Organoruthenium complexes containing new phosphorus-carbon and phosphorus-carbon-sulfur ligands generated in the coordination sphere by nucleophilic addition reactions

Article abstract of DOI:10.1021/om400487g

The reaction of the dimeric complex [RuCl(μ-Cl)(η⁶-C ₁₀H₁₄)]₂ (C₁₀H₁₄ = p-cymene) with an excess of allyldiisopropylphosphane (ADIP) leads to the complex [RuCl(η⁶-C₁₀H₁₄) {κ²(P,C)-iPr₂PCH₂CH(iPr ₂PCH₂CH=CH₂)CH₂}]⁺ (1⁺), which presents a new bidentate κ²(P,C) ligand. The same cationic complex can be prepared by nuclephilic attack of 1 equiv of the free ADIP at the coordinated κ³(P,C,C)-iPr ₂PCH₂CH=CH₂ ligand in [RuCl(η⁶- C₁₀H₁₄){κ³(P,C,C)-iPr₂PCH ₂CH=CH₂}]⁺ (3⁺). Addition of different phosphane ligands to complex 3⁺ allows to the synthesis of ruthenium complexes with new bidentate ligands κ²(P,C). The unusual complexes [Ru{κ³(P,C,S)-iPr₂PCH ₂CH(SR)CH₂}(η⁶-C₁₀H ₁₄)]⁺ (11a-c⁺) containing new κ³(P,C,S) ligands can be obtained by the reaction of 3 ⁺ with anionic nucleophiles RS^-. For comparative purposes, the indenyl complex [Ru(η⁵-C₉H₇) {κ³(P,C,C)-iPr₂PCH₂CH=CH ₂}(PPh₃)]⁺ (8⁺) has been also prepared and differences in the reactivities of cationic complexes 3⁺ and 8⁺ toward nucleophiles are pointed out.

Full text of DOI:10.1021/om400487g

Article
pubs.acs.org/Organometallics
Organoruthenium Complexes Containing New Phosphorus−Carbon
and Phosphorus−Carbon−Sulfur Ligands Generated in the
Coordination Sphere by Nucleophilic Addition Reactions
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Isaac Garcıa de la Arada, Josefina Dıez, M. Pilar Gamasa, and Elena Lastra*
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Departamento de Quımica Organica e Inorganica, Instituto de Quımica Organometalica “Enrique Moles” (Unidad Asociada al
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CSIC), Universidad de Oviedo, 33006 Oviedo, Principado de Asturias, Spain
S
* Supporting Information
ABSTRACT: The reaction of the dimeric complex [RuCl(μ-Cl)(η6-C10H14)]2 (C10H14 = p-cymene) with an excess of
allyldiisopropylphosphane (ADIP) leads to the complex [RuCl(η6-C10H14){κ2(P,C)-iPr2PCH2CH(iPr2PCH2CHCH2)CH2}]+
(1+), which presents a new bidentate κ2(P,C) ligand. The same cationic complex can be prepared by nuclephilic attack of 1 equiv
of the free ADIP at the coordinated κ3(P,C,C)-iPr2PCH2CHCH2 ligand in [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CH
CH2}]+ (3+). Addition of different phosphane ligands to complex 3+ allows to the synthesis of ruthenium complexes with new
bidentate ligands κ2(P,C). The unusual complexes [Ru{κ3(P,C,S)-iPr2PCH2CH(SR)CH2}(η6-C10H14)]+ (11a−c+) containing
new κ3(P,C,S) ligands can be obtained by the reaction of 3+ with anionic nucleophiles RS−. For comparative purposes, the
indenyl complex [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}(PPh3)]+ (8+) has been also prepared and differences in the
reactivities of cationic complexes 3+ and 8+ toward nucleophiles are pointed out.
addition reactions,6 oxidative coupling reactions,7 and stereo-
INTRODUCTION
■
selective nucleophilic additions to afford ruthenaphosphacyclo-
Functionalized phosphanes bearing a multiple carbon−carbon
bond display a versatile behavior as ligands in coordination
chemistry1 and have been reasonably well explored to date.
One key feature of these hybrid phosphane−olefin ligands is
their hemilability, since they are able to easily dissociate the C−
C double bond and to allow interaction between the metal
center and organic substrates. Indeed, metal-coordinated
alkenylphosphanes act as dienophiles in Diels−Alder reactions2
and can be involved in [2 + 2] cycloaddition reactions3 and
nucleophilic addition reactions onto the C−C double bond.4
In the last few years, our interest has been focused on the
chemistry of half-sandwich ruthenium complexes bearing
alkenylphosphanes. Thus, we have previously described the
synthesis and characterization of a series of ruthenium(II)
complexes [Ru(η5-CnHm){κ3(P,C,C)-Ph2PCH2CHCH2}-
(PPh3)]+ (CnHm = C9H7, C5H5), which feature a κ3(P,C,C)
coordination mode of the allyldiphenylphosphane as well as a
diastereofacial coordination of the olefin at the ruthenium
center. The hemilabile character of alkenylphosphane ligands in
ruthenium complexes has been corroborated by kinetic
studies.5 In addition, we have approached the study of their
reactivity, particularly as substrates in intramolecular cyclo-
pentane complexes.5b
Continuing with these studies, we report here the synthesis
of new half-sandwich arene complexes of ruthenium(II)
containing the allyldiisopropylphosphane (ADIP) ligand as
well as the nucleophilic addition of neutral P-donor
nucleophiles to the κ3(P,C,C) complexes, which lead to the
formation of new complexes bearing κ2(P,C) ligands. To our
knowledge, these are the first examples of nucleophilic attack of
a free phosphane at the allylic group of a coordinated
alkenylphosphane. In addition, nucleophilic attack of NaSR at
the κ3(P,C,C) complexes leads to the formation of
unprecedented complexes with κ3(P,C,S)-coordinated ligands.
Comparative studies using the indenyl complex [Ru(η5-
C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}(PPh3)]+ (8+) have also
been performed, and relevant differences in the reactivity
toward nucleophiles have been found.
Received: May 29, 2013
Published: July 12, 2013
© 2013 American Chemical Society
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RESULTS AND DISCUSSION
■
Synthesis of [RuCl(η6-C10H14){κ2(P,C)-iPr2PCH2CH-
(iPr2PCH2CHCH2)CH2}][Cl] (1-Cl). The reaction of the
dimeric complex [RuCl(μ-Cl)(η6-C10H14)]2 with an excess of
allyldiisopropylphosphane (ADIP) in methanol, at low temper-
ature, leads diastereoselectively to the compound [RuCl(η6-
C10H14){κ2(P,C)-iPr2PCH2CH(iPr2PCH2CHCH2)CH2}]-
[Cl] (1-Cl) (Scheme 1). The complex 1a+ presents a new
tridentate ligand showing a bidentate κ2(P,C) coordination
mode.
Scheme 1. Synthesis of [RuCl(η6-C10H14){κ2(P,C)-
iPr2PCH2CH(iPr2PCH2CHCH2)CH2}]+ (1+)
Compound 1-Cl is an air-stable yellow solid which has been
characterized by analytical and spectroscopic methods. The
diastereoselectivity of this reaction is readily assessed by the
31P{1H} NMR spectrum, which shows two doublets in accord
with the two different phosphorus atoms in the molecule. Thus,
the phosphorus atom bonded to ruthenium appears at 86.6
ppm and the phosphorus atom bonded to carbon appears at
36.5 ppm (3JPP = 63.2 Hz). Other significant spectroscopic
features are as follows. (i) The IR spectrum exhibits an
absorption corresponding to the CC double bond at 1635
the p-cymene group and the κ2(P,C)-iPr2PCH2CH-
(iPr2PCH2CHCH2)CH2 ligand. Hydrogen atoms of the
olefin of the allylphosphane appear as two doublets at 5.38 and
5.61 ppm (CH2) and a multiplet at 5.81 ppm (CH). (iii) The
signals for the RuCH2 protons were unambiguously assigned
through HSQC experiments as two multiplets at 2.24 and 3.18
ppm. These chemical shifts agree with those previously
reported for the complexes [Ru(η5-C9H7){κ2(P,C)-
Ph2PCH2CH(R)CH2}(PPh3)]5b and [Ru(η5-C9H7){κ2(P,C)-
Ph2PCH2CHCHCH2}(L)].18 (iv) 13C{1H} NMR spectrum
shows the CH2 bonded to ruthenium as a broad singlet at 18.2
ppm.The structure of 1-Cl was determined by single-crystal X-
ray diffraction analysis (Figure 1).
The most remarkable feature is the presence of the
ruthenaphosphacycle with one allyldiisopropylphosphonium
substituent. The bond distance C(12)−P(2) (1.834(2) Å) is
typical of a phosphorus−carbon single bond, and the bond
distance C(21)−C(22) (1.312(3) Å) and the bond angle
C(22)−C(21)−C(20) (122.48(19)°) agree with the presence
of the olefin group in the side chain. All of the carbon atoms in
the ruthenaphosphacycle present a sp3 hybridization, as shown
by the bond angles around the carbon atoms C(11), C(12),
and C(13) in the range 103−115°.
Figure 1 shows the complex with absolute configuration R for
the ruthenium and S for the stereogenic carbon C(12).
However, both enantiomers (RRuSC and SRuRC) are present in
the crystal in equal proportion, as the crystal belongs to the
centric space group P21/n.
Figure 1. Molecular structure and atom-labeling scheme for the
cationic complex [RuCl(η6-C10H14){κ2(P,C)-iPr2PCH2CH-
(iPr2PCH2CHCH2)CH2}]+ (1+). Hydrogen atoms of arene and
isopropyl groups (except for the ruthenaphosphacycle and the allyl
group) have been omitted for clarity. Non-hydrogen atoms are
represented by their 10% probability ellipsoids. C* = centroid of the
η6-p-cymene ligand. Selected bond lengths (Å): Ru(1)−Cl(1) =
2.435(1), Ru(1)−P(4) = 2.323(1), Ru(1)−C(11) = 2.142(2), Ru(1)-
C* = 1.735(1), C(11)−C(12) = 1.538(2), C(12)−C(13) = 1.526(2),
C(13)−P(4) = 1.846(2), C(12)−P(2) = 1.834(2), P(2)−C(20) =
1.816(2), C(20)−C(21) = 1.498(3), C(21)−C(22) = 1.312(3).
Selected bond angles (deg): C(11)−Ru(1)−Cl(1) = 85.59(6),
C(11)−Ru(1)−P(4) = 82.37(5), P(4)−Ru(1)−Cl(1) = 87.18(2),
C*−Ru(1)−C(11) = 124.60(5), C*−Ru(1)−Cl(1) = 125.18(1), C*−
Ru(1)−P(4) = 135.77(1), C(13)−C(12)−C(11) = 111.62(14),
C(13)−C(12)−P(2) = 111.14(12), C(11)−C(12)−P(2) =
113.14(12), C(22)−C(21)−C(20) = 122.48(19).
1
cm−1. (ii) The H NMR spectrum agrees with the presence of
The formation of complex 1+ can be explained through the
nucleophilic addition of 1 equiv of the allylphosphane to the
coordinated ADIP ligand. In order to prove this hypothesis,
although to our knowledge no nucleophilic attacks of neutral
phosphanes at coordinated κ3(P,C,C)-R2PCH2CHCH2
ligands have been described to date, the synthesis of the
potential intermediate complex [RuCl(η6-C10H14){κ3(P,C,C)-
iPr2PCH2CHCH2}]+ was achieved.
Synthesis of [RuCl2(η6-C10H14){κ1(P)-iPr2PCH2CH
CH2}] (2) and [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CH
CH2}][BPh4] (3-BPh4). When the reaction of the complex
[RuCl(μ-Cl)(η6-C10H14)]2 with a stoichiometric amount of
ADIP was performed in dichloromethane, the complex
[RuCl2(η6-C10H14){κ1(P)-iPr2PCH2CHCH2}] (2) was iso-
lated. Treatment with NaBPh4 of a methanol suspension of
complex 2 led to the cationic complex [RuCl(η6-C10H14)-
{κ3(P,C,C)-iPr2PCH2CHCH2}]+ (3+), which was isolated as
its BPh4 salt as an air-stable yellow solid (see Scheme 2). Both
products have been characterized by elemental analysis and
NMR data, which confirm the coordination mode of the
allylphosphane as κ1(P) for complex 2 and κ3(P,C,C) for the
salt 3-BPh4. In particular, the 1H and 13C{1H} NMR spectra of
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Scheme 2. Synthesis of the Complexes [RuCl2(η6-C10H14){κ1(P)-iPr2PCH2CHCH2}] (2) and [RuCl(η6-C10H14){κ3(P,C,C)-
iPr2PCH2CHCH2}]+ (3+)
3-BPh4 show CHCH2 resonances which appear at higher
field than those observed in complex 2 bearing the non-
coordinated olefinic system κ1(P) (see the Experimental
Section). 31P{1H} NMR spectra at room temperature also
reveal the effect of the olefin coordination, showing the signal
for the allylphosphane shifted toward higher field (δ −48.5 ppm
for 3+) with respect to that of the corresponding κ1(P)
precursor (δ 33.6 ppm for 2).
