Intramolecular C-C bond formation from β-keto phosphine and allenylidene ligands in related ruthenium(II) cyclopentadienyl and indenyl complexes. X-ray crystal structure of (SRURc/RRu,Sc)-[Ru(η 5-C9H7)(PPh3)

Article abstract of DOI:10.1021/om970513n

The reaction ofβ-keto phosphines Ph₂PCH(R′)C(=O)R (a, R = Bu^t, R′ = H; b, R = Ph, R′ = H; c, R = Bu^t, R′ = Me) with [RuCl(η⁵-C_nH_m)(PPh3)2] complexes (1, C_nH_m = cyclopentadienyl; 1′, C_nH_m = indenyl) affords neutral [RuCl(η⁵-C_nH_m)(PPh₃){η ¹(P)-keto phosphine}] (2a,b and 2′a). Cationic derivatives, [Ru(η⁵-C_nH_m)(PPh₃) {η²(P,O)-keto phosphine}][PF₆] (3a,b and 3′a-c), are obtained by the reactions of complexes 1 and 1′ with the keto phosphines in the presence Of NH₄PF₆. Complex 3′c is diastereoselectively obtained as the S_RU,R_C/R_RU,S_C enantiomeric pair, as shown by an X-ray crystal structure analysis. Owing to the hemilabile ability of the keto phosphine ligand, complexes 3a and 3′a easily react with 1,1-diphenyl-2-propyn-1-ol to yield the allenylidene complexes [Ru(=C=C=CPh₂)(η⁵-C_nH_m)(PPh ₃){η¹(P)-Ph₂PCH₂C(=O)Bu ^t}][PF₆] (5a and 5′a, respectively). Treatment of complexes 3a and 3′a with K₂CO₃ in methanol leads to the deprotonation of the coordinated keto phosphine to give the neutral phosphino enolate derivatives [Ru(η⁵-C_nH_m)(PPh3){η ²(P,O)-Ph₂PCH=C-(Bu_t)O}] (6a and 6′a, respectively). In contrast, allenylidene complexes 5a and 5′a react with K₂CO₃ or KOH in methanol to afford the alkynyl complexes [Ru{C=CC(OMe)Ph₂}(η⁵-C_nH _m)(PPh₃){η¹(P)-Ph₂PCH ₂C(=O)Bu^t)] (7a and T′a), which are formed through the nucleophilic addition of the methoxy group to the Cγ atom of the allenylidene chain. Similarly, the ethoxy alkynyl derivative 8a is obtained by the reaction of 5a with KOH in ethanol. Under mild basic conditions (K₂CO₃/THF) complexes 5a and 5′a are deprotonated, resulting conversion into the neutral derivatives [Ru{η²(C,P)-C(=C=CPh₂)CH[C(=O)Bu^t]PPh ₂}-(η⁷C_nH_m)(PPh₃)] (9a and 9′a, respectively) through the generation of a novel phosphamet-allacyclobutane ring and in accord with a diastereoselective process. The molecular structure of 9′a, determined by an X-ray crystal structure analysis, discloses a S_RU,R_c/R_RU,S_c configuration and shows a nearly planar Ru-P(2)-C(2B)-C(1) ring bearing an almost linear η¹(C)-coordinated allenyl group (C(1)-C(2A)-(3A) = 169.6(8)°). The formation of the four-membered ring probably takes place in a putative intermediate arising from the deprotonation of the η¹-(P)-keto phosphine ligand in 5a and 5′a. The subsequent intramolecular carbon-carbon bond formation between the allenylidene group and the nucleophilic η¹(P)-phosphino enolate ligands is geometrically constrained to occur at the electrophilic Cα site of the allenylidene ligand, and the ruthenium fragment efficiently directs the configuration of the new stereogenic carbon atom in the resulting metallacycle ring.

Full text of DOI:10.1021/om970513n

5406
Organometallics 1997, 16, 5406-5415
In tr a m olecu la r C-C Bon d F or m a tion fr om â-Keto
P h osp h in e a n d Allen ylid en e Liga n d s in Rela ted
Ru th en iu m (II) Cyclop en ta d ien yl a n d In d en yl Com p lexes.
X-r a y Cr ysta l Str u ctu r e of (SRu ,RC/RRu ,SC)-
[Ru (η5-C9H7)(P P h 3){η2(P ,O)-P h 2P CH(Me)C(Bu t)dO}][P F 6]
a n d (SRu ,RC/RRu ,SC)-
[Ru {η2(C,P )-C(dCdCP h 2)CH[C(dO)Bu t]P P h 2}(η5-C9H7)(P P h 3)]
Pascale Crochet, Bernard Demerseman,* and M. Isabel Vallejo
Laboratoire de Chimie de Coordination Organique, UMR-CNRS 6509, Campus de Beaulieu,
Universite´ de Rennes I, 35042 Rennes Ce´dex, France
M. Pilar Gamasa, J ose´ Gimeno,* J avier Borge, and Santiago Garc´ıa-Granda
Instituto Universitario de Qu´ımica Organometa´lica “Enrique Moles” (Unidad Asociada al
CSIC), Departamento de Quı´mica Orga´nica e Inorga´nica and Departamento de Quı´mica
Fı´sica y Anal´ıtica, Facultad de Quı´mica, Universidad de Oviedo, 33071 Oviedo, Spain
Received J une 16, 1997X
The reaction of â-keto phosphines Ph2PCH(R′)C(dO)R (a , R ) But, R′ ) H; b, R ) Ph, R′
) H; c, R ) But, R′ ) Me) with [RuCl(η5-CnHm)(PPh3)2] complexes (1, CnHm ) cyclopenta-
dienyl; 1′, CnHm ) indenyl) affords neutral [RuCl(η5-CnHm)(PPh3){η1(P)-keto phosphine}]
(2a ,b and 2′a ). Cationic derivatives, [Ru(η5-CnHm)(PPh3){η2(P,O)-keto phosphine}][PF6] (3a ,b
and 3′a -c), are obtained by the reactions of complexes 1 and 1′ with the keto phosphines in
the presence of NH4PF6. Complex 3′c is diastereoselectively obtained as the SRu,RC/RRu,SC
enantiomeric pair, as shown by an X-ray crystal structure analysis. Owing to the hemilabile
ability of the keto phosphine ligand, complexes 3a and 3′a easily react with 1,1-diphenyl-
2-propyn-1-ol to yield the allenylidene complexes [Ru(dCdCdCPh2)(η5-CnHm)(PPh3){η1(P)-
Ph2PCH2C(dO)But}][PF6] (5a and 5′a , respectively). Treatment of complexes 3a and 3′a
with K2CO3 in methanol leads to the deprotonation of the coordinated keto phosphine to
give the neutral phosphino enolate derivatives [Ru(η5-CnHm)(PPh3){η2(P,O)-Ph2PCHdC-
(But)O}] (6a and 6′a , respectively). In contrast, allenylidene complexes 5a and 5′a react
with K2CO3 or KOH in methanol to afford the alkynyl complexes [Ru{CtCC(OMe)Ph2}(η5-
CnHm)(PPh3){η1(P)-Ph2PCH2C(dO)But}] (7a and 7′a ), which are formed through the nucleo-
philic addition of the methoxy group to the Cγ atom of the allenylidene chain. Similarly,
the ethoxy alkynyl derivative 8a is obtained by the reaction of 5a with KOH in ethanol.
Under mild basic conditions (K2CO3/THF) complexes 5a and 5′a are deprotonated, resulting
in conversion into the neutral derivatives [Ru{η2(C,P)-C(dCdCPh2)CH[C(dO)But]PPh2}-
(η5-CnHm)(PPh3)] (9a and 9′a , respectively) through the generation of a novel phosphamet-
allacyclobutane ring and in accord with a diastereoselective process. The molecular structure
of 9′a , determined by an X-ray crystal structure analysis, discloses a SRu,RC/RRu,SC
configuration and shows a nearly planar Ru-P(2)-C(2B)-C(1) ring bearing an almost linear
η1(C)-coordinated allenyl group (C(1)-C(2A)-(3A) ) 169.6(8)°). The formation of the four-
membered ring probably takes place in a putative intermediate arising from the deproto-
nation of the η1(P)-keto phosphine ligand in 5a and 5′a . The subsequent intramolecular
carbon-carbon bond formation between the allenylidene group and the nucleophilic η1(P)-
phosphino enolate ligands is geometrically constrained to occur at the electrophilic CR site
of the allenylidene ligand, and the ruthenium fragment efficiently directs the configuration
of the new stereogenic carbon atom in the resulting metallacycle ring.
In tr od u ction
complexes from aldehyde acetals1a or allenylidene
ligands,1b (ii) formation of C- and O-bonded enolates
from a coordinated γ-keto phosphine,2 (iii) reactivity of
neutral vinylidene complexes,3 (iv) synthesis of amino
Organometallic chemistry of (cyclopentadienyl)ruthe-
nium(II) complexes has very recently provided a note-
worthy series of novel results: (i) generation of carbene
(1) (a) Grotjahn, D. B.; Lo, H. C. Organometallics 1996, 15, 2860.
(b) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.; On˜ate,
E.; Oro, L. A. Organometallics 1996, 15, 3423.
X Abstract published in Advance ACS Abstracts, November 1, 1997.
S0276-7333(97)00513-X CCC: $14.00 © 1997 American Chemical Society

Ru(II) Cyclopentadienyl and Indenyl Complexes
Organometallics, Vol. 16, No. 25, 1997 5407
allenylidene complexes,4 (v) cycloaromatization of a
cationic vinylidene-ene-yne precursor,5 and (vi) cyclo-
propanation of deprotonated vinylidene complexes.6
Moreover, cyclopentadienyl and related ruthenium(II)
complexes have revealed efficiency in several catalytic
processes. The complexes [RuCl(η5-C5H5)(PPh3)2] and
[RuCl(η5-C5H5)(cod)] behave as catalyst precursors in
several coupling reactions involving 1-alkynes,7 whereas
the parent complexes [RuCl(η5-C9H7)(PPh3)2] and
[RuCl(η5-C5Me5)(L)H3] are active in the redox isomer-
ization of allyl and propargyl alcohols8 and in the
dimerization of terminal alkynes,9 respectively. Such
useful developments have generated renewed interest
in extending the routes leading to (cyclopentadienyl)-
ruthenium(II) and related derivatives.10 We report
herein (i) an efficient access to novel (cyclopentadienyl)-
and (indenyl)ruthenium(II) complexes containing one
â-keto phosphine ligand, (ii) the synthesis of alle-
nylidene derivatives, which are easily obtained from the
former complexes through the hemilabile ability of the
coordinated â-keto phosphine ligand, and (iii) the in-
tramolecular nucleophilic attack of the η1(P)-coordinated
phosphino enolate anion at the CR atom of the alle-
nylidene ligand, which leads to the formation of a
phosphametallacyclobutane ring. Complexes containing
the chiral â-keto phosphines Ph2PCH(Me)C(But)dO and
the corresponding enolate derivative are obtained in a
diastereoselective manner. The molecular structures of
the complexes [Ru(η5-C9H7)(PPh3){η2(P,O)-Ph2PCH-
Sch em e 1. Syn th esis of
[Ru Cl(η5-Cn Hm )(P P h 3){η1(P )-k eto p h osp h in e}] a n d
[Ru (η5-Cn Hm )(P P h 3){η2(P ,O)-k eto p h osp h in e}][P F 6]
Com p lexes
(Me)C(But)dO}][PF6] and [Ru{η2(C,P)-C(dCdCPh2)CH-
[C(dO)But]PPh2}(η5-C9H7)(PPh3)] determined by X-ray
diffraction reveal that they are obtained as the SRu,RC/
RRu,SC enantiomeric pair.
