Areneruthenium(II) complexes with functionalized phosphines coordinating as mono-, bi- or tridentate ligands

Article abstract of DOI:10.1002/1522-2675(20011017)84:10<3162::AID-HLCA3162>3.0.CO;2-R

Areneruthenium(II) compounds [Ru(p-cym)Cl₂{κ-P-ⁱPrP(CH₂CH ₂OMe)₂}], 3, and [Ru(arene)Cl₂{κ-P-RP(CH₂CO₂Me) ₂}] 4-7 (arene = p-cym (= 1-methyl-4-isopropylbenzene), mes (= 1,3,5-trimethylbenzene); R = ⁱPr, ′Bu) were prepared from the dimers [Ru(arene)Cl₂]₂ and the corresponding functionalized phosphine. Treatment of 6 and 7 with 1 equiv. of AgPF₆ affords the monocationic complexes [Ru(mes)Cl{κ²-P,O-RP(CH₂C(O)OMe)(CH ₂CO₂Me)}]PF₆, 10 and 11, while the related reaction of 5-7 with 2 equiv. of AgPF₆ produces the dicationic compounds [Ru(p-cym){κ³-P,O,O-′BuP(CH₂C(O)OMe) ₂}](PF₆)₂ (12) and [Ru(mes){κ³-P,O,O-RP(CH₂C(O)OMe)₂}] (PF₆)₂, 13 and 14. Partial hydrolysis of one hexafluorophosphate anion of 12-14 leads to the formation of [Ru(arene){κ²-P,O-RP(CH₂C(O)OMe)(CH ₂CO₂Me)}(κ-O-O₂PF₂)]PF ₆, 15-17, of which 17 (arene = mes; R = ′Bu) has been characterized by X-ray crystallography. Compounds 13 and 14 react with 2 equiv. of KO′Bu in ′BuOH/toluene to give the unsymmetrical complexes [Ru(mes){κ³-P,C,O-RP-(CHCO₂Me)(CH=C(O)OMe)}], 18 and 19, containing both a five-membered phosphinoenolate and a three-membered phosphinomethanide ring. The molecular structure of compound 18 has been determined by X-ray structure analysis. The neutral bis(carboxylate)phosphanidoruthenium(II) complexes [Ru(arene){κ³-P,O,O-RP-(CH₂C(O)O)₂}], 20-23 are obtained either by hydrolysis of 18 and 19, or by stepwise treatment of 4 and 5 with KO′Bu and basic Al₂O₃. Novel tripodal chelating systems are generated via insertion reactions of 19 with PhNCO and PhNCS.

Full text of DOI:10.1002/1522-2675(20011017)84:10<3162::AID-HLCA3162>3.0.CO;2-R

3162
Helvetica Chimica Acta ± Vol. 84 (2001)
Areneruthenium(II) Complexes with Functionalized Phosphines
Coordinating as Mono-, Bi- or Tridentate Ligands
by Helmut Werner*, Jürgen Bank, Bettina Windmüller, Olaf Gevert, and Werner Wolfsberger
Institut für Anorganische Chemie der Universität Würzburg, Am Hubland, D-97074 Würzburg
Dedicated to the Memory of Luigi M. Venanzi, one of the pioneers of modern coordination chemistry
Areneruthenium(II) compounds [Ru(p-cym)Cl2{k-P-iPrP(CH2CH2OMe)2}], 3, and [Ru(arene)Cl2{k-P-
RP(CH2CO2Me)2}] 4 ± 7 (arene ˆ p-cym (ˆ1-methyl-4-isopropylbenzene), mes (ˆ1,3,5-trimethylbenzene);
R ˆ iPr, tBu) were prepared from the dimers [Ru(arene)Cl2]2 and the corresponding functionalized phosphine.
Treatment of 6 and 7 with 1 equiv. of AgPF6 affords the monocationic complexes [Ru(mes)Cl{k2-P,O-
RP(CH2C(O)OMe)(CH2CO2Me)}]PF6, 10 and 11, while the related reaction of 5 ± 7 with 2 equiv. of AgPF6
produces the dicationic compounds [Ru(p-cym){k3-P,O,O-tBuP(CH2C(O)OMe)2}](PF6)2 (12) and [Ru(mes)-
{k3-P,O,O-RP(CH2C(O)OMe)2}](PF6)2, 13 and 14. Partial hydrolysis of one hexafluorophosphate anion of 12 ±
14 leads to the formation of [Ru(arene){k2-P,O-RP(CH2C(O)OMe)(CH2CO2Me)}(k-O-O2PF2)]PF6, 15 ± 17, of
which 17 (arene ˆ mes; R ˆ tBu) has been characterized by X-ray crystallography. Compounds 13 and 14 react
with 2 equiv. of KOtBu in tBuOH/toluene to give the unsymmetrical complexes [Ru(mes){k3-P,C,O-RP-
(CHCO2Me)(CHˆC(O)OMe)}], 18 and 19, containing both a five-membered phosphinoenolate and a three-
membered phosphinomethanide ring. The molecular structure of compound 18 has been determined by X-ray
structure analysis. The neutral bis(carboxylate)phosphanidoruthenium(II) complexes [Ru(arene){k3-P,O,O-RP-
(CH2C(O)O)2}], 20 ± 23 are obtained either by hydrolysis of 18 and 19, or by stepwise treatment of 4 and 5 with
KOtBu and basic Al2O3. Novel tripodal chelating systems are generated via insertion reactions of 19 with
PhNCO and PhNCS.
Introduction. ± In the search of finding useful ligands for catalytically active
transition-metal complexes, the chemistry of substituted phosphines of general
composition R2P(CH2)nY has become an area of great interest in recent years (for
reviews, see [1]). By far, the most attention was given to compounds where the
functional group Y is MeO, C(O)R' or C(O)OR', since it was anticipated that the O-
donors temporarily are able to protect a vacant coordination site and thus allow the
addition of more powerful ligands to the metal center under fairly mild conditions.
Moreover, with b-phosphino ketones or esters as coordinating groups, a number of O-
metallated phosphinoenolate metal complexes have been prepared and found to be
appropriate starting materials for C,C coupling reactions with activated alkynes and
isocyanates [2], for the generation of metal acetylides from alk-1-ynes [3], and for
reversibly binding CO2 [4].
As a continuation of our work on the reactivity of phosphino esters R2PCH2CO2R'
toward d6 and d8 metal centers [5], we have recently developed a synthetic route to the
trifunctional phosphines RP(CH2CO2R')2 [6] and started to investigate their coordi-
nation capabilities [7]. In this paper, we describe the synthesis of a series of
areneruthenium(II) complexes containing the potentially tridentate monophosphanes
RP(CH2CO2Me)2 (R ˆ iPr, tBu) and the remarkable conversion of these molecules to

Helvetica Chimica Acta ± Vol. 84 (2001)
3163
novel unsymmetrical k3-P,C,O-bonded tripod-type ligands. Moreover, the metal-
mediated hydrolysis of these tripodal ligands to coordinated tridentate dianions
[RP(CH2CO2)2]2 and the different course of insertion reactions of PhNCO and
PhNCS into one of the C H bonds of the k3-P,C,O-bonded ligands will also be
reported. Some preliminary results of this work have already been published [8].
Results and Discussion. ± Similarly to PMe3 and other tertiary phosphines, the
t
phosphine derivatives BuP(CH2CH2OMe)2 and RP(CH2CO2Me)2 (R ˆ iPr,tBu) react
with the dimers 1 and 2 in CH2Cl2 at room temperature via cleavage of the chloro
bridges to give the mononuclear air-stable compounds 3 ± 7 in 90 ± 95% yield
(Scheme 1). The 31P-NMR spectra of 3 ± 7 display a singlet resonance which is shifted
downfield by 30 ± 40 ppm compared with the free phosphine. The assumption that the
MeO and CO2Me groups of the ligands are not involved in the coordination to the
metal is supported by the IR spectra in which only one C O or CˆO stretching mode
t
in the same region as for BuP(CH2CH2OMe)2 or RP(CH2CO2Me)2 appears.
Scheme 1
Attempts to displace the more weakly bound p-cymene (ˆ1-methyl-4-(1-methyl-
ethyl)benzene) ligand by PiPr3 and generate an arene-free RuII complex of general
composition [RuCl2(PiPr3){k3-P,O,O-RP(\O)2}] failed. Treatment of 3 or 4 with
1equiv. of PiPr3 in benzene leads to ligand exchange and affords both [Ru(p-
cym)Cl2(PiPr3)] [9] and the uncoordinated functionalized phosphine (Scheme 2).
Heating the solution to 608 for 6 ± 8 h yields a mixture of products in which, apart from
some unidentified compounds, the complexes 8 and 9 [7b] are the dominating species.