When the ADIP ligand is bound in a bidentate manner, the
two faces of the alkene are diastereotopic.18,19 The 31P{1H}
NMR spectrum of complex 3+ in CD2Cl2 shows one signal (δ
−48.5 ppm for 3+) and remains unchanged within a wide range
of temperature (−60 to +25 °C). These NMR data agree either
with the formation of only one isomer or with an equilibrium in
which there is never a significant concentration (<0.01%) of the
alternative-face isomer. Thus, the generation of the chelate ring
[Ru{κ3(P,C,C)-iPr2PCH2CHCH2}] proceeds in a highly
diastereoselective manner. This result agrees with those
reported by us for the compounds [Ru(η5-C9H7){κ3(P,C,C)-
Ph2PCH2CHCH2}(PPh3)][PF6]5b and [Ru(η5-C5H5)-
{κ3(P,C,C)-Ph2PCH2CHCH2}(PPh3)][PF6]6b and contrast
Figure 2. Molecular structure and atom-labeling scheme for the
with those reported for the analogous compound [Ru(η5-
cationic complex [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CH
CH2}]+ (3+). Hydrogen atoms, except those of the coordinated
C 5 M e 5 ) { κ 1 ( P ) - P h 2 P C H 2 C H  C H 2 } { κ 3 ( P , C , C ) -
Ph2PCH2CHCH2}][PF6],19 for which a rapid fluxional
olefin, have been omitted for clarity. Non-hydrogen atoms are
represented by their 10% probability ellipsoids. C* = centroid of the
equilibrium between the two diastereoisomers on the NMR
η6-p-cymene ligand. Selected bond lengths (Å): Ru(1)−Cl(1) =
time scale is observed.
2.395(1), Ru(1)−P(1) = 2.337(1), Ru(1)−C(11) = 2.261(4), Ru(1)−
In order to find out the coordination of the olefin, the
C(12) = 2.298(4), Ru(1)−C* = 1.747(1), C(11)−C(12) = 1.363(7).
structure of complex 3+ was determined by single-crystal X-ray
diffraction analysis. Suitable crystals were obtained by slow
Selected bond angles (deg): C*−Ru(1)−P(1) = 132.95(4), C*−
Ru(1)−Cl(1) = 124.30(3), C*−Ru(1)−C(11) = 123.78(15), C*−
diffusion of diethyl ether into a solution of 3-BPh4 in CH2Cl2.
Ru(1)−C(12) = 133.79(13), P(1)−Ru(1)−Cl(1) = 85.11(5), C(11)−
An ORTEP type representation of the complex is shown in
Figure 2, and selected bond lengths and angles are presented in
the caption.
C(12)−C(13) = 123.9(5).
Scheme 3. Synthesis of [RuCl(η6-C10H14){κ2(P,C)-
The molecule exhibits a pseudooctahedral three-legged
piano-stool geometry with the ruthenium atom bonded to
the η6-p-cymene ligand, to one chlorine atom, and to the ADIP
ligand, which is bonded through the phosphorus atom and the
η2-coordinated olefin. Bond distances Ru−C(11) (2.261(4) Å)
and Ru−C(12) (2.298(4) Å) indicate the symmetrical bonding
of the olefin to the metal atom. Figure 2 shows the complex
with relative configuration RRu and olefin coordination through
the si enantioface, although both enantiomers are present in
equal proportion in the crystal.
iPr2PCH2CH(iPr2PCH2CHCH2)CH2}][BPh4] (1-BPh4)
In order to prove our initial hypothesis, the reaction of free
ADIP with 3-BPh4 was achieved. From this reaction, we could
isolate the compound [RuCl(η6-C10H14){κ2(P,C)-
iPr2PCH2CH(iPr2PCH2CHCH2)CH2}][BPh4] (1-BPh4),
as expected (Scheme 3). 1-BPh4 shows the same spectroscopic
data as 1-Cl except for those corresponding to the BPh4 anion.
Reaction of [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CH
CH2}]+ (3+) with P-Donor Nucleophiles: Synthesis of
[RuCl(η6-C10H14){κ2(P,C)-iPr2PCH2CH(PR3)CH2}]+ (R = Ph
(4a+), Me (4b+)) and [RuCl(η6-C10H14){κ1(P)-iPr2PCH2CH
CH2}{P(OR)3}]+ (R = Ph (5a+), Me (5b+), Et (5c+)). In order to
generalize the behavior reported above, the reaction of complex
3+ with different P-donor ligands was carried out.
Thus, the reaction of complex 3+ with the phosphanes PPh3
and PMe3 in THF resulted in the isolation of the complexes
[RuCl(η6-C10H14){κ2(P,C)-iPr2PCH2CH(PR3)CH2}]+ (R = Ph
(4a+), Me (4b+)). However, when the same reaction was
carried out using P(OR)3 as nucleophiles, the substitution
complexes [RuCl(η6-C10H14){κ1(P)-iPr2PCH2CHCH2}{P-
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(OR)3}]+ (R = Ph (5a+), Me (5b+), Et (5c+)) were isolated as
the result of an olefin−nucleophile exchange, showing the
competition between the nuclephilic addition to the
allylphosphane ligand and the substitution reaction on the
ruthenium center (Scheme 4).
Scheme 5. Synthesis of the Complexes [RuCl(η6-
C10H14){κ1(P)-iPr2PCH2CHCH2}(L)] (L = NCMe (6+), py
(7+))
Scheme 4. Synthesis of the Complexes [RuCl(η6-
C10H14){κ2(P,C)-iPr2PCH2CH(PR3)CH2}]+ (R = Ph (4a+),
Me (4b+)) and [RuCl(η6-C10H14){κ1(P)-
iPr2PCH2CHCH2}{P(OPh)3}]+ (R = Ph (5a+), Me (5b+), Et
(5c+))
additions at the internal Cβ atom of the coordinated allylic
group.5b For comparative purposes, the synthesis of the indenyl
complex [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}-
(PPh3)]+ (8+) was achieved.
Reaction of the complex [RuCl(η5-C9H7)(PPh3)2] with
ADIP in refluxing THF in the presence of NaBPh4 led to the
synthesis of the complex [Ru(η5-C9H7){κ3(P,C,C)-
iPr2PCH2CHCH2}(PPh3)]+ (8+) (Scheme 6), which was
Scheme 6. Synthesis of the Complexes [Ru(η5-
C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}(PPh3)]+ (8+) and
[Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}{P(OMe)3}]+
(9+)
The complexes 4a,b+ and 5a−c+ were isolated as their
tetraphenylborate salts in good yields as yellow stable solids
which have been fully characterized by analytical and
spectroscopic methods. In particular, 31P{1H} NMR spectra
are indicative of the coordination mode of the allylphosphane.
Thus, for complexes 4a,b+ two doublets appear for the
phosphorus atoms bonded to ruthenium and carbon atoms,
respectively, at δ 80.2 and 24.6 ppm (3JPP = 65.6 Hz) for
complex 4a+ and δ 86.8 and 28.7 ppm (3JPP = 70.5 Hz) for
isolated as its tetraphenylborate salt in 85% yield. Attempts to
obtain the complex [RuCl(η5-C9H7){κ1(P)-iPr2PCH2CH
CH2}(PPh3)] analogous to that reported with ADPP were
unsuccessful.5b
Spectroscopic data agree with the proposed structure (see
the Experimental Section). In particular, the 31P{1H} NMR
spectrum at room temperature showed the expected doublets at
δ 51.7 (PPh3) and −51.6 (κ3(P,C,C)-ADIP) (2JPP = 32.3 Hz).
As reported for complex 3+, the formation of complex 8+ is
an highly diastereoselective process, since NMR data agree with
the formation of only one isomer.
complex 4b+. For complexes 5a−c+ the two doublets (2JPP
=
71.7 −75.3 Hz) appear at δ 45.9 (5a+), 44.3 (5b+), and 43.4
(5c+) for the κ1(P)-allylphosphane and 112.3 (5a+), 117.4
(5b+) and 112.1 (5c+) for the P(OR)3 ligand (see the
Experimental Section). For all compounds, molar conductivity
values in acetone are in the range expected for 1/1
electrolytes20 and the analyses and electrospray mass spectra
agree with the proposed stoichiometries.
Reaction of [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CH
CH2}]+ (3+) with N-Donor Nucleophiles: Synthesis of
[RuCl(η6-C10H14){κ1(P)-iPr2PCH2CHCH2}(L)]+ (L = NCMe
(6+), py (7+)). When the complex [RuCl(η6-C10H14)-
{κ3(P,C,C)-iPr2PCH2CHCH2}]+ (3+) was dissolved in
acetonitrile, the complex [RuCl(η6-C10H14){κ1(P)-
iPr2PCH2CHCH2}(NCMe)]+ (6+) was immediately formed.
In the same way, the reaction of 3+ in THF with 1 equiv of
pyridine led to the complex [RuCl(η6-C10H14){κ1(P)-
iPr2PCH2CHCH2}(py)]+ (7+) (Scheme 5). The synthesis
of these complexes agrees with the hemilabile character of the
ADIP ligand in complex 3+.
The structure of complex 8+ was determined by single-crystal
X-ray diffraction analysis. Suitable crystals were obtained by
slow diffusion of diethyl ether into a solution of compound 8-
BPh4 in CH2Cl2. An ORTEP representation is shown in Figure
3, and selected bonding data are collected in the caption.
The molecule exhibits a pseudooctahedral three-legged
piano-stool geometry, with the η5-indenyl ligand displaying
the usual allylene coordination mode. The interligand angles
P(1)−Ru(1)−P(2) and those between the five-membered-ring
centroid C* and the legs show values typical of a
pseudooctahedron (see the caption to Figure 3). The Ru−
C(1) and Ru−C(2) bond distances reflect the coordination of
the olefin to the metal center and the C(1)−C(2) bond
distance, 1.388(3) Å, is similar to those in complex 3+
(1.363(7) Å) and the complex [Ru(η5-C9H7){κ3(P,C,C)-
Ph2PCH2CHCH2}(PPh3)][PF6] (1.391(8) Å).5b It is also
interesting to note that the benzo ring of the indenyl ligand is
oriented over the olefin ligand, slightly displaced toward the
PPh3 ligand. Figure 3 shows the complex with relative
configuration RRu and olefin coordination through the si
enantioface. However, both enantiomers are present in equal
Synthesis of [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}-
(PPh3)][BPh4] (8-BPh4) and Reaction of 8+ with P- and N-
Donor Nucleophiles To Give [Ru(η5-C9H7){κ3(P,C,C)-
iPr2PCH2CHCH2}{P(OPh)3}][BPh4] (9-BPh4). We have
previously described the indenyl complexes [Ru(η5-C9H7)-
{κ3(P,C,C)-Ph2PCH2CHCH2}(PPh3)]+ bearing the allyldi-
phenylphosphane ligand (ADPP) and their reactivity toward
anionic nucleophiles (H−, Me−, nBu−), giving rise to
ruthenaphosphacyclopentane complexes through regioselective
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iPr2PCH2CH(SR)CH2}(η6-C10H14)]+ (11a−c+) were isolated
as their BPh4 salts (Scheme 7).
Scheme 7. Synthesis of the Complexes [Ru{κ3(P,C,S)-
iPr2PCH2CH(SR)CH2}(η6-C10H14)]+ (R = Me (11a+), iPr
(11b+), tBu (11c+))
Complexes 11a−c+ were spectroscopically characterized.21
The most significant spectroscopic features are as follows. (i)
The 31P{1H} NMR spectra exhibit a singlet at δ 75.7 (11a+),
76.0 (11b+), and 74.6 (11c+) ppm. (ii) For all complexes, the
Figure 3. Molecular structure and atom-labeling scheme for the
cationic complex [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}-
(PPh3)]+ (8+). Phenyl rings, except Cipso, and hydrogen atoms, except
those of the coordinated olefin, have been omitted for clarity. Non-
hydrogen atoms are represented by their 20% probability ellipsoids.
C* = centroid of the η5-indenyl ligand. Selected bond lengths (Å):
Ru(1)−P(1) = 2.3295(7), Ru(1)−P(2) = 2.3396(9), Ru(1)−C(1) =
2.213(2), Ru(1)−C(2) = 2.222(2), Ru(1)-C* = 1.9155(6), C(1)−
C(2) = 1.388(3). Selected bond angles (deg): C*−Ru(1)−P(1) =
125.33(2), C*−Ru(1)−P(2) = 120.67(2), C*−Ru(1)−C(1) =
123.86(7), C*−Ru(1)−C(2) = 120.42(7), P(1)−Ru(1)−P(2) =
98.89(3), C(1)−C(2)−C(3) = 121.8(2).