Resu lts a n d Discu ssion
Rea ction of â-Keto P h osp h in es w ith [Ru Cl(η5-
Cn Hm )(P P h 3)2] Com p lexes. The sparingly soluble
precursor [RuCl(η5-C5H5)(PPh3)2] (1) reacts with â-keto
phosphines Ph2PCH2C(dO)R (a , R ) But; b, R ) Ph) in
methanol at reflux, to afford deep orange solutions
which deposit orange crystals of the neutral derivatives
[RuCl(η5-C5H5)(PPh3){η1(P)-Ph2PCH2C(dO)R}] (2a ,b)
after standing at room temperature (Scheme 1). An
analogous treatment in the presence of NH4PF6 im-
mediately results in the formation of a yellow precipitate
identified as the cationic derivatives [Ru(η5-C5H5)-
(PPh3){η2(P,O)-Ph2PCH2C(R)dO}][PF6] (3a ,b), which
were isolated in high yields (Scheme 1). The indenyl
parent precursor [RuCl(η5-C9H7)(PPh3)2] (1′) showed a
similar reactivity and yielded the analogous neutral and
cationic complexes 2′a and 3′a ,b, respectively (Scheme
1). The indenyl complex [Ru(η5-C9H7)(PPh3){η2(P,O)-
Ph2PCH(Me)C(But)dO}][PF6] (3′c) was similarly ob-
tained by starting from 1′ and the PCR-substituted keto
phosphine Ph2PCH(Me)C(dO)But (c), but surprisingly,
we failed to detect any reaction between 1 and keto
phosphine c.
All the complexes are air-stable in the solid state and
have been characterized by IR and NMR spectroscopy
and elemental analysis. The IR spectra (Table 1) of
complexes 3a ,b and 3′a -c show, besides the typical
(2) Rasley, B. T.; Rapta, M.; Kulawiec, R. J . Organometallics 1996,
15, 2852.
(3) (a) Braun, T.; Meuer, P.; Werner, H. Organometallics 1996, 15,
4075. (b) Braun, T.; Gevert, O.; Werner, H. J . Am. Chem. Soc. 1995,
117, 7291.
(4) Bruce, M. I.; Hinterding, P.; Low, P. J .; Skelton, B. W.; White,
A. H. J . Chem. Soc., Chem. Commun. 1996, 1009.
(5) Finn, M. G.; Wang, Y. J . Am. Chem. Soc. 1995, 117, 8045.
(6) Ting, P.-C.; Lin, Y.-C.; Lee, G.-H.; Cheng, M.-C.; Wang, Y. J . Am.
Chem. Soc. 1996, 118, 6433.
(7) (a) Trost, B. M.; Kulawiec, R. J . J . Am. Chem. Soc. 1992, 114,
5579. (b) Trost, B. M.; Portnoy, M.; Kurihara, H. J . Am. Chem. Soc.
1997, 119, 836. (c) Merlic, C. A.; Pauly, M. E. J . Am. Chem. Soc. 1996,
118, 11319.
-
absorptions due to the presence of the PF6 anion, a
strong ν(CdO) absorption in the range 1610-1552 cm-1
indicating the coordination of the oxygen atom from the
keto phosphine ligand, whereas the IR spectra of
complexes 2a ,b and 2′a display the ν(CdO) absorption
in the range 1702-1665 cm-1, in accordance with an
uncoordinated keto group.11 The 31P{1H} NMR spectra
(Table 1) exhibit two doublet resonances consistent with
an AX spin system, as expected from two nonequivalent
coordinating phosphorus atoms. Whereas the chemical
shifts related to the two nuclei appear very close in the
(8) (a) Trost, B. M.; Kulawiec, R. J . J . Am. Chem. Soc. 1993, 115,
2027. (b) Trost, B. M.; Livingston, R. C. J . Am. Chem. Soc. 1995, 117,
9586.
(9) Yi, C. S.; Liu, N. Organometallics 1996, 15, 3968.
(10) Davies, S. G.; McNally, J . P.; Smallridge, A. J . Adv. Organomet.
Chem. 1990, 30, 1.
(11) Demerseman, B.; Guilbert, B.; Renouard, C.; Gonzalez, M.;
Dixneuf, P. H.; Masi, D.; Mealli, C. Organometallics 1993, 12, 3906.

5408 Organometallics, Vol. 16, No. 25, 1997
Ta ble 1. IR a n d 31P {1H} NMR Da ta for th e New Com p lexes
Crochet et al.
31P{1H} NMR
IRa
compd
ν(CdO)
δP
δP′
2J PP′
[RuCl(C5H5)(PPh3){η1(P)-Ph2PCH2C(dO)But}] (2a )
1697
1665
1702
1600
1552
1610
1555
1587
1704
1708
1708
1491b
1494b
1699
1705
1701
1694
44.2
43.9
50.7
61.6
61.7
72.6
73.6
95.5
45.2
48.6
50.9
58.9
73.8
54.4
53.9
54.4
59.9
39.7
43.2
46.2
46.3
47.4
46.4
47.2
42.7
35.1
39.8
40.1
49.0
46.9
47.5
50.2
45.9
18.5
42.1c
42.1d
43.8c
35.1d
36.7c
31.7d
32.2d
30.5d
27.2c
29.5d
26.5c
39.0d
34.3c
34.1c
35.8d
38.2d
41.7d
[RuCl(C5H5)(PPh3){η1(P)-Ph2PCH2C(dO)Ph}] (2b)
[RuCl(C9H7)(PPh3){η1(P)-Ph2PCH2C(dO)But}] (2′a )
[Ru(C5H5)(PPh3){η2(P,O)-Ph2PCH2C(But)dO}][PF6] (3a )
[Ru(C5H5)(PPh3){η2(P,O)-Ph2PCH2C(Ph)dO}][PF6] (3b)
[Ru(C9H7)(PPh3){η2(P,O)-Ph2PCH2C(But)dO}][PF6] (3′a )
[Ru(C9H7)(PPh3){η2(P,O)-Ph2PCH2C(Ph)dO}][PF6] (3′b)
[Ru(C9H7)(PPh3){η2(P,O)-Ph2PCH(Me)C(But)dO}][PF6] (3′c)
[Ru(C5H5)(CO)(PPh3){η1(P)-Ph2PCH2C(dO)But}][PF6] (4a )
[Ru(CdCdCPh2)(C5H5)(PPh3){η1(P)-Ph2PCH2C(dO)But}][PF6] (5a )
[Ru(CdCdCPh2)(C9H7)(PPh3){η1(P)-Ph2PCH2C(dO)But}][PF6] (5′a )
[Ru(C5H5)(PPh3){η2(P,O)-Ph2PCHdC(But)O}] (6a )
[Ru(C9H7)(PPh3){η2(P,O)-Ph2PCHdC(But)O}] (6′a )
[Ru{CtCC(OMe)Ph2}(C5H5)(PPh3){η1(P)-Ph2PCH2C(dO)But}] (7a )
[Ru{CtCC(OMe)Ph2}(C9H7)(PPh3){η1(P)-Ph2PCH2C(dO)But}] (7′a )
[Ru{CtCC(OEt)Ph2}(C5H5)(PPh3){η1(P)-Ph2PCH2C(dO)But}] (8a )
[Ru{η2(C,P)C(dCdCPh2)CH[C(dO)But]PPh2}(C5H5)(PPh3)] (9a )
[Ru{η2(C,P)C(dCdCPh2)CH[C(dO)But]PPh2}(C9H7)(PPh3)] (9′a )
1677
55.7
13.1
31.0d
ν in cm-1
.
ν(CdCO). c In CDCl3. In CD2Cl2.
a
b
d
case of complexes 2a ,b and 2′a (δ 50.7-39.7 ppm), the
ring formation in complexes 3a ,b and 3′a -c results in
a deshielding of the keto phosphine resonance (δ 95.5-
61.6 ppm) but that attributable to the phosphorus
nucleus from PPh3 remains almost unaffected (δ 47.4-
1
42.7 ppm). The H and 13C{1H} NMR spectra are also
in accordance with the proposed formulations. Along
with the resonances attributable to the cyclopentadienyl
1
and indenyl ligands, the H NMR spectra of derivatives
which contain the keto phosphine Ph2PCH2C(dO)R (a ,
b) show the two PCH2 protons to be diastereotopic, as
expected from the presence of a chiral ruthenium center.
Furthermore, the 13C{1H} NMR spectra provide evi-
dence for the presence of two inequivalent Ph2P phenyl
groups.
The NMR data for complex 3′c, wherein the keto
phosphine c adds a second chiral PC(H)Me center,
clearly indicates the presence of only one diastereomer.
Further structural specification was inferred from the
X-ray diffraction study.
F igu r e 1. View of the molecular structure of [Ru(η5-
C9H7)(PPh3){η2(P,O)-Ph2PCH(Me)C(But)dO}][PF6] (3′c; only
the enantiomer SRu,RC is shown). Priority order for the
assignment of the absolute configurations: (a) for Ru,
indenyl > PPh3 > CPPh2 > (CdO)tBu; (b) for C(1), PPh2 >
(CdO)tBu > Me > H.
Figure 1 shows the ORTEP drawing of the SRuRC
diastereomer of 3′c, and a listing of selected bond
distances and angles is given in Table 2. The molecule
has a pseudooctahedral three-legged piano-stool coor-
dination around the ruthenium atom, which is bonded
to the indenyl group acting as an η5 ligand, the
phosphorus atom from PPh3, and the oxygen and
phosphorus atoms from the chelating keto phosphine
ligand. The Ru-PPh2 and Ru-PPh3 bond lengths are
similar to each other (2.239(2), 2.357(2) Å, respectively)
and to those of 1 (2.337(1) and 2.335(1) Å).12 The Ru-O
bond length (2.129(4) Å) is normal relative to the simple
σ-coordination of the keto function through the oxygen
atom and is close to those (2.13(1) and 2.20(1) Å) in the
typical cationic keto phosphine-ruthenium complex
3′c. The value for the O-Ru-PPh3 angle (89.9(1)°) is
in accordance with an approximately octahedral envi-
ronment around the metal center.
The reaction of keto phosphines a -c with complexes
1 and 1′, which selectively results in the substitution
of one triphenylphosphine ligand, occurs in refluxing
methanol, and two chemical pathways may be consid-
ered: (i) a direct substitution of a triphenylphosphine
ligand from complexes 1 and 1′ by the keto phosphine
and (ii) a cleavage of the ruthenium-chloride bond in
1 and 1′ to generate initially a tris(phosphine) cationic
intermediate. The first mechanism would lead directly
to the neutral complexes 2 and 2′. A subsequent
cleavage of the ruthenium-chloride bond in 2 and 2′
allows the coordination of the keto oxygen atom from
the functional ligand to achieve the formation of the
cationic derivatives 3 and 3′. The second mechanism
is depicted in Scheme 1. The cleavage of the ruthenium-
chloride bond in 1 and 1′ results in the η1(P) coordina-
tion (or alternatively η1(O) coordination) of the keto
phosphine. Further removal of one triphenylphosphine
[Ru(MeCN)2{η2(P,O)-Ph2PCH2C(Ph)dO}2]2+ 13
.
