Addition of Secondary and Primary Amines to the Allenylidene Ligand of [Ru(η5-C5H5)(C=C=CPh 2)(CO)(PiPr3)]BF4: Synthesis of Azoniabutadienyl, Aminoallenyl, and Azabutadienyl Derivatives of Ruthenium(II)

Article abstract of DOI:10.1021/om9904706

The allenylidene complex [Ru(η⁵-C₅H₅)(C=C=CPh ₂)(CO)(PⁱPr₃)]BF₄ (1) reacts with diethylamine and piperidine to give the azoniabutadienyl derivatives [Ru(η⁵-C₅H₅){C(CH= CPh₂)=NEt₂}(CO)(PⁱPr₃)]BF ₄ (2) and [Ru(η⁵-C₅H₅){C(CH=CPh₂)=NCH ₂(CH₂)₃CH₂}(CO)(PⁱPr ₃)]BF₄ (3), respectively. The molecular structure of 2 has been determined by X-ray crystallography. The geometry around the ruthenium center is close to octahedral with the cyclopentadienyl ligand occupying three sites of a face. The Ru-C_α bond length is 2.063(6) A?, whereas the C_α-N distance is 1.306(7) A?. Treatment of 2 and 3 with sodium methoxide produces the deprotonation of the CH=CPh₂ fragment to afford the aminoallenyl derivatives Ru(η⁵-C₅H₅){C(NEt₂)=C=CPh ₂}(CO)(PⁱPr₃) (4) and Ru(η⁵-C₅H₅){C(NCH₂(CH ₂)₃CH₂)=C= CPh₂}(CO)(PⁱPr)₃ (5). Complex 1 also reacts with n-propylamine and aniline. In this case, the reaction products are [Ru(η⁵-C₅H₅){C(CH=CPh₂)=NH ⁿPr}(CO)(PⁱPr₃)]BF₄ (6) and [Ru(η⁵-C₅H₅){C(CH=CPh ₂)=NHPh}(CO)(PⁱPr₃)]BF₄ (7). Treatment of 6 and 7 with sodium methoxide produces the deprotonation of the nitrogen atom of the unsaturated η¹-carbon ligand, to give the azabutadienyl compounds Ru(η⁵-C₅H₅){C(CH=CPh₂)=N ⁿPr}(CO)(PⁱPr₃) (8) and Ru(η⁵-C₅H₅){C(CH=CPh ₂)=NPh}(CO)(PⁱPr₃) (9), respectively. The ellipticities of the Ru-C_α and C_α-N bonds of the model compounds [Ru(η⁵-C₅H₅){C(CH=CH₂)=NH ₂}(CO)(PH₃)]⁺ (10), Ru(η⁵-C₅H₅){C(NH₂)=C=CH ₂}(CO)(PH₃) (11), and Ru(η⁵-C₅H₅){C(CH=CH₂)= NH}(CO)(PH₃) (12) have been studied using the AIMPAC series of programs. The obtained values are 0.07 and 0.12 (10), 0.05 and 0.07 (11), and 0.07 and 0.10 (12), respectively.

Full text of DOI:10.1021/om9904706

Organometallics 1999, 18, 4995-5003
4995
Ad d ition of Secon d a r y a n d P r im a r y Am in es to th e
Allen ylid en e Liga n d of
[Ru (η5-C5H5)(CdCdCP h 2)(CO)(P iP r 3)]BF 4: Syn th esis of
Azon ia bu ta d ien yl, Am in oa llen yl, a n d Aza bu ta d ien yl
Der iva tives of Ru th en iu m (II)
D. J avier Bernad,† Miguel A. Esteruelas,*,† Ana M. Lo´pez,*,† J avier Modrego,†
M. Carmen Puerta,‡ and Pedro Valerga‡
Departamento de Quı´mica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, 50009 Zaragoza, Spain, and Departamento de Ciencia de
Materiales e Ingenierı´a Metalu´rgica y Quı´mica Inorga´nica, Universidad de Ca´diz,
11510 Puerto Real, Ca´diz, Spain
Received J une 17, 1999
The allenylidene complex [Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4 (1) reacts with di-
ethylamine and piperidine to give the azoniabutadienyl derivatives [Ru(η5-C5H5){C(CHd
CPh2)dNEt2}(CO)(PiPr3)]BF4 (2) and [Ru(η5-C5H5){C(CHdCPh2)dNCH2(CH2)3CH2}(CO)-
(PiPr3)]BF4 (3), respectively. The molecular structure of 2 has been determined by X-ray
crystallography. The geometry around the ruthenium center is close to octahedral with the
cyclopentadienyl ligand occupying three sites of a face. The Ru-CR bond length is 2.063(6)
Å, whereas the CR-N distance is 1.306(7) Å. Treatment of 2 and 3 with sodium methoxide
produces the deprotonation of the CHdCPh2 fragment to afford the aminoallenyl derivatives
Ru(η5-C5H5){C(NEt2)dCdCPh2}(CO)(PiPr3) (4) and Ru(η5-C5H5){C(NCH2(CH2)3CH2)dCd
CPh2}(CO)(PiPr)3 (5). Complex 1 also reacts with n-propylamine and aniline. In this case,
the reaction products are [Ru(η5-C5H5){C(CHdCPh2)dNHnPr}(CO)(PiPr3)]BF4 (6) and [Ru-
(η5-C5H5){C(CHdCPh2)dNHPh}(CO)(PiPr3)]BF4 (7). Treatment of 6 and 7 with sodium
methoxide produces the deprotonation of the nitrogen atom of the unsaturated η1-carbon
ligand, to give the azabutadienyl compounds Ru(η5-C5H5){C(CHdCPh2)dNnPr}(CO)(PiPr3)
(8) and Ru(η5-C5H5){C(CHdCPh2)dNPh}(CO)(PiPr3) (9), respectively. The ellipticities of the
Ru-CR and CR-N bonds of the model compounds [Ru(η5-C5H5){C(CHdCH2)dNH2}(CO)-
(PH3)]+ (10), Ru(η5-C5H5){C(NH2)dCdCH2}(CO)(PH3) (11), and Ru(η5-C5H5){C(CHdCH2)d
NH}(CO)(PH3) (12) have been studied using the AIMPAC series of programs. The obtained
values are 0.07 and 0.12 (10), 0.05 and 0.07 (11), and 0.07 and 0.10 (12), respectively.
In tr od u ction
Carbene complexes of the chromium triad have proven
to be attractive reagents in modern organic synthesis,1
in particular, the alkenylalkoxycarbene and alkenyl-
aminocarbene derivatives.2 X-ray diffraction,3 spectro-
scopic,4 and theoretical5 studies indicate that for an
shown in eq 1 must be considered. For aminocarbene
complexes (X ) N) the structure B is a major contribu-
tor.
adequate description of the bonding situation in these
types of compounds the three resonance structures
† Universidad de Zaragoza-CSIC.
