Access to the first (iminophosphoranyl)(selenophosphoranyl)methane ligands Ph2P(Se)CH2P(NR)Ph2: Coordination of their methanide and methandiide anions to ruthenium

Article abstract of DOI:10.1039/b916554a

A family of mixed (iminophosphoranyl)(selenophosphoranyl)methane ligands of general composition Ph₂P(Se)CH₂P(NR)Ph₂ have been synthesized by oxidation of Ph₂PCH₂P(NR)Ph ₂ with elemental selenium. In the presence of Et₃N, these ligands react with [{RuCl(μ-Cl)(η⁶-p-cymene)}₂] to afford mononuclear Ru(ii) species in which the resulting methanide anions adopt a tridentate coordination. Further deprotonation with KH generates carbenic ruthenium derivatives which participate, under remarkably mild conditions, in C-C coupling processes with isocyanides.

Full text of DOI:10.1039/b916554a

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Access to the first (iminophosphoranyl)(selenophosphoranyl)methane ligands
=
=
Ph2P( Se)CH2P( NR)Ph2: coordination of their methanide and
methandiide anions to ruthenium†
´
Victorio Cadierno,* Josefina D´ıez, Joaqu´ın Garc´ıa-Alvarez* and Jose´ Gimeno
Received 13th August 2009, Accepted 12th October 2009
First published as an Advance Article on the web 19th November 2009
DOI: 10.1039/b916554a
A family of mixed (iminophosphoranyl)(selenophosphoranyl)methane ligands of general composition
=
=
=
Ph2P( Se)CH2P( NR)Ph2 have been synthesized by oxidation of Ph2PCH2P( NR)Ph2 with elemental
selenium. In the presence of Et3N, these ligands react with [{RuCl(m-Cl)(h -p-cymene)}2] to afford
6
mononuclear Ru(II) species in which the resulting methanide anions adopt a tridentate coordination.
Further deprotonation with KH generates carbenic ruthenium derivatives which participate, under
remarkably mild conditions, in C–C coupling processes with isocyanides.
Introduction
Methanide and methandiide anions derived from bis(iminopho-
=
sphoranyl)methanes CH2{Ph2P( NR)}2 have been the focus
of intense research activity due to their unique properties as
ligands for both main-group and transition metals.1 Although
different coordination modes have been described for these anions,
the formation of six-membered metallacycles A (in some cases
metal-carbon interactions have been observed) and “pincer”-type
carbenic structures B largely dominate their chemistry (Fig. 1).1
Similar coordinative trends have also been observed for the
singly and doubly deprotonated forms of the disulfide species
=
CH2{Ph2P( S)}2, leading to the isolation of several complexes
of type C2,3 and D,4 respectively. The rich and versatile reactivity
of the “pincer”-type carbenes B and D is worth highlighting since
Fig. 2 Structure of the half-sandwich ruthenium(II) complexes E–G.
=
the M C bond is able to participate in different C–C coupling,
insertion and carbene transfer reactions,5 under mild conditions.
structure B, the carbene moiety in complexes G, which is also
able to participate in C–C coupling processes with alkynes and
isocyanides,8 forms part of a single four-membered chelate ring,
a coordination mode that has only been described for platinum9
and germanium.10
More recently, our attention was turned to mixed (iminopho-
=
sphoranyl)(thiophosphoranyl)methane compounds Ph2P( S)-
=
CH2P( NR)Ph2, from which the ruthenium(II) complexes H–I
Fig.
1
The most common coordination modes described for
(Fig. 3), showing a tridentate coordination of the corresponding
methanide anions, could be prepared via initial monodeproto-
nation of the PCH2P backbone by the action of LinBu and
subsequent treatment with [{RuCl(m-Cl)(h -p-cymene)}2].11,12
=
=
the methanide and methandiide anions of Ph2P( X)CH2P( X)Ph2
(X = NR, S).
6
The contribution of our group to this field has been the
preparation of the half-sandwich derivatives E–G (Fig. 2) by
coordination of the methanide and methandiide anions de-
rived from the N-phosphorylated or thiophosphorylated ligands
6
=
=
CH2[Ph2P{ NP( X)(OR)2}]2 (X = O, S; R = Et, Ph) to (h -p-
cymene)-Ru(II) fragments.6,7 In contrast to the classical “pincer”
Departamento de Qu´ımica Orga´nica e Inorga´nica, Instituto Universitario de
Qu´ımica Organometa´lica “Enrique Moles” (Unidad Asociada al CSIC),
Facultad de Qu´ımica, Universidad de Oviedo, E-33071 Oviedo, Spain.
E-mail: vcm@uniovi.es, garciajoaquin@uniovi.es; Fax: +(34) 985103446;
Tel: +(34) 985102985
† CCDC reference numbers 743960–743964. For crystallographic data in
CIF or other electronic format see DOI: 10.1039/b916554a
Fig. 3 Structure of the half-sandwich ruthenium(II) complexes H and I.
Dalton Trans., 2010, 39, 941–956 | 941
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In the presence of NaH all these species undergo a further
deprotonation reaction. However, only the ruthenium-carbene
After a simple work-up consisting of the filtration and evapo-
ration of the dichloromethane solution, and subsequent washing
of the solid residue with n-pentane, compounds 2a–h could be
isolated as air-stable microcrystalline white solids in excellent
yields (81–92%). Characterization of these mixed oxidized species
was straightforwardly achieved by means of elemental analyses,
IR and multinuclear NMR spectroscopy (details are given in the
Experimental section). In particular, the most relevant feature in
=
complex J (Fig. 4), in which the Ru C bond is also part of
a single four-membered ring, was stable enough to be isolated
and characterized. This nucleophilic carbene showed a remarkable
reactivity towards 2,6-dimethylphenyl isocyanide since, in addition
to the expected ketenimine-ruthenium derivative K, the octahedral
complex L could also be synthesized using an excess of the
isocyanide.11 The formation of this rare ruthenacycle involves
an unprecedented insertion of one isocyanide molecule into the
1
the 31P{ H} NMR spectra is the strong downfield shift observed
for the signal of the Ph2P unit which suffered the selenation with
=
=
Ru C bond of J, which is accompanied by the displacement of
the p-cymene ligand.
respect to that shown by the corresponding Ph2PCH2P( NR)Ph2
=
precursors 1a–h (DdP ª 50 ppm; see Table 1), the Ph2P NR
resonance remaining in all cases almost unchanged (DdP ≤ 6 ppm).
=
As expected, the Ph2P Se signals show characteristic selenium
satellites with 1J(SeP) coupling constants of 748.6–761.2 Hz. These
values are in complete accord with those described previously
1
=
for the closely related symmetric CH2{Ph2P( Se)}2 ( J(SeP) =
=
=
751.7 Hz) and unsymmetric Ph2P( Se)CH2P( X)Ph2 (X = O,
1J(SeP) = 739.2 Hz; X = S, J(SeP) = 746.5 Hz) ligands.16 The
1
remaining 31P chemical shifts and coupling constants observed (see
Table 1) are quite similar to those found in their thiophosphoranyl
11
1
=
=
counterparts Ph2P( S)CH2P( NR)Ph2. Regarding the H and
the 13C{ H} NMR spectra of 2a–h the most significant features are
1
those associated to the methylenic PCH2P group, whose protons
and carbon resonate as doublet of doublets signals (ca. dH 4 ppm
and dC 33 ppm) due to the coupling with the phosphorus atoms
2
=
=
of the adjacent Ph2P Se and Ph2P N units (ca. J(HP) = 13.7–
Fig. 4 Structure of the ruthenium(II) complexes J–L.
14.9 Hz and 1J(CP) = 37.9–54.0 Hz).
Moreover, the structure of 2a could be unambiguously con-
firmed by means of a single-crystal X-ray diffraction study.
An ORTEP-type view of the molecule is shown in Fig. 5;
selected bond distances and angles are listed in the caption.
Following with our interest in the coordination chemistry
of iminophosphoranes,6,8,11,13 a related study using previously
unknown
(iminophosphoranyl)(selenophosphoranyl)methane
14
=
=
species Ph2P( Se)CH2P( NR)Ph2 is herein reported.
=
The observed P Se bond distance (P(1)–Se(1) = 2.1086(14)
˚
A) compares well with those previously reported for the struc-
Results and discussion
turally characterized bis(selenophosphoranyl)methane derivative
17
˚
=
CH2{Ph2P( Se)}2 (P–Se = 2.103(3) and 2.097(4) A). Similarly,
Synthesis and characterization of the mixed
(iminophosphoranyl)(selenophosphoranyl)methane ligands
˚
=
the P N bond length (P(2)–N(1) = 1.584(4) A) falls within the
expected range for a phosphorus-nitrogen double bond in an
=
=
Ph2P( Se)CH2P( NR)Ph2 (R = 2,4,6-C6H2Me3 2a, 4-C6F4CHO
=
=
2b, 4-C6F4CN 2c, 4-C5F4N 2d, P( O)(OEt)2 2e, P( O)(OPh)2
=
=
2f, P( S)(OEt)2 2g, P( S)(OPh)2 2h)
=
=
As shown in Scheme 1, compounds Ph2P( Se)CH2P( NR)Ph2
2a–h, which represent the first examples of (iminophospho-
ranyl)(selenophosphoranyl)methane derivatives reported to date
in the literature, were easily obtained by oxidation of the
diphenylphosphino unit of the known iminophosphoranyl-
13b,c,e,15
=
phosphines Ph2PCH2P( NR)Ph2
under mild conditions (CH2Cl2/r.t.).
with elemental selenium
Fig. 5 ORTEP-type view of the structure of compound 2a showing the
crystallographic labelling scheme. Hydrogen atoms have been omitted for
clarity. Thermal ellipsoids are drawn at 10% probability level. Selected
˚
bond distances (A): P(1)–Se(1) 2.1086(14); P(2)–N(1) 1.548(4); P(1)–C(1)
1.829(5); P(2)–C(1) 1.845(4); N(1)–C(26) 1.404(6). Selected bond angles
(◦): Se(1)–P(1)–C(1) 116.34(17); P(1)–C(1)–P(2) 123.6(3); C(1)–P(2)–N(1)
109.0(2); P(2)–N(1)–C(26) 132.8(4).
=
=
Scheme 1 Synthesis of the mixed Ph2P( Se)CH2P( NR)Ph2 ligands
2a–h.
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1
Table 1 31P{ H} NMR data for compounds 2a–h, 3a–f, 4a and 5g–ha
1J(PASe)
Ph2PB NR
2J(PAPB)
X
2J(PBPC)
=
=
=
(R¢O)2PC
Compound
Ph2PA Se
=
=
Ph2P( Se)CH2P( NR)Ph2
R = 2,4,6-C6H2Me3 2ab
R = 4-C6F4CHO 2bb
R = 4-C6F4CN 2cb
24.0 (td)
21.9 (td)
21.6 (td)
21.9 (td)
25.1 (td)
24.9 (td)
25.1 (td)
24.3 (td)
748.6
759.4
761.2
759.2
748.6
749.2
749.4
752.0
-12.1 (d)
6.5 (dt)d
6.2 (dt)e
6.9 (dt)f
10.8 (dd)
12.7 (dd)
9.8 (dd)
11.8 (dd)
15.5
11.1
9.9
11.1
13.3
12.8
12.6
9.8
R = 4-C5F4N 2db
b
=
R = P( O)(OEt)2 2e
4.1 (d)
28.8
31.4
31.6
31.7
b
=
R = P( O)(OPh)2 2f
-6.2 (d)
58.5 (d)
51.1 (d)
b
=
R = P( S)(OEt)2 2g
b
=
R = P( S)(OPh)2 2h
3
6
=
=
[Ru{k (C,N,Se)-Ph2P( Se)CHP( NR)Ph2}(h -p-cymene)][SbF6]
R = 2,4,6-C6H2Me3 3ac
R = 4-C6F4CHO 3bc
R = 4-C6F4CN 3cc
34.1 (td)
28.3 (t)
28.3 (t)
29.3 (t)
28.8 (t)
28.2 (t)
521.4
508.0
506.8
509.6
514.0
511.2
45.9 (d)
52.9 (s)
53.3 (s)
55.5 (s)
52.0 (d)
51.4 (d)
8.9
R = 4-C5F4N 3dc
c
=
R = P( O)(OEt)2 3e
6.9 (d)
-3.4 (d)
19.4
17.8
c
=
R = P( O)(OPh)2 3f
=
=
[Ph2P( Se)CH2P( NHR)Ph2][SbF6]
R = 2,4,6-C6H2Me3 4ac
19.8 (td)
722.2
37.3 (d)
6.5
3.6
3
6
=
=
=
[Ru(k (C,S,Se)-Ph2P( Se)CHP{ NP( S)(OR¢)2}Ph2)(h -p-cymene)][SbF6]
R¢ = Et 5gc
49.3 (t)
503.4
502.0
26.1 (d)
26.9 (dd)
54.7 (d)
47.9 (d)
19.8
17.5
R¢ = Ph 5hc
47.0 (td)
a
d in ppm and J in Hz. Abbreviations: s, singlet; d, doublet; dd, doublet of doublets; dt, doublet of triplets; t, triplet; td, triplet of doublets. b Spectra
recorded in CDCl3. c Spectra recorded in CD2Cl2. d 4J(PF) = 5.4 Hz. e 4J(PF) = 5.2 Hz. f 4J(PF) = 4.7 Hz.
6
electronically delocalized aryl-iminophosphoranyl group
–
˚
found that treatment of the ruthenium(II) dimer [{RuCl(m-Cl)(h -
p-cymene)}2] with a two-fold excess of the mesityl-substituted
=
=
Ph2P N–Ar (e.g. P N bond distances of 1.555(3) and 1.573(3) A
=
=
have been reported for the bis(iminophosphoranyl)methane
ligand Ph2P( Se)CH2P( N-2,4,6-C6H2Me3)Ph2 2a, in reflux-
ing methanol and in the presence of a chloride abstractor
(NaSbF6), results in the formation of an equimolar mixture
of the mononuclear metallabicyclic complex 3a and the phos-
phiniminium salt 4a, along with an extensive amount of the
15a
=
=
species Ph2P( NPh)CH2P( NMes)Ph2).
-
=
=
Coordination of the methanide [Ph2P( Se)CHP( NR)Ph2]
anions to the half-sandwich ruthenium(II) fragment
[Ru(g6-p-cymene)]2+
cationic dinuclear species [{Ru(h -p-cymene)}2(m-Cl)3][SbF6].18
6
Apparently, the coordination of 2a to ruthenium strongly en-
hances the acidity of its methylenic PCH2P hydrogens lead-
ing to the immediate deprotonation of the transient chelate
Once synthesized and characterized, the ability of the novel ligands
=
=
Ph2P( Se)CH2P( NR)Ph2 2a–h to coordinate arene-Ru(II) frag-
ments was explored. Thus, in our first experiment (Scheme 2), we
2
6
=
=
intermediate [RuCl{k (N,Se)-Ph2P( Se)CH2P( NR)Ph2}(h -p-
cymene)][SbF6] (R = 2,4,6-C6H2Me3) by a second molecule
of 2a.19 Although this intermediate could not be isolated or
even detected by NMR spectroscopy, its formation would be
consistent with published work describing the preparation, un-
der similar reaction conditions, of related arene-ruthenium(II)
2
6
+
=
complexes [RuCl(k (X,X)-CH2{Ph2P( X)}2)(h -arene)] starting
2c,14e,d
=
from CH2{Ph2P( X)}2 (X = S, Se) ligands.
