Six-coordinate ruthenium(II) complexes containing unsymmetrical 1,2-bis(phosphanyl)ethanes and 1-arsanyl-2-phosphanylethanes as ligands

Article abstract of DOI:10.1002/1099-0682(200012)2000:12<2597::AID-EJIC2597>3.0.CO;2-F

The bis(η³-2-methallyl)ruthenium(II) complexes [Ru(η³-2-MeC₃H₄)₂(κ²-Ph₂PCH₂CH₂PR₂)] [R = iPr (2), Cy (3)] were prepared from the cycloocta-1,5-di

Full text of DOI:10.1002/1099-0682(200012)2000:12<2597::AID-EJIC2597>3.0.CO;2-F

FULL PAPER
Six-Coordinate Ruthenium(II) Complexes Containing Unsymmetrical 1,2-
Bis(phosphanyl)ethanes and 1-Arsanyl-2-phosphanylethanes as Ligands
Guido Fries,[a] Kerstin Ilg,[a] Matthias Pfeiffer,[a] Dietmar Stalke,[a] and Helmut Werner*[a]
Dedicated to Professor Herbert Schumann on the occasion of his 65th birthday
Keywords: Acetylacetonato complexes / Allyl complexes / Ruthenium / Chelates / Phosphorus / Arsenic
The bis(η3-2-methallyl)ruthenium(II) complexes [Ru(η3-2-
MeC3H4)2(κ2-Ph2PCH2CH2PR2)] [R = iPr (2), Cy (3)] were
prepared from the cycloocta-1,5-diene derivative [Ru(η3-2-
MeC3H4)2(η4-C8H12)] (1) and the unsymmetrical 1,2-bis-
(phosphanyl)ethanes Ph2PCH2CH2PR2. The As,P analogue
acac)2(κ2-iPr2PCH2CH2PPh2)], whereas treatment of 2 and 3
with pentachlorophenol gave the related, more labile com-
plexes [Ru(κ2-O,Cl-OC6Cl5)2(κ2-R2PCH2CH2PPh2)] [R = iPr
(6), Cy (7)]. Preparation of the parent bis(acac) compound
[Ru(κ2-acac)2(κ2-iPr2PCH2CH2PPh2)] (8), which could not be
[Ru(η3-2-MeC3H4)2(κ2-Ph2PCH2CH2AstBu2)] (4) was ob- obtained from 2 and acacH, was achieved by ligand ex-
tained by the same route. The reaction of 2 with hexafluoro- change of 6 and acetylacetone. The molecular structures of
acetylacetone afforded the chelate compound [Ru(κ2-[F6]-
2 and 6 were determined by X-ray crystallography.
Introduction
Results and Discussion
The preparation of the chelate complexes 2 and 3
(Scheme 1) followed the route which was used by Holle,
Jolly, and Kuhnigk to obtain the related bis(η3-allyl)ruth-
enium(II) compounds with iPr2P(CH2)nPiPr2 (n ϭ 1, 2, and
3) as ligands.[4] The reaction proceeds in hexane under re-
flux conditions and affords the products as yellow solids in
about 70% isolated yield. Compounds 2 and 3 are only
slightly air-sensitive and, apart from pentane and ether,
readily soluble in most common organic solvents. The 31P
NMR spectra of both 2 and 3 display two sharp doublets
for the nonequivalent phosphorus nuclei with 31P-31P coup-
ling constants of 8.5 and 7.6 Hz, respectively. Due to the
presence of the unsymmetrical 1.2-bis(phosphanyl)ethane
ligand, the 1H NMR spectra of 2 and 3 are rather complex,
thus making an exact assignment of the signals for the CH2
allyl protons difficult.
By attempting to modify the donor/acceptor properties
of bidentate ligands with P, As, and Sb as donor atoms,
we recently described two new synthetic methodologies for
unsymmetrical bis(phosphanyl)methanes and 1,2-bis(phos-
phanyl)ethanes as well as for their As,P analogues.[1,2] While
the methane derivatives R2PCH2ERЈ2 were prepared from
the stannylated phosphanes R2PCH2SnRЈЈ3 by metalation
with MeLi or PhLi in the presence of tetramethylethylenedi-
amine followed by treatment with RЈ2PCl or RЈ2AsCl,[1] the
corresponding disubstituted ethanes R2PCH2CH2ERЈ2
were obtained in a one-pot reaction from the cyclic sulfate
C2H4O2SO2 by stepwise addition of RЈ2ELi and R2PLi, re-
spectively. The latter method is also suitable for the pre-
paration of chiral bidentate P,P donors of the general com-
position R2PCH2CH(Me)PPh2 and R2PCH2CH2CH(Me)-
PPh2 where the substituent R is a bulky alkyl or cycloalkyl
group such as iPr, tBu, or C6H11.[2,3]
In the initial phase of these studies, we tested the coor-
dination properties of the new ligands toward rhodium(I)
and isolated a series of square-planar and half-sandwich-
type
complexes
including
[Rh(η4-C8H12)(κ2-R-
[3]
Ph2PCH(Me)CH2PCy2)]PF6
and [(η6-C6H5R)Rh(κ2-
Cy2PCH2PiPr2)]PF6 (R ϭ H, Me).[1] In this paper we report
the synthesis of a series of ruthenium(II) compounds with
both Ph2PCH2CH2PR2 and Ph2PCH2CH2AstBu2 as chelat-
ing ligands and η3-2-methallyl, pentachlorphenolate, and
acetylacetonates as ancillary bidentate units. Some prelim-
inary results of this work have already been communi-
cated.[2]
Scheme 1
The molecular structure of compound 2, of which single
crystals were obtained from a saturated solution in hexane,
was determined by X-ray crystallography. The molecular
[a]
Institut für Anorganische Chemie der Universität Würzburg,
Am Hubland, 97074 Würzburg, Germany