Since the advent of Grubbs’ ROMP catalyst RuCl2-
‡ Universidad de Ca´diz.
6
(CHCHdCPh2)(PR3)2 a great deal of interest has been
(1) (a) Do¨tz, K. H. In Transition Metal Carbene Complexes; Verlag
Chemie: Weinheim, Germany, 1983; p 191. (b) Do¨tz, K. H. Angew.
Chem., Int. Ed. Engl. 1984, 23, 587. (c) Schwindt, M. A.; Miller, J . R.;
Hegedus, L. S. J . Organomet. Chem. 1991, 413, 143.
(2) (a) Anderson, B. A.; Wulff, W. D.; Powers, T. S.; Tribbit, S.;
Rheingold, A. L. J . Am. Chem. Soc. 1992, 114, 10784. (b) Barluenga,
J . Pure Appl. Chem. 1996, 68, 543.
(3) Schubert, U. In Transition Metal Carbene Complexes; Verlag
Chemie: Weinheim, Germany, 1983; p 73.
(4) (a) Fischer, H.; Kreissl, F. R. In Transition Metal Carbene
Complexes; Verlag Chemie: Weinheim, Germany, 1983; p 69. (b)
Hafner, A.; Hegedus, L. S.; de Weck, G.; Hawkins, B.; Do¨tz, K. H. J .
Am. Chem. Soc. 1988, 110, 8413.
(6) (a) Nguyen, S. T.; J ohnson, L. K.; Grubbs, R. H.; Ziller, J . W. J .
Am. Chem. Soc. 1992, 114, 3974. (b) Nguyen, S. T.; Grubbs, R. H.;
Ziller, J . W. J . Am. Chem. Soc. 1993, 115, 9858. (c) Wu, Z.; Nguyen, S.
T.; Grubbs, R. H.; Ziller, J . W. J . Am. Chem. Soc. 1995, 117, 5503. (d)
Kanaoka, S.; Grubbs, R. H. Macromolecules 1995, 28, 4707. (e)
Hillmyer, M. A.; Laredo, W. R.; Grubbs, R. H. Macromolecules 1995,
28, 6311. (f) Nguyen, S. T.; Grubbs, R. H. J . Organomet. Chem. 1995,
497, 195. (g) Wilhelm, T. E.; Belderrain, T. R.; Brown, S. N.; Grubbs,
R. H. Organometallics 1997, 16, 3867. (h) Belderrain, T. R.; Grubbs,
R. H. Organometallics 1997, 16, 4001. (i) Dias, E. L.; Nguyen, S. T.;
Grubbs, R. H. J . Am. Chem. Soc. 1997, 119, 3887. (j) Weck, M.; J ackiw,
J . J .; Rossi, R. R.; Weiss, P. S.; Grubbs, R. H. J . Am. Chem. Soc. 1999,
121, 4088.
(5) Hoffmann, P. In Transition Metal Carbene Complexes; Verlag
Chemie: Weinheim, Germany, 1983; p 113.
10.1021/om9904706 CCC: $18.00 © 1999 American Chemical Society
Publication on Web 11/02/1999

4996 Organometallics, Vol. 18, No. 24, 1999
Bernad et al.
given to the synthesis of alkenylcarbenes of the iron
triad.7 However, as far as we know, alkenylaminocar-
benes of ruthenium have not been previously reported.
Aminocarbene complexes are usually prepared by
exchange processes involving the displacement with
secondary and primary amines of alkoxy groups from
alkoxycarbenes,8 or by addition of these amines to
vinylidene precursors.9 In 1993, Fischer and co-workers
reported that also (diarylallenylidene)pentacarbon-
ylchromium and -tungsten complexes react with second-
ary and primary amines to afford alkenylaminocarbene
derivatives.10
Diarylallenylidene complexes of the iron triad have
attracted a great deal of attention in recent years, as a
new type of organometallic intermediate that may have
unusual reactivity in stoichiometric11 and catalytic12
processes. The reactivity of these types of compounds
strongly depends on the particular metallic fragment
which stabilizes the allenylidene unit. Thus, three
different behaviors have been observed.
dppe, dppm),15 [RuCl(CdCdCPh2)(dppm)2]PF6,16 [Ru-
(η5-CnHm)(CdCdCPh2)(PPh3){κ1-Ph2PCH2C(O)But}]-
PF6 (CnHm ) C5H5, C9H7),17 and [RuCl(CdCdCPh2){N-
18
(CH2CH2PPh2)3}]PF6 have a moderate electrophilic
character. These complexes do not undergo intermo-
lecular addition of weak nucleophilic reagents (i.e. water
and alcohols), and the reactions with strong nucleophiles
lead to functionalized alkynyl compounds as a result of
the regioselective addition of the reagents at the Cγ atom
of the allene ligand. Diphenylallenylidene groups sta-
bilized by less basic metallic fragments, such as [Ru-
(η5-C5H5)(CO)(PiPr3)]+,19 [Ru(η5-C9H4Me3)(CO)(PPh3)]+,20
and [RuCl(η6-C6H4X2)(PMe3)]+ (X ) H, Me)21 show
stronger electrophilic character and add alcohols at the
CR-Câ double bond of the allenylidene moiety to afford
R,â-unsaturated alkoxycarbene derivatives.
Because EHT-MO calculations on transition-metal
allenylidene complexes indicate that the CR and Câ
atoms are electrophilic and nucleophilic centers, respec-
tively,15a,22 and the H-O hydrogen atom of alcohols is
electrophilic, it has been proposed that the transition
state for the RXH additions to allenylidene ligands
requires a heteroatom-CR interaction, which labilizes
the H-X bond, favoring the migration of the H-X
hydrogen atom to the Câ atom of the allenylidene
ligand.22c In agreement with this, it has been recently
observed that the complex [Ru(η5-C5H5)(CdCdCPh2)-
(CO)(PiPr3)]BF4 adds PRPh2 (R ) H, Me, Ph) selectively
at the CR atom to afford the derivatives [Ru(η5-C5H5)-
{C(PRPh2)dCdCPh2}(CO)(PiPr3)]BF4.23 Surprisingly,
the complex [Ru(η5-C5H5){C(PHPh2)dCdCPh2}(CO)-
(PiPr3)]BF4 is stable and does not evolve by migration
of the H-P hydrogen atom to the Câ atom of the allenyl
unit. Interest in the behavior of the diphenylalle-
nylidene ligand in the presence of EHR2 (E ) group 15
donor atom) molecules, and in the synthesis of “ami-
nocarbenes” of ruthenium, led us to investigate the
reactivity of the complex [Ru(η5-C5H5)(CdCdCPh2)-
(CO)(PiPr3)]BF4 toward secondary and primary amines.