1
RSCH proton appears in the H NMR spectra as a broad
doublet centered at 4.89 ppm (3JHP = 41.7 Hz) for 11a+, 4.81
ppm (3JHP = 43.2 Hz) for 11b, and 4.84 ppm (3JHP = 46.8 Hz)
for 11c+. These unusually large coupling constants22 can be
explained, since three routes are available for coupling between
this proton and phosphorus atom in compounds 11a−c+. An
1H{31P} NMR experiment allowed us to confirm this statement
for complex 11a+, since the two peaks of the doublet at 4.83
and 4.93 ppm collapse into one broad singlet at 4.89 ppm for
1
that hydrogen. (iii) All other signals in the H NMR spectra
agree with the proposed structures (see the Experimental
Section). (iv) 13C{1H} NMR spectra show the CH2 bonded to
ruthenium as a doublet at 3.0 ppm (3JCP = 7.9 Hz) for 11a, 5.2
ppm (3JCP = 9.6 Hz) for 11b+, and 5.7 ppm (3JCP = 11.6 Hz) for
11c+.
proportion in the crystal, which belongs to a centrosymmetric
space group.
Reaction of complex 8+ with neutral P-donor nucleophiles
was tested. Thus, the reaction of 8+ with P(OMe)3 led to the
PPh3 substitution product [Ru(η5-C9H7){κ3(P,C,C)-
iPr2PCH2CHCH2}{P(OMe)3}]+ (9+), which has been fully
characterized (see the Experimental Section). No reaction was
observed when PPh3 was used.
The structure of complex 11a+ was determined by single-
crystal X-ray diffraction analysis. For this complex, the
asymmetric unit consists of two rotamers which present
absolute configuration S for the ruthenium and R for the
stereogenic carbon. However, for each rotamer both
enantiomers (SRuRC and RRuSC) are present in the crystal in
equal proportion, as the crystal belongs to the centric space
The differences in reactivity between complexes 3+ and 8+
are also stated in the reactivity toward N-donor ligands. Thus,
while complex 3+ reacted with pyridine, leading to complex 7+,
complex 8+ did not react with pyridine under the same reaction
conditions. On the other hand, the complex [Ru(η5-C9H7)-
{κ1(P)-iPr2PCH2CHCH2}(PPh3)(NCMe)]+ (10+) was inmedi-
ately formed when complex 8+ was dissolved in NCMe.
However, all attempts to isolate the salt 10-BPh4 failed and
complex 8-BPh4 was recovered unchanged. Complex 10+ has
been spectroscopically characterized in NCMe-d3 solution (see
the Experimental Section).
The differences observed in the behaviors of the two metal
fragments can be explained by electronic effect, since the
arene−chloride−ruthenium fragment is electronically poorer
than the indenyl−phosphane−ruthenium fragment, thus
making the olefin more susceptible to nucleophilic attack.
Reaction of [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CH
CH2}]+ (3+) with Anionic S-Donor Nucleophiles: Syn-
thesis of [Ru{κ3(P,C,S)-iPr2PCH2CH(SR)CH2}(η6-C10H14)]+ (R
= Me (11a+), iPr (11b+), tBu (11c+)) and [Ru{κ2(P,C)-
iPr2PCH2CH(SPhCH3)CH2}(η6-C10H14)] (12). In order to
determine the behavior of complex 3+ with different donors,
the reaction with the sulfur-donor salts NaSR were achieved.
From this reaction, unexpected cationic complexes containing
unprecedented tridentate κ3(P,C,S) ligands: [Ru{κ3(P,C,S)-
group P1. Figure 4 shows an ORTEP type representation of the
̅
two rotamers of the complex, and selected bond lengths and
angles for one of the two rotamers are presented in the caption.
As shown in Figure 4, both molecules are rotamers, the
major difference being the orientation of the iPr group of the p-
cymene ring with respect to the ruthenabicycle ligand.
The Ru(1)−C(11) and Ru(2)−C(31) bond distances
(2.147(4) and 2.162(4) Å, respectively) as well as the
Ru(1)−S(1) and Ru(2)−S(2) distances (2.3701(11) and
2.3807(12) Å, respectively) agree with Ru−C and Ru−S single
bonds. Also, the bond distances C(12)−S(1) (1.845(4) Å) and
C(32)−S(2) (1.851(5) Å) are typical of a sulfur−carbon single
bond (1.808(4) Å for C(14)−S(1) and 1.818(5) Å for C(34)−
S(2)).
The formation of complexes 11a−c+ can be formally
explained through nucleophilic attack of the thiolate anion at
both the olefin of the ADIP ligand and the ruthenium atom.
However, when this reaction was carried out using
NaSC6H4Me as a nucleophile, the neutral complex [RuCl-
{κ2(P,C)-iPr2PCH2CH(SC6H4Me)CH2}(η6-C10H14)] (12) was
obtained (Scheme 8).
Complex 12 has been spectroscopically21 characterized.
Thus, the 31P{1H} NMR spectrum exhibits a singlet at δ 70.2
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Figure 4. Molecular structure and atom-labeling scheme for the cation of the two rotamers found in the asymmetric unit for the compound
[Ru{κ3(P,C,S)-iPr2PCH2CH(SCH3)CH2}(η6-C10H14)][BPh4] (11a-BPh4). Hydrogen atoms of arene and isopropyl groups (except for the
ruthenaphosphacycle) have been omitted for clarity. Non-hydrogen atoms are represented by their 10% probability ellipsoids. C* = centroid of the
η6-p-cymene ligand. Selected bond lengths (Å): Ru(1)−S(1) = 2.3701(11), Ru(1)−P(1) = 2.3260(11), Ru(1)−C(11) = 2.147(4), Ru(1)−C* =
1.7363(6), S(1)−C(12) = 1.845(4), S(1)−C(14) = 1.808(4). Selected bond angles (deg): C*−Ru(1)−P(1) = 136.34(3), C*−Ru(1)−S(1) =
136.03(3), C*−Ru(1)−C(11) = 130.75(11), P(1)−Ru(1)−S(1) = 81.34(4), Ru(1)−S(1)−C(12) = 81.68(13), Ru(1)−S(1)−C(14) = 108.12(15),
C(12)−S(1)−C(14) = 100.5(2), C(11)−C(12)−C(13) = 109.5(3).
Complexes 13a−c were spectroscopically characterized.21 In
particular, the 31P{1H} NMR spectra exhibit doublet signals in
the range 75.2−77.3 ppm for the ADIP phosphane and 60.1−
60.8 ppm for the PPh3 ligand. All other signals in the 1H NMR
and 13C{1H} spectra agree with the proposed structures (see
the Experimental Section).
Scheme 8. Synthesis of the Complex [RuCl{κ2(P,C)-
iPr2PCH2CH(SC6H4Me)CH2}(η6-C10H14)] (12)
All attempts to promote the intramolecular nucleophilic
attack of the sulfur atom at the ruthenium center leading to
complexes analogous to complexes 11a−c+ failed. Thus,
heating THF solutions of complexes 13a−c gives the precursor
complex [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}-
(PPh3)]+.
1
ppm and the H NMR and 13C{1H} NMR spectra agree with
the proposed structure (see the Experimental Section). In this
complex the electron pair of the sulfur can be delocalized into
the aromatic ring, which makes the sulfur a poorer nucleophile.
In addition, probably the steric hindrance of the p-tolyl group
prevents sulfur coordination to the metal.
SUMMARY
■
In summary, nucleophilic attack at the coordinated ADIP ligand
in the complex [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CH
CH2}] (3+) allows the synthesis of complexes with bidentate
κ2(P,C) or unprecedented tridentate κ3(P,C,S) ligands. This
nucleophilic addition to the κ3(P,C,C)-alkenylphosphane ligand
is competitive with the coordination of the nucleophile to the
ruthenium and substitution of the coordinated π-olefin group as
occurs for the P(OR)3 ligands. The indenyl complex [Ru(η5-
C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}(PPh3)]+ (8+) has been
synthesized for comparative purposes, showing great differences
in its reactivity pattern toward nucleophiles.
Reaction of [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}-
(PPh3)]+ (8+) with Anionic S-Donor Nucleophiles: Syn-
thesis of [Ru(η5-C9H7){κ2(P,C)-iPr2PCH2CH(SR)CH2}(PPh3)]
(R = Me (13a), iPr (13b), tBu (13c)). The complex [Ru(η5-
C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}(PPh3)]+ (8+) reacts
with S-donor anionic nucleophiles to yield the κ2(P,C)
complexes [Ru(η5-C9H7){κ2(P,C)-iPr2PCH2CH(SR)CH2}-
(PPh3)] (R = Me (13a), iPr (13b), tBu (13c)) (Scheme 9).
Scheme 9. Synthesis of the Complexes [Ru(η5-
C9H7){κ2(P,C)-iPr2PCH2CH(SR)CH2}(PPh3)] (R = Me
(13a), iPr (13b), tBu (13c))
EXPERIMENTAL SECTION
■
General Procedures. All manipulations were perfomed under an
atmosphere of dry nitrogen using vacuum-line and standard Schlenk
techniques. All reagents were obtained from commercial suppliers and
used without further purification. Solvents were dried by standard
methods and distilled under nitrogen before use. The complexes
8
[RuCl(μ-Cl)(η6-C10H14)]2 and [RuCl(η5-C9H7)(PPh3)2]9 and the
phosphane iPr2P(C3H5)10 were prepared by previously reported
procedures. Infrared spectra were recorded on a Perkin-Elmer 1720-
XFT spectrometer. The C, H, and N analyses were carried out with
Perkin-Elmer 240-B and LECO CHNS-TruSpec microanalyzers. Mass
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spectra (ESI) were determined with a Bruker Esquire 6000
spectrometer, operating in positive mode and using dichloromethane
and methanol solutions. NMR spectra were recorded on a Bruker
AV400 spectrometer operating at 400.1 (1H), 100.6 (13C), and 162.1
MHz (31P), an AV300 spectrometer operating at 300.1 (1H), 75.5
(13C), and 121.5 MHz (31P), and an AV600 spectrometer operating at
600.1 (1H) and 150.9 MHz (13C). DEPT and bidimensional COSY
HH, HSQC, and HMBC experiments were carried out for all of the
compounds. Chemical shifts are reported in parts per million and
referenced to TMS or 85% H3PO4 as standard. Coupling constants J
are given in hertz. Abbreviations used: s, singlet; d, doublet; dd, double
doublet; t, triplet; sept, septuplet; c, cuatriplet; m, multiplet; bd, broad
doublet; br, broad.
evaporated, and the yellow solid was washed with diethyl ether and
dried under reduced pressure. Yield: 83%. 31P{1H} NMR (121.5 MHz,
CDCl3, 20 °C): δ −48.5 (s). 1H NMR (400.1 MHz, CDCl3, 20 °C): δ
1.13 − 1.30 (m, 12H, Me2CH-P), 1.31−1.43 (m, 6H, CHMe2), 1.54 (s,
3H, Me), 2.23 (m, 1H, PCH2), 2.40 (m, 3H, Me2CH-P, CHMe2), 3.10
3
(m, 1H, PCH2), 3.58 (m, 1H, =CH), 3.95 (d, JHH = 13.6 Hz, 1H,
2
3
=CH2), 4.34 (dd, JHH = 4.4 Hz, JHH = 8.0, 1H, =CH2), 5.12, 5.40,
5.49, 5.68 (4d, 3JHH = 6.0 Hz, 4 × 1H, p-cym), 6.92 (t, 3JHH = 7.2 Hz,
3
4H, BPh4), 7.05 (t, JHH = 7.2 Hz, 8H, BPh4), 7.42 (s, br, 8H, BPh4).
13C{1H} NMR (100.6 MHz, CDCl3, 20 °C): δ 17.6 (s, Me), 18.3,
18.7, 19.1, 19.5 (4s, Me2CH-P), 21.6−22.3 (m, CHMe2, Me2CH−P),
1
1
25.5 (d, JCP = 31.4 Hz, PCH2), 28.0 (d, JCP = 22.1 Hz, Me2CH−P),
30.8 (s, CHMe2), 65.5 (d, 2JCP = 18.9 Hz, =CH), 72.0 (s, =CH2), 89.6,
90.9, 92.2, 95.3, 101.7, 115.3 (6s, p-cym), 122.0, 125.7, 136.3 (3s,
Synthesis of [RuCl(η6-C10H14){κ2(P,C)-iPr2PCH2CH-
(iPr2PCH2CHCH2)CH2}][Cl] (1-Cl). To a solution of the complex
[RuCl(μ-Cl)(η6-C10H14)]2 (0.1 g, 0.16 mmol) in methanol (10 mL)
was added 5 equiv of diisopropylallylphosphane (122 μL, 0.8 mmol).