Eur. J. Inorg. Chem. 2000, 2597Ϫ2601
WILEY-VCH Verlag GmbH, D-69451 Weinheim, 2000
1434Ϫ1948/00/1212Ϫ2597 $ 17.50ϩ.50/0
2597

G. Fries, K. Ilg, M. Pfeiffer, D. Stalke, H. Werner
FULL PAPER
diagram (Figure 1) reveals that the coordination geometry
The reaction of 2 with two equivalents of hexafluorace-
around the metal center can be described as a distorted tet- tylacetone affords, by protonation of both 2-methallyl li-
rahedron with the two phosphorus atoms P1 and P2 and gands (and elimination of isobutene), the chelate complex
the two central carbon atoms C40 and C50 of the allylic 5 (Scheme 2) as a red air-stable solid in almost quantitative
moieties at the corners of the tetrahedron. The bond lengths yield. Due to the coordination of the unsymmetrical 1,2-
RuϪC40 and RuϪC50 are somewhat shorter than those bis(phosphanyl)ethane, the two [F6]acac units are non-
from the ruthenium center to the terminal carbon atoms of equivalent and therefore the 13C NMR as well as the 19F
the 2-methallyl ligands. This results in dihedral angles of NMR spectrum of 5 display four resonances for the carbon
37.7(1)° and 34.9(1)° between the planes [C40,C41,C42] and and fluorine nuclei of the CF3 groups. The appearance of
[C50,C51,C52] of the π-allyl units and the plane of the five- four quadruplets for the CF3CO and of two singlets for the
membered chelate ring [Ru,P1,C2,C1,P2]. The distances COCHCO carbon atoms equally illustrates the stereochem-
RuϪP1 and RuϪP2 differ only slightly to those in similar ical nonequivalence of the [F6]acac ligands.
phosphaneruthenium(II) complexes[5Ϫ7] while the bite angle
P1ϪRuϪP2 of 85.32(3)° is nearly identical to that in
[Ru(η3-2-MeC3H4)2(κ2-Cy2PCH2CH2PCy2)] [85.03(4)°].[5]
Figure 1. Molecular structure of compound 2; selected bond
˚
lengths [A] and angles [°]: RuϪP1 2.3278(9), RuϪP2 2.2981(8),
RuϪC40 2.178(3), RuϪC41 2.237(4), RuϪC42 2.232(4), RuϪC50
2.181(3), RuϪC51 2.247(3), RuϪC52 2.230(4), P1ϪC2 1.854(3),
P2ϪC1 1.851(3); P1ϪRuϪP2 85.32(3), C1ϪP2ϪRu 110.07(11),
C2ϪP1ϪRu 107.03(11), C1ϪC2ϪP1 111.9(2), C2ϪC1ϪP2
Scheme 2
110.1(2), C41ϪC40ϪC42 116.4(3), C51ϪC50ϪC52 117.9(3)
In contrast to iPr2PCH2AstBu2, which does not react
In contrast to the hexafluoro derivative [F6]acacH, the
with the starting material 1 by substitution of the cyclo- parent compound acacH does not react, even in refluxing
octadiene ligand,[3] the reaction of the ethane derivative toluene, with the starting material 2. The lower acidity of
Ph2PCH2CH2AstBu2 with 1 affords the chelate complex 4 acetylacetone (pKa ϭ 9.0) compared to the hexafluoro ana-
(see Scheme 1) as a yellow solid in 51% isolated yield. While logue (pKa ϭ 5.3)[9] presumably causes the difference in the
the 31P NMR spectrum of 4 displays, in agreement with the reactivity of the two diketones toward the η3-2-methallylru-
1
proposed structure, a single resonance at δ ϭ 79.4, the H thenium(II) complex 2.
NMR spectrum is very complex and shows several overlap-
However, the bis(acac) compound 8 is accessible in a
ping signals between δ ϭ 2.95 and 0.51, which originate stepwise route via the intermediate bis(pentachlorophenol-
from the allyl, the tert-butyl and the CH2 protons of the ato) complex 6. Both 6 and 7 are obtained in excellent yield
coordinated As,P donor unit. In the 13C NMR spectrum of as orange, moderately air-sensitive solids upon treatment of
4, the CH2 carbon atoms of the 2-methallyl units give rise 2 and 3 with two equivalents of C6Cl5OH in toluene at
to four doublets at δ ϭ 39.6, 36.9, 36.3, and 33.4, thus con- room temperature. With regard to the spectroscopic data of
firming the presence of an additional unsymmetrical bi- 6 and 7, the interesting feature is that the 13C NMR spectra
dentate ligand.
(in [D8]toluene) display at both 295 K and 188 K only one
Similarly to the starting material 1, the substituted com- signal for the ortho- and one signal for the meta-carbon
pounds 2 and 3 are also quite reactive towards Brönsted atoms of the OC6Cl5 units. This observation indicates that
acids. However, in contrast to 1 which reacts cleanly with a fluxional process takes place in solution, which involves
CF3CO2H to give [Ru(η4-C8H12)(µ-O2CCF3)2]2,[8] treat- (on the NMR time scale) rapid coordination/decoordina-
ment of 2 or 3 with trifluoroacetic acid leads to a mixture tion of the chlorine atoms in ortho position of the six-mem-
of products which could not be separated by conventional bered rings to the metal center. There is good reason to
techniques.