In this paper, we report the synthesis and characteriza-
tion of the first azoniabutadienyl, aminoallenyl, and
azabutadienyl complexes of ruthenium(II).
The diphenylallenylidene ligand of the complex Os-
(η5-C5H5)Cl(CdCdCPh2)(PiPr3) shows nucleophilic char-
acter, reacting with HBF4 and dimethyl acetylenedicar-
boxylate to give [Os(η5-C5H5)Cl(CCHdCPh2)(PiPr3)]BF4
and Os(η5-C5H5)Cl{CdC(CO2Me)C(CO2Me)dCdCPh2}-
(PiPr3), respectively.13 In contrast, the cationic com-
pounds [Os{C[C(O)OMe]dCH2}(CdCdCPh2)(CO)(PiPr3)]-
BF4,14 [Ru(η5-C9H7)(CdCdCPh2)L2]PF6 (L2 ) 2PPh3,
(7) (a) Le Bozec, H.; Ouzzine, K.; Dixneuf, P. H. Chem. Commun.
1989, 219. (b) Devanne, D.; Dixneuf, P. H. Chem. Commun. 1990, 641.
(c) Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E., Oro, L. A.; Zeier, B.
Organometallics 1994, 13, 1662. (d) Esteruelas, M. A.; Lahoz, F. J .;
On˜ate, E.; Oro, L. A.; Zeier, B. Organometallics 1994, 13, 4258. (e)
Esteruelas, M. A.; Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Valero, C.; Zeier,
B. J . Am. Chem. Soc, 1995, 117, 7935. (f) Ruiz, N.; Pe´ron, D.; Dixneuf,
P. H. Organometallics 1995, 14, 1095. (g) Ku¨hn, J .; Schollmeyer, D.;
Ru¨ck-Braun, K. Chem. Ber. 1997, 130, 1647. (h) Esteruelas, M. A.;
Liu, F.; On˜ate, E.; Sola, E.; Zeier, B. Organometallics 1997, 16, 2919.
(i) Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa, J . I. Organome-
tallics 1997, 16, 4657. (j) Xia, H. P.; J ia, G. Organometallics 1997, 16,
1. (k) J ia, G.; Wu, W. F.; Yeung, R. C. Y.; Xia, H. J . Organomet. Chem.
1997, 538, 31. (l) Gamasa, M. P.; Gimeno, J .; Martin-Vaca, B. M.
Organometallics 1998, 17, 3707. (m) Harlow, K. J .; Hill, A. I.; Welton,
T.; White, A. J . P.; Williams, D. J . Organometallics 1998, 17, 1916. (n)
Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Mart´ınez, M. P.; Oliva´n,
M.; On˜ate, E.; Ruiz, N. Organometallics 1998, 17, 4500. (o) Esteruelas,
M. A.; Go´mez, A. V.; Lo´pez, A. M.; Puerta, M. C.; Valerga, P.
Organometallics 1998, 17, 4959. (p) Herndon, J . W. Coord. Chem. Rev.
1999, 181, 177.
(15) (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 .; Lo´pez-Gonza´lez, M. C.; Borge, J .; Garc´ıa-Granda, S. Organometallics
1997, 16, 4453.
(16) (a) Pirio, N.; Touchard, D.; Toupet, L.; Dixneuf, P. H. J . Chem.
Soc., Chem. Commun. 1991, 980. (b) Touchard, D.; Pirio, N.; Dixneuf,
P. H. Organometallics 1995, 14, 4920.
(8) Kreissl, F. R. In Transition Metal Carbene Complexes; Verlag
Chemie: Weinheim, Germany, 1983; p 151.
(9) (a) Gamasa, M. P.; Gimeno, J .; Martin-Vaca, B. M.; Borge, J .;
Garc´ıa-Granda, S.; Pe´rez-Carren˜o, E. Organometallics 1994, 13, 4045.
(b) Morran, P. D.; Mawby, R. J .; Wilson, G. D.; Moore, M. H. Chem.
Commun. 1996, 261. (c) Bianchini, C.; Purches, G.; Zanobini, F.;
Peruzzini, M. Inorg. Chim. Acta 1998, 272, 1. (d) Yam, V. W.-W.; Chu,
B. W.-K.; Cheung, K.-K. Chem. Commun. 1998, 2261.
(17) Crochet, P.; Demerseman, B.; Vallejo, M. I.; Gamasa, M. P.;
Gimeno, J .; Borge, J .; Garc´ıa-Granda, S. Organometallics 1997, 16,
5406.
(10) Fischer, H.; Roth, G.; Reindl, D.; Troll, C. J . Organomet. Chem.
1993, 454, 133.
(11) (a) Bruce, M. I. Chem. Rev. 1998, 98, 2797. (b) Touchard, D.;
Dixneuf, P. H. Coord. Chem. Rev. 1998, 178, 409. (c) Buriez, B.; Burns,
I. D.; Hill, A. F.; White, A. J . P.; Williams, D. J .; Wilton-Ely, J . D. E.
T. Organometallics 1999, 18, 1504.
(12) (a) Trost, B. M.; Flygare, J . A. J . Am. Chem. Soc. 1992, 114,
5476. (b) Trost, B. M.; Flygare, J . A. Tetrahedron Lett. 1994, 35, 4059.
(c) Fu¨rstner, A.; Picquet, M.; Bruneau, C.; Dixneuf, P. H. Chem.
Commun. 1998, 1315. (d) Picquet, M. Touchard, D.; Bruneau, C.;
Dixneuf, P. H. New J . Chem. 1999, 141. (e) Fu¨rstner, A.; Hill, A. F.;
Liebl, M.; Wilton-Ely, J . D. E. T. Chem. Commun. 1999, 601. (f) Harlow,
K. J .; Hill, A. F.; Wilton-Ely, J . D. E. T. J . Chem. Soc., Dalton Trans.
1999, 285.
(13) Crochet, P.; Esteruelas, M. A.; Lo´pez, A. M.; Ruiz, N.; Tolosa,
J . I. Organometallics 1998, 17, 3479.
(14) Bohanna, C.; Callejas, B.; Edwards, A. J .; Esteruelas, M. A.;
Lahoz, F. J .; Oro, L. A.; Ruiz, N.; Valero, C. Organometallics 1998,
17, 373.
(18) Wolinska, A.; Touchard, D.; Dixneuf, P. J .; Romero, A. J .