Chromatographic work-up of the reaction mixture on silica-gel
allowed the separation of the novel compounds 3a and 4a, which
were isolated as air-stable solids (25 and 34% yield, respectively)
and characterized by standard spectroscopic techniques (IR and
31P{ H}, H, 13C{ H} NMR), conductance measurements (1 : 1
electrolytes; KM = 119 and 109 X-1 cm2 mol-1), as well as
elemental analysis (details are given in the Experimental section).
Noteworthy, the NMR data obtained for complex 3a, which will be
discussed jointly with those of the related species 3b–f and 5g,h (see
1
1
1
3
below), supported the diastereoselective k (C,N,Se)-coordination
of the methanide anion to the arene-ruthenium(II) fragment (two
stereogenic centers are generated, i.e. the ruthenium atom and the
methynic PCHP carbon).
The molecular structures of 3a and 4a were unambiguously
confirmed through single-crystal X-ray diffraction analyses.
6
Scheme 2 Reaction of [{RuCl(m-Cl)(h -p-cymene)}2] with ligand 2a.
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ORTEP-type views of the molecules are shown in Fig. 6 and
7, respectively (selected bonding parameters are listed in the
captions). Concerning the structure of the metallabicycle 3a,20
the coordination sphere around ruthenium consists of the
6
h -p-cymene ring, the methynic PCHP carbon, the selenium
=
atom of the Ph2P Se group, and the nitrogen atom of the
N-mesitylated iminophosphorane unit, all disposed in a classical
pseudo-octahedral three-legged piano stool geometry. The
˚
Ru–C(1) bond length (2.213(5) A) showed the expected value for
a Ru-carbon single bond,21 comparing well with those described
3
in the literature for the related ruthenabicycles [Ru(k (C,N,N)-
6
7a,b
˚
=
CH{Ph2P( NPh)}2)(h -p-cymene)][OTf] (2.230(4) A)
and
3
6
=
=
[Ru{k (C,N,S)-Ph2P( S)CHP( NR)Ph2}(h -p-cymene)][SbF6]
11
˚
=
(R
=
P( O)(OPh)2; 2.205(6) A).
The Ru–N(1) bond
˚
distance (2.147(4) A) is also similar to those observed in
˚
these compounds (2.147(4)–2.175(4) A), while the Ru–Se(1)
˚
bond length (2.6031(7) A) falls within the range of values
reported for ruthenium(II) complexes containing coordinated
22
˚
=
selenophosphoranyl fragments R3P Se (2.45–2.60 A).
Fig. 7 ORTEP-type view of the structure of compound 4a showing the
crystallographic labelling scheme. SbF6- anion and hydrogen atoms (except
those on C(1) and N(1)) have been omitted for clarity. Thermal ellipsoids
˚
are drawn at 10% probability level. Selected bond distances (A): P(1)–Se(1)
2.1018(8); P(2)–N(1) 1.623(2); P(1)–C(1) 1.834(3); P(2)–C(1) 1.814(3);
N(1)–C(26) 1.442(4). Selected bond angles (◦): Se(1)–P(1)–C(1) 113.35(10);
P(1)–C(1)–P(2) 118.08(15); C(1)–P(2)–N(1) 112.85(14); P(2)–N(1)–C(26)
127.4(2).
3a, avoiding the undesired formation of the phosphiniminium
derivative 4a. This target could be easily accomplished by just
performing the reaction in the presence of an equimolar amount
of Et3N (Scheme 3). Applying these new conditions the desired
metallabicycle 3a could be isolated in high yield (73% yield), the
1
31P{ H} NMR spectrum of the crude reaction mixture showing
any trace of 4a.
Fig. 6 ORTEP-type view of the structure of compound 3a showing
-
the crystallographic labelling scheme. Phenyl groups, SbF6 anion
and hydrogen atoms (except that on C(1)) have been omitted for
clarity. Thermal ellipsoids are drawn at 10% probability level. Selected
˚
bond distances (A): Ru–C(1) 2.213(5); Ru–Se(1) 2.6031(7); Ru–N(1)
2.147(4); Ru–C* 1.6893(4); P(1)–Se(1) 2.1419(15); P(2)–N(1) 1.609(5);
P(1)–C(1) 1.765(5); P(2)–C(1) 1.780(6); N(1)–C(26) 1.419(7). Selected
bond angles (◦): C*–Ru–C(1) 136.94(14); C*–Ru–Se(1) 128.06(2);
C*–Ru–N(1) 132.98(14); C(1)–Ru–Se(1) 77.13(13); C(1)–Ru–N(1)
72.01(19); Se(1)–Ru–N(1) 88.28(12); Se(1)–P(1)–C(1) 100.72(18);
P(1)–C(1)–P(2) 119.6(3); C(1)–P(2)–N(1) 98.2(2); P(2)–N(1)–C(26)
133.1(4).
Regarding the molecular structure of 4a (Fig. 7), the expected
=
elongation of the P N bond length with respect to that of its non-
˚
protonated precursor 2a was observed (1.623(2) vs. 1.548(4) A),
the rest of the distances remaining almost unaffected. Moreover,
=
this P N bond length value is in complete accord with those
reported in the literature for related phosphiniminium salts
23
=
[R3P NHR¢][X]. We also note that the N-protonation of the
iminophosphorane group is clearly reflected in the 31P{ H} NMR
1
=
spectrum of 4a by an appreciable downfield shift of the Ph2P N
signal with respect to that of 2a (Dd 50 ppm, see Table 1).
The reaction outcome depicted in Scheme 2 prompted us
to design a more efficient and selective route of access to
Scheme 3 Synthesis of the arene-Ru(II) complexes 3a–f and 5g,h.
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Following the same route, the related complexes 3b–f could
also be synthesized (76–89% yield) starting from 2b–f (Scheme 3).
In contrast, when the reactions were performed with the N-
3
thiophosphorylated derivatives 2g,h, preference for the k (C,S,Se)
3
vs. k (C,N,Se) coordination of the in situ generated methanide
anions was observed, leading to the high-yield formation of
compounds 5g,h (77–82% yield). These observations are in com-
plete accord with (i) our previous results using similar thiophos-
11
=
=
phoranyl ligands Ph2P( S)CH2P( NR)Ph2 and (ii) the well-
documented domination of the sulfur atom in the coordination
=
chemistry of N-thiophosphorylated iminophosphoranes R3P N–
6b,13c,d,h,24
=
P( S)(OR¢)2.
Complexes 3a–f and 5g,h have been characterized by standard
spectroscopic techniques (IR and 31P{ H}, H, 13C{ H} NMR),
conductance measurements (1 : 1 electrolytes; KM = 112–126
X-1 cm2 mol-1), as well as elemental analysis, all data being fully
consistent with the proposed formulations (details are given in
the Experimental section and Table 1). In particular, their NMR
spectra support: (i) the diastereoselective formation of all these
species, which probably arises from the steric hindrance between
the p-cymene ligand and the aromatic rings of the diphenylphos-
1
1
1
Fig. 8 ORTEP-type view of the structure of compound 5g showing
-
the crystallographic labelling scheme. Phenyl groups, SbF6 anion
and hydrogen atoms (except that on C(1)) have been omitted for
clarity. Thermal ellipsoids are drawn at 10% probability level. Selected
˚
bond distances (A): Ru–C(1) 2.209(5); Ru–Se(1) 2.5634(8); Ru–C*
3
3
1.7104(5); Ru–S(1) 2.4402(19); P(1)–Se(1) 2.1565(14); P(2)–N(1) 1.583(5);
P(1)–C(1) 1.799(5); P(2)–C(1) 1.784(6); N(1)–P(3) 1.573(5); P(3)–S(1)
1.994(3). Selected bond angles (◦): C*–Ru–C(1) 127.76(15); C*–Ru–Se(1)
129.85(3); C*–Ru–S(1) 122.45(5); C(1)–Ru–Se(1) 79.02(14); C(1)–Ru–S(1)
97.47(15); Se(1)–Ru–S(1) 87.24(4); Se(1)–P(1)–C(1) 100.45(17);
P(1)–C(1)–P(2) 117.5(3); C(1)–P(2)–N(1) 115.5(3); P(2)–N(1)–P(3)
128.8(3); N(1)–P(3)–S(1) 117.8(2).
phino groups, and (ii) the different k (C,N,Se) and k (C,S,Se)
coordination modes adopted by the methanide anions in 3a–f and
5g,h, respectively. Thus, for complexes 3a–f, appreciable downfield
=
=
shifts of both the Ph2P N (ca. Dd 46 ppm) and Ph2P Se (ca.
Dd 6 ppm) resonances in comparison with those shown by the
free ligands 2a–f are observed, confirming the direct involvement
of these groups in the bonding (see Table 1). In addition, an
important reduction in the P–Se coupling constant is also observed
3J(CP) = 2.6–16.2 Hz). The remarkable high-field chemical shifts
observed for the PCHP carbon compare well with those previously
described by us for related metallacyclic species derived from
1
(ca. J(PSe) = 500 vs. 750 Hz), a fact that is well-recognized as
a characterization tool for the coordination of seleno-phosphines
25
=
R3P Se to transition metals. Concerning complexes 5g,h, even
when downfield shifts are also observed for the Ph2P N and
Ph2P Se signals with respect to those of 2g,h, the Dd values differ
considerably from those shown by 3a–f (16 vs. 46 and 23 vs. 6 ppm,
respectively). These facts, along with the slight high-field shifting
of the (RO)2P S resonances (ca. Dd -3 ppm compared to 2g,h),
strongly suggest that complexation of the N-thiophosphorylated-
Ph2P( S)CH2P( NR)Ph2,11 supporting the direct bonding of the
methynic PCHP unit to ruthenium.
=
=
=
=
At this point it is important to note that, to the best of our
knowledge, compounds 3a–f and 5g,h represent the first examples
reported in the literature of mononuclear ruthenium complexes
26
=
3
3
containing terdentate k (C,N,Se)- and k (C,S,Se)-chelate ligands.
iminophosphorane arm of these ligands is taking place through
=
=
the (RO)2P S vs. Ph2P N unit. Unambiguous confirmation of
this bonding situation was achieved by means of a single-crystal
X-ray diffraction study performed on complex 5g (see Fig. 8).27
The most remarkable features of this structure are that, despite the
less strained coordination mode adopted by the methanide ligand,
Deprotonation of complexes 3a–f and 5g,h: reactivity of the
resulting carbenes towards 2,6-dimethylphenyl isocyanide
As previously observed in the related methanide complexes
E–F (Fig. 2)6 and H–I (Fig. 3),11 the methynic PCHP hydrogen
in 3a–f and 5g,h is acidic enough to be deprotonated under
mild conditions. Thus, we have found that treatment at room
temperature of THF solutions of these compounds with an excess
of KH leads to an immediate colour change from orange to
deep violet, a characteristic colour for bis-phosphorus stabilised
ruthenium-carbene complexes.6,11,28 Monitoring the course of these
˚
˚
the Ru–C(1) (2.209(5) A) and P(2)–N(1) (1.583(5) A) bond lengths
are quite similar to those observed for complex 3a (2.213(5) and
1.609(5) A, respectively; see Fig. 6).
The different k (C,N,Se) and k (C,S,Se) coordination modes
˚
3
3
1
adopted by the methanide ligands also left their mark in the H
and 13C{ H} NMR spectra of complexes 3a–f and 5g,h. Thus,
1
1
while for 3a–f the methynic PCHP proton resonates as a broad
singlet at dH 2.76–3.80 ppm, a more deshielded doublet of doublets
deprotonation reactions by 31P{ H} NMR spectroscopy (internal
D2O capillary) showed after ca. 4 h the total consumption of the
starting materials and clean appearance of a novel set of signals,
tentatively assigned to carbene complexes 6a and 7b–h (Scheme 4).
Unfortunately, after solvent removal and extraction of the prod-
2
signal is observed for 5g,h (dH 4.78–5.78 ppm; J(HP) = 5.5–
9.0 Hz). A similar trend is also observed in the 13C spectra,
the PCHP carbon resonating at ca. dC -21 ppm for 3a–f and
-13 ppm for 5g,h. Concerning the multiplicity of the signals,
well-resolved doublet of doublets (3a–d) or doublet of doublets
of doublets (3e,f and 5g,h) are observed due to the coupling
with the vicinal phosphorous atoms (1J(CP) = 17.4–87.1 Hz;
2
ucts with diethyl ether, only the carbene complex [Ru(k (C,Se)-
6
=
=
=
Ph2P( Se)CP{ NP( S)(OEt)2}Ph2)(h -p-cymene)] 7g could be
isolated in pure form (83%). In the rest of the cases, extensive re-
protonation occurs during work-up, due probably to the moisture
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Scheme 4 Deprotonation reactions of complexes 3a–f and 5g,h: reactivity of the resulting carbene complexes towards 2,6-dimethylphenyl isocyanide.
=
traces present in the solvent, leading to mixtures containing the
starting materials 3a–f and 5h as the major components. Only in
the presence of excess of KH compounds 6a and 7b–h are able to
survive.
the M C bond is contained within a four-membered M–C–P–
Se ring. We also note that, despite the potential hemilability of
2
2
=
the Ph2P X units, no fluxional k (C,N)/k (C,Se) behaviour was
detected in solution for both 6a and 7b–h.
=
The absence of the characteristic methynic PCHP signal in
the 1H NMR spectrum of 7g unambiguously confirmed that
deprotonation of this unit has taken place. This fact, along with the
appearance of a low-field doublet of doublets of doublets signal
at 125.4 ppm (1J(CP) = 52.2 and 22.9 Hz, 3J(CP) = 6.0 Hz) in the
Despite their high instability, the capacity of the Ru C bond of
complexes 6a and 7b–h to participate in C–C coupling processes
could be conveniently explored. Thus, we have found that the
addition of one equivalent of 2,6-dimethylphenyl isocyanide to
THF solutions containing the in situ generated complexes 7b–h
leads to the immediate formation of the ketenimine-ruthenium
derivatives 8b–h (Scheme 4), which could be isolated as moisture
and air-stable yellow solids in 79–89% yield. Characterization
of these new compounds was straightforward by following their
analytical, and IR and NMR spectroscopic data (details are given
in the Experimental section and Table 2), the latter indicating
clearly their diastereoselective formation (note that once again
two stereogenic centers are generated, i.e. the ruthenium atom and
1
13C{ H} NMR spectrum,6,11,28 strongly supports the formation of
=
a Ru C bond in these reactions.
We note that the different coordination modes proposed for
=
=
the carbenic Ph2P( Se)CP( NR)Ph2 units in complexes 6a and
1
7b–h (see Scheme 4) are based on the 31P{ H} NMR data
obtained for these compounds from the crude reaction mixtures
=
(see Table 2). Thus, for complex 6a, the Ph2P N unit resonates
at dP 62.2 ppm, a chemical shift that compares well with those
1
=
previously reported by us for the coordinated Ph2P N unit in
the PCP carbon atom). In particular, the 13C{ H} NMR spectra
the closely related complexes G (Fig. 2)6 and J (Fig. 4).11 In
contrast, for 7b–h, this group resonates at much more higher fields
(dP 13–22 ppm) suggesting that, in these cases, involvement of
the iminophosphorane unit on the bonding is not taking place.