believe that the stability of the chelating bonding mode (via
2598
Eur. J. Inorg. Chem. 2000, 2597Ϫ2601

Six-Coordinate Ruthenium(II) Complexes
FULL PAPER
oxygen and chlorine) of the pentachlorophenolato ligands oligomerization or decomposition process. We note that
to the ruthenium center depends significantly on the coor- quite recently Baratta et al. reported another example of a
dination sphere since the tris(chelate) complexes [Ru(κ2- ruthenium(II) complex with a formal 14-electron configura-
OC6Cl5)2(κ2-Ph2PCH2PR2)] (R ϭ iPr, Cy) are fluxional at tion; in this case two strong agostic RuHC interactions re-
295 K but rigid at 188 K,[10] while the hydrido compound lieve part of the electronic unsaturation at the metal
[RuH(κ2-OC6Cl5)(CO)(PiPr3)2] is nonfluxional on the center.[16]
NMR timescale even at room temperature.[11]
The X-ray crystal structure analysis of 6 (Figure 2) con-
firms the existence of weak RuϪCl interactions comparable
Experimental Section
to those between transition metals and other CϪCl
All operations were carried out under argon using Schlenk tech-
niques. The starting material 1[17] as well as the ligands
Ph2PCH2CH2PR2 (R ϭ iPr, Cy) and Ph2PCH2CH2AstBu2[2,3] were
prepared as described in the literature. Ϫ IR: PerkinϪElmer 1320.
Ϫ NMR: Bruker AC 200 and AMX 400. Ϫ Melting points deter-
mined by DTA.
bonds.[12] The RuϪCl distances of 2.498(1) A and 2.524(1)
˚
A
are significantly longer than in trans-[RuCl2(κ2-
˚
[13]
˚
Ph2PCH2CH2PPh2)2] [2.4325(12) A]
and trans-
2
[RuCl2(κ -Ph2PCH2PPh2)2] [2.426(1) A,[14] where ‘‘normal’’
covalent RuϪCl bonds are present. The coordination geo-
metry around the metal center in 6 is a distorted octahe-
dron with a bite angle P1ϪRuϪP2 of 84.32(5)° that is al-
most identical to that in compound 2. The bond angles
RuϪO1ϪC1 [120.6(3)°] and RuϪO2ϪC7 [119.3(3)°] are
considerably smaller than in the hydrido complex trans-[Ru-
H(OC6H4-4-Me)(κ2-Me2PCH2CH2PMe2)2] [137.58(16)°][15]
where no additional interaction between the CϪH units of
the phenolato ligand and the metal exists.
˚
1. Preparation of [Ru(η3-2-MeC3H4)2(κ2-Ph2PCH2CH2PiPr2)] (2):
A suspension of 1 (261 mg, 0.8 mmol) in hexane (8 mL) was treated
with Ph2PCH2CH2PiPr2 (252 mg, 0.8 mmol) and heated at reflux
for 12 h. After cooling to room temperature, the solvent was evap-
orated in vacuo, the residue was washed with pentane (10 mL) and
dried. A yellow microcrystalline solid was obtained; yield 308 mg
1
(72%); m.p. 114 °C. Ϫ H NMR (400 MHz, C6D6): δ ϭ 7.96 (m,
2 H, C6H5), 7.30 (m, 4 H, C6H5), 7.00 (m, 4 H, C6H5), 2.93 (br m,
1 H, one H of PCH2), 2.48, 2.25 (both s, 3 H each, CH3 of 2-
MeC3H4), 2.42Ϫ2.15 (br m, 5 H, PCH2 and CH2 of 2-MeC3H4),
2.10 [sept, 2 H, J(PH) ϭ 1.7 Hz, PCHCH3], 1.73Ϫ1.52 (br m, 4 H,
CH2 of 2-MeC3H4), 1.47 [dd, 3 H, J(PH) ϭ 14.2, J(HH) ϭ 7.2 Hz,
PCHCH3], 1.24 [dd, 3 H, J(PH) ϭ 11.3, J(HH) ϭ 7.2 Hz,
PCHCH3], 1.13 [dd, 1 H, J(PH) ϭ 15.1, J(HH) ϭ 4.8 Hz, one H
of 2-MeC3H4], 0.92 [dd, 3 H, J(PH) ϭ 9.4, J(HH) ϭ 7.3 Hz,
PCHCH3], 0.89 [dd, 3 H, J(PH) ϭ 9.6, J(HH) ϭ 7.3 Hz, PCHCH3],
0.50 [d, 1 H, J(PH) ϭ 13.5 Hz, one H of 2-MeC3H4]. Ϫ 13C NMR
(100.6 MHz, C6D6): δ ϭ 140.5 [d, J(PC) ϭ 40.5 Hz, ipso-C of
C6H5], 138.9 [d, J(PC) ϭ 21.0 Hz, ipso-C of C6H5], 133.8 [d,
J(PC) ϭ 10.5 Hz, ortho-C of C6H5], 131.3 [d, J(PC) ϭ 6.7 Hz, or-
tho-C of C6H5], 129.2 [d, J(PC) ϭ 1.9 Hz, para-C of C6H5], 126.9
(s, para-C of C6H5), 126.7 [d, J(PC) ϭ 8.6 Hz, meta-C of C6H5],
126.3 [d, J(PC) ϭ 7.6 Hz, meta-C of C6H5], 95.2 (s, CCH3 of 2-
MeC3H4), 94.2 [d, J(PC) ϭ 1.9 Hz, CCH3 of 2-MeC3H4], 41.6 [dd,
J(P1C) ϭ 19.1, J(P2C) ϭ 1.9 Hz, CH2 of 2-MeC3H4], 38.0, 36.8
(both m, CH2 of 2-MeC3H4), 34.2, 34.0 [both d, J(PC) ϭ 1.9 Hz,
CCH3 of 2-MeC3H4], 32.7 [dd, J(P1C) ϭ 25.3, J(P2C) ϭ 18.1 Hz,
PCH2], 31.1 [dd, J(P1C) ϭ J(P2C) ϭ 21.9 Hz, PCH2], 26.8 [d,
J(PC) ϭ 28.6 Hz, PCHCH3], 26.6 [d, J(PC) ϭ 18.6 Hz, PCHCH3],
21.2 [d, J(PC) ϭ 4.8 Hz, PCHCH3], 20.7, 19.8 (both s, PCHCH3),
19.6 [d, J(PC) ϭ 2.9 Hz, PCHCH3]. Ϫ 31P NMR (162.0 MHz,
C6D6): δ ϭ 81.4 [d, J(PP) ϭ 8.5 Hz, iPr2P], 73.9 [d, J(PP) ϭ 8.5 Hz,
Ph2P]. Ϫ C28H42P2Ru (541.4): calcd. C 62.09, H 7.82; found C
61.81, H 8.07.
