Trimethylstannyl (diphenylphosphino)acetate: A source of (diphenylphosphino)acetate ligand in the synthesis of coordination compounds

Article abstract of DOI:10.1016/j.jorganchem.2004.07.060

Trimethylstannyl (diphenylphosphino)acetate (1), which is readily accessible from potassium (diphenylphosphino)acetate and trimethylstannyl chloride, may serve as the source of (diphenylphosphino)acetate anion in the preparation of coordination compounds. Thus, the reactions between [M(cod)Cl₂ (M = Pd and Pt; cod = η²:η²-cycloocta-1, 5-diene) and two equivalents of 1 give [M(Ph₂PCH₂ CO₂-κ²O,P)₂] (2 and 3), while the reaction of [{Pd(μ-Cl)Cl(PFur₃)}₂] (4; Fur = 2-furyl) with one equivalent of 1 yields [SP-4-3]-[PdCl(Ph₂ PCH₂CO₂-κ²O,P)(PFur₃)] (5). The reactions of 1 with the dimers [{Rh(η⁵ C₅Me₅)Cl(μ-Cl)}₂] and [{Ru(η⁶-1,4-MeC₆H₄(CHMe₂ Cl(μ-Cl)}₂] (at 1-to-metal ratio 1:1) produce O,P-chelated complexes as well, albeit as stable adducts with the liberated Me₃SnCl: [RhCl(η⁵-C₅Me₅) (Ph₂PCH₂CO₂-κ²O,P)] Me₃SnCl (6) and[RuCl(η⁶-1,4-MeC₆ H₄(CHMe₂))(Ph₂PCH₂ CO₂-κ²O,P)] · Me₃SnCl (8). The related complexes with P-monodentate (diphenylphosphino)acetic acid, [RhCl₂(η⁵-C₅Me₅) (Ph₂PCH₂-CO₂H₂-κ,P)] (7) and [RuCl₂(η⁶-1,4-MeC₆ H₄(CHMe₂))(Ph₂PCH₂ CO₂H-κP)] (9), were obtained by bridge splitting in the dimers with the phosphinocarboxylic ligand. All new compounds were characterized by spectral methods and combustion analyses, and the structures of 2·3CH₂Cl₂, 3, 4, 5, 6 and 8 were determined by X-ray crystallography.

Full text of DOI:10.1016/j.jorganchem.2004.07.060

Journal of Organometallic Chemistry 689 (2004) 3556–3566
www.elsevier.com/locate/jorganchem
Trimethylstannyl (diphenylphosphino)acetate: a source
of (diphenylphosphino)acetate ligand in the synthesis of
coordination compounds
a,b
Petra Zoufala , Robert Gyepes , Petr Stepnicka
a
a,
*
ˇ
´
´
ˇ
ˇ
a
Department of Inorganic Chemistry, Faculty of Science, Charles University, Hlavova 2030, 128 40 Prague, Czech Republic
ˇ
Department of General and Inorganic Chemistry, Faculty of Chemical Technology, University of Pardubice, nam. Cs. legiı 565,
b
´
´
532 10 Pardubice, Czech Republic
Received 19 April 2004; accepted 11 July 2004
Available online 17 September 2004
Abstract
Trimethylstannyl (diphenylphosphino)acetate (1), which is readily accessible from potassium (diphenylphosphino)acetate and tri-
methylstannyl chloride, may serve as the source of (diphenylphosphino)acetate anion in the preparation of coordination com-
pounds.Thus, the reactions between [M(cod)Cl2] (M = Pd and Pt; cod = g2:g2-cycloocta-1,5-diene) and two equivalents of 1 give
[M(Ph2PCH2CO2-j2O,P)2] (2 and 3), while the reaction of [{Pd(l-Cl)Cl(PFur3)}2] (4; Fur = 2-furyl) with one equivalent of 1 yields
[SP-4-3]-[PdCl(Ph2PCH2CO2-j2O,P)(PFur3)] (5).The reactions of 1 with the dimers [{Rh(g5-C5Me5)Cl(l-Cl)}2] and [{Ru(g6-1,4-
MeC6H4(CHMe2))Cl(l-Cl)}2] (at 1-to-metal ratio 1:1) produce O,P-chelated complexes as well, albeit as stable adducts with the
liberated Me3SnCl: [RhCl(g5-C5Me5)(Ph2PCH2CO2-j2O,P)] Æ Me3SnCl (6) and[RuCl(g6-1,4-MeC6H4(CHMe2))(Ph2PCH2CO2-
j2O,P)] Æ Me3SnCl (8). The related complexes with P-monodentate (diphenylphosphino)acetic acid, [RhCl2(g5-C5Me5)(Ph2PCH2-
CO2H-j,P)] (7) and [RuCl2(g6-1,4-MeC6H4(CHMe2))(Ph2PCH2CO2H-jP)] (9), were obtained by bridge splitting in the dimers with
the phosphinocarboxylic ligand. All new compounds were characterized by spectral methods and combustion analyses, and the
structures of 2 Æ 3CH2Cl2, 3, 4, 5, 6 and 8 were determined by X-ray crystallography.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Tin; Phosphines; Phosphinocarboxylic ligands; Palladium; Platinum; Rhodium; Ruthenium; X-ray diffraction
1. Introduction
SnCl3 reacts with palladium and platinum complexes
[ML2Cl2] (M = Pd(II) and Pt(II); L2 = g2:g2-cyclo-
octa-1,5-diene (cod) or (SEt2)2) to give zwitterionic com-
pounds [M+L2(Cl)(Ph2P(CH2)2SnꢀCl4)] at 1:1 molar
metal-to-phosphine ratio, and diphosphine complexes
resulting from the replacement of both labile ligands L
when two equivalents of the phosphine per metal atom
are used. With [PdMe(cod)Cl], the reaction at 1:1 molar
ratio gave a product resulting from transmetallation
from tin to palladium, [Pd+(cod)(Cl) (Ph2P(CH2)2-
SnꢀMeCl3)] [3]. These findings initiated our interest in
the reactivity of phosphinocarboxylic stannyl esters.
First, we focused our interest on the very basic
Organotin monophosphines, e.g. Ph2P(CH2)nSnR3,
usually coordinate to transition metals as monodentate
P-donors [1]. In specific cases, they also provide an ac-
cess to metalacycles involving a tin atom and a P-coor-
dinated transition metal through oxidative addition of
the C–Sn bond across a suitable, low-valent transition
metal precursor compound [2]. Recently, it has been
shown that trichlorostannylphosphine Ph2P(CH2)2-
*
Corresponding author.
E-mail address: stepnic@mail.natur.cuni.cz (P. Stepnicka).
ˇ
ˇ
ˇ
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.07.060

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P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3557
representative, trimethylstannyl (diphenylphosphino)ac-
etate (1). The organotin moiety and the carboxyphos-
phine moieties in 1 are connected by a reactive Sn–O
bond and, hence, the compound may open new syn-
thetic possibilities for the preparation of novel com-
plexes involving this versatile phosphinocarboxylic
ligand [4].
(diphenylphosphino)acetate [10]. Likewise, the reaction
of dipalladium(II) complex 4 in dichloromethane with
two equivalents of 1 gave a yellow solid, which was char-
acterized as an O,P-chelated complex with cis-disposed
phosphine donors, 5, and Me3SnCl as the side product.
Complex 5 apparently results from a bridge splitting
with the carboxyphosphine and chloride transfer to
tin, similarly to the previous cases. The starting bridged,
trans-diphosphine complex 4 was obtained as a bright
orange solid from the reaction of the stoichiometric
amounts of tri(2-furyl)phosphine and Na2[PdCl4]
according to a general procedure in ref. [11].