Organomet. Chem. 1991, 420, 217.
(19) (a) Esteruelas, M. A.; Go´mez, A. V.; Lahoz, F. J .; Lo´pez, A. M.;
On˜ate, E.; Oro, L. A. Organometallics 1996, 15, 3423. (b) Esteruelas,
M. A.; Go´mez, A. V.; Lo´pez, A. M.; On˜ate, E.; Ruiz, N. Organometallics
1998, 17, 2297.
(20) Gamasa, M. P.; Gimeno, J .; Gonza´lez-Bernardo, C.; Borge, J .;
Garc´ıa Granda, S. Organometallics 1997, 16, 2483.
(21) Pilette, D.; Ouzzine, K.; Le Bozec, H.; Dixneuf, P. H.; Rickard,
C. E. F.; Roper, W. R. Organometallics 1992, 11, 809.
(22) (a) Berke, H.; Huttner, G.; Von Seyerl, J . Z. Naturforsch. 1981,
36B, 1277. (b) Edwards, A. J .; Esteruelas, M. A.; Lahoz, F. J .; Modrego,
J .; Oro, L. A.; Schrickel, J . Organometallics 1996, 15, 3556. (c)
Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Modrego, J .; On˜ate, E.
Organometallics 1997, 15, 55826.
(23) Esteruelas, M. A.; Go´mez, A. V.; Lo´pez, A. M.; Modrego, J .;
On˜ate, E. Organometallics 1998, 17, 5434.

Butadienyl and Allenyl Derivatives of Ru(II)
Organometallics, Vol. 18, No. 24, 1999 4997
Sch em e 1
Resu lts a n d Discu ssion
1. Rea ction s of [Ru (η5-C5H5)(CdCdCP h 2)(CO)-
(P iP r 3)]BF 4 w ith Secon d a r y Am in es. Treatment at
room temperature of red dichloromethane solutions of
the allenylidene complex [Ru(η5-C5H5)(CdCdCPh2)(CO)-
(PiPr3)]BF4 (1) with 1 equiv of diethylamine and piper-
idine leads to yellow solutions, from which the azonia-
butadienyl compounds [Ru(η5-C5H5){C(CHdCPh2)d
NEt2}(CO)(PiPr3)]BF4 (2) and [Ru(η5-C5H5){C(CHd
CPh2)dNCH2(CH2)3CH2}(CO)(PiPr3)]BF4 (3) are isolated
as yellow solids in 95 and 90% yields, respectively. The
formation of these compounds is the result of the
addition of the N-H bond of the amines to the CR-Câ
double bond of the allenylidene ligand of 1 (Scheme 1).
The orientation observed for the addition (NfCR, HfCâ)
agrees well with the participation of Ru{C(NHR2)dCd
CPh2} species as intermediates or transition states.
Complexes 2 and 3 were characterized by MS, el-
F igu r e 1. Molecular diagram for [Ru(η5-C5H5){C(CHd
CPh2)dNEt2}(CO)(PiPr3)]BF4 (2). Thermal ellipsoids are
shown at 50% probability.
1
emental analysis, and IR and H, 13C{1H}, and 31P{1H}
NMR spectroscopy. Complex 2 was further character-
ized by an X-ray crystallographic study. A view of the
molecular geometry of this compound is shown in Figure
1. Selected bond distances and angles are listed in Table
1.
Ta ble 1. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) for th e Com p lex [Ru (η5-C5H5)-
{C(CHdCP h 2)dNEt2}(CO)(P iP r 3)]BF 4 (2)
The geometry around the ruthenium center is close
to octahedral, with the cyclopentadienyl ligand occupy-
ing three sites of a face. The angles formed by the
triisopropylphosphine, the carbonyl, and the unsatur-
ated η1-carbon ligand are all close to 90°.
The Ru-C(7) distance (2.063(6) Å) is significantly
longer than the related bond lengths in the R,â-unsatur-
ated carbene compound [RuCl(CHCHdCPh2)(CO)(PiPr3)2]-
BF4 (1.874(3) Å),7d the alkoxycarbene complex [Ru(κ3-
HBpz3){C(OCH3)CH2CO2CH3}(dippe)]BPh4 (1.86(2) Å),24
and the cyclopentadienyl-carbene complexes [Ru(η5-
C5H5){C(OCH3)CH2CH3}(PPh3)2]PF6 (1.956(6) Å)25 and
[Ru(η5-C5H5){C(OCH3)CH2Ph}(CHIRAPHOS)]PF6 (1.93-
(2) Å)26and is even longer than the ruthenium-carbon
Ru(1)-P(1)
Ru(1)-C(1)
Ru(1)-C(2)
Ru(1)-C(3)
Ru(1)-C(4)
Ru(1)-C(5)
Ru(1)-C(6)
Ru(1)-C(7)
2.374(2)
2.254(6)
2.224(6)
2.255(6)
2.262(7)
2.285(6)
1.846(6)
2.063(6)
C(6)-O(1)
C(7)-N(1)
C(7)-C(8)
C(8)-C(9)
C(9)-C(10)
C(9)-C(16)
N(1)-C(22)
N(1)-C(24)
1.139(7)
1.306(7)
1.481(7)
1.339(7)
1.474(7)
1.490(7)
1.506(9)
1.476(7)
P(1)-Ru(1)-C(6)
P(1)-Ru(1)-C(7)
C(6)-Ru(1)-C(7)
Ru(1)-C(6)-O(1)
Ru(1)-C(7)-N(1)
Ru(1)-C(7)-C(8)
N(1)-C(7)-C(8)
88.6(2)
95.7(2)
91.2(2)
173.4(5)
127.5(4)
117.5(4)
114.9(5)
C(7)-C(8)-C(9)
C(8)-C(9)-C(10)
C(8)-C(9)-C(16)
C(10)-C(9)-C(16)
C(7)-N(1)-C(22)
C(7)-N(1)-C(24)
C(22)-N(1)-C(24)
132.0(5)
124.5(5)
119.3(5)
116.2(5)
122.5(5)
123.2(5)
114.3(5)
distances in the complexes [Ru{CCdCHPh)OC(O)CH3}-
(CO){κ1-OC(CH3)2}(PiPr3)2]BF4 (1.967(8) Å),27 [Ru(η5-
C5H5){CCHdC(OEt)OCdCPh2}(CO)(PiPr3)BF4 (2.017(6)
Å), [Ru(η5-C5H5){CCHdC(CH3)OCdCPh2}(CO)(PiPr3)-
(24) J ime´nez-Tenorio, M. A.; J ime´nez-Tenorio, M.; Puerta, M. C.;
Valerga, P. Organometallics 1997, 16, 5528.