The
P-Ru-O angle in 3′c (79.3(1)°) is similar to those in
the bis-chelate complex (80.6(4) and 80.9(3)°), but the
P-Ru-P value in 3′c is significantly smaller (97.44(7)°
vs 106.2(2)°), suggesting a lack of steric hindrance in
(12) Bruce, M. I.; Wong, F. S.; Skelton, B. W.; White, A. H. J . Chem.
Soc., Dalton Trans. 1981, 1398.
(13) Braunstein, P.; Chauvin, Y.; Na¨hring, J .; Dusausoy, Y.; Bayeul,
D.; Tiripicchio, A.; Ugozzoli, F. J . Chem. Soc., Dalton Trans. 1995, 851.

Ru(II) Cyclopentadienyl and Indenyl Complexes
Organometallics, Vol. 16, No. 25, 1997 5409
phine ligand relative to the η1(P)-coordinated keto
phosphine. Although only a minor steric effect might
be expected in 3′c as compared to 3′a as a consequence
of the introduction of a methyl group in the keto
phosphine, the diastereoselectivity inherent in the
formation of 3′c becomes easier to understand if it is
assumed that the intermediate complex [Ru(η5-
C9H7)(PPh3)2{η1(P)-Ph2PCH(Me)C(dO)But}]+ is formed.
Steric repulsion between the PCMe methyl group and
the triphenylphosphine ligands could probably induce
diastereoselectively the substitution of one triphenylphos-
phine ligand by the keto oxygen atom of the keto
phosphine and would be responsible for the SRu,RC/
RRu,SC configuration. The lack of reactivity of the
cyclopentadienyl complex 1 toward the keto phosphine
c, in contrast to the case for indenyl complex 1′, which
gives 3′c, although surprising since the cyclopentadienyl
ring is smaller than the indenyl ligand, may be kineti-
cally assisted according to the well-known indenyl
effect.16
Ta ble 2. Selected Bon d Dista n ces a n d Slip
P a r a m eter ∆a (Å) a n d Bon d An gles a n d
Dih ed r a l An gles F A,b HA,c a n d CAd (d eg) for
[Ru (η5-C9H7)(P P h 3){η2-P h 2P CH(Me)C(Bu t)dO)}][P F 6]
(3′c)
Distances
Ru-C*
1.892(6)
2.357(2)
2.239(2)
2.315(7)
2.210(7)
2.165(7)
2.186(7)
2.351(6)
1.834(7)
1.824(7)
1.828(7)
1.808(7)
1.832(7)
0.135(7)
Ru-O
2.129(4)
1.249(7)
1.500(9)
1.885(7)
1.43(1)
1.431(9)
1.43(1)
1.42(1)
1.420(9)
1.431(9)
1.43(1)
1.36(1)
1.38(1)
1.36(1)
Ru-P(1)
Ru-P(2)
Ru-C(70)
Ru-C(71)
Ru-C(72)
Ru-C(73)
Ru-C(74)
P(1)-C(11)
P(1)-C(21)
P(1)-C(31)
P(2)-C(41)
P(2)-C(51)
∆
C(3)-O
C(3)-C(1)
C(1) -P(2)
C(70)-C(78)
C(70)-C(74)
C(70)-C(71)
C(71)-C(72)
C(72)-C(73)
C(73)-C(74)
C(74)-C(75)
C(75)-C(76)
C(76)-C(77)
C(77)-C(78)
Angles
125.9(2)
123.8(2)
127.6(2)
89.9(1)
79.3(1)
C*-Ru-O
C(78)-C(70)-C(74) 119.0(7)
C(78)-C(70)-C(71) 131.3(8)
C(74)-C(70)-C(71) 109.7(7)
C(72)-C(71)-C(70) 105.8(7)
C(71)-C(72)-C(73) 110.1(7)
C*-Ru-P(1)
C*-Ru-P(2)
O-Ru-P(1)
Hem ila bile Rea ctivity of th e Keto P h osp h in e
Liga n d in Com p lexes 3a a n d 3′a . Revealing the
hemilabile character of the chelating η2(P,O)-keto phos-
phine functional ligand, complex 3a reacts with carbon
monoxide (1 atm, room temperature) to yield the cat-
ionic derivative [Ru(η5-C5H5)(CO)(PPh3){η1(P)-Ph2PCH2C-
(dO)But}][PF6] (4a ; eq 1).
O-Ru-P(2)
P(1)-Ru-P(2)
Ru-O-C(3)
O-C(3)-C(1)
C(3)-C(1)-P(2)
C(1)-P(2)-Ru
C(3)-C(1)-C(2)
97.44(7) C(72)-C(73)-C(74) 107.2(7)
126.6(4)
119.1(6)
107.5(5)
104.7(2)
118.7(6)
C(75)-C(74)-C(70) 120.6(7)
C(75)-C(74)-C(73) 132.6(7)
C(73)-C(74)-C(70) 106.8(7)
C(76)-C(75)-C(74) 117.1(8)
C(77)-C(78)-C(70) 117.8(8)
C(78)-C(77)-C(76) 122.7(8)
C(75)-C(76)-C(77) 122.6(8)
FA
CA
173.3(5)
164.4(3)
HA
174.0(5)
a
b
∆ ) d[Ru-C(74), C(70)] - d[Ru-C(71), C(73)]. FA (fold
angle) is the angle between normals to least-squares planes
defined by C(71), C(72), C(73) and C(70), C(74), C(75), C(76), C(77),
C(78). c HA (hinge angle) is the angle between normals to least-
squares planes defined by C(71), C(72), C(73) and C(71), C(74),
(1)
d
C(70), C(73). CA (conformational angle) is the angle between
normals to least-squares planes defined by C**, C*, Ru and C*,
Ru, P(2). C* is the centroid of C(70), C(71), C(72), C(73), C(74).
C** is the centroid of C(70), C(74), C(75), C(76), C(77), C(78).
However, the formation of 4a is peculiarly slow, since
it remains uncompleted after more than 1 week, and
the synthesis of 4a under these mild conditions is more
conveniently achieved by reacting 2a with carbon
monoxide. A subsequent exchange reaction of the
chloride anion with NH4PF6 allows the process to be
completed (eq 1). The IR spectrum of 4a shows a strong
ν(CtO) absorption at 1977 cm-1, providing evidence for
the presence of coordinated carbon monoxide, together
with a ν(CdO) absorption at 1704 cm-1 indicating the
η1(P)-coordinating mode of the keto phosphine. Hemi-
labile functional phosphine ligands have also proved
useful in the access to complexes involving a cumulenic
type ligand.17 Analogously, complexes 3a and 3′a react
with 1,1-diphenyl-2-propyn-1-ol in methanol at reflux,
to efficiently yield the highly colored allenylidene de-
rivatives [Ru(dCdCdCPh2)(η5-CnHm)(PPh3){η1(P)-Ph2-
PCH2C(dO)But}][PF6] (5a and 5′a , respectively; eq 2).
Significant IR and NMR spectroscopic characterization
arises from the comparison of 5a and 5′a with the
analogouscomplexes[Ru(dCdCdCPh2)](η5-C5H5)(PMe3)2]-
ligand allows the formation of the cationic derivatives
3 and 3′ to be completed. In this mechanism, the
formation of the neutral complexes 2 and 2′ only arises
through the competition between the chloride anion and
the keto oxygen atom, in coordinating at the ruthenium
center. The first mechanism appears unlikely when the
conditions of the reaction are compared to the conditions
where the straightforward substitution of triphenylphos-
phine in 1 by functional ether phosphines is achieved.14
In this case, significantly more drastic conditions (pro-
longed reflux in toluene) are required and unavoidably
result in mixtures consisting of mono- and disubstituted
derivatives.14 Of further interest, the chloride ligand
in 1 is already known to be substituted in methanol by
phosphorus ligands to afford cationic tris(phosphine)
complexes, despite the fact that formation of the species
[Ru(η5-C5H5)(PPh3)3]+ is believed to be sterically hin-
dered.15 Ketophosphines a -c are roughly comparable
to triphenylphosphine, and the expulsion of one phos-
phorus ligand from the analogous species [Ru(η5-
CnHm)(PPh3)2{η1(P)-Ph2PCHRC(dO)R′}]+ may be ex-
pected. In such a key intermediate, the chelate effect
is expected to favor the expulsion of a triphenylphos-
(16) Gamasa, M. P.; Gimeno, J .; Gonzalez-Bernardo, C.; Martin-
Vaca, B. M.; Monti, D.; Bassetti, M. Organometallics 1996, 15, 302
and references cited therein.
(17) (a) Werner, H.; Stark, A.; Steinert, P.; Gru¨nwald, C.; Wolf, J .
Chem. Ber. 1995, 128, 49. (b) Braun, T.; Steinert, P.; Werner, H. J .
Organomet. Chem. 1995, 488, 169. (c) Lindner, E.; Gepra¨gs, M.;
Gierling, K.; Fawzi, R.; Steimann, M. Inorg. Chem. 1995, 34, 6106. (d)
Lindner, E.; Haustein, M.; Fawzi, R.; Steimann, M.; Wegner, P.
Organometallics 1994, 13, 5021. (e) Werner, H.; Stark, A.; Schulz, M.;
Wolf, J . Organometallics 1992, 11, 1126.
(14) De Klerk-Engels, B.; Groen, J . H.; Vrieze, K.; Mo¨ckel, A.;
Lindner, E.; Goubitz, K. Inorg. Chim. Acta 1992, 195, 237.
(15) Ashby, G. S.; Bruce, M. I.; Tomkins, I. B.; Wallis, R. C. Aust. J .
Chem. 1979, 32, 1003.

5410 Organometallics, Vol. 16, No. 25, 1997
Crochet et al.
Under similar reaction conditions (K2CO3 or KOH, in
methanol) the allenylidene complexes 5a and 5′a af-
forded the methoxide acetylide derivatives 7a and 7′a ,
and the analogous ethoxide derivative 8a was obtained
by using ethanol instead of methanol (eq 4). Thus,
(2)
(4)
under mild conditions, 5a and 5′a undergo the formal
addition of an alkoxide anion to the electrophilic Cγ-
carbon atom of the allenylidene ligand according to the
reversible process that has been previously reported in
the case of the parent complex [Ru(dCdCdCPh2)(η5-
C9H7)(PPh3)2][PF6].19 Furthermore, indicating a similar
reversibility, the recrystallization of the methoxide
derivative 7a from dichloromethane and ethanol af-
forded a mixture of crystals of 8a and 7a . As expected,
the IR spectra of the acetylide derivatives show a sharp
absorption at ca. 2065 cm-1 that is attributable to the
[PF6] and [Ru(dCdCdCPh2)(η5-C9H7)(PPh3)2][PF6].18,19
The main features are relevant to the presence of the
allenylidene ligand: the IR spectra of 5a and 5′a show
the typical very strong ν(CdCdC) absorption at ca. 1935
cm-1, and the 13C{1H} NMR spectra disclose resonances
at δ 294.4 (CR), 207.0 (Câ), and 161.2 ppm (Cγ) for 5a
and at δ 290.2 (CR), 205.7 (Câ), and 156.5 ppm (Cγ) for
5′a , attributable to the carbon nuclei forming the
cumulenic chain RudCRdCâdCγ.