3164
Helvetica Chimica Acta ± Vol. 84 (2001)
Scheme 2
Scheme 3
The reaction of the mesitylene (ˆ1,3,5-trimethylbenzene; mes) compounds 6 and 7
with an equimolar amount of AgPF6 in CH2Cl2 results in the abstraction of one chloride
and the formation of the cationic chelate complexes 10 and 11 in nearly quantitative
yields (Scheme 3). The composition of 10 and 11, which are orange-yellow, moderately
air-sensitive solids dissolving in polar solvents such as acetone, MeNO2, and CH2Cl2,
has been confirmed by elemental analysis and conductivity measurements. As
1
expected, the H- and 13C-NMR spectra of 10 and 11 display two sets of signals for
the configurationally different CH2CO2Me moieties indicating that there is no
intramolecular exchange of the coordinated and the dangling CH2COOMe groups at
room temperature. In contrast to 6 and 7, the IR spectra of 10 and 11 show two strong
1
1
nÄ(CˆO) bands at 1713 and 1610 cm (10), and 1721 and 1613 cm (11), supporting
the assumption that one of the CO2Me units is coordinated (via the CˆO O-atom)

Helvetica Chimica Acta ± Vol. 84 (2001)
3165
while the other is free (for a discussion of the IR data of coordinated and non-
coordinated CˆO groups, see [10]).
The coordination of both CˆO bonds of RP(CH2CO2Me)2 to the Ru-center can be
achieved upon treatment of 5 ± 7 with 2 equiv. of AgPF6 in CH2Cl2. After removal of
the solvent and extraction of the residue with acetone, the complexes 12 ± 14, in which
the intact phosphine behaves as a tridentate bis-chelating ligand, were isolated as
orange, practically air-stable solids in 78 ± 82% yield. The structural proposal for 12 ±
14, shown in Scheme 4, is well-supported by the spectroscopic data and the conductivity
1
in MeNO2. Since there is only one CˆO stretching mode at ca. 1610 ± 1620 cm , which
1
is lowered by ca. 110 cm compared with the monodentate phosphine in 5 ± 7, the IR
spectra in particular leave no doubt that both CH2CO2Me units are involved in the
coordination to the metal.
Scheme 4
In polar solvents such as CH2Cl2, in the presence of small amounts of H2O, partial
hydrolysis of the hexafluorophosphate anion of 12 ± 14 occurs, leading to the
monocationic difluorophosphinatoruthenium(II) complexes 15 ± 17 in excellent yields.
Such a transition-metal-mediated conversion of PF6 to PO2F2 is not without
precedence [11], and, with areneruthenium(II) compounds has been observed in the
formation of [(C6Me6Ru)2(m-O2PF2)3]PF6 from [Ru(acetone)3(C6Me6)](PF6)2 and
H2O [12]. Typical spectroscopic features of 15 ± 17 are the PˆO and the two CˆO
stretching modes in the IR spectra, the two sets of signals for the H- and C-atoms of the
inequivalent CH2CO2Me fragments in the 1H- and 13C-NMR spectra, and the doublet-
of-doublets-of-doublets (due to P,P and twofold P,F couplings) for the P-atom of the
PO2F2 ligand in the 31P-NMR spectra. The 19F-NMR spectra of 15 ± 17 display apart

3166
Helvetica Chimica Acta ± Vol. 84 (2001)
Fig. 1. ORTEP Diagram of compound 17 (H-atoms omitted for clarity). Selected bond distances [Š] and
angles [deg]: Ru O(1) 2.112(3), Ru O(5) 2.114(3), Ru P(1) 2.3645(12), O(1) C(6) 1.227(5), O(2) C(6),
1.311(5), C(5) C(6) 1.479(7), P(1) C(1) 1.870(5), P(1) C(5) 1.829(5), P(1) C(8) 1.826(5), P(2) O(5)
1.471(3), P(2) O(6) 1.415(5); O(1) Ru O(5) 84.29(12), O(1) Ru P(1) 79.63(9), O(5) Ru P(1)
88.58(10), Ru O(1) C(6) 122.5(3), Ru O(5) P(2) 136.1(2), Ru P(1) C(1) 124.7(17), Ru P(1) C(5)
100.13(16), Ru P(1) C(8) 116.15(17), C(1) P(1) C(5) 106.2(2), C(1) P(1) C(8) 103.6(2),
C(5) P(1) C(8) 103.7(2), P(1) C(5) C(6) 108.5(3), O(1) C(6) C(5) 123.7(4).
from the signal for the PF6 anion a resonance for the F-atoms of the PO2F2 unit which
appears as the AB part of an ABX spin system.
The molecular structure of the cation of compound 17 is shown in Fig. 1. In
agreement with the spectroscopic data, the phosphinodiester is bonded to Ru in a k2-
P,O-mode, forming a five-membered chelate ring and leaving one CO2Me group
uncoordinated. The ꢀbite angleꢁ O(1) Ru P(1) of 79.63(9)8 is quite similar to that of
the neutral complex [RuCl2{k2-P,O-tBuP(CH2C(O)OMe)(CH2CO2Me)}2] (81.8(2)8
and (82.0(2)8) [13] and also to that of the related Os cation [OsCl(mes)(k2-P,N-
‡
iPr2PCH2CH2NMe2)] (81.74(10)8) [14]. Moreover, the Ru O(1) and Ru P(1)
distances are comparable with those of cationic Ru compounds containing
R2PCH2CO2R' as bidentate ligands [15]. The geometry of the coordinated PO2F2
anion is distorted tetrahedral, the bond angle O(6) P(2) O(5) (121.8(3)8) being the
largest and F(7) P(2) F(8) (97.0(4)8) the smallest. The bond lengths P(2) O(5),
P(2) O(6), P(2) F(7) and P(2) F(8) are in the expected range [16] and thus deserve
no further comment.
The mes complexes 13 and 14 react with 2 equiv. of KOtBu in a 1:1 mixture of
t-BuOH and toluene to give instead of the anticipated bis(enolate)ruthenium(II)
compounds [Ru(mes){k3-P,O,O-RP(CHˆC(O)OMe)2}] the moisture-sensitive bicyclic
products 18 and 19 in 60 ± 65% yield (Scheme 5). The spectroscopic data of 18 and 19
indicate quite clearly that the two PCHCO2Me units are not equally bonded to the
metal center. While one chelating moiety forms a five-membered phosphinoenolate

Helvetica Chimica Acta ± Vol. 84 (2001)
3167
Scheme 5
ring resulting from O-metallation of one PCHCO2Me group, the other one constitutes a
three-membered Ru-phosphinomethanide unit, which is the C-metallation product.
Characteristic features illustrating the different bonding mode of the PCHCO2Me
fragments in 18 and 19 are the two signals for the PCH protons at, respectively, d 3.45 or
1
3.55 (PCHenolate), and d 1.69 or 1.67 ppm (PCHmethanide) in the H-NMR, and the two
resonances for the corresponding carbon nuclei at d 44.6 or 44.0 (PCHenolate) and d 4.9
or 8.7 (PCHmethanide) in the 13C-NMR spectra. We note first that attempts to prepare a
structurally related p-cymene derivative [Ru(p-cym){k3-P,C,O-tBuP(CHˆC(O)OMe)-
(CHCO2Me)}] by treatment of 12 with KOtBu in the molar ratio of 1:2 failed, and,
second, that complexes with a Ru(k2-P,C-Me2PCH2) moiety but without an arene
ligand are well-known [17] and have recently been used for the synthesis of monomeric
hydroxo, phenolato, and amido Ru derivatives [18]. It should also be mentioned that,
upon treatment of 18 or 19 with 2 equiv. of gaseous HCl in toluene, the dichloro
compounds 6 and 7 are regenerated.
The molecular structure of 18 was confirmed by a single-crystal X-ray structure
analysis (see Fig. 2). The five-membered phosphinoenolate-metal unit is nearly planar
with the MeO substituent lying in the ring plane. The electron delocalization within the
RuPC2O cycle is indicated by the short distances P C(2) and C(1) C(2) and also by
the C(1) O(1) bond length, which is between a C O and a CˆO bond. The
interatomic bond distances and angles of the three-membered phosphinomethanide-
metal fragment are comparable to those found in [Mn(CO)4(k2-P,C-Ph2PCH2)] [19],
[Mo(CO)2(C5H5)(k2-P,C-Ph2PCH2)] [20], and [MCl(mes)(k2-P,C-iPr2PCHCO2Me)]
(M ˆ Ru, Os) [21]. The dihedral angle between the planes of the five-membered
RuPC2O and the three-membered RuPC ring in 18 is 81.778.
If instead of 13 or 14 the dichlororuthenium(II) derivatives 4 and 5 are reacted with
2 equiv. of KOtBu in t-BuOH/toluene 1:1 and, after removal of the solvent, the crude
products are chromatographed on basic Al2O3 with MeOH, the neutral phosphino-
bis(carboxylate) complexes 20 and 21 are obtained as orange-yellow, nearly air-stable

3168
Helvetica Chimica Acta ± Vol. 84 (2001)
Fig. 2. ORTEP Diagram of compound 18 (H-atoms omitted for clarity). Selected bond distances [Š] and
angles [deg]: Ru O(1) 2.053(3), Ru C(3) 2.217(4), Ru P 2.301(2), O(1) C(1) 1.295(5), C(1) O(2)
1.323(4), C(1) C(2) 1.394(5), P C(2) 1.671(4), P C(3) 1.727(4), P C(6) 1.884(4), C(3) C(4) 1.374(5);
O(1) Ru C(3) 88.03(14), O(1) Ru
Ru C(2) 104.2(2), Ru C(3) 64.98(13), Ru
Ru C(3) P 70.11(13), O(1) C(1) C(2) 127.7(3), O(2) C(1) C(2) 118.0(3), O(1) C(1) O(2) 114.2(3),
C(1) C(2) 110.5(3), C(2) C(3) 106.1(2), C(2) C(6) 112.5(2), C(3) C(6) 119.8(2),
C(3) C(4) 118.0(3).
P
80.65(11), C(3) Ru
P 44.91(11), Ru O(1) C(1) 116.7(2),
P
P
P
C(6) 138.25(14), Ru C(3) C(4) 111.3(3),
P
P
P
P
P
solids in moderate yields (Scheme 6). The strucutrally analogous mes compounds 22
and 23 are more conveniently prepared by treatment of a solution of 18 or 19 in acetone
with an excess of H2O. In this case the yield is 81 ± 83%. In agreement with the proposed
structure, the NMR spectra of 20 ± 23 are quite simple and confirm the symmetrical
bonding mode of the tridentate [RP(CH2CO2)2]2 unit. The IR spectra of 20 ± 23
1
display one strong nÄ(CˆO) band at 1637 or 1647 cm , corresponding to previously
published data [22]. In the 1H-NMR spectra, the diastereoisotopic CH2 protons of the
CH2CO2 fragments give rise to two doublets-of-doublets at d ca. 2.65 ppm presenting
the AB part of an ABX spectrum. With regard to the formation of 20 and 21 from 4 and
5, it should be mentioned that recently a similar CH3 O-bond cleavage of bifunctional
phosphines R2PCH2CO2Me has been observed in the coordination sphere of RuII [23]
and also of IrI [5d]. As far as the mechanism of the reactions of 18 and 19 to yield 22
and 23 is concerned, we assume that the ring strain of the bicyclic rutheniumphosphi-
noenolate/-methanide system facilitates the hydrolysis of the CO2Me units. In this
context we note, that the phosphinoenolate compound [RuCl(mes){k2-P,O-iPr2-
PCHˆC(O)OMe}] equally reacts almost instantaneously with traces of H2O to give
the related phosphinoacetate derivative [RuCl(mes){k2-P,O-iPr2PCH2C(O)O}] [21a].
While compound 19, in contrast to some phosphinoenolate-metal complexes
studied by Braunstein et al. [4], is inert toward CO2, it reacts quite smoothly with