(25) Bruce, M. I.; Humphrey, M. G.; Snow, M. R.; Tiekink, E. R. T.
J . Organomet. Chem. 1986, 314, 213.
(26) Consiglio, G.; Morandini, F.; Ciani, G. F.; Sirani, A. Organo-
metallics 1986, 5, 1976.
(27) Esteruelas, M. A.; Lahoz, F. J .; Lo´pez, A. M.; On˜ate, E.; Oro,
L. A. Organometallics 1994, 13, 1669.

4998 Organometallics, Vol. 18, No. 24, 1999
Bernad et al.
BF4 (2.010(6) Å),7o and [Ru(η5-C5Me5)(µ-SiPr)}2(µ-C18H15)]-
BF4 (2.04(3), 1.98(2) Å),28 where a ruthenium-carbon
bond between single and double has been proposed.
The Ru-C(7) distance lies between those reported for
the allenyl derivatives Ru(η5-C5H5){C(CtCPh)dCd
CPh2}(CO)(PiPr3) (2.004(5) Å)22c and [Ru(η5-C5H5)-
{C(PHPh2)dCdCPh2}(CO)(PiPr3) (2.139(5) Å),23 where
a Ru-C(sp2) single bond is proposed to exist.
compounds. In the 13C{1H} NMR spectrum of 2, the CR
resonance appears as a doublet at 240.8 ppm, with a
C-P coupling constant of 9.7 Hz, and the Câ and Cγ
resonances are observed as singlets at 141.4 and 137.7
ppm, respectively. These chemical shifts are similar to
those observed in the 13C{1H} NMR spectrum of Ru(η5-
C5H5){C(O)(CHdCPh2)}(CO)(PiPr3) for the related reso-
nances 249.5, 144.5, and 130.6 ppm.
The difference between the N(1)-C(7) distance (1.306-
(7) Å) and the separations between the nitrogen atom
and the ethyl groups is very illustrative. The N(1)-C(22)
(1.506(9) Å) and N(1)-C(24) (1.476(7) Å) distances are
statistically identical and agree well with a C-N single
bond, while the N(1)-C(7) bond length compares well
with the N-C double-bond length found in Schiff bases,
hydrazones, and related compounds (about 1.29 Å). The
angles around N(1) are between 114.3(5) and 123.2(5)°,
whereas the angles around C(7) are between 114.9(5)
and 127.5(4)°.
In agreement with the presence of a C-N double bond
in the azoniabutadienyl ligand of 2 the IR spectrum of
this complex in Nujol shows a ν(CdN) band at 1499
cm-1. In the 1H NMR spectrum the most noticeable
resonances are a singlet at 6.69 ppm corresponding to
the dCH proton and four multiplets between 4.35 and
3.76 ppm, due to the four CH2 protons of the ethyl
groups. The presence of two inequivalent ethyl groups
in the spectrum agrees with a double bond between the
atoms C(7) and N(1). This double bond prevents the
rotation of the NEt2 unit in solution at room tempera-
ture. The total blockage was confirmed by a NOE
experiment. Saturation of the dCH resonance increases
the intensity (2.8%) of only one CH2 multiplet.
If we extrapolate eq 1 to the case of complex 2, we
obtain eq 2. The previously mentioned structural pa-
The spectroscopic data of 3 agree with those of 2. In
the 13C{1H} NMR spectrum, the CR resonance appears
as a doublet at 237.4 ppm, with a C-P coupling constant
of 9.7 Hz, while the Câ and Cγ resonances are observed
as singlets at 137.9 and 141.9 ppm, respectively. In the
IR spectrum in Nujol the ν(CdN) band is observed at
1
1500 cm-1. The H NMR spectrum shows a singlet at
6.54 ppm corresponding to the dCH proton.
Treatment of 2 and 3 with sodium methoxide in
tetrahydrofuran produces the deprotonation of the
CHdCPh2 group of the azoniabutadienyl ligands to
give the aminoallenyl derivatives Ru(η5-C5H5)-
{C(NEt2)dCdCPh2}(CO)(PiPr3) (4) and [Ru(η5-C5H5)-
rameters indicate not only that the resonance structure
E (related to B in eq 1) is the major contributor to the
structure of 2 but also that the contribution of the
resonance structure D (related to A in eq 1) is not really
relevant. The contribution of the latter is similar to the
contribution of the resonance structure F (eq 3) to the
structure of the previously reported acyl compound Ru-
(η5-C5H5){C(O)CHdCPh2)}(CO)(PiPr3).19
The similarity between the acyl ligand and the
unsaturated η1-carbon donor ligand of 2 is surprising.
The Ru-C(7) bond length and the C(8)-C(9) olefinic
bond distance (1.339(7) Å) are exactly the same as the
related parameters in the acyl complex (2.060(2) Å and
1.333(4) Å, respectively). Moreover, the C(sp2)-C(sp2)
single-bond distance (C(7)-C(8) ) 1.481(7) Å) in 2 and
the related bond length in the acyl complex (1.502(3)
Å) are statistically identical. The above-mentioned C-C
double-bond and C(sp2)-C(sp2) single-bond values agree
well with the mean values described for double and
single C(sp2)-C(sp2) bonds (1.34 and 1.48 Å, respec-
tively),29 which indicates that the delocalization of
π-electron density along the X-C-CH-CPh2 (X ) N,
O) chain is not appreciable in both compounds.
{C(NCH2(CH2)3CH2)dCdCPh2}(CO)(PiPr)3 (5), which
were isolated as yellow solids in 85 and 80% yields,
respectively (Scheme 1). Characteristic spectroscopic
features of 4 and 5 are the CdCdC stretching frequency
in the IR spectra at 1963 (4) and 1935 cm-1 (5) and three
resonances in the 13C{1H} NMR spectra at 199.5 (d,
J (PC) ) 2.7 Hz), 117.2 (d, J (PC) ) 13.2 Hz), and 101.2
(s) ppm (4) and at 198.1 (d, J (PC) ) 2.7 Hz), 120.8 (d,
J (PC) 12.0 Hz), and 101.5 (s) (5) ppm for the Câ, CR,
and Cγ allenyl carbon atoms, respectively.
Although a variety of η1-allenyl transition-metal
compounds have been previously reported,19,22c,23,30 the
aminoallenyl derivatives of ruthenium are unknown.