The resulting suspension was stirred for 5 min at −20 °C. The
solution was then evaporated and the yellow residue was washed with
11B
BPh4), 164.6 (c, JC = 48.3 Hz, BPh4). Conductivity (acetone, 20
°C): Λ = 134 S cm2 mol−1. IR (KBr, cm−1): ν(CC) 1477 (m),
ν(BPh4) 737, 707 (s). Anal. Calcd for C49H49BClPRu: C, 69.03; H,
7.14. Found: C, 69.15; H, 7.27.
Synthesis of [RuCl(η6-C10H14){κ2(P,C)-iPr2PCH2CH-
(iPr2PCH2CHCH2)CH2}][BPh4] (1-BPh4). To a solution of [RuCl-
(η6-C10H14){κ3(P,C,C)-iPr2PCH2CHCH2}][BPh4] (3-BPh4; 0.0374
g, 0.05 mmol) in THF (8 mL) was added ADIP (0.05 mmol, 8 μL),
and the mixture was stirred at room temperature for 2 min. The
solution was then concentrated under vacuum to a volume of
approximately 1 mL. Addition of hexane (20 mL) afforded a yellow
precipitate. Solvents were decanted, and the solid was washed with
hexane (2 × 10 mL) and dried under reduced pressure. Spectroscopic
data for complex 1-BPh4 are the same as for complex 1-Cl except for
those signals due to the BPh4 anion. Yield: 63%. IR (KBr, cm−1):
ν(CC) 1580 (w), ν(BPh4) 733, 705 (s). MS-ESI (m/z): 587 ([M]+,
100%), 429 ([M − ADIP]+, 15%). Anal. Calcd for C52H72BClP2Ru: C,
68.90; H, 8.01. Found: C, 69.01; H, 8.02.
diethyl ether (3 × 20 mL) and dried under reduced pressure. Yield:
3
80%. 31P{1H} NMR (121.5 MHz, CDCl3, 20 °C): δ 86.6 (d, JPP
=
3
1
63.2 Hz, Ru−PiPr2), 36.5 (d, JPP = 63.2 Hz, CH-PiPr2). H NMR
(400.1 MHz, CDCl3, −20 °C): δ 1.32 - 1.52 (m, 30H, CHMe2,
Me2CH-P), 1.61 (m, 1H, Ru-PCH2), 2.13 (s, 3H, Me), 2.24 (m, 1H,
Ru-CH2), 2.34 (m, 3H, Ru-PCH2, CHP, Me2CH-P), 2.62 (m, 1H,
3
Me2CH-P), 2.73 (sept, JHH = 6.8 Hz, 1H, C−CHMe2), 2.96 (m, 2H,
Me2CH-P), 3.18 (m, 1H, Ru-CH2), 3.50 (m, 2H, PCH2CH), 4.86,
4.97 (2d, JHH = 6.0 Hz, 2 × 1H, p-cym), 5.38 (d, 3JHH = 9.6 Hz, 1H,
3
3
3
=CH2), 5.61 (d, JHH = 17.4 Hz, 1H, CH2), 5.65, 5.70 (2d, JHH
=
6.0 Hz, 2 × 1H, p-cym), 5.81 (m, 1H, CH). 13C{1H} NMR (100.6
MHz, CDCl3, −20 °C): δ 17.5−18.0 (m, Me2CH-P), 18.2 (s, br, Ru-
CH2), 18.6 (s, Me), 19.2, 19.5, 20.1, 20.6 (4s, Me2CH-P), 21.2, 21.5
(2d, 1JCP = 40.0 Hz, Me2CH-P), 22.7, 22.8 (2s, CHMe2), 22.9 (d, 1JCP
= 41.7 Hz, PCH2CH), 25.6 (d, 1JCP = 24.2 Hz, Me2CH-P), 28.5 (d,
1JCP = 20.0 Hz, Me2CH-P), 29.3 (d, 1JCP = 24.7 Hz, Ru-PCH2), 30.7 (s,
Synthesis of [RuCl(η6-C10H14){κ2(P,C)-iPr2PCH2CH(PR3)CH2}]-
[BPh4] (R = Ph (4a-BPh4), Me (4b-BPh4)). To a solution of
[RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CHCH2}][BPh4] (3-BPh4;
0.0374 g, 0.05 mmol) in THF (8 mL) was added 1 equiv of the
corresponding phosphane (0.05 mmol; 0.0131 mg for PPh3 and 4.5 μL
for PMe3), and the mixture was stirred for 2 min at room temperature.
The solution was then concentrated under vacuum to a volume of
approximately 1 mL. Addition of diethyl ether (20 mL) afforded a
yellow precipitate. Solvents were decanted, and the solid was washed
with diethyl ether (2 × 10 mL) and dried under reduced pressure. R =
Ph (4a-BPh4): yield 57%; 31P{1H} NMR (121.5 MHz, CDCl3, 20 °C)
δ 80.2 (d, 3JPP = 65.6 Hz, Ru-PiPr2), 24.6 (d, 3JPP = 65.6 Hz, PPh3); 1H
1
2
CHMe2), 34.1 (dd, JCP = 26.1 Hz, JCP = 19.6 Hz, CHP), 83.7, 84.3,
87.2, 91.3, 95.8, 111.3 (6s, p-cym), 124.4 (d, 3JCP = 10.4 Hz, CH2),
2
125.3 (d, JCP = 9.1 Hz, CH). Conductivity (acetone, 20 °C): Λ =
103 S cm2 mol−1. IR (KBr, cm−1): ν(CC) 1635 (w). MS-ESI (m/z):
587 ([M]+, 100%), 429 ([M − ADIP]+, 81%). Anal. Calcd for
C28H52Cl2P2Ru: C, 54.01; H, 8.42. Found: C, 53.93; H, 8.31.
Synthesis of [RuCl2(η6-C10H14){κ1(P)-iPr2PCH2CHCH2}] (2).
To a solution of the complex [RuCl(μ-Cl)(η6-C10H14)]2 (0.5 g, 0.81
mmol) in dichloromethane (15 mL) was added 2 equiv of
diisopropylallylphosphane (255 μL, 16.2 mmol). The resulting dark
red mixture was stirred at room temperature for 10 min. The solution
was then evaporated, and the orange residue was washed with diethyl
ether (3 × 10 mL) and dried under reduced pressure. Yield: 93%.
3
3
NMR (400.1 MHz, CDCl3, 20 °C) δ 0.81 (dd, JHH = 7.2 Hz, JHP
=
14.7 Hz, 3H, Me2CH-P), 0.85 (m, 1H, Ru-PCH2), 1.06 (m, 6H,
3
Me2CH-P, CHMe2), 1.15 (d, JHH = 6.8 Hz, 3H, CHMe2), 1.32 (m,
3H, Me2CH-P), 1.46 (m, 1H, Ru-CH2), 1.49 (dd, 3JHH = 7.2 Hz, 3JHP
=
31P{1H} NMR (121.5 MHz, CDCl3, 20 °C): δ 33.6 (s). H NMR
1
16.5 Hz, 3H Me2CH-P), 1.89 (s, 3H, Me), 2.05 (m, 2H, Ru-PCH2,
3
3
3
(300.1 MHz, CDCl3, 20 °C): δ 1.27 (dd, JHP = 12.9 Hz, JHH = 7.2
Me2CH-P), 2.48 (sept, JHH = 6.8 Hz, 1H, CHMe2), 2.57 (m, 1H,
3
Hz, 6H, Me2CH-P), 1.30 (d, JHH = 7.2 Hz, 6H, CHMe2), 1.33 (dd,
Me2CH-P), 2.90 (m, 1H, Ru-CH2), 4.16 (m, CHP), 4.76 (m, 2H, p-
3
3
3JHP = 14.0 Hz, 3JHH = 7.2 Hz, 6H, Me2CH-P), 2.10 (s, 3H, Me), 2.58
(m, 2H, Me2CH-P), 2.82 (sept, 3JHH = 6.9 Hz, 1H, CHMe2), 3.37 (dd,
cym), 5.46, 5.61 (2d, JHH = 5.7 Hz, 2 × 1H, p-cym), 6.86 (t, JHH =
3
7.2 Hz, 4H, BPh4), 7.00 (t, JHH = 7.2 Hz, 8H, BPh4), 7.41 (m, 8H,
BPh4), 7.50−7.70 (PPh3); 13C{1H} NMR (100.6 MHz, CDCl3, 20 °C)
δ 15.9 (m, Ru-CH2), 17.9 (s, Me), 18.0, 18.8, 19.1, 20.3 (4s, Me2CH-
P), 22.4, 22.7 (2s, CHMe2), 25.1 (d, 1JCP = 20.7 Hz, Me2CH−P), 26.5
2JHP = JHH = 9.0 Hz, 2H, PCH2), 5.04 (d, JHH = 10.2 Hz, 1H, 
3
3
3
CH2), 5.08 (d, JHH = 17.4 Hz, 1H, CH2), 5.62 (s, br, 4H, p-cym),
5.83 (m, 1H, CH). 13C{1H} NMR (150.9 MHz, CDCl3, 20 °C): δ
1
1
18.1 (s, Me), 18.7, 19.3 (2s, Me2CH-P), 22.4 (s, CHMe2), 24.0 (d, 1JCP
(d, JCP = 25.7 Hz, Ru-PCH2), 28.6 (d, JCP = 23.0 Hz, Me2CH-P),
30.5 (s, CHMe2), 31.9 (dd, 1JCP = 32.1 Hz, 2JCP = 16.0 Hz, CHP), 83.5,
1
= 22.3 Hz, PCH22), 27.8 (d, JCP = 22.5 Hz, Me2CHP), 30.7 (s,
1
2
86.3, 87.3, 89.2, 98.3, 110.1 (6s, p-cym), 118.6 (d, JCP = 81.0 Hz,
CHMe2), 83.0 (d, JCP = 4.8 Hz, 2C, p-cym), 88.5 (d, JCP = 2.7 Hz,
PPh3), 121.6, 125.4 (2s, BPh4), 130.5 (d, 2JCP = 11.7 Hz, PPh3), 133.2
2C, p-cym), 94.1, 108.3 (2s, p-cym), 118.6 (d, 3JCP = 8.0 Hz, CH2),
3
132.5 (d, JCP = 11.6 Hz, CH). IR (KBr, cm−1): ν(CC) 1630
2
(d, JCP = 8.7 Hz, PPh3), 135.0 (s, PPh3), 136.4 (s, BPh4), 164.3 (c,
JC = 49.5 Hz, BPh4); conductivity (acetone, 20 °C) Λ = 141 S cm2
11
(m). Anal. Calcd for C19H33Cl2PRu: C, 49.14; H, 7.16. Found: C,
49.03; H, 7.15.