Helvetica Chimica Acta ± Vol. 84 (2001)
3169
Scheme 6
PhNCO in toluene at room temperature to afford the 1:1 adduct 24 as a yellow
microcrystalline solid in 70% isolated yield (Scheme 7). The ring-substituted derivative
formally results from the addition of the C H bond of the PCHˆ unit of the enolate
across the CˆN bond of the substrate. Although such an insertion reaction is not
without precedence [2][13][14], the formation of 24 is noteworthy insofar as, even in
the presence of excess PhNCO, no insertion into the C H bond of the phosphino-
methanide ligand and also no enlargement of the RuPC three-membered ring takes
place. Characteristic spectroscopic features of 24 are the N H stretching mode at
1
1
3380 cm in the IR, the signal for the NH proton at d 9.10 in the H-NMR, and the
three resonances for the CˆO C-atoms at d 176.2 (doublet), 173.9 (singlet), and
165.5 ppm (doublet) in the 13C-NMR spectrum.
Not only PhNCO but also the corresponding PhNCS reacts with 19 in toluene at
258. In this case, however, instead of the anticipated 1:1, the 1:2 adduct 25 is formed.
Based on the elemental analysis (C, H, N, S) and the spectroscopic data of 25, the
structure shown in Scheme 7 is tentatively assigned. The presence of noncoordinated
CO2Me groups is indicated in the IR spectrum by the strong nÄ(CˆO) absorption at
1
1726 cm which appears at almost the same position as found for 5. The 13C-NMR
spectrum of 25 displays four signals at around d 170.9 to 167.2 ppm, which are assigned

3170
Helvetica Chimica Acta ± Vol. 84 (2001)
Scheme 7
to the C-atoms of the CO2Me and CˆNPh fragments. The alternative structure for 25,
in which the tridentate ligand contains two exocyclic CˆS bonds while the metal center
is coordinated to P- and to two N-atoms, can be excluded, since the IR spectrum shows
no absorption between 1050 and 1200 cm 1 (typical for a CˆS stretching mode) but an
1
intensive nÄ(CˆN) band for the CˆNPh units at 1577 cm . Regarding the mechanism
of formation of 25, a reasonable assumption is that the insertion of the two
isothiocyanates occurs stepwise, and an 1:1 adduct is generated as an intermediate.
However, we can only speculate about the structure of this hypothetical species
because all our attempts to isolate such a compound from the reaction of 19 with an
equimolar amount of PhNCS failed.
In conclusion, the work presented in this paper has shown that trifunctionalized
phosphines of the general composition RP(CH2CO2Me)2 containing bulky substituents
R are able to behave as mono-, bi-, or tridentate ligands. In the coordination sphere of
RuII, they can also be converted to unsymmetrical dianionic k3-P,C,O-bonded tripod-
type units, which can further be modified by insertion of both PhNCO and PhNCS into
one of the C H bonds of the bicyclic skeleton. Although some tentative experiments
remained unsuccessful, the new complexes 24 and 25 offer the opportunity to generate
by acid cleavage of the metal ligand bonds the formation of oligofunctional chiral
phosphines.

Helvetica Chimica Acta ± Vol. 84 (2001)
3171
We thank the Deutsche Forschungsgemeinschaft (SFB 347) and the Fonds der Chemischen Industrie for
generous support. Moreover, we gratefully acknowledge support by R. Schedl and C. P. Kneis (DTA and
elemental analysis), M.-L. Schäfer and Dr. W. Buchner (NMR spectra), Dr. G. Lange and F. Dadrich (mass
spectra), and K. Ilg and C. D. Brandt (assistance by X-ray structure analysis). We are also grateful to Dr. G.
Henig and Dr. J. Wolf for helpful discussions.
Experimental Part
General. All experiments were carried out under Ar by Schlenk techniques. Solvents were dried by known
t
procedures and distilled under Ar before use. The starting materials 1, 2 [24], and the phosphines BuP(CH2-
t
CH2OMe)2 and RP(CH2CO2Me)2 (R ˆ iPr, Bu) [6] were prepared as described in the literature. Melting and
decomposition points were determined by DTA. IR Spectra: in cm 1; Perkin-Elmer 1420 spectrophotometer.
NMR Spectra: at r.t., Bruker AC-200 and Bruker AMX-400 instruments; chemical shifts d are expressed in ppm
downfield from SiMe4 (1H and 13C) and 85% H3PO4 (31P). MS: Finnigan MAT instrument. The conductivity L
was measured in MeNO2 with a Schott Konduktometer CG 851.
[RuCl2(p-cym){k-P-tBuP(CH2CH2OMe)2}] (3). A suspension of 1 (1.0 g, 1.63 mmol) in 40 ml of CH2Cl2
was treated with tBuP(CH2OMe)2 (842 mg, 4.08 mmol) and stirred for 3 h at r.t. The mixture was filtered, and
the filtrate was concentrated to ca. 5 ml in vacuo. After addition of 20 ml of hexane, a red-brown solid
precipitated, which was separated from the mother liquor, washed three times with 10-ml portions of hexane,
1
and dried: 1.51 g (90%) of 3. M.p. 1188 (dec.). IR (CH2Cl2): 1096 (C O). H-NMR (200 MHz, CDCl3): 5.55
(m, C6H4); 3.72 ± 3.51 (m, 2 PCH2CH2O); 3.26 (s, 2 MeO); 2.80 (sept., 3J(H,H) ˆ 6.9, Me2CH); 2.39 ± 2.22
(m, 2 PCH2CH2O); 2.07 (s, MeC6H4); 1.29 (d, 3J(P,H) ˆ 13.1, 3 PCMe); 1.25 (d, 3J(H,H) ˆ 6.9, Me2CH).
13C-NMR (50.3 MHz, CDCl3): 108.1, 94.5 (2s, ipso-C of C6H4); 88.6 (d, 2J(P,C) ˆ 3.9, C6H4); 83.6
(d, 2J(P,C) ˆ 5.2, C6H4); 68.4 (s, PCH2CH2O); 58.1 (s, MeO); 35.4 (d, 1J(P,C) ˆ 21.4, PCMe); 30.4 (s, Me2CH);
28.1 (d, 2J(P,C) ˆ 3.2, PCMe); 25.0 (d, 1J(P,C) ˆ 21.4, PCH2); 22.2 (s, Me2CH); 17.7 (s, Me C6H4). 31P-NMR
(81.0 MHz, CDCl3): 28.2 (s). Anal. calc. for C20H37Cl2O2PRu (512.5): C 46.88, H 7.28; found: C 47.02, H 7.16.
[RuCl2(p-cym){k-P-iPrP(CH2CO2Me)2}] (4). As described for 3, from 1 (1.0 g, 1.63 mmol) and iPrP(CH2-
CO2Me)2 (900 mg, 4.09 mmol): 1.58 g (92%) of 4. Red-brown solid. M.p. 1378. IR (CH2Cl2): 1723 (CˆO).
1H-NMR (400 MHz, CDCl3): 5.58 (m, C6H4); 3.68 (s, 2 MeO); 3.38 (AB of ABX; d(HA) 3.40, d(HB) 3.35,
2J(P,HA) ˆ 7.9, 2J(P,HB) ˆ 12.5, 2J(H,H) ˆ 15.8, 2 PCH2); 3.01 (m, Me2CHP); 2.80 (sept., 3J(H,H) ˆ 7.0,
Me2CH), 2.06 (s, Me C6H4); 1.30 (dd, 3J(P,H) ˆ 15.6, 3J(H,H) ˆ 7.2, Me2CHP); 1.20 (d, 3J(H,H) ˆ 7.0,
Me2CH). 13C-NMR (100.6 MHz, CDCl3): 170.3 (d, 2J(P,C) ˆ 5.7, CO2); 109.0, 94.4 (2s, ipso-C of C6H4); 89.8
(d, 2J(P,C) ˆ 4.0, C6H4); 83.9 (d, 2J(P,C) ˆ 6.1, C6H4); 52.1 (s, MeO); 30.5 (s, Me2CH); 29.1 (d, 1J(P,C) ˆ 21.5
Me2CHP); 27.1 (d, 1J(P,C) ˆ 23.0, PCH2); 21.9 (s, Me2CH); 17.8 (s, Me C6H4); 17.7 (s, Me2CHP). 31P-NMR
(81.0 MHz, CDCl3): 27.6 (s). Anal. calc. for C19H31Cl2O4PRu (526.4): C 43.35, H 5.94; found: C 43.18, H 6.19.
[RuCl2(p-cym){k-P-tBuP(CH2CO2Me)2}] (5). As described for 3, from 1 (1.0 g, 1.63 mmol) and tBuP(CH2-
CO2Me)2 (956 mg, 4.08 mmol): 1.61 g (91%) of 5. Red-brown solid. M.p. 1348 (dec.). IR (CH2Cl2): 1722
1
(CˆO). H-NMR (200 MHz, CDCl3): 5.81 ± 5.61 (m, C6H4); 3.67 (s, 2 MeO); 3.44 (AB of ABX; d(HA) 3.52,
d(HB) 3.30, 2J(P,HA) ˆ 12.2, 2J(P,HB) ˆ 7.7, 2J(H,H) ˆ 15.2, 2 PCH2); 2.89 (sept., 3J(H,H) ˆ 7.0, Me2CH); 2.08
t
(s, Me C6H4); 1.36 (d, 3J(P,H) ˆ 14.5, Bu); 1.23 (d, 3J(H,H) ˆ 7.0, Me2CH). 13C-NMR (50.3 MHz, CDCl3):
170.4 (d, 2J(P,C) ˆ 5.6, CO2); 109.1, 94.0 (2s, ipso-C of C6H4); 89.7 (d, 2J(P,C) ˆ 3.7, C6H4); 84.0 (d, 2J(P,C) ˆ 6.5,
C6H4); 52.0 (s, MeO); 36.4 (d, 1J(P,C) ˆ 16.6, Me3C); 30.4 (s, Me2CH); 28.7 (s, Me3C); 28.4 (d, 1J(P,C) ˆ 21.3,
PCH2); 22.0 (s, Me2CH); 17.3 (s, Me C6H4). 31P-NMR (81.0 MHz, CDCl3): 35.5 (s). Anal. calc. for
C20H33Cl2O4PRu (540.3): C 44.46, H 6.16; found: C 44.37, H 6.21.
i
[RuCl2(mes){k-P-iPrP(CH2CO2Me)2}] (6). As described for 3, from 2 (1.0 g, 1.71 mmol) and PrP(CH2-
CO2Me)2 (942 mg, 4.28 mmol): 1.67 g (95%) of 6. Red-brown solid. M.p. 1728. IR (CH2Cl2): 1715 (CˆO).
1H-NMR (400 MHz, CDCl3): 5.08 (s, C6H3), 3.64 (s, 2 MeO); 3.37 (AB of ABX; d(HA) 3.48, d(HB) 3.26,
2J(P,HA) ˆ 9.3, 2J(P,HB) ˆ 11.1, 2J(H,H) ˆ 14.8, 2 PCH2); 2.69 (m, Me2CHPh); 2.17 (s, Me C6H3); 1.27
(dd, 3J(P,H) ˆ 15.5, 3J(H,H) ˆ 7.1, Me2CHP). 13C-NMR (100.6 MHz, CDCl3): 170.1 (d, 2J(P,C) ˆ 5.7, CO2);
103.0 (d, 2J(P,C) ˆ 2.8, MeC of mes); 84.5 (d, 2J(P,C) ˆ 3.9, CH of mes); 52.1 (s, MeO); 29.1 (d, 1J(P,C) ˆ 21.1,
Me2CHP); 27.3 (d, 1J(P,C) ˆ 20.1, PCH2); 18.8 (s, Me2CHP); 18.1 (s, Me C6H3). 31P-NMR (81.0 MHz, CDCl3):
31.5 (s). Anal. calc. for C18H29Cl2O4PRu (512.4): C 42.20, H 5.71; found: C 41.91, H 5.59.
t
[RuCl2(mes){k-P-tBuP(CH2CO2Me)2}] (7). As described for 3, from 2 (1.0 g, 1.71 mmol) and BuP(CH2-
CO2Me)2 (1.0 g, 4.28 mmol): 1.66 g (92%) of 7. Red-brown solid. M.p. 1408. IR (CH2Cl2): 1730 (CˆO).
1H-NMR (400 MHz, CDCl3): 5.11 (s, C6H3); 3.64 (s, 2 MeO); 3.45 (AB of ABX; d(HA) 3.51, d(HB) 3.38,