The chemical shifts and 1J(PSe) coupling constants observed
show signals for the PCP and C N carbon atoms at ca. dC -16 and
=
199 ppm, respectively, chemical shifts which can be considered as
characteristic fingerprints of C–C bound ketenimine complexes,29
and are also in complete accord with those observed in the related
complex K (Fig. 4).11
=
for the Ph2P Se group (see Table 2) also support the proposed
In contrast to the behaviour shown by 7b–h, the reaction of
6a with an equimolar amount of 2,6-dimethylphenyl isocyanide
generates instead a mixture containing the starting material and
the octahedral derivative 9a. As expected, selective formation of
2
2
k (C,N)- and k (C,Se)-coordinations in complexes 6a and 7b–h,
respectively. Remarkably, as far as we are aware, compounds 7b–
h represent the first examples of carbene complexes in which
946 | Dalton Trans., 2010, 39, 941–956
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1
Table 2 31P{ H} NMR data for compounds 6a, 7b–h, 8b–h, 9a and 10b–ha
1J(PASe)
Ph2PB NR
2J(PAPB)
X
2J(PBPC)
=
=
=
(R¢O)2PC
Compound
Ph2PA Se
2
6
=
=
[Ru{k (C,N)-Ph2P( Se)CP( NR)Ph2}(h -p-cymene)]
R = 2,4,6-C6H2Me3 6ab
30.6 (td)
680.6
62.2 (d)
72.6
2
6
=
=
[Ru{k (C,Se)-Ph2P( Se)CP( NR)Ph2}(h -p-cymene)]
R = 4-C6F4CHO 7bb
R = 4-C6F4CN 7cb
R = 4-C5F4N 7db
45.4 (td)
45.5 (td)
44.0 (td)
42.8 (tdd)c
41.7 (td)
37.5 (td)
40.7 (td)
361.4
374.6
382.4
365.8
373.4
384.6
347.2
22.0 (d)
22.2 (d)
20.7 (d)
14.4 (dd)
13.8 (dd)
14.9 (dd)
16.6 (dd)
72.6
69.6
71.4
71.1
75.3
47.6
60.8
b
b
R = P( O)(OEt)2 7e
1.3 (dd)c
-10.7 (d)
55.1 (d)
47.0 (d)
32.6
31.4
21.1
18.7
=
=
R = P( O)(OPh)2 7f
d
=
R = P( S)(OEt)2 7g
b
=
R = P( S)(OPh)2 7h
2
6
=
=
=
[Ru{k (C,C,Se)-Ph2P( Se)C(C N-2,6-C6H3Me2)P( NR)Ph2}(h -p-cymene)]
R = 4-C6F4CHO 8bd
R = 4-C6F4CN 8cd
R = 4-C5F4N 8dd
39.2 (td)
40.1 (td)
39.2 (td)
37.3 (tdd)e
34.4 (td)
38.6 (td)
35.9 (td)
482.6
485.8
481.6
458.0
483.6
480.8
482.4
24.0 (d)
24.5 (d)
24.6 (d)
20.6 (dd)
28.2 (dd)
20.8 (dd)
23.7 (dd)
52.8
54.4
52.5
42.7
39.2
43.6
38.5
d
d
R = P( O)(OEt)2 8e
1.0 (dd)e
-9.7 (d)
59.2 (d)
49.6 (d)
30.5
28.4
19.8
16.3
=
=
R = P( O)(OPh)2 8f
d
=
R = P( S)(OEt)2 8g
d
=
R = P( S)(OPh)2 8h
2
=
=
[Ru{k (C,N)-Ph2P( Se)C(C N-2,6-C6H3Me2)P(NR)Ph2}(CN-2,6-C6H3Me2)4]
R = 2,4,6-C6H2Me3 9f
18.6 (td)
616.8
52.0 (d)
106.2
2
=
=
[Ru{k (C,Se)-Ph2P(Se)C(C N-2,6-C6H3Me2)P( NR)Ph2}(CN-2,6-C6H3Me2)4]
R = 4-C6F4CHO 10bd
R = 4-C6F4CN 10cd
R = 4-C5F4N 10dd
34.2 (td)
34.2 (td)
35.1 (td)
34.4 (td)
34.8 (td)
39.9 (td)
33.3 (td)
423.6
426.0
420.2
430.8
426.0
479.0
482.4
20.1 (d)
19.8 (d)
20.6 (d)
22.4 (dd)
21.9 (dd)
15.2 (dd)
21.3 (dd)
58.3
58.3
57.5
59.5
59.5
32.9
58.3
f
=
R = P( O)(OEt)2 10e
0.7 (d)
13.5
17.1
18.2
11.9
d
=
R = P( O)(OPh)2 10f
-9.3 (d)
54.5 (d)
47.0 (d)
g
=
R = P( S)(OEt)2 10g
h
=
R = P( S)(OPh)2 10h
a
d in ppm and J in Hz. Abbreviations: d, doublet; dd, doublet of doublets; td, triplet of doublets; tdd, triplet of doublets of doublets. b Spectra recorded in
THF (internal D2O capillary). c 3J(PAPC) = 5.9 Hz. d Spectra recorded in C6D6. e 3J(PAPC) = 3.9 Hz. f Spectra recorded in acetone-d6. g Spectra recorded
in CDCl3. h Spectra recorded in CD2Cl2.
9a could be achieved by increasing the amount of the isocyanide
employed from 1 to 10 equivalents.
Complex 9a, isolated as a moisture and air-stable yellow solid in
77% yield, is the result of the insertion of one isocyanide molecule
The NMR data obtained for 10b–h confirmed both the displace-
=
ment of the arene ligand and the complete cleavage of the Ru CP2
bond of 7b–h (details are given in the Experimental section and
Table 2). Probably, the most noticeable spectroscopic features
of these complexes are those associated with the PCP and
=
into the Ru C bond of 6a and concomitant coordination of four
=
molecules of the isocyanide to ruthenium, via displacement of
the p-cymene ligand, a process already observed in the formation
of the closely related complex L starting from the carbenic
derivative J (Fig. 4).11 In accord with the proposed structure,
no signals for the p-cymene ligand were observed in the 1H
iminic C N carbons, which resonate at ca. dC 58 (dd or ddd
signals) and 196 (d or dd signals) ppm, respectively, chemical
shifts that fit well with those of observed for the same carbons
in 9a. Moreover, definitive evidence of the isocyanide inser-
tion was provided by a single-crystal X-ray diffraction analysis
on complex 10d. An ORTEP-type drawing of the molecular
structure is depicted in Fig. 9; selected bond distances and
angles are listed in the caption. The ruthenium atom is in a
slightly distorted octahedral environment, being bounded to four
2,6-dimethylphenyl isocyanide molecules, the selenium atom of
selenophosphoranyl group, and the carbon atom of the iminic
1
and 13C{ H} NMR spectra of this complex, the appearance of
characteristic resonances for the coordinated 2,6-dimethylphenyl
isocyanide units being instead observed (see the Experimental
1
section). In addition, the 13C{ H} NMR spectrum also displays
=
characteristic signals for the PCP and iminic C N carbons at dC
1
2
60.7 (dd, J(CP) = 169.4 and 72.2 Hz) and 190.5 (d, J(CP) =
31.5 Hz) ppm, respectively, which mimic the chemical shifts and
multiplicities showed by compound L (Fig. 4).11
=
C N-2,6-C6H3Me2 unit. As expected, all the isocyanides are
bound to ruthenium in a nearly linear fashion (Ru–C–N angles
Related isocyanide insertions into the Ru C bond of 7b–h
within the range 165.3(3)–178.0(4)◦) with metal-carbon distances
=
˚
could also be achieved by treatment of these complexes with a 10-
fold excess of 2,6-dimethylphenyl isocyanide at room temperature
(Scheme 4). By this method, the new octahedral derivatives
10b–h, featuring unprecedented five-membered Ru–C–C–P–Se
metallacyclic frameworks, could be synthesized in excellent yields
(76–90%). Moreover, the involvement of the ketenimine derivatives
8b–h as intermediates in the formation of 10b–h could also be
confirmed by reacting 8b–h with an excess of CN-2,6-C6H3Me2
(Scheme 4).
of 1.941(4)–2.017(4) A. All these bonding parameters compare
well with those reported in the literature for other isocyanide-
ruthenium(II) complexes.11,30 The Ru–C(2) and C(2)–N(1) bond
˚
lengths (2.177(3) and 1.287(5) A, respectively) also agree with
those observed in the related ruthenacycle L (Fig. 4) previously
11
˚
described by us (2.148(3) and 1.297(4) A), falling within the
expected range for Ru–C single21 and C(sp ) N double bonds.
Bond distances within the Se(1)–P(1)–C(1)–P(2)–N(2) seems to
indicate that electronic delocalization is present in this part of the
2
31
=
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cymene)] 7g, was stable enough to be isolated and characterized.
Apparently, the enhanced nucleophilic character of the carbenic
carbon atom in the rest of the derivatives, which are very prone
to undergo a reversible protonation, precludes their isolation.
Nevertheless, all of them could be trapped in situ by addition of
2,6-dimethylphenyl isocyanide to generate: (i) new examples of the
limited series of half-sandwich ketenimine-ruthenium complexes
and/or (ii) unusual octahedral derivatives featuring rare or
unprecedented five-membered Ru–C–C–P–N or Ru–C–C–P–Se
metallacyclic frameworks, respectively. In summary, the results
presented herein represent new evidence of the rich and versatile
organometallic chemistry of the methanide and methandiide an-
=
=
ions derived from compounds Ph2P( X)CH2P( Y)Ph2 (X/Y =
O, S, Se, NR).
Experimental
General comments
Synthetic procedures were performed under an atmosphere of
dry nitrogen using vacuum-line and standard Schlenk techniques.
Solvents were dried by standard methods and distilled under
nitrogen before use. All reagents were obtained from commercial
suppliers and used without further purification with the exception
15a
=
of compounds Ph2PCH2P( NR)Ph2 (R = 2,4,6-C6H2Me3 1a,
Fig. 9 ORTEP-type view of the structure of compound 10d showing the
crystallographic labelling scheme. Phenyl groups and hydrogen atoms have
been omitted for clarity. Thermal ellipsoids are drawn at 10% probability
4-C6F4CHO 1b,13e 4-C6F4CN 1c,15b 4-C5F4N 1d,15b P( O)(OEt)2
=
13b
13c
13c
1e,13b P( O)(OPh)2 1f, P( S)(OEt)2 1g, P( S)(OPh)2 1h
)
=
=
=
and [{RuCl(m-Cl)(h -p-cymene)}2],32 which were prepared by
following the methods described in the literature. Infrared spec-
tra were recorded on a Perkin-Elmer 1720-XFT spectrometer.
The conductivities were measured at room temperature, in ca.
10-3 mol dm-3 acetone solutions, with a Jenway PCM3 conduc-
timeter. The C, H and N analyses were carried out with a Perkin-
Elmer 2400 microanalyzer. NMR spectra were recorded on a
Bruker DPX300 instrument at 300 MHz (1H), 121.5 MHz (31P),
282.4 MHz (19F) or 75.4 MHz (13C) using SiMe4, CFCl3 or 85%
H3PO4 as standards. DEPT experiments have been carried out for
all the compounds reported in this paper.
6
˚
level. Selected bond distances (A): Ru–Se(1) 2.5504(5); Ru–C(2) 2.177(3);
Ru–C(40) 1.995(4); Ru–C(49) 2.017(4); Ru–C(58) 1.941(4); Ru–C(67)
1.994(4); C(2)–N(1) 1.287(5); C(40)–N(4) 1.153(5); C(49)–N(5) 1.149(5);
C(58)–N(6) 1.167(5); C(67)–N(7) 1.158(5); C(1)–C(2) 1.469(4); C(1)–P(1)
1.728(4); C(1)–P(2) 1.753(3); P(1)–Se(1) 2.1795(9); P(2)–N(2) 1.594(3).
Selected bond angles (◦): Ru–C(40)–N(4) 176.9(3); Ru–C(49)–N(5)
178.0(4);
Ru–C(58)–N(6)
165.3(3);
Ru–C(67)–N(7)
177.9(3);
Ru–C(2)–C(1) 119.1(2); Ru–C(2)–N(1) 127.5(2); C(2)–C(1)–P(1) 121.9(2);
C(2)–C(1)–P(2) 117.8(3); C(2)–C(1)–P(1) 121.9(2); C(1)–P(1)–Se(1)
106.73(11); P(1)–Se(1)–Ru 94.02(3).
molecule (ascribed to the required negative charge to maintain the
overall neutral character of this Ru(II) complex) as reflected in: (i)
the shortening of the P(1)–C(1) and C(1)–P(2) bond lenghts (up
Preparations
˚
to 0.1 A) and (ii) the elongation of the P(1)–Se(1) and P(2)–N(2)
=
=
Synthesis of compounds Ph2P( Se)CH2P( NR)Ph2 (R =
˚
(up to 0.07 A) bond distances in comparison with the structure of
2,4,6-C6H2Me3 2a, 4-C6F4CHO 2b, 4-C6F4CN 2c, 4-C5F4N 2d,
the free ligand 2a (Fig. 5).
=
=
=
P( O)(OEt)2 2e, P( O)(OPh)2 2f, P( S)(OEt)2 2g,
=
P( S)(OPh)2 2h)
Conclusions
A solution of the corresponding iminophosphorane-phosphine
3
=
Ph2PCH2P( NR)Ph2 (1a–h; 2 mmol) in dichloromethane (40 cm )
In this work the first examples of mixed (iminophosphoranyl)-
was treated, at room temperature, with elemental selenium powder
(100 mesh; 0.158 g, 2.1 mmol) for 4 h. The solution was then
filtered over silica-gel and evaporated to dryness. The resulting
solid residue was washed with n-pentane (3 ¥ 20 cm3) and dried
in vacuo.
=
=
(selenophosphoranyl)methane species Ph2P( Se)CH2P( NR)-
Ph2 have been synthesised and the capacity of their methanide
anions to act as tridentate ligands clearly demonstrated.
Thus, several half-sandwich ruthenium complexes containing
3
=
=
these anions, i.e. [Ru{k (C,N,Se)-Ph2P( Se)CHP( NR)Ph2}-
6
3
=
(h -p-cymene)][SbF6] 3a–f and [Ru(k (C,S,Se)-Ph2P( Se)CHP-
2a. Yield: 1.02 g, 85% (Found: C, 68.31; H, 5.43; N, 2.47.
C34H33P2NSe requires C, 68.46; H, 5.58; N, 2.53%); nmax/cm-1
(KBr) 474m, 492s, 512s, 529m, 582w, 616w, 657m, 690s, 726s,
748s, 768s, 789m, 857w, 998w, 1027w, 1046m, 1097m, 1114m,
1153m, 1171w, 1188w, 1290m, 1308m, 1348vs, 1435vs, 1477vs,
1572w, 2915w, 2930w, 2952w, 3006w, 3052w; dH (CDCl3) 2.04 (s,
6
=
=
{ NP( S)(OR)2}Ph2)(h -p-cymene)][SbF6] 5g,h, have been pre-
pared and structurally characterized. All these new species
readily undergo deprotonation of the C-coordinated methynic
PCHP unit in the presence of KH to generate the corresponding
ruthenium-carbene complexes. However, only one representative,
2
6
4
=
=
=
namely [Ru(k (C,Se)-Ph2P( Se)CP{ NP( S)(OEt)2}Ph2)(h -p-
6H, CH3), 2.22 (d, 3H, J(HH) = 1.7 Hz, CH3), 4.10 (dd, 2H,
948 | Dalton Trans., 2010, 39, 941–956
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2J(HP) = 13.9 and 13.9 Hz, PCH2P), 6.75–7.88 (m, 22H, CHarom);
1588w, 2826w, 2910w, 2970w; dH (CDCl3) 1.24 (t, 6H, 3J(HH) =
7.0 Hz, CH3), 4.01 (m, 4H, OCH2), 4.98 (dd, 2H, 2J(HP) = 14.9
and 14.9 Hz, PCH2P), 7.27–7.45 (m, 12H, CHarom), 7.79–7.95 (m,
8H, CHarom); dC (CDCl3) 16.5 (d, 3J(CP) = 8.4 Hz, CH3), 30.5 (dd,
1
dC (CDCl3) 20.5 and 21.4 (s, CH3), 34.2 (dd, J(CP) = 49.5 and
39.4 Hz, PCH2P), 127.6–143.2 (m, Carom and CHarom).
2b. Yield: 1.21 g, 92% (Found: C, 58.52; H, 3.47; N, 2.06.