B
mol−1; IR (KBr, cm−1) ν(BPh4) 731, 704 (s); MS-ESI (m/z) 691
([M]+, 100%), 429 ([M − PPh3]+, 18%). Anal. Calcd for
C61H68BClP2Ru: C, 72.51; H, 6.78. Found: C, 72.55; H, 6.47. R =
Me (4b-BPh4): yield 68%; 31P{1H} NMR (121.5 MHz, (CD3)2CO, 20
°C) δ 86.8 (δ, 3JPP = 70.5 Hz, Ru-PiPr2), 28.7 (δ, 3JPP = 70.5 Hz, CH-
Synthesis of [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CHCH2}]-
[BPh4] (3-BPh4). A suspension of the complex [RuCl2(η6-C10H14)-
{κ1(P)-iPr2PCH2CHCH2}] (2; 0.464 g, 1 mmol) was stirred with 3
equiv of NaBPh4 (3 mmol, 1.03 g) in MeOH (20 mL) at room
temperature for 2.5 h. Solvents were then decanted, the solid residue
was extracted with dichloromethane, and the resultant solution was
filtered through Kieselguhr and collected in hexane. Solvents were
1
2
PMe3); H NMR (400.1 MHz, CDCl3, 20 °C) δ 0.86 (d, JHP = 13.2
Hz, 9H, PMe3), 1.20−1.50 (m, 20H, Me2CH-P, C-CHMe2, Ru-PCH2,
Ru-CH2CH), 1.61 (m, 1H, Ru-PCH2), 1.89 (m, 1H, Ru-CH2), 2.04 (s,
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1
3H, C-Me), 2.15 (m, 1H, Me2CH-P), 2.65 (m, 3H, Ru-CH2, Me2CH-
P, C-CHMe2), 4.83, 5.72 (2d, JHH = 5.2 Hz, 2 × 1H, p-cym), 4.97,
= 75.3 Hz, P(OEt)3); H NMR (400.1 MHz, CDCl3, 20 °C) δ 1.11
(m, 6H, Me2CH-P), 1.28 (m, 21H, Me2CH-P, CHMe2, CH2CH3), 1.61
3
3
3
3
5.62 (2d, JHH = 6.0 Hz, 2 × 1H, p-cym), 6.89 (t, JHH = 7.2 Hz, 4H,
(s, 3H, Me), 2.36 (m, 2H, Me2CH-P), 2.58 (sept, JHH = 6.8 Hz, 1H,
BPh4), 7.06 (t, 3JHH = 7.2 Hz, 8H, BPh4) 7.50 (bs, 8H, BPh4); 13C{1H}
CHMe2), 2.66, 3.02 (2m, 2 × 1H, PCH2), 4.14 (m, 6H, CH2CH3),
5.12 (d, 3JHH = 18.4 Hz, 1H, CH2), 5.17 (d, 3JHH = 10.4 Hz, 1H, 
CH2), 5.44 (m, 3H, p-cym), 5.76 (m, 1H, p-cym), 5.78 (m, 1H, 
1
NMR (100.6 MHz, CDCl3, 20 °C) δ 6.2 (d, JCP = 52.5 Hz, PMe3),
15.3 (m, Ru-CH2), 18.0 (s, C-Me), 18.9, 19.2, 19.8, 20.4 (4s, Me2CH-
P) 22.5, 22.8 (2s, C-CHMe2), 25.5 (d, 1JCP = 26.2 Hz, Me2CH-P), 27.8
3
3
CH), 6.92 (t, JHH = 7.2 Hz, 4H, BPh4), 7.03 (t, JHH = 7.2 Hz, 8H,
1
1
BPh4), 7.38 (m, 8H, BPh4). 13C{1H} NMR (100.6 MHz, CDCl3, 20
(d, JCP = 24.4 Hz, Ru-PCH2), 28.5 (d, JCP = 20.6 Hz, Me2CH-P),
30.8 (s, C-CHMe2), 35.9 (dd, JHP = 37.5 Hz, JHP = 18.7 Hz,
CHPMe3), 84.3, 84.5, 87.5, 91.7, 95.0, 110.9 (6s, p-cym), 121.8, 125.8,
1
2
3
°C) δ 16.0 (d, JCP = 6.3 Hz, CH2CH3), 17.8 (s, C-Me), 18.1, 18.3,
19.2, 19.3 (4s, Me2CH-P), 21.1, 22.1 (2s, CHMe2), 24.7 (d, 1JCP = 22.9
Hz, PCH2), 26.4 (d, 1JCP = 27.1 Hz, Me2CH-P), 31.1 (s, CHMe2), 31.5
(d, 1JCP = 23.4 Hz, Me2CH-P), 64.7 (d, 2JCP = 10.6 Hz, CH2CH3), 86.4
(d, 2JCP = 8.4 Hz, p-cym), 90.1 (d, 2JCP = 13.8 Hz, p-cym), 92.6, 97.9,
11B
136.3, (3s, BPh4), 164.3 (c, JC = 49.3 Hz, BPh4); conductivity
(acetone, 20 °C) Λ = 142 S cm2 mol−1; IR (KBr, cm−1) ν(BPh4) 731,
703 (s); MS-ESI (m/z) 505 ([M]+, 100%), 429 ([M − PMe3]+, 24%).
Anal. Calcd for C46H62BClP2Ru: C, 67.03; H, 7.58. Found: C, 67.28;
H, 7.21.
3
100.0 (3s, p-cym), 119.8 (d, JCP = 8.4 Hz, CH2), 121.7, 125.5 (2s,
2
BPh4), 128.3 (s, p-cym), 131.6 (d, JCP = 11.5 Hz, CH), 136.3 (s,
Synthesis of [RuCl(η6-C10H14){κ1(P)-iPr2PCH2CHCH2}{P-
(OR)3}][BPh4] (R = Ph (5a-BPh4), Me (5b-BPh4), Et (5c-BPh4)).
To a solution of [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CHCH2}]-
[BPh4] (3-BPh4; 0.0374 mg, 0.05 mmol) in THF (8 mL) was added 1
equiv of P(OR)3 (0.05 mmol; 13.1 μL for R = Ph, 5.9 μL for R = Me,
and 8.6 μL for R = Et), and the mixture was stirred at room
temperature for 2 min. The solution was then concentrated under
vacuum to a volume of approximately 1 mL. Addition of hexane (20
mL) afforded a yellow precipitate. Solvents were decanted, and the
solid was washed with hexane (2 × 10 mL) and dried under reduced
pressure. The complex can be recrystallized from dichloromethane/
diethyl ether if required. R = Ph (5a-BPh4): yield 72%; 31P{1H} NMR
11
BPh4), 164.2 (c, JC B = 49.3 Hz, BPh4); conductivity (acetone, 20 °C)
Λ = 117 S cm2 mol−1; IR (KBr, cm−1) ν(CC) 1573 (m), ν(BPh4)
730, 704 (s); MS-ESI (m/z) 595 ([M]+, 100%), 461 ([M − p-cym]+,
23%). Anal. Calcd for C49H68BClO3P2Ru·1/4 CH2Cl2: C, 63.23; H,
7.38. Found: C, 63.55; H, 7.08.
Synthesis of [RuCl(η6-C10H14){κ1(P)-iPr2PCH2CHCH2}-
(MeCN)][BPh4] (6-BPh4). The compound [RuCl(η6-C10H14)-
{κ3(P,C,C)-iPr2PCH2CHCH2}][BPh4] (3-BPh4) was dissolved in
the minimum volume of acetonitrile. The addition of diethyl ether (2
mL) and hexane (15 mL) afforded a yellow precipitate. Solvents were
decanted, and the solid residue was dried in air, since vacuum drying
results in reversibility of the reaction. Yield: 62%. IR (KBr, cm−1):
ν(CN) 2287 (m), ν(CC) 1579 (m), ν(BPh4) 734, 706 (s).
2
(121.5 MHz, CDCl3, 20 °C) δ 45.9 (d, JPP = 71.7 Hz, ADIP), 112.3
(d, 2JPP = 71.7 Hz, P(OPh)3); 1H NMR (400.1 MHz, CDCl3, 20 °C) δ
31P{1H} NMR (121.5 MHz, CD3CN, 20 °C): δ 41.6 (s). H NMR
1
3
1.02, 1.18 (2d, JHH = 6.8 Hz, 2 × 3H, CHMe2), 1.27 (m, 12H,
(400.1 MHz, CD3CN, 20 °C): δ 1.23−1.36 (m, 18H, Me2CH-P, C−
CHMe2), 2.08 (s, 3H, Me), 2.17 (s, 3H, CH3CN), 2.55 (m, 1H,
PCH2), 2.67 (m, 3H, Me2CH-P, C−CHMe2), 2.99 (m, 1H, PCH2),
5.20 (m, 2H, CH2), 5.86 (d, 3JHH = 6.0 Hz, 1H, p-cym), 5.89−5.98
Me2CH-P), 1.61 (s, 3H, Me), 2.37 (m, 3H, Me2CH-P, C-CHMe2),
2.61 (m, 1H, PCH2), 2.99 (m, 1H, PCH2), 4.04, 5.30 (2d, JHP = 6.0
3
Hz, 2 × 1H, p-cym), 4.78 (d, JHH = 17.2 Hz, 1H, CH2), 4.99 (d,
3JHH = 9.6 Hz, 1H, =CH2), 5.47 (s, br, 1H, p-cym), 5.65 (m, 1H,
=CH), 5.95 (s, br, 1H, p-cym), 6.86 (t, 3JHH = 7.2 Hz, 4H, BPh4), 7.00
3
(m, 4H, CH, p-cym), 6.87 (t, JHH = 7.2 Hz, 4H, BPh4), 7.02 (t,
3JHH = 7.2 Hz, 8H, BPh4), 7.30 (bs, 8H, BPh4). 13C{1H} NMR (100.6
MHz, CD3CN, 20 °C): δ 0.8 (s, CH3CN), 17.4 (s, Me), 17.5, 17.7,
18.0, 18.1 (4s, Me2CH-P), 21.3, 21.9 (2s, CHMe2), 25.2 (d, 1JCP = 22.4
3
3
(t, JHH = 7.2 Hz, 8H, BPh4), 7.10 (d, JHH = 8.0 Hz, 6H, P(OPh)3),
7.27−7.38 (m, 17H, BPh4, P(OPh)3); 13C{1H} NMR (100.6 MHz,
CDCl3, 20 °C) δ 17.9 (s, Me), 18.3, 18.7, 19.0, 19.1 (4s, Me2CH-P),
20.9, 21.8 (2s, CHMe2), 24.5 (d, 1JCP = 24.1 Hz, PCH2), 26.8 (d, 1JCP
1
Hz, PCH2), 27.1, 27.3 (2d, JCP = 24.1 Hz, Me2CH-P), 31.1 (s,
2
2
1
CHMe2), 86.5 (d, JCP = 4.7 Hz, p-cym), 87.0 (d, JCP = 4.2 Hz, p-
= 27.6 Hz, Me2CH-P), 31.1 (d, JCP = 23.4 Hz, Me2CH-P), 31.2 (s,
cym), 88.1, 91.9, 100.0, 110.3 (4s, p-cym), 119.0 (d, 3JCP = 8.5 Hz, 
CHMe2), 84.7, 89.0, 95.0, 98.7, 108.5 (5s, p-cym), 120.2 (d, 3JCP = 8.8
2
CH2), 121.8, 125.6 (2s, BPh4), 128.6 (s, CH3CN), 131.8 (d, JCP
=
Hz, =CH2), 121.2 (s, P(OPh)3), 121.7, 125.6 (2s, BPh4), 126.2, 130.1
11B
2
10.4 Hz, CH), 135.7 (s, BPh4), 163.9 (c, JC = 49.1 Hz, BPh4).
(2s, P(OPh)3), 131.0 (d, JCP = 11.3 Hz, CH), 132.5 (s, p-cym),
Conductivity (acetone, 20 °C): Λ = 142.4 S cm2 mol−1. The instability
of this complex prevented us from obtaining any satisfactory analysis.
Synthesis of [RuCl(η6-C10H14){κ1(P)-iPr2PCH2CHCH2}(py)]-
[BPh4] (7-BPh4). To a solution of [RuCl(η6-C10H14){κ3(P,C,C)-
iPr2PCH2CHCH2}][BPh4] (0.0748 g, 0.1 mmol) in THF (10 mL)
was added 1 equiv of pyridine (0.1 mmol, 8 μL). The mixture was
stirred for 5 min at room temperature. The addition of hexane (50
mL) afforded a yellow precipitate, which was washed with hexane (3 ×
10 mL) and dried under reduced pressure in the air, since vacuum
drying results in reversibility of the reaction. Yield: 60%. 31P{1H}
NMR (162.1 MHz, CD2Cl2, 20 °C): δ 32.0 (s). 1H NMR (300.1 MHz,
CD2Cl2, 20 °C): δ 1.07−1.33 (m, 18H, Me2CH-P, C-CHMe2), 1.98 (s,
2
11
136.3 (s, BPh4), 151.1 (d, JCP = 14.1 Hz, P(OPh)3), 164.1 (c, JC
=
B
50.3 Hz, BPh4); conductivity (acetone, 20 °C) Λ = 111 S cm2 mol−1;
IR (KBr, cm−1) ν(CC) 1587 (m), ν(BPh4) 733, 705 (s); MS-ESI
( m / z ) 7 3 9 ( [ M ] +
,
1 0 0 % ) . A n a l . C a l c d f o r
C61H68BClO3P2Ru·1/2CH2Cl2: C, 67.10; H, 6.31. Found: C, 67.34;
H, 6.68. R = Me (5b-BPh4): yield 72%; 31P{1H} NMR (121.5 MHz,
CDCl3, 20 °C) δ 44.3 (d, 2JPP = 75.3 Hz, ADIP), 117.4 (d, 2JPP = 75.3
Hz, P(OMe)3); 1H NMR (400.1 MHz, CDCl3, 20 °C) δ 1.09 (m, 6H,
Me2CH-P), 1.28 (m, 12H, Me2CH-P, CHMe2), 1.58 (s, 3H, Me), 2.35
(m, 2H, Me2CH-P), 2.56 (m, 2H, PCH2, CHMe2), 3.00 (m, 1H,
3
3
PCH2), 3.76 (d, JHP = 10.8 Hz, 9H, P(OMe)3), 5.13 (d, JHH = 19.2
Hz, 1H, CH2), 5.17 (d, 3JHH = 10.8 Hz, 1H, CH2), 5.47 (m, 3H,
p-cym), 5.72 (m, 1H, p-cym), 5.77 (m, 1H, =CH), 6.92 (t, 3JHH = 7.2
Hz, 4H, BPh4), 7.03 (t, 3JHH = 7.2 Hz, 8H, BPh4), 7.38 (m, 8H, BPh4);
13C{1H} NMR (100.6 MHz, CDCl3, 20 °C) δ 18.0 (s, Me), 18.2, 19.2
3
3H, Me), 2.33 (sept, JHH = 7.2 Hz, 1H, CHMe2), 2.50 (m, 1H,
Me2CH-P), 2.65 (m, 3H, PCH2, Me2CH-P), 5.13 (m, 2H, CH2),
3
5.30, 5.39 (2d, JHH = 6.0 Hz, 2 × 1H, p-cym) 5.55 (m, 1H, CH),
3
3
1
5.65 5.76 (2d, JHH = 6.0 Hz, 2 × 1H, p-cym), 6.92 (t, JHH = 7.2 Hz,
(2s, Me2CH-P), 21.1, 22.1 (2s, CHMe2), 25.0 (d, JCP = 23.5 Hz,
3
PCH2), 26.2 (d, 1JCP = 26.9 Hz, Me2CH-P), 31.0 (s, CHMe2), 31.5 (d,
4H, BPh4), 7.06 (t, JHH = 7.2 Hz, 8H, BPh4), 7.36 (m, 10H, py,
BPh4), 7.87 (t, 3JHH = 7.8 Hz, 1H, py), 8.85 (d, 3JHH = 4.8 Hz, 2H, py).