Figure 2. Molecular structure of compound 6; the THF molecule is
˚
omitted for clarity; selected bond lengths [A] and angles [°]: RuϪP1
2.2341(13), RuϪP2 2.2578(13), RuϪO1 2.088(3), RuϪO2 2.078(3),
RuϪCl2 2.5240(13), RuϪCl8 2.4978(13); P1ϪRuϪP2 84.32(5),
P1ϪRuϪO1 99.45(9), P1ϪRuϪO2 89.24(9), P1ϪRuϪCl2
176.70(4),
P1ϪRuϪCl8
94.03(5),
P2ϪRuϪO1
94.51(9),
P2ϪRuϪO2 93.00(8), P2ϪRuϪCl2 98.90(5), P2ϪRuϪCl8
174.32(4), O1ϪRuϪO2 169.03(11), O1ϪRuϪCl2 79.60(9),
O1ϪRuϪCl8 91.12(9), O2ϪRuϪCl2 91.34(9), O2ϪRuϪCl8
81.53(8), Cl2ϪRuϪCl8 82.85(4)
2. Preparation of [Ru(η3-2-MeC3H4)2(κ2-Ph2PCH2CH2PCy2)] (3):
Analogous to the procedure described for 2, using 1 (152 mg,
0.5 mmol) and Ph2PCH2CH2PCy2 (189 mg, 0.5 mmol) as starting
materials. Yellow microcrystalline solid; yield 308 mg (70%); m.p.
In contrast to 2, compound 6 reacts with acetylacetone
in the presence of Na2CO3 to afford the bis(acac) complex
8 as a yellow air-stable solid in 89% isolated yield. More-
over, the bis(pentachlorophenolato) derivative 6 affords the
bis([F6]acac) complex 5 almost instantaneously upon treat-
ment with [F6]acacH in toluene. This pattern of reactivity
indicates that 6 (and equally 7) could be considered as a
masked 14-electron species in which the additional interac-
tion between the chlorine atoms in ortho position of the
1
108 °C. Ϫ H NMR (200 MHz, C6D6): δ ϭ 7.76Ϫ6.66 (br m, 10
H, C6H5), 3.25Ϫ0.43 (br m, 40 H, PCH2, CH2 and CH3 of 2-
MeC3H4 and C6H11). Ϫ 13C NMR (50.3 MHz, C6D6): δ ϭ 134.8
[d, J(PC) ϭ 13.2 Hz, ipso-C of C6H5], 134.6 [d, J(PC) ϭ 9.0 Hz,
ipso-C of C6H5], 133.7 [d, J(PC) ϭ 14.2 Hz, ortho-C of C6H5], 131.4
[d, J(PC) ϭ 8.3 Hz, ortho-C of C6H5], 129.5, 128.1 [both d, J(PC) ϭ
1.9 Hz, para-C of C6H5], 128.3 [d, J(PC) ϭ 7.5 Hz, meta-C of
OC6Cl5 units and the metal center prevents a subsequent C6H5], 127.7 [d, J(PC) ϭ 8.5 Hz, meta-C of C6H5], 95.4, 94.6 (both
Eur. J. Inorg. Chem. 2000, 2597Ϫ2601 2599

G. Fries, K. Ilg, M. Pfeiffer, D. Stalke, H. Werner
FULL PAPER
s, CCH3 of 2-MeC3H4), 43.0 [dd, J(P1C) ϭ 10.3, J(P2C) ϭ 6.1 Hz, J(PC) ϭ 10.5 Hz, ortho-C of C6H5], 132.0 [d, J(PC) ϭ 43.9 Hz,
CH of C6H11], 39.4 [d, J(PC) ϭ 3.4 Hz, CH2 of 2-MeC3H4], 38.8 ipso-C of C6H5], 130.6 [d, J(PC) ϭ 9.5 Hz, ortho-C of C6H5], 129.2
[d, J(PC) ϭ 4.2 Hz, CH2 of 2-MeC3H4], 38.6 [d, J(PC) ϭ 5.1 Hz,
CH of C6H11], 36.1, 36.0 [both d, J(PC) ϭ 4.0 Hz, CH2 of 2- meta-C of C6H5], 118.5, 117.7, 116.3, 116.1 [all q, J(FC) ϭ
MeC3H4], 33.1 [dd, J(P1C) ϭ 24.7, J(P2C) ϭ 16.9 Hz, PCH2], 31.1
284.2 Hz, CF3], 91.2, 89.9 (both s, CH of acac-f6), 27.8 [dd,
[dd, J(P1C) ϭ 22.7, J(P2C) ϭ 18.9 Hz, PCH2], 30.4, 30.2 (both s, J(P1C) ϭ 34.3, J(P2C) ϭ 8.6 Hz, PCH2], 25.3 [d, J(PC) ϭ 22.9 Hz,
[d, J(PC) ϭ 2.9 Hz, para-C of C6H5], 128.3 [d, J(PC) ϭ 9.5 Hz,
CH2 of C6H11), 30.6 [d, J(PC) ϭ 4.0 Hz, CH2 of C6H11], 29.3 [d,
PCHCH3], 25.0 [d, J(PC) ϭ 23.8 Hz, PCHCH3], 23.9 [dd, J(P1C) ϭ
J(PC) ϭ 3.1 Hz, CH2 of C6H11], 28.5 [d, J(PC) ϭ 12.2 Hz, CH2 of 38.6, J(P2C) ϭ 12.4 Hz, PCH2], 18.3, 18.3, 18.2, 18.0 (all s,
C6H11], 27.6 [d, J(PC) ϭ 9.2 Hz, CH2 of C6H11], 27.5 [d, J(PC) ϭ PCHCH3). Ϫ 19F NMR (376.5 MHz, CDCl3): δ ϭ Ϫ75.7, Ϫ75.4,
7.3 Hz, CH2 of C6H11], 27.1 [d, J(PC) ϭ 10.1 Hz, CH2 of C6H11], Ϫ74.6, Ϫ74.2 (all s). Ϫ 31P NMR (162.0 MHz, CDCl3): δ ϭ 90.4
26.8, 26.7 (both s, CH2 of C6H11), 26.6, 25.9 (both s, CCH3 of 2-
[d, J(PP) ϭ 25.4 Hz, iPr2P], 79.1 [d, J(PP) ϭ 25.4 Hz, Ph2P]. Ϫ
MeC3H4). Ϫ 31P NMR (81.0 MHz, C6D6): δ ϭ 81.5 [d, J(PP) ϭ C30H30F12O4P2Ru (845.6): calcd. C 42.61, H 3.58; found C 42.30