C32H23F4P2NOSe requires C, 58.74; H, 3.54; N, 2.14%); nmax/cm-1
(KBr) 489s, 519s, 537m, 627m, 690s, 735w, 774m, 879s, 974s, 998w,
1044w, 1110m, 1158w, 1223vs, 1311w, 1328w, 1399s, 1436s, 1491vs,
1517vs, 1639s, 1690s, 2777w, 2871w, 2938w, 3055w; dH (CDCl3)
4.22 (dd, 2H, 2J(HP) = 13.4 and 13.4 Hz, PCH2P), 7.30–7.56 (m,
12H, CHarom), 7.71–7.88 (m, 8H, CHarom), 10.08 (s, 1H, CHO); dC
(CDCl3) 34.9 (dd, 1J(CP) = 53.9 and 39.5 Hz, PCH2P), 103.9 (t,
2J(CF) = 9.9 Hz, CCHO), 128.6–149.9 (m, Carom, CHarom and CF),
183.0 (t, 3J(CF) = 3.3 Hz, CHO); dF (CDCl3) -155.2 and -150.5
(m, 2F each, C6F4CHO).
2
1J(CP) = 53.9 and 38.3 Hz, PCH2P), 62.5 (d, J(CP) = 6.0 Hz,
OCH2), 128.1–133.2 (m, Carom and CHarom).
2h. Yield: 1.29 g, 89% (Found: C, 61.33; H, 4.49; N, 1.94.
C37H32P3O2NSSe requires C, 61.16; H, 4.34; N, 2.03%); nmax/cm-1
(KBr) 496m, 525w, 601w, 689s, 740s, 776m, 837m, 891s, 915m,
1026w, 1094w, 1118w, 1159w, 1200vs, 1298m, 1436m, 1487m,
1592m, 2858w, 2905w, 3052w; dH (CDCl3) 4.75 (dd, 2H, 2J(HP) =
14.9 and 14.9 Hz, PCH2P), 7.14–7.45 (m, 18H, CHarom), 7.70–
1
7.88 (m, 12H, CHarom); dC (CDCl3) 30.3 (dd, J(CP) = 54.0 and
38.3 Hz, PCH2P), 121.6–132.8 (m, Carom and CHarom), 151.8 (d,
2J(CP) = 9.0 Hz, Cipso of OPh).
2c. Yield: 1.12 g, 86% (Found: C, 59.12; H, 3.45; N, 4.31.
C32H22F4N2P2Se requires C, 59.00; H, 3.40; N, 4.44%); nmax/cm-1
(KBr) 489m, 518m, 537w, 687m, 735s, 774m, 791w, 872w, 980s,
1014m, 1110m, 1167w, 1222vs, 1328w, 1437s, 1516vs, 1646s,
2226m, 2878w, 2935w, 3058w; dH (CDCl3) 4.19 (dd, 2H, 2J(HP) =
13.3 and 13.3 Hz, PCH2P), 7.30–7.56 (m, 12H, CHarom), 7.69–7.84
(m, 8H, CHarom); dC (CDCl3) 34.7 (dd, 1J(CP) = 53.6 and 39.7 Hz,
PCH2P), 78.6 (t, 3J(CF) = 18.3 Hz, CN), 110.4 (t, 2J(CF) = 3.3 Hz,
CCN), 128.6–149.8 (m, Carom, CHarom and CF); dF (CDCl3) -152.7
and -139.1 (m, 2F each, C6F4CN).
=
=
Reaction of Ph2P( Se)CH2P( NR)Ph2 (R = 2,4,6-C6H2Me3 2a)
with [{RuCl(l-Cl)(g6-p-cymene)}2]
A solution of the (iminophosphoranyl)(selenophosphoranyl)-
6
methane ligand 2a (0.596 g, 1 mmol) and [{RuCl(m-Cl)(h -p-
cymene)}2] (0.306 g, 0.5 mmol) in 30 cm3 of MeOH was treated,
under refluxing conditions, with NaSbF6 (2.587 g, 10 mmol) for
8 h. The solvent was then removed under vacuum, the crude
product extracted with dichloromethane (ca. 30 cm3), and the
extract filtered over Kieselguhr and concentrated to ca. 1 cm3.
The resulting solution was chromatographed on SiO2. Using
pure CH2Cl2 two fractions were eluted, the first one (colourless)
2d. Yield: 1.02 g, 81% (Found: C, 57.51; H, 3.57; N, 4.51.
C30H22F4N2P2Se requires C, 57.43; H, 3.53; N, 4.46%); nmax/cm-1
(KBr) 487m, 521m, 539m, 573w, 691s, 733s, 779m, 915w, 955s,
998w, 1027w, 1102s, 1176vs, 1306m, 1370w, 1436s, 1468vs, 1516vs,
1638s, 2869w, 2943w, 3054w; dH (CDCl3) 4.17 (dd, 2H, 2J(HP) =
13.5 and 13.5 Hz, PCH2P), 7.29–7.55 (m, 12H, CHarom), 7.70–
=
=
containing compound [Ph2P( Se)CH2P( NHR)Ph2][SbF6] 4a,
which was isolated in 34% yield (0.283 g), and the second one
6
(orange) containing the dimeric species [{Ru(h -p-cymene)}2(m-
1
Cl)3][SbF6]. Further elution with a CH2Cl2–MeOH mixture
(10 : 1) led to a third orange band from which the mononu-
7.87 (m, 8H, CHarom); dC (CDCl3) 34.3 (dd, J(CP) = 52.4 and
38.9 Hz, PCH2P), 128.1–146.6 (m, Carom, CHarom and CF); dF
(CDCl3) -157.3 and -97.6 (m, 2F each, C5F4N).
3
6
=
=
clear complex [Ru{k (C,N,Se)-Ph2P( Se)CHP( NR)Ph2}(h -p-
cymene)][SbF6] 3a could be isolated in 25% yield (0.266 g). Char-
acterization data for 3a will be reported jointly with compounds
3b–f and 5g,h. Data for 4a are as follows: (Found: C, 48.82; H, 4.03;
N, 1.64. C34H34F6P2NSbSe requires C, 49.01; H, 4.11; N, 1.68%);
conductivity (acetone, 20 ◦C) 109 X-1 cm2 mol-1; nmax/cm-1 (KBr)
487m, 525m, 543w, 662vs, 690s, 703w, 725m, 746s, 769s, 784s,
864w, 945w, 979w, 999w, 1026w, 1101s, 1117s, 1161m, 1212m,
1260w, 1312w, 1358m, 1375w, 1437s, 1483m, 2857w, 2921w, 2961w,
3060w, 3223w; dH (CD2Cl2) 2.11 (s, 3H, CH3), 2.22 (s, 6H, CH3),
4.42 (dd, 2H, 2J(HP) = 12.9 and 12.9 Hz, PCH2P), 6.69–7.77 (m,
22H, CHarom), NH not observed; dC (CD2Cl2) 20.4 and 20.6 (s,
CH3), 31.3 (dd, 1J(CP) = 56.1 and 37.5 Hz, PCH2P), 129.2–137.8
(m, Carom and CHarom).
2e. Yield: 1.11 g, 90% (Found: C, 56.79; H, 5.18; N, 2.22.
C29H32O3P3NSe requires C, 56.69; H, 5.25; N, 2.28%); nmax/cm-1
(KBr) 489m, 505m, 543m, 690s, 741s, 793m, 832w, 955m, 998m,
1057m, 1097m, 1203m, 1265m, 1366w, 1387w, 1436m, 1484m,
1589m, 2898w, 2977w, 3055w; dH (CDCl3) 1.12 (t, 6H, 3J(HH) =
6.6 Hz, CH3), 3.87 (m, 4H, OCH2), 4.54 (dd, 2H, 2J(HP) = 14.7
and 14.7 Hz, PCH2P), 7.20-7.30 (m, 12H, CHarom), 7.68–7.83 (m,
8H, CHarom); dC (CDCl3) 16.2 (d, 3J(CP) = 7.6 Hz, CH3), 32.7 (dd,
2
1J(CP) = 52.4 and 39.0 Hz, PCH2P), 61.4 (d, J(CP) = 5.8 Hz,
OCH2), 127.9–132.4 (m, Carom and CHarom).
2f. Yield: 1.25 g, 88% (Found: C, 62.33; H, 4.50; N, 2.00.
C37H32O3P3NSe requires C, 62.54; H, 4.54; N, 1.93%); nmax/cm-1
(KBr) 510m, 524m, 568w, 668m, 688s, 725m, 747s, 765m, 816w,
917m, 1025w, 1096m, 1161m, 1200vs, 1262w, 1436m, 1488m,
1590w, 2886w, 2982w, 3052w; dH (CDCl3) 4.50 (dd, 2H, 2J(HP) =
14.7 and 14.7 Hz, PCH2P), 7.08–7.45 (m, 18H, CHarom), 7.68–
Synthesis of complexes [Ru{j3(C,N,Se)-
6
=
=
Ph2P( Se)CHP( NR)Ph2}(g -p-cymene)][SbF6] (R =
2,4,6-C6H2Me3 3a, 4-C6F4CHO 3b, 4-C6F4CN 3c, 4-C5F4N 3d,
1
=
=
P( O)(OEt)2 3e, P( O)(OPh)2 3f)
7.85 (m, 12H, CHarom); dC (CDCl3) 33.0 (dd, J(CP) = 53.6 and
37.9 Hz, PCH2P), 120.6–132.6 (m, Carom and CHarom), 152.5 (d,
A solution of the corresponding ligand 2a–f (1 mmol) and
2J(CP) = 7.6 Hz, Cipso of OPh).
6
[{RuCl(m-Cl)(h -p-cymene)}2] (0.306 g, 0.5 mmol) in 30 cm3
2g. Yield: 1.15 g, 89% (Found: C, 55.11; H, 5.07; N, 2.19.
C29H32P3O2NSSe requires C, 55.24; H, 5.12; N, 2.22%); nmax/cm-1
(KBr) 488m, 509w, 535w, 612w, 693m, 731s, 749m, 801m, 834m,
948m, 1027s, 1044s, 1108m, 1188w, 1284vs, 1360w, 1439w, 1486w,
of MeOH was treated, under refluxing conditions, with NEt3
(0.153 cm3, 1.1 mmol) and NaSbF6 (2.587 g, 10 mmol) for
8 h. The solvent was then removed under vacuum, the crude
product extracted with dichloromethane (ca. 30 cm3), and the
This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 941–956 | 949
©

View Article Online
extract filtered over Kieselguhr and concentrated to ca. 1 cm3.
The resulting solution was chromatographed on SiO2 using a
CH2Cl2–MeOH mixture (10 : 1) as eluent. An orange fraction was
in all cases collected and evaporated to dryness. The resulting oily
residue was then dissolved in CH2Cl2 (ca. 5 cm3) and treated with
hexanes (ca. 50 cm3) to afford an orange solid precipitate, which
was filtered, washed with diethyl ether (3 ¥ 10 cm3) and dried
in vacuo.
conductivity (acetone, 20 ◦C) 125 X-1 cm2 mol-1; nmax/cm-1 (KBr)
475w, 516m, 517m, 539s, 618w, 650s, 698m, 737m, 803w, 915w,
978m, 1105m, 1153vs, 1316w, 1383w, 1438s, 1468s, 1494s, 1636s,
2871w, 2927w, 2965w, 3057w; dH (CD2Cl2) 1.01 and 1.22 (d, 3H
each, 3J(HH) = 6.8 Hz, CH(CH3)2), 1.50 (s, 3H, CH3), 2.31 (m, 1H,
CH(CH3)2), 2.77 (broad s, 1H, PCHP), 4.34 and 4.95 (d, 1H each,
3J(HH) = 5.7 Hz, CH of p-cymene), 5.06 and 5.08 (d, 1H each,
3J(HH) = 4.2 Hz, CH of p-cymene), 6.90–8.18 (m, 20H, CHarom);
dC (CD2Cl2) -19.3 (dd, 1J(CP) = 81.6 and 44.6 Hz, PCHP), 18.2
(s, CH3), 23.0 and 23.7 (s, CH(CH3)2), 31.8 (s, CH(CH3)2), 80.5,
81.2, 82.6 and 83.1 (s, CH of p-cymene), 100.6 and 111.1 (s, C of
p-cymene), 126.5-147.0 (m, Carom, CHarom and CF); dF (CD2Cl2)
-94.8 and -150.5 (m, 2F each, C6F4N).
3a. Yield: 0.781 g, 73% (Found: C, 49.62; H, 4.45; N, 1.41.
RuC44H46F6P2NSbSe requires C, 49.55; H, 4.35; N, 1.31%);
conductivity (acetone, 20 ◦C) 119 X-1 cm2 mol-1; nmax/cm-1 (KBr)
523w, 534m, 545m, 658vs, 694m, 710w, 743m, 801w, 860w, 999w,
1026w, 1104s, 1156w, 1255m, 1304w, 1383w, 1436m, 2922w, 2962w,
3
3e. Yield: 0.922 g, 85% (Found: C, 43.27; H, 4.09; N, 1.35.
RuC39H45F6O3P3NSbSe requires C, 43.19; H, 4.18; N, 1.29%);
conductivity (acetone, 20 ◦C) 126 X-1 cm2 mol-1; nmax/cm-1 (KBr)
476m, 514m, 539s, 591w, 658vs, 692s, 736s, 750s, 803m, 820m,
867w, 908w, 956m, 1025vs, 1044vs, 1103s, 1115s, 1156s, 1240s,
1260w, 1388w, 1438s, 1472w, 2870w, 2930w, 2965w, 3055w; dH
(CD2Cl2) 1.12 (d, 3H, 3J(HH) = 7.0 Hz, CH(CH3)2), 1.16 (t, 3H,
3056w; dH (CD2Cl2) 1.01 (d, 3H, J(HH) = 6.1 Hz, CH(CH3)2),
3
1.25 (d, 3H, J(HH) = 5.7 Hz, CH(CH3)2), 1.36, 2.12, 2.18 and
2.84 (s, 3H each, CH3), 2.33 (m, 1H, CH(CH3)2), 3.80 (broad s,
1H, PCHP), 3.87 and 4.45 (d, 1H each, 3J(HH) = 5.7 Hz, CH of
p-cymene), 5.12 (d, 2H, 3J(HH) = 5.4 Hz, CH of p-cymene), 6.62–
8.28 (m, 22H, CHarom); dC (CD2Cl2) -24.0 (dd, 1J(CP) = 87.1 and
42.6 Hz, PCHP), 19.7, 20.5, 20.6, 22.9, 23.8 and 23.9 (s, CH3), 31.4
(s, CH(CH3)2), 78.5, 79.7, 81.8 and 87.0 (s, CH of p-cymene), 98.0
and 106.4 (s, C of p-cymene), 127.7–141.3 (m, Carom and CHarom).
