Regioselective nucleophilic additions on indenyl-ruthenium(II)-allenylidene complexes. X-ray crystal structure of the alkynyl complex [Ru{C≡CC(C≡CH)Ph2}(η5-C9H 7)(PPh3)2]

Article abstract of DOI:10.1021/om970358c

The diphenylallenylidene complexes [Ru(=C=C=CPh₂)(η⁵-C₉H₇)L ₂][PF₆] (L = PPh₃; L₂ = l,2-bis(diphenylphosphino)ethane (dppe), bis(diphenylphosphino)methane (dppm)) (la-c) react with NaOMe to yield the methoxyalkynyl derivatives [Ru{C≡CC(OMe)Ph₂}(η⁵-C₉H ₇)-L2] (3a-c). Protonation of these species gives back the starting allenylidene derivatives. Regioselective additions on the C^γ are also observed when la,b are treated with LiR (R = Me, ⁿBu), giving the alkynyl complexes [Ru{C≡CC(R)Ph₂}(η⁵-C₉H ₇)L₂] (4a,b, 5a,b). Vinylidene derivatives [Ru{=C=C(H)C(R)Ph₂}(η⁵-C₉H ₇)(PPh₃)₂][BF₄] (6a, 7a) can be prepared by protonation of complexes 4a and 5a with HBF₄. The diphenylallenylidene compound 1c reacts with Li^tBu to yield the metallacycle complex [Ru{(k³C,P,P)-C=C=CPh₂(Ph₂PCHPPh ₂)}-(η₅-C₉H₇)] (8c). The alkynyl complexes [Ru{C≡CC(C=CR)Ph₂}(η⁵-C₉H ₇)(PPh₃)₂] (R = Ph, ⁿPr, H) (9a-11a) have been obtained by reaction of 1a with lithium or sodium acetylides. Protonation of these derivatives yields the vinylidene complexes [Ru{=C=C(H)C(C=CR)-Ph₂}(η⁵-C₉H ₇)(PPh₃)₂][BF₄](12a-14a). The crystal structure of [Ru{C≡CC(C≡CH)Ph₂}(η⁵-C ₉H₇)(PPh₃)₂] (11a) was determined by X-ray diffraction methods. In the structure the alkynyl chain is nearly linear (Ru-C(l)-C(2) = 175.0(2)°) with Ru-C(1) and C(1)-C(2) distances of 1.993(2) and 1.209(3) A?, respectively. The monosubstituted allenylidene complex [Ru{=C=C=C(H)Ph}η-C₉H₇)(PPh₃) ₂][PF₆] (2a) reacts with PMe₃, PMe₂Ph, PMePh₂, and PPh₃ to yield the cationic alkynyl-phosphonio derivatives [Ru{C≡CC(PR₃)(H)Ph}(η⁵-C₉H ₇)-(PPh₃)₂][PF6] (17a-20a) in a regioselective way. Similarly, allenylidene complexes la-c add PMe₃ to give the corresponding alkynyl-phosphonio derivatives 15a-c. [Ru{C≡CC-(PMe₃)Ph2}(η⁵-C₉H ₇)(dppm)][PF₆] (15c) undergoes an isomerization process to yield the thermodynamically more stable allenyl-phosphonio complex [Ru{C(PMe₃)=C=CPh₂}(η⁵-C₉H ₇)(dppm)][PF₆] (21c). [Ru{C(PMe₂Ph)=C=CPh₂} (η⁵-C₉H₇)(dppm)][PF₆] (22c) can be obtained directly by addition of PMe₂Ph to the Cα atom of 1c. The behavior of the diphenylallenylidene complexes 1a-c toward sodium 2-methylthiophenolate is also discussed.

Full text of DOI:10.1021/om970358c

Organometallics 1997, 16, 4453-4463
4453
Regioselective Nu cleop h ilic Ad d ition s on
In d en yl-Ru th en iu m (II)-Allen ylid en e Com p lexes. X-r a y
Cr ysta l Str u ctu r e of th e Alk yn yl Com p lex
[Ru {CtCC(CtCH)P h 2}(η5-C9H7)(P P h 3)2]†
Victorio Cadierno,‡ M. Pilar Gamasa,‡ J ose´ Gimeno,*,‡
M. Carmen Lo´pez-Gonza´lez,‡ J avier Borge,§ and Santiago Garc´ıa-Granda§
Departamento de Quı´mica Orga´nica e Inorga´nica and Departamento de Quı´mica Fı´sica y
Anal´ıtica, Instituto Universitario de Quı´mica Organometa´lica “Enrique Moles” (Unidad
Asociada al CSIC), Facultad de Qu´ımica, Universidad de Oviedo, E-33071 Oviedo, Spain
Received April 28, 1997X
The diphenylallenylidene complexes [Ru(dCdCdCPh2)(η5-C9H7)L2][PF6] (L ) PPh3; L2 )
1,2-bis(diphenylphosphino)ethane (dppe), bis(diphenylphosphino)methane (dppm)) (1a -c)
react with NaOMe to yield the methoxyalkynyl derivatives [Ru{CtCC(OMe)Ph2}(η5-C9H7)-
L2] (3a -c). Protonation of these species gives back the starting allenylidene derivatives.
Regioselective additions on the Cγ are also observed when 1a ,b are treated with LiR (R )
Me, nBu), giving the alkynyl complexes [Ru{CtCC(R)Ph2}(η5-C9H7)L2] (4a ,b, 5a ,b). Vi-
nylidene derivatives [Ru{dCdC(H)C(R)Ph2}(η5-C9H7)(PPh3)2][BF4] (6a , 7a ) can be prepared
by protonation of complexes 4a and 5a with HBF4. The diphenylallenylidene compound 1c
reacts with LitBu to yield the metallacycle complex [Ru{(κ3(C,P,P)-CdCdCPh2(Ph2PCHPPh2)}-
(η5-C9H7)] (8c). The alkynyl complexes [Ru{CtCC(CtCR)Ph2}(η5-C9H7)(PPh3)2] (R ) Ph,
nPr, H) (9a -11a ) have been obtained by reaction of 1a with lithium or sodium acetylides.
Protonation of these derivatives yields the vinylidene complexes [Ru{dCdC(H)C(CtCR)-
Ph2}(η5-C9H7)(PPh3)2][BF4] (12a -14a ). The crystal structure of [Ru{CtCC(CtCH)Ph2}(η5-
C9H7)(PPh3)2] (11a ) was determined by X-ray diffraction methods. In the structure the
alkynyl chain is nearly linear (Ru-C(1)-C(2) ) 175.0(2)°) with Ru-C(1) and C(1)-C(2)
distances of 1.993(2) and 1.209(3) Å, respectively. The monosubstituted allenylidene complex
[Ru{dCdCdC(H)Ph}(η5-C9H7)(PPh3)2][PF6] (2a ) reacts with PMe3, PMe2Ph, PMePh2, and
PPh3 to yield the cationic alkynyl-phosphonio derivatives [Ru{CtCC(PR3)(H)Ph}(η5-C9H7)-
(PPh3)2][PF6] (17a -20a ) in a regioselective way. Similarly, allenylidene complexes 1a -c
add PMe3 to give the corresponding alkynyl-phosphonio derivatives 15a -c. [Ru{CtCC-
(PMe3)Ph2}(η5-C9H7)(dppm)][PF6] (15c) undergoes an isomerization process to yield the
thermodynamically more stable allenyl-phosphonio complex [Ru{C(PMe3)dCdCPh2}(η5-
C9H7)(dppm)][PF6] (21c). [Ru{C(PMe2Ph)dCdCPh2}(η5-C9H7)(dppm)][PF6] (22c) can be
obtained directly by addition of PMe2Ph to the CR atom of 1c. The behavior of the
diphenylallenylidene complexes 1a -c toward sodium 2-methylthiophenolate is also discussed.
In tr od u ction
their chemistry has not been so extensively studied
compared with that of the vinylidene complexes.3 How-
ever, during the last few years the study of metal-
allenylidene complexes has notably increased, probably
due to the discovery of a general synthetic method,
based on the direct activation of propargyl alcohols.4 The
high degree of unsaturation of the organic chain, which
contains three activated carbon atoms, has provided
potential utility as reagents in organic synthesis analo-
gous with the well-known chemistry of metal-carbene
complexes.5 Since the reactivity of the allenylidene
chain still remains largely unexplored, the usefulness
in chemical transformations has not been exploited yet.
The involvement of allenylidene complexes in the cata-
Metallacumulenes [M])(Cd)nCR2 are a new class of
unsaturated carbene complexes containing cumulative
MdC and CdC double bonds. Metal-vinylidene (n )
1) and metal-allenylidene (n ) 2) derivatives are the
first members of this family.1 Even though the first
allenylidene complexes have been known since 1976,2
† Dedicated to Prof. Pascual Royo (Universidad de Alcala´ de
Henares) on the occasion of his 60th birthday.
‡ Departamento de Qu´ımica Orga´nica e Inorga´nica.
§ Departamento de Qu´ımica F´ısica y Anal´ıtica.
X Abstract published in Advance ACS Abstracts, August 15, 1997.
(1) Isolation of pentatetraenylidene complexes [M])(Cd)4CR2 has
been recently reported: (a) [M] ) trans-[RuCl(dppe)2]+: Touchard, D.;
Haquette, P.; Daridor, A.; Toupet, L.; Dixneuf, P. H. J . Am. Chem.
Soc. 1994, 116, 11157. (b) [M] ) [RuCl(η6-C6Me6)(PMe3)]+: Peron, D.;
Romero, A.; Dixneuf, P. H. Gazz. Chim. Ital. 1994, 124, 497. (c) [M] )
trans-[IrCl(PiPr3)2]: Lass, R. W.; Steinert, P.; Wolf, J .; Werner, H.
Chem. Eur. J . 1996, 2, 19. (d) [M] ) Cr(CO)5 or W(CO)5: Roth, G.;
Fischer, H. Organometallics 1996, 15, 1139.
(3) (a) Bruce, M. I.; Swincer, A. G. Adv. Organomet. Chem. 1983,
22, 59. (b) Bruce, M. I. Chem. Rev. 1991, 91, 197. (c) Antonova, A. B.;
J ohansson, A. A. Russ. Chem. Rev. (Engl. Trans.) 1989, 58, 693.
(4) (a) Selegue, J . P. Organometallics 1982, 1, 217. (b) Le Bozec,
H.; Dixneuf, P. H. Russ. Chem. Bull. 1995, 44, 801 and references cited
therein. (c) Werner H. J . Chem. Soc., Chem. Commun. 1997, 903 and
references cited therein.
(2) (a) Fischer, E. O.; Kalder, H.-J .; Franck, A.; Ko¨hler, F. H.;
Huttner, G. Angew. Chem., Int. Ed. Engl. 1976, 15, 623. (b) Berke, H.
Angew. Chem., Int. Ed. Engl. 1976, 15, 624.