2. Rea ction s of [Ru (η5-C5H5)(CdCdCP h 2)(CO)-
(P iP r 3)]BF 4 w ith P r im a r y Am in es. Complex 1 also
reacts with primary amines. Similarly to the reactions
with secondary amines, the addition at room tempera-
ture of 1 equiv of propylamine and aniline to dichlo-
romethane solutions of 1 affords the azoniabutadienyl
(30) (a) J acobs, T. L. In The Chemistry of the Allenes; Landor, S. R.;
Ed.; Academic Press: London, 1982; Vol. 2, p 334. (b) Schuster, H. F.;
Coppola, G. M. Allenes in Organic Chemistry; Wiley-Interscience: New
York, 1984. (c) Wojcicki, A.; Shuchart, C. E. Coord. Chem. Rev. 1990,
105, 35. (d) Keng, R.-S.; Lin, Y.-C. Organometallics 1990, 9, 289 (e)
Shuchart, C. E.; Willis, R. R.; Wojicicki, A. J . Organomet. Chem. 1992,
424, 185. (f) Wouters, J . M. A.; Klein, R. E.; Elsevier, C. J .; Ha¨ming,
L.; Stam, C. H. Organometallics 1994, 13, 4586. (g) Esteruelas, M. A.;
Lahoz, F. J .; On˜ate, E.; Oro, L. A.; Rodr´ıguez, L. Organometallics 1996,
15, 3670. (h) Esteruelas, M. A.; Lahoz, F. J .; Mart´ın, M.; On˜ate, E.;
Oro, L. A. Organometallics 1997, 16, 4572. (i) Esteruelas, M. A.; Go´mez,
A. V.; Lo´pez, A. M.; On˜ate, E. Organometallics 1998, 17, 3567.
The similarity between the acyl ligand and the
unsaturated η1-carbon donor ligand of 2 is also revealed
by comparison of the 13C{1H} NMR spectra of both
(28) Matsuzaka, J .; Hirayama, Y.; Nishio, M.; Mizobe, Y.; Hidai, M.
Organometallics 1993, 12, 36.
(29) Orpen, A. G.; Brammer, L.; Allen, F. H.; Kennard, O.; Watson,
D. G.; Taylor, R. J . Chem. Soc., Dalton Trans. 1989, S1.

Butadienyl and Allenyl Derivatives of Ru(II)
Organometallics, Vol. 18, No. 24, 1999 4999
Sch em e 2
compounds [Ru(η5-C5H5){C(CHdCPh2)dNHnPr}(CO)-
(PiPr3)]BF4 (6) and [Ru(η5-C5H5){C(CHdCPh2)dNHPh}-
(CO)(PiPr3)]BF4 (7), respectively, which were isolated
as yellow crystals in 90% yield (Scheme 2).
Complexes 8 and 9 were characterized by MS, el-
1
emental analysis, and IR and H, 13C{1H}, and 31P{1H}
NMR spectroscopy. In the IR spectra in Nujol the most
noticeable absorptions are the ν(CdN) bands, which
appear at 1605 (8) and 1542 (9) cm-1. The 1H NMR
spectrum of 8 shows the CHd resonance as a singlet at
6.89 ppm and at 3.71 and 3.59 ppm (CH2N) and at 1.89
and 1.73 ppm (CH2) the CH2 resonances of the n-propyl
group. The saturation of the CH2N resonances increases
the intensity of both the phenyl (8.8%) and CHd (3.1%)
resonances, while it has no effect on the cyclopentadi-
enyl and triisopropyl signals. This NOE experiment
strongly supports the trans disposition of the metallic
fragment and the n-propyl group at the C-N double
bond of the azabutadienyl ligand. In the NMR spec-
trum of 9 the CH resonance lies within the phenyl
signals.
The spectroscopic data of 6 and 7 agree with those
found for 2 and 3. The IR spectrum of 6 in Nujol shows
a ν(NH) band at 3321 cm-1 and a ν(CdN) band at 1529
cm-1, in agreement with the presence of a C-N double
bond in the azoniabutadienyl ligand. In the IR spectrum
of 7 these bands appear at 3271 and 1592 cm-1
,
1
respectively. In the H NMR spectra, the most notice-
able resonances are those due to the dNH and dCH
protons, which are observed as singlets at 9.75 and 6.45
ppm (6) and at 11.13 and 6.70 ppm (7), respectively. The
13C{1H} NMR spectra reflect the similarity between
these compounds and the acyl derivatives Ru(η5-C5H5)-
{C(O)CHdCR2}(CO)(PiPr3). The resonances correspond-
ing to the Ru-C carbon atoms appear as doublets at
242.2 (6) and 248.7 (7) ppm, with C-P coupling con-
stants of 10.6 and 11.5 Hz, respectively. The resonances
due to the CHd and dCPh2 carbon atoms are observed
as singlets at 133.7 and 138.8 ppm (6) and at 136.8 and
139.9 (7) ppm.
The 13C{1H} NMR spectrum of 8 shows a doublet at
193.0 ppm with a C-P coupling constant of 11.5 Hz,
corresponding to the Ru-C atom, and singlets at 141.6
and 132.0 ppm due to the HCd and CPh2 carbon atoms,
respectively. The 13C{1H} NMR spectrum of 9 agrees
well with that of 8; the Ru-C resonance appears as a
doublet at 204.5 ppm with a C-P coupling constant of
9.0 Hz, whereas the HCd and dCPh2 resonances are
observed as singlets at 142.0 and 130.1 ppm.
3. Th eor etica l An a lysis. We have previously shown
that the addition of secondary and primary amines to
the allenylidene ligand of 1 affords the complexes 2, 3,
6, and 7. At first glance, for an adequate description of
the bonding situation in this type of compound, two
resonance structures should be considered (eq 2), the
aminocarbene (D) and the azoniabutadienyl (E). The
structural parameters of 2 suggest that the azonia-
butadienyl resonance form is the major contributor to
the real structure of this type of compound and that the
contribution of the aminocarbene resonance form is not
very significant.
To reaffirm the formulation of 2, 3, 6, and 7 as azo-
niabutadienyl complexes, we performed electronic struc-
ture calculations on [Ru(η5-C5H5){C(CHdCH2)dNH2}-
(CO)(PH3)]+ (10), Ru(η5-C5H5){C(NH2)dCdCH2}(CO)-
(PH3) (11), and Ru(η5-C5H5){C(CHdCH2)dNH}(CO)-
(PH3) (12) as simplified models of the azoniabutadienyl
derivatives 2, 3, 6, and 7, the aminoallenyl compounds
4 and 5, and the azabutadienyl complexes 8 and 9,
respectively. For comparative purposes the electronic
structure of [Ru(η5-C5H5)(CH2)(CO)(PH3)]+ (13) was also
The stereochemistry at the C-N double bond of the
azoniabutadienyl ligands of these compounds was in-
ferred on the basis of NOE experiments. The saturation
of the NH resonance of 6 increases the intensities of the
cyclopentadienyl (11.5%), NCH2 (6.8%), and CH3 (PiPr3,
12%) resonances, while the CHd resonance does not
show an NOE effect. However, the saturation of the
NCH2 resonances increases the intensity of the CHd
resonance (3.3%), while it has no effect on the cyclopen-
tadienyl and triisopropylphosphine signals. Similarly to
6, the saturation of the NH resonance of 7 increases the
intensity (21.1%) of the cyclopentadienyl resonance.