3
3J(HH) = 7.4 Hz, OCH2CH3), 1.22 (d, 3H, J(HH) = 7.9 Hz,
3
CH(CH3)2), 1.32 (t, 3H, J(HH) = 7.8 Hz, OCH2CH3), 1.52 (s,
3H, CH3), 2.81 (m, 1H, CH(CH3)2), 2.87 (broad s, 1H, PCHP),
4.07 (m, 4H, OCH2), 4.26 and 4.88 (d, 1H each, 3J(HH) = 5.6 Hz,
3b. Yield: 0.862 g, 77% (Found: C, 44.52; H, 3.21; N, 1.27.
RuC42H36F10P2NOSbSe requires C, 44.86; H, 3.23; N, 1.25%);
conductivity (acetone, 20 ◦C) 116 X-1 cm2 mol-1; nmax/cm-1 (KBr)
505w, 539m, 659vs, 697m, 737m, 803w, 891w, 997w, 1027w, 1105m,
1197s, 1261w, 1312w, 1401s, 1438s, 1483s, 1639s, 1696m, 2874w,
2941w, 2960w, 3066w; dH (CD2Cl2) 1.01 (d, 3H, 3J(HH) = 6.8 Hz,
3
CH of p-cymene), 4.97 and 5.57 (d, 1H each, J(HH) = 5.5 Hz,
CH of p-cymene), 6.95–8.31 (m, 20H, CHarom); dC (CD2Cl2) -23.0
(ddd, 1J(CP) = 80.8 and 45.7 Hz, 3J(CP) = 15.5 Hz, PCHP), 16.3
3
and 16.6 (d, J(CP) = 8.1 Hz, OCH2CH3), 18.5 (s, CH3), 22.2
2
and 23.9 (s, CH(CH3)2), 32.1 (s, CH(CH3)2), 63.1 (d, J(CP) =
3
CH(CH3)2), 1.22 (d, 3H, J(HH) = 7.0 Hz, CH(CH3)2), 1.51 (s,
6.1 Hz, OCH2), 63.4 (d, 2J(CP) = 5.3 Hz, OCH2), 80.5, 81.3, 83.0
and 84.2 (s, CH of p-cymene), 98.4 and 110.4 (s, C of p-cymene),
127.0–134.4 (m, Carom and CHarom).
3H, CH3), 2.31 (m, 1H, CH(CH3)2), 2.76 (broad s, 1H, PCHP),
3
4.35 and 4.96 (d, 1H each, J(HH) = 5.9 Hz, CH of p-cymene),
3
5.08 and 5.10 (d, 1H each, J(HH) = 5.7 Hz, CH of p-cymene),
3f. Yield: 1.050 g, 89% (Found: C, 47.96; H, 3.75; N, 1.16.
RuC47H45F6O3P3NSbSe requires C, 47.82; H, 3.84; N, 1.19%);
conductivity (acetone, 20 ◦C) 112 X-1 cm2 mol-1; nmax/cm-1 (KBr)
484w, 510w, 539s, 658vs, 694s, 717w, 737s, 747m, 777m, 798w,
821m, 906m, 922s, 998w, 1026w, 1105m, 1102s, 1146s, 1196s,
1229w, 1275m, 1379w, 1437s, 1491s, 1591m, 2868w, 2924w, 2965w,
6.88–8.17 (m, 20H, CHarom), 10.03 (s, 1H, CHO); dC (CD2Cl2) -19.3
(dd, 1J(CP) = 81.8 and 44.2 Hz, PCHP), 17.8 (s, CH3), 22.6 and
23.2 (s, CH(CH3)2), 31.4 (s, CH(CH3)2), 80.3, 80.7, 82.2 and 82.7
(s, CH of p-cymene), 100.1 and 110.5 (s, C of p-cymene), 106.5 (t,
2J(CF) = 8.8 Hz, CCHO), 126.5–149.7 (m, Carom, CHarom and CF),
181.8 (s, CHO); dF (CD2Cl2) -147.9 (m, 4F, C6F4CHO).
3
3061w; dH (CD2Cl2) 1.19 (d, 3H, J(HH) = 7.0 Hz, CH(CH3)2),
3c. Yield: 0.864 g, 77% (Found: C, 44.71; H, 3.12; N, 2.58.
RuC42H35F10N2P2SbSe requires C, 44.98; H, 3.15; N, 2.50%);
conductivity (acetone, 20 ◦C) 121 X-1 cm2 mol-1; nmax/cm-1 (KBr)
486w, 506m, 539s, 628m, 658vs, 697s, 737s, 803w, 872w, 915w,
990s, 1107s, 1104s, 1162m, 1188s, 1206m, 1315w, 1388w, 1437vs,
1485vs, 1645s, 2236m, 2870w, 2926w, 2964w, 3056w; dH (CD2Cl2)
3
1.25 (d, 3H, J(HH) = 6.7 Hz, CH(CH3)2), 1.60 (s, 3H, CH3),
2.79 (m, 1H, CH(CH3)2), 3.09 (broad s, 1H, PCHP), 4.41 and
3
4.94 (d, 1H each, J(HH) = 5.9 Hz, CH of p-cymene), 5.01 and
5.68 (d, 1H each, 3J(HH) = 5.6 Hz, CH of p-cymene), 6.80–8.36
1
(m, 30H, CHarom); dC (CD2Cl2) -23.5 (ddd, J(CP) = 80.0 and
45.1 Hz, 3J(CP) = 16.2 Hz, PCHP), 18.3 (s, CH3), 22.1 and 23.3
(s, CH(CH3)2), 31.7 (s, CH(CH3)2), 80.3, 80.8, 82.8 and 83.7 (s,
CH of p-cymene), 98.7 and 110.2 (s, C of p-cymene), 120.1–134.2
(m, Carom and CHarom), 150.9 and 151.5 (d, 2J(CP) = 7.4 Hz, Cipso
of OPh).
3
3
1.01 (d, 3H, J(HH) = 7.1 Hz, CH(CH3)2), 1.21 (d, J(HH) =
7.8 Hz, CH(CH3)2), 1.49 (s, 3H, CH3), 2.30 (m, 1H, CH(CH3)2),
2.76 (broad s, 1H, PCHP), 4.33 and 4.97 (d, 1H each, 3J(HH) =
3
6.0 Hz, CH of p-cymene), 5.07 and 5.09 (d, 1H each, J(HH) =
5.6 Hz, CH of p-cymene), 6.88–8.17 (m, 20H, CHarom); dC (CD2Cl2)
-19.2 (dd, 1J(CP) = 81.5 and 44.9 Hz, PCHP), 17.8 (s, CH3), 22.6
and 23.3 (s, CH(CH3)2), 31.4 (s, CH(CH3)2), 80.2, 80.5, 82.2 and
82.7 (s, CH of p-cymene), 82.7 (t, 3J(CF) = 17.8, CN), 100.1 and
110.6 (s, C of p-cymene), 108.5 (broad s, CCN), 126.4-149.4 (m,
Carom, CHarom and CF); dF (CD2Cl2) -145.7 and -136.2 (m, 2F each,
C6F4CN).
3
=
Synthesis of complexes [Ru(j (C,S,Se)-Ph2P( Se)CHP-
6
=
=
{ NP( S)(OR)2}Ph2)(g -p-cymene)][SbF6] (R = Et 5 g, Ph 5h)
Complexes 5g,h, isolated as orange solids, were prepared as
described for 3a–f but starting from ligands 2g,h (1 mmol) and
6
[{RuCl(m-Cl)(h -p-cymene)}2] (0.306 g, 0.5 mmol).
3d. Yield: 0.831 g, 76% (Found: C, 43.89; H, 3.29; N, 2.40.
5g. Yield: 0.847 g, 77% (Found: C, 42.49; H, 4.22; N, 1.39.
RuC40H35F10N2P2SbSe requires C, 43.78; H, 3.21; N, 2.55%);
RuC39H45F6P3O2NSSbSe requires C, 42.56; H, 4.12; N, 1.27%);
950 | Dalton Trans., 2010, 39, 941–956
This journal is
The Royal Society of Chemistry 2010
©

View Article Online
conductivity (acetone, 20 ◦C) 123 X-1 cm2 mol-1; nmax/cm-1 (KBr)
469w, 495m, 527m, 542s, 561s, 594w, 602w, 658w, 689vs, 723s,
749vs, 828m, 878m, 957s, 998m, 1037vs, 1102m, 1154m, 1191w,
1249s, 1435s, 1481w, 2924w, 2972w, 3050w; dH (CD2Cl2) 0.78 and
CH of p-cymene), 5.16 (d, 2H, 3J(HH) = 5.7 Hz, CH of p-cymene),
7.06–8.31 (m, 20H, CHarom); dC (C6D6) 16.3 (d, 3J(CP) = 8.1 Hz,
OCH2CH3), 18.9 (s, CH3), 22.9 (s, CH(CH3)2), 30.7 (s, CH(CH3)2),
2
61.6 (d, J(CP) = 6.1 Hz, OCH2), 81.3 and 82.7 (s, CH of p-
3
0.83 (d, 3H each, J(HH) = 6.8 Hz, CH(CH3)2), 1.21 (s, 3H,
cymene), 92.6 and 100.9 (s, C of p-cymene), 125.4 (ddd, 1J(CP) =
3
3
CH3), 1.43 and 1.52 (t, 3H each, J(HH) = 7.0 Hz, OCH2CH3),
52.2 and 22.9 Hz, J(CP) = 6.0 Hz, PCP), 129.5–132.5 (m, Carom
1.67 (m, 1H, CH(CH3)2), 4.05–4.33 (m, 4H, OCH2), 5.13 and 5.37
and CHarom).
3
(d, 1H each, J(HH) = 5.3 Hz, CH of p-cymene), 5.60 (d, 2H,
2
3J(HH) = 5.3 Hz, CH of p-cymene), 5.76 (dd, 1H, 2J(HP) = 7.1
and 7.1 Hz, PCHP), 6.84–8.83 (m, 20H, CHarom); dC (CD2Cl2)
-14.0 (ddd, 1J(CP) = 52.7 and 17.4 Hz, 3J(CP) = 2.6 Hz, PCHP),
15.4 (d, 3J(CP) = 9.9 Hz, OCH2CH3), 16.1 (d, 3J(CP) = 7.8 Hz,
OCH2CH3), 16.7 (s, CH3), 20.8 and 23.1 (s, CH(CH3)2), 30.0 (s,
CH(CH3)2), 62.4 (d, 2J(CP) = 7.8 Hz, OCH2), 62.9 (d, 2J(CP) =
5.0 Hz, OCH2), 81.9, 83.0, 86.0 and 87.1 (s, CH of p-cymene), 97.3
and 108.7 (s, C of p-cymene), 127.2–134.0 (m, Carom and CHarom).
=
=
Synthesis of complexes [Ru{j (C,C,Se)-Ph2P( Se)C(C N-2,6-
6
=
C6H3Me2)P( NR)Ph2}(g -p-cymene)] (R = 4-C6F4CHO 8b,
=
=
4-C6F4CN 8c, 4-C5F4N 8d, P( O)(OEt)2 8e, P( O)(OPh)2 8f,
=
=
P( S)(OEt)2 8g, P( S)(OPh)2 8h)
To a THF solution of the corresponding carbene complex 7b–h,
generated in situ from 3b–f or 5g,h (0.5 mmol) as described above,
2,6-dimethylphenyl isocyanide (0.066 g, 0.5 mmol) was added at
room temperature. An immediate change of colour from violet
to bright-yellow was observed. The solvent was then removed
under vacuum, the crude product extracted with diethyl ether (ca.
60 cm3) and the extract filtered over Kieselguhr. Concentration
of the resulting solution to ca. 5 cm3 followed by the addition
of hexanes (ca. 30 cm3) precipitated a bright-yellow solid, which
was filtered, washed with hexanes (2 ¥ 5 cm3) and dried in vacuo.
Alternatively, complex 8g can also be synthesized starting from
the pre-isolated carbene complex 7g.
5h. Yield: 0.981 g, 82% (Found: C, 47.37; H, 3.83; N, 1.23.
RuC47H45F6P3O2NSSbSe requires C, 47.17; H, 3.79; N, 1.17%);
conductivity (acetone, 20 ◦C) 123 X-1 cm2 mol-1; nmax/cm-1 (KBr)
464w, 490m, 540s, 594w, 619s, 659vs, 687s, 731s, 742s, 758s, 821m,
883s, 936vs, 998w, 1025m, 1110m, 1141m, 1169s, 1195vs, 1256w,
1387w, 1436s, 1488s, 1591m, 2868w, 2926w, 2963w, 3060w; dH
(CD2Cl2) 0.83 (d, 3H, 3J(HH) = 6.8 Hz, CH(CH3)2), 0.90 (d, 3H,
3J(HH) = 7.0 Hz, CH(CH3)2), 1.34 (s, 3H, CH3), 1.90 (m, 1H,
CH(CH3)2), 4.78 (dd, 1H, 2J(HP) = 9.0 and 5.5 Hz, PCHP), 4.87
8b. Yield: 0.402 g, 79% (Found: C, 60.21; H, 4.31; N, 2.78.
3
and 4.98 (d, 1H each, J(HH) = 5.9 Hz, CH of p-cymene), 5.15
RuC51H44F4N2P2OSe requires C, 60.12; H, 4.35; N, 2.75%);
and 5.39 (d, 1H each, 3J(HH) = 5.8 Hz, CH of p-cymene), 6.67–
8.26 (m, 30H, CHarom); dC (CD2Cl2) -12.0 (ddd, 1J(CP) = 51.2 and
18.8 Hz, 3J(CP) = 4.4 Hz, PCHP), 17.3 (s, CH3), 21.4 and 22.6 (s,
CH(CH3)2), 30.3 (s, CH(CH3)2), 84.0, 84.1, 84.2 and 85.0 (s, CH
of p-cymene), 99.7 and 108.4 (s, C of p-cymene), 120.7-133.6 (m,
Carom and CHarom), 150.9 (d, 2J(CP) = 9.5 Hz, Cipso of OPh), 151.5
(d, 2J(CP) = 10.3 Hz, Cipso of OPh).
n
max/cm-1 (KBr) 487w, 516w, 526w, 627w, 658w, 690m, 726w,
741m, 802s, 971m, 1025s, 1099vs, 1158m, 1210s, 1261s, 1313w,
1395s, 1437s, 1486vs, 1586m, 1629m, 2111m, 2855w, 2924w,
2961w, 3055w; dH (C6D6) 0.94–1.06 (m, 12H, CH(CH3)2 and 2,6-
C6H3Me2), 2.09 (m, 1H, CH(CH3)2), 2.16 (s, 3H, CH3), 4.59 and
5.39 (d, 1H each, 3J(HH) = 5.0 Hz, CH of p-cymene), 4.79 and 5.26
3
(d, 1H each, J(HH) = 5.9 Hz, CH of p-cymene), 6.81–8.44 (m,
23H, CHarom), 9.97 (s, 1H, COH); dC (C6D6) -16.0 (dd, 1J(CP) =
114.6 and 48.2 Hz, PCP), 19.4, 22.4, 24.0 and 24.5 (s, CH3), 31.5 (s,
CH(CH3)2), 76.0, 81.0, 84.1 and 90.1 (s, CH of p-cymene), 106.3
and 109.5 (s, C of p-cymene), 109.1 (t, 2J(CF) = 4.7 Hz, CCHO),
122.2-151.7 (m, Carom, CHarom and CF), 180.5 (s, CHO), 199.0 (s,
Ru-CN); dF (C6D6) -153.1 and -152.6 (m, 2F each, C6F4CHO).