S0276-7333(97)00358-0 CCC: $14.00 © 1997 American Chemical Society

4454 Organometallics, Vol. 16, No. 20, 1997
Cadierno et al.
Sch em e 1
lytic coupling of allylic alcohols and propargyl alcohols
in the presence of [RuCl(η5-C5H5)(PPh3)2] has just been
reported.6
of the reactivity of the complexes [Ru(dCdCdCRR′)-
(η5-C9H7)L2]+ with a variety of nucleophiles. In par-
ticular we were interested in finding out to what extent
the electronic density and the steric properties of these
metal fragments affect the reactivity of the cumulene
system. Recent theoretical calculations (EHMO) carried
out on the model [Ru(dCdCdCH2)(η5-C9H7)(PH3)2]+
show that the LUMO of the molecule is centered on CR
(25%) and Cγ (33%) of the unsaturated chain.16a Part
of this work has been previously communicated.17
Theoretical studies (MO) on the model [Mn(dCd
CdCH2)(η5-C5H5)(CO)2] showed7 that CR and Cγ atoms
of the allenylidene chain are electrophilic centers and
that Câ is nucleophilic. The nucleophilic character of
Câ has been experimentally confirmed by Kolovoba and
co-workers8 on the neutral allenylidene complexes [Mn-
t
(dCdCdCR2)(η5-C5H5)(CO)2] (R ) Ph, Bu) which un-
dergo Câ protonation additions to give the cationic
alkenyl-carbyne derivatives [Mn{tCC(H)dCR2}(η5-
C5H5)(CO)2]+.9 Although reactivity studies on neutral
and cationic allenylidene complexes also confirm the
electrophilic character of the CR and Cγ atoms, the
nucleophilic additions seem to be dependent on the
metal fragment as well as on the Cγ substituents, as is
shown in the regioselective additions of alcohols. Thus,
alcohols can be added either at the CR atom to give
alkenyl-carbene derivatives10 [M]dC(OR)C(H)dCR2 or
at the Cγ to yield vinylidene complexes10f,11 [M]dCdC-
(H)C(OR)R2. In contrast, Dixneuf and co-workers and
ourselves have demonstrated that the use of sterically
hindered and/or electron rich metal fragments, such as
trans-[RuCl(dppm)2],12 [Ru{N(CH2CH2PPh2)3}3],13 or
[Ru(η5-C9H7)L2] (L2 ) 2PPh3, dppe, dppm),10f,14 prevents
the nucleophilic addition of alcohols on the allenylidene
chain.15
Resu lts a n d Discu ssion
Rea ction of Allen ylid en e Com p lexes w ith So-
d iu m Meth oxid e. The diphenylallenylidene complexes
[Ru(dCdCdCPh2)(η5-C9H7)L2][PF6] (L2 ) 2PPh3, dppe,
dppm) (1a -c) react with NaOMe in tetrahydrofuran,
at room temperature, to give selectively the yellow
methoxyalkynyl derivatives 3a -c (90-96%) (Scheme 1).
Under similar reaction conditions the monosubstituted
allenylidene complex [Ru{dCdCdC(H)Ph}(η5-C9H7)-
(PPh3)2][PF6] (2a ) also reacts with NaOMe to yield a
mixture of products containing mainly the previously
reported methoxyalkynyl complex [Ru{CtCC(OMe)(H)-
Ph}(η5-C9H7)(PPh3)2].10f
The novel alkynyl complexes are air stable in the solid
state. They have been characterized by microanalysis,
mass spectra (FAB), infrared spectrometry, and NMR
(1H, 31P{1H}, 13C{1H}) spectroscopy (details are given
in the Experimental Section and Tables 1 and 2). The
formation of the alkynyl chain is clearly confirmed by
the appearance in the IR spectra (KBr) of a ν(CtC)
absorption in the range 2058-2086 cm-1. The NMR
data of 3a -c can be compared with those reported for
similar indenyl-ruthenium-alkynyl complexes [Ru-
(CtCR)(η5-C9H7)L2].18 Thus, the 31P{1H} NMR spectra
show a single resonance consistent with the chemical
As part of our continuing interest in investigating the
reactivity patterns of vinylidene- and allenylidene-
ruthenium(II) complexes here we report a general study
(5) (a) Doyle, M. P. In Comprehensive Organometallic Chemistry II;
Abel, E. W.; Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: New
York, 1995; Vol. 5, pp 387-420. (b) Wulff, W. D. In Comprehensive
Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson,
G., Eds.; Pergamon Press: New York, 1995; Vol. 5, pp 469-548. (c)
Hegedus, L. S. In Comprehensive Organometallic Chemistry II; Abel,
E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon Press: New York,
1995; Vol. 5, pp 549-576.
(6) (a) Trost, B. M.; Flygare, J . A. J . Am. Chem. Soc. 1992, 114, 5476.
(b) Trost, B. M. Chem. Ber. 1996, 129, 1313.
(14) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E.; Borge, J .;
Garc´ıa-Granda, S.; Organometallics 1994, 13, 745.
(7) Schilling, B. E. R.; Hoffmann, R.; Lichtenberger, D. L. J . Am.
Chem. Soc. 1979, 101, 585.
(15) C-C coupling reactions on allenylidene complexes have been
reported recently: (a) Wiedemann, R.; Steinert, P.; Gevert, O.; Werner,
H. J . Am. Chem. Soc. 1996, 118, 2495. (b) Werner, H.; Laubender, M.;
Wiedemann, R.; Windmu¨ller, B. Angew. Chem., Int. Ed. Engl. 1996,
35, 1237. (c) Braun, T.; Meuer, P.; Werner, H. Organometallics 1996,
15, 4075.
(16) (a) The absence of reactivity of these allenylidene-indenyl-
ruthenium(II) complexes toward alcohols seems to indicate an effective
steric protection of the electrophilic sites in the allenylidene chain by
the indenyl and the ancillary phosphine ligands: Pe´rez-Carren˜o, E.
Ph.D. Thesis, University of Oviedo, 1996. (b) The trans conformation
on the model [Ru(CtCCH3)(η5-C9H7)(PH3)2] is 5.48 kcal/mol more
stable than the cis: Pe´rez-Carren˜o, E. Ph.D. Thesis, University of
Oviedo, 1996.
(8) Kolovoba, N. E.; Ivanov, L. L.; Zhavanko, O. S.; Khitrova, O. M.;
Batsanov, A. S.; Struchkov, Y. T. J . Organomet. Chem. 1984, 262, 39.
(9) Câ protonations on neutral allenylidene-ruthenium complexes
also have been reported: Werner, H.; Stark, A.; Steinert, G.; Gru¨nwald,
G.; Wolf, J . Chem. Ber. 1995, 128, 49.
(10) [M]
)
[RuCl(η6-arene)(PR3)]+: (a) Dussel, R.; Pilette, D.;
Dixneuf, P. H. Organometallics 1991, 10, 3287. (b) Pilette, D.; Le Bozec,
H.; Romero, A.; Dixneuf, P. H. J . Chem. Soc., Chem. Commun. 1992,
1220. [M] ) Cr(CO)5 or W(CO)5: (c) Cosset, C.; del Rio, I.; Le Bozec,
H. Organometallics 1995, 14, 1938. (d) Cosset, C.; del Rio, I.; Peron,
V.; Windmu¨ller, B.; Le Bozec, H. Synlett 1996, 435. [M] ) [Ru(η5-
C5H5)(CO)(PiPr3)]+: (e) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .;
Lo´pez, A. M.; On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423.
[M] ) [Ru(η5-C9H7)(PPh3)2]+: (f) Cadierno, V.; Gamasa, M. P.; Gimeno,
J .; Gonza´lez-Cueva, M.; Lastra, E.; Borge, J .; Garc´ıa-Granda, S.; Pe´rez-
Carren˜o, E. Organometallics 1996, 15, 2137.
(17) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Lastra, E. J . Orga-
nomet. Chem. 1994, 474, C27.
(18) (a) Gamasa, M. P.; Gimeno, J .; Mart´ın-Vaca, B. M.; Borge, J .;
Garc´ıa-Granda, S.; Pe´rez-Carren˜o, E. Organometallics 1994, 13, 4045.
(b) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Borge, J .; Garc´ıa-Granda,
S. J . Chem. Soc., Chem. Commun. 1994, 2495. (c) Gamasa, M. P.;
Gimeno, J .; Godefroy, I.; Lastra, E.; Mart´ın-Vaca, B. M.; Garc´ıa-
Granda, S.; Gutie´rrez-Rodr´ıguez, A. J . Chem. Soc., Dalton Trans. 1995,
1901. (d) Houbrechts, S.; Clays, K.; Persoons, A.; Cadierno, V.; Gamasa,
M. P.; Gimeno, J . Organometallics 1996, 15, 5266.
(11) [M] ) [Ru(η5-C5H5)L2]+: Le Lagadec, R.; Roma´n, E.; Toupet,
L.; Mu¨ller, U.; Dixneuf, P. H. Organometallics 1994, 13, 5030.
(12) Touchard, D.; Pirio, N.; Dixneuf, P. H. Organometallics 1995,
14, 4920.
(13) Wolinska, A.; Touchard, D.; Dixneuf, P. H.; Romero, A. J .
Organomet. Chem. 1991, 420, 217.