Complexes 6 and 7 also undergo a deprotonation
process in the presence of base. However, the deproto-
nation does not take place at the CHdCPh2 olefinic
group, as in the case of 2 and 3, but at the nitrogen
atom. Thus, the treatment of tetrahydrofuran solutions
of 6 and 7 with 2 equiv of sodium methoxide leads to
the azabutadienyl derivatives Ru(η5-C5H5){C(CHd
CPh2)dNnPr}(CO)(PiPr3) (8) and Ru(η5-C5H5){C(CHd
CPh2)dNPh}(CO)(PiPr3) (9), which were isolated as
yellow solids in 90% yield (Scheme 2). As far as we
know, transition-metal complexes containing this type
of unsaturated η1-carbon ligand have not been previ-
ously reported.

5000 Organometallics, Vol. 18, No. 24, 1999
Bernad et al.
Ta ble 2. Ellip ticities of th e Bon d s Ru -Cr, Cr-N,
Cr-Câ, a n d Câ-Cγ of th e Com p lexes
[Ru (η5-C5H5){C(CHdCH2)dNH2}(CO)(P H3)]+ (10),
Ru (η5-C5H5){C(NH2)dCdCH2}(CO)(P H3) (11),
Ru (η5-C5H5){C(CHdCH2)dNH}(CO)(P H3) (12), a n d
Ru (η5-C5H5)(CH2)(CO)(P H3) (13)
Ru-CR
CR-Ν
CR-Câ
Câ-Cγ
10
11
12
13
0.07
0.05
0.07
0.11
0.12
0.07
0.10
0.03
0.26
0.03
0.21
0.21
0.22
reaches a maximum. The electron density is minimum
along the bond path, and thus the corresponding eigen-
value λ3 has a positive sign. When λ1 and λ2 are equal,
the bond has cylindrical symmetry. However, when
electronic charge is preferentially accumulated in a
given plane along the bond path (as it is for a bond with
π-character), then λ1 and λ2 have different values. If λ2
is the value of smallest magnitude, then the quantity ꢀ
(eq 4), the ellipticity of the bond, provides a measure of
the extent to which charge is preferentially accumulated
in a given plane, and therefore of the grade of π-char-
acter of the bond:
λ1
F igu r e 2. Optimized structures of [Ru(η5-C5H5){C(CHd
CH2)dNH2}(CO)(PH3)]+ (10), Ru(η5-C5H5){C(NH2)dCd
CH2}(CO)(PH3) (11), Ru(η5-C5H5){C(CHdCH2)dNH}(CO)-
(PH3) (12), and [Ru(η5-C5H5)(CH2)(CO)(PH3)]+ (13), obtained
by ab initio calculations at the MP2 level.
ꢀ ) - 1
(4)
λ2
To analyze the extent of double- or single-bond
character in the metal-unsaturated η1-carbon ligand
interactions and in the internal structures of these
ligands in complexes 10-13, we have studied the
ellipticity of the Ru-CR, CR-N, CR-Câ, and Câ-Cγ
bonds, using the AIMPAC series of programs. The
obtained results are collected in Table 2.
According to the ellipticities of the Ru-CR and CR-N
bonds, the azoniabutadienyl character of 2, 3, 6 and 7
is unanswerable. The ellipticity of the Ru-CR bond of
10 is similar to those of 11 and 12, which without a
shadow of a doubt correspond to Ru-C single bonds,
while it is significantly smaller than the ellipticity of
the Ru-CR double bond of 13. Moreover, the ellipticities
of the CR-N bonds of 10 and 12 are similar (the
ellipticity of 10 is even higher than that of 12) and are
significantly higher than the ellipticity of the CR-N
single bond of the allenylamino complex 11.
In agreement with the allenyl formulation of the
unsaturated η1-carbon ligand of 11, the ellipticities of
the CR-Câ and Câ-Cγ bonds of this ligand are ap-
proximately equal and are 1 order of magnitude higher
than the ellipticities of the CR-Câ single bonds of 10
and 12. The ellipticities of the Câ-Cγ double bonds of
10 and 12 agree well with those corresponding to the
CR-Câ and Câ-Cγ double bonds of 11.
calculated. Figure 2 shows the optimized structures at
the MP2 level of the four model compounds.
The theoretical structure of 10 is in excellent agree-
ment with the experimental X-ray structure of 2. The
main discrepancy is found in the Ru-CR distance (2.00
Å), which is about 0.06 Å shorter than that determined
from the X-ray diffraction study.
In addition, it should be noted that the CR-N distance
in 10 (1.34 Å) is only 0.02 Å longer than the calculated
one for 12 (1.32 Å), while it is 0.09 Å shorter than the
related parameter of 11. This is remarkable and strongly
supports the presence of a double bond between the CR
and N atoms of 10.
The azoniabutadienyl character of the unsaturated η1-
carbon donor ligand of 10 also seems to be clear from
the point of view of the Ru-CR distances. Although the
Ru-CR distance in 10 is 0.07 Å shorter than that of 12
(2.07 Å), it is 0.13 Å longer than the related parameter
in the carbene model complex 13 (1.87 Å).
The CR-Câ and Câ-Cγ distances in 10 are identical
with those found in 12 (1.49 and 1.36 Å, respectively)
and agree with the expected ones for single and double
C(sp2)-C(sp2) bonds. The CR-Câ (1.33 Å) and Câ-Cγ
(1.34 Å) bond lengths in 11 are in agreement with those
obtained from X-ray diffraction analysis in ruthenium30i
and rhodium30h allenyl complexes.
The degree of π-character of a bond can be analyzed
on the basis of Bader’s atoms-in-molecules (AIM) theory.31
At the bond critical point two of the eigenvalues (λ1 and
λ2) of the Hessian (second derivatives matrix) of the
electron density are negative. They correspond to per-
pendicular directions to the bond as the electron density
Con clu d in g Rem a r k s
This study has revealed a new finding in the chem-
istry of the diarylallenylidene complexes of the iron
triad. The diphenylallenylidene ligand of the complex
[Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4 adds at the
CR-Câ double bond the N-H bond of secondary and
primary amines to afford azoniabutadienyl derivatives
of the type [Ru(η5-C5H5){C(CHdCPh2)dNR2}(CO)-
(PiPr3)]BF4 and [Ru(η5-C5H5){C(CHdCPh2)dN(R)H}(CO)-
(PiPr3)]BF4, respectively. Although, at first glance, an
(31) Bader, R. F. W. In Atoms in Molecules: A Quantum Theory;
Oxford University Press: New York, 1990.