2. Results and discussion
2.1. Syntheses and spectra
Similar transfer of (diphenylphosphino)acetate from
1 to a transition metal occurs also with chloride bridged
dimers [{Rh(g5-C5Me5)Cl(l-Cl)}2] and [{Ru(g6-1,4-
MeC6H4(CHMe2))Cl(l-Cl)}2]. However, unlike the
above cases, these reactions produce adducts of the
O,P-chelated products with the liberated Me3SnCl:
[RhCl(g5-C5Me5)(Ph2PCH2CO2-j2O,P)] Æ Me3SnCl (6)
Trimethylstannyl (diphenylphosphino)acetate (1) was
obtained as a white solid from salt metathesis between
trimethylstannyl chloride and potassium (diph-
enylphosphino)acetate, which was generated only in situ
by reacting (diphenylphosphino)acetic acid with one
molar equivalent of potassium tert-butoxide. The com-
pound exhibits typical strong carboxylate bands in the
IR spectra at 1574 and 1554 cmꢀ1, which are shifted
to lower energies than for the parent acid (1700 cmꢀ1
[5]), sodium (diphenylphosphino)acetate (1595 cmꢀ1
[5]), and even for ethyl (diphenylphosphino)acetate
and
[RuCl(g6-1,4-MeC6H4(CHMe2))(Ph2PCH2CO2-
j2O,P)] Æ Me3SnCl (8) (Scheme 2). The tin atom in the
adducts is coordinated with the carbonyl oxygen of the
chelating carboxylate and thus acquires a coordination
number of five and the regular trigonal-bipyramidal
geometry.
1
(1728 cmꢀ1 [6]). In H and 13C NMR spectra, 1 shows
typical 117/119Sn satellites (SnMe3) and splittings due to
the phosphorus atom. The 31P and 119Sn NMR spectra
rule out any tin-phosphorus interaction by showing,
respectively, a single resonance close to the parent acid
(dP 1, ꢀ16.3; the acid, ꢀ15.1 [7]) and a signal at dSn
140.1, which is similar to organic trimethylstannyl carb-
oxylates (cf. dSn 129 for MeCO2SnMe3 and 150 for
HCO2SnMe3 [8,9]).
The stannyl ester 1 reacts with a half molar equiva-
lent of [M(cod)Cl2] (M = Pd and Pt) under substitution
of the diene ligand with a concurrent chloride transfer
from palladium to tin (a formal transmetallation) to give
Me3SnCl and chelated complexes cis-[M(Ph2PCH2CO2-
j2O,P)2], M = Pd (2), and Pt (3) (Scheme 1), which have
been previously synthesized from K2[MCl4] and sodium
Adduct formation is best reflected by 119Sn NMR
spectra: the tin resonances of 6 and 8 are shifted from
the region expected for tetracoordinated organotin com-
pounds (Me3SnCl: dSn ca. 164 in CDCl3 [12]) to higher
fields, i.e. towards values typical for pentacoordinated
tin compounds (cf. Me3SnCl Æ L, dSn: L = dmso, +3
(in dmso-d6) [12], and dSn 110–137 for 2–72 mol%
Me3SnCl in acetone [8]). A different extent of this
high-field shift in 6 (dSn 85.7) and 8 (dSn 127.2) most
likely corresponds with the strength of the C = O ! Sn
donation and, consequently, with the nature of the
bonding between the carboxylate and the central atom.
The donation from the carboxylate carbonyl group is re-
flected also by a lowering of the frequency due to the
carboxylate bands in IR spectra, the magnitude of the
Ph
P
Ph
P
Ph
Ph
+ 2 1
[MCl (cod)]
M
2
- 2 Me SnCl
3
O
O
O
O
- co d
M = Pd (2), Pt (3)
Ph
P
Ph
Cl
Cl
Cl
(Fur) P
(Fur )P
3
3
1
_
2
+ 1
Pd
Pd
Pd
- Me SnCl
3
P(Fur)
Cl
O
Cl
O
3
4
5
Scheme 1.

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P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3558
(Ph2PCH2CO2H-jP)] (7) and [RuCl2(g6-1,4-MeC6H4-
(CHMe2))(Ph2PCH2CO2H-jP)] (9), which were synthe-
sized by bridge splitting reactions from the above
mentioned dimeric precursors (Scheme 2; HA =
Ph2PCH2CO2H). Due to a poor solubility in halogen-
ated solvents, the NMR spectra of complexes 7 and 8
were recorded in dmso-d6, which prevents a direct com-
parison of NMR spectral data in the pairs 6–7 and 8–9.
Nevertheless, when neglecting a possible solvent effect
on the 31P NMR resonance of the metal bonded phos-
phine group, there is a shift to lower field on going from
P-bonded acid to O,P-bonded carboxylated, much smal-
ler for the rhodium(I) complexes than for their ruthe-
nium(II) analogues. In IR spectra of 7 and 9, the
bands of the carboxyl group (both 1690 cmꢀ1) are ob-
served at nearly the same position as for the free pho-
sphinocarboxylic acid (see above), indicating that the
carboxyl groups do not participate in coordination.
1
Ph
Rh
Cl
P
Ph
O
O
Me
Sn
Me
[{(C Me )RhCl } ]
2 2
5
5
Cl
Me
6
HA
Ph
Rh
Cl
P
Ph
Cl
CO H
2
7
2.2. The molecular structures of palladium and platinum
complexes
1
Ph
Ph
The structures of phosphinoacetate complexes
2 Æ 3CH2Cl2 (Fig. 1, Table 1), 3 (Fig. 2, Table 1), and 5
(Fig. 3, Table 2) as determined by X-ray crystallography
are rather unexceptional, corroborating the cis-P–P,
square-planar coordination geometries in all cases. The
solvated complex 2 Æ 3CH2Cl2 crystallizes in a centro-
symmetric triclinic unit cell, different from the mono-
clinic cell of unsolvated 2; however, the molecular
geometries of both solvatomorphs do not differ noticea-
bly [13]. Likewise, the arrangements of the
Ru
Cl
P
O
O
Me
Cl
Sn
Me
[{(p-cymene)RuCl } ]
2 2
Me
8
HA
Ph
Ph
Ru
Cl
P
Cl
CO H
2
9
Scheme 2.
C10
C30
C29
shift being in agreement with the trend in dSn values (6,
1569; 8, 1580 cmꢀ1). Notably, the adducts are firmly
bonded; for instance, compound 8 was recovered un-
changed even after treating its dichloromethane solution
with a large excess of pyridine.
C9
C1
P2
P1
C21
C24
Complexes 6 and 8 are chiral at the metal atoms, pos-
sessing the expected three-legged piano stool structures
with the stereogenic metal atoms surrounded by the p-
ligand, the O,P-coordinated phosphinocarboxylate,
and the terminal chloride ligand, and result as racemic
mixtures. The presence of the chiral center renders the
protons of the PCH2 group in 6 and 8 as well as the
CH resonances of the arene ligand in 8 diastereotopic
and anisochronic in the NMR spectra. This is not ob-
served for analogous achiral complexes with P-bonded
(diphenylphosphino)acetic acid: [RhCl2(g5-C5Me5)
C23
C4
C3
Pd
C2
C22
O2
O21
O1
O22
Fig. 1. A view of the molecular structure of complex 2 Æ 3CH2Cl2.
Thermal motion ellipsoids are drawn with 30% probability. The
solvent molecules are omitted for clarity.