Indenyl-Ruthenium(II)-Allenylidene Complexes
Ta ble 1. 31P {1H} a n d 1H NMR Da ta for th e Neu tr a l Alk yn yl Com p lexesa
1H
Organometallics, Vol. 16, No. 20, 1997 4455
η5-C9H7
c
complex
31P{1H} H-1,3 H-2 J HH H-4,7, H-5,6
others
[Ru{CtCC(OMe)Ph2}(η5-C9H7)(PPh3)2] (3a )
[Ru{CtCC(OMe)Ph2}(η5-C9H7)(dppe)] (3b)
53.55 s 4.59 d 5.29 t 2.4 6.61 m, b
87.93 s 4.89 d 5.12 t 2.5 b, b
6.83-8.00 m (PPh3 and Ph)
1.75 m, 2.15 m (P(CH2)2P); 3.05 s (OCH3);
6.69-7.68 m (PPh2 and Ph)
[Ru{CtCC(OMe)Ph2}(η5-C9H7)(dppm)] (3c)
20.05 s 5.48 d 5.42 t 2.6 b, b
3.34 s (OCH3); 3.98 m, 4.23 m (PCHaHbP);
7.15-7.81 m (PPh2 and Ph)
[Ru{CtCC(Me)Ph2}(η5-C9H7)(PPh3)2] (4a )
[Ru{CtCC(nBu)Ph2}(η5-C9H7)(PPh3)2] (5a )
54.28 s 4.86 d 5.53 t 2.2 6.87 m, b
53.34 s 4.34 d 5.09 t 2.2 6.27 m, b
2.30 s (CH3); 7.00-8.07 m (PPh3 and Ph)
0.57 t (CH3, J HH ) 3.3); 1.03 m, 1.22 m,
2.09 m (CH2); 6.53-7.45 m (PPh3 and Ph)
1.52 s (CH3); 1.82 m, 2.16 m (P(CH2)2P);
6.99-7.67 m (PPh2 and Ph)
[Ru{CtCC(Me)Ph2}(η5-C9H7)(dppe)] (4b)
[Ru{CtCC(nBu)Ph2}(η5-C9H7)(dppe)] (5b)
88.77 s 4.95 d 5.08 t 2.3 b, b
88.35 s 4.96 d 5.12 t 2.4 b, b
0.87 t (CH3, J HH ) 5.7); 1.24 m, 1.82 m,
2.14 m (3CH2 and P(CH2)2P);
7.00-7.39 m (PPh2 and Ph)
[Ru{CtCC(CtCPh)Ph2}(η5-C9H7)(PPh3)2] (9a ) 53.33 s 4.64 d 5.38 t 2.2 6.58 m, b
6.86-7.75 m (PPh3 and Ph)
[Ru{CtCC(CtCnPr)Ph2}(η5-C9H7)(PPh3)2]
(10a )
53.90 s 4.34 d 5.10 t 2.4 6.50 m,
6.82 m
1.03 t (CH3, J HH ) 7.3); 1.60 m (CH2);
2.34 t (CH2, J HH ) 7.1); 6.92-7.68 m
(PPh3 and Ph)
[Ru{CtCC(CtCH)Ph2}(η5-C9H7)(PPh3)2] (11a ) 54.52 s 4.57 d 5.29 t 2.4 b, b
[Ru{CtCC[S(o-C6H4Me)]Ph2}(η5-C9H7)(PPh3)2] 52.13 s 4.65 d 5.29 t 2.4 6.39 m, b
(23a )
2.45 s (≡CH); 6.65-8.03 m (PPh3 and Ph)
2.39 s (CH3); 6.77-7.89 m (PPh3 and Ph)
a
b
Spectra recorded in C6D6; δ in ppm and J in Hz. Abbreviations: s, singlet; d, doublet; t, triplet; m, multiplet. Overlapped by PPh3,
PPh2, or Ph protons. c Legend for indenyl skeleton:
Ta ble 2. 13C{1H} NMR Da ta for th e Neu tr a l Alk yn yl Com p lexesa
η5-C9H7
complex C-1,3 C-2 C-3a,7a ∆δ(C-3a,7a)b
C-4,7, C-5,6
RuCR
2J CP
Câ
Cγ
others
3a
3b
3c
74.86 95.68 110.83
-19.87
-21.59
c
124.56, 126.88 105.78 t 24.3 112.29 83.16 52.43 s (OCH3); 127.17-148.92 m
(PPh3 and Ph)
124.65, 125.40 109.20 t 24.0 108.72 82.62 28.34 m (P(CH2)2P); 51.70 s (OCH3);
126.84-148.48 m (PPh2 and Ph)
70.76 92.29 109.11
68.64 89.20
c
124.16, d
c
c
c
82.61 49.54 t (PCH2P, J CP ) 19.5); 51.79 s
(OCH3); 126.03-148.61 m
(PPh2 and Ph)
4a
5a
73.09 93.13 108.21
72.66 93.92 108.78
-22.49
-21.92
122.27, d
94.43 t 26.2 115.35 46.24 30.97 s (CH3); 124.20-137.57 m
(PPh3 and Ph)
122.55, 124.08
92.48 t 24.1 114.10 50.78 13.20 s (CH3); 22.54 s, 27.10 s,
41.91 s (CH2); 124.50-149.21 m
(PPh3 and Ph)
4b
5b
69.94 91.88 108.84
69.90 91.66 108.53
-21.86
-22.17
d, d
d, d
97.18 t 25.1 114.83 47.01 28.24 m (P(CH2)2P); 31.74 s (CH3);
123.80-150.80 m (PPh2 and Ph)
97.28 t 24.5 112.32 51.64 14.79 s (CH3); 23.78 s, 28.25 s, 42.52 s
(CH2); 27.75 m (P(CH2)2P); 123.85-
149.87 m (PPh2 and Ph)
9a
74.68 95.20 110.54
74.70 95.29 110.54
-20.16
-20.16
124.45, d
124.41, d
101.06 t 25.0 109.55 49.36 84.58 s, 95.49 s (CtC); 126.87-
148.73 m (PPh3 and Ph)
10a
99.12 t 23.9 110.54 48.85 14.70 s (CH3); 22.37 s, 23.72 s (CH2);
83.92 s, 85.82 s (CtC); 126.77-
149.31 m (PPh3 and Ph)
11a
23a
73.92 94.10 109.47
74.58 96.90 110.97
-21.23
-19.73
123.43, d
d, d
100.34 t 23.4 108.57 47.71 71.33 s (≡CH); 88.17 s (≡C); 125.87-
147.24 m (PPh3 and Ph)
103.78 t 21.9 112.93 62.73 22.64 s (CH3); 124.50-146.77 m
(PPh3 and Ph)
a
b
Spectra recorded in C6D6; δ in ppm and J in Hz. Abbreviations: s, singlet; t, triplet; m, multiplet. ∆δ(C-3a,7a) ) δ(C-3a,7a(η-
indenyl complex)) - δ(C-3a,7a(sodium indenyl)), δ(C-3a,7a) for sodium indenyl 130.70 ppm. c 108.37-110.30 ppm (m, C-3a,7a, RuCR, Câ).
Overlapped by PPh3, PPh2, or Ph carbons.
d
1
equivalence of the two phosphorus atoms (Table 1). H
and 13C{1H} NMR spectra exhibit resonances for aro-
matic, indenyl, and methylene ((CH2)2P2 or CH2P)
groups, in accordance with the proposed structures
(Tables 1 and 2). The methoxy group appears as a
the ranges δ 108.37-112.29 and 82.61-83.16 ppm,
respectively.
Indenyl carbon resonances (Table 2) have been also
assigned and are in accordance with the proposed η5-
coordination with values of ∆δ(C-3a,7a),19 indicative of
a slightly distorted η5-indenyl coordination.20
It is well-known that alkynyl derivatives react with
electrophiles at the â position to afford vinylidene
complexes.3 However, the treatment of 3a -c with
strong acids (HBF4 or HPF6) in diethyl ether or THF,
even at -20 °C, gives back the precursor allenylidene
1
single resonance in both H and 13C{1H} NMR spectra
at δ 3.05-3.50 and 51.70-52.43 ppm, respectively. In
the 13C{1H} NMR spectra the CR resonance appears as
a triplet due to coupling with the two equivalent
phosphorus atoms (δ 105.78-110.20 ppm, 2J CP ca. 24.0
Hz). The Câ and Cγ nuclei resonate as two singlets in

4456 Organometallics, Vol. 16, No. 20, 1997
Cadierno et al.
Sch em e 2
complexes 1a -c in almost quantitative yields (see
Scheme 1). The elimination of methanol also occurs in
the reactions of the methoxyalkynyl-ruthenium com-
plex trans-[Ru{CtCC(OMe)Ph2}Cl(dppm)2] with ac-
ids.12
Rea ction of Allen ylid en e Com p lexes w ith LiR (R
) Me, n Bu , tBu ). Allenylidene complexes [Ru(dCdCd
CPh2)(η5-C9H7)L2][PF6] (L2 ) 2PPh3, dppe) (1a ,b) add
selectively alkyl groups (Me, nBu) at the Cγ atom to
afford the neutral alkynyl derivatives [Ru{CtCC(Me)-
Ph2}(η5-C9H7)L2] (4a ,b) and [Ru{CtCC(nBu)Ph2}(η5-
C9H7)L2] (5a ,b) (Scheme 2). However, no reaction
occurs with LitBu. The spectroscopic properties of 4a ,b
and 5a ,b are similar to those of the methoxyalkynyl
complexes 3a ,b (see Experimental Section and Tables
1 and 2).
mixture of complexes. 31P{1H} NMR spectra of these
solutions show two singlet resonances which reveal the
formation of the expected alkynyl species [Ru{CtCC-
n
(R)Ph2}(η5-C9H7)(dppm)] (R ) Me, Bu) along with an
additional species. The latter can be selectively ob-
tained by treatment of a THF solution of 1c with LitBu
at -20 °C and isolated (80% yield) as a yellow solid
(Scheme 3). Complex 8c is identified on the basis of
1
analytical and spectroscopic data (IR and H, 31P{1H},
and 13C{1H} NMR) as an allenyl metallacycle. Thus,
the IR spectrum (KBr) shows a typical ν(CdCdC)
absorption band at 1903 cm-1. In the 31P{1H} NMR
spectrum appears a single signal at δ 4.78 ppm which
indicates the chemical equivalence of the two phospho-
rus atoms. The most remarkable feature of the 1H NMR
spectrum is the presence of a triplet signal at δ 5.57
(2J HP ) 2.3 Hz) ppm assigned to the (Ph2P)2CH proton.
The 13C{1H} NMR spectrum exhibits triplet signals at
δ 66.76 (J CP ) 21.1 Hz), 83.15 (2J CP ) 50.3 Hz), 105.48
(4J CP ) 7.2 Hz), and 209.39 (3J CP ) 15.2 Hz) ppm
corresponding to the (Ph2P)2CH, CR, Cγ, and Câ carbon
resonances, respectively. These chemical shifts and
coupling constants can be compared to those observed
In contrast to the behavior of the methoxyalkynyl
complexes 3a -c, protonation of alkynyl complexes 4a
and 5a with HBF4 in diethyl ether at room temperature
yields the corresponding monosubstituted vinylidene
derivatives 6a (83%) and 7a (79%) (Scheme 2). They
have been isolated as air stable tetrafluoroborate salts
and have been analytically and spectroscopically char-
acterized (see Experimental Section). The most remark-
able features of the NMR spectra are (i) (1H NMR) the
singlet resonance at δ 4.49 (6a ) and 4.45 (7a ) ppm of
the RudCdCH proton and (ii) (13C NMR) the typical
low-field resonance of the carbenic CR, which appears
as a triplet at δ 346.99 (2J CP ) 16.7 Hz, 6a ) and 344.64
(2J CP ) 17.3 Hz, 7a ) ppm, as well as the expected Câ
singlet resonance (δ 123.48 (6a ) and 119.16 (7a ) ppm).
The ∆δ(C-3a,7a) values -14.32 (6a ) and -13.12 (7a ) are
higher than that of the alkynyl complexes 4a and 5a
(see Table 2), indicating a moderate distortion on the
η5-coordination of the indenyl ligand.
for the analogous indenyl-ruthenium complex [Ru-
{κ2(C,P)-CdCdCPh2)CH(PPh2)C(dO)tBu}(η5-C9H7)(P-
Ph3)2].21
The formation of metallacycle 8c is probably the
result of the competitive dppm deprotonation vs nucleo-
philic addition to the Cγ atom. It is apparent that the
initial deprotonation of one of the methylenic protons
on the coordinated dppm ligand is taking place followed
by a favorable intramolecular addition of the resulting
methanide carbon atom at the R position of the allen-
ylidene group.22 It is possible that the more sterically
demanding tert-butyl group compared to the methyl or
n-butyl may prevent nucleophilic addition at the Cγ
The reactions of LiMe and LinBu with the allenylidene
complex [Ru(dCdCdCPh2)(η5-C9H7)(dppm)][PF6] (1c)
follow, however, a different pathway, resulting in a
(21) Crochet, P.; Demerseman, B.; Vallejo-Roales, M. I.; Gamasa,
M. P.; Gimeno, J .; Borge, J .; Garc´ıa-Granda, S. Organometallics, in
press.