7.6 Hz, Cy2P], 66.6 [d, J(PP) ϭ 7.6 Hz, Ph2P]. Ϫ C34H50P2Ru H 3.22.
(621.8): calcd. C 65.68, H 8.11; found C 65.57, H 7.82.
5. Preparation of [Ru(κ2-O,Cl-OC6Cl5)2(κ2-Ph2PCH2CH2PiPr2)]
(6): A solution of 2 (135 mg, 0.3 mmol) in toluene (5 mL) was
3. Preparation of [Ru(η3-2-MeC3H4)2(κ2-Ph2PCH2CH2AstBu2)] (4):
treated at Ϫ30 °C with a solution of pentachlorophenol (133 mg,
Analogous to the procedure described for 2, using 1 (281 mg,
0.5 mmol) in toluene (5 mL). After warming to room temperature
0.9 mmol) and Ph2PCH2CH2AstBu2 (355 mg, 0.88 mmol) as start-
and stirring for 10 min, the solvent was evaporated in vacuo. The
ing materials. Yellow microcrystalline solid; yield 275 mg (51%);
residue was washed with pentane (5 mL) and dried. An orange mi-
m.p. 99 °C. Ϫ 1H NMR (400 MHz, C6D6): δ ϭ 7.89 (m, 2 H,
crocrystalline solid was obtained; yield 221 mg (92%); m.p. 165 °C.
C6H5), 7.22Ϫ7.09 (br m, 4 H, C6H5), 6.87 (m, 4 H, C6H5),
1
Ϫ H NMR (400 MHz, C6D6): δ ϭ 8.09 (m, 2 H, C6H5), 7.19 (m,
2.95Ϫ0.51 (br m, 36 H, CH2 and CH3 of 2-MeC3H4, PCH2, and
3 H, C6H5), 6.87 (m, 2 H, C6H5), 6.69 (m, 3 H, C6H5), 2.17Ϫ1.96
AsCCH3). Ϫ 13C NMR (100.6 MHz, C6D6): δ ϭ 140.4 [d, J(PC) ϭ
(br m, 2 H, PCH2), 1.72 (m, 1 H, PCHCH3), 1.60Ϫ1.49 (br m, 2
37.2 Hz, ipso-C of C6H5], 139.3 [d, J(PC) ϭ 22.9 Hz, ipso-C of
H, PCH2), 1.43Ϫ1.29 (br m, 1 H, PCHCH3), 1.21 [dd, 3 H,
C6H5], 134.1 [d, J(PC) ϭ 11.4 Hz, ortho-C of C6H5], 131.7 [d,
J(PH) ϭ 14.1, J(HH) ϭ 7.0 Hz, PCHCH3], 1.15 [dd, 3 H, J(PH) ϭ
J(PC) ϭ 6.7 Hz, ortho-C of C6H5], 129.2 [d, J(PC) ϭ 1.9 Hz, para-
13.9, J(HH) ϭ 7.7 Hz, PCHCH3], 0.60 [dd, 3 H, J(PH) ϭ 11.4,
C of C6H5], 126.9 (s, para-C of C6H5), 126.5 [d, J(PC) ϭ 9.5 Hz,
J(HH) ϭ 7.0 Hz, PCHCH3], 0.56 [dd, 3 H, J(PH) ϭ 11.7, J(HH) ϭ
meta-C of C6H5], 126.3 [d, J(PC) ϭ 6.7 Hz, meta-C of C6H5], 95.0,
7.0 Hz, PCHCH3]. Ϫ 13C NMR (100.6 MHz, C6D6): δ ϭ 163.6,
91.2 (both s, CCH3 of 2-MeC3H4), 39.6, 36.3 [both d, J(PC) ϭ
162.7 (both s, ipso-C of C6Cl5), 134.6 [d, J(PC) ϭ 10.5 Hz, ortho-
2.9 Hz, CH2 of 2-MeC3H4], 39.1, 39.0 (both s, AsCCH3), 36.9 [d,
C of C6H5], 133.8 [d, J(PC) ϭ 47.7 Hz, ipso-C of C6H5], 132.6 [d,
J(PC) ϭ 4.8 Hz, CH2 of 2-MeC3H4], 33.4 [d, J(PC) ϭ 2.3 Hz, CH2
J(PC) ϭ 45.8 Hz, ipso-C of C6H5], 131.7 [d, J(PC) ϭ 8.6 Hz, ortho-
of 2-MeC3H4], 32.8 [d, J(PC) ϭ 24.8 Hz, PCH2], 32.2, 31.5 (both
C of C6H5], 131.3, 129.4 [both d, J(PC) ϭ 1.9 Hz, para-C of C6H5],
s, AsCCH3), 25.9, 25.7 (both s, CCH3 of 2-MeC3H4), 21.6 [d,
128.6 [d, J(PC) ϭ 10.5 Hz, meta-C of C6H5], 127.5 [d, J(PC) ϭ
J(PC) ϭ 20.2 Hz, AsCH2]. Ϫ 31P NMR (162.0 MHz, C6D6): δ ϭ
9.5 Hz, meta-C of C6H5], 125.7, 125.4, 118.0, 117.8, 116.4, 115.6
79.4 (s). Ϫ C30H46AsPRu (613.7): calcd. C 58.72, H 7.56; found C
(all s, C6Cl5), 28.1 [dd, J(P1C) ϭ 36.2, J(P2C) ϭ 7.2 Hz, PCH2],
58.37, H 7.06.