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P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3559
Table 1
˚
Selected geometric parameters for 2 Æ 3CH2Cl2 and 3 (in A and ꢁ)
C21
Compound
M
2 Æ 3CH2Cl2
Pd
3
Pt
C22
C4
C20
M–P(1)
M–P(2)
M–O(2)
2.220(1)
2.217(1)
2.081(3)
2.073(3)
1.826(6)
1.825(5)
1.530(8)
1.221(7)
1.297(7)
1.510(7)
1.224(6)
1.298(6)
2.2142(8)
2.2070(9)
2.069(2)
2.074(2)
1.824(3)
1.818(3)
1.533(4)
1.222(4)
1.305(4)
1.529(4)
1.227(4)
1.298(4)
O4
C16
C19
C15
P2
C3
M–O(22)
P(1)–C(1)
P(2)–C(21)
C(1)–C(2)
C(2)–O(1)
C(2)–O(2)
C(21)–C(22)
C(22)–O(21)
C(22)–O(22)
C1
C17
Pd
P1
C2
O1
O2
O5
C23
C9
Cl
C18
O3
C10
C26
C24
C25
P(1)–M–P(2)
P(1)–M–O(2)
102.82(5)
81.58(9)
83.88(8)
91.7(1)
105.05(3)
83.03(6)
82.68(6)
89.18(8)
109.0(2)
108.8(2)
116.2(2)
117.0(3)
123.1(3)
122.5(3)
P(2)–M–O(22)
O(2)–M–O(22)
P(1)–C(1)–C(2)
P(2)–C(21)–C(22)
C(1)–C(2)–O(2)
C(21)–C(22)–O(22)
O(1)–C(2)–O(2)
O(21)–C(22)–O(22)
Fig. 3. A view of the molecular structure of complex 5. Thermal
motion ellipsoids are drawn with 30% probability.
108.2(4)
111.6(3)
116.0(4)
115.6(4)
124.0(5)
123.2(5)
Table 2
a
˚
Selected intratomic distances and angles for 5 (in A and ꢁ)
Pd–Cl
2.334(2)
2.235(2)
2.234(2)
2.075(6)
Cl–Pd–P(2)
Cl–Pd–O(2)
P(1)–Pd–P(2)
P(1)–Pd–O(2)
88.18(8)
90.1(2)
99.85(8)
82.2(2)
Pd–P(1)
Pd–P(2)
Pd–O(2)
P(1)–C(1)–C(2)–O(2)
P(2)–C(21)–C(22)–O(22)
ꢀ27.6(5)
ꢀ27.6(3)
ꢀ25.1(3)
27.0(5)
P(1)–C(1)
C(1)–C(2)
C(2)–O(1)
C(2)–O(2)
a
1.824(8)
1.53(1)
P(1)–C(1)–C(2)
C(1)–C(2)–O(1)
C(1)–C(2)–O(2)
O(1)–C(2)–O(2)
108.8(5)
123.2(5)
120.6(5)
116.1(4)
1.215(7)
1.298(6)
Further data: P(1)–C(3) 1.814(4), P(1)–C(9) 1.804(3), P(2)–C(15)
˚
1.80(1), P(2)–C(19) 1.774(8), P(2)–C(23) 1.77(1) A; P(1)–C(1)–C(2)–
C10
C9
C30
C29
O(2) ꢀ29.2(6)ꢁ.
the coordination polyhedra at the edge accommodating
the phosphorus ligands. This is compensated by a clo-
sure of the remaining interligand angles, though without
an observable tetrahedral deformation. A similar but
less pronounced deformation is observed also for 5.
The compounds exhibit interesting intermolecular
interactions: the molecules of 2 are connected via offset
pꢁ ꢁ ꢁp interactions of exactly parallel phenyl rings C(3–
8): Phꢁ ꢁ ꢁPh & (2 ꢀ x, 1 ꢀ y, 1 ꢀ z), at a ring centroid dis-
C23
Pt
P1
C2
C1
P2
C4
C21
C22
C3
O2
C24
O21
O22
O1
˚
˚
tance of 3.883(4) A (interplanar separation 3.70 A). The
individual molecules feature similar, though intramolecu-
lar interactions between the aromatic rings C(9–14) and
Fig. 2. A view of the molecular structure of complex 3. Thermal
motion ellipsoids are drawn with 30% probability.
˚
C(29–34) (Cgꢁ ꢁ ꢁCg 3.671(3) A), which are mutually ro-
tated by only ca. 19 ꢁ. The molecules of complex 3 also
associate predominantly via graphite-like pꢁ ꢁ ꢁp stacking
of parallel aromatic rings (Fig. 4). The orientation of the
neighbouring phenyl rings C(9–14) and C(23–28), which
seems to stabilize the conformation of 2, is less favoura-
ble in 3: the distance of the ring centroids is as long as
M(Ph2PCH2CO2-j2O,P) motifs (M = Pd and Pt), i.e.,
the respective bond distances and angles, and the con-
formation at the PC–CO2 bond, in all the O,P-chelated
complexes 2 Æ 3CH2Cl2, 3, and 5 are similar to each
other, and to those in unsolvated
2
and
[PtBr(Ph2PCH2CO2-j2O,P)(Ph2PCH2CO2H-jP)] Æ H2O
[14]. The cis-arrangement of the bulky phosphino
groups in 2 Æ 3CH2Cl2 and 3 results in an opening of
5.057(2) A and the planes are tilted (the dihedral angle
of the ring planes amounts to 25ꢁ). In additon to the
mentioned p-interactions, the molecules of complex 3
˚

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P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3560
1
a
3
2
1
0,b
c
Fig. 4. A view of the crystal packing of 3 along the crystallographic b axis. The pꢁ ꢁ ꢁp interactions are indicated as dotted lines. Selected parameters
for the interactions:
˚
˚
Interplanar distance (A)
Code
Phenyl ring
Cgꢁ ꢁ ꢁCg (A)
3.664(2)
4.359(2)
4.995(2)
1
2
3
C(29–34)ꢁ ꢁ ꢁC(29–34)i
C(3–8)ꢁ ꢁ ꢁC(3–8)ii
3.41
3.42
4.95
C(9–14)ꢁ ꢁ ꢁC(9–14)iii
The rings are exactly parallel due to the crystallographic symmetry. Symmetry codes: (i) 1 ꢀ x, 1 ꢀ y, ꢀz; (ii) 1 ꢀ x, ꢀy, 1 ꢀ z; (iii) 1 ꢀ x, 1 ꢀ y, 1 ꢀ z.
Cg denotes the ring centroid.
are involved in weak, intermolecular C–Hꢁ ꢁ ꢁO hydrogen
bonding to carboxylate oxygen atoms.
pendent. The coordination environment around the pal-
ladium atoms are almost perfectly planar and the
interligand angles do not differ much from the right an-
gle. Distances from palladium to bridging chloride lig-
ands are slightly elongated (significantly with respect
to esd) when compared to the bond length to the termi-
nal chloride (relatively by 2 and 6% for Cl(1) and Cl(1)ii,
respectively; ii: 2 ꢀ x, 1 ꢀ y, ꢀz). The crystal packing of
4 shows no significant intermolecular contacts except for
offset pꢁ ꢁ ꢁp stacking of the parallel furane rings involv-
ing O(3) oxygen atom, the respective ring centroid and
The solid-state assembly of 5 is analogous to the pac-
kings of the bis(chelated) complexes since the molecules
of the complex associate to centrosymmetric dimers via
pꢁ ꢁ ꢁp stacking of the phenyl rings C(3–8) (Cgꢁ ꢁ ꢁCgi
˚
˚
3.821(2) A, interplanar separation 3.63 A; i: 1 ꢀ x,
1 ꢀ y, 1 ꢀ z). The molecular network is further intercon-
nected by intermolecular C–Hꢁ ꢁ ꢁO hydrogen bonds to
carboxylate [O(1) and O(2)] and furane oxygen [O(4)]
˚
atoms (Cꢁ ꢁ ꢁO 3.23(1)ꢀ3.488(6) A).
The molecule of the dimer 4 (Fig. 5, Table 3) resides
on the crystallographic inversion centre, which renders
only the half of the molecule crystallographically inde-
interplanar distances being Cgꢁ ꢁ ꢁCgiii 3.713(2) A and
˚
˚
ca. 3.45 A; iii: 1 ꢀ x, ꢀy, ꢀz. The other furane rings
stack as well but at much longer distances, cf. Cgꢁ ꢁ ꢁCgiv

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P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3561
C7
C16
Cl1
C15
C6
C8
C20
Cl1’
P’
C21
Cl2
C9
Rh
Pd’
C5
Pd
C4
C3
O2
O1
C4
Cl1
P
Cl2’
C1
C2
P
O2
C9
C3
C26
C1
C2
O1
O3
C10
C11
C10
C12
C27
Sn
Cl2
Fig. 5. A view of the molecular structure of complex 4. Thermal
motion ellipsoids are drawn with 30% probability.