(22) We have reported similar intramolecular C-C coupling pro-
cesses on cationic vinylidene-iron(II)-dppm complexes. Gamasa, M.
P.; Gimeno, J .; Lastra, E.; Mart´ın, B. M.; Aguirre, A.; Garc´ıa-Granda,
S.; Pertierra, P. J . Organomet. Chem. 1992, 429, C19.
(23) Borge, J .; Garc´ıa-Granda, S. Unpublished results.
(24) Cadierno, V.; Gamasa, M. P.; Gimeno, J .; Borge, J .; Garc´ıa-
Granda, S. Organometallics, in press.
(19) As has been proven previously, the parameter ∆δ(C-3a,7a) )
δ(C-3a,7a(η-indenyl complex)) - δ(C-3a,7a(sodium indenyl)) can be
used as an indication of the indenyl distortion: (a) Baker, R. T.; Tulip,
T. H. Organometallics 1986, 5, 839. (b) Kohler, F. G. Chem. Ber. 1974,
107, 570.
(20) (a) Zhou, Z.; J ablonski, C.; Bridson, J . J . Organomet. Chem.
1993, 461, 215 and references therein. (b) Ceccon, A.; Elsevier, C. J .;
Ernsting, J . M.; Gambaro, A.; Santi, S.; Venzo, A. Inorg. Chim. Acta
1993, 204, 15.

Indenyl-Ruthenium(II)-Allenylidene Complexes
Organometallics, Vol. 16, No. 20, 1997 4457
Sch em e 3
Sch em e 4
F igu r e 1. ORTEP view of the structure of the alkynyl
complex [Ru{CtCC(CtCH)Ph2}(η5-C9H7)(PPh3)2] (11a ).
For clarity, aryl groups of the triphenylphosphine ligands
are omitted (C* ) centroid of the indenyl ring).
position of the unsaturated chain. In accordance with
this the allenylidene complexes 1a ,b do not react with
LitBu.
The behavior of the monosubstituted allenylidene
complex [Ru{dCdCdC(H)Ph}(η5-C9H7)(PPh3)2][PF6] (2a)
toward LiR (R ) Me, nBu, tBu) under different reaction
conditions also has been examined; however, the reac-
tions led to complex mixtures of compounds, which were
not identified.
Reaction of Allen yliden e Com plexes with Acetyl-
id es. Regioselective additions to the Cγ of the allen-
ylidene chain of the complex [Ru(dCdCdCPh2)(η5-
C9H7)(PPh3)2][PF6] (1a ) also take place when acetylides
are used as nucleophiles. Thus, complex 1a reacts in
THF with an equimolar amount of LiCtCR (R ) Ph,
nPr) at -20 °C or with a large excess of NaCtCH at
room temperature to furnish yellow solutions, from
which the alkynyl complexes 9a -11a are isolated (67-
96% yield) (Scheme 4).
The analytical and spectroscopic data for 9a -11a are
fully consistent with these formulations (see Experi-
mental Section and Tables 1 and 2). Moreover, the
structure of complex 11a has been confirmed by an
X-ray diffraction study. A drawing of the molecular
structure is shown in Figure 1. Selected bond distances
and angles are listed in Table 3. The molecule exhibits
the usual allylene structure of the η5-indenyl ligand in
the pseudooctahedral three-legged piano-stool geometry.
The interligand angles P(1)-Ru-P(2), C(1)-Ru-P(1),
and C(1)-Ru-P(2) and those between the centroid C*
and the legs show values typical of a pseudooctahedron
(Table 3). The alkynyl ligand, which is nearly linear
(Ru-C(1)-C(2) angle of 175.0(2)°), is bound to ruthe-
nium, showing bond lengths of Ru-C(1) of 1.993(2) Å
and of C(1)-C(2) of 1.209(3) Å. These bonding param-
eters can be compared to those of the analogous alkynyl
complex [Ru(CtCC{CH2C(OMe)dW(CO)5}Ph2)(η5-C9H7)-
(PPh3)2].18b The C(4)-C(5) bond length (1.170(4) Å)
shows a typical value of a CtC bond.
Although the indenyl group is η5-bonded to the metal
atom, the structure shows a slight distortion of the five-
carbon ring from planarity with a hinge angle (HA) of
6.0(2)° and a fold angle (FA) of 11.8(2)° (Table 3). The
characteristic slippage of the indenyl ring is also ob-
served with a slip-fold (∆) value of 0.168(2) Å, which is
significantly lower than those shown by the analogous
vinylidene derivatives (Table 4). The slight distortions
toward an η3 binding mode in the solid state appear to

4458 Organometallics, Vol. 16, No. 20, 1997
Cadierno et al.
dependent on the nature of the unsaturated chain.10f,18a
Thus, while the preferred conformation of the indenyl
ligand in vinylidene complexes is such that the benzo
ring is oriented trans to the vinylidene group (CA ≈
180°), the preferred conformation is cis (CA ≈ 0°) in
allenylidene complexes (Table 4). The conformational
angle (CA) in complex 11a of 161.9(1)° (trans orienta-
tion) is in accordance with theoretical calculations
(EHMO) carried out on the model [Ru(CtCCH3)(η5-
C9H7)(PH3)2] showing that the trans orientation is
energetically more favored than the cis.16b
As described above for complexes 4a and 5a the
ruthenium-alkynyl complexes 9a -11a can be also
protonated with HBF4 in diethyl ether to yield the
vinylidene derivatives 12a-14a (77-82% yield) (Scheme
4). Spectroscopic data of 12a -14a are in accordance
with the proposed structures (see Experimental Sec-
tion).
Rea ction of Allen ylid en e Com p lexes w ith P h os-
p h in es. Phosphines are added regioselectively to the
allenylidene group, the position of the addition (CR or
Cγ) being controlled by the ancillary ligands on the
ruthenium atom. Thus, PMe3 and PMe2Ph react with
complex 1a , in THF at room temperature, to yield the
air stable cationic alkynyl-phosphonio complexes 15a
(86%) and 16a (65%) (Scheme 5). Similarly, alkynyl-
phosphonio complexes 17a -20a are obtained from the
addition of PMe3, PMe2Ph, PMePh2, and PPh3 to the
monosubstituted allenylidene complex [Ru{dCdCdC-
(H)Ph}(η5-C9H7)(PPh3)2][PF6] (2a ) in 52-98% yields
(Scheme 5). However, the diphenylallenylidene complex
1a does not react with PMePh2 or PPh3 even under
refluxing THF, probably due to the steric requirements
of the two bulky phenyl substituents on the Cγ atom.
Complexes 15a -20a have been analytically and
spectroscopically (IR and 31P{1H}, 1H, and 13C{1H}
NMR) characterized (see Experimental Section and
Tables 5 and 6 for details). The 31P{1H} NMR spectra
of 15a -16a and 17a exhibit the expected resonances
of an A2M and an ABM spin system, respectively (Table
5). The unequivalency of the PPh3 ligands in complex
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 DA,d a n d CAe (d eg) for
Com p lex 11a
Distances
Ru-C*
1.942(2)
2.3145(9)
2.292(1)
2.376(2)
2.207(2)
2.196(2)
2.250(2)
2.416(2)
1.842(2)
1.833(2)
1.836(2)
0.168(2)
P(2)-C(41)
P(2)-C(51)
P(2)-C(61)
Ru-C(1)
C(1)-C(2)
C(2)-C(3)
C(3)-C(81)
C(3)-C(91)
C(3)-C(4)
C(4)-C(5)
C(5)-H(5)
1.844(2)
1.849(2)
1.840(2)
1.993(2)
1.209(3)
1.484(3)
1.549(3)
1.550(3)
1.489(3)
1.170(4)
0.94(3)
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)
∆
Angles
C*-Ru-C(1)
C*-Ru-P(1)
C*-Ru-P(2)
C(1)-Ru-P(1)
C(1)-Ru-P(2)
P(1)-Ru-P(2)
Ru-C(1)-C(2)
C(1)-C(2)-C(3)
120.5(1)
125.6(1)
121.6(2)
85.44(7)
89.73(6)
103.55(4)
175.0(2)
176.7(2)
C(2)-C(3)-C(81)
C(2)-C(3)-C(91)
C(2)-C(3)-C(4)
C(81)-C(3)-C(4)
C(91)-C(3)-C(4)
C(3)-C(4)-C(5)
C(4)-C(5)-H(5)
108.9(2)
113.4(2)
108.2(2)
111.1(2)
107.6(2)
178.1(3)
178.(2)
FA
DA
11.8(2)
177.0(2)
HA
CA
6.0(2)
161.9(1)
a
∆ ) d(Ru-C(74),C(70)) - d(Ru-C(71),C(73)). b FA (fold angle)
) 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) ) angle between normals to least-squares planes
d
defined by C(71), C(72), C(73) and C(71), C(74), C(70), C(73). DA
(dihedral angle) ) angle between normals to least-squares planes
defined by C*, Ru, C(1) and C(1), C(2), C(3). e CA (conformational
angle) ) angle between normals to least-squares planes defined
by C**, C*, Ru and C*, Ru, C(1). C* ) centroid of C(70), C(71),
C(72), C(73), C(74). C** ) centroid of C(70), C(74), C(75), C(76),
C(77), C(78).
be maintained in solution, according to the value of ∆δ-
(C-3a,7a) ) -21.23 ppm obtained from the 13C{1H}
NMR spectra.