Deprotonation reactions of complexes 3a–f and 5g,h: Synthesis and
2
=
=
=
characterization of [Ru(j (C,Se)-Ph2P( Se)CP{ NP( S)-
(OEt)2}Ph2)(g6-p-cymene)] 7g
A solution of the corresponding cationic complex 3a–f and 5g,h
(0.5 mmol) in 25 cm3 of dry THF was treated, at room temperature,
with KH (0.201 g, 5 mmol) for 4 h. Monitoring the reaction
8c. Yield: 0.452 g, 89% (Found: C, 60.15; H, 4.38; N,
1
course by 31P{ H} NMR (internal D2O capillary) showed total
4.21. RuC51H43F4N3P2Se requires C, 60.30; H, 4.27; N, 4.14%);
consumption of the starting materials and clean formation of the
corresponding carbene derivatives 6a and 7b–h. However, except
for 7g, attempts to isolate these complexes in pure form failed due
to their extensive reprotonation during work-up. Isolation of 7g
involved solvent removal under vacuum, extraction of the crude
product with diethyl ether (ca. 60 cm3) and filtration of suspension
over Kieselguhr. Concentration of the resulting solution (ca. 5 cm3)
followed by the addition of hexanes (ca. 30 cm3) precipitated
a violet solid, which was washed with hexanes (2 ¥ 5 mL) and
dried in vacuo. Yield: 0.357 g, 83% (Found: C, 54.30; H, 5.17; N,
1.63. RuC39H44P3O2NSSe requires C, 54.23; H, 5.13; N, 1.62%);
n
max/cm-1 (KBr) 484w, 520w, 555w, 692m, 719w, 743w, 771m,
801m, 1027m, 1055s, 1104s, 1155w, 1212w, 1261m, 1382w, 1435s,
1468s, 1524m, 1590w, 2087vs, 2854w, 2920w, 2960w, 3050w; dH
(C6D6) 0.84–0.95 (m, 12H, CH(CH3)2 and 2,6-C6H3Me2), 1.96 (m,
1H, CH(CH3)2), 2.03 (s, 3H, CH3), 4.42 and 5.25 (d, 1H each,
3J(HH) = 5.3 Hz, CH of p-cymene), 4.66 and 5.11 (d, 1H each,
3J(HH) = 5.6 Hz, CH of p-cymene), 6.70–8.33 (m, 23H, CHarom);
1
dC (C6D6) -16.0 (dd, J(CP) = 113.9 and 47.8 Hz, PCP), 19.6,
22.6, 24.2 and 25.7 (s, CH3), 30.2 (s, CH(CH3)2), 76.4, 81.3, 84.6
3
and 90.3 (s, CH of p-cymene), 80.9 (t, J(CF) = 10.2 Hz, CN),
89.8 (t, 2J(CF) = 10.2, CCN), 106.4 and 109.9 (s, C of p-cymene),
122.6–151.8 (m, Carom, CHarom and CF), 198.9 (d, 2J(CP) = 3.7 Hz,
Ru-CN); dF (C6D6) -150.2 and -141.6 (m, 2F each, C6F4CN).
n
max/cm-1 (KBr) 469w, 503m, 542m, 561m, 599w, 617w, 709s,
722m, 742s, 799s, 881w, 950m, 1027vs, 1097s, 1158m, 1260s, 1386w,
1435s, 1480w, 2854w, 2923w, 2960w, 3052w; dH (C6D6) 1.18 (d,
6H, 3J(HH) = 6.8 Hz, CH(CH3)2), 1.36 (t, 6H, 3J(HH) = 7.0 Hz,
OCH2CH3), 1.95 (s, 3H, CH3), 2.96 (sept, 1H, 3J(HH) = 6.8 Hz,
CH(CH3)2), 4.33 (m, 4H, OCH2), 5.05 (d, 2H, 3J(HH) = 5.6 Hz,
8d. Yield: 0.426 g, 86% (Found: C, 59.47; H, 4.33; N,
4.31. RuC49H43F4N3P2Se requires C, 59.34; H, 4.37; N, 4.24%);
n
max/cm-1 (KBr) 486w, 503w, 538w, 658s, 693m, 726w, 741m,
This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 941–956 | 951
©

View Article Online
802w, 859w, 955m, 998w, 1027w, 1102s, 1155s, 1177s, 1261w,
1308w, 1437s, 1471vs, 1495s, 1517s, 1635s, 2122s, 2854w, 2924w,
2961w, 3056w; dH (C6D6) 0.95–1.05 (m, 12H, CH(CH3)2 and 2,6-
C6H3Me2), 2.08 (m, 1H, CH(CH3)2), 2.19 (s, 3H, CH3), 4.59 and
5.39 (d, 1H each, 3J(HH) = 5.1 Hz, CH of p-cymene), 4.79 and 5.26
9.3 Hz, OCH2CH3), 20.0, 22.3, 24.1 and 24.6 (s, CH3), 30.0 (s,
CH(CH3)2), 61.3 (d, 2J(CP) = 4.7 Hz, OCH2), 61.5 (d, 2J(CP) =
9.3 Hz, OCH2), 75.9, 81.5, 84.2 and 88.8 (s, CH of p-cymene),
106.6 and 108.9 (s, C of p-cymene), 122.2–152.0 (m, Carom and
CHarom), 198.4 (d, 2J(CP) = 3.7 Hz, Ru-CN).
3
(d, 1H each, J(HH) = 5.5 Hz, CH of p-cymene), 6.79–8.48 (m,
8h. Yield: 0.486 g, 89% (Found: C, 61.72; H, 4.84; N, 2.66.
23H, CHarom); dC (C6D6) -16.1 (dd, 1J(CP) = 114.0 and 47.9 Hz,
PCP), 19.4, 22.3, 22.8, 24.1 and 24.5 (s, CH3), 31.7 (s, CH(CH3)2),
75.9, 81.3, 84.1 and 90.1 (s, CH of p-cymene), 106.3 and 109.2 (s,
C of p-cymene), 122.3–151.7 (m, Carom, CHarom and CF), 199.1 (d,
2J(CP) = 3.7 Hz, Ru-CN); dF (C6D6) -155.9, -155.2, -99.8 and
-95.9 (m, 1F each, C5F4N).
RuC56H53P3N2O2SSe requires C, 61.65; H, 4.90; N, 2.57%);
n
max/cm-1 (KBr) 500m, 526w, 595w, 620w, 658m, 688s, 741m,
769m, 801vs, 890m, 911m, 1023vs, 1096vs, 1159s, 1198s, 1261s,
1383w, 1436m, 1488s, 1588m, 1622m, 2122m, 2853w, 2926w,
2968w, 3055w; dH (C6D6) 0.83–0.91 (m, 12H, CH(CH3)2 and 2,6-
C6H3Me2), 1.87 (m, 1H, CH(CH3)2), 2.43 (s, 3H, CH3), 4.58 and
5.19 (d, 1H each, 3J(HH) = 5.5 Hz, CH of p-cymene), 4.78 and 5.10
8e. Yield: 0.421 g, 86% (Found: C, 58.95; H, 5.32; N,
3
(d, 1H each, J(HH) = 5.9 Hz, CH of p-cymene), 6.70–8.61 (m,
2.98. RuC48H53O3P3N2Se requires C, 58.89; H, 5.46; N, 2.86%);
33H, CHarom); dC (C6D6) -15.6 (ddd, 1J(CP) = 97.9 and 47.8 Hz,
3J(CP) = 10.6 Hz, PCP), 20.5, 22.3, 23.0 and 25.8 (s, CH3), 30.2 (s,
CH(CH3)2), 75.4, 82.5, 84.7 and 89.7 (s, CH of p-cymene), 107.4
and 107.8 (s, C of p-cymene), 122.1–152.3 (m, Carom and CHarom),
153.1 (d, 2J(CP) = 7.6 Hz, Cipso of OPh), 153.2 (d, 2J(CP) = 8.7 Hz,
Cipso of OPh), 198.3 (d, 2J(CP) = 5.1 Hz, Ru-CN).
n
max/cm-1 (KBr) 505m, 551w, 658s, 692m, 743m, 800s, 955w,
1037vs, 1056vs, 1097vs, 1160s, 1261s, 1384w, 1437m, 1467w,
1587w, 1623w, 2126m, 2854w, 2925w, 2962w, 3055w; dH (C6D6)
1.01–1.09 (m, 12H, CH(CH3)2 and 2,6-C6H3Me2), 1.12 (t, 6H,
3J(HH) = 7.1 Hz, OCH2CH3), 2.09 (m, 1H, CH(CH3)2), 2.47
(s, 3H, CH3), 4.03 (m, 4H, OCH2), 4.78 and 5.27 (d, 1H each,
3J(HH) = 5.4 Hz, CH of p-cymene), 4.95 and 5.31 (d, 1H each,
3J(HH) = 5.9 Hz, CH of p-cymene), 6.91–8.61 (m, 23H, CHarom);
2
=
=
Synthesis of complexes [Ru{j (C,N)-Ph2P( Se)C(C N-2,6-
1
C6H3Me2)P(N-2,4,6-C6H2Me3)Ph2}(CN-2,6-C6H3Me2)4] (9a) and
dC (C6D6) -15.8 (dd, J(CP) = 87.0 and 45.2 Hz, PCP), 16.4
2
=
=
(d, 3J(CP) = 5.1 Hz, OCH2CH3), 16.6 (d, 3J(CP) = 7.1 Hz,
[Ru{j (C,Se)-Ph2P(Se)C(C N-2,6-C6H3Me2)P( NR)Ph2}(CN-
2,6-C6H3Me2)4] (4-C6F4CHO 10b, 4-C6F4CN 10c, 4-C5F4N 10d,
OCH2CH3), 19.9, 22.2, 24.1 and 24.7 (s, CH3), 30.0 (s, CH(CH3)2),
=
=
=
2
P( O)(OEt)2 10e, P( O)(OPh)2 10f, P( S)(OEt)2 10g,
60.5 and 61.2 (d, J(CP) = 6.1 Hz, OCH2), 75.6, 82.1, 84.1 and
=
P( S)(OPh)2 10h)
89.1 (s, CH of p-cymene), 106.9 and 108.2 (s, C of p-cymene),
2
122.2–152.1 (m, Carom and CHarom), 198.8 (d, J(CP) = 4.1 Hz,
A THF solution of the corresponding carbene complex 6a or 7b–h,
generated in situ from 3a–f or 5g,h (0.5 mmol), was treated with 2,6-
dimethylphenyl isocyanide (0.660 g, 5 mmol) at room temperature
for 6 h. The solvent was then removed under vacuum, the crude
product extracted with diethyl ether (ca. 60 cm3) and the extract
filtered over Kieselguhr. The solvent was then removed in vacuo
and the resulting oily residue dissolved in dichloromethane (ca.
3 cm3). Addition of hexanes (ca. 50 cm3) precipitated a yellow
solid, which was washed with hexanes (5 ¥ 10 cm3) and dried
in vacuo. Alternatively, complexes 10b–h can be prepared, in
similar yields, by treatment of THF solutions of 8b–h with a ten-
fold excess of 2,6-dimethylphenyl isocyanide at r.t.
Ru-CN).
8f. Yield: 0.467 g, 87% (Found: C, 62.65; H, 4.89; N,
2.59. RuC56H53O3P3N2Se requires C, 62.57; H, 4.97; N, 2.61%);
n
max/cm-1 (KBr) 465w, 503m, 565w, 596w, 658s, 689s, 725m,
742m, 786vs, 865w, 920s, 1021vs, 1101vs, 1158s, 1201s, 1263s,
1383m, 1437m, 1489s, 1588m, 1622m, 1659w, 2128m, 2854w,
2912w, 2963w, 3058w; dH (C6D6) 0.97 (m, 12H, CH(CH3)2 and
2,6-C6H3Me2), 2.03 (m, 1H, CH(CH3)2), 2.76 (s, 3H, CH3), 4.73
3
and 5.32 (d, 1H each, J(HH) = 5.1 Hz, CH of p-cymene), 4.87
and 5.27 (d, 1H each, 3J(HH) = 5.8 Hz, CH of p-cymene), 6.82–
8.73 (m, 33H, CHarom); dC (C6D6) -15.7 (ddd, 1J(CP) = 95.8 and
3
47.5 Hz, J(CP) = 9.3 Hz, PCP), 20.2, 22.0, 24.1 and 25.0 (s,
9a. Yield: 0.520 g, 77% (Found: C, 70.01; H, 5.59; N, 6.20.
RuC79H76N6P2Se requires C, 70.21; H, 5.67; N, 6.22%); nmax/cm-1
(KBr) 506m, 539m, 658m, 692m, 726w, 740m, 769w, 802w, 980m,
998m, 1102s, 1160w, 1211m, 1261w, 1383w, 1435s, 1494vs, 1587w,
1641s, 2113m, 2177m, 2853w, 2923w, 2958w, 3055w; dH (acetone-
d6) 1.13, 1.53, 1.99 and 2.05 (s, 6H each, CH3), 2.12 (s, 3H, CH3),
2.55 (s, 12H, CH3), 6.31–8.06 (m, 37H, CHarom); dC (acetone-d6)
CH3), 31.4 (s, CH(CH3)2), 74.7, 82.5, 84.4, and 90.0 (s, CH of
p-cymene), 106.5 and 108.5 (s, C of p-cymene), 120.5–152.2 (m,
Carom and CHarom), 153.3 (d, 2J(CP) = 7.5 Hz, Cipso of OPh), 153.5
2
2
(d, J(CP) = 8.4 Hz, Cipso of OPh), 198.5 (d, J(CP) = 5.6 Hz,
Ru-CN).
8g. Yield: 0.413 g, 83% (Found: C, 57.89; H, 5.34; N, 2.91.
1
17.3, 17.9, 18.8, 19.8, 19.9 and 20.2 (s, CH3), 60.7 (dd, J(CP) =
RuC48H53P3N2O2SSe requires C, 57.94; H, 5.37; N, 2.82%);
169.4 and 72.7 Hz, PCP), 118.9–154.7 (m, Carom and CHarom), 159.1,
n
max/cm-1 (KBr) 489m, 502m, 595w, 658m, 691m, 744m, 799m,
159.5 and 165.6 (s, Ru-CN), 190.5 (d, 2J(CP) = 31.5 Hz, Ru-CN).