C25
v
˚
˚
4.077(1) A for the ring involving O(2), and Cgꢁ ꢁ ꢁCg
Fig. 6. A view of the molecular structure of adduct 6. Thermal motion
ellipsoids are drawn with 30% probability.
5.832(2) A for the ring involving O(1) [iv: 1 ꢀ x, ꢀy,
1 ꢀ z; v: (2 ꢀ x, ꢀy, 1 ꢀ z].
2.3. The molecular structures of the adducts 6 and 8
C23
The views of the molecular structures of 6 and 8 are
shown in Figs. 6 and 7, and the selected geometric data
are given in Tables 4 and 5. Adduct 8 forms racemic
crystals, which accommodate equal numbers of the
enantiomeric molecules within the centrosymmetric unit
cells (monoclinic P21/n). In the case of 6, a chiral crystal
with an orthorhombic P212121 symmetry was selected
from the racemic reaction batch. The structure refine-
ment revealed an (S)-configuration at the stereogenic
rhodium atom.
The compounds possess similar pseudotetrahedral
structures as proposed from the spectral data. In both
compounds, the steric hindrance between the p-ligand
and the bulky diphenylphosphino group causes the
Cg–M–P angles (Cg is the centroid of the aromatic lig-
and, M = Rh or Ru) to be more opened that the other
C21
C22
C15
C16
C18
C20
C17
C19
Cl1
Ru
C24
O2
C27
Sn
Cl2
C26
P
C3
C2
C9
C1
C10
O1
C4
C25
Fig. 7. A view of the molecular structure of adduct 8. Thermal motion
ellipsoids are drawn with 30% probability.
Table 3
a
˚
Selected intratomic distances and angles for 4 (in A and ꢁ)
Pd–Cl(1)
Pd–Cl(2)
Pd–Cl(1)i
Pd–P
Pdꢁ ꢁ ꢁPdi
2.3268(5)
2.2793(5)
2.4230(6)
2.2141(6)
3.4853(2)
Cl(1)–Pd–P
Cl(1)–Pd–Cl(1)i
Cl(2)–Pd–P
Cl(2)–Pd–Cl(1)i
Pd–Cl(1)–Pdi
93.32(2)
85.61(2)
87.39(2)
93.64(2)
94.39(2)
P–C(1)
1.792(2)
1.358(3)
1.371(3)
1.343(4)
1.429(4)
1.327(4)
P–C(5)
1.772(2)
1.374(3)
1.369(3)
1.352(3)
1.425(4)
1.336(4)
P–C(9)
1.785(2)
1.374(3)
1.371(3)
1.347(4)
1.424(3)
1.337(4)
O(1)–C(1)
O(1)–C(4)
C(1)–C(2)
C(2)–C(3)
C(3)–C(4)
a
O(2)–C(5)
O(2)–C(8)
C(5)–C(6)
C(6)–C(7)
C(7)–C(8)
O(3)–C(9)
O(3)–C(12)
C(9)–C(10)
C(10)–C(11)
C(11)–C(12)
Symmetry operations: (i) 2 ꢀ x, 1 ꢀ y, ꢀz.

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P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3562
˚
Table 4
tance in 6 is by ca. 0.015 A shorter than in 8,
which is in accordance with the spectral data (see
above).
a
˚
Selected intratomic distances and angles for 6 (in A and ꢁ)
Rh–Cg
Rh–Cl(1)
Rh–P
1.807(3)
2.395(2)
2.299(2)
2.143(3)
5.7286(6)
1.820(6)
1.807(6)
1.815(6)
1.515(8)
1.245(6)
1.273(7)
Cg–Rh–Cl(1)
Cg–Rh–P
125.33(9)
135.2(1)
124.89(2)
86.04(6)
89.2(2)
Cg–Rh–O(2)
Cl(1)–Rh–P
Rh–O(2)
Rhꢁ ꢁ ꢁSn
P–C(1)
3. Experimental
Cl(1)–Rh–O(2)
P–Rh–O(2)
80.9(1)
P–C(3)
P–C(9)
P–C(1)–C(2)
O(1)–C(2)–O(2)
O(1)–C(2)–C(1)
O(2)–C(2)–C(1)
110.3(4)
124.2(5)
118.0(5)
117.7(4)
3.1. Materials and methods
C(1)–C(2)
C(2)–O(1)
C(2)–O(2)
All syntheses were carried out under argon blanket.
Dichloromethane was dried over anhydrous potassium
carbonate. Solvents for crystallizations were used with-
out purification (p.a. quality). (Diphenylphosphino)acetic
acid [5], [Pd(cod)Cl2], [Pt(cod)Cl2] [18], and [{Rh(g5-
C5Me5)Cl(l-Cl)}2] [19] were synthesized according to
the literature methods. Other chemicals were commer-
cial products and were used as obtained from the suppli-
ers (Strem, Aldrich, and Fluka).
Snꢁ ꢁ ꢁO(1)
Sn–Cl(2)
Sn–C(25)
Sn–C(26)
Sn–C(27)
a
2.357(4)
2.561(2)
2.106(5)
2.109(7)
2.116(7)
C(2)–O(1)ꢁ ꢁ ꢁSn
O(1)–Sn–Cl(2)
Cl(2)–Sn–Meb
O(1)–Sn–Meb
Me–Sn–Meb
130.9(4)
176.7(1)
91.2(2)–93.9(2)
84.4(2)–92.0(2)
117.1(3)–125.6(3)
Cg is the centroid of the cyclopentadienyl ring C(15–19).
Me = C(25), C(26), and C(27).
b
NMR spectra were recorded on a Varian UNITY In-
ova 400 spectrometer (1H, 399.95; 13C, 100.58; 31P,
161.9; 119Sn 149.14 MHz) at 298 K. Chemical shifts
(d/ppm) are given relative to internal tetramethylsilane
(1H and 13C), external 85% aqueous H3PO4 (31P), and
external neat SnMe4 (119Sn). IR spectra were recorded
on an a Perkin–Elmer 684 FT IR spectrometer in the
Table 5
Selected intratomic distances and angles for 8 (in A and ꢁ)
a
˚
Ru–Cg
Ru–Cl(1)
Ru–P
1.700(1)
2.4063(6)
2.3185(8)
2.100(2)
5.3491(3)
1.826(3)
1.813(3)
1.815(3)
1.517(4)
1.254(3)
1.275(3)
Cg–Ru–Cl(1)
Cg–Ru–P
129.38(4)
132.51(4)
127.12(7)
86.45(2)
84.65(5)
79.14(6)
108.0(2)
122.3(3)
119.2(2)
118.5(2)
Cg–Ru–O(2)
Cl(1)–Ru–P
Ru–O(2)
Ruꢁ ꢁ ꢁSn
P–C(1)
range of 400–4000 cmꢀ1
.
Cl(1)–Ru–O(2)
P–Ru-O(2)
P–C(3)
P–C(9)
P–C(1)–C(2)
O(1)–C(2)–O(2)
O(1)–C(2)–C(1)
O(2)–C(2)–C(1)
3.2. Preparation of trimethylstannyl (diphenylphosph-
ino)acetate (1)
C(1)–C(2)
C(2)–O(1)
C(2)–O(2)
Potassium tert-butoxide (0.7322 g, 6.52 mmol) was
added into a solution of (diphenylphosphino)acetic
acid (1.532 g, 6.27 mmol) in dichloromethane (10
mL). After stirring the resulting suspension for 1 h at
room temperature, a solution of Me3SnCl (1.251 g,
6.27 mmol) in dichloromethane (10 mL) was intro-
duced and stirring was continued overnight (the sus-
pension dissolved quickly upon addition; however,
the formation of a white precipitate started simultane-
ously). Then, the reaction mixture was diluted with
equal volume of hexane and, after standing for 1 h, fil-
tered. The filtrate was evaporated and the solid residue
dried under vacuum to give 1 as an off-white solid
(1.684 g, 66%).