In contrast, indicating an irreversible and strong
coordination of carbon monoxide, complex 4a was found
to be unreactive toward the alkynol.
1
ν(CtC) bond, and the H NMR spectra clearly confirm
the presence of the alkoxide group.
Phosphino enolato ligands have shown to react with
coordinated 1-alkynes and thus to disturb the 1-alkyne-
to-vinylidene rearrangement in generating phospha-
metallacyclic compounds.20 Therefore, derivatives 5a
and 5′a offered an unprecedented opportunity to exam-
ine the generation of a phosphino enolate anion within
the coordination sphere of a metal center bearing a
cumulenic-type ligand. In order to preclude the reaction
consisting of alkoxide addition leading to acetylide
complexes, the deprotonation of 5a and 5′a was at-
tempted in THF. Under such conditions, the neutral
derivatives 9a and 9′a were formed and subsequently
isolated as yellow and red crystals, respectively (eq 5).
Rea ctivity of Com p lexes 3a a n d 3′a Rela ted to
th e Keton e-to-En ol Tau tom er ism in th e Keto P h os-
p h in e Liga n d . Under mild basic conditions (K2CO3 in
methanol), the 4e-donor keto phosphine ligand in com-
plexes 3a and 3′a is deprotonated into the 3e-donor
phosphino enolato ligand in the neutral derivatives [Ru-
(η5-CnHm)(PPh3){η2(P,O)-Ph2PCHdC(But)O}] (6a and
6′a , respectively; eq 3).
(3)
The IR spectra of 6a and 6′a show the expected
absorption attributable to the functionalized CdC(O)
1
bond at 1491 and 1494 cm-1, respectively. Both H and
(5)
13C NMR spectra indicate the presence of a PCHd
bonding pattern. Of special interest, the broadness of
the 13C{1H} NMR resonances attributable to the phenyl
groups of the triphenylphosphine ligand in 6′a likely
arises from a sterically hindered rotation around the
Ru-P bond on the NMR time scale.
The 13C and 1H NMR spectra of 9a and 9′a are
structurally informative and unambiguously indicated
a PCH sp3 carbon atom resulting from the removal of
one hydrogen atom in the keto phosphine ligand.
Another interesting feature of the 13C NMR spectrum
(18) Selegue, J . P. Organometallics 1982, 1, 217.
(20) (a) Crochet, P.; Demerseman, B. Organometallics 1995, 14,
2173. (b) Crochet, P.; Demerseman, B.; Rocaboy, C.; Schleyer, D.
Organometallics 1996, 15, 3048. (c) The molecular model of the
corresponding diastereomer RRu,RC shows a significant steric hindrance
of the phenyl and tert-butyl groups.
(19) (a) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Gonza´lez-Cueva,
M.; Lastra, E.; Borge, J .; Garc´ıa-Granda, S.; Pe´rez-Carren˜o, E. Orga-
nometallics 1996, 15, 2137. (b) Cadierno, V.; Gamasa, M. P.; Gimeno,
J .; Lastra, E. J . Organomet. Chem. 1994, 474, C27.

Ru(II) Cyclopentadienyl and Indenyl Complexes
Organometallics, Vol. 16, No. 25, 1997 5411
Ta ble 3. Selected Bon d Dista n ces a n d Slip
P a r a m eter ∆a (Å) a n d Bon d An gles a n d Dih ed r a l
An gles F A,b HA,c a n d CAd (d eg) for
[Ru {η2(C,P )-C(dCdCP h 2)CH[C(dO)Bu t]P P h 2}-
(η5-C9H7)(P P h 3)] (9′a )
Distances
Ru-C*
1.935(8)
2.299(2)
2.121(8)
2.266(2)
2.338(7)
2.222(8)
2.208(7)
2.246(7)
2.381(8)
1.841(8)
1.848(8)
1.833(7)
1.814(7)
1.829(8)
0.125(8)
C(3B)-O
1.193(8)
1.283(9)
1.33(1)
1.523(9)
1.839(8)
1.41(1)
1.41(1)
1.43(1)
1.41(1)
1.40(1)
1.44(1)
1.42(1)
1.35(1)
1.39(1)
1.34(1)
Ru-P(1)
Ru-C(1)
Ru-P(2)
Ru-C(70)
Ru-C(71)
Ru-C(72)
Ru-C(73)
Ru-C(74)
P(1)-C(11)
P(1)-C(21)
P(1)-C(31)
P(2)-C(41)
P(2)-C(51)
∆
C(1)-C(2A)
C(2A)-C(3A)
C(1)-C(2B)
C(2B)-P(2)
C(70)-C(78)
C(70)-C(74)
C(70)-C(71)
C(71)-C(72)
C(72)-C(73)
C(73)-C(74)
C(74)-C(75)
C(75)-C(76)
C(76)-C(77)
C(77)-C(78)
F igu r e 2. View of the molecular structure of [Ru{η2(C,P)-
Angles
125.2(3)
125.1(3)
129.2(2)
92.1(2)
68.8(2)
C(dCdCPh2)[CH(dO)But]PPh2}(η5-C9H7)(PPh3)] (9′a ; only
the enantiomer SRu,RC is shown). Priority order for the
assignment of the absolute configurations: (a) for Ru,
indenyl > PPh3 > CPPh2 > CdCdCPh2; (b) for C(2B), PPh2
> C(Ru)dCdCdCPh2 > (CdO)tBu > H.
C*-Ru-C(1)
C*-Ru-P(1)
C(78)-C(70)-C(74) 119(1)
C(78)-C(70)-C(71) 132.7(9)
C(74)-C(70)-C(71) 107.8(8)
C(72)-C(71)-C(70) 107.6(7)
C(71)-C(72)-C(73) 109.1(8)
C*-Ru-P(2)
C(1)-Ru-P(1)
C(1)-Ru-P(2)
P(1)-Ru-P(2)
Ru-C(1)-C(2A)
Ru-C(1)-C(2B)
99.47(8) C(72)-C(73)-C(74) 107.4(8)
123.4(6)
104.2(5)
C(75)-C(74)-C(70) 120(1)
C(75)-C(74)-C(73) 132(1)
C(73)-C(74)-C(70) 107.9(7)
C(76)-C(75)-C(74) 119(1)
C(77)-C(78)-C(70) 118(1)
C(78)-C(77)-C(76) 123(1)
is the observation of resonances attributable to a
σ-bonded allenyl ligand,21 indicating that a carbon-
carbon bond is formed from the coupling of the nucleo-
philic enolate carbon atom and the electrophilic CR-
carbon atom of the allenylidene ligand to give a four-
membered phosphametallacycle. The 31P{1H} NMR
spectra (Table 1) consists of two doublet resonances, in
accordance with the nonequivalence of the phosphorus
nuclei. The location of one resonance at δ ca. 18 also
suggests that the formation of a small ring has oc-
curred.22 The structure of 9a and 9′a involves two
stereogenic centers, but only one diastereoisomer was
detected by NMR spectroscopy. The X-ray structure
determination of the indenyl complex 9′a discloses the
expected phosphametallacyclobutane ring and a SRu,RC/
RRu,SC configuration.
C(1)-C(2A)-C(3A) 169.6(8)
C(1)-C(2B)-P(2)
Ru-P(2)-C(2B)
94.7(5)
89.3(2)
C(75)-C(76)-C(77) 120.(1)
FA
CA
172.6(6)
170.1(4)
HA
175.4(6)
a
b
∆ ) d[Ru-C(74), C(70)] - d[Ru-C(71), C(73)]. FA (fold
angle) is the angle between normals to least-squares planes
defined by C(71), C(72), C(73) and C(70), C(74), C(75), C(76), C(77),
C(78). c HA (hinge angle) is the angle between normals to least-
squares planes defined by C(71), C(72), C(73) and C(71), C(74),
d
C(70), C(73). CA (conformational angle) is the angle between
normals to least-squares planes defined by C**, C*, Ru and C*,
Ru, C(1). C* is the centroid of C(70), C(71), C(72), C(73), C(74).
C** is the centroid of C(70), C(74), C(75), C(76), C(77), C(78).
ligand. Such an orientation is in contrast with the cis
orientation exhibited in allenylidene (indenyl) ruthe-
nium(II) complexes but is similar to the orientation
adopted in vinylidene (indenyl) ruthenium(II)
complexes.19a As in 3′c, the Ru-PPh2 bond (2.266(2)
Å) is slightly shorter than the Ru-PPh3 bond (2.299(2)
Å). The main features concerning the four-membered
ring in 9′a are the following: (a) the bonding distances
Ru-C(1), P(2)-C(2B), and C(1)-C(2B) (2.121(8), 1.839-
(8),1.523(9) Å, respectively) are consistent with a simple
σ-bond. The ring is almost planar, as inferred from the
torsion angle Ru-C(1)-C(2B)-P(2) ) 15.1(5)°. Accord-
ingly, the sum of the four angles Ru-C(1)-C(2B), C(1)-
C(2B)-P(2), Ru-P(2)-C(2B), and C(1)-Ru-P(2) in the
ring (357°) is close to 360°. None of the four bond
distances are exceptional,21c and the flatness of the
phosphametallacyclobutane ring likely results from
steric demand. The CdC bond distances (C(1)-C(2A)
) 1.283(9), C(2A)-C(3A) ) 1.33(1) Å) in the almost
linear allenyl skeleton (C(1)-C(2A)-C(3A) ) 169.6(8)°)
compares fairly well with the values (CR-Câ ) 1.307-
(8), Câ-Cγ ) 1.302(9) Å; CR-Câ-Cγ ) 175.4(6)°) re-
ported for the osmium complex [OsCl2(CHdCdCPh2)-
The crystal structure consists of a molecule of 9′a and
one CH2Cl2 molecule of crystallization. An ORTEP
drawing of the molecule displaying the RC,SRu config-
uration is shown in Figure 2. Selected bond distances
and angles are listed in Table 3. The molecular
structure shows the typical pseudooctahedral three-
legged piano-stool coordination around the ruthenium
atom, which is bonded to the indenyl group acting as
an η5 ligand, the phosphorus atom from PPh3, and the
phosphorus and one carbon atom from the phosphamet-
allacyclobutane ring.
Of special interest, the orientation of the allenyl chain
is almost trans relative to the benzo ring of the indenyl
(21) (a) Werner, H.; Flu¨gel, R.; Windmu¨ller, B.; Michenfelder, A.;
Wolf, J . Organometallics 1995, 14, 612. (b) As far as we are aware,
this (σ-allenyl)ruthenium complex is the first to be crystallographically
characterized. We have recently prepared a further example, namely:
[Ru{η3(C,P,P)-C(dCdCPh2)(Ph2PCHPPh2)}(η5-C9H7)]: Cadierno,V.;
Gamasa, M. P.; Gimeno, J .; Lopez-Gonzalez, M. C.; Borge, J .; Garc´ıa-
Granda, S. Organometallics, in press. The complex [Ru(η5-C5H5)(CO)2-
(CHdCdCH2)] has been also described: Shuchart, C. E.; Willis, R. R.;
Wojcicki, A. J . Organomet. Chem. 1992, 424, 185. (c) A similar four-
membered phosphametallacycle has been described and crystallo-
graphically characterized: Bruce, M. I.; Cifuentes, M. P.; Humphrey,
M. G.; Poczman, E.; Snow, M. R.; Tiekink, E. R. T. J . Organomet. Chem.
1988, 338, 237.