We have previously reported that the orientation of
the benzo ring of the indenyl ligand in vinylidene- and
allenylidene-indenyl-ruthenium(II) complexes is clearly
Ta ble 4. Slip P a r a m eter ∆ a n d Dih ed r a l An gles F A, HA, a n d CA for In d en yl Ru th en iu m (II) Com p lexesa
complex
Ru-C* (Å)
∆ (Å)
FA (deg)
HA (deg)
CA (deg)
ref
[{Ru}(dCdCMe2)]+
1.97(9)
0.197(7)
0.175(6)
0.1974(1)
0.0820(4)
0.121(5)
0.217(5)
0.1320
13.1(6)
11.9(5)
12.2(4)
5.1(5)
8.1(3)
14.8(4)
7.7(7)
8.1(6)
6.6(5)
7.5(4)
5.3(5)
6.2(4)
8.4(4)
4.4(7)
6.0(2)
157.8(4)
164.6(3)
160.0(3)
12.2(6)
18a
23
24
14
10f
24
[{Ru}(dCdC(H)Ph)]+
1.964(6)
1.970(9)
1.942(5)
1.951(5)
1.981(5)
1.942(8)
1.942(2)
[{Ru}(dCdC(Me)(C6H9))]+
[{Ru}(dCdCdC(C13H20))]+
[{Ru}(dCdCdCPh2)]+
9.6(3)
(E)-[{Ru}(C(H)dC(PPh3)(C6H9))]+
[{Ru}(CtCC{CH2C(OMe)dW(CO)5}Ph2)]
[{Ru}(CtCC(CtCH)Ph2)]
160.5(2)
120.7(6)
161.9(1)
18b
b
0.168(2)
11.8(2)
a
∆ ) d[Ru-C(74),C(70)] - d[Ru-C(71),C(73)]; FA ) C(71), C(72), C(73)/C(70), C(74), C(75), C(76), C(77), C(78); HA ) C(71), C(72),
C(73)/C(71), C(74), C(70), C(73); CA ) C**, C*, Ru/C*, Ru, C(1); {Ru} ) Ru(η5-C9H7)(PPh3)2. This work.
b
Sch em e 5

Indenyl-Ruthenium(II)-Allenylidene Complexes
Ta ble 5. 31P {1H} a n d 1H NMR Da ta for th e Alk yn yl-P h osp h on io Com p lexesa
1H
Organometallics, Vol. 16, No. 20, 1997 4459
η5-C9H7
H-4,7,
H-5,6
31P{1H}
2J PP J PP H-1,3
H-2 J HH
others
5
complex
[Ru{CtCC(PMe3)Ph2}-
30.25 t (PMe3)
4.1 4.55 d 5.02 t
3.2 4.84 d 5.37 t
2.1 6.56 m, d 1.76 d (CH3, 2J HP ) 12.6);
6.94-7.38 m (PPh3 and Ph)
(η5-C9H7)(PPh3)2][PF6] (15a )b 52.57 d (PPh3)
2
[Ru{CtCC(PMe2Ph)Ph2}-
28.78 t (PMe2Ph)
2.1 6.81 m, d 2.64 d (CH3, J HP ) 12.8);
(η5-C9H7)(PPh3)2][PF6] (16a )c 53.74 d (PPh3)
7.24-7.95 m (PPh3, PPh, and Ph)
[Ru{CtCC(PMe3)(H)Ph}-
29.23 m (PMe3)
3.6 4.68 bs 4.92 bs
4.71 bs
6.64 m, d 1.79 d (CH3, 2J HP ) 13.5); 5.01 d
(η5-C9H7)(PPh3)2][PF6] (17a )c 52.80 dd (PPh3)
29.1
29.2
30.6
(CH, J HP ) 18.5); 7.08-7.60 m
2
53.64 dd (PPh3)
27.09 s (PMe2Ph)
(PPh3 and Ph)
2.38 m (CH3); 5.38 d (CH, J HP ) 18.6);
6.95-7.98 m (PPh3, PPh, and Ph)
2
[Ru{CtCC(PMe2Ph)(H)Ph}-
4.54 bs 5.23 bs
4.72 bs
6.33 m,
6.92 m
(η5-C9H7)(PPh3)2][PF6] (18a )c 52.87 d (PPh3)
53.33 d (PPh3)
23.08 s (PMePh2)
[Ru{CtCC(PMePh2)(H)Ph}-
4.36 bs 5.16 bs
4.57 bs
d, e
2.68 d (CH3, 2J HP ) 13.1);
6.64-8.42 m (PPh3, PPh and Ph)
(η5-C9H7)(PPh3)2][PF6] (19a )c 51.36 d (PPh3)
52.61 d (PPh3)
19.20 s (CPPh3)
2
[Ru{CtCC(PPh3)(H)Ph}-
4.47 bs 5.19 bs
4.59 bs
6.00 m, d 6.05 d (CH, J HP ) 9.8);
6.80-7.97 m (PPh3 and Ph)
(η5-C9H7)(PPh3)2][PF6] (20a )c 50.76 d (RuPPh3) 30.9
51.16 d (RuPPh3)
32.14 t (PMe3)
[Ru{CtCC(PMe3)Ph2}-
3.9 5.64 bs 5.20 bs
2.8 5.78 bs 5.67 bs
d, d
1.57 d (CH3, 2J HP ) 13.1); 2.52 m
(P(CH2)2P); 7.12-7.41 m
(PPh2 and Ph)
(η5-C9H7)(dppe)][PF6] (15b)c 88.51 d (dppe)
[Ru{CtCC(PMe3)Ph2}-
18.45 d (dppm)
d, d
1.68 d (CH3, 2J HP ) 13.0); 4.11 m,
5.03 m (P(CHaHb)P); 6.97-7.86 m
(PPh2 and Ph)
(η5-C9H7)(dppm)][PF6] (15c)c 32.05 t (PMe3)
a
b
δ in ppm and J in Hz. Abbreviations: s, singlet; bs, broad singlet; d, doublet; t, triplet; m, multiplet. Spectra recorded in CD2Cl2.
c Spectra recorded in (CD3)2CO. Overlapped by PPh3, PPh2, PPh, or Ph protons. e 5.93-6.06 ppm (m, CH, H-4,7 or H-5,6).
d
Ta ble 6. 13C{1H} NMR Da ta for th e Alk yn yl-P h osp h on io Com p lexesa
η5-C9H7
complex C-1,3
C-2
C-3a,7a ∆δ(C-3a,7a)d
C-4,7, C-5,6
e, e
Ru-CR
Câ
2J CP
Cγ
J CP
others
15a b
15bc
17a c
18a c
19a c
72.66 94.99 109.86
-20.84
-19.49
-21.89
-21.68
-19.96
117.82 m 103.27 d 12.3 53.24 d 54.0 7.97 d (J CP ) 53.8, CH3);
123.91-139.27 m
(PPh3 and Ph)
73.45 96.31 111.21
125.07, 127.55 120.68 m 104.98 d
9.3 56.67 d 47.6 8.24 d (J CP ) 58.6, CH3);
128.27-139.37 m
(PPh3, PPh, and Ph)
75.44 92.94 108.62
109.00
123.85, 124.20 114.75 m 96.53 d
126.67, 126.99
10.9 39.55 d 50.3 6.51 d (J CP ) 54.4, CH3);
127.74-138.51 m
(PPh3 and Ph)
73.68 93.32 108.56
74.81
123.48, 124.03 115.97 m 96.47 d
126.48, 126.93
9.9 41.63 d 48.0 5.53 m (CH3); 119.24-
109.47
138.07 m (PPh3, PPh,
and Ph)
74.11 94.82 110.74
74.50
119.79, 120.46 114.82 m 98.32 d
121.47, 122.01
9.8 40.09 d 47.1 4.25 d (J CP ) 59.0, CH3);
123.20-138.79 m
(PPh3, PPh2, and Ph)
20a c
15bc
74.47 94.59 111.86
74.97
69.39 91.95 108.49
-18.84
-22.21
e, e, e, e
e, e
117.92 m 99.10 d
121.45 m 99.45 d
8.6 42.57 d 45.8 120.36-139.30 m
(PPh3 and Ph)
10.7 52.48 d 54.0 7.24 d (J CP ) 54.3, CH3);
27.15 m (P(CH2)2P);
124.10-133.43 m
(PPh2 and Ph)
a
b
δ in ppm and J in Hz. Abbreviations: s, singlet; d, doublet; m, multiplet. Spectra recorded in CD2Cl2. c Spectra recorded in (CD3)2CO.
∆δ(C-3a,7a) ) δ(C-3a,7a(η-indenyl complex)) - δ(C-3a,7a(sodium indenyl)), δ(C-3a,7a) for sodium indenyl 130.70 ppm. e Overlapped by
PPh3, PPh2, PPh, or Ph carbons.
d
17a is due to the presence of the chiral Cγ atom in the
alkynyl group. The 31P{1H} NMR spectra for complexes
18a -20a are similar to that of 17a , but in these cases
the 5J PP could not be determined. 1H and 13C{1H} NMR
spectra (Tables 5 and 6) are in accordance with the
proposed structures. In particular: (i) the CH proton
resonance of the alkynyl group in complexes 17a -20a
appears as a doublet at δ 5.01-6.06 (2J HP ) 9.8-18.6
Hz) ppm due to the coupling with the phosphorus atom
of the phosphine linked to the alkynyl group, and (ii)
the CR atom resonance for all the alkynyl-phosphonio
complexes appears as a multiplet at δ 114.75-121.45
ppm, showing an effective coupling to the two phospho-
rus atoms of triphenylphosphine bonded to the metal
and also to that of the phosphonio group. Câ and Cγ
resonances appear as doublets at δ 96.53-103.27 (2J CP
) 8.6-12.3 Hz) and δ 39.55-53.24 (J CP ) 45.8-54.0
Hz) ppm, respectively.
Allenylidene complexes 1b and 1c also react with
PMe3 to yield the alkynyl-phosphonio complexes 15b
(75%) and 15c (90%), respectively (Scheme 6). Although
complex 15b is stable in solution, 15c slowly rearranges
in THF solution (14 h room temperature) to give the
thermodynamically more stable allenyl-phosphonio
complex [Ru{C(PMe3)dCdCPh2}(η5-C9H7)(dppm)][PF6]
(21c) (70%), probably promoted by the steric require-
ments of the two bulky phenyl groups at the Cγ position
(Scheme 6).
The IR spectrum (KBr) of 21c shows a typical ν-
(CdCdC) absorption band at 1865 cm-1
.
1H and 13C-
{1H} NMR spectra are also in accordance with the
proposed structure. In particular, the carbon reso-

4460 Organometallics, Vol. 16, No. 20, 1997
Cadierno et al.
Sch em e 6
Sch em e 7
nances of the allenyl moiety appear in the 13C{1H} NMR
spectrum at δ 83.46 (m, CR), 210.81 (s, Câ) and 100.58
(d, J CP ) 29.2 Hz, Cγ) ppm. These resonances have
analogous 21c (see Experimental Section). In contrast,
the reaction of diphenylallenylidene complex 1b yields
a mixture of the corresponding alkynyl-phosphonio and
allenyl-phosphonio complexes. All attempts to form
these complexes regioselectively were unsuccessful.
3
been assigned accordingly to the data reported for the
analogous allenyl-phosphonio complex [Cr{C(PMe3)d
CdCPh2}(CO)5].25 The 31P{1H} NMR spectrum of 21c
exhibits the expected resonances of an A2M system at
δ 11.79 (3J PP ) 6.8 Hz, dppm) and δ 26.38 (3J PP ) 6.8
Hz, PMe3) ppm. The higher values of the coupling
constants compared to that of 15c (5J PP ) 2.8 Hz) (see
Table 5) are consistent with the position of PMe3 in the
CR atom of the allenyl chain.