Snꢁ ꢁ ꢁO(1)
Sn–Cl(2)
Sn–C(25)
Sn–C(26)
Sn–C(27)
a
2.372(2)
2.5440(9)
2.121(3)
2.133(3)
2.130(3)
C(2)–O(1)ꢁ ꢁ ꢁSn
O(1)–Sn–Cl(2)
Cl(2)–Sn–Meb
O(1)–Sn–Meb
Me–Sn–Meb
120.5(2)
175.52(5)
91.5(1)–95.2(1)
85.2(1)–92.3(1)
115.7(1)–126.0(1)
Cg is the centroid of the g6-arene ring C(15–20).
b
Me = C(25), C(26), and C(27).
two Cg–M–donor angles. This deformation is larger in
the rhodium(I) complex 6, bearing the bulky pentameth-
ylcyclopentadienyl ligand. The geometry around the
ruthenium atom in 8 does not differ significantly from
that in an analogous complex with chelating ferrocene-
carboxylate, (RRu,Sp)-chloro-(g6-p-cymene)-{2-(diph-
enylphosphino)ferrocenecarboxylate-j2O,P}ruthe-
nium(II) [4b].
1H NMR (CDCl3): d 0.43 (s with tin satellites:
2
2J119SnH = 58.5, J117SnH = 56.0 Hz, 9H, SnMe3), 3.14
(s, 2H, CH2), 7.29–7.49 (m, 10H, PPh2). 13C{1H}
The arrangements around tin atoms in 6 and 8 are
trigonal-bipyramidal with the bond angles deviating
only slightly from the theoretical ones. The Snꢁ ꢁ ꢁO(1)
separation in both compounds roughly correspond to
the distances observed for solid adducts Me3Sn-
NMR (CDCl3):
d
ꢀ2.49 (s with tin satellites:
1J119SnC = 396, J117SnC = 377 Hz, SnMe3), 35.87 (d,
1JPC = 20 Hz, CH2), 128.39 (d, JPC = 7 Hz), 128.78 (s),
132.69 (d, JPC = 20 Hz) (3· CH of PPh2); 137.93 (d,
1
1JPC = 14 Hz, Cipso of PPh2), 175.49 (d, JPC = 8 Hz,
2
Cl Æ O = C(Me)CH = PPh3 (Snꢁ ꢁ ꢁO 2.332 A [15]) and
COO). 31P{1H} NMR (CDCl3): d ꢀ16.3 (s). 119Sn{1H}
NMR (CDCl3): d 140.1 (s). IR (Nujol): ~m=cmꢀ1 1574 s,
1554 s, 1192 w, 1147 w, 1100 w, 860 m 774 m, 740 s,
696 s, 556 m, 546 m, 507 m, 486 m, 429 m. Anal. Calcd.
˚
Ph3SnL Æ L,
where
L = N,NN0N0-tetramethylurea
˚
˚
(2.384 A [16]), e-caprolactone (2.399 A), and diph-
enylcyclopropenone (2.510 A [17]). The Snꢁ ꢁ ꢁO dis-
˚

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P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3563
for C17H21O2PSn: C, 50.16; H, 5.20%. Found: C, 50.07;
H, 5.40%.
1H NMR (CDCl3): d 6.55 (br dt, J ꢂ 1.9, 1.3 Hz, 1H),
7.34 (br d, J ꢂ 3.3 Hz, 1H), 7.77 (br s, 1H) (3·CH of
Fur). 13C{1H} NMR (CDCl3): d 111.74 (d, JPC = 9
Hz), 127.50 (d, JPC = 23 Hz) (3· CH of Fur); 138.10
3.3. The reaction of 1 with [Pd(cod)Cl2]
1
(d, JPC = 99 Hz, Cipso of Fur), 149.78 (d, JPC = 5 Hz,
[PdCl2(cod)] (57 mg, 0.20 mmol) and 1 (179 mg,
0.44 mmol) were dissolved in dichloromethane
(10 mL) and the clear was mixture stirred for 3 days
at room temperature, whereupon it deposited a yellow-
ish solid. The mixture was cooled in a refrigerator
(ꢀ18 ꢁC) overnight, the solid was filtered off, washed
well with diethyl ether and dried under vacuum to af-
ford cis-bis{(diphenylphosphino)acetate-j2P,O}palla-
dium(II) (2) as a yellowish microcrystalline solid.
Yield: 97 mg (82%).
CH of Fur). 31P{1H} NMR (CDCl3): d ꢀ25.5 (s). Anal.
Calcd. for C24H18Cl4O6P2Pd2: C, 35.20; H, 2.22%.
Found: C, 34.96; H, 2.44%.
3.6. The reaction of 1 with 4
A solution of 1 (82 mg, 0.20 mmol) in dichloromethane
(3 mL) was added to a solution of 4 (82 mg, 0.10 mmol) in
the same solvent (5 mL), and the reaction mixture was
stirred for two days at room temperature. Then, it was
evaporated under reduced pressure, and the solid residue
was washed thoroughly with diethyl ether and dried un-
der vacuum to give [SP-4-3]-chloro-{(diphenylphosph-
ino)acetate-j2P,O}-tri(2-furyl)phosphinepalladium(II)
(5) as a yellowish microcrystalline solid (103 mg, 84%).
The compound can be further purified by dissolving in
2
1H NMR (CD2Cl2): d 3.60 (d, JPH = 12.5 Hz, 2H,
CH2), 7.26–7.54 (m, 10 H, PPh2). 31P{1H} NMR
ꢀ1
~
(CD2Cl2): d 13.7 (s). IR (Nujol): m=cm 1652 vs, 1626
vs, 1604 vs, 1300 s, 1100 s, 998 m, 914 m, 904 m, 863
m composite, 745 s, 739 s, 694 s, 532 m, 500 m.
3.4. The reaction of 1 with [Pt(cod)Cl2]
dichloromethane and precipitation with hexane.
2
1H NMR (CD2Cl2):
d
3.57 (dd, JPH = 11.9,
[PtCl2(cod)] (75 mg, 0.20 mmol) and 1 (179 mg, 0.44
mmol) were reacted as described in Sect. 3.3 The isola-
tion as above gave cis-bis{(diphenylphosphino)acetate-
j2P,O}platinum(II) (3) as a fine, white solid. Yield: 95
mg (70%).
4JPH = 1.0 Hz, 2H, CH2), 6.39 (dt, J = 3.6, 1.8 Hz, 3H,
Fur), 7.03 (ddd, J ꢂ 2.9, 2.0, 0.4 Hz, 3H, Fur), 7.38–
7.64 (m, 13H, PPh2 and Fur). 13C{1H} NMR (CD2Cl2):
1
3
d 43.22 (dd, JPC = 35, JPC = 2 Hz, CH2), 112.03 (d,
1
JPC = 8 Hz, CH of Fur), 125.46 (dd, JPC = 57,
2
1H NMR (CD2Cl2): d 3.47 (d, JPH = 11.5 Hz, 2H,
3JPC = 2 Hz, Cipso of PPh2), 126.61 (d, JPC = 21 Hz,
CH of Fur), 129.66 (d, JPC = 11 Hz, CH of PPh2),
132.88 (d, JPC = 3 Hz, CH of PPh2), 133.60 (d,
CH2), 7.25–7.50 (m, 10H, PPh2). 31P{1H} NMR
(CD2Cl2): d ꢀ12.1 (s with 195Pt satellites, JPtP = 3404
1
1
ꢀ1
~
Hz). IR (Nujol): m=cm 1664 vs, 1628 vs, 1609 vs,
1101 s, 906 m, 862 s, 738 s, 693 m, 501 m.
JPC = 11 Hz, CH of PPh2), 140.25 (dd, JPC = 94,
3JPC = 2 Hz, Cipso of Fur), 149.40 (d, JPC = 6 Hz, CH
2
of Fur), 175.20 (dd, JPC = 10, JPC = 2 Hz, CO2).