830w, 951w, 1032vs, 1056s, 1096vs, 1156s, 1260s, 1296m, 1384w,
1436m, 1465w, 1585m, 1616m, 2114m, 2854w, 2924w, 2963w,
3055w; dH (C6D6) 1.00–1.07 (m, 12H, CH(CH3)2 and 2,6-
10b. Yield: 0.557 g, 79% (Found: C, 65.71; H, 4.74; N,
5.91. RuC77H66N6F4P2OSe requires C, 65.62; H, 4.72; N, 5.96%);
n
max/cm-1 (KBr) 490m, 519m, 627w, 657m, 692m, 719w, 743w,
775m, 800m, 969m, 1032s, 1097s, 1166m, 1208s, 1261m, 1316w,
1396m, 1437s, 1481vs, 1590w, 1635m, 1690w, 2125vs, 2150m,
2855w, 2921w, 2961w, 3055w; dH (C6D6) 1.77, 1.94 and 2.06 (s, 6H
each, CH3), 2.40 (s, 12H, CH3), 6.81–8.44 (m, 35H, CHarom), 9.98
(s, 1H, CHO); dC (C6D6) 17.9, 18.6, 19.0 and 19.9 (s, CH3), 51.9
3
C6H3Me2), 1.14 (t, 6H, J(HH) = 7.0 Hz, OCH2CH3), 2.16 (m,
1H, CH(CH3)2), 2.40 (s, CH3), 4.15 (m, 4H, OCH2), 4.77 and 5.26
3
(d, 1H each, J(HH) = 4.9 Hz, CH of p-cymene), 4.95 and 5.33
3
(d, 1H each, J(HH) = 5.5 Hz, CH of p-cymene), 6.92–8.51 (m,
1
23H, CHarom); dC (C6D6) -15.7 (dd, J(CP) = 86.0 and 45.9 Hz,
3
3
PCP), 16.0 (d, J(CP) = 8.4 Hz, OCH2CH3), 16.2 (d, J(CP) =
952 | Dalton Trans., 2010, 39, 941–956
This journal is
The Royal Society of Chemistry 2010
©

View Article Online
(dd, 1J(CP) = 117.7 and 35.9 Hz, PCP), 101.0 (t, 2J(CF) = 9.5 Hz,
CCHO), 119.7–155.4 (m, Carom, CHarom and CF), 160.1, 160.9 and
(CDCl3) 1.26 (broad s, 6H, OCH2CH3), 2.03, 2.15 and 2.45 (s, 6H
each, CH3), 2.30 (s, 12H, CH3), 4.09 (m, 4H, OCH2), 7.05–7.81 (m,
35H, CHarom); dC (CDCl3) 16.1 (d, 3J(CP) = 7.8 Hz, OCH2CH3),
18.7, 18.9 and 19.3 (s, CH3), 49.3 (ddd, 1J(CP) = 57.5 and 26.5 Hz,
2
162.6 (s, Ru-CN), 180.3 (s, CHO), 195.1 (d, J(CP) = 23.2 Hz,
Ru-CN); dF (C6D6) -152.3 and -146.3 (m, 2F each, C6F4CHO).
2
3J(CP) = 9.9 Hz, PCP), 63.2 (d, J(CP) = 6.3 Hz, OCH2), 63.4
10c. Yield: 0.534 g, 76% (Found: C, 65.85; H, 4.70; N,
2
(d, J(CP) = 7.0 Hz, OCH2), 127.8–135.2 (m, Carom and CHarom),
6.95. RuC77H65N7F4P2Se requires C, 65.76; H, 4.66; N, 6.97%);
160.1, 160.8 and 161.3 (s, Ru-CN), 199.1 (dd, 2J(CP) = 34.3 Hz,
n
max/cm-1 (KBr) 492m, 519m, 602w, 694w, 773w, 819w, 974m,
Ru-CN).
1055m, 1085s, 1110s, 1182w, 1228w, 1261w, 1297w, 1384w, 1435s,
1507s, 1526s, 1551m, 1640w, 2113vs, 2166m, 2920w, 2958w, 3053w;
dH (C6D6) 1.76, 1.93 and 2.06 (s, 6H each, CH3), 2.40 (s, 12H,
CH3), 6.30–8.33 (m, 35H, CHarom); dC (CDCl3) 18.4, 18.9, 19.2,
10h. Yield: 0.637 g, 86% (Found: C, 66.59; H, 5.17; N,
5.62. RuC82H75N6P3O2SSe requires C, 66.48; H, 5.10; N, 5.67%);
n
max/cm-1 (KBr) 485m, 502m, 543w, 657m, 694m, 715m, 744m,
1
800s, 954m, 1027vs, 1095s, 1158m, 1261s, 1383w, 1436m, 1472w,
1590w, 1635w, 1653w, 2112vs, 2159m, 2854w, 2924w, 2962w,
3053w; dH (CD2Cl2) 2.06, 2.11 and 2.13 (s, 6H each, CH3), 2.17 (s,
12H, CH3), 6.00–8.26 (m, 45H, CHarom); dC (CD2Cl2) 18.2, 18.7,
19.1 and 19.5 (s, CH3), 51.2 (dd, 1J(CP) = 52.2 and 22.4 Hz, PCP),
119.5–136.9 (m, Carom and CHarom), 152.6 (d, 2J(CP) = 7.8 Hz, Cipso
of OPh), 154.8 (d, 2J(CP) = 4.0 Hz, Cipso of OPh), 159.1, 159.7 and
162.1 (s, Ru-CN), 196.0 (d, 2J(CP) = 33.4 Hz, Ru-CN).
19.3 and 19.7 (s, CH3), 66.4 (dd, J(CP) = 124.8 and 122.8 Hz,
PCP), 72.6 (broad s, CN), 109.8 (broad s, CCN), 119.6–155.9 (m,
Carom, CHarom and CF), 159.0, 159.8 and 162.1 (s, Ru-CN), 195.8
(d, 2J(CP) = 42.0 Hz, Ru-CN); dF (C6D6) -150.2 and -137.5 (m,
2F each, C6F4CN).
10d. Yield: 0.594 g, 86% (Found: C, 65.29; H, 4.88; N,
7.01. RuC75H65N7F4P2Se requires C, 65.17; H, 4.74; N, 7.09%);
n
max/cm-1 (KBr) 491m, 507m, 519m, 658w, 656w, 692w, 741w,
776m, 874w, 954m, 1054m, 1089s, 1132s, 1152s, 1166m, 1261w,
1435m, 1472s, 1503s, 1633m, 2111vs, 2163m, 2854w, 2920w,
2960w, 3054w; dH (C6D6) 1.88, 2.04 and 2.17 (s, 6H each, CH3),
2.51 (s, 12H, CH3), 6.43–8.55 (m, 35H, CHarom); dC (CDCl3) 18.9,
19.3, 19.6 and 20.0 (s, CH3), 66.8 (dd, 1J(CP) = 126.5 and 121.3 Hz,
PCP), 119.0–155.9 (m, Carom, CHarom and CF), 159.6, 160.3 and
162.5 (s, Ru-CN), 196.0 (d, 2J(CP) = 41.9 Hz, Ru-CN); dF (C6D6)
-156.9 and -101.7 (m, 2F each, C5F4N).
X-Ray crystal structure determination of compounds 2a, 3a, 4a, 5g
and 10d
Crystals suitable for X-ray diffraction analysis were obtained by
slow diffusion of hexanes into a saturated solution of compounds
2a, 3a, 4a and 5g in dichloromethane or, in the case of 10d, by slow
evaporation of a saturated benzene solution. The most relevant
crystal and refinement data are collected in Table 3.
For 3a, 4a and 10d data collection was performed on a Oxford
Diffraction Xcalibur Nova single crystal diffractometer, using
10e. Yield: 0.547 g, 80% (Found: C, 65.10; H, 5.56; N,
6.20. RuC74H75N6O3P3Se requires C, 64.90; H, 5.52; N, 6.09%);
˚
Cu Ka radiation (l = 1.5418 A). Images were collected at a
n
max/cm-1 (KBr) 491m, 520m, 601w, 696m, 719m, 772m, 802s,
65 mm fixed crystal-detector distance (45 mm in the case of
4a), using the oscillation method, with 1◦ oscillation and variable
exposure time per image (4–20 s). Data collection strategy was
calculated with the program CrysAlis Pro CCD.33 Data reduction
and cell refinement were performed with the program CrysAlis Pro
RED.33 An empirical absorption correction was applied using the
SCALE3 ABSPACK algorithm as implemented in the program
CrysAlis Pro RED.33
879w, 954w, 1055s, 1098s, 1164m, 1261s, 1388vs, 1431s, 1465m,
1552m, 1603m, 1653m, 2111s, 2167m, 2912w, 2960w, 3057w; dH
3
(acetone-d6) 0.63 (t, 6H, J(HH) = 7.0 Hz, OCH2CH3), 2.07,
2.11 and 2.24 (s, 6H each, CH3), 2.47 (s, 12H, CH3), 3.86 (m,
4H, OCH2), 6.66–8.32 (m, 35H, CHarom); dC (acetone-d6) d 15.6
3
(d, J(CP) = 8.4 Hz, OCH2CH3), 17.7, 18.5, 18.7 and 19.6 (s,
CH3), 55.2 (dd, 1J(CP) = 56.8 and 30.0 Hz, PCP), 58.6 (d,
2J(CP) = 4.6 Hz, OCH2), 119.2–154.9 (m, Carom and CHarom),
For 2a and 5g diffraction data were recorded on a Nonius
KappaCCD single crystal diffractometer, using Mo Ka radiation
2
159.3, 159.9 and 162.2 (s, Ru-CN), 195.6 (d, J(CP) = 43.7 Hz,
Ru-CN).
˚
(l = 0.71073 A). Images were collected at a 35 mm fixed crystal-
detector distance, using the oscillation method, with 1◦ oscillation
and 80 s exposure time per image. Data collection strategy was
calculated with the program Collect.34 Data reduction and cell
refinement were performed with the programs HKL Denzo and
Scalepack.35 A semi-empirical absorption correction was applied
using the program SORTAV.36
10f. Yield: 0.659 g, 90% (Found: C, 67.39; H, 5.24; N,
5.76. RuC82H75N6O3P3Se requires C, 67.21; H, 5.16; N, 5.73%);
n
max/cm-1 (KBr) 488m, 518w, 601w, 690 m, 741w, 800s, 912m,
1024vs, 1087vs, 1200s, 1258s, 1402w, 1436w, 1489w, 1518w, 1590w,
1624w, 2104s, 2162m, 2845w, 2922w, 2951m, 3037w; dH (C6D6)
1.69, 1.96 and 2.04 (s, 6H each, CH3), 2.41 (s, 12H, CH3), 6.31-
8.60 (m, 45H, CHarom); dC (C6D6) 17.9, 18.6, 19.0 and 19.9 (s, CH3),
67.1 (dd, 1J(CP) = 58.1 and 17.7 Hz, PCP), 119.5–137.4 (m, Carom
In all cases the software package WINGX37 was used for
space group determination, structure solution and refinement. The
structure for the complex 2a were solved by direct methods using
SIR92.38 For 3a, 5g, 4a and 10d the structures were solved by
Patterson interpretation and phase expansion using DIRDIF.39 In
the crystal of 3a one hexane molecule of solvation per formula unit
of the complex was found, and in the crystal of 10d two bencene
molecules of solvation per formula unit of the complex were found.
Isotropic least-squares refinement on F2 using SHELXL9740 was
performed. During the final stages of the refinements, all the
positional parameters and the anisotropic temperature factors of
2
and CHarom), 153.6 (d, J(CP) = 7.1 Hz, Cipso of OPh), 155.1 (d,
2J(CP) = 4.0 Hz, Cipso of OPh), 160.4, 160.9 and 162.7 (s, Ru-CN),
194.5 (dd, 2J(CP) = 40.9 Hz, 3J(CP) = 5.6 Hz, Ru-CN).
10g. Yield: 0.603 g, 87% (Found: C, 64.29; H, 5.51; N,
6.20. RuC74H75N6P3O2SeS requires C, 64.15; H, 5.46; N, 6.07%);
n
max/cm-1 (KBr) 485m, 502m, 543w, 657m, 694m, 744m, 800s,
954m, 1027vs, 1095vs, 1158m, 1261s, 1383w, 1436m, 1472w,
1590w, 1635w, 2112vs, 2160m, 2854w, 2924w, 2962w, 3053w; dH
This journal is
The Royal Society of Chemistry 2010
Dalton Trans., 2010, 39, 941–956 | 953
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Table 3 Crystal data and structure refinement for compounds 2a, 3a, 4a, 5g and 10d
2a
3a
4a
5g
10d
Empirical formula
C34H33P2NSe
RuC44H46F6P2NSbSe· C34H34F6P2NSbSe
RuC39H45F6P3O2NSSbSe RuC75H65N7F4P2Se·2C6H6
C6H14
Formula weight
596.51
150(2)
0.71073
Orthorhombic
Pbca
1152.71
150(2)
1.5418
Monoclinic
C2/c
833.27
293(2)
1.5418
Monoclinic
1100.51
293(2)
0.71073
Triclinic
¯
P1
1538.53
293(2)
T/K
Wavelength/A
˚
1.5418
Triclinic
Crystal system
Space group
¯
P21/n
P1
Crystal size/mm
0.15 ¥ 0.12 ¥ 0.12 0.27 ¥ 0.06 ¥ 0.04
0.068 ¥ 0.094 ¥ 0.13 0.15 ¥ 0.12 ¥ 0.05
0.064 ¥ 0.05 ¥ 0.029
14.3993(5)
15.7608(4)
18.2825(4)
76.770(2)
85.316(2)
73.684(2)
2
˚
a/A
15.9884(4)
15.1347(8)
24.3470(12)
90
90
90
19.3086(2)
28.7968(2)
17.8805(2)
90
100.4550(10)
90
10.1945(1)
18.4859(1)
18.8762(1)
90
95.525(1)
90
11.2800(2)
11.7876(4)
16.7661(5)
82.1360(10)
80.647(2)
88.881(2)
2
2178.96(11)
1.677
2.020
˚
b/A
˚
c/A
a/◦
b/◦
g /◦
Z
8
8
4
3
˚
Volume/A
5891.5(5)
1.345
1.407
9776.96(18)
1.566
8.833
3540.78(4)
1.563
8.699
3875.66(19)
1.318
3.036
Calculated density/g cm-3
m/mm-1
F(000)
2464
4640
1656
1092
1584
q range/◦
1.67 to 25.40
0 ≤ h ≤ 19
0 ≤ k ≤ 18
-29 ≤ l ≤ 0
99.9%
2.79 to 73.89
-23 ≤ h ≤ 23
-35 ≤ k ≤ 34
-22 ≤ l ≤ 19
96.7%
3.35 to 66.92
-12 ≤ h ≤ 12
-21 ≤ k ≤ 21
-18 ≤ l ≤ 22
99.5%
1.74 to 25.35
-13 ≤ h ≤ 13
-13 ≤ k ≤ 14
0 ≤ l ≤ 20
99.8%
2.99 to 73.90
-17 ≤ h ≤ 17
-18 ≤ k ≤ 18
-14 ≤ l ≤ 202
90.5%
Index ranges
Completeness to qmax
No. of reflns collected
No. of unique reflns
No. of parameters/restraints
No. of reflns. [I > 2s(I)]a
Goodness-of-fit on F2
Weight function (a, b)
R1 [I > 2s(I)]a
60 417
42 104
31 360
20 290
23 124
5418 (Rint = 0.116) 9600 (Rint = 0.0304) 6274 (Rint = 0.0404) 7981 (Rint = 0.053)
14 214 (Rint = 0.0298)
346/0
2321
0.820
569/0
7721
1.024
0.0863, 42.1756
0.0510
0.1368
0.0654
0.1543
2.142 and -0.857
457/0
4747
0.886
0.0446, 0.000
0.0274
0.0626
0.0378
0.0646
0.381 and -0.306
501/0
5243
1.086
0.0791, 0.000
0.0420
0.1097
0.0783
0.1500
0.820 and -1.088
929/0
10527
1.052
0.0667, 0.7560
0.0394
0.0982
0.0597
0.1251
0.485 and -0.703
0.0620, 0.000
0.0481
0.1142
0.0991
0.1754
wR2 [I > 2s(I)]a
R1 (all data)
wR2 (all data)
-3
˚
Largest diff. peak and hole/e A 0.474 and -0.556
ꢀ
ꢀ
ꢀ
ꢀ
1
2
a R1 = (|Fo| - |Fc|)/ |Fo|; wR2 = { [w(Fo - Fc2)2]/ [w(Fo ) ]} .