3172
Helvetica Chimica Acta ± Vol. 84 (2001)
2J(P,HA) ˆ 10.6, 2J(P,HB) ˆ 8.3, 2J(H,H) ˆ 14.2, 2 PCH2); 2.26 (s, 3 Me C6H3); 1.34 (d, 3J(P,H) ˆ 14.3, t-Bu);
13C-NMR (50.3 MHz, CDCl3): 169.9 (d, 2J(P,C) ˆ 5.5, CO2); 103.9 (d, 2J(P,C) ˆ 2.8, MeC of mes); 83.9
(d, 2J(P,C) ˆ 4.6, CH of mes); 52.0 (s, MeO); 35.7 (d, 1J(P,C) ˆ 20.3, Me3C); 28.7 (d, 2J(P,C) ˆ 3.7, Me3C), 26.8
(d, 1J(P,C) ˆ 15.7, PCH2); 19.0 (s, Me C6H3). 31P-NMR (81.0 MHz, CDCl3): 39.0 (s). Anal. calc. for
C19H31Cl2O4PRu (526.4): C 43.35, H 5.94; found: C 42.96, H 5.76.
[RuCl(mes){k-P,O-iPrP(CH2C(O)OMe)(CH2CO2Me)}]PF6 (10). A soln. of 6 (120 mg, 0.23 mmol) in
20 ml of CH2Cl2 was treated with AgPF6 (59 mg, 0.23 mmol) and stirred for 1 h at r.t. A change of color from
red-brown to orange occurred. The mixture was filtered, and the filtrate was evaporated to dryness in vacuo. The
remaining orange solid was washed twice with 5-ml portions of Et2O and dried: 133 mg (91%) of 10. M.p. 1658
(dec.). L 72 cm2W 1mol 1. IR (KBr): 1713 ((CˆO)uncoord), 1610 ((CˆO)coord). 1H-NMR (400 MHz, (D6)ace-
tone): 5.45 (s, C6H3); 4.05, 3.82 (2s, 2 MeO); 3.73 (m, PCH2); 3.41 (AB of ABX; d(HA) 3.53, d(HB) 3.28,
2J(P,HA) ˆ 11.4, 2J(P,HB) ˆ 9.1, 2J(H,H) ˆ 17.4, PCH2); 2.84 (m, Me2CH); 2.28 (s, 3 Me C6H3); 1.38
(dd, 3J(P,H) ˆ 20.7, 3J(H,H) ˆ 7.4, 3 H, Me2CH); 1.33 (dd, 3J(P,H) ˆ 14.4, 3J(H,H) ˆ 7.1, 3 H, Me2CH).
13C-NMR (100.6 MHz, (D6)acetone): 187.1 (d, 2J(P,C) ˆ 10.2, CO2coord), 170.5 (s, CO2uncoord); 109.6 (s, MeC of
mes); 79.8 (d, 2J(P,C) ˆ 4.7, CH of mes); 57.1, 53.5 (2s, 2 MeO); 35.9 (d, 1J(P,C) ˆ 33.4, PCH2); 28.5 (d, 1J(P,C) ˆ
17.3, PCH2); 26.0 (d, 1J(P,C) ˆ 33.3, Me2CH); 19.6 (s, Me C6H3); 18.5 (d, 2J(P,C) ˆ 4.8, 1 C, Me2CH); 17.3
(d, 2J(P,C) ˆ 7.4, 1 C, Me2CH). 31P-NMR (81.0 MHz, CD2Cl2): 48.3 (s), 145.8 (sept., 1J(P,F) ˆ 707.9, PF6 ).
Anal. calc. for C18H29ClF6O4P2Ru (621.9): C 34.76, H 4.70; found: C 35.01, H 4.66.
[RuCl(mes){k2-P,O-tBuP(CH2C(O)OMe)(CH2CO2Me)}]PF6 (11). As described for 10, from 7 (135 mg,
0.26 mmol) and AgPF6 (65 mg, 0.26 mmol): 150 mg (92%) of 11. Orange solid. M.p. 1708 (dec.). L
75 cm2W 1mol 1. IR (CH2Cl2): 1721 ((CˆO)uncoord), 1613 ((CˆO)coord). 1H-NMR (400 MHz, (D6)acetone): 5.45
(s, C6H3); 4.04, 3.77 (2s, 2 MeO); 3.69, 3.39 (2m, 2 PCH2); 2.29 (s, 3 Me C6H3); 1.42 (d, 3J(P,H) ˆ 16.1, t-Bu).
13C-NMR (100.6 MHz, (D6)acetone): 186.8 (d, 2J(P,C) ˆ 8.8, CO2coord); 169.8 (s, CO2uncoord); 110.0 (s, MeC of
mes); 79.4 (d, 2J(P,C) ˆ 4.3, CH of mes); 57.1, 53.3 (2s, 2 MeO); 35.6 (d, 1J(P,C) ˆ 23.9, Me3C); 33.9
(d, 1J(P,C) ˆ 28.7, PCH2); 31.4 (d, 1J(P,C) ˆ 14.3, PCH2); 28.3 (d, 2J(P,C) ˆ 2.9, Me3C); 19.7 (s, Me C6H3).
31P-NMR (81.0 MHz, CD2Cl2): 47.3 (s), 145.8 (sept., 1J(P,F) ˆ 707.9, PF6 ). Anal. calc. for C19H31ClF6O4P2Ru
(635.9): C 35.89, H 4.91, Ru 15.89; found: C 35.73, H 5.20, Ru 15.92.
[Ru(p-cym){k3-P,O,O-tBuP(CH2C(O)OMe)2}](PF6)2 (12). A soln. of 5 (313 mg, 0.58 mmol) in 20 ml of
CH2Cl2 was treated with AgPF6 (293 mg, 1.16 mmol) and stirred for 30 min at r.t. After a short time, an orange-
yellow solid precipitated. The solvent was evaporated in vacuo, the residue was extracted with 20 ml of acetone,
and the extract was brought to dryness in vacuo. An orange solid was isolated, which was washed twice with
small quantities of THFand dried: 361 mg (82%) of 12. M.p. 1828 (dec.). L 111 cm2W 1mol 1. IR (CH2Cl2): 1622
(CˆO). 1H-NMR (400 MHz, (D6)acetone): 6.79 ± 6.61 (m, C6H4), 4.09 (s, 2 MeO); 4.12 ± 3.76 (m, 2 PCH2);
2.80 (sept., 3J(H,H) ˆ 6.9, Me2CH); 2.19 (s, Me C6H4); 1.72 (d, 3J(P,H) ˆ 18.4, t-Bu); 1.31 (d, 3J ˆ 6.9, Me2CH).
13C-NMR (100.6 MHz, (D6)acetone): 187.9 (d, 2J(P,C) ˆ 13.5, CO2); 106.3, 100.9 (2s, ipso-C of C6H4); 87.9
(d, 2J(P,C) ˆ 3.6, C6H4); 87.6 (d, 2J(P,C) ˆ 2.8, C6H4); 58.4 (s, MeO); 33.4 (d, 1J(P,C) ˆ 29.9, PCH2); 32.7
(d, 1J(P,C) ˆ 31.2, Me3C); 32.0 (s, Me2CH); 26.6 (d, 2J(P,C) ˆ 3.4, Me3C); 22.4 (s, Me2CH); 18.5
(s, Me C6H4).31P-NMR (81.0 MHz, (D6)acetone): 65.8 (s), 139.1 (sept., 1J(P,F) ˆ 707.0, PF6 ). Anal. calc.
for C20H33F12O4P3Ru (759.5): C 31.63, H 4.38; found: C 31.70, H 4.11.
[Ru(mes){k3-P,O,O-iPrP(CH2C(O)OMe)2}](PF6)2 (13). As described for 12, from 6 (243 mg, 0.47 mmol)
and AgPF6 (240 mg, 0.95 mmol): 271 mg (78%) of 13. Orange solid. M.p. 1578 (dec.). L 108 cm2W 1mol 1. IR
(CH2Cl2): 1609 (CˆO). 1H-NMR (400 MHz, CD3NO2): 5.76 (s, C6H3); 4.09 (s, 2 MeO); 3.61 (AB of ABX;
d(HA) 3.69, d(HB) 3.52, 2J(P,HA) ˆ 8.6, 2J(P,HB) ˆ 12.7, 2J(H,H) ˆ 19.0, 2 PCH2); 3.21 (dsept., 2J(P,H) ˆ 3.2,
3J(H,H) ˆ 7.0, Me2CH); 2.35 (s, 3 Me C6H3); 1.55 (dd, 3J(P,H) ˆ 19.2, 3J(H,H) ˆ 7.0, Me2CH). 31P-NMR
(81.0 MHz, CD3NO2): 50.1 (s), 142.9 (sept., 1J(P,F) ˆ 707.2, PF6 ). Anal. calc. for C18H29F12O4P3Ru (731.4):
C 29.56, H 4.00; found: C 29.69, H 4.25.
[Ru(mes){k3-P,O,O-tBuP(CH2C(O)OMe)2}](PF6)2 (14). As described for 12, from 7 (250 mg, 0.47 mmol)
and AgPF6 (240 mg, 0.95 mmol). 283 mg (80%) of 14. Orange solid. M.p. 1678 (dec.). L 116 cm2W 1mol 1. IR
(CH2Cl2): 1621 (CˆO). 1H-NMR (200 MHz, CD2Cl2): 5.66 (s, C6H3); 4.06 (s, 2 MeO); 3.88 (AB of ABX; d(HA)
3.66, d(HB) 3.11, 2J(P,HA) ˆ 7.7, 2J(P,HB) ˆ 12.0, 2J(H,H) ˆ 18.3, 2 PCH2); 2.35 (s, 3 Me C6H3); 1.54
(d, 3J(P,H) ˆ 18.0, t-Bu). 13C-NMR (100.6 MHz, CD3NO2): 187.7 (d, 2J(P,C) ˆ 13.2, CO2); 111.6 (d, 2J(P,C) ˆ
0.9, MeC of mes); 80.1 (d, 2J(P,C) ˆ 3.3, CH of mes); 59.0 (s, MeO); 34.1 (d, 1J(P,C) ˆ 27.8, PCH2); 32.7
(d, 1J(P,C) ˆ 28.4, Me3C); 26.9 (d, 2J(P,C) ˆ 4.0, Me3C); 20.4 (s, Me C6H3). 31P-NMR (81.0 MHz, CD3NO2):
54.6 (s); 141.2 (sept., 1 J(P,F) ˆ 707.0, PF6 ). Anal. calc. for C19H31F12O4P3Ru (745.4): C 30.61, H 4.19; found:
C 30.49, H 4.06.