3
2
3.5. Preparation of trans-bis{(l-chloro)chloro-tri
(2-furyl)phosphinepalladium(II)} (4)
31P{1H} NMR (CD2Cl2): d ꢀ22.2 (d, JPP = 6 Hz,
PFurꢀ3)1, 18.2 (d, 2JPP = 6 Hz, Ph2PCH2CO2). IR (Nujol):
~
m=cm 1645 vs composite, 1553 m, 1290 s, 1133 m, 1122
Na2[PdCl4] (294 mg, 1.0 mmol) was dissolved in
warm (ca. 50 ꢁC) absolute ethanol (25 mL), the solution
was filtered, and the filtrate mixed with a solution of
tri(2-furyl)phosphine (233 mg, 1.0 mmol) in chloroform
(25 ml). The reaction flask was flushed with argon and
the mixture was heated to reflux for 90 min. Then, it
was cooled to room temperature, the solvent was re-
moved under reduced pressure, and the solid residue
was taken up with little chloroform, transferred on a
glass frit, and washed with the same solvent until the fil-
trate remained colourless (from bright yellow-orange,
ca. 30 mL). The product was precipitated from the fil-
trate by adding hexane (ca. 100 mL), filtered off and
dried under vacuum (80 ꢁC/1 Torr/2 h). Yield: 361 mg
(88%), rusty orange powder. (Note: well-developed,
bright orange red microcrystals of 4 can be obtained
when the dichloromethane extract is layered with hexane
and the mixture allowed to crystallize by diffusion for
several days.)
m, 1106 m, 1016 m, 907 m, 882 m, 856 m, 773 s, 745 s,
695 m, 554 s, 536 s, 522 s, 494 s. Anal. Calcd. for
C26H21ClO5P2Pd: C, 50.59; H, 3.42%. Found: C,
50.37; H, 3.69%.
3.7. The reaction of 1 with [{Rh(g5-C5Me5)Cl(l-Cl)}2]
[{Rh(g5-C5Me5)Cl(l-Cl)}2] (54 mg, 0.087 mmol) and
1 (71 mg, 0.174 mmol) were dissolved in dichlorometh-
ane (5 mL). The resulting clear solution was stirred
overnight and layered with hexane. Crystallization by
liquid-phase diffusion over several days afforded
chloro-{(diphenylphosphino)acetate-j2P,O}(g5-penta-
methylcyclopentadienyl)rhodium(I)-trimethylstannyl
chloride (1/1) (6) as well-developed red crystals
(111 mg, 90%).
1H NMR (CDCl3): d 0.71 (s with tin satellites,
2
2J119SnH = 63.7, J117SnH = 60.9 Hz, 9H, SnMe3), 1.53
3
(d, JRhH or JPH = 3.6 Hz, 15 H, C5Me5), 3.31 (ddd,
4

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P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3564
2
3
2JHH = 16.1, JPH = 9.9 Hz, JRhH = 0.5 Hz, 1H, CH2),
trimethylstannyl chloride adduct (1/1) (8) that formed
after standing for several days, were filtered off and dried
in air. Yield: 73 mg (51%).
2
2
3.67 (dd, JHH = 16.1, JPH = 10.3 Hz, 1H, CH2), 7.27–
7.65 (m, 10 H, PPh2). 13C{1H} NMR (CDCl3): d 1.10
(SnMe3), 8.99 (Me of C5Me5), 39.77 (d, JPC = 34 Hz,
1
1H NMR (CDCl3): d 0.69 (s with tin satellites,
CH2), 98.15 (dd, JRhC/2JPC ꢂ 3 and 8 Hz, Cipso of
2J119SnH = 61.0, J117SnH = 58.3 Hz, 9H, SnMe3), 1.08,
1
2
1
2
3
C5Me5), 125.51 (dd, JPC = 42 Hz, JRhC unresolved,
Cipso of PPh2), 129.00 (d, JPC = 11 Hz), 129.09 (d,
JPC = 10 Hz), 131.07 (d, JPC = 9 Hz), 131.32 (d,
JPC = 2 Hz), 132.22 (d, JPC = 2 Hz) (5· CH of PPh2);
1.22 (2· d, JHH = 6.9 Hz, 3H, CHMe2), 1.94 (s, 3H,
Me), 2.56 (septuplet, JHH = 6.9 Hz, 1H, CHMe2),
3
2
3.08 (dd, JHH = 16.2, JPH = 12.4 Hz, 1H, CH2), 3.37
2
2
2
(dd, JHH = 16.2, JPH = 10.5 Hz, 1H, CH2), 5.12–5.64
(m, 4H, C6H4), 7.38–7.72 (m, 10 H, PPh2). 13C{1H}
NMR (CDCl3): d 0.17 (SnMe3), 18.10, 22.07, 22.19
1
132.75 (d, JPC = 42 Hz, Cipso of PPh2), 134.78 (d,
2
JPC = 11 Hz, CH of PPh2); 178.25 (d, JPC = 9 Hz,
COO). 31P{1H} NMR (CDCl3): d 29.7 (d, JRhP = 133
(Me and CHMe2); 30.49 (CHMe2), 35.77 (d, JPC = 34
1
1
Hz). 119Sn{1H} NMR (CDCl3): d 85.7 (s). IR (Nujol):
2
Hz, CH2), 84.86 (d, JPC = 3 Hz), 85.66 (d, JPC = 5
2
2
2
Hz), 86.27 (d, JPC = 4 Hz), 89.09 (d, JPC = 4 Hz)
ꢀ1
~
m=cm 1569 vs, 1139 m, 1108 m, 1028 m, 928 m, 860
2
(CH of C6H4); 96.48, 108.76 (d, JPC = 2 Hz) (Cipso of
m, 789 br m, 758 m, 746 s, 694 s, 553 m, 514 s, 502 m.
Anal. Calcd. for C27H36Cl2O2PRhSn: C, 45.29; H,
5.07%. Found: C, 45.44; H, 4.92%.
1
C6H4); 126.92 (d, JPC = 54 Hz, Cipso of PPh2), 128.83
(d, JPC = 11 Hz), 129.33 (d, JPC = 10 Hz), 130.48 (d,
JPC = 9 Hz), 130.95 (d, JPC = 3 Hz), 131.93 (d, JPC = 3
Hz), 134.54 (d, JPC = 11 Hz) (6· CH of PPh2); 136.54
3.8. Preparation of dichloro-{(diphenylphosphino)acetic
acid-jP}(g5-pentamethylcyclopentadienyl)rhodium(I) (7)
1
2
(d, JPC = 47 Hz, Cipso of PPh2), 179.10 (d, JPC = 10
Hz, COO). 31P{1H} NMR (CDCl3): d 31.5 (s).
119Sn{1H} NMR (CDCl3): d 127.2 (s). IR (Nujol):
~m=cmꢀ1 1639 m, 1580 vs, 1310 m, 1196 m, 1108 s, 930
m, 854 m, 786 m, 749 s, 699 s, 553 m, 521 s, 503 m,
486 m. Anal. Calcd. for C27H35Cl2O2PRuSn: C, 45.47;
H, 4.95%. Found; C, 45.74; H, 4.94%.
A solution of Ph2PCH2CO2H (98 mg, 0.40 mmol) in
dichloromethane (2 mL) was added into a solution of
[{Rh(g5-C5Me5)Cl(l-Cl)}2] (124 mg, 0.20 mmol) in the
same solvent (3 mL). The resulting, clear orange-red
solution was stirred for 2 h, filtered, and the filtrate
was layered with hexane. The solid deposited after
standing for several days was filtered off, washed well
with diethyl ether and dried under vacuum to give 7 as
an orange-red powdery solid. Yield: 175 mg (79%).
