj; wR2 ¼f ½wðF 2o ꢀF c2Þ ꢁ= ½wðF o2Þ ꢁg
.
e-mail: deposit@ccdc.cam.ac.uk or www: http://
www.ccdc.cam.ac.uk).
P
P
1=2
tion minimized was ½ wðF 2o ꢀ F c2Þ= wðF o2Þꢁ where
2
2
w ¼ 1=½r2ðF oÞ þ ð0:0369PÞ ꢁ with r2ðF oÞ from counting
statistics and P ¼ MaxðF 2o þ 2F c2Þ=3. The maximum
shift-to-esd ratio in the last full-matrix least-squares cy-
cle was 0.000. Atomic scattering factors were taken from
the International Tables for X-ray Crystallography [30].
Geometrical calculations were made with PARST [31].
The crystallographic plots were made with PLATON
[32].
2
Acknowledgements
We are indebted to the Ministerio de Ciencia y Tec-
´
nologıa (MCyT) of Spain (Project BQU2003-00255)
and the Gobierno del Principado de Asturias (Project
PR-01-GE-6) for financial support. V.C. thanks the
´
MCyT for a ‘‘Ramon y Cajal’’ contract.
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