Helvetica Chimica Acta ± Vol. 84 (2001)
3173
[Ru(p-cym){k2-P,O-tBuP(CH2C(O)OMe)(CH2CO2Me)}(k-O-O2PF2)]PF6 (15). A soln. of 12 (107 mg,
0.20 mmol) in 20 ml of CH2Cl2 was treated with AgPF6 (100 mg, 0.40 mmol) at r.t. In a few s, an orange-yellow
solid precipitated. After the mixture had been stirred for 12 h in the absence of light, the solvent was evaporated
in vacuo. The residue was extracted with 20 ml of acetone, the extract was brought to dryness in vacuo, and the
remaining oily residue recrystallized from CH2Cl2/OEt2 1:5. Orange-red crystals were obtained, which were
washed with Et2O and dried: 126 mg (89%) of 15. M.p. 1878 (dec.). L 81 cm2W 1mol 1. IR (CH2Cl2): 1720
((CˆO)uncoord), 1611 ((CˆO)coord), 1292 (PˆO). 1H-NMR (400 MHz, CDCl3): 6.48, 5.98, 5.72 (3m, C6H4); 4.02
(s, MeO); 3.75 ± 3.53 (m, PCH2); 3.70 (s, MeO); 2.94 (AB of ABX; d(HA) 3.14, d(HB) 2.73, 2J(P,HA) ˆ 13.0,
2J(P,HB) ˆ 7.3, 2J(H,H) ˆ 17.2, 2 PCH2); 2.50 (sept., 3J(H,H) ˆ 6.8, Me2CH); 2.00 (s, Me C6H4), 1.31
(d, 3J(P,H) ˆ 16.5, t-Bu); 1.30 (d, 3J(H,H) ˆ 7.3, 3 H, Me2CH); 1.24 (d, 3J(H,H) ˆ 6.8, 3 H, Me2CH). 13C-NMR
(100.6 MHz, CDCl3): 186.9 (d, 2J(P,C) ˆ 10.7, CO2coord); 168.6 (d, 2J(P,C) ˆ 1.7, CO2uncoord); 103.1, 96.0 (2s, ipso-C
of C6H4); 87.7 (d, 2J(P,C) ˆ 5.7, C6H4); 87.3, 85.5 (2s, C6H4); 84.3 (d, 2J(P,C) ˆ 4.1, C6H4); 57.2, 53.1 (2s, 2 MeO);
34.3 (d, 1J(P,C) ˆ 23.8, Me3C); 31.4 (s, Me2CH); 30.1 (m, PCH2); 26.8 (d, 2J(P,C) ˆ 3.6, Me3C); 22.5, 21.7 (2s,
Me2CH); 18.0 (s, Me C6H4). 31P-NMR (81.0 MHz, (D6)acetone): 65.1 (s),
13.0 (m, O2PF2),
139.1
(sept., 1J(P,F) ˆ 707.7, PF6 ). Anal. calc. for C20H33F8O6P3Ru (715.5): C 33.58, H 4.65; found: C 33.70, H 4.82.
[Ru(mes){k2-P,O-iPrP(CH2C(O)OMe)(CH2CO2Me)}(k-O-O2PF2)]PF6 (16). As described for 15, from 13
(97 mg, 0.19 mmol) and AgPF6 (96 mg, 0.38 mmol): 117 mg (90%) of 16. Orange-brown solid. M.p. 1688 (dec.).
L 84 cm2W 1mol 1. IR (CH2Cl2): 1721 ((CˆO)uncoord), 1609 ((CˆO)coord), 1298 (PˆO). 1H-NMR (400 MHz,
(D6)acetone): 5.65 (s, C6H3); 4.14, 3.81 (2s, 2 MeO); 3.89 (m, PCH2); 3.42 (AB of ABX; d(HA) 3.63, d(HB) 3.21,
2J(P,HA) ˆ 12.2, 2J(P,HB) ˆ 8.3, 2J(H,H) ˆ 17.9, PCH2); 2.56 (m, Me2CH); 2.32 (s, 3 Me C6H3); 1.50
(dd, 3J(P,H) ˆ 19.7, 3J(H,H) ˆ 7.3, 3 H, Me2CH); 1.39 (dd, 3J(P,H) ˆ 15.7, 3J(H,H) ˆ 7.1, 3 H, Me2CH):
13C-NMR (100.6 MHz, (D6)acetone): 188.9 (d, 2J(P,C) ˆ 11.7, CO2coord); 170.0 (s, CO2uncoord); 109.5 (s, MeC of
mes); 78.3 (s, CH of mes), 57.8, 53.6 (2s, 2 MeO); 32.0 (d, 1J(P,C) ˆ 27.7, PCH2); 29.2 (d, 1J(P,C) ˆ 17.2, PCH2);
19.4 (s, Me C6H3); 18.6 (d, 2J(P,C) ˆ 2.8, Me2CH); 17.6 (d, 2J(P,C) ˆ 4.8, 1 C, Me2CH). 19F-NMR (188.3 MHz,
CD3NO2): 72.6 (d, 1J(P,F) ˆ 707.7, PF6 ); 80.1 (AB of ABX; d(FA) 78.7, d(FB) 81.5, 1J(P,FA) ˆ 957.6,
1J(P,FB) ˆ 970.7, 2J(F,F) ˆ 107.4, O2PF2). 31P-NMR (81.0 MHz, (D6)acetone): 50.0 (d, 3J(P,P) ˆ 4.4, iPrP), 12.7
(ddd, 1J(P,FA) ˆ 957.6, 1J(P,FB) ˆ 970.7, 3J(P,P) ˆ 4.4, O2PF2), 142.7 (sept., 1J(P,F) ˆ 707.7, PF6 ). Anal. calc.
for C18H29F8O6P3Ru (687.4): C 31.45, H 4.25; found: C 31.37, H 4.27.
[Ru(mes){k2-P,O-tBuP(CH2C(O)OMe)(CH2CO2Me)}(k-O-O2PF2)]PF6 (17). As described for 15, from 14
(100 mg, 0.19 mmol) and AgPF6 (96 mg, 0.38 mmol): 121 mg (91%) of 17. Orange-brown solid. M.p. 1668 (dec.).
L 82 cm2W 1mol 1. IR (CH2Cl2): 1722 ((CˆO)uncoord), 1609 ((CˆO)coord), 1302 (PˆO). 1H-NMR (400 MHz,
(D6)acetone): 5.67 (s, C6H3); 4.11, 3.75 (2s, 2 MeO); 3.93 (m, PCH2); 3.46 (AB of ABX; d(HA) 3.61, d(HB) 3.30,
2J(P,HA) ˆ 12.4, 2J(P,HB) ˆ 7.1, 2J(H,H) ˆ 17.9, PCH2); 2.30 (s, 3 Me C6H3); 1.41 (d, 3J(P,H) ˆ 16.3, t-Bu).
13C-NMR (100.6 MHz, (D6)acetone): 188.8 (d, 2J(P,C) ˆ 10.4, CO2coord); 169.6 (s, CO2uncoord); 110.1 (d, 2J(P,C) ˆ
7.6, MeC of mes); 77.7 (d, 2J(P,C) ˆ 3.8, CH of mes); 57.8, 53.6 (2s, 2 MeO); 34.7 (d, 1J(P,C) ˆ 23.6, Me3C); 32.3
(d, 1J(P,C) ˆ 27.5, PCH2); 29.5 (d, 1J(P,C) ˆ 19.1, PCH2); 27.0 (d, 2J(P,C) ˆ 3.6, Me3C); 19.6 (s, Me C6H3). 19F-
NMR (188.3 MHz, CD2Cl2): 74.8 (d, 1J(P,F) ˆ 707.7, PF6 ), 82.0 (AB of ABX; d(FA) 80.3, d(FB) 83.8,
1J(P,Fa) ˆ 963.6, 1J(P,FB) ˆ 972.5, 2J(F,F) ˆ 109.5, O2PF2). 31P-NMR (81.0 MHz, (D6)acetone): 52.7
(d, 3J(P,P) ˆ 2.9, tBuP);
13.1 (ddd, 1J(P,FA) ˆ 963.6,1J(P,FB) ˆ 972.5, 3J(P,P) ˆ 2.9, O2PF2);
142.7
(sept., 1J(P,F) ˆ 707.7, PF6 ). Anal. calc. for C19H31F8O6P3Ru (701.4): C 32.53, H 4.45, Ru 14.41; found:
C 32.85, H 4.46, Ru 14.77.
[Ru(mes){k3-P,C,O-iPrP(CHCO2Me)(CHˆC(O)OMe)}] (18). A suspension of 13 (220 mg, 0.30 mmol) in
20 ml of t-BuOH/toluene (1:1) was treated with KOtBu (68 mg, 0.60 mmol) and irradiated in an ultrasound bath
for 15 min. The solvent was evaporated in vacuo, the residue was extracted with 15 ml of Et2O, and the extract
was brought to dryness in vacuo. To the oily residue 10 ml of hexane was added, and the mixture was stirred for
12 h at r.t. A yellow solid was obtained which was filtered, washed twice with small quantities of hexane, and
dried: 79 mg (60%) of 18. M.p. 938 (dec.). IR (C6H6): 1661 (CˆO). 1H-NMR (400 MHz, C6D6): 4.46 (s, C6H3);
3.51, 3.42 (2s, 2 MeO); 3.45 (d, 2J(P,H) ˆ 12.9, PCHenolate), 2.84 (m, Me2CH); 1.95 (s, 3 Me C6H3); 1.67
(s, PCHmethanide); 1.31 (dd, 3J(P,H) ˆ 21.2, 3J(H,H) ˆ 7.2, 3 H, Me2CH); 1.28 (dd, 3J(P,H) ˆ 15.5, 3J(H,H) ˆ 7.2,
3 H, Me2CH). 13C-NMR (100.6 MHz, (D8)toluene): 179.7 (d, 2J(P,C) ˆ 7.6, CO2ester); 179.1 (d, 2J(P,C) ˆ 25.2,
CO2enolate); 99.8 (s, MeC of mes); 78.9 (d, 2J(P,C) ˆ 3.3, CH of mes); 52.3 (d, 4J(P,C) ˆ 2.1, MeO); 50.0
(d, 4J(P,C) ˆ 1.3, MeO); 44.6 (d, 1J(P,C) ˆ 74.6, PCHenolate); 20.6 (d, 2J(P,C) ˆ 8.4, 1 C, Me2CH); 19.6
(d, 1J(P,C) ˆ 33.5, Me2CH); 19.5 (s, Me C6H3); 18.0 (d, 2J(P,C) ˆ 5.1, 1 C, Me2CH); 4.9 (d, 1J(P,C) ˆ 9.8,
‡
‡
PCHmethanide). 31P-NMR (81.0 MHz, C6D6): 50.5 (s). EI-MS: 440 (47, M ), 397 (85, [M C3H7] ). Anal. calc. for
C18H27O4PRu (439.5): C 49.20, H 6.19; found: C 49.23, H 6.09.