2
2 2
all the non-H atoms were refined. The H atoms were geometrically
located and their coordinates were refined riding on their parent
atoms (except H1N–N, H1A–C1 and H1B–C1 for 4a, the coordinates
of these H atoms were found from different Fourier maps and
included in a refinement with isotropic parameters). For 3a the
maximum residual electron density is located near to heavy atoms.
Notes and references
1 For reviews and accounts covering this topic, see: (a) T. K. Panda
and P. W. Roesky, Chem. Soc. Rev., 2009, 38, 2782; (b) P. W. Roesky,
Z. Anorg. Allg. Chem., 2006, 632, 1918; (c) N. D. Jones and R. G. Cavell,
J. Organomet. Chem., 2005, 690, 5485–5496; (d) P. W. Roesky, Heteroat.
Chem., 2002, 13, 514; (e) R. G. Cavell, R. P. K. Babu and K. Aparna,
J. Organomet. Chem., 2001, 617–618, 158.
ꢀ
ꢀ
The function minimized was [ wFo - Fc )/ w(Fo2)]1/2 where
2
2
2 See, for example: (a) M. Valderrama and R. Contreras, J. Organomet.
Chem., 1996, 513, 7; (b) M. Valderrama and R. Contreras, Bol. Soc.
Chil. Qu´ım., 1995, 40, 111; (c) M. Valderrama, R. Contreras, M.
Bascun˜an, S. Alegria and D. Boys, Polyhedron, 1995, 14, 2239; (d) J.
Browning, G. W. Bushnell, K. R. Dixon and R. W. Hilts, J. Organomet.
Chem., 1992, 434, 241.
2
w = 1/[s (Fo2) + (aP)2 + bP] (a and b values are collected in
2
Table 3) with s (Fo2) from counting statistics and P = (Max
2
2
(Fo + 2Fc )/3. Atomic scattering factors were taken from the
International Tables for X-Ray Crystallography.41 Geometrical
calculations were made with PARST.42 The crystallographic plots
were made with PLATON.43
3 Quite
recently
an
interesting
C–H
activation
process
involving one of the aromatic rings of the methanide anion
-
=
=
[Ph2P( S)CHP( S)Ph2]
in the transient iridium complex
=
3
=
[Ir{k (C,S,S)-Ph2P( S)CHP( S)Ph2}(coe)] (coe
=
cyclooctene)
has been described: M. Blug, H. Heuclin, T. Cantat, X.-F. Le Goff, N.
Me´zailles and P. Le Floch, Organometallics, 2009, 28, 1969.
Acknowledgements
4 Accounts covering the synthesis and reactivity of this type of complexes
are available: (a) M. Doux, O. Piechaczyk, T. Cantat, N. Me´zailles and
P. Le Floch, C. R. Chimie, 2007, 10, 573; (b) T. Cantat, N. Me´zailles,
A. Auffrant and P. Le Floch, Dalton Trans., 2008, 1957.
5 See, for example: (a) A. Kasani, R. McDonald and R. G. Cavell,
Organometallics, 1999, 18, 3775; (b) R. P. K. Babu, R. McDonald
and R. G. Cavell, Organometallics, 2000, 19, 3462; (c) T. Cantat, N.
Me´zailles, L. Ricard, Y. Jean and P. Le Floch, Angew. Chem., Int.
Ed., 2004, 43, 6382; (d) T. Cantat, F. Jaroschik, F. Nief, L. Ricard,
N. Me´zailles and P. Le Floch, Chem. Commun., 2005, 5178; (e) T.
Financial support by the Ministerio de Educacio´n y Ciencia
(MEC) of Spain (Projects CTQ2006-08485/BQU, CTQ2008-
00506/BQU and Consolider Ingenio 2010 (CSD2007-00006)) and
the Gobierno del Principado de Asturias (FICYT Project IB08-
036) is gratefully acknowledged. J.G.-A. also thanks MEC and
the European Social Fund for the award of a “Juan de la Cierva”
contract.
954 | Dalton Trans., 2010, 39, 941–956
This journal is
The Royal Society of Chemistry 2010
©

View Article Online
Cantat, F. Jaroschik, L. Ricard, P. Le Floch, F. Nief and N. Me´zailles,
Organometallics, 2006, 25, 1329; (f) T. Cantat, L. Ricard, N. Me´zailles
and P. Le Floch, Organometallics, 2006, 25, 6030; (g) L. Orzechowski,
G. Jansen and S. Harder, J. Am. Chem. Soc., 2006, 128, 14676; (h) M.
Fang, N. D. Jones, R. Lukowski, J. Tjathas, M. J. Ferguson and R. G.
Cavell, Angew. Chem., Int. Ed., 2006, 45, 3097; (i) L. Orzechowski and
S. Harder, Organometallics, 2007, 26, 2144; (j) L. Orzechowski and S.
Harder, Organometallics, 2007, 26, 5501; (k) T. Cantat, T. Arliguie, A.
Noe¨l, P. Thue´ry, M. Ephritikhine, P. Le Floch and N. Me´zailles, J. Am.
Chem. Soc., 2009, 131, 963.
15 (a) M. S. Hill and P. B. Hitchcock, J. Chem. Soc., Dalton Trans., 2002,
4694; (b) K. V. Katti and R. G. Cavell, Organometallics, 1989, 8, 2147.
16 S. O. Grim and E. D. Walton, Inorg. Chem., 1980, 19, 1982.
17 P. J. Carroll and D. D. Titus, J. Chem. Soc., Dalton Trans., 1977,
824.
18 This well-known compound results from the abstraction of a chloride
6
ligand in [{RuCl(m-Cl)(h -p-cymene)}2]: (a) M. A. Bennett and A. K.
Smith, J. Chem. Soc., Dalton Trans., 1974, 233; (b) T. Arthur and T. A.
Stephenson, J. Organomet. Chem., 1981, 208, 369.
19 Iminophosphoranes are known to be very strong non-ionic bases. See,
for example: (a) G. Garrido, E. Koort, C. Ra`fols, E. Bosch, T. Rodima,
I. Leito and M. Rose´s, J. Org. Chem., 2006, 71, 9062; (b) T. Rodima,
V. M a¨emets and I. Koppel, J. Chem. Soc., Perkin Trans. 1, 2000, 2637;
(c) P. Ilankumaran, G. Zhang and J. G. Verkade, Heteroat. Chem., 2000,
11, 251 and references cited therein.
20 As expected, two enantiomers are present in the unit cell of this
compound displaying RRu SC/SRu RC configurations. Only the RRu SC
enantiomer is represented in Fig. 6.
´
6 (a) V. Cadierno, J. D´ıez, J. Garc´ıa-Alvarez, J. Gimeno, M. J. Calhorda
and L. F. Veiros, Organometallics, 2004, 23, 2421; (b) V. Cadierno, J.
´
D´ıez, J. Garc´ıa-Alvarez and J. Gimeno, J. Organomet. Chem., 2005,
690, 2087.
-
=
7 The coordination of the related methanide anion [CH{Ph2P( NPh)}2]
to half-sandwich ruthenium(II) fragments has been described by
K. G. Caulton, and co-workers: (a) C. Bibal, M. Pink, Y. D. Smurnyy,
J. Tomaszewski and K. G. Caulton, J. Am. Chem. Soc., 2004, 126, 2312;
(b) Y. Smurnyy, C. Bibal, M. Pink and K. G. Caulton, Organometallics,
2005, 24, 3849; (c) C. Bibal, Y. D. Smurnyy, M. Pink and K. G. Caulton,
J. Am. Chem. Soc., 2005, 127, 8944.
21 E. A. Seddon and K. R. Seddon, in The Chemistry of Ruthenium,
Elsevier, Amsterdam, 1984.
22 See, for example: (a) Q.-F. Zhang, H. Zheng, W.-Y. Wong and W.-H.
Leung, Inorg. Chem., 2000, 39, 5225; (b) Q.-F. Zhang, F. K. M. Cheung,
W.-Y. Wong, I. D. Williams and W.-H. Leung, Organometallics, 2001,
20, 3777; (c) S. Evans, J. W. Faller and J. Parr, J. Organomet. Chem.,
2003, 674, 56.
´
8 (a) V. Cadierno, J. D´ıez, J. Garc´ıa-Alvarez and J. Gimeno,
Organometallics, 2005, 24, 2801; (b) V. Cadierno, J. Garc´ıa-Alvarez,
´
J. Gimeno and J. Rubio-Garc´ıa, J. Organomet. Chem., 2005, 690, 5856.
9 (a) N. D. Jones, G. Lin, R. A. Gossage, R. McDonald and R. G. Cavell,
Organometallics, 2003, 22, 2832; (b) G. Lin, N. D. Jones, R. A. Gossage,
R. McDonald and R. G. Cavell, Angew. Chem., Int. Ed., 2003, 42,
4054.
23 See, for example: (a) E. Bo¨hm, K. Dehnicke, J. Beck, W. Hiller, J. Stra¨hle,
A. Maurer and D. Fenske, Z. Naturforsch., 1988, 43b, 138; (b) A. L.
Llamas-Saiz, C. Foces-Foces, J. Elguero, P. Molina, M. Alajar´ın and A.
Vidal, J. Chem. Soc., Perkin Trans. 2, 1991, 1667; (c) A. L. Llamas-Saiz,
C. Foces-Foces, J. Elguero, P. Molina, M. Alajar´ın and A. Vidal, Acta
Crystallogr., Sect. C: Cryst. Struct. Commun., 1992, 48, 1940; (d) C.
Lo´pez-Leonardo, M. Alajar´ın, P. Llamas-Lorente, D. Bautista, M. L.
Jimeno, I. Alkorta and J. Elguero, Struct. Chem., 2003, 14, 391.
24 (a) C. Larre´, B. Donnadieu, A. M. Caminade and J. P. Majoral, Chem.–
Eur. J., 1998, 4, 2031; (b) O. Rossell, M. Seco, A. M. Caminade and J. P.
Majoral, Gold Bull., 2001, 34, 88; (c) C. O. Turrin, B. Donnadieu, A. M.
Caminade and J. P. Majoral, Z. Anorg. Allg. Chem., 2005, 631, 2881;
(d) A. Maraval, G. Magro, V. Maraval, L. Vendier, A. M. Caminade
and J. P. Majoral, J. Organomet. Chem., 2006, 691, 1333.
10 (a) W.-P. Leung, Z.-X. Wang, H.-W. Li and T. C. W. Mak, Angew.
Chem., Int. Ed., 2001, 40, 2501; (b) W.-P. Leung, C.-W. So, Z.-X.
Wang, J.-Z. Wang and T. C. W. Mak, Organometallics, 2003, 22, 4305;
(c) W.-P. Leung, C.-W. So, K.-W. Kan, H.-S. Chan and T. C. W. Mak,
Organometallics, 2005, 24, 5033; (d) W.-P. Leung, C.-W. So, K.-W. Kan,
H.-S. Chan and T. C. W. Mak, Inorg. Chem., 2005, 44, 7286; (e) W.-
P. Leung, K.-W. Kan, C.-W. So and T. C. W. Mak, Appl. Organomet.
Chem., 2007, 21, 814; (f) W.-P. Leung, K.-W. Kan, C.-W. So and T. C. W.
Mak, Organometallics, 2007, 26, 3802.
´
11 V. Cadierno, J. D´ıez, J. Garc´ıa-Alvarez and J. Gimeno, Organometallics,
2008, 27, 1809.
25 See, for example: (a) M. L. Clarke, G. L. Holliday, A. M. Z. Slawin
and J. D. Woollins, Inorg. Chem. Commun., 2001, 4, 115; (b) D. K.
Dutta, J. D. Woollins, A. M. Z. Slawin, D. Konwar, M. Sharma, P.
Bhattacharyya and S. M. Aucott, J. Organomet. Chem., 2006, 691,
1229.
12 Only one related work dealing with the coordination chemistry of
this type of mixed methanide anions exists (platinum complexes)
(a) M. W. Avis, M. Gossen, C. J. Elsevier, N. Veldman, H. Kooi-
jman and A. L. Spek, Inorg. Chim. Acta, 1997, 264, 43; (b) The
synthesis and X-ray structural characterization of the dilithium salt
26 Similar trends have been already observed in the S-coordination of
=
[Li2C{Ph2P( S)}{Ph2P(=NSiMe3)}] has been recently described: J.-
=
=
related -Ph2P N–P( S)(OR)2 units to Ru(II), Ru(IV), Au(I), Ag(I) and
Cu(I) metal fragments. See references 6b,13c,d,h and 24.
27 As expected, two enantiomers are present in the unit cell of this
compound displaying RRu SC/SRu RCconfigurations. Only the RRu SC
enantiomer is represented in Fig. 8.
H. Chen, J. Guo, Y. Li and C.-W. So, Organometallics, 2009, 28, 4617.
13 (a) V. Cadierno, J. D´ıez, S. E. Garc´ıa-Garrido, S. Garc´ıa-Granda and J.
Gimeno, J. Chem. Soc., Dalton Trans., 2002, 1465; (b) V. Cadierno, P.
´
Crochet, J. D´ıez, J. Garc´ıa-Alvarez, S. E. Garc´ıa-Garrido, J. Gimeno,
S. Garc´ıa-Granda and M. A. Rodr´ıguez, Inorg. Chem., 2003, 42, 3293;
28 A dark brown color has been described for the five-coordinate ruthe-
´
(c) V. Cadierno, P. Crochet, J. D´ıez, J. Garc´ıa-Alvarez, S. E. Garc´ıa-
3
=
nium(II) carbene [Ru(k (C,S,S)-C{Ph2P( S)}2)(PPh3)2]: T. Cantat,
Garrido, S. Garc´ıa-Granda, J. Gimeno and M. A. Rodr´ıguez, Dalton
M. Demange, N. Me´zailles, L. Ricard, Y. Jean and P. Le Floch,
Organometallics, 2005, 24, 4838.
´
Trans., 2003, 3240; (d) V. Cadierno, J. D´ıez, J. Garc´ıa-Alvarez and J.
Gimeno, Organometallics, 2004, 23, 3425; (e) V. Cadierno, J. D´ıez, J.
29 See, for example: (a) B. Strecker, G. Ho¨rlin, M. Schulz and H. Werner,
Chem. Ber., 1991, 124, 285; (b) P. M. Treichel, D. W. Firsich and T. H.
Lemmen, J. Organomet. Chem., 1980, 202, C77; (c) R. Fandos, M.
Lanfranchi, A. Otero, M. A. Pellinghelli, M. J. Ruiz and J. H. Teuben,
Organometallics, 1997, 16, 5283; (d) H. Werner, B. Strecker, G. Ho¨rlin
and W. D. Jones, J. Organomet. Chem., 1998, 562, 45; (e) L. Busetto, F.
Marchetti, S. Zacchini and V. Zanotti, Organometallics, 2008, 27, 5058.
See also reference 8b.
30 See, for example: V. Cadierno, P. Crochet, J. D´ıez, S. E. Garc´ıa-Garrido
and J. Gimeno, Organometallics, 2004, 23, 4836 and references cited
therein.
31 See for example: (a) F. H. Allen, O. Kennard, D. G. Watson,
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14 We
note
that
the
coordination
chemistry
of
the
-
=
bis(selenophosphoranyl)methanide anion [CH{Ph2P( Se)}2] has
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©