(NO)(PPri ) ], which is one of the rare examples21a of
3 2
mononuclear complexes wherein an allenyl group simply
(22) Garrou, P. E. Chem. Rev. 1981, 81, 229.
acts as a σ-bonded ligand.21b

5412 Organometallics, Vol. 16, No. 25, 1997
Crochet et al.
phines Ph2PCH(R′)C(dO)R (a -c)11,25 were prepared according
to the literature.
The C(3B)-O distance (1.193(8) Å) is typical of a CdO
bond. The keto group is located far away from the metal
center, as required by the SRu,RC/ RRu,SC configuration
of 9′a . We have recently reported the synthesis of the
complexes [Ru(η6-arene){η3(C,O,P)-C(dCH2)C(Me)-
(COBut)PPh2}][PF6], which display a comparable four-
membered phosphametallacyclobutane ring but differ
from 9′a in the supplementary coordination of the keto
oxygen atom to the ruthenium center.20a,b This com-
parison seems to indicate that the diastereoselectivity
of the formation of 9′a is sterically required,20c since the
alternative configuration would force the keto group to
lie very close to the metal center that is coordinatively
saturated.
[Ru Cl(C5H5)(P P h 3){(η1(P )-P h 2P CH2C(dO)Bu t}] (2a ). A
mixture consisting of a 4.00 g (5.51 mmol) sample of 1, 1.75 g
(6.15 mmol) of Ph2PCH2C(dO)But, and methanol (100 mL) was
heated at reflux for 1 h. The hot solution was filtered, and
the orange filtrate was kept at room temperature to afford
orange crystals of 2a . Yield: 3.26 g, 79%. 1H NMR (CDCl3;
2
2
δ): 7.94-7.19 (m, 25 H, Ph), 4.34 (dd, 1 H, J HH ) 16.7, J PH
) 2.2, PCH2, Ha), 4.14 (s, 5 H, C5H5), 1.45 (dd, 1 H, 2J PH ) 9.6,
PCH2, Hb), 0.57 (s, 9 H, But). 13C{1H} NMR (CD2Cl2; δ): 210.3
2
1
3
(d, J PC ) 10.8, CO), 139.7 (dd, J PC ) 38.6, J PC ) 4.5, PhP,
ipso), 138.3 (d, 1J PC ) 39.5, Ph3P, ipso), 137.9 (dd, 1J PC ) 44.9,
3J PC ) 2.2, PhP, ipso), 134.7 (d, 3J PC ) 10.8, Ph3P, meta), 134.1
3
3
(d, J PC ) 10.8, PhP, meta), 132.3 (d, J PC ) 9.0, PhP, meta),
4
129.6 (s, Ph3P, para), 129.5 (d, J PC ) 1.8, PhP, para), 129.2
2
2
(s, PhP, para), 128.2 (d, J PC ) 9.0, PhP, ortho), 128.0 (d, J PC
2
Con clu sion s
) 9.9, Ph3P, ortho), 127.6 (d, J PC ) 9.9, PhP, ortho), 81.3 (ta,
2J PC ≈ J P′C ≈ 1.8, C5H5), 45.7 (s, CMe3), 29.0 (d, J PC ) 14.4,
PCH2), 25.9 (s, CMe3). Anal. Calcd for C41H41ClOP2Ru: C,
65.81; H, 5.52; Cl, 4.74; P, 8.28. Found: C, 65.57; H, 5.28; Cl,
4.82; P, 8.06.
2
1
The reaction of the complexes [RuCl(η5-CnHm)(PPh3)2]
with â-keto phosphines provides a convenient, high-yield
access to (cyclopentadienyl)- and (indenyl)ruthenium-
(II) derivatives containing η1(P)- and η2(P,O)-â-keto
phosphine ligands. The formation of only one diaste-
reomer for complex 3′c, containing two stereogenic
centers at the ruthenium atom and at the chiral keto
phosphine Ph2PCH(Me)C(dO)But, emphasizes a note-
worthy stereoselectivity. The complexes containing η2-
(P,O) keto phosphines proved to be excellent precursors
for the straightforward synthesis of allenylidene deriva-
tives through their reaction with 1,1-diphenyl-2-propyn-
1-ol, due to the hemilabile ability of the keto phosphine
ligand. The opening of the chelate η2(P,O) ring is easily
achieved, allowing the coordination of the alkynol and
the subsequent favorable tautomerization to the alle-
nylidene group. The deprotonation of the methylene
group of the η1(P)- Ph2PCH2C(dO)R keto phosphines in
allenylidene complexes 5a and 5′a generates a transient
phosphino enolate ligand, which is subsequently added
regioselectively to the electrophilic CR-carbon atom of
the allenylidene chain. This intramolecular coupling
reaction results in the diastereoselective formation of
complexes 9a and 9′a , which contain an unusual phos-
phametallacyclobutane ring. The formation of only one
diastereomer for both 3′c and 9′a emphasizes a note-
worthy stereoselectivity, likely promoted by the steric
properties of the metal fragments.
[R u Cl(C5H 5)(P P h 3){(η1(P )-P h 2P CH 2C(dO)P h }] (2b ).
Dark orange crystals of 2b were similarly obtained in 76%
yield by starting from 1 and Ph2PCH2C(dO)Ph. 1H NMR (CD2-
2
Cl2; δ): 7.70-6.94 (m, 30 H, Ph), 4.84 (dd, 1 H, J HH ) 14.5,
2
2J PH ) 7.1, PCH2, Ha), 4.17 (s, 5 H, C5H5), 1.81 (dd, 1 H, J PH
) 8.1, PCH2, Hb). Anal. Calcd for C43H37ClOP2Ru: C, 67.23;
H, 4.85; Cl, 4.61; P, 8.06. Found: C, 66.74; H, 4.88; Cl, 4.40;
P, 8.27.
[R u Cl(C9H 7)(P P h 3){η1(P )-P h 2P CH 2C(dO)Bu t }] (2′a ).
Thin orange needles of 2′a were obtained in 35% yield by
starting from 1′ and Ph2PCH2C(dO)But. 1H NMR (CDCl3; δ):
7.87-6.29 [m, 29 H, Ph and C9H7 (4 H)], 4.83 (m, 1 H, C9H7),
2
2
4.77 (m, 1 H, C9H7), 4.50 (dd, 1 H, J HH ) 17.2, J PH ) 3.3,
2
PCH2, Ha), 3.07 (s, broad, 1 H, C9H7), 1.49 (dd, 1 H, J PH
)
10.0, PCH2, Hb), 0.60 (s,
9
H, But). Anal. Calcd for
C
45H43ClOP2Ru: C, 67.70; H, 5.43. Found: C, 68.10; H, 5.36.
[R u (C5H 5)(P P h 3){η2(P ,O)-P h 2P CH 2C(Bu t )dO}][P F 6]‚-
CH2Cl2 (3a ). As a typical procedure, a mixture consisting of
a 10.0 g (13.8 mmol) sample of 1, 4.00 g (14.1 mmol) of Ph2-
PCH2C(dO)But, 2.50 g (15.3 mmol) of NH4PF6, and methanol
(100 mL) was heated at reflux for 3 h. The resulting slurry
was evaporated to leave a residue that was stirred with diethyl
ether (70 mL). The yellow precipitate was collected by
filtration, washed with diethyl ether, and then extracted with
dichloromethane (45 mL). The solution was filtered and the
filtrate covered with methanol (20 mL) and then diethyl ether
(170 mL) to afford orange crystals of 3a . Yield: 10.2 g, 79%.
1H NMR (CD2Cl2, δ): 7.50-6.83 (m, 25 H, Ph), 4.50 (s, 5 H,
C5H5), 3.80 (dd, 1 H, 2J HH ) 18.9, 2J PH ) 10.9, PCH2, Ha), 2.14
2
(dd, 1 H, J PH ) 7.9, PCH2, Hb), 1.07 (s, 9 H, But). 13C{1H}
Exp er im en ta l Section
2
1
NMR (CD2Cl2, δ): 233.2 (d, J PC ) 6.6, CO), 141.8 (dd, J PC
)
3
1
Gen er a l Com m en ts. The reactions were performed ac-
cording to Schlenk type techniques under an inert atmosphere
of argon or nitrogen, but only the handling of â-keto phos-
phines requires a rigorous exclusion of oxygen. Solvents were
distilled under an inert atmosphere after drying according to
conventional methods. Infrared spectra were recorded as
Nujol mulls. NMR spectra (1H, 300.13 MHz; 13C, 75.47 MHz;
31P, 121.50 MHz; absolute values of coupling constants in Hz)
were recorded at 297 K and referenced internally to the solvent
peak. The following abbreviations are used: s, singlet; d,
doublet; t, triplet; ta, apparent triplet; q, quadruplet; m,
unresolved multiplet. The starting complexes [RuCl(η5-C5H5)-
(PPh3)2] (1)23 and [RuCl(η5-C9H7)(PPh3)2] (1′)24 and keto phos-
43.9, J PC ) 2.8, PhP, ipso), 134.7 (d, J PC ) 42.7, Ph3P, ipso),
3
3
134.3 (d, J PC ) 12.9, PhP, meta), 134.0 (d, J PC ) 10.9, Ph3P,
4
4
meta), 132.4 (d, J PC ) 2.2, PhP, para), 131.1 (d, J PC ) 1.8,
4
3
Ph3P, para), 130.8 (d, J PC ) 2.0, PhP, para), 129.8 (d, J PC
)
2
11.2, PhP, meta), 129.5 (d, J PC ) 10.9, PhP, ortho), 129.3 (d,
2J PC ) 10.9, PhP, ortho), 129.1 (d, J PC ) 2.7, part of dd, PhP,
3
2
ipso, the other part is overlapped), 128.9 (d, J PC ) 9.7, Ph3P,
3
1
ortho), 80.5 (s, C5H5), 46.6 (d, J PC ) 2.4, CMe3), 45.6 (d, J PC
) 25.8, PCH2), 27.0 (s, CMe3). 13C NMR (CD2Cl2; δ (selected
1
1
values)): 45.6 (ddd, J HC ) 135 and 125, J PC ) 25.8, PCH2).
Anal. Calcd for C41H41F6OP3Ru‚CH2Cl2: C, 53.51; H, 4.60; Cl,
7.52; P, 9.86. Found: C, 53.42; H, 4.76; Cl, 6.70; P, 9.58. The
low chlorine value is likely attributable to easy loss of some
dichloromethane.
[Ru (C5H5)(P P h 3){η2(P ,O)-P h 2P CH2C(P h )dO}][P F6] (3b).
Red crystals of 3b were obtained in 86% yield by starting from
(23) (a) Bruce, M. I.; Windsor, N. J . Aust. J . Chem. 1977, 30, 1601.
(b) Bruce, M. I.; Hameister, C.; Swincer, A. G.; Wallis, R. C. Inorg.