3174
Helvetica Chimica Acta ± Vol. 84 (2001)
[Ru(mes){k3-P,C,O-tBuP(CHCO2Me)(CHˆC(O)OMe)}] (19). As described for 18, from 14 (224 mg,
0.30 mmol) and KOtBu (68 mg, 0.60 mmol): yield 89 mg (65%) of 19. Yellow solid. M.p. 998 (dec.). IR (C6H6):
1687 ((CˆO)ester), 1646 ((CˆO)enolate). 1H-NMR (400 MHz, C6D6): 4.32 (s, C6H3); 3.64, 3.55 (2s, 2 MeO); 3.54
(d, 2J(P,H) ˆ 11.2, PCHenolate); 1.94 (s, 3 Me C6H3); 1.69 (d, 2J(P,H) ˆ 15.3, PCHmethanide); 1.10 (d, 3J(P,H) ˆ 16.3,
t-Bu). 13C-NMR (100.6 MHz, (D6)acetone): 179.6 (d, 2J(P,C) ˆ 24.1, CO2enolate); 179.5 (d, 2J(P,C) ˆ 4.8, CO2ester);
101.6 (d, 2J(P,C) ˆ 1.8, MeC of mes); 77.5 (d, 2J(P,C) ˆ 2.7, CH of mes); 52.7 (d, 4J(P,C) ˆ 2.0, MeO); 49.8
(s, MeO); 44.0 (d, 1J(P,C) ˆ 72.8, PCHenolate); 28.9 (d, 1J(P,C) ˆ 35.0, Me3C); 27.3 (d, 2J(P,C) ˆ 3.6, Me3C); 20.2
‡
(s, Me C6H3); 8.7 (d, 1J(P,C) ˆ 3.3, PCHmethanide). 31P-NMR (81.0 MHz, C6D6): 62.5 (s). EI-MS: 454 (16, M ),
‡
397 (100, [M C4H9] ). Anal. calc. for C19H29O4PRu (453.5): C 50.32, H 6.45; found: C 49.99, H 6.37.
Reactions of Compounds 18 and 19 with HCl. A slow stream of gaseous HCl was passed through a soln. of
18 or 19 (0.09 mmol) in 10 ml of toluene for 20 s at r.t. A quick change of color from yellow to brown occurred.
After stirring the soln. for 10 min, the solvent was evaporated in vacuo. The 1H-NMR spectrum of the residue
confirmed that compounds 6 or 7 were obtained in quantitative yields.
[Ru(p-cym){k3-P,O,O-iPrP(CH2C(O)O)2}] (20). A suspension of 4 (190 mg, 0.36 mmol) in 20 ml of t-
BuOH/toluene 1:1 was treated with KOtBu (81 mg, 0.72 mmol) and stirred for 1 h at r.t. The solvent was
evaporated in vacuo, the residue was dissolved in 2 ml of MeOH, and the soln. was chromatographed on Al2O3
(basic, activity grade III, height of column 5 cm). With MeOH, an orange fraction was eluted, which was
brought to dryness in vacuo. The remaining orange-yellow solid was washed three times with 5-ml portions of
Et2O and dried: 54 mg (35%) of 20. M.p. 868 (dec.). IR (CH2Cl2): 1637 (CˆO). 1H-NMR (400 MHz, CDCl3):
5.72 (m, C6H4), 2.66 (AB of ABX; d(HA) 2.78, d(HB) 2.54, 2J(P,HA) ˆ 7.0, 2J(P,HB) ˆ 8.7, 2J(H,H) ˆ 17.2,
2 PCH2); 2.66 (m, Me2CH); 1.97 (s, Me C6H4); 1.34 (dd, 3J(P,H) ˆ 17.3, 3J(H,H) ˆ 7.0, Me2CHP); 1.12
(d, 3J(H,H) ˆ 6.8, Me2CH); signal of 1 Me2 not exactly located. 13C-NMR (100.6 MHz, CDCl3): 177.2
(d, 2J(P,C) ˆ 11.4, CO2), 102.2, 97.4 (2s, ipso-C of C6H4); 86.3 (d, 2J(P,C) ˆ 4.1, C6H4), 86.1 (d, 2J(P,C) ˆ 3.4,
C6H4); 30.7 (s, Me2CH); 30.2 (d, 1J(P,C) ˆ 29.8, PCH2); 25.0 (d, 1J(P,C) ˆ 31.0, Me2CHP); 22.4 (s, Me2CH); 18.0
(d, 2J(P,C) ˆ 1.5, Me2CHP); 17.9 (s, Me C6H4). 31P-NMR (81.0 MHz, CDCl3): 38.2 (s). Anal. calc. for
C17H25O4PRu (425.4): C 48.00, H 5.92; found: C 47.67, H 6.16.
[Ru(p-cym){k3-P,O,O-tBuP(CH2C(O)O)2}] (21). As described for 20, from 5 (220 mg, 0.41 mmol) and
KOtBu (91 mg, 0.81 mmol): 29 mg (23%) of 21. Orange-yellow solid. 1198 (dec.). IR (CH2Cl2): 1647 (CˆO).
1H-NMR (200 MHz, CDCl3): 5.78 (m, C6H4); 2.63 (AB of ABX, d(HA) 2.78, d(HB) 2.49, 2J(P,HA) ˆ 7.9,
2J(P,HB) ˆ 12.1, 2J(H,H) ˆ 17.2, 2 PCH2); 2.57 (sept., 3J(H,H) ˆ 6.9, Me2CH); 1.98 (s, Me C6H4); 1.38
(d, 3J(P,H) ˆ 16.1, t-Bu); 1.14 (d, 3J(H,H) ˆ 6.9, Me2CH). 13C-NMR (100.6 MHz, CDCl3): 177.1 (d, 2J(P,C) ˆ
11.2, CO2); 102.7, 95.4 (2s, ipso-C of C6H4); 87.4, 85.7 (2d, 2J(P,C) ˆ 4.0, C6H4); 30.7 (s, Me2CH); 30.1
(d, 1J(P,C) ˆ 29.5, Me3C); 30.0 (d, 1J(P,C) ˆ 28.1, PCH2); 26.5 (d, 2J(P,C) ˆ 3.0, Me3C); 22.3 (s, Me2CH); 17.9
(s, Me C6H4). 31P-NMR (81.0 MHz, CDCl3): 46.2 (s). Anal. calc. for C18H27O4PRu (439.5): C 49.20, H 6.19;
found: C 49.45, H 5.78.
[Ru(mes){k3-P,O,O-iPrP(CH2C(O)O)2}] (22). A soln. of 18 (61 mg, 0.14 mmol) in 5 ml of acetone was
treated with H2O (ca. 100 ml) and stirred for 12 h at r.t. The workup procedure was the same as described for 20:
1
47 mg (83%) of 22. Yellow solid. M.p. 1018 (dec.). IR (CH2Cl2): 1647 (CˆO). H-NMR (400 MHz, CDCl3):
5.10 (s, C6H3); 2.69 (AB of ABX; d(HA) 2.79, d(HB) 2.58, 2J(P,HA) ˆ 8.1, 2J(P,HB) ˆ 12.4, 2J(H,H) ˆ 17.1,
2 PCH2); 2.16 (s, 3 Me C6H3); 1.33 (dd, 3J(P,H) ˆ 16.6, 3J(H,H) ˆ 7.1, Me2CH); signal of Me2CH not exactly
located. 13C-NMR (100.6 MHz, CD3NO2): 178.8 (d, 2J(P,C) ˆ 10.9, CO2); 106.8 (s, MeC of mes); 81.2
(d, 2J(P,C) ˆ 3.9, CH of mes); 31.8 (d, 1J(P,C) ˆ 29.3, PCH2); 23.3 (d, 1J(P,C) ˆ 29.7, Me2CH); 19.2
(s, Me C6H3); 18.1 (d, 2J(P,C) ˆ 2.7, Me2CH). 31P-NMR (81.0 MHz, CDCl3): 36.2 (s). Anal. calc. for
C16H23O4PRu (411.4): C 46.71, H 5.64; found: C 46.91, H 5.53.
[Ru(mes){k3-P,O,O-tBuP(CH2C(O)O)2}] (23). As described for 22, from 19 (54 mg, 0.12 mmol) and H2O
(ca. 100 ml). 41 mg (81%) of 23. Yellow solid. M.p. 1558 (dec.). IR (CH2Cl2): 1647 (CˆO). 1H-NMR (400 MHz,
2
2
2
CDCl3): 5.27 (s, C6H3); 2.65 (AB of ABX; d(HA) 2.79, d(HB) 2.50, J(P,HA) ˆ 7.3, J(P,HB) ˆ 12.3, J(H,H) ˆ
17.0, 2 PCH2); 2.20 (s, 3 Me C6H3); 1.36 (d, 3J(P,H) ˆ 15.7, t-Bu). 13C-NMR (100.6 MHz, CDCl3): 177.4
(d, 2J(P,C) ˆ 10.5, CO2); 101.8 (d, 2J(P,C) ˆ 1.7, MeC of mes); 83.2 (d, 2J(P,C) ˆ 2.3, CH of mes); 31.0
(d, 1J(P,C) ˆ 27.3, PCH2); 29.7 (d, 1J(P,C) ˆ 26.9, Me3C); 26.5 (d, 2J(P,C) ˆ 3.9, Me3C); 19.4 (s, Me C6H3). 31P-
NMR (81.0 MHz, CDCl3): 42.2 (s). Anal. calc. for C17H25O4PRu (425.4): C 48.00, H 5.92; found: C 47.84, H 6.15.
[Ru(mes){k3-P,C,O-tBuP(CHCO2Me)(C(C(O)NHPh)ˆC(O)OMe)}] (24).
A soln. of 19 (63 mg,
0.14 mmol) in 10 ml of toluene was treated with PhNCO (33 mg, 0.28 mmol) and stirred for 2 h at r.t. The
solvent was evaporated in vacuo, the remaining yellow solid was washed three times with small quantities of
hexane, and dried: 56 mg (70%) of 24. M.p. 1248 (dec.). IR (C6H6): 3380 (NH), 1679 ((CˆO)ester), 1628
1
((CˆO)enolate). H-NMR (400 MHz, CDCl3): 9.10 (s, NH); 7.87 ± 6.84 (m, C6H5), 4.35 (s, C6H3); 3.43, 3.39 (2s,