Complex 1c also reacts with the bulkier phosphine
PMe2Ph leading to the direct formation of the allenyl-
phosphonio complex 22c (Scheme 6) identified on the
basis of the NMR data by comparison with those of the
Rea ction of Allen ylid en e Com p lexes w ith So-
d iu m 2-Meth ylth iop h en ola te. The reaction of di-
phenylallenylidene ruthenium(II) complexes 1a -c to-
ward sodium 2-methylthiophenolate is similar to their
reaction toward PMe2Ph. Thus, starting from 1a the
alkynyl complex 23a can be obtained in 45% yield, while
using 1c the allenyl derivative 24c was formed in 56%
yield (Scheme 7). Similarly, when complex 1b was used
a mixture of the corresponding alkynyl and allenyl
complexes was obtained.
Analytical and spectroscopic data (IR and 31P{1H}, 1H,
and 13C{1H} NMR) of 23a and 24c are in accordance
with the proposed structures (see Experimental Section
and Tables 1 and 2).
(25) (a) Fischer, H.; Reindl, D.; Troll, C.; Leroux, F. J . Organomet.
Chem. 1995, 490, 221. (b) For comparison with other mononuclear
allenyl-ruthenium complexes, see ref 21.

Indenyl-Ruthenium(II)-Allenylidene Complexes
Organometallics, Vol. 16, No. 20, 1997 4461
or 1c yielding the alkynyl complex 23a or the allenyl
complex 24c, respectively.
In summary, it is shown that the regioselectivity of
the nucleophilic additions to the allenylidene group is
accomplished by the appropriate selection both of the
substituents on the hydrocarbon unsaturated chain and
of the ancillary ligands on the ruthenium atom. This
strategy provides a good synthetic methodology for the
generation of a wide series of derivatives showing the
ability of the allenylidene complexes as precursors of
novel hydrocarbon functionalities.
Exp er im en ta l Section
The reactions were carried out under dry nitrogen using
Schlenk techniques. All solvents were dried by standard
methods and distilled under nitrogen before use. The allen-
ylidene complexes [Ru{dCdCdC(R)Ph}(η5-C9H7)L2][PF6] (1a -
c, 2a ) were prepared as previously reported.10f All reagents
were purchased from commercial suppliers and used as
received.
F igu r e 2. Space-filling representation of the allenylidene
complex [Ru(dCdCdCPh2)(η5-C9H7)(PPh3)2]+ (1a ).
Infrared spectra were recorded on a Perkin-Elmer 1720-XFT
spectrometer; mass spectra (FAB) were recorded using a VG-
Autospec spectrometer, operating in the possitive mode; 3-ni-
trobenzyl alcohol (NBA) was used as the matrix. The conduc-
tivities were measured at room temperature, in ca. 10-3 mol
dm-3 acetone solutions, with a J enway PCM3 conductimeter.
The C and H analyses were carried out with a Perkin-Elmer
240-B microanalyzer (uncompleted combustion was observed
for complex 3c). NMR spectra were recorded on a Bruker
AC300 instrument at 300 MHz (1H), 121.5 MHz (31P), or 75.4
MHz (13C) using SiMe4 or 85% H3PO4 as standards. 1H, 13C-
{1H}, and 31P{1H} NMR spectroscopic data for the alkynyl
complexes are collected in Tables 1, 2, 4 and 5.
Con clu d in g Rem a r k s
In this work a systematic study of nucleophilic addi-
tions to indenyl-ruthenium(II)-allenylidene complexes
is reported. Although theoretical calculations (EHMO)
only show small differences in the electrophilicity of CR
and Cγ atoms (LUMO is centered on CR 25% and Cγ
33%),16 the preferred cis orientation of the benzo ring
of the indenyl ligand and the presence of bulky ancillary
phosphine ligands on the ruthenium atom protect the
electrophilic CR atom of the unsaturated chain sterically.
In contrast, the Cγ atom is more accessible and nucleo-
philes may be added to this position (Figure 2). Thus
complexes [Ru(dCdCdCPh2)(η5-C9H7)L2]+ (L2 ) 2PPh3
(1a ), dppe (1b)) undergo regioselective additions to the
Cγ atom with typical nucleophiles such as methoxide,
alkyl, acetylide, and phosphines to give functionalized
alkynyl derivatives [Ru{CtCC(Nu)Ph2}(η5-C9H7)L2]n+
(n ) 0 (3a ,b-5a ,b, 9a -11a ) and n ) 1 (15a ,b, 16a ,
19a -20a )) in good yields.
The substitution of dppe or the two triphenylphos-
phine ligands by the small-bite chelating dppm de-
creases the steric protection of the electrophilic CR atom.
This allows the formation of the allenyl complexes [Ru-
{C(PR3)dCdCPh2}(η5-C9H7)(dppm)]+ (21c, 22c) which
are obtained by the reaction of the complex [Ru-
(dCdCdCPh2)(η5-C9H7)(dppm)]+ (1c) with PMe3 and
PMe2Ph. It is also apparent that the generation of the
allenyl complex 21c appears to be thermodynamically
controlled since the alkynyl-phosphonio complex [Ru-
{CtCC(PMe3)Ph2}(η5-C9H7)(dppm)]+ (15c) is formed
initially. The steric influence of the two bulky phenyl
groups in the Cγ position of the unsaturated chain vs
dppm seems to determine the regioselective formation
of the allenyl complex 22c through the addition of the
bulkier phosphine PMe2Ph to the CR atom (the putative
alkynyl intermediate has not been detected). The subtle
competence in the steric control between the ancillary
ligands and the substituents in the Cγ atom is confirmed
in the nucleophilic addition of PMe2Ph to the complex
[Ru(dCdCdCPh2)(η5-C9H7)(PPh3)2]+ which takes place
on the Cγ atom of the allenylidene chain to give the
phosphonio-alkynyl complex 16a .
Syn th esis of [Ru {C≡CC(R)P h 2}(η5-C9H7)L2] (L ) P P h 3,
R ) OMe (3a ), Me (4a ), n Bu (5a ), CtCP h (9a ), CtCn P r
(10a ), CtCH (11a ); L2 ) d p p e, R ) OMe (3b), Me (4b),
n Bu (5b); L2 ) d p p m , R ) OMe (3c)). To a solution of the
corresponding allenylidene complex [Ru(dCdCdCPh2)(η5-
C9H7)L2][PF6] (1a -c) (1 mmol) in 50 mL of THF was added,
at -20 °C, NaOMe (0.08 g, 1.5 mmol), or the corresponding
LiR (in hexane solution, 2 mmol), or a THF solution of the
corresponding LiCtCR (R ) Ph, nPr) (1 mmol), or a large
excess (ca. 1:10) of NaCtCH (suspension in xylene). The
mixture was allowed to warm to room temperature, and the
solvent was then removed in vacuo. The solid residue was
extracted with hexane (for complexes 4a ,b, 5a ,b) or diethyl
ether (for complexes 3a -c and 9a -11a ) and filtered. Evapo-
ration of the solvent gave the alkynyl complexes 3a -c, 4a ,b,
5a ,b and 9a -10a as yellow-orange solids. Complex 11a was
purified by column chromatography (silica gel) collecting the
orange band eluted with a mixture of hexane/diethyl ether (4/
1). Yield (%) IR data (KBr, ν(CtC), cm-1), analytical data,
and mass spectral data (FAB, m/ e) are as follows. 3a : 90;
2058. Anal. Calcd for RuC61H50P2O: C, 76.15; H, 5.24.
Found: C, 75.60; H, 5.12. [M+ + 1] ) 963, [M+ - R + 1] )
932, [M+ - R - PPh3] ) 669, [M+ - R - C9H7 - PPh3] ) 553.
(R ) OCH3). 3b: 94; 2086. Anal. Calcd for RuC51H44P2O:
C, 73.27; H, 5.30. Found: C, 72.78; H, 5.35. [M+] ) 835, [M+
- R] ) 805. (R ) OCH3). 3c: 96; 2081. Anal. Calcd for Ru-
C
50H42P2O: C, 73.04; H, 5.15. Found: C, 72.03; H, 5.13. [M+
- R] ) 791. (R ) OCH3). 4a : 75; 2086. Anal. Calcd for Ru-
61H50P2: C, 77.36; H, 5.43. Found: C, 77.03; H, 5.50. 4b:
C
62; 2089. Anal. Calcd for RuC51H44P2: C, 74.70; H, 5.41.
Found: C, 74.27; H, 5.48. 5a : 71; 2077. Anal. Calcd for Ru-
C
64H56P2: C, 77.79; H, 5.71. Found: C, 78.09; H, 6.19. 5b:
75; 2088. Anal. Calcd for RuC54H50P2: C, 75.24; H, 5.85.
Found: C, 75.15; H, 5.94. 9a : 67; 1953, 2074. Anal. Calcd
for RuC68H52P2: C, 79.12; H, 5.07. Found: C, 77.73; H, 5.43.
[M+ + 1] ) 1033, [M+ - R] ) 741. (R ) CtCCPh2CtCPh).
10a : 70; 1943, 2078. Anal. Calcd for RuC65H54P2: C, 78.21;
H, 5.45. Found: C, 77.84; H, 5.65. [M+ + 1] ) 999, [M+ - R]
A similar behavior is also observed in the nucleophilic
addition of sodium 2-methylthiophenolate to complex 1a

4462 Organometallics, Vol. 16, No. 20, 1997
Cadierno et al.
) 741. (R ) CtCCPh2CtCnPr). 11a : 96; 1962, 2077. Anal.
Calcd for RuC62H48P2: C, 77.87; H, 5.06. Found: C, 76.87; H,
5.68.
residue was extracted with diethyl ether and filtered. Evapo-
ration of the diethyl ether gave complex 8c as a yellow solid.