Synth. 1982, 21, 78. (c) J oslin, F. L.; Mague, J . T.; Roundhill, D. M.
Organometallics 1991, 10, 521.
(24) Oro, L. A.; Ciriano, M. A.; Campo, M.; Foces-Foces, C.; Cano,
F. H. J . Organomet. Chem. 1985, 289, 117.
(25) Bouaoud, S. E.; Braunstein, P.; Grandjean, D.; Matt, D.; Nobel,
D. Inorg. Chem. 1986, 25, 3765.

Ru(II) Cyclopentadienyl and Indenyl Complexes
Organometallics, Vol. 16, No. 25, 1997 5413
H, J PH ) 10.9, PCH2, Hb), 0.31 (s, 9 H, But). 13C{1H} NMR
(CD2Cl2, δ): 294.4 (ta, J PC ≈ J P′C ≈ 18.0, CR), 207.5 (d, J PC
) 10.5, CO), 207.0 (s, Câ), 161.2 (s, Cγ), 144.2 (s, Ph2C, ipso),
1 and Ph2PCH2C(dO)Ph. 1H NMR (CDCl3, δ): 7.85-6.79 (m,
2
2
2
2
2
2
30 H, Ph), 4.52 (s, 5 H, C5H5), 4.06 (dd, 1 H, J HH ) 19.3, J PH
) 11.2, PCH2, Ha), 2.18 (dd, 1 H, 2J PH ) 7.5, PCH2, Hb). Anal.
1
1
Calcd for
C
43H37F6OP3Ru: C, 58.84; H, 4.25; P, 10.59.
135.7 (d, J PC ) 52.1, PhP, ipso), 135.2 (d, J PC ) 49.4, Ph3P,
Found: C, 59.25; H, 4.32; P, 10.52.
ipso), 134.1 (d, 3J PC ) 10.8, Ph3P, meta), 133.0 (d, 1J PC ) 48.5,
3
[Ru (C9H7)(P P h 3){η2(P ,O)-P h 2P CH2C(Bu t)dO}][P F6] (3′a).
Orange crystals of 3′a were obtained in 75% yield by starting
from 1′ and Ph2PCH2C(dO)But. 1H NMR (CD2Cl2; δ): 7.53-
6.59 [m, 29 H, Ph and C9H7 (4 H)], 4.86-4.33 (m, 3 H, C9H7),
PhP, ipso), 133.0 (d, J PC ) 10.8, PhP, meta), 132.7 (s, Ph2C,
3
4
para), 132.6 (d, J PC ) 9.9, PhP, meta), 131.7 (d, J PC ) 2.7,
4
4
PhP, para), 131.5 (d, J PC ) 1.8, Ph3P, para), 131.2 (d, J PC
)
2.7, PhP, para), 130.8 (s, Ph2C, meta), 129.9 (s, Ph2C, ortho),
2
2
2
2
129.2 (d, J PC ) 9.8, PhP, ortho), 128.9 (d, J PC ) 10.8, Ph3P,
3.74 (dd, 1 H, J HH ) 18.9, J PH ) 11.3, PCH2, Ha), 2.21 (dd, 1
2
H, J PH ) 8.5, PCH2, Hb), 1.08 (s, 9 H, But). 13C{1H} NMR
2
ortho), 128.5 (d, J PC ) 11.7, PhP, ortho), 93.7 (s, C5H5), 45.2
1
2
1
(s, CMe3), 35.1 (d, J PC ) 27.8, PCH2), 25.5 (s, CMe3). Anal.
(CD2Cl2, δ): 232.1 (d, J PC ) 4.5, CO), 139.2 (dd, J PC ) 46.7,
3J PC ) 2.7, PhP, ipso), 133.8 (d, 3J PC ) 10.8, Ph3P, meta), 133.6
Calcd for C56H51F6OP3Ru: C, 64.18; H, 4.91; P, 8.87. Found:
C, 63.95; H, 4.86; P, 8.72.
3
1
(d, J PC ) 11.7, PhP, meta), 133.2 (d, J PC ) 41.3, Ph3P, ipso),
4
4
[Ru (dCdCdCP h 2)(C9H7)(P P h 3){η1(P )-P h 2P CH2C(dO)-
Bu t}][P F 6] (5′a ). With 3′a as the starting material, the same
procedure afforded dark violet crystals of 5′a in 75% yield.
132.3 (d, J PC ) 2.7, PhP, para), 130.9 (d, J PC ) 2.7, PhP,
4
para), 130.8 (d, J PC ) 2.7, Ph3P, para), 130.3 (s, CH, C9H7),
3
2
130.1 (d, J PC ) 9.9, PhP, meta), 129.5 (d, J PC ) 10.8, PhP,
2
1
IR: ν(RudCdCdC), 1932 cm-1 1H NMR (CDCl3; δ): 7.66-
.
ortho), 129.4 (d, J PC ) 10.8, PhP, ortho), 129.4 (dd, J PC
)
52.1, 3J PC ) 2.7, PhP, ipso), 129.4 (s, CH, C9H7), 128.8 (d, 2J PC
) 8.9, Ph3P, ortho), 124.8 (s, CH, C9H7), 123.4 (s, CH, C9H7),
110.7 (d, 2J PC ) 3.5, C9H7), 108.0 (d, 2J PC ) 4.4, C9H7), 87.8 (s,
6.75 [m, 39 H, Ph and C9H7 (4 H)], 5.69-4.66 (m, 3 H, C9H7),
2
2
3.25 (dd, 1 H, J HH ) 17.4, J PH ) 2.0, PCH2, Ha), 1.96 (dd, 1
H, J PH ) 10.8, PCH2, Hb), 0.23 (s, 9 H, But). 13C{1H} NMR
2
2
(CD2Cl2; δ): 290.2 (ta, 2J PC ≈ J P′C ≈ 17.9, CR), 207.4 (d, 2J PC
)
2
CH, C9H7), 65.3 (d, J PC ) 8.4, CH, C9H7), 61.8 (s, CH, C9H7),
46.6 (d, 3J PC ) 2.8, CMe3), 45.7 (d, 1J PC ) 27.5, PCH2), 27.1 (s,
CMe3). Anal. Calcd for C45H43F6OP3Ru: C, 59.53; H, 4.78.
Found: C, 59.30; H, 4.61.
10.3, CO), 205.7 (s, Câ), 156.5 (s, Cγ), 140.3-86.0 (m, 7 Ph and
1
C9H7), 45.4 (s, CMe3), 35.8 (d, J PC ) 30.2, PCH2), 25.8 (s,
CMe3). Anal. Calcd for C60H53F6OP3Ru: C, 65.63; H, 4.87; P,
[Ru (C9H7)(P P h 3){η2(P ,O)-P h 2P CH2C(P h )dO}][P F6] (3′b).
Red crystals of 3′b were obtained in 75% yield by starting from
1′ and Ph2PCH2C(dO)Ph. 1H NMR (CD2Cl2; δ): 7.77-6.72 [m,
8.46. Found: C, 65.83; H, 4.85; P, 8.04.
[R u (C5H 5)(P P h 3){η2(P ,O)-P h 2P CHC(Bu t )dO}] (6a ).
A
mixture consisting of 3a (or 2a ), an excess of K2CO3, and
methanol was stirred overnight to afford a yellow slurry. The
precipitate was collected by filtration then washed with water
and methanol to afford 6a in nearly quantitative yield.
Despite the fact that 6a is poorly soluble in common solvents,
yellow crystals may be obtained by adding diethyl ether to a
saturated solution in dichloromethane. 1H NMR (CD2Cl2, δ):
7.48-6.97 (m, 25 H, Ph), 4.64 (dd, 1 H, 2J PH ) 1.8, 4J PH ) 0.5,
PCH), 3.93 (s, 5 H, C5H5), 0.92 (s, 9 H, But). 13C{1H} NMR
34 H, Ph and C9H7 (4 H)], 4.89 (s, broad, 1 H, C9H7), 4.64 (s,
2
broad, 1 H, C9H7), 4.52 (m, 1 H, C9H7), 4.04 (dd, 1 H, J HH
)
2
2
18.9, J PH ) 11.7, PCH2, Ha), 1.99 (dd, 1 H, J PH ) 7.9, PCH2,
Hb). Anal. Calcd for C47H39F6OP3Ru: C, 60.84; H, 4.24; P,
10.02. Found: C, 60.88; H, 4.27; P, 10.02.
[R u (C9H 7)(P P h 3){η2(P ,O)-P h 2P CH (Me )C(Bu t )dO}]-
[P F 6] (3′c). After a mixture consisting of 1′, Ph2PCH(Me)C-
(dO)But, and NH4PF6 in methanol was heated at reflux for
15 h, subsequent work allowed orange crystals of 3′c to be
obtained in 74% yield. 1H NMR (CD2Cl2, δ): 7.81-6.31 [m,
29 H, Ph and C9H7 (4 H)], 5.13-3.55 (m, 3 H, C9H7), 2.93 (dq,
1 H, 2J PH ) 11.5, 3J HH ) 7.3, PCH), 1.29 (dd, 3 H, 3J PH ) 11.2,
PCMe), 1.12 (s, 9 H, But). Anal. Calcd for C46H45F6OP3Ru:
C, 59.93; H, 4.92; P, 10.08. Found: C, 59.77; H, 4.92; P, 9.94.
[R u (C O )(C 5 H 5 )(P P h 3 ){η1 (P )-P h 2 P C H 2 C (dO )B u t }]-
[P F 6] (4a ). F r om 3a . A 0.50 g (0.53 mmol) sample of 3a was
2
1
(CD2Cl2, δ): 199.9 (d, J PC ) 18.3, dCO), 147.6 (dd, J PC
)
3
1
42.7, J PC ) 2.4, PhP, ipso), 138.4 (d, J PC ) 37.8, Ph3P, ipso),
1
3
3
138.1 (dd, J PC ) 47.6, J PC ) 5.5, PhP, ipso), 134.3 (d, J PC
)
3
11.6, Ph3P, meta), 132.9 (d, J PC ) 11.0, PhP, meta), 130.8 (d,
3J PC ) 10.4, PhP, meta), 128.9 (d, 4J PC ) 1.8, Ph3P, para), 128.3
4
2
(d, J PC ) 1.8, PhP, para), 127.8 (d, J PC ) 9.2, PhP, ortho),
2
127.5 (d, J PC ) 9.2, Ph3P, and overlapped, PhP, ortho), 79.0
(ta, 2J PC ≈ J P′C ≈ 2.3, C5H5), 75.2 (d, 1J PC ) 58.0, PCHd), 38.6
2
3
dissolved in
a
mixture of dichloromethane (15 mL) and
(d, J PC ) 11.0, CMe3), 29.6 (s, CMe3); a PhP-para resonance
methanol (15 mL). The solution was stirred for 2 weeks under
a carbon monoxide atmosphere and then evaporated to dry-
ness. The remaining solid was recrystallized from dichlo-
romethane (10 mL) and diethyl ether (110 mL) to afford yellow
crystals of 4a . Yield: 0.37 g, 79%.
was not located. Anal. Calcd for C41H40OP2Ru: C, 69.18; H,
5.66; P, 8.70. Found: C, 68.97; H, 5.69; P, 8.64.