Helvetica Chimica Acta ± Vol. 84 (2001)
3175
2 MeO); 1.84 (s, 3 Me C6H3); 1.76 (d, 2J(P,H) ˆ 14.8, PCHmethanide); 1.58 (d, 3J(P,H) ˆ 18.1, t-Bu). 13C-NMR
(100.6 MHz, C6D6): 176.2 (d, 2J(P,C) ˆ 28.0, CO2enolate); 173.9 (s, C(O)R); 141.3, 128.9, 122.1, 119.6 (4s, C6H5);
100.7 (s, MeC of mes); 78.7 (d, 2J(P,C) ˆ 1.7, CH of mes); 69.3 (d, 1J(P,C) ˆ 67.0, PCHenolate); 52.3, 50.4 (2s,
2 MeO); 33.0 (d, 1J(P,C) ˆ 30.4, Me3C); 29.5 (d, 2J(P,C) ˆ 4.8, Me3C); 19.7 (s, Me C6H3); 3.5 (d, 1J(P,C) ˆ
‡
‡
2.8, PCHmethanide). 31P-NMR (81.0 MHz, (D8)toluene): 56.7 (s). EI-MS: 573 (1, M ), 516 (9, [M C4H9] ). Anal.
calc. for C26H24NO5PRu (572.6): C 54.54, H 5.99, N 2.45; found: C 53.96, H 5.77, N 2.89.
[Ru(mes){k3-P,S,S-tBuP(C(C(ˆNHPh)S)2CO2Me)(CH2CO2Me)}] (25). A soln. of 19 (72 mg, 0.16 mmol)
in 10 ml of toluene was treated with PhNCS (200 ml, 1.67 mmol) and stirred for 6 h at r.t. The solvent was
evaporated in vacuo, the remaining brown solid was washed three times with small quantities of hexane, and
dried: 87 mg (76%) of 25. M.p. 938 (dec.). IR (C6H6): 1726 (CˆO), 1577 (CˆN). 1H-NMR (400 MHz, CDCl3):
7.27 ± 6.85 (m, 2 Ph); 5.02 (s, C6H3); 3.95 (m, 1 H, PCH2); 3.81, 3.58 (2s, 2 MeO); 2.98 (dd, 2J(P,H) ˆ 8.6,
2J(H,H) ˆ 13.1, 1 H, PCH2); 2.11 (s, 3 Me C6H3); 1.42 (d, 3J(P,H) ˆ 14.3, t-Bu). 13C-NMR (100.6 MHz, CDCl3):
170.9 (d, 2J(P,C) ˆ 9.9, CO2); 169.9 (s, C(ˆNPh)S); 169.0 (d, 2J(P,C) ˆ 16.7, C(ˆNPh)S); 167.2 (d, 2J(P,C) ˆ 3.7,
CO2); 153.0, 151.9, 128.4, 128.1, 122.6, 122.3, 121.2, 120.3 (8s, Ph); 108.0 (d, 2J(P,C) ˆ 1.7, MeC of mes), 87.2
(d, 2J(P,C) ˆ 3.9, CH of mes); 81.6 (d, 1J(P,C) ˆ 34.7, CCO2Me); 52.5, 52.0 (2s, 2 MeO); 37.7 (d, 1J(P,C) ˆ 15.0,
Me3C); 30.8 (d, 1J(P,C) ˆ 11.5, PCH2); 28.9 (d, 2J(P,C) ˆ 3.1, Me3C); 19.0 (s, Me C6H3). 31P-NMR (162.0 MHz,
CDCl3): 87.6 (s). Anal. calc. for C33H39N2O4PS2Ru (723.9): C 54.76, H 5.43, N 3.87, S 8.86; found: C 54.92,
H 5.40, N 3.84, S 9.17.
X-Ray Structure Determination of Compounds 17 and 18. Single crystals of 17 were grown from a sat. soln.
in toluene at r.t., and those of 18 by diffusion of Et2O into a sat. soln. in CH2Cl2 at r.t. Crystal-data collection
Table 1. Crystal-Structure Data of Compounds 17 and 18
17
18
Formula
Mol. mass
Crystal size [mm]
Crystal system
Space group
a [Š]
b [Š]
c [Š]
a [8]
b [8]
C19H31F8O6P3Ru
701.42
C18H27O4PRu
439.44
0.60 Â 0.33 Â 0.23
monoclinic
P21/c (No. 14)
17.001(5)
10.6463(14)
17.221(5)
90.0
117.693(12)
90.0
2760.0(12)
4
0.30 Â 0.20 Â 0.15
triclinic
P1 (No. 2)
7.913(8)
10.195(11)
13.475(18)
99.47(7)
103.91(7)
111.92(5)
1706.3(4)
2
g [8]
V [Š3]
Z
1
dcalcd [g cm
]
1.688
1.554
Diffractometer
Radiation (graphite-monochromated)
Enraf-Nonius CAD4
MoKa (0.71073 Š)
293(2)
Enraf-Nonius CAD 4
MoKa (0.71073 Š)
293(2)
T [K]
m [mm
1
]
0.820
0.925
transmission min. [%]
Scan method
97.00
w/q
no absorption correction
w
2q(max) [8]
51.82
53.08
Total reflections
Unique reflections
Observed reflections
5592
5399
4188
3456
3181
2784
[I > 2s(I)]
360
[I > 2s(I)]
224
Parameters refined
R1
0.0418
0.0283
wR2
0.1129
0.0764
GOF
1.086
1.108
Reflection/parameter ratio
Residual electron density [eŠ
15.0
‡ 0.473/ 0.551
14.2
‡ 0.487/ 0.573
3
]