Yield (%), IR data (KBr, ν(CdCdC), cm-1), analytical data,
NMR spectroscopic data, and mass spectral data (FAB, m/ e)
are as follows: 80; 1903. Anal. Calcd for RuC49H38P2: C,
74.51; H, 4.85. Found: C, 73.85; H, 4.88. NMR: 31P{1H}
Syn th esis of [Ru {dCdC(H)C(R)P h 2}(η5-C9H7)(P P h 3)2]-
[BF 4] (R ) Me (6a ), n Bu (7a ), CtCP h (12a ), CtCn P r (13a ),
CtCH (14a )). A solution of the corresponding alkynyl
complex [Ru{CtCC(R)Ph2}(η5-C9H7)(PPh3)2] (4a , 5a , or 9a -
11a ) (1 mmol) in 100 mL of diethyl ether, at -20 °C, was
treated dropwise with strong stirring with a dilute solution of
HBF4‚Et2O in diethyl ether. Immediately, an insoluble solid
precipitated, but the addition was continued until no further
solid was formed. The solution was then decanted and the
brown solid washed with diethyl ether (3 × 20 mL) and
vacuum-dried. Yield (%), IR data (KBr, ν(BF4-), cm-1),
analytical data, conductivity data (acetone, 20 °C, Ω-1 cm2
mol-1), and NMR spectroscopic data are as follows. 6a : 83;
1058. Anal. Calcd for RuC61H51F4P2B: C, 70.86; H, 4.97.
Found: C, 70.08; H, 5.01. 121. NMR: 31P{1H} (CDCl3) δ 38.04
(s) ppm; 1H (CDCl3) δ 1.54 (s, 3H, CH3), 4.49 (s, 1H, RudCdCH),
5.37 (d, 2H, J HH ) 2.3 Hz, H-1,3), 5.70 (t, 1H, J HH ) 2.3 Hz,
H-2), 5.75 (m, 2H, H-4,7 or H-5,6), 6.69-7.50 (m, 42H, Ph,
H-4,7 or H-5,6) ppm; 13C{1H} (CDCl3) δ 30.51 (s, CH3), 47.62
(s, Cγ), 82.62 (s, C-1,3), 98.70 (s, C-2), 116.38 (s, C-3a,7a),
123.48 (s, Câ), 123.82 and 127.23 (s, C-4,7 and C-5,6), 127.50-
1
2
(C6D6) δ 4.78 (s) ppm; H (C6D6) δ 5.57 (t, 1H, J HP ) 2.3 Hz,
(Ph2P)2CH), 5.66 (d, 2H, J HH ) 3.0 Hz, H-1,3), 6.17 (t, 1H, J HH
) 3.0 Hz, H-2), 6.80-8.00 (m, 34H, Ph, H-4,7, H-5,6) ppm;
13C{1H} (C6D6) δ 66.08 (s, C-1,3), 66.76 (t, J CP ) 21.1 Hz,
2
(Ph2P)2CH), 83.15 (t, J CP ) 50.3 Hz, Ru-CR), 87.17 (s, C-2),
4
102.22 (s, C-3a,7a), 105.48 (t, J CP ) 7.2 Hz, Cγ), 122.47 (s,
C-4,7 or C-5,6), 123.47-150.26 (m, Ph, C-4,7 or C-5,6), 209.39
3
(t, J CP ) 15.2 Hz, Câ) ppm. ∆δ(C-3a,7a) ) -28.48. [M+ + 1]
) 791, [M+ - C9H7] ) 675.
Syn th esis of [Ru {C≡CC(P R3)(R′)P h }(η5-C9H7)L2][P F 6]
(L ) P P h 3, R′ ) P h , P R3 ) P Me3 (15a ), P Me2P h (16a ); L )
P P h 3, R′ ) H, P R 3 ) P Me3 (17a ), P Me2P h (18a ), P MeP h 2
(19a ), P P h 3 (20a ); L2 ) d p p e, R′ ) P h , P R3 ) P Me3 (15b);
L2 ) d p p m , R′ ) P h , P R3 ) P Me3 (15c)). To a solution of
the corresponding allenylidene complex 1a -c or 2a -c (1
mmol) in 50 mL of THF was added, at room temperature, the
corresponding PR3 (1.5 mmol), and the resulting solution was
stirred for 15 min. The solvent was then removed in vacuo,
and the yellow-brown solid residue was washed with diethyl
ether (3 × 20 mL) and vacuum-dried. Yield (%), IR data (KBr,
ν(PF6-), ν(CtC), cm-1), analytical data, and mass spectral data
(FAB, m/ e) are as follows. 15a : 86; 840, 2041. Anal. Calcd
for RuC63H56F6P4Ru: C, 65.68; H, 4.90. Found: C, 64.91; H,
5.01. [M+] ) 1007, [M+ - R] ) 931, [M+ - R - C9H7 - PPh3]
) 553. (R ) PMe3). 16a : 65; 839, 2035: Anal. Calcd for
RuC68H58F6P4Ru: C, 67.27; H, 4.81. Found: C, 66.79; H, 5.15.
17a : 82; 840, 2082. Anal. Calcd for RuC57H52F6P4Ru: C,
2
149.06 (m, Ph), 346.99 (t, J CP ) 16.7 Hz, RudCR) ppm. ∆δ-
(C-3a,7a) ) -14.32. 7a : 79; 1061. Anal. Calcd for RuC64
-
H
57F4P2B: C, 71.44; H, 5.34. Found: C, 71.96; H, 5.16. 115.
1
NMR: 31P{1H} (CDCl3) δ 36.78 (s) ppm; H (CDCl3) δ 0.77 (t,
3H, J HH ) 7.1 Hz, CH3), 1.14 (m, 2H, CH2), 1.61 (m, 2H, CH2),
1.70 (m, 2H, CH2), 4.45 (s, 1H, RudCdCH), 5.21 (d, 2H, J HH
) 2.1 Hz, H-1,3), 5.32 (m, 2H, H-4,7 or H-5,6), 5.92 (t, 1H,
J HH ) 2.1 Hz, H-2), 6.57-7.54 (m, 42H, Ph, H-4,7 or H-5,6)
ppm; 13C{1H} (CDCl3) δ 14.87 (s, CH3), 23.40 (s, CH2), 27.56
(s, CH2), 41.73 (s, CH2), 51.62 (s, Cγ), 80.96 (s, C-1,3), 98.86 (s,
C-2), 117.58 (s, C-3a,7a), 119.16 (s, Câ), 123.92 and 127.22 (s,
C-4,7 and C-5,6), 127.83-147.87 (m, Ph), 344.64 (t, 2J CP ) 17.3
Hz, RudCR) ppm. ∆δ(C-3a,7a) ) -13.12. 12a : 82; 1058, 1967:
Anal. Calcd for RuC68H53F4P2B: C, 72.92; H, 4.77. Found:
C, 73.25; H, 4.90. 125. NMR: 31P{1H} (CDCl3) δ 38.46 (s)
63.62; H, 4.87. Found: C, 63.21; H, 4.96. [M+] ) 931, [M+
-
R] ) 855, [M+ - R - PPh3] ) 593. (R ) PMe3). 18a : 52; 840,
2080. Anal. Calcd for RuC62H54F6P4Ru: C, 65.43; H, 4.78.
Found: C, 64.24; H, 4.73. 19a : 98; 838, 2076. Anal. Calcd
for RuC67H56F6P4Ru: C, 70.46; H, 4.94. Found: C, 69.79; H,
4.98. 20a : 98; 839, 2070. Anal. Calcd for RuC72H58F6P4Ru:
C, 68.51; H, 4.63. Found: C, 68.68; H, 4.66. 15b: 75; 838,
2051. Anal. Calcd for RuC53H50F6P4Ru: C, 61.98; H, 4.91.
Found: C, 61.03; H, 5.04. [M+] ) 881, [M+ - R] ) 805. (R )
PMe3). 15c: 90; 838, 2054: Anal. Calcd for RuC52H48F6P4Ru:
C, 61.65; H, 4.78. Found: C, 60.95; H, 4.79.
1
ppm; H (CDCl3) δ 4.42 (s, 1H, RudCdCH), 5.47 (d, 2H, J HH
) 2.5 Hz, H-1,3), 5.83 (m, 3H, H-2 and H-4,7 or H-5,6), 6.73-
7.44 (m, 47H, Ph, H-4,7 or H-5,6) ppm; 13C{1H} (CDCl3) δ 46.84
(s, Cγ), 82.31 (s, C-1,3), 86.77 and 93.03 (s, CtC), 98.47 (s, C-2),
116.00 (s, C-3a,7a), 120.82 (s, Câ), 122.57-145.50 (m, Ph, C-4,7,
2
C-5,6), 345.41 (t, J CP ) 16.2 Hz, RudCR) ppm. ∆δ(C-3a,7a)
Syn th esis of [Ru {C(P Me3)dCdCP h 2}(η5-C9H7)(d p p m )]-
[P F 6] (21c). A solution of [Ru{CtCC(PMe3)Ph2}(η5-C9H7)-
(dppm)][PF6] (15c) (1.012 g, 1 mmol) in 50 mL of THF was
stirred, at room temperature, for 14 h. The solvent was then
removed in vacuo, and the yellow-brown solid residue was
washed with diethyl ether (2 × 20 mL) and vacuum-dried.
Yield (%), IR data (KBr, ν(PF6-), ν(CdCdC) cm-1), analytical
data, NMR spectroscopic data, and mass spectral data (FAB,
) -14.70. 13a : 77; 1059, 1967: Anal. Calcd for RuC65H55F4-
P2B: C, 71.89; H, 5.10. Found: C, 71.22; H, 5.13. 119.
1
NMR: 31P{1H} (CDCl3) δ 38.51 (s) ppm; H (CDCl3) δ 0.95 (t,
3H, J HH ) 7.3 Hz, CH3), 1.55 (m, 2H, CH2), 2.19 (t, 2H, J HH
)
7.0 Hz, CH2), 4.40 (s, 1H, RudCdCH), 5.37 (d, 2H, J HH ) 2.0
Hz, H-1,3), 5.81 (m, 3H, H-2 and H-4,7 or H-5,6), 6.73-7.47
(m, 42H, Ph, H-4,7 or H-5,6) ppm; 13C{1H} (CDCl3) δ 13.66 (s,
CH3), 21.39 (s, CH2), 22.21 (s, CH2), 46.55 (s, Cγ), 81.72 (s,
C-1,3), 84.11 and 87.37 (s, CtC), 98.61 (s, C-2), 116.18 (s,
C-3a,7a), 121.23 (s, Câ), 123.21 and 130.40 (s, C-4,7 and C-5,6),
127.09-146.09 (m, Ph), 347.62 (t, 2J CP ) 16.4 Hz, RudCR) ppm.
∆δ(C-3a,7a) ) -14.52. 14a : 79; 1059, 1966. Anal. Calcd for
RuC62H49F4P2B: C, 71.33; H, 4.73. Found: C, 71.02; H, 4.68.
103. NMR: 31P{1H} (CDCl3) δ 40.22 (s) ppm; 1H (CDCl3) δ
3.63 (s, 1H, tCH), 4.65 (s, 1H, RudCdCH), 5.70 (d, 2H, J HH
) 2.6 Hz, H-1,3), 5.95 (t, 1H, J HH ) 2.6 Hz, H-2), 6.17 (m, 2H,
H-4,7 or H-5,6), 6.89-7.53 (m, 42H, Ph, H-4,7 or H-5,6) ppm;
13C{1H} (CDCl3) δ 47.16 (s, Cγ), 78.09 (s, tCH), 84.60 (s, C-1,3),
88.32 (s, tC), 99.97 (s, C-2), 116.87 (s, C-3a,7a), 122.30 (s, Câ),
124.55 (s, C-4,7 or C-5,6), 128.31-146.52 (m, Ph, C-4,7 or
m/ e) are as follows: 70; 839, 1865. Anal. Calcd for RuC52
-
H
48F6P4Ru: C, 61.65; H, 4.78. Found: C, 60.95; H, 4.79.