[Ru (C9H7)(P P h 3){η2(P ,O)-P h 2P CHC(Bu t)dO}] (6′a ). A
mixture consisting of a 1.80 g (1.98 mmol) sample of 3′a , 0.28
g (2.03 mmol) of K2CO3, and methanol (40 mL) was stirred
overnight. The resulting mixture was evaporated, and the
remaining solid was extracted with tepid toluene (30 mL). The
solution was filtered and the filtrate covered with hexane (110
mL) to afford dark orange crystals of 6′a . Yield: 1.16 g, 77%.
1H NMR (CDCl3, δ): 7.45-6.36 [m, 29 H, Ph and C9H7 (4 H)],
F r om 2a . A 2.50 g (3.34 mmol) sample of 2a was dissolved
in dichloromethane (20 mL), and methanol (80 mL) was then
added. The resulting slurry was stirred for 1 week under a
carbon monoxide atmosphere to obtain a clear yellow solution.
NH4PF6 (0.60 g, 3.68 mmol) was then added, and the mixture
was stirred overnight. Subsequent work as above afforded 4a .
2
4.49 (d, 1 H, J PH ) 2.9, PCH), 4.23 (m, 1 H, C9H7), 4.14 (m, 1
Yield: 2.61 g, 88%. IR: ν(CtO), 1977 cm-1 1H NMR (CDCl3,
.
H, C9H7), 3.36 (m, 1 H, C9H7), 0.93 (s, 9 H, But). 13C{1H} NMR
2
1
δ): 7.70-6.93 (m, 25 H, Ph), 4.99 (s, 5 H, C5H5), 3.02 (dd, 1 H,
(CD2Cl2, δ): 199.5 (d, J PC ) 15.3, dCO), 145.7 (dd, J PC
)
2
2
2J HH ) 16.9, J PH ) 2.6, PCH2, Ha), 2.28 (dd, 1 H, J PH ) 10.9,
PCH2, Hb), 0.61 (s, 9 H, But). Anal. Calcd for C42H41F6O2P3-
Ru: C, 56.95; H, 4.67. Found: C, 56.59; H, 4.55.
3
1
3
45.8, J PC ) 2.7, PhP, ipso), 135.1 (dd, J PC ) 53.0, J PC ) 5.4,
PhP, ipso), 134.2 (broad resonance, Ph3P, ipso and meta), 132.5
3
3
(d, J PC ) 9.9, PhP, meta), 131.6 (d, J PC ) 9.9, PhP, meta),
[Ru (dCdCdCP h 2)(C5H5)(P P h 3){η1(P )-P h 2P CH2C(dO)-
Bu t}][P F 6] (5a ). A mixture consisting of a 2.00 g (2.12 mmol)
sample of 3a , 0.85 g (4.08 mmol, an excess) of 1,1-diphenyl-
2-propyn-1-ol, and methanol (70 mL) was heated at reflux for
6 h. The resulting violet solution was evaporated, and the
residue was washed with diethyl ether. The solid was dis-
solved in dichloromethane, and this solution was covered with
diethyl ether to afford highly colored dark green crystals of
128.8 (s, broad, Ph3P, para), 128.5 (d, J PC ) 2.7, PhP, para),
4
4
2
128.1 (d, J PC ) 2.7, PhP, para), 127.8 (d, J PC ) 9.9, PhP,
2
2
ortho), 127.7 (d, J PC ) 9.9, PhP, ortho), 127.4 (d, broad, J PC
) 9.0, Ph3P, ortho), 126.9 (s, CH, C9H7), 125.5 (s, CH, C9H7),
2
124.8 (s, CH, C9H7), 122.5 (s, CH, C9H7), 112.1 (d, J PC ) 4.5,
2
C9H7), 105.0 (d, J PC ) 7.2, C9H7), 86.4 (s, CH, C9H7), 75.5 (d,
1J PC ) 60.1, PCHd), 64.5 (s, CH, C9H7), 63.9 (d, J PC ) 13.5,
2
CH, C9H7), 38.4 (d, J PC ) 11.7, CMe3), 29.6 (s, CMe3). 13C
3
5a . Yield: 1.83 g, 82%. IR: ν(RudCdCdC), 1938 cm-1
.
1H
NMR (CD2Cl2; δ (selected values)): 75.5 (dd, J HC ) 161, J PC
) 60, PCHd). Anal. Calcd for C45H42OP2Ru: C, 70.95; H,
5.56; P, 8.13. Found: C, 71.08; H, 5.57; P, 8.20.
1
1
NMR (CD2Cl2, δ): 7.75-6.93 (m, 35 H, Ph), 5.07 (s, 5 H, C5H5),
2
2
3.40 (dd, 1 H, J HH ) 17.3, J PH ) 2.1, PCH2, Ha), 2.03 (dd, 1

5414 Organometallics, Vol. 16, No. 25, 1997
Crochet et al.
[R u {CtCC(OMe)P h 2}(C5H 5)(P P h 3){η1(P )-P h 2P CH 2C-
(dO)Bu t}] (7a ). A mixture consisting of a 0.93 g (0.89 mmol)
sample of 5a , 0.30 g (2.17 mmol, an excess) of K2CO3, and
methanol (35 mL) was stirred overnight. The resulting slurry
was evaporated to dryness, and the residue was extracted with
dichloromethane (25 mL). The solution was filtered, and
methanol (30 mL) was added to the filtrate. The mixture was
slowly concentrated under reduced pressure to afford yellow
Ta ble 4. Cr ysta llogr a p h ic Da ta for th e Str u ctu r a l
An a lysis of
[Ru (η5-C9H7)(P P h 3)[η2(P ,O)-P h 2P CH(Me)C(Bu t)dO)}]-
[P F 6] (3′c) a n d
[Ru {η2(C,P )-C(dCdCP h 2)CH[C(dO)Bu t]P P h 2}-
(η5-C9H7)(P P h 3)]‚CH2Cl2 (9′a )
3′c
9′a ‚CH2Cl2
crystals of 7a . Yield: 0.65 g, 78%. IR: ν(CtC), 2061 cm-1
.
formula
fw
cryst syst
space group
a (Å)
C46H45F6OP3Ru
921.80
monoclinic
P21/c
11.469(8)
20.985(6)
17.913(4)
90
91.73(3)
90
4309(4)
4
C61H54Cl2OP2Ru
1036.95
orthorombic
Pbca
18.896(8)
15.16(1)
35.35(2)
90
1H NMR (CDCl3, δ): 8.00-7.02 (m, 35 H, Ph), 4.41 (s, 5 H,
2
2
C5H5), 4.21 (dd, 1 H, J HH ) 16.8, J PH ) 2.3, PCH2, Ha), 3.39
(s, 3 H, OMe), 1.32 (dd, 1 H, 2J PH ) 10.3, PCH2, Hb), 0.51 (s, 9
H, But). Anal. Calcd for C57H54O2P2Ru: C, 73.29; H, 5.83; P,
6.63. Found: C, 73.49; H, 5.75; Cl, P, 6.67. Attempts to
enhance the procedure by performing the recrystallization
from dichloromethane and ethanol afforded a mixture of
b (Å)
c (Å)
R (deg)
â (deg)
90
90
1
γ (deg)
crystals of 8a and 7a (∼3/1 by H NMR).
V (Å3)
10128(11)
8
1.36
[R u {CtCC(OMe)P h 2}(C9H 7)(P P h 3){(η1(P )-P h 2P CH 2C-
(dO)Bu t}] (7′a ). A mixture consisting of a 0.50 g (0.46 mmol)
sample of 5′a , 0.05 g (0.5 mmol) of KOH, and methanol (30
mL) was stirred for 2 days. The resulting orange precipitate
was collected by filtration and then washed with methanol.
Z
calcd density (g cm-3
F(000)
)
1.42
1888
4288
radiation (λ, Å)
cryst size (mm)
temp (K)
monochromator
Mo KR (0.710 73) Mo KR (0.710 73)
0.16 × 0.20 × 0.26 0.10 × 0.26 × 0.30
293
293
Yield: 0.38 g, 85%. IR: ν(CtC), 2066 cm-1 1H NMR (CD2-
.
graphite cryst
0.53
graphite cryst
0.52
Cl2, δ): 7.90-6.19 [m, 39 H, Ph and C9H7 (4 H)], 5.07 (m, 1 H,
µ (mm-1
)
2
C9H7), 4.79 (s, broad, 1 H, C9H7), 4.43 (dd, 1 H, J HH ) 17.8,
range of abs
0.52-1.00
0.57-1.00
2J PH ) 3.0, PCH2, Ha), 3.91 (s, broad, 1 H, C9H7), 3.40 (s, 3 H,
diffraction geom
θ range for data
collection (deg)
index ranges for
data collection
ω-2θ
ω-2θ
2
OMe), 1.57 (dd, 1 H, J PH ) 9.6, PCH2, Hb), 0.53 (s, 9 H, But).
1.50-24.97
1.15-24.97
Anal. Calcd for C61H56O2P2Ru: C, 75.68; H, 5.83; P, 6.40.
Found: C, 75.90; H, 5.92; P, 6.25.
-13 e h e 13
0 e h e 20
[Ru {CtCC(OEt)P h 2}(C5H5)(P P h 3){η1(P )-P h 2P CH2C(dO)-
Bu t}] (8a ). The reaction of 5a in ethanol with KOH at room
temperature or with K2CO3 at reflux (1 h) afforded a yellow
precipitate of 8a in a nearly quantitative yield. Recrystalli-
zation from dichloromethane and ethanol yielded yellow
0 e k e 24
0 e l e 21
9647
7567
519
0 e k e 16
0 e l e 38
9707
8626
609
no. of rflns measd
no. of indep rflns
no. of variables
agreement between
equiv rflnsa
0.085
0.000
crystals. IR: ν(CtC), 2065 cm-1
.
1H NMR (CD2Cl2, δ): 7.90-
2
7.02 (m, 35 H, Ph), 4.38 (s, 5 H, C5H5), 4.19 (dd, 1 H, J HH
)
)
final R factors (I > 2σ(I)) R1 ) 0.052
R1 ) 0.048
wR2 ) 0.090
R1 ) 0.247
wR2 ) 0.138
2
2
17.0, J PH ) 2.2, PCH2, Ha), 3.86 and 3.31 (2 dq, 2 H, J HH
wR2 ) 0.115
3
2
8.8, J HH ) 7.1, CH2Me), 1.37 (dd, 1 H, J PH ) 10.0, PCH2,
Hb), 1.16 (ta, 3 H, 3J HH ) 7.1, CH2Me), 0.47 (s, 9 H, But). Anal.
Calcd for C58H56O2P2Ru: C, 73.47; H, 5.96; P, 6.53. Found:
C, 73.56; H, 5.75; P, 6.36.
final R factors (all data) R1 ) 0.173
wR2 ) 0.153
a
Rint ) ∑(I - I )/∑I.
1
1
(dd, J HC ) 133, J PC ) 26.3, PCH). Anal. Calcd for C56H50
-
[R u {η2(C,P )-C(dCdCP h 2)CH [C(dO)Bu t }P P h 2}(C5H 5)-
(P P h 3)] (9a ). A mixture consisting of a 0.77 g (0.73 mmol)
sample of 5a , 0.40 g (2.89 mmol) of K2CO3, and THF (60 mL)
was stirred at room temperature for 3 days. The solvent was
evaporated under vacuum, and the remaining solid was
extracted with diethyl ether (50 mL). The solution was filtered
and the filtrate evaporated to leave a yellow powder that was
washed with hexane (35 mL). This crude product (yield 0.52
g, 79%) was recrystallized from toluene/hexane to obtain yellow
OP2Ru: C, 74.57; H, 5.59; P, 6.87. Found: C, 74.79; H, 5.50;
P, 6.53.