26.7, 26.2 [both d, J(PC) ϭ 24.8 Hz, PCHCH3], 20.9 [dd, J(P1C) ϭ
30.0, J(P2C) ϭ 11.0 Hz, PCH2], 19.3, 18.5, 18.1, 18.0 (all s,
4. Preparation of [Ru(κ2-[F6]acac)2(κ2-Ph2PCH2CH2PiPr2)] (5): a)
PCHCH3). Ϫ 31P NMR (162.0 MHz, C6D6): δ ϭ 99.2 [d, J(PP) ϭ
A solution of 2 (104 mg, 0.2 mmol) in toluene (5 mL) was treated
28.8 Hz, iPr2P], 84.8 [d, J(PP) ϭ 28.8 Hz, Ph2P]. Ϫ C32H28Cl10O2-
at Ϫ78 °C with hexafluoroacetylacetone (88 µL, 0.4 mmol), which
P2Ru (962.2): calcd. C 39.95 H 2.91; found C 40.04 H 3.22.
ing to room temperature and stirring the solution for 20 min, the 6. Preparation of [Ru(κ2-O,Cl-OC6Cl5)2(κ2-Ph2PCH2CH2PCy2)]
led to a rapid change of color from yellow to dark red. After warm-
solvent was evaporated in vacuo and the residue was dissolved in
pentane (2 mL). The solution was chromatographed on Al2O3 (ba-
sic, activity grade I, height of column 10 cm). With pentane a red
fraction was eluted, from which a dark red microcrystalline solid
was obtained upon removal of the solvent; yield 147 mg (92%). Ϫ
(7): Analogous to the procedure described for 6, using 3 (246 mg,
0.5 mmol) and pentachlorophenol (245 mg, 1.0 mmol) as starting
materials. Orange microcrystalline solid; yield 221 mg (92%); m.p.
1
208 °C. Ϫ H NMR (200 MHz, C6D6): δ ϭ 8.10Ϫ6.60 (br m, 10
H, C6H5), 2.32Ϫ0.38 (br m, 26 H, PCH2 and C6H11). Ϫ 13C NMR
b) A solution of 6 (164 mg, 0.2 mmol) in toluene (5 mL) was (50.3 MHz, C6D6): δ ϭ 162.6, 162.5 (both s; ipso-C of C6Cl5), 135.1
treated with hexafluoroacetylacetone (71 µL, 0.4 mmol), which led
to a rapid change of color from orange to dark red. The solvent
was evaporated in vacuo, the residue was washed with pentane
(5 mL, Ϫ20 °C) and dried. Orange microcrystalline solid; yield
133 mg (93%); m.p. 148 °C. Ϫ IR (CH2Cl2): ν([F6]acac) ϭ 1611,
[d, J(PC) ϭ 43.2 Hz, ipso-C of C6H5], 134.8 [d, J(PC) ϭ 39.8 Hz,
ipso-C of C6H5], 133.8 [d, J(PC) ϭ 14.1 Hz, ortho-C of C6H5], 131.3
[d, J(PC) ϭ 8.0 Hz, ortho-C of C6H5], 129.9, 128.0 [both d, J(PC) ϭ
1.9 Hz, para-C of C6H5], 128.4, 127.3 [both d, J(PC) ϭ 7.1 Hz,
meta-C of C6H5], 125.6, 125.4, 118.7, 118.0, 116.7, 116.1 (all s,
1522 cmϪ1. Ϫ 1H NMR (400 MHz, CDCl3): δ ϭ 7.97 (m, 2 H, C6Cl5), 43.3 [dd, J(P1C) ϭ 12.1, J(P2C) ϭ 5.8 Hz, CH of C6H11],
C6H5), 7.63 (m, 3 H, C6H5), 7.46Ϫ7.34 (br m, 3 H, C6H5), 7.18 38.4 [d, J(PC) ϭ 6.1 Hz, CH of C6H11], 32.5 [dd, J(P1C) ϭ 24.2,
(m, 2 H, C6H5), 6.37, 5.67 (both s, 1 H each, CH of acac-f6),
J(P2C) ϭ 16.7 Hz, PCH2], 31.0 [dd, J(P1C) ϭ 22.5, J(P2C) ϭ
3.40Ϫ2.76 (br m, 2 H, PCH2), 2.64Ϫ2.52 (br m, 1 H, PCHCH3), 18.9 Hz, PCH2], 30.8, 30.0, 26.5, 26.4 (all s, CH2 of C6H11), 30.4,
2.48Ϫ2.34 (br m, 2 H, PCH2), 2.28Ϫ2.12 (br m, 1 H, PCHCH3), 29.9 [both d, J(PC) ϭ 4.3 Hz, CH2 of C6H11], 29.0 [d, J(PC) ϭ
1.49 [dd, 3 H, J(PH) ϭ 9.4, J(HH) ϭ 7.0 Hz, PCHCH3], 1.45 [dd, 9.7 Hz, CH2 of C6H11], 26.9 [d, J(PC) ϭ 9.4 Hz, CH2 of C6H11],
3 H, J(PH) ϭ 10.4, J(HH) ϭ 7.2 Hz, PCHCH3], 1.18 [dd, 3 H, 26.8 [d, J(PC) ϭ 6.9 Hz, CH2 of C6H11], 26.7 [d, J(PC) ϭ 10.6 Hz,
J(PH) ϭ 14.1, J(HH) ϭ 7.0 Hz, PCHCH3], 1.07 [dd, 3 H, J(PH) ϭ
CH2 of C6H11]. Ϫ 31P NMR (81.0 MHz, C6D6): δ ϭ 91.3 [d,
J(PP) ϭ 28.7 Hz, Cy2P], 85.4 [d, J(PP) ϭ 28.7 Hz, Ph2P]. Ϫ
14.2, J(HH) ϭ 7.2 Hz, PCHCH3]. Ϫ 13C NMR (100.6 MHz,
CDCl3): δ ϭ 175.1, 174.0, 172.1, 171.3 [all q, J(FC) ϭ 34.3 Hz, CO C38H36Cl10O2P2Ru (1042): calcd. C 43.78 H 3.48; found C 44.08
of acac-f6], 134.9 [d, J(PC) ϭ 42.9 Hz, ipso-C of C6H5], 133.3 [d,
H 3.45.