13C{1H} NMR (100.6 MHz, CD2Cl2, 20 °C): δ 18.1 (s, Me), 18.2,
1JCP = 23.7 Hz, Me2CH-P), 55.5 (d, JCP = 10.6 Hz, P(OMe)3), 86.9
2
(d, 2JCP = 8.3 Hz, p-cym), 90.4 (d, JCP = 13.4 Hz, p-cym), 92.6, 99.0,
2
1
3
18.3, 18.9, 19.2 (4s, Me2CH-P), 21.6, 22.4 (2s, CHMe2), 26.2 (d, JCP
100.0 (3s, p-cym), 120.0 (d, JCP = 8.3 Hz, CH2), 121.7, 125.5 (2s,
1
2
= 24.1 Hz, Me2CH-P), 26.5 (d, JCP = 21.1 Hz, Me2CH-P), 26.8 (d,
BPh4), 128.3 (s, p-cym), 131.4 (d, JCP = 11.7 Hz, CH), 136.3 (s,
1JCP = 22.1 Hz, PCH2), 30.7 (s, CHMe2), 83.0, 85.7, 90.0, 90.2, 97.5,
11
BPh4), 164.1 (c, JC B = 48.3 Hz, BPh4); conductivity (acetone, 20 °C)
3
Λ = 107 S cm2 mol−1; IR (KBr, cm−1) ν(CC) 1580 (m), ν(BPh4)
733, 705 (s); MS-ESI (m/z) 533 ([M]+, 100%), 419 ([M − p-cym]+,
19%). Anal. Calcd for C46H62BClO3P2Ru: C, 63.34; H, 7.16. Found:
C, 63.18; H, 7.05. R = Et (5c-BPh4): yield 68%; 31P{1H} NMR (121.5
113.9 (6s, p-cym), 120.0 (d, JCP = 9.1 Hz, CH2), 122.0, 125.9 (2s,
BPh4) 126.3 (s, py), 129.9 (d, 2JCP = 7.0 Hz, CH), 135.8 (s, BPh4),
11
139.7, 156.2 (2s, py), 9 163.9 (c, JC B = 49.3 Hz, BPh4). Conductivity
(acetone, 20 °C): Λ = 139 S cm2 mol−1. IR (KBr, cm−1): ν(CC)
MHz, CDCl3, 20 °C) δ 43.4 (d, 2JPP = 75.3 Hz, ADIP), 112.1 (d, JPP
1601 (m), ν(BPh4) 733, 703 (s). MS-ESI (m/z): 425 ([M − py]+,
2
4349
dx.doi.org/10.1021/om400487g | Organometallics 2013, 32, 4342−4352

Organometallics
Article
3
100%), 395 ([M − py − Cl]+, 62%). Anal. Calcd for C48H58BClNPRu:
C, 69.69; H, 7.07; N, 1.31. Found: C, 69.74; H, 6.85; N, 1.64.
Synthesis of [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}-
(PPh3)][BPh4] (8-BPh4). To a solution of the complex [RuCl(η5-
C9H7)(PPh3)2] (0.388 g, 0.5 mmol) in THF (50 mL) were added 3
equiv of NaBPh4 (1.5 mmol, 0.513 g) and allyldiisopropylphosphane
(1.5 mmol, 224 μL). The mixture was refluxed for 30 min. Within this
period of time, the initially red solution turned yellow. Once the
reaction was complete, the solution was evaporated to dryness. The
solid residue was extracted with dichloromethane and the resultant
solution filtered through Kieselghur and concentrated. Addition of
hexane (30 mL) afforded a yellow solid, which was washed with
hexane (2 × 15 mL) and vacuum-dried. Yield: 85%. 31P{1H} NMR
(162.1 MHz, CD2Cl2, 20 °C): δ 51.7 (d, 2JPP = 32.3 Hz, Ph3P), −51.6
4.79 (d, 1H, JHH = 11.4 Hz, CH2), 4.05, 5.33, 5.38 (3s, 3 × 1H,
C9H7), 5.67 (m, 1H, CH), 6.39 (d, 3JHH = 8.7 Hz, 1H, C9H7), 6.86
3
3
(t, JHH = 7.2 Hz, 4H, BPh4), 7.02 (t, JHH = 7.2 Hz, 8H, BPh4), 7.30
(m, 8H, BPh4), 6.84−7.60 (m, 18H, C9H7, PPh3). 13C{1H} NMR
(75.5 MHz, CD3CN, 20 °C): δ 2.0 (s, MeCN), 17.9−18.8 (m,
1
1
Me2CH-P), 28.8 (d, JCP = 17.0 Hz, PCH2), 29.0 (d, JCP = 24.3 Hz,
1
2
Me2CH−P), 29.9 (d, JCP = 24.2 Hz, Me2CH-P), 64.4 (d, JCP = 8.7
Hz, C9H7), 65.9, 88.4, 108.3, 110.1 (4s, C9H7), 117.9 (d, 3JCP = 9.8 Hz,
11B
CH2), 121.8, 125.6, 135.8 (3s, BPh4), 163.8 (c, JC = 48.8 Hz,
BPh4), 123.8−135.0 (CH, C9H7, PPh3). Conductivity (acetonitrile,
20 °C): Λ = 134 S cm2 mol−1.
Synthesis of [Ru{κ3(P,C,S)-iPr2PCH2CH(SCH3)CH2}(η6-C10H14)]-
[BPh4] (11a-BPh4). To a solution of the complex [RuCl(η6-
C10H14){κ3(P,C,C)-iPr2PCH2CHCH2}][BPh4] (3-BPh4; 0.053
mmol, 0.040 g) in THF (10 mL) was added 2 equiv of NaSCH3
(0.106 mmol, 0.007 g), and the mixture was stirred at room
temperature for 1 h. The solution was then evaporated under reduced
pressure, and the yellow residue was extracted with dichloromethane.
The resulting solution was filtered through Kieselguhr and
concentrated under vacuum to a volume of approximately 1 mL.
The addition of hexane (20 mL) afforded a yellow precipitate. Solvents
were decanted, and the solid residue was washed with hexane (2 × 15
mL) and vacuum-dried. Yield: 62%. 31P{1H} NMR (162.1 MHz,
CDCl3, 20 °C): δ 75.7 (s). 1H NMR (400.1 MHz, CD2Cl2, 20 °C): δ
1.18−1.30 (m, 19H, Me2CH-P, CHMe2, Ru-CH2), 1.88−1.92 (m, 2H,
PCH2), 2.13 (s, 3H, Me), 2.21 (m, 1H, Ru-CH2), 2.29 (s, 3H, SCH3),
2
1
(d, JPP = 32.3 Hz, ADIP). H NMR (400.1 MHz, CD2Cl2, 20 °C): δ
0.75 (dd, 3JHH = 7.2 Hz, 3JHP = 14.0 Hz, 3H, Me2CH-P), 1.10 (m, 3H,
Me2CH-P), 1.30 (m, 1H, CH2), 1.56 (m, 3H, Me2CH-P), 1.78 (dd,
3
3JHH = 7.2 Hz, JHP = 15.6 Hz, 3H, Me2CH-P), 1.86−1.95 (m, 2H,
Me2CH-P), 2.78 (m, 1H, PCH2), 2.87 (m, 1H, CH2), 3.15 (m, 1H,
CH), 3.41 (m, 1H, PCH2), 4.97, 5.41, 5.82 (3s, 3 × 1H, C9H7), 6.34
(d, 3JHH = 8.4 Hz, 1H, C9H7), 6.92 (t, 3JHH = 7.2 Hz, 4H, BPh4), 7.07
(t, 3JHH = 7.2 Hz, 8H, BPh4), 7.48 (m, 8H, BPh4), 6.90−7.57 (m, 18H,
C9H7, PPh3). 13C{1H} NMR (100.6 MHz, CD2Cl2, 20 °C): δ 17.7−
1
20.2 (m, Me2CH-P), 18.2 (d, JCP = 7.5 Hz, Me2CH-P), 29.2 (s br,
1
2
Me2CH-P), 31.1 (d, JCP = 22.6 Hz, PCH2), 46.4 (d, JCP = 19.2 Hz,
CH), 52.3 (s br, CH2), 73.9, 79.3, 85.8, 103.9, 105.4 (5s, C9H7),
3
11B
2.31−2.41 (m, 2H, Me2CH-P), 2.62 (sept, JHH = 6.8 Hz, 1H,
121.7, 125.7, 135.8 (3s, BPh4), 164.1 (c, JC = 49.0 Hz, BPh4),
CHMe2), 4.89 (bd, 3JHP = 41.7 Hz, 1H, S-CH), 5.00, 5.75 (2d, 3JHH
=
121.6−133.8 (C9H7, PPh3). Conductivity (acetone, 20 °C): Λ = 134 S
cm2 mol−1. IR (KBr, cm−1): ν(CC) 1479 (m), ν (BPh4) 732, 703
(s). MS-ESI (m/z): 637 ([M]+, 100%). Anal. Calcd for C60H61BP2Ru:
C, 75.38; H, 6.43. Found: C, 75.48; H, 6.66.
6.0 Hz, 2 × 1H, p-cym), 5.38, 5.62 (2d, 3JHH = 6.4 Hz, 2 × 1H, p-cym),
3
3
6.92 (t, JHH = 7.2 Hz, 4H, BPh4), 7.07 (t, JHH = 7.2 Hz, 8H, BPh4),
7.36 (m, 8H, BPh4). 13C{1H} NMR (100.6 MHz, CD2Cl2, 20 °C): δ
3.0 (d, 3JCP = 7.9 Hz, Ru-CH2), 18.6−18.8 (s, Me2CH-P), 18.8 (s, Me),
21.7 (s, SCH3), 22.2 (s, CHMe2), 23.6 (d, 1JCP = 27.3 Hz, Ru-PCH2),
Synthesis of [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}{P-
(OMe)3}][BPh4] (9-BPh4). To a suspension of the complex [Ru(η5-
C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}(PPh3)][BPh4] (0.05 mmol,
0.048 g) in a THF/toluene mixture (2/1, 15 mL) was added 3
equiv of P(OMe)3 (0.15 mmol, 18 μL). The suspension was heated at
70 °C for 8 h. Once the reaction was completed and cooled, the yellow
solution was concentrated and the adition of hexane (20 mL) afforded
a yellow precipitate. Solvents were decanted, and the solid was washed
with hexane (2 × 10 mL) and vacuum-dried. Yield: 65%. 31P{1H}
1
1
24.1 (s, CHMe2), 27.4 (d, JCP = 25.4 Hz, Me2CH-P), 28.0 (d, JCP
=
25.4 Hz, Me2CH-P), 32.2 (s, CHMe2), 67.2 (d, 2JCP = 4.8 Hz, S-CH),
81.5, 84.8, 86.4, 87.9, 102.3, 113.8 (6s, p-cym), 121.8, 125.7, 135.9 (3s,
11B
BPh4), 164.1 (c, JC = 49.3 Hz, BPh4). Conductivity (acetone, 20
°C): Λ = 104 S cm2 mol−1. IR (KBr, cm−1): ν(BPh4) 736, 705 (s).
MS-ESI (m/z): 441 ([M]+, 100%).