3176
Helvetica Chimica Acta ± Vol. 84 (2001)
parameters are summarized in the Table. Intensity data were corrected for Lorentz and polarization effects, and
an empirical absorption correction was applied for 17 (y-scans). The structures were solved by direct methods
(SHELXS-97) [25]. Atomic coordinates and anisotropic thermal parameters of the non-H-atoms were refined
by the full-matrix least-squares method (SHELXL-97) [26]. The positions of all H-atoms were calculated
according to ideal geometry (distance C H ˆ 0.95 Š) and used only in structure-factor calculation. Crystallo-
graphic data (excluding structure factors) for 17 have been deposited with the Cambridge Crystallographic Data
Centre (CCDC) as deposition No. CCDC-166427. Copies of the data can be obtained, free of charge, on
application to the CCDC, 12 Union Road, Cambridge CB21EZ, UK (fax: ‡ 44(1223)336033; e-mail:
deposit@ccdc.cam.ac.uk). Ref. code for 18 ZIQBAC, Cambridge Structural Database System, 2001.
REFERENCES
[1] a) A. Bader, E. Lindner, Coord. Chem. Rev. 1991, 108, 27; b) E. Lindner, S. Pautz, M. Haustein, Coord.
Chem. Rev. 1996, 155, 145; c) P. Braunstein, F. Naud, Angew. Chem., Int. Ed. 2001, 40, 680.
[2] a) S.-E. Bouaoud, P. Braunstein, D. Grandjean, D. Matt, D. Nobel, Inorg. Chem. 1988, 27, 2279; b) P.
Braunstein, T. M. Gomes Carneiro, D. Matt, F. Balegroune, D. Grandjean, Organometallics 1989, 8, 1737;
c) P. Braunstein, D. Nobel, Chem. Rev. 1989, 89, 1927.
[3] S. D. Perera, B. L. Shaw, M. Thornton-Pett, J. D. Vessey, Inorg. Chim. Acta 1992, 198 ± 200, 149.
[4] a) P. Braunstein, D. Matt, Y. Dusausoy, J. Fischer, A. Mitschler, L. Ricard, J. Am. Chem. Soc. 1981, 103,
5115; b) P. Braunstein, D. Matt, D. Nobel, Chem. Rev. 1988, 88, 747.
[5] a) H. Werner, A. Stark, M. Schulz, J. Wolf, Organometallics 1992, 11, 1126; H. Werner, A. Stark, P. Steinert,
C. Grünwald, J. Wolf, Chem. Ber. 1995, 128, 49; T. Braun, P. Steinert, H. Werner, J. Organomet. Chem. 1995,
488, 169; b) H. Werner, B. Weber, O. Nürnberg, J. Wolf, Angew. Chem., Int. Ed. 1992, 31, 1025; B. Weber, P.
Steinert, B. Windmüller, J. Wolf, H. Werner, J. Chem. Soc., Chem. Commun. 1994, 2595; c) W. Wolfsberger,
W. Burkart, S. Bauer, A. Hampp, J. Wolf, H. Werner, Z. Naturforsch., B 1994, 49, 1659; d) P. Steinert, H.
Werner, Organometallics 1994, 13, 2677; P. Steinert, H. Werner, Chem. Ber. Recl. 1997, 130, 1591.
[6] W. Wolfsberger, J. Bank, H. Werner, Z. Naturforsch., B 1995, 50, 1319.
[7] a) G. Henig, H. Werner, Z. Naturforsch., B 1998, 53, 540; b) H. Werner, J. Bank, P. Steinert, W.
Wolfsberger, Z. Anorg. Allg. Chem. 1999, 625, 2178.
[8] J. Bank, O. Gevert, W. Wolfsberger, H. Werner, Organometallics 1995, 14, 4972.
[9] S. A. Serron, S. P. Nolan, Organometallics 1995, 14, 4611.
[10] S. D. Robinson, M. F. Uttley, J. Chem. Soc., Dalton Trans. 1973, 1912.
[11] a) C. White, S. J. Thompson, P. M. Maitlis, J. Organomet. Chem. 1977, 134, 319; b) P. R. Holland, B.
Howard, R. J. Mawby, J. Chem. Soc., Dalton Trans. 1983, 231; c) M. I. Bruce, M. P. Cifuentes, K. R. Grundy,
M. J. Liddell, M. R. Snow, E. R. T. Tiekink, Aust. J. Chem. 1988, 41, 597; d) S. Kitagawa, S. Kawata, Y.
Nozaka, M. Munakata, J. Chem. Soc., Dalton Trans. 1993, 1399.
[12] M. A. Bennett, T. W. Matheson, G. B. Robertson, W. L. Steffen, T. W. Turney, J. Chem. Soc., Chem.
Commun. 1979, 32.
[13] J. Bank, P. Steinert, B. Windmüller, W. Wolfsberger, H. Werner, J. Chem. Soc., Dalton Trans. 1996, 1153.
[14] H. Werner, G. Henig, B. Windmüller, O. Gevert, C. Lehmann, R. Herbst-Irmer, Organometallics 1999, 18,
1185.
[15] a) B. Demerseman, B. Guilbert, C. Renouard, M. Gonzalez, P. H. Dixneuf, D. Masi, C. Mealli,
Organometallics 1993, 12, 3906; b) P. Braunstein, Y. Chauvin, J. Nähring, Y. Dusausoy, D. Bayeul, A.
Tiripicchio, F. Ugozzoli, J. Chem. Soc., Dalton Trans. 1995, 851.
[16] a) D. L. Reger, M. F. Huff, L. Lebioda, Acta Crystallogr., Sect. C 1991, 47, 1167; b) R. Fernandez-Galan,
B. R. Manzano, A. Otero, M. Lanfranchi, M. A. Pellinghelli, Inorg. Chem. 1994, 33, 2309.
[17] a) H. Werner, R. Werner, J. Organomet. Chem. 1981, 209, C60; b) J. Gotzig, R. Werner, H. Werner, J.
Organomet. Chem. 1985, 285, 99.
[18] a) J. F. Hartwig, R. A. Andersen, R. G. Bergman, Organometallics 1991, 10, 1875; b) M. J. Burn, M. G.
Fickes, J. F. Hartwig, F. J. Hollander, R. G. Bergman, J. Am. Chem. Soc. 1993, 115, 5875.
[19] E. Lindner, K. A. Starz, H.-J. Eberle, W. Hiller, Chem. Ber. 1983, 116, 1209.
[20] E. Lindner, E. U. Küster, W. Hiller, R. Fawzi, Chem. Ber. 1984, 117, 127.
[21] a) G. Henig, M. Schulz, H. Werner, Chem. Commun. 1997, 2349; b) H. Werner, G. Henig, U. Wecker, N.
Mahr, K. Peters, H. G. von Schnering, Chem. Ber. 1995, 128, 1175.
[22] P. Braunstein, D. Matt, D. Nobel, S.-A. Bouaoud, D. Grandjean, J. Organomet. Chem. 1986, 301, 401.

Helvetica Chimica Acta ± Vol. 84 (2001)
3177
[23] B. Demerseman, C. Renouard, R. Le Lagadec, M. Gonzalez, P. Chrochet, P. H. Dixneuf, J. Organomet.
Chem. 1994, 471, 229.
[24] M. A. Bennett, A. K. Smith, J. Chem. Soc., Dalton Trans. 1974, 233.
[25] G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467.
[26] G. M. Sheldrick, ꢀSHELXL-97, Program for Crystal Structure Refinementꢁ, Universität Göttingen, 1997.
Received July 3, 2001