2600
Eur. J. Inorg. Chem. 2000, 2597Ϫ2601

Six-Coordinate Ruthenium(II) Complexes
FULL PAPER
7. Preparation of [Ru(κ2-acac)2(κ2-Ph2PCH2CH2PiPr2)] (8): A solu-
tion of 6 (189 mg, 0.2 mmol) in toluene (8 mL) was treated with
solved by Patterson methods with SHELXS-97.[19] All structures
were refined by full-matrix least-squares procedures on F2, using
acetylacetone (55 mg, 0.6 mmol) and Na2CO3 (69 mg, 0.7 mmol) SHELXL-97.[20] The positions of all hydrogen atoms were calcu-
and then heated for 1 h at 65 °C. After cooling to room temper-
ature, the solvent was evaporated in vacuo. The residue was dis-
solved in pentane (5 mL), the solution filtered and the filtrate was
brought to dryness in vacuo. A yellow microcrystalline solid was
obtained; yield 112 mg (89%); m.p. 157 °C. Ϫ IR (CH2Cl2):
lated according to ideal geometry and refined by employing the
riding method, except for H41a, H41b, H42a, H42b, H51a, H51b,
H52a, and H52b of 2, which were found in a differential Fourier
synthesis and refined without restraints.
1
ν(acac) ϭ 1580, 1518 cmϪ1. Ϫ H NMR (200 MHz, CDCl3): δ ϭ
Acknowledgments
7.88Ϫ7.76 (br m, 2 H, C6H5), 7.30Ϫ6.95 (br m, 8 H, C6H5), 5.14,
4.55 (both s, 1 H each, CH of acac), 2.62Ϫ2.50, 2.24Ϫ2.12 (both
br m, 2H each, PCH2), 1.99Ϫ1.83 (br m, 2 H, PCHCH3), 1.86,
1.68, 1.62, 1.20 (all s, 3H each, CH3 of acac), 1.24Ϫ1.18 (br m,
6 H, PCHCH3), 0.86Ϫ0.76 (br m, 6 H, PCHCH3). Ϫ 13C NMR
(100.6 MHz, CDCl3): δ ϭ 184.7, 183.9, 183.3, 182.7 (all s, CO of
acac), 138.6 [d, J(PC) ϭ 37.6 Hz, ipso-C of C6H5], 136.3 [d,
J(PC) ϭ 36.6 Hz, ipso-C of C6H5], 134.0, 131.1 [both d, J(PC) ϭ
8.1 Hz, C6H5], 129.1, 127.7, 127.3 (all s, C6H5), 127.2 [d, J(PC) ϭ
8.4 Hz, C6H5], 97.1, 96.6 (both s, CH of acac), 27.9 [dd, J(P1C) ϭ
34.8, J(P2C) ϭ 8.6 Hz, PCH2], 27.8, 27.6, 27.3, 27.1 (all s, CH3 of
acac), 25.2 [d, J(PC) ϭ 18.9 Hz, PCHCH3], 25.0 [d, J(PC) ϭ
23.8 Hz, PCHCH3], 22.9 [dd, J(P1C) ϭ 29.6, J(P2C) ϭ 10.4 Hz,
PCH2], 18.4, 18.3, 18.2, 18.0 (all s, PCHCH3). Ϫ 31P NMR
(81.0 MHz, CDCl3): δ ϭ 91.2 [d, J(PP) ϭ 23.4 Hz, iPr2P], 82.5 [d,
J(PP) ϭ 23.4 Hz, Ph2P]. Ϫ C30H42O4P2Ru (629.7): calcd. C 57.22
H 6.73; found C 56.89 H 7.03.
This work was supported by the Deutsche Forschungsgemeinschaft
(SFB 347) and the Fonds der Chemischen Industrie. We are grate-
ful to the latter in particular for a Ph.D. scholarship (to K. I.).
We also thank Dr. W. Buchner and Mrs. M.-L. Schäfer for NMR
measurements, Mrs. R. Schedl and Mr. C. P. Kneis for elemental
analysis and DTA measurements. Generous support by the BASF
AG and the Degussa-Hüls AG is also gratefully acknowledged.
[1]
J. Wolf, M. Manger, U. Schmidt, G. Fries, D. Barth, B.
Weberndörfer, D. A. Vice, W. D. Jones, H. Werner, J. Chem.
Soc., Dalton. Trans. 1999, 1867Ϫ1875.