Synthesis of [Ru{κ3(P,C,S)-iPr2PCH2CH(SR)CH2}(η6-C10H14)]-
[BPh4] (R = iPr (11b-BPh4), tBu (11c-BPh4)). The thiolate RS−
was formed in situ by stirring NaOH (0.1 mmol, 4 mg) and the
corresponding thiol (0.1 mmol) in THF (10 mL) for 30 min. Then,
the complex [RuCl(η6-C10H14){κ3(P,C,C)-iPr2PCH2CHCH2}]-
[BPh4] (3-BPh4; 0.05 mmol, 0.04 g) was added and the mixture
was stirred at room temperature for 45 min. Once the reaction was
completed, the solution was evaporated to dryness. The residue was
extracted with CH2Cl2 and the extract filtered through Kieselghur. The
resulting yellow solution was concentrated, and the addition of hexane
(20 mL) afforded a brownish yellow solid precipitate. The solvent was
decanted, and the solid was washed with hexane (2 × 15 mL) and
vacuum-dried. R = iPr (11b-BPh4): yield 56%; 31P{1H} NMR (162.1
2
NMR (162.1 MHz, CDCl3, 20 °C): δ 154.9 (d, JPP = 52.0 Hz,
2
i
1
P(OMe)3), −39.6 (d, JPP = 52.0 Hz, Pr2P). H NMR (400.1 MHz,
3
3
CDCl3, 20 °C): δ 0.98 (dd, JHH = 7.2 Hz, JHP = 14.8 Hz, 3H,
Me2CH-P), 1.05 (m, 1H, CH2), 1.09 (dd, 3JHH = 7.2 Hz, 3JHP = 17.6
3
3
Hz, 3H, Me2CH-P), 1.37 (dd, JHH = 7.2 Hz, JHP = 15.2 Hz, 3H,
3
3
Me2CH-P), 1.51 (dd, JHH = 7.2 Hz, JHP = 14.8 Hz, 3H, Me2CH-P),
1.59−1.71 (m, 2H, Me2CH-P, PCH2), 2.45−2.59 (m, 2H, Me2CH-P,
3
CH), 2.76 (m, 1H, CH2), 3.10 (m, 1H, PCH2), 3.55 (d, JHP
=
=
=
11.2 Hz, 9H, P(OMe)3), 5.42, 5.77 (2s, 2 × 1H, C9H7), 5.35 (t, 3JHH
3
3
2.4 Hz, 1H, C9H7), 6.92 (t, JHH = 7.2 Hz, 4H, BPh4), 7.06 (t, JHH
7.2 Hz, 8H, BPh4), 7.44 (m, 8H, BPh4), 7.00−7.72 (m, 4H, C9H7).
13C{1H} NMR (100.6 MHz, CDCl3, 20 °C): δ 18.3 (d, 1JCP = 7.0 Hz,
1
1
MHz, CDCl3, 20 °C) δ 76.0 (s); H NMR (400.1 MHz, CDCl3, 20
Me2CH−P), 18.4, 19.7 (2s br, Me2CH-P), 27.5 (d, JCP = 22.5 Hz,
1
2
°C) δ 1.10−1.31 (m, 25H, Me2CH-P, C-CHMe2, Me2CHS, Ru-CH2),
Me2CH−P), 29.7 (d, JCP = 33.8 Hz, PCH2), 46.3 (d, JCP = 18.8 Hz,
2
1.68 (m, 2H, PCH2), 1.93 (m, 1H, Ru-CH2), 1.99 (s, 3H, C-Me), 2.25
CH), 50.4 (s br, CH2), 53.9 (d, JCP = 9.4 Hz, P(OMe)3), 73.7,
3
(m, 2H, Me2CH-P), 2.55 (sept, JHH = 6.8 Hz, 1H, C−CHMe2), 2.81
74.0 (2s, C9H7), 84.3, 104.3, 105.2 (3s, C9H7), 121.6, 125.5, 136.4 (3s,
3
3
(sept, JHH = 6.8 Hz, 1H, Me2CH-S), 4.71 (d, JHH = 5.6 Hz, 1H, p-
cym), 4.81 (bd, 1H, JHP = 43.2 Hz, S-CHCH2), 5.32, 5.36, 5.59 (3d,
3JHH = 5.6 Hz, 3 × 1H, p-cym), 6.91 (t, 3JHH = 7.2 Hz, 4H, BPh4), 7.05
11B
BPh4), 164.3 (c, JC = 48.3 Hz, BPh4), 122.3−132.2 (C9H7).
Conductivity (acetone, 20 °C): Λ = 122 S cm2 mol−1. IR (KBr, cm−1):
ν(CC) 1478 (m), ν(BPh4) 733, 702 (s).
(t, JHH = 7.2 Hz, 8H, BPh4), 7.43 (m, 8H, BPh4); 13C{1H} NMR
3
Synthesis of [Ru(η5-C9H7){κ1(P)-iPr2PCH2CHCH2}(PPh3)-
(NCMe)][BPh4] (10-BPh4). The compound [Ru(η5-C9H7){κ1(P)-
iPr2PCH2CHCH2}(PPh3)(NCMe)][BPh4] (10-BPh4) was inme-
diatly formed when [Ru(η5-C9H7){κ3(P,C,C)-iPr2PCH2CHCH2}-
(PPh3)][BPh4] (8-BPh4) was dissolved in the minimum volume of
acetonitrile. This complex was spectroscopically characterized in
acetonitrile solution. 31P{1H} NMR (121.5 MHz, CD3CN, 20 °C): δ
3
(100.6 MHz, CDCl3, 20 °C) δ 5.2 (d, JCP = 9.6 Hz, Ru-CH2), 18.4,
18.8, 19.0, 19.1, 21.6, 21.9, 22.1 (7s, Me2CH-P, Me2CH-S, C-Me), 23.5
(d, 1JCP = 29.2 Hz, Ru-PCH2), 24.9 (s, C-CHMe2), 27.4, 28.0 (2d, 1JCP
= 25.3 Hz, Me2CH-P), 32.1 (s, C-CHMe2), 42.2 (s, Me2CH-S), 63.9
2
(d, JCP = 5.8 Hz, S-CHCH2), 79.9, 85.0, 85.7, 104.4, 113.7 (5s, p-
11
cym), 121.6, 125.5, 136.3 (3s, BPh4), 164.3 (c, JC B = 50.3 Hz, BPh4);
2
2
i
1
50.2 (d, JPP = 30.3 Hz, Ph3P), 47.4 (d, JPP = 30.3 Hz, Pr2P). H
NMR (300.1 MHz, CD3CN, 20 °C): δ 1.12−1.30 (m, 12H, Me2CH-
P), 1.68 (m, 1H, Me2CH-P), 1.83 (m, 1H, Me2CH-P), 2.12 (s, 3H,
MeCN), 2.39 (m, 2H, PCH2), 4.75 (d, 1H, JHH = 16.8 Hz, CH2),
conductivity (acetone, 20 °C): Λ = 102 S cm2 mol−1; IR (KBr, cm−1)
ν(BPh4) 733, 705 (s); MS-ESI (m/z) 469 ([M]+, 100%). R = tBu
(11c-BPh4): yield 42%; 31P{1H} NMR (162.1 MHz, CDCl3, 20 °C) δ
74.6 (s); 1H NMR (400.1 MHz, CDCl3, 20 °C δ 0.89 (m, 1H,
3
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Organometallics
Article
RuCH2), 1.08−1.28 (m, 18H, Me2CH-P, C-CHMe2), 1.33 (s, 9H,
3H, Me2CH-P), 1.00 (dd, 3JHH = 7.6 Hz, 3JHP = 14.4 Hz, 3H, Me2CH-
3
3
Me3C), 1.69 (m, 2H, PCH2), 1.98 (s, 3H, C-Me), 2.19 (m, 2H, Ru-
P), 1.24 (m, 4H, Me2CH-P, PCH2), 1.34 (dd, JHH = 6.8 Hz, JHP =
3
3
CH2, Me2CH-P), 2.29 (m, 1H, Me2CH-P), 2.53 (sept, JHH = 6.8 Hz,
12.8 Hz, 3H, Me2CH-P), 1.41, 1.43 (2d, JHH = 6.8 Hz, 2 × 3H,
Me2CH-S), 1.62 (m, 1H, Me2CH-P), 1.81 (m, 1H, RuCH2), 2.28 (m,
2H, Me2CH-P, PCH2), 2.87 (m, 1H, RuCH2), 3.12 (m, 1H,
1H, C-CHMe2), 4.77 (d, 3JHH = 5.2 Hz, 1H, p-cym), 4.84 (bd, 1H, JHP
= 46.8 Hz, S−CHCH2), 5.42, 5.60 (2d, 3JHH = 5.6 Hz, 2 × 1H, p-cym),
5.72 (d, 3JHH = 5.2 Hz, 1H, p-cym), 6.91 (t, 3JHH = 7.2 Hz, 4H, BPh4),
7.05 (t, 3JHH = 7.2 Hz, 8H, BPh4), 7.41 (m, 8H, BPh4); 13C{1H} NMR
(100.6 MHz, CDCl3, 20 °C) δ 5.7 (d, 3JCP = 11.6 Hz, Ru-CH2), 18.6,
18.8, 19.0, 19.1, 19.2 (5s, Me2CH-P, C-Me), 22.4, 24.8 (2s, C-CHMe2),
3
RuCH2CH), 3.19 (sept, JHH = 6.8 Hz, 1H, Me2CH-S), 4.82, 5.03
(2s, 2 × 1H, C9H7), 5.14 (t, 3JHH = 2.4 Hz, C9H7), 6.37 (d, 3JHH = 8.4
Hz, 1H, C9H7), 6.89−7.87 (m, 18H, C9H7, PPh3); 13C{1H} NMR
(100.6 MHz, C6D6, 20 °C) δ 14.4 (m, Ru-CH2), 18.2, 18.6, 20.5, 21.6,
1
1
1
24.9 (d, JCP = 31.0 Hz, Ru-PCH2), 27.9, 28.2 (2d, JCP = 25.4 Hz,
Me2CH−P), 29.1 (s, Me3C), 32.1 (s, C-CHMe2), 49.4 (s, Me3C-S),
64.7 (d, 2JCP = 5.5 Hz, S-CHCH2), 80.0, 85.0, 86.2, 103.8, 113.5 (5s, p-
(4s, Me2CH-P), 24.3 (s, Me2CH-S), 29.1 (d, JCP = 19.6 Hz, Me2CH-
1
P), 32.6 (d, JCP = 22.8 Hz, Me2CH-P), 34.8 (s, Me2CH-S), 35.1 (d,
2
1JCP = 19.5 Hz, Ru-PCH2), 49.6 (d, JCP = 26.2 Hz, RuCH2CH), 71.0
2
2
11
cym), 121.7, 125.6, 136.4 (3s, BPh4), 164.3 (c, JC B = 49.3 Hz, BPh4);
(d, JCP = 6.0 Hz, C9H7), 71.5 (d, JCP = 8.0 Hz, C9H7), 91.8, 105.9,
107.7 (3s, C9H7), 122.5−139.4 (C9H7, PPh3); conductivity (acetone,
20 °C): Λ = 16 S cm2 mol−1; MS-ESI (m/z) 637 ([M − SiPr]+,
100%). R = tBu (13c): yield 66%; 31P{1H} NMR (121.5 MHz, C6D6,
Conductivity (acetone, 20 °C) Λ = 100 S cm2 mol−1; IR (KBr, cm−1)
ν(BPh4) 731, 702 (s); MS-ESI (m/z) 483 ([M]+, 100%).
Synthesis of [RuCl{κ2(P,C)-iPr2PCH2CH(SC6H4Me)CH2}(η6-
C10H14)] (12). The thiolate C7H7S− was formed in situ by stirring
NaOH (0.1 mmol, 0.004 g) and p-toluenethiol (0.1 mmol, 0.0124 g)
in THF (10 mL) for 30 min. Then, the complex [RuCl{κ3(P,C,C)-
iPr2PCH2CHCH2}(η6-C10H14)][BPh4] (3-BPh4; 0.05 mmol, 0.04
g) was added and the mixture was stirred at room temperature for 45
min. Once the reaction was completed, the solution was evaporated to
dryness under reduced pressure and the solid residue was extracted
with hexane. The resulting yellow solution was filtered through
Kieselguhr and evaporated to dryness, affording a brownish solid.