3
NMR: 31P{1H} ((CD3)2CO) δ 11.79 (d, J PP ) 6.8 Hz, dppm),
3
1
26.38 (t, J PP ) 6.8 Hz, PMe3) ppm; H ((CD3)2CO) δ 1.54 (d,
9H, J HP ) 12.7 Hz, CH3), 4.18 (m, 2H, PCHaHbP), 5.16 (d,
2
2H, J HH ) 2.5 Hz, H-1,3), 6.10 (t, 1H, J HH ) 2.5 Hz, H-2), 6.84-
7.63 (m, 34H, Ph, H-4,7, H-5,6) ppm; 13C{1H} ((CD3)2CO) δ
14.34 (d, J CP ) 55.2 Hz, CH3), 50.31 (t, J CP ) 21.7 Hz, PCH2P),
67.77 (s, C-1,3), 83.46 (m, RuCR), 88.45 (s, C-2), 100.58 (d, 3J CP
) 29.2 Hz, Cγ), 109.34 (s, C-3a,7a), 124.69-138.41 (m, Ph,
C-4,7, C-5,6), 210.81 (s, Câ) ppm. ∆δ(C-3a,7a) ) -21.36. [M+]
) 867, [M+ - R] ) 791. (R ) PMe3).
Syn t h esis of [R u {C(P Me2P h )dCdCP h 2}(η5-C9H 7)-
(d p p m )][P F 6] (22c). This compound was prepared from 1c
(0.936 g, 1 mmol) and PMe2Ph (0.143 mL, 1 mmol) in a reaction
analogous to that used for the preparation of 15a -20a . Yield
(%), IR data (KBr, ν(PF6-), ν(CdCdC) cm-1), analytical data,
and NMR spectroscopic data are as follows: 67; 838, 1858.
Anal. Calcd for RuC57H50F6P4Ru; C, 63.74; H, 4.60. Found:
2
C-5,6), 347.74 (t, J CP ) 16.7 Hz, RudCR) ppm. ∆δ(C-3a,7a)
) -13.83.
Syn th esis of [Ru {(K3(C,P ,P )-CdCdCP h 2(P h 2P CHP P h 2)}-
(η5-C9H7)] (8c). To a solution of [Ru(dCdCdCPh2)(η5-C9H7)-
(dppm)][PF6] (1c) (0.936 g, 1 mmol) in 50 mL of THF was
added, at -20 °C, LitBu (0.6 mL of a solution 1.6 M in hexane,
1 mmol). The mixture was allowed to warm to room temper-
ature, and the solvent was then removed in vacuo. The solid
C, 63.83; H, 4.62. NMR: 31P{1H} ((CD3)2CO) δ 8.85 (d, 3J PP
)
3
5.1 Hz, dppm), 22.16 (t, J PP ) 5.1 Hz, PMe2Ph) ppm; 1H

Indenyl-Ruthenium(II)-Allenylidene Complexes
Organometallics, Vol. 16, No. 20, 1997 4463
2
Ta ble 7. Cr ysta llogr a p h ic Da ta for Com p lex 11a
((CD3)2CO) δ 1.82 (d, 6H, J HP ) 12.5 Hz, CH3), 4.27 (m, 1H,
PCHaHbP), 5.19 (d, 2H, J HH ) 2.4 Hz, H-1,3), 5.25 (m, 1H,
PCHaHbP), 6.32 (t, 1H, J HH ) 2.4 Hz, H-2), 6.79-7.96 (m, 39H,
formula
a, Å
b, Å
C62H48P2Ru
11.568(3)
14.157(6)
14.950(3)
96.46(3)
104.59(2)
90.91(6)
956.01
Ph, H-4,7, H-5,6) ppm; 13C{1H} ((CD3)2CO) δ 13.06 (d, J CP
)
58.1 Hz, CH3), 49.85 (t, J CP ) 22.4 Hz, PCH2P), 67.62 (s, C-1,3),
c, Å
3
R, deg
â, deg
γ, deg
mol wt
Z
81.82 (m, RuCR), 87.76 (s, C-2), 99.94 (d, J CP ) 24.3 Hz, Cγ),
108.61 (s, C-3a,7a), 124.61 and 125.78 (s, C-4,7 and C-5,6),
126.21-138.53 (m, Ph), 212.50 (s, Câ) ppm. ∆δ(C-3a,7a) )
-22.09.
2
Syn t h esis of [R u {C≡CC[S(o-C6H4Me)]P h 2}(η5-C9H7)-
(P P h 3)2] (23a ). To a solution of [Ru(dCdCdCPh2)(η5-C9H7)-
(PPh3)2][PF6] (1a ) (1.075 g, 1 mmol) in 50 mL of THF was
added, at room temperature, NaS(o-C6H4Me) (0.146 g, 1 mmol),
and the resulting solution was stirred for 15 min. The solvent
was then removed in vacuo. The solid residue was extracted
with hexane and filtered. Evaporation of the hexane gave
complex 23a as a yellow solid. Yield (%), IR data (KBr, ν-
(CtC) cm-1), and analytical data are as follows. 45; 2050.
Anal. Calcd for RuC67H54P2SRu: C, 76.30; H, 5.17. Found:
C, 76.94; H, 5.01.
V, Å3
2352.0(1)
1.35
988
0.71073
293
D
calcd, g cm-3
F(000)
wavelength, Å
temp, K
radiation
Mo KR
monochromator
space group
cryst syst
graphite cryst
P1h
triclinic
cryst size, mm
0.40, 0.30, 0.26
0.44
0.73-1.00
ω-2θ
1.42-24.97
-13 e h e 13
-16 e k e 16
0 e l e 17
9003
µ, mm-1
range of abs
diffraction geom
θ range, deg
index ranges for data collecn
Syn th esis of [Ru {C[S(o-C6H4Me)]dCdCP h 2}(η5-C9H7)-
(d p p m )] (24c). This compound was prepared from 1c (0.936
g, 1 mmol) and NaS(o-C6H4Me) (0.146 g, 1 mmol) in a reaction
analogous to that used for the preparation of 23a . Yield (%),
IR data (KBr, ν(CdCdC) cm-1), analytical data, and NMR
spectroscopic data are as follows. 56; 1875. Anal. Calcd for
RuC56H46P2SRu: C, 73.58; H, 5.07. Found: C, 73.22; H, 4.98.
NMR: 31P{1H} (C6D6) δ 16.92 (s) ppm; 1H (C6D6) δ 2.11 (s, 3H,
CH3), 3.57 (m, 2H, PCHaHbP), 5.26 (d, 2H, J HH ) 2.2 Hz,
H-1,3), 5.57 (t, 1H, J HH ) 2.2 Hz, H-2), 6.58-7.16 (m, 38H,
Ph, H-4,7, H-5,6) ppm; 13C{1H} (C6D6) δ 22.01 (s, CH3), 46.23
(t, J CP ) 21.6 Hz, PCH2P), 69.47 (s, C-1,3), 89.06 (s, C-2),
no. of rflns measd
no. of indep rflns
no. of variables
8245
590
0.015
agreement between equiv rflnsa
final R factors (I > 2σ(I))
final R factors (all data)
R1 ) 0.026, wR2 ) 0.071
R1 ) 0.037, wR2 ) 0.072
a
Rint ) ∑(I - I )/∑I.
2
100.41 (t, J CP ) 12.8 Hz, RuCR), 104.14 and 109.65 (s, C-3a,-
hydrogen atoms were isotropically refined with a common
thermal parameter, riding on their parent atoms. Coordinates
for H(5) were also refined. The function minimized was
7a and Cγ), 124.96-142.35 (m, Ph, C-4,7, C-5,6), 199.25 (s, Câ)
ppm.
[∑w(Fo2 - Fc )2/∑w (Fo2)2]1/2, w ) 1/[σ2 (Fo2) + (0.0403P)2] where
2
X-r a y Diffr a ction Stu d y. Data collection, crystal, and
refinement parameters are collected in Table 7. The unit cell
parameters were obtained from the least-squares fit of 25
reflections (with θ between 15° and 20°). 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 final drift
correction factors were between 1.00 and 1.11. On all reflec-
tions, a profile analysis26,27 was performed. Lorentz and
polarization corrections were applied, and the data were
reduced to |Fo| values.
P ) (Max (Fo2,0) + 2Fc )/3 with σ2(Fo2) from counting statistics.
2
The maximum shift to esd ratio in the last full-matrix least-
squares cycle was -0.002. The final difference Fourier map
showed no peaks higher than 0.27 e Å-3 nor deeper than -0.35
e Å-3. Atomic scattering factors were taken from International
Tables for X-Ray Crystallography (1974).31 Geometrical cal-
culations were made with PARST.32 The crystallographic plots
were made with EUCLID.33 All calculations were made at the
University of Oviedo on the Scientific Computer Center and
X-Ray Group DEC-ALPHA computers.
The structure was solved by DIRDIF28 (Patterson methods
and phase expansion). Isotropic full-matrix least-squares
2
refinement on |Fo| using SHELXL9329 converged to R ) 0.08.
Ack n ow led gm en t. This work was supported by the
Direccio´n General de Investigacio´n Cient´ıfica y Te´cnica
(Project PB93-0325) and the EU (Human Capital
Mobility programme, Project ERBCHRXCT 940501). We
thank the Fundacio´n para la Investigacio´n Cient´ıfica y
Te´cnica de Asturias (FICYT) for a fellowship to V. C.
At this stage an empirical absorption correction was applied
using XABS2.30 Maximum and minimum transmission factors
were 1.00 and 0.73, respectively.
Finally, all hydrogen atoms (except H(5)) were geometrically
placed. During the final stages of the refinement, the posi-
tional parameters and the anisotropic thermal parameters of
the non-H atoms were refined. The geometrically placed
Su p p or tin g In for m a tion Ava ila ble: Crystal structure
data for 11a , including tables of atomic parameters, anisotropic
thermal parameters, bond distances, and bond angles (19
pages). Ordering information is given on any current mast-
head page.
(26) Grant, D. F.; Gabe, E. J . J . Appl. Crystallogr. 1978, 11, 114.
(27) Lehman, M. S.; Larsen, F. K. Acta Crystallogr., Sect. A 1974,
30, 580.
(28) Beurkens, 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; Crystallographic Labora-
tory, University of Nijmegen: Nijmegen, The Netherlands, 1992.
(29) Sheldrick, G. M. SHELXL93. In Crystallographic Computing
6; Flack, P., Parkanyi, P., Simon, K., Eds.; IUCr/Oxford University
Press: Oxford, U.K., 1993.
OM970358C
(31) International Tables for X-Ray Crystallography; Kynoch
Press: Birminghan, U.K., 1974; Vol. IV.
(32) Nardelli, M. Comput. Chem. 1983, 7, 95.
(30) Parkin, S.; Moezzi, B.; Hope, H. J . Appl. Crystallogr. 1995, 28,
53.
(33) Spek, A. L. The EUCLID Package. In Computational Crystal-
lography; Sayre, D., Ed.; Clarendon Press; Oxford, U.K., 1982; p 528.