[R u {η2(C,P )-C(dCdCP h 2)CH [C(dO)Bu t ]P P h 2}(C9H 7)-
(P P h 3)] (9′a ). Red crystals of 9′a were similarly obtained in
89% yield by starting from 5′a . IR: ν(CdCdC), 1876 cm-1
.
1H NMR (CD2Cl2; δ): 7.62-6.20 [m, 39 H, Ph and C9H7 (4 H)],
4.96 (m, 1 H, C9H7), 4.40 (s, broad, 1 H, C9H7), 4.15 (d, 1 H,
2J PH ) 9.9, PCH), 3.76 (s, broad, 1 H, C9H7), 0.54 (s, 9 H, But).
13C{1H} NMR (CD2Cl2, δ): 209.0 (d, 2J PC ) 9.0, CO), 195.6 (dd,
crystals. Yield: 0.33 g, 50%. IR: ν(CdCdC), 1887 cm-1 1H
.
5
3J PC ) 16.2 and 2.7, Câ), 141.3 (dd, J PC ) 3.6 and 1.8, PhCγ,
2
NMR (CDCl3, δ): 7.59-7.11 (m, 35 H, Ph), 4.28 (d, 1 H, J PH
ipso), 140.5 (dd, 5J PC ) 2.7 and 1.8, PhCγ, ipso), 138.7 (dd, 1J PC
) 37.7, 3J PC ) 1.8, PhP, ipso), 138.6 (d, 1J PC ) 38.6, Ph3P, ipso),
) 9.7, PCH), 4.13 (s, 5 H, C5H5), 0.63 (s, 9 H, But). 13C{1H}
2
3
NMR (CD2Cl2, δ): 209.3 (d, J PC ) 9.0, CO), 196.3 (dd, J PC
)
3
134.9 (d, J PC ) 10.8, Ph3P, meta, includes as a shoulder one
5
17.9 and 2.7, Câ), 141.6 (dd, J PC ) 4.5 and 1.8, PhCγ, ipso),
140.6 (dd, J PC ) 3.6 and 1.8, PhCγ, ipso), 139.3 (dd, J PC
3
part of dd, PhP, ipso), 134.5 (d, J PC ≈ 1, second part of dd,
5
1
)
3
3
PhP, ipso), 133.7 (d, J PC ) 9.9, PhP, meta), 133.6 (d, J PC
)
3
1
37.7, J PC ) 1.8, PhP, ipso), 139.2 (d, J PC ) 38.6, Ph3P, ipso),
11.7, PhP, meta), 130.2 (d, 4J PC ) 1.8, PhP, para), 129.4-129.2
(m, Ph3P, para, and PhCγ, meta, and PhP, para), 128.6 (s,
PhCγ, ortho), 128.4 and 128.3 (2 s, PhCγ, meta and ortho), 127.9
(d, J PC ) 9.0, PhP, ortho), 127.7 (d, J PC ) 9.0, Ph3P, ortho),
127.1 (d, 2J PC ) 9.9, PhP, ortho), 126.2, 125.5, 124.2, and 124.0
(4 s, PhCγ, para, 2 C, and C9H7, 2 C), 123.5, 123.3, 106.9, 105.1
134.8 (d, 3J PC ) 10.8, Ph3P, meta), 134.7 (dd, 1J PC ) 25.1, 3J PC
3
) 1.8, PhP, ipso), 134.2 (d, J PC ) 12.6, PhP, meta), 133.5 (d,
3J PC ) 9.9, PhP, meta), 130.5 (d, J PC ) 1.8, PhP, para), 129.9
2
2
4
4
(s, PhCγ, meta), 129.5 (d, J PC ) 1.8, Ph3P, para), 129.1 (d,
4J PC ) 1.8, PhP, para), 128.4 and 128.3 (2 s, PhCγ, ortho and
2
2
4
meta), 128.0 (d, J PC ) 9.9, PhP, ortho), 127.9 (d, J PC ) 9.0,
Ph3P, ortho), 127.6 (s, PhCγ, ortho), 126.9 (d, J PC ) 9.0, PhP,
(4 s, C9H7), 102.0 (d, J PC ) 1.9, PhCγ), 96.2 (s, C9H7), 84.9
2
2
2
(dd, J PC ) 51.2 and 13.6, CR), 77.6 (d, J PC ) 9.9, C9H7), 74.2
(d, 2J PC ) 9.1, C9H7), 68.6 (d, 1J PC ) 25.1, PCH), 44.5 (s, CMe3),
26.7 (s, CMe3). 13C NMR (CD2Cl2; δ (selected values)): 84.9
ortho), 126.0 (s, PhCγ, para), 124.8 (s, PhCγ, para), 99.9 (ta,
4
4J PC ≈ J P′C ≈ 2.3, Cγ), 86.2 (dd, 2J PC ) 53.9 and 15.3, CR), 83.4
2
2
1
2
2
1
(ta, J PC ≈ J P′C ≈ 2.3, C5H5), 67.8 (d, J PC ) 26.3, PCH), 44.5
(s, CMe3), 26.6 (s, CMe3). 13C NMR (CD2Cl2; δ (selected
values)): 86.2 (ddd, 2J PC ) 53.9 and 15.3, 2J HC ) 9.9, CR), 67.8
(ddd, J PC ) 51.2 and 13.5, J HC ) 9.9, CR), 68.6 (dd, J HC
)
1
133, J PC ) 25.0, PCH). Anal. Calcd for C60H52OP2Ru: C,
75.69; H, 5.51; P, 6.51. Found: C, 75.96; H, 5.92; P, 6.07.

Ru(II) Cyclopentadienyl and Indenyl Complexes
Organometallics, Vol. 16, No. 25, 1997 5415
Cr ysta l Str u ctu r e An a lysis of 3′c a n d 9′a ‚CH2Cl2.
X-ray-quality suitable single crystals of complex 3′c were
obtained directly, while those of 9′a ‚CH2Cl2 were elaborated
through the slow diffusion of methanol into a concentrated
solution in dichloromethane. Experimental data collection,
crystal, and refinement parameters are collected in Table 4.
The unit cell parameters were obtained from the least-squares
fit of 25 reflections (with θ between 10 and 12°). Data were
collected with the ω-2θ scan technique and a variable scan
rate, with a maximum scan time of 60 s per reflection. The
intensity of the primary beam was checked throughout the
data collection by monitoring three standard reflections every
60 min. Profile analysis was performed on all reflections.26
Lorentz and polarization corrections were applied, and the
∑w(Fo2)2]1/2, with w ) 1/[σ2(Fo2) + (0.0610P)2], where P ) [max-
2
(Fo2,0) + 2Fc )/3] and σ2(Fo2) is derived from counting statistics.
The maximum shift to esd ratio in the last full-matrix least-
squares cycle was -0.001. The final difference Fourier map
showed no peaks higher than 0.55 e Å-3 nor deeper than -0.74
e Å-3
.
2
Com p lex 9′a ‚CH2Cl2. The function minimized was [∑w(Fo
- Fc2)2/∑w(Fo2)2]1/2, with w ) 1/[σ2(Fo2) + (0.0367P)2], where P
) [max(Fo2,0) + 2Fc2)/3] and σ2(Fo2) is derived from counting
statistics. The maximum shift to esd ratio in the last full-
matrix least-squares cycle was -0.043. The final difference
Fourier map showed no peaks higher than 0.43 e Å-3 nor
deeper than -1.57 e Å-3. The CH2Cl2 solvent molecule was
affected by structural disorder and was anisotropically refined,
showing the maximum hole on the final electronic density map.
The CH2Cl2 hydrogen atoms were geometrically placed, fixing
their thermal parameters to 0.40.
2
data were reduced to |Fo| values. The structures were solved
by DIRDIF (Patterson methods and phase expansion).27 Iso-
2
tropic full-matrix least-squares refinement on |Fo| was per-
formed using SHELX93.28 At this stage an empirical absorp-
tion correction was applied using XABS2.29 Hydrogen atoms
(except H(1) in 3′c and H(2B) in 9′a ) were geometrically placed.
During the final stages of the refinement, the positional
parameters and the anisotropic thermal parameters of the
non-H atoms were refined. The geometrically placed hydrogen
atoms were isotropically refined, riding on their parent atoms,
with a common thermal parameter. H(1) in 3′c and H(2B) in
9′a were independently (and also isotropically) refined. Atomic
scattering factors were taken from ref 30. Geometrical
calculations were made with PARST.31 The crystallographic
plots were made with EUCLID.32
Ack n ow led gm en t. This work was supported by the
“Centre National de la Recherche Scientifique”, the
“Direccio´n General de Investigacio´n Cientifica y Te´cnica
(Grant No. PB93-0325)”, and the EU (Human Capital
and Mobility Programme, Project No. ERBCHRXCT
940501). Crystallographic work and calculations were
performed in Oviedo on the Scientific Computer Center
and X-ray group DEC-ALPHA computers. Elemental
analyses were performed by the “Service de Microanal-
yse du CNRS”, Vernaison, France. The recording of the
NMR spectra was conducted in Rennes by J .-P. Gue´gan.
Both the grant to P.C. and the fellowship to M.I.V, given
by the “Conseil Re´gional de Bretagne” and the “Euro-
pean Erasmus Program” are gratefully acknowledged.
Com p lex 3′c. The function minimized was [∑w(Fo2 - Fc2)2/
(26) (a) Grant, D. F.; Gabe, E. J . J . Appl. Crystallogr. 1978, 11, 114.
(b) Lehman, M. S.; Larsen, F. K Acta Crystallogr. 1974, A30, 580.
(27) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
Garc´ıa-Granda, S.; Gould, R. O.; Smits, J . M. M.; Smykalla, C. The
DIRDIF Program System; Technical Report of the Crystallography
Laboratory; University of Nijmegen, Nijmegen, The Netherlands.
(28) Sheldrick, G. M. SHELX 93. In Crystallographic Computing;
Flack, H. D., Parkanyi, P., Simon, K., Eds.; IUCr/Oxford University
Press: Oxford, U.K., 1993; Vol. 6, p 111.
Su p p or tin g In for m a tion Ava ila ble: For 3′c and 9′a , text
giving further details of the X-ray study and tables of bond
distances and angles, atomic coordinates, positional and
thermal parameters, and torsion angles (37 pages). Ordering
information is given on any current masthead page.
OM970513N
(29) Parkin, S.; Moezzi B.; Hope, H. J . Appl. Crystallogr. 1995, 28,
53.
(30) International Tables for X-Ray Crystallography; Kynoch
Press: Birmingham, U.K., 1974; Vol. IV (present distributor: Kluwer
Academic Publishers, Dordrecht, The Netherlands).
(31) Nardelli, M. Comput. Chem. 1983, 7, 95.
(32) Spek, A. L. in Computational Crystallography, 1982, 528; Sayre,
D. Ed., Clarendon Press., Oxford.