Yield: 65%. 31P{1H} NMR (162.1 MHz, CDCl3, 20 °C): δ 70.2 (s). 1H
NMR (400.1 MHz, CDCl3, −30 °C): δ 1.09−1.40 (m, 18H, Me2CH-
P, C-CHMe2), 1.45 (m, 1H, PCH2), 1.99 (s, 3H, C-Me), 2.09 (m, 1H,
PCH2), 2.20 (m, 2H, Me2CH-P, RuCH2), 2.37 (s, 3H, C6H4Me), 2.60
2
i
2
20 °C) δ 76.1 (d, JPP = 27.4 Hz, Pr2P), 60.1 (d, JPP = 27.4 Hz,
PPh3); 1H NMR (400.1 MHz, C6D6, 20 °C) δ 0.77 (dd, 3JH3H = 6.8 Hz,
3JHP = 10.4 Hz, 3H, Me2CH-P), 0.98 (dd, JHH = 7.6 Hz, JHP = 14.4
3
Hz, 3H, Me2CH-P), 1.16 (m, 1H, PCH2), 1.28 (dd, 3JH3H = 6.8 Hz, 3JHP
3
= 10.4 Hz, 3H, Me2CH-P), 1.40 (dd, JHH = 6.8 Hz, JHP = 13.1 Hz,
3H, Me2CH-P), 1.54 (s, 9H, Me3C-S), 1.66 (m, 1H, Me2CH-P), 1.98
(m, 1H, RuCH2), 2.33 (m, 2H, Me2CH-P, PCH2), 3.00 (m, 1H,
RuCH2), 3.12 (m, 1H, RuCH2CH), 4.80, 5.08, 5.21 (3s, 3 × 1H,
C9H7), 6.32 (d, 3JHH = 8.0 Hz, 1H, C9H7), 6.87−7.87 (m, 18H, C9H7,
PPh3); 13C{1H} NMR (100.6 MHz, C6D6, 20 °C) δ 17.6 (m, Ru-
1
CH2), 18.2, 18.3, 20.5, 21.8, (4s, Me2CH-P), 28.8 (d, JCP = 19.4 Hz,
1
Me2CH-P), 29.8 (d, JCP = 18.7 Hz, Me2CH-P), 32.2 (s, Me3CH-S),
1
2
36.3 (d, JCP = 22.7 Hz, Ru-PCH2), 42.6 (s, Me3C-S), 49.2 (d, JCP
=
=
3
2
2
(m, 1H, Me2CH-P), 2.71 (sept, JHH = 6.8 Hz, 1H, C-CHMe2), 2.96
23.5 Hz, RuCH2CH), 70.7 (d, JCP = 8.7 Hz, C9H7), 71.7 (d, JCP
(m, 1H, RuCH2CH), 3.43 (m, 1H, RuCH2), 4.63, 5.76 (2d, 3JHH = 5.6
11.8 Hz, C9H7), 92.1, 104.7, 106.2 (3s, C9H7), 122.5−139.2 (C9H7,
PPh3); conductivity (acetone, 20 °C) Λ = 24 S cm2 mol−1; MS-ESI
(m/z) 637 ([M − StBu]+, 100%).
X-ray Crystal Structure Determination of 1-Cl, 3-BPh4, 8-
BPh4·CH2Cl2, and 11a-BPh4. Crystals suitable for X-ray diffraction
analysis were obtained from a dichloromethane/hexane solvent
system. The most relevant crystal and refinement data are collected
in Table 1 (Supporting Information).
3
Hz, 2 × 1H, p-cym), 4.87, 5.67 (2d, JHH = 6.0 Hz, 2 × 1H, p-cym),
3
7.07, 7.29 (2d, JHH = 9.2 Hz, 2 × 2H, p-tol). 13C{1H} NMR (100.6
MHz, CDCl3, −30 °C): δ 17.8 (s, C-Me), 18.5, 19.5, 19.9, 20.4 (4s,
Me2CH-P), 21.4 (s, C6H4Me), 21.7, 23.6 (2s, C-CHMe2), 25.2 (d, 1JCP
1
= 22.5 Hz, Me2CH-P), 27.8 (d, JCP = 20.3 Hz, Me2CH-P), 28.4 (d,
2JCP = 11.3 Hz, RuCH2), 30.2 (s, C-CHMe2), 34.1 (d, 1JCP = 22.4 Hz,
2
PCH2), 53.5 (d, JCP = 22.5 Hz, RuCH2CH), 80.6, 85.8, 87.1, 93.3,
111.6, 116.4 (6s, p-cym), 129.6, 130.0, 132.6, 133.4 (4s, C6H4Me).
Conductivity (acetone, 20 °C): Λ = 16 S cm2 mol−1. MS- ESI (m/z):
517 ([M − Cl]+, 100%).
In all cases, diffraction data were recorded on a Oxford Diffraction
Xcalibur Nova (Agilent) single-crystal diffractometer, using Cu Kα
radiation (λ = 1.5418 Å). Images were collected at a 63 mm fixed
crystal−detector distance, using the oscillation method, with 1°
oscillation and variable exposure times per image: 16−50, 6−26, 3.5−
12, and 5−30 s, respectively. The data collection strategy was
calculated with the program CrysAlis Pro CCD.11 Data reduction and
cell refinement was performed with the program CrysAlis Pro RED.11
An empirical absorption correction was applied using the SCALE3
ABSPACK algorithm as implemented in the program CrysAlis Pro
RED.11
Synthesis of [Ru(η5-C9H7){κ2(P,C)-iPr2PCH2CH(SR)CH2}(PPh3)]
(R = Me (13a), iPr (13b), tBu (13c)). When NaOH (0.1 mmol, 0.004
g) and the thiol (0.1 mmol, 0.0124 g) were stirred in THF (10 mL)
for 30 min, the corresponding thiolate was formed. Then, [Ru(η5-
C9H7){κ3(P,C,C)-iPrPCH2CHCH2}(PPh3)][BPh4] (0.05 mmol,
0.048 g) was added. The mixture was stirred at room temperature
for 30 min. Once the reaction was completed, the orange solution was
evaporated to dryness. The residue was extracted with hexane and
filtered. The resulting solution was evaporated to dryness, affording an
orange solid. R = Me (13a): yield 72%; 31P{1H} NMR (121.5 MHz,
C6D6, 20 °C) δ 75.2 (d, 2JPP = 27.5 Hz, iPr2P), 60.8 (d, 2JPP = 27.5 Hz,
PPh3); 1H NMR (400.1 MHz, C6D6, 20 °C) δ 0.79 (dd, 3JH3H = 7.3 Hz,
The software package WINGX12 was used for space group
determination, structure solution, and refinement. The structure of
complex 1-Cl was solved by Patterson interpretation and phase
expansion using DIRDIF.13 For 3-BPh4, 8-BPh4, and 11a-BPh4,
structures were solved by direct methods using SIR2004.14
In the crystal of 8-BPh4 a CH2Cl2 solvent molecule per unit formula
of the complex is present. For 11a-BPh4 electron density peaks could
not be sensibly modeled as solvent and the SQUEEZE/PLATON
algorithm15 was applied.
3
3JHP = 10.4 Hz, 3H, Me2CH-P), 0.98 (dd, JHH = 7.4 Hz, JHP = 14.2
Hz, 3H, Me2CH-P), 1.14 (m, 1H, PCH2), 1.24 (dd, 3JH3H = 7.1 Hz, 3JHP
3
= 11.6 Hz, 3H, Me2CH-P), 1.29 (dd, JHH = 7.2 Hz, JHP = 12.7 Hz,
3H, Me2CH-P), 1.61 (m, 1H, Me2CH-P), 1.75 (m, 1H, RuCH2), 2.11
(s, MeS), 2.25 (m, 2H, Me2CH-P, PCH2), 2.84 (m, 1H, RuCH2), 2.92
(m, 1H, RuCH2CH), 4.73, 5.04 (2s, 2 × 1H, C9H7), 5.10 (t, 3JHH = 2.3
Isotropic least-squares refinement on F2 using SHELXL9716 was
performed. During the final stages of the refinements, all the positional
parameters and the anisotropic temperature factors of all the non-H
atoms were refined and the H atoms were geometrically located and
their coordinates were refined riding on their parent atoms. For 3, the
crystal studied was a racemic twin, the ratio of the twin components
being 0.499(10)/0.511(10).
3
Hz, C9H7), 6.33 (d, JHH = 8.2 Hz, 1H, C9H7), 6.87−7.87 (m, 18H,
C9H7, PPh3); 13C{1H} NMR (100.6 MHz, C6D6, 20 °C) δ 13.1 (m,
Ru-CH2), 14.4 (s, MeS), 18.2, 18.7, 20.5, 21.5, (4s, Me2CH-P), 29.3
1
1
(d, JCP = 19.5 Hz, Me2CH-P), 32.8 (d, JCP = 20.9 Hz, Me2CH-P),
1
2
34.5 (d, JCP = 21.2 Hz, Ru-PCH2), 52.3 (d, JCP = 23.2 Hz, Ru-
CH2CH), 71.1, 71.4 (2d, 2JCP = 7.3 Hz, C9H7), 92.4, 105.5, 108.3 (3s,
C9H7), 122.1−138.8 (C9H7, PPh3); conductivity (acetone, 20 °C) Λ =
27 S cm2 mol−1; MS-ESI (m/z) 637 ([M − SMe]+, 100%). R = iPr
(13b): yield 77%; 31P{1H} NMR (121.5 MHz, C6D6, 20 °C) δ 77.3
2
2
The function minimized was ([∑wFo − Fc2)/∑w(Fo )]1/2, where
2
w = 1/[σ2(Fo ) + (aP)2 + bP] (a and b values are collected in Table 1)
from counting statistics and P = (Max(Fo , 0) + 2Fc2)/3.
2
2
i
2
1
(d, JPP = 27.9 Hz, Pr2P), 60.3 (d, JPP = 27.9 Hz, PPh3); H NMR
Atomic scattering factors were taken from ref 17. The crystallo-
(400.1 MHz, C6D6, 20 °C) δ 0.77 (dd, 3JHH = 7.2 Hz, 3JHP = 10.4 Hz,
graphic plots were made with PLATON.15
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Article
(10) The ADIP ligand was synthesized following the method for
ADPP: Clark, P.; Curtis, J. L. S.; Garrou, P. E.; Hartwell, G. E. Can. J.
ASSOCIATED CONTENT
* Supporting Information
■
S
Chem. 1974, 52̧ 1714−1720.
1H, 31P{1H}, and 13C{1H} NMR spectra for complexes 6+, 9+,
10+, 11a−c+, 12, and 13a−c and CIF files and a table giving X-
ray crystallographic data of 1-Cl, 3-BPh4, 8-BPh4 and 11a-
BPh4 (CCDC: 916383, 1-Cl; 941935, 3-BPh4; 941936, 8-
BPh4; 916384, 11a-BPh4). This material is available free of
charge via the Internet at http://pubs.acs.org.
(11) CrysAlisPro CCD, CrysAlisPro RED; Oxford Diffraction Ltd.,
Abingdon, Oxfordshire, U.K., 2008.
(12) Farrugia, L. J. J. Appl. Crystallogr. 1999, 32, 837−838.
(13) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
García-Granda, S.; Gould, R. O.; Smits, J. M. M.; Smykalla, C. The
DIRDIF Program System; Technical Report of the Crystallographic
Laboratory; University of Nijmegen, Nijmegen, The Netherlands,
1999.
(14) SIR200: Burla, M. C.; Caliandro, R.; Camalli, M.; Carrozzini, B.;
Cascarano, G. L.; De Caro, L.; Giacovazzo, C.; Polidori, G.; Spagna, R.
J. Appl. Crystallogr. 2005, 38, 381−388.
(15) Spek, A. L. PLATON: A Multipurpose Crystallographic Tool;
University of Utrecht, Utrecht, The Netherlands, 2007.
(16) Sheldrick, G. M. SHELXL97: Program for the Refinement of
AUTHOR INFORMATION
Corresponding Author
*E.L.: fax, 34 985103446; e-mail, elb@uniovi.es.
Notes
■
The authors declare no competing financial interest.
Crystal Structures; University of Gottingen, Gottingen, Germany, 2008.
̈
̈
ACKNOWLEDGMENTS
This work was supported by the Spanish Ministerio de
■
(17) Tables for X-Ray Crystallography; Kynoch Press: Birminghan,
U.K., 1974; Vol. IV (present distributor Kluwer Academic Publishers:
Dordrecht, The Netherlands).
Educacio
n y Ciencia (CTQ-2010-17005 and CTQ-2011-
26481) and Consolider Ingenio 2010 (CSD2007-00006).
I.G.d.l.A. thanks the Spanish Ministerio de Educacion Cultura
́
(18) Dıez, J.; Gamasa, M. P.; Gimeno, J.; Lastra, E.; Villar, A. Eur. J.
Inorg. Chem. 2006, 691, 78−87.
́
(19) Barthel-Rosa, L. P.; Maitra, K.; Fischer, J.; Nelson, J. H. Inorg.
Chem. 1998, 37, 633.
y Deporte for a scholarship.
(20) Geary, W. J. Coord. Chem. Rev. 1971, 7, 81−122.
(21) Analyses for the sulfur-containing complexes 11a−c, 12, and
13a−c were not satisfactory, probably due to incomplete combustion.
REFERENCES
■
(1) Julienne, D.; Toulgoat, F.; Delacroix, O.; Gaumont, A.-C. Curr.
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1
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