3.10. Preparation of dichloro-(g6-1-methyl-4-(1- methyl-
ethyl)benzene){(diphenylphosphino)aceticacid-j,P}-
ruthenium(II) (9)
1H NMR ((CD3)2SO): d 1.25 (d, JRhH or JPH = 3.7
3
4
2
Hz, 15H, C5Me5), 3.66 (d, JPH = 9.9 Hz, CH2), 7.49–
A solution of Ph2PCH2CO2H (98 mg, 0.40 mmol) in
dichloromethane (2 mL) was added to a solution of
[{Ru(g6-1,4-MeC6H4(CHMe2))Cl(l-Cl)}2] (122.5 mg,
0.20 mmol) in the same solvent (5 mL). A red precipitate
was formed immediately. The mixture was mixed with
hexane and, after standing overnight, the precipitate
was filtered off, washed with diethyl ether and dried under
vacuum to give 9 as an orange-red solid (220 mg, 98%).
7.92 (m, 10H, PPh2). 13C{1H} NMR ((CD3)2SO): d
2
3
8.16 (d, JRhC or JPC ꢂ 1 Hz, Me of C5Me5), 34.05
(d, JPC = 22 Hz, CH2), 98.48 (dd, JRhC/2JPC ꢂ 3 and
1
1
7 Hz, Cipso of C5Me5), 127.82 (d, JPC = 10 Hz, CH of
1
PPh2), 127.96 (d, JPC = 42 Hz, Cipso of PPh2), 131.01
(d, JPC = 3 Hz), 133.53 (d, JPC = 10 H) (2· CH of
PPh2); 169.05 (d, JPC = 12 Hz, COO). 31P{1H} NMR
2
1
3
((CDꢀ3)12SO): d 28.8 (d, JRhP = 244 Hz). IR (Nujol):
1H NMR ((CD3)2SO): d 0.72 (d, JHH = 6.9 Hz, 6H,
3
CHMe2), 1.78 (s, 3H, Me), 2.27 (septuplet, JHH = 6.9
~
m=cm 1690 s, 1271 m, 1136 m, 1105 m, 1098 m, 851
2
Hz, 1H, CHMe2), 3.46 (d, JPH = 9.8 Hz, 2H, CH2),
m, 756 m, 746 m, 696 m, 560 m, 513 m, 447 m. Anal.
Calcd. for C24H28Cl2O2PRh: C, 52.10; H, 5.10%.
Found: C, 51.88; H, 5.14%.
5.26 (d, J = 6.2 Hz, 2H), 5.47 (dd, J = 6.3, 1.5 Hz, 2H)
(AAꢀBBꢀ system of C6H4); 7.46–7.90 (m, 10 H, PPh2).
13C{1H} NMR ((CD3)2SO): d 16.82 (Me), 20.78
3.9. The reaction of 1 with [{Ru(g6-p-cymene)Cl(l-
Cl)}2]
(CHMe2), 29.38 (CHMe2), 30.02 (d, JPC = 23 Hz,
1
2
CH2), 85.35 (d, JPC = 6 Hz), 90.12 (d, JPC = 6 Hz)
2
(CH of C6H4); 90.37, 106.47 (Cipso of C6H4); 127.65
1
[{Ru(g6-1,4-MeC6H4(CHMe2))Cl(l-Cl)}2] (61 mg,
0.10 mmol) and 1 (81 mg, 0.20 mmol) were dissolved in
dichloromethane (5 mL) and the mixture was stirred
for 2 days (precipitate is formed). The mixture was evap-
orated, the residue was dissolved in chloroform, the solu-
tion filtered and layered with hexane. Bright orange-red
crystals of chloro-(g6-1-methyl-4-(1-methylethyl)ben-
zene){(diphenylphosphino)acetate-j2P,O}ruthenium(II)-
(d, JPC = 10 Hz), 130.52 (d, JPC = 2 Hz) (2· CH of
PPh2); 131.76 (d, JPC = 45 Hz, CH of PPh2), 133.12
1
2
(d, JPC = 10 Hz, CH of PPh2), 169.03 (d, JPC = 12
Hz, COO). 31P{1H} NMR ((CD3)2SO): d 25.5 (s). IR
ꢀ1
~
(Nujol): m=cm 1690 vs, 1294 s, 1195 m, 1185 m, 1115
m, 920 m composite, 886 m, 862 w, 842 m, 747 s, 693
m, 583 m, 514 s, 450 m. Anal. Calcd. for C24H27Cl2O2-
PRu: C, 52.37; H, 4.94%. Found; C, 52.31; H, 4.86%.

´
P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3565
3.11. X-ray crystallography
ourless plate, 0.05 · 0.10 · 0.20 mm3; 6: orange frag-
ment, 0.13 · 0.20 · 0.28 mm3; 8: orange needle,
0.18 · 0.20 · 0.85 mm3.
Single crystals were grown by recrystallization from
hexane/dichloromethane: 2 Æ 3 CH2Cl2: colourless prism,
0.18 · 0.25 · 0.43 mm3; 3: colourless plate, 0.03 · 0.15 ·
0.35 mm3; 4: yellow plate, 0.10 · 0.20 · 0.25 mm3; 5: col-
The selected specimens were mounted on a glass fibre
with was and transfered to a Nonius KappaCCD dif-
Cryostream Cooler
fractometer equipped with
a
Table 6
Crystallographic data, data collection parameters and structure refinement for 2 Æ 3CH2Cl2, 3, 4, 5, 6, and 8
Compound
2 Æ 3CH2Cl2
3
4
Formula
M (g molꢀ1
C
847.59
31H30Cl6O4P2Pd
C28H24O4P2Pt
681.50
C24H18Cl4O6P2Pd2
818.92
Triclinic
)
Crystal system
Space group
T (K)
Triclinic
ꢀ
Monoclinic
P21/n (no. 14)
150(2)
ꢀ
P1 (no. 2)
150(2)
P1 (no. 2)
150(2)
˚
a (A)
9.6801(3)
13.2589(5)
13.8520(4)
96.530(1)
102.757(2)
91.640(2)
1720.1(1)
2
14.342(1)
9.6896(8)
18.303(2)
90
8.1300(2)
8.8564(2)
10.1067(2)
79.260(1)
89.723(1)
77.8879(8)
698.60(3)
1
˚
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
90.468(5)
90
3
˚
V (A )
2543.5(4)
4
1.780
Z
Dc (g cmꢀ3
)
1.636
25.07
28819
1.947
27.45
11493
hmax (ꢁ)
Collected diffractions
27.43
11186
Unique/observedb diffractions
Data completeness (%)
6100/4914
99.7
1.134
5794/4928
99.7
5.675
3183/2946
99.4
21.823
l (Mo Ka) (mmꢀ1
Tmin, Tmax
)
a
0.713–0.831
397
4.58
0.281–0.861
316
2.37
0.776–0.837
172
2.41
No. of parameters
R observed diffractions (%)c
R, wR all data (%)c
6.45, 11.7
0.61, ꢀ0.87
3.36, 5.20
2.00, ꢀ1.26
2.76, 5.99
0.62, ꢀ0.98
ꢀ3
˚
Dq (eA
)
Compound
5
6
8
Formula
M (gmolꢀ1
C
26H21ClO5P2Pd
C27H36Cl2O2PRhSn
716.03
C27H35Cl2O2PRuSn
713.18
)
617.22
Monoclinic
P21,lc (no. 14)
150(2)
Crystal system
Space group
T (K)
Orthorhombic
P212121 (no. 19)d
150(2)
Monoclinic
P21/n (no. 14)
150(2)
˚
a (A)
10.6904(4)
17.088(1)
16.1850(8)
90
9.2556(4)
16.7621(4)
18.8871(9)
90
9.4920(2)
20.9110(3)
14.7960(3)
90
˚
b (A)
˚
c (A)
a(ꢁ)
b (ꢁ)
c (ꢁ)
122.328(3)
90
90
90
105.2080(9)
90
3
˚
V (A )
2498.4(2)
4
1.641
2930.2(2)
4
1.623
2833.97(9)
4
1.672
Z
Dc (g cmꢀ3
)
hmax (ꢁ)
Collected diffractions
25.99
21590
27.48
16612
27.88
23304
Unique/observedb diffractions
Data completeness (%)
4854/3179
99.2
1.014
6574/4660
99.7
1.674
6742/5941
99.2
1.682
l (Mo Ka) (mmꢀ1
Tmin, Tmax
)
a
–
280
0.768, 0.812
315
4.58
0.443, 0.796
314
3.42
No. of parameters
R observed diffractions (%)c
R, wR all data (%)c
5.84
10.9, 20.7
ꢀ0.97, 1.26
7.55, 8.89
ꢀ0.86, 0.82
4.06, 8.74
ꢀ1.53, 1.15
ꢀ3
˚
Dq (eA
)
a
The range of transmission coefficients.