[2]
G. Fries, J. Wolf, M. Pfeiffer, D. Stalke, H. Werner, Angew.
Chem. 2000, 112, 575Ϫ578; Angew. Chem. Int. Ed. Engl. 2000,
39, 564Ϫ566.
[3]
G. Fries, Dissertation, Universität Würzburg, 2000.
[4]
S. Holle, P. W. Jolly, J. Kuhnigk, J. Organomet. Chem. 1997,
543, 255Ϫ258.
[5]
C. Six, B. Gabor, H. Görls, R. Mynott, P. Philipps, W. Leitner,
Organometallics 1999, 18, 3316Ϫ3326.
[6]
X-ray Structure Determination of Compounds 2 and 6:[18] Single
crystals of 2 were grown from hexane at 25 °C and those of 6
from THF at 25 °C. Crystal data collection parameters for these
structures are presented in Table 1. The data were collected with
an EnrafϪNonius CAD4 diffractometer using monochromated
J. P. Genet, X. Pfister, V. Ratovelomanana-Vidal, C. Pinel, J.
A. Laffitte, S. Malort, M. C. Cano de Andrade, Tetrahedron:
Asymm. 1994, 5, 665Ϫ674.
[7]
H. Werner, T. Braun, T. Daniel, O. Gevert, M. Schulz, J. Or-
ganomet. Chem. 1997, 541, 127Ϫ141.
[8]
B. Heiser, E. A. Broger, Y. Crameri, Tetrahedron: Asymmetry
˚
1991, 2, 51Ϫ62.
Mo-Kα radiation (λ ϭ 0.71073 A). Intensity data were corrected
[9]
J. R. Jones, S. P. Patel, J. Am. Chem. Soc. 1974, 96, 574Ϫ575.
for Lorentz and polarization effects. An empirical absorption cor-
rection was applied for both structures [Ψ scans; Tmin ϭ 0.90,
[10]
H. Werner, G. Fries, B. Weberndörfer, J. Organomet. Chem.,
in press.
Tmax ϭ 1.00 (2); Tmin ϭ 0.59, Tmax ϭ 0.80 (6)]. The structures were
[11]
M. A. Tena, O. Nürnberg, H. Werner, Chem. Ber. 1993, 126,
1597Ϫ1602.
[12] [12a] M. F. Richardson, G. Wulfsberg, R. Marlow, S. Zaghonni,
D. McCorkle, K. Shadid, J. Gagliardi, Jr., B. Farris, Inorg.
Table 1. Crystal data for complexes 2 and 6
[12b]
Chem. 1993, 32, 1913Ϫ1919. Ϫ
W. Beck, K. Schloter, Z.
Naturforsch., B 1978, 33, 1214Ϫ1222. Ϫ [12c] R. J. Kulawiec, R.
H. Crabtree, Coord. Chem. Rev. 1990, 99, 89Ϫ115.
C.-W. Chang, P.-C. Ting, Y.-C. Lin, G.-H. Lee, Y. Wang, J.
Organomet. Chem. 1998, 553, 417Ϫ425.
2
6 · C4H8O
[13]
[14]
[15]
[16]
[17]
[18]
Empirical formula
M
C27H42P2Ru
541.38
C36H36Cl10O3P2Ru
1034.16
A. R. Chakravarty, F. A. Cotton, W. Schwotzer, Inorg. Chim.
Acta 1984, 84, 179Ϫ185.
M. J. Burn, M. G. Fickes, F. J. Hollander, R. G. Bergman,
Organometallics 1995, 14, 137Ϫ150.
Crystal system
Space group
monoclinic
triclinic
¯
C2/c (no. 15) P1 (no. 2)
˚
a [A]
22.795(2)
10.982(1)
23.162(3)
Ϫ
12.381(4)
13.088(2)
14.374(4)
66.69(2)
80.19(2)
71.57(2)
2027.7(7)
2
˚
b [A]
˚
W. Baratta, E. Herdtweck, P. Rigo, Angew. Chem. 1999, 111,
1733Ϫ1735; Angew. Chem. Int. Ed. Engl. 1999, 38, 1629Ϫ1631.
M. O. Albers, E. Singleton, Y. E. Yates, Inorg. Synth. 1989,
26, 253Ϫ254.
Crystallograhic data (excluding structure factors) for the struc-
tures of 2 and 6 have been deposited with the Cambridge Crys-
tallograhic Data Centre as supplementary publication no.
CCDC-143547 (2) and -133284 (6). Copies of the data can be
obtained free of charge on application to CCDC, 12 Union
Road, Cambridge CB2 1EZ, UK [Fax: (internat.) ϩ 44-1223/
336-033; E-mail: deposit@ccdc.cam.ac.uk].
c [A]
α [°]
β [°]
γ [°]
112.856(5)
Ϫ
3
˚
V [A ]
5342.8(10)
8
Z
Dc [g cmϪ3
]
1.314
1.695
Temperature [K]
193(2)
0.718
193(2)
µ [mmϪ1
]
1.162
No. reflections measured
4814
7185
No. unique reflections (Rint
)
4682 (0.0241) 5269 (0.0245)
R1[a]
0.034
0.072
0.035
0.083
[19]
[20]
G. M. Sheldrick, Acta Crystallogr., Sect. A 1990, 46, 467Ϫ473.
G. M. Sheldrick, Program for crystal structure refinement, Uni-
versität Göttingen, 1996.
wR2[b]
[a]
[b]
2
R1ϭ Σ|Fo Ϫ Fc|/ΣFo [for Fo Ͼ 2σ(Fo)]. Ϫ
wR2 ϭ [Σw(Fo
Ϫ
Received April 17, 2000
2 2
2 2 1/2
Fc ) /Σw(Fo ) ]
.
[I00149]
Eur. J. Inorg. Chem. 2000, 2597Ϫ2601
2601