Diffractions with Io > 2r(Io).
b
c
P
P
P
P
2
2 1=2
R(F) = jjFoj ꢀ sjFcjj/ jFoj, wRðF 2Þ ¼ ½ fwðF o2 ꢀ F 2c Þ g= wðF o2Þ ꢃ
Flackꢀs enantiomorph parameter: ꢀ0.02(3).
.
d

´
P. Zoufala et al. / Journal of Organometallic Chemistry 689 (2004) 3556–3566
3566
(b) J. Grobe, E.M. Reifer, B. Krebs, M. La¨ge, M. Prill, Z. Anorg.
Allg. Chem. 626 (2000) 478;
(Oxford Cryosystems). Full-set diffraction data
( h k l) were collected using graphite monochroma-
(c) U. Baumeister, H. Hartung, A. Krug, K. Merzweiler, T.
Schulz, C. Wagner, H. Weichmann, Z. Anorg. Allg. Chem. 626
(2000) 2185.
˚
tized Mo Ka radiation (k = 0.71073 A) and processed
with the HKL program package [20] (Table 6). Except
for 5, the data were corrected for absorption anisotropy
using either a multiscan routine incorporated in the dif-
fractometer software (4; Sortav procedure [21]), an
empirical correction (2 Æ 3 CH2Cl2, 6, and 8; Platon
[22]) or an analytical correction based on the indexed
crystal shape (3; Platon, the crystal shape was optimized
with Euhedral program [23]). Transmission factor
ranges are given in Table 6.
[2] (a) H. Weichmann, J. Organomet. Chem. 238 (1982) C49;
(b) U. Schubert, S. Grubert, U. Schulz, S. Mock, Organometallics
11 (1992) 3163.
[3] M. Siebert, K. Merzweiler, C. Wagner, H. Weichmann, J.
Organomet. Chem. 687 (2003) 131.
[4] (a) For an overview about the coordinatin chemistry and practical
utility of phosphinocarboxylic ligands, see A. Bader, E. Lindner,
Coord. Chem. Rev. 108 (1991) 27;
ˇ
(b) P. Stepnicka, New J. Chem. 26 (2002) 567, and refs. therein;
ˇ
ˇ
ˇ
(c) P.P. Stepnicka, I. Cisarova, Organometallics 22 (2003) 1728,
ˇ
ˇ
ˇ
´
The structures were solved by direct methods (SIR97
[24]) and refined by weighted full-matrix least-squares
procedure on F2 (SHELXL97 [25]). Final geometric calcu-
lations were carried out with a recent version of Platon
program. All non-hydrogen atoms were refined with
anisotropic thermal motion parameters. The hydrogen
atoms were included in the calculated positions [C–H
bond lengths: 0.93 (aromatic), 0.97 (methylene) and
and refs. therein.
´
´
[5] T. Jarolım, J. Podlahova, J. Inorg. Nucl. Chem. 38 (1976) 125.
[6] P. Braunstein, D. Matt, J. Chem. Res., Miniprint (1978) 3041.
[7] D.A. Edwards, M.F. Mahon, T.J. Paget, Polyhedron 17 (1998)
4121.
ˇ
[8] P.J. Smith, A.P. Tupciauskas, Ann. Rep. NMR Spectrosc. 8
(1978) 281.
[9] HCO2SnMe3 is known to readily associate at higher concentra-
tions in CDCl3, affording pentacoordinated tin species (cf. dSn 2.5
for 3 M and dSn 150 for 0.05 M solutions).
ˇ ´ ´
[10] (a) J. Ru˘zˇickova, J. Podlahova, Collect. Czech. Chem. Commun.
43 (1978) 2853;
˚
0.96 (methyl) A] and assigned Uiso(H) = 1.2 Ueq(C) (aro-
matic and methylene) or 1.5 Ueq(C) (methyl). The phe-
nyl ring in the structure of 5 were constrained to
´ ´
(b) J. Pangrac, J. Podlahova, Collect. Czech. Chem. Commun. 46
˚
regular hexagons with C–C distances of 1.39 A.
(1981) 1222.
[11] J. Chatt, L.M. Venanzi, J. Chem. Soc. (1957) 2351.
[12] B. Wrackmeyer, Ann. Rep. NMR Spectrosc. 16 (1985) 73.
ˇ ´ ˇ ´
[13] S. Civis, J. Podlahova, J. Loub, J. Jecny, Acta Crystallogr. B 36
4. Supplementary material
(1980) 1395.
[14] A.C. Hazel, R.G. Hazel, B. Kratochv´ıl, J. Podlahova´, Acta
Crystallogr. B 37 (1981) 2068.
Crystallographic data (CIF files) have been depos-
ited at the Cambridge Crystallographic Data Centre
under the deposition numbers CCDC-235449
(2 Æ 3CH2Cl2), ꢀ235447 (3), ꢀ235448 (5), ꢀ235450 (6),
and ꢀ235451 (8). Copies of the data may be obtained
free of charge upon request to CCDC, 12 Union Road,
Cambridge CB2 1EZ, UK (fax: +44 1223 336033,
e-mail: deposit@ccdc.cam.ac.uk, www: http://www.
ccdc.cam.ac.uk).
[15] J. Buckle, P.G. Harrison, T.J. King, J.A. Richards, J. Chem.
Soc., Dalton Trans. (1975) 1552.
[16] S. Calogero, G. Valle, U. Russo, Organometallics 3 (1984) 1205.
[17] S.W. Ng, V.G.K. Das, J. Crystallogr. Spectrosc. Res. 23 (1993)
929.
[18] D. Drew, J.R. Doyle, in: F.A. Cotton (Ed.), Inorganic Synthesis,
13, McGraw-Hill, New York, 1972, pp. 47–55.
[19] C. White, D. Yates, P.M. Maitlis, in: R.N. Grimes (Ed.),
Inorganic Synthesis, 29, Wiley, New York, 1992, pp. 228–
234.
[20] Z. Otwinowski, W. Minor, HKL Denzo and Scalepack program
package by Nonius BV, Delft, The Netherlands, 1997. For a
reference, see: Z. Otwinowski, W. Minor, Methods Enzymol. 276
(1997) 307.
Acknowledgements
[21] R.H. Blessing, J. Appl. Cryst. 30 (1997) 421.
[22] A.L. Spek, Platon, version 2001. <http://www.cryst.chem.uu.nl/
platon/>.
This work was supported by Grant Agency of the
Czech Republic (Grant Nos. 203/04/0223 and 203/99/
M037) and is a part of a long-term Research plan of
the Faculty of Sciences, Charles University.
[23] Euhedral, Program for the refinement of the crystal shape against
intensities of multiple measured diffractions. <http://www.crys-
tal.chem.uu.nl/distr/euhedral>.
[24] A. Altomare, M.C. Burla, M. Camalli, G.L. Cascarano, C.
Giacovazzo, A. Guagliardi, A.G.G. Moliterni, G. Polidori, R.
Spagna, J. Appl. Cryst. 32 (1999) 115.
References
[25] G.M. Sheldrick, SHELXL97. Program for Crystal Structure
Refinement from Diffraction Data, University of Go¨ttingen,
Go¨ttingen, 1997.
[1] (a) J. Grobe, E.M. Reifer, B. Krebs, M. La¨ge, M. Prill, Z. Anorg.
Allg. Chem. 623 (1997) 264;