Butadienyl and Allenyl Derivatives of Ru(II)
Organometallics, Vol. 18, No. 24, 1999 5001
48.7 (both s, NCH2), 28.4 (d, J (PC) ) 23.2, PCHCH3), 19.9 and
19.7 (both s, PCHCH3), 12.8 and 11.8 (both s, NCH2CH3). MS
(FAB+): m/z 618 (M+).
important contribution of the aminocarbene resonance
form to the structure of these compounds should be
expected, the X-ray structure determination of the
complex [Ru(η5-C5H5){C(CHdCPh2)dNEt2}(CO)(PiPr3)]-
BF4 and the analysis of the ellipticities of the Ru-CR
and CR-N bonds of the model compound [Ru(η5-C5H5)-
{C(CHdCH2)dNH2}(CO)(PH3)]+ indicate that the con-
tribution of this resonance form is not relevant. Accord-
ing to the values of the ellipticities 0.07, for the Ru-CR
bond, and 0.12, for the CR-N bond, the respective single-
and double-bond characters of the Ru-CR and CR-N
bonds are unanswerable.
There is a marked difference, in the presence of bases,
in behavior between the tertiary azoniabutadienyl com-
plexes [Ru(η5-C5H5){C(CHdCPh2)dNR2}(CO)(PiPr3)]BF4
and the secondary azoniabutadienyl compounds [Ru-
(η5-C5H5){C(CHdCPh2)dN(R)H}(CO)(PiPr3)]BF4. Treat-
ment of [Ru(η5-C5H5){C(CHdCPh2)dNR2}(CO)(PiPr3)]-
BF4 with sodium methoxide produces the deprotonation
of the CHdCPh2 group of the unsaturated η1-carbon do-
nor ligand and the formation of the corresponding ami-
noallenyl derivatives Ru(η5-C5H5){C(NR2)dCdCPh2)}-
(CO)(PiPr3). Under the same conditions, the deprotona-
tion of Ru(η5-C5H5){C(CHdCPh2)dN(R)H}(CO)(PiPr3)]-
BF4 does not occur at the CHdCPh2 group but at the
nitrogen atom. Thus, the reactions of the latter with
sodium methoxide lead to the azabutadienyl derivatives
[Ru(η5-C5H5){C(CHdCPh2)dNR}(CO)(PiPr3).
P r ep a r a tion of [Ru (η5-C5H5){C(CHdCP h 2)dNCH2-
(CH2)3CH2}(CO)(P iP r )]BF 4 (3). A dark red solution of 1 (150
mg, 0.24 mmol) in 5 mL of dichloromethane was treated with
piperidine (15 mg, 0.26 mmol), and the mixture was stirred
for 5 min. The solution became brown, and the solvent was
removed in vacuo. The residue was washed with diethyl ether
to afford a brown solid, which was crystallized from dichlo-
romethane/diethyl ether to give yellow crystals. Yield: 155 mg
(90%). Anal. Calcd for C35H47BF4NOPRu: C, 58.67; H, 6.61;
N, 1.95. Found: C, 58.42; H, 6.22, N, 1.87. IR (Nujol, cm-1):
ν(CO) 1947 (vs), ν(CdN) 1500 (m), ν(BF4), 1052 (vs, br). 1H
NMR (300 MHz, 293 K, CDCl3): δ 7.50-7.00 (m, 10H, Ph),
6.54 (s, 1H, dCH), 4.65 (s, 5H, Cp), 4.32-4.00 (m, 4H, NCH2),
2.29 (m, 3H, PCHCH3), 1.85-1.62 (m, 4H, NCH2CH2), 1.55 and
1.40 (both m, 2H, NCH2CH2CH2), 1.20 (dd, 9H, J (HH) ) 6.6,
J (PH) ) 15.0, PCHCH3), 1.19 (dd, 9H, J (HH) ) 6.6, J (PH) )
15.8, PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, CDCl3): δ
64.4 (s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3): δ 237.4 (d,
J (PC) ) 9.7, RuC), 204.8 (d, J (PC) ) 18.4, CO), 141.9 (s, CPh2),
139.0 and 138.8 (both s, Cipso), 137.9 (s, HCd), 130.4, 129.1,
128.8, 128.6, and 128.3, (all s, Ph), 86.6 (s, Cp), 60.5 and 56.1
(both s, NCH2), 28.5 (d, J (PC) ) 22.6, PCHCH3), 26.3 and 26.1
(both s, NCH2CH2), 22.3 (s, NCH2CH2CH2), 19.9 and 19.7 (both
s, PCHCH3). MS (FAB+): m/z 630 (M+).
P r ep a r a tion of [Ru (η5-C5H5){C(NEt2)dCdCP h 2}(CO)-
(P iP r 3)] (4). A yellow suspension of 2 (185 mg, 0.26 mmol) in
10 mL of tetrahydrofuran was treated with sodium methoxide
(29 mg, 0.54 mmol) and stirred for 1 h. The solvent was
removed in vacuo. Toluene (10 mL) was added, and the
suspension was filtered to eliminate sodium tetrafluoroborate.
Solvent was evaporated, and the residue was washed with
pentane to afford a yellow solid. Yield: 140 mg (85%). Anal.
Calcd for C34H46NOPRu: C, 66.15; H, 7.61; N, 2.26. Found:
C, 65.80; H, 7.41; N, 2.21. IR (Nujol, cm-1): ν(CO) 1917 (vs),
ν(CdCdC) 1963 (m). 1H NMR (300 MHz, 293 K, CDCl3): δ
7.60-7.00 (m, 10H, Ph), 4.91 (s, 5H, Cp), 3.32 (m, 4H, NCH2),
2.05 (m, 3H, PCHCH3) 1.01, (t, 6H, J (HH) ) 7.1, NCH2CH3),
0.96 (dd, 9H, J (HH) ) 7.2, J (PH) ) 13.8, PCHCH3), 0.77 (dd,
9H, J (HH) ) 7.1, J (PH) ) 13.1, PCHCH3). 31P{1H} NMR (121.4
MHz, 293 K, CDCl3): δ 69.5 (s). 13C{1H} NMR (75.4 MHz, 293
K, CDCl3): δ 208.6 (d, J (PC) ) 22.4, CO), 199.5 (d, J (PC) )
2.7, CdCdC), 142.3 and 142.0 (both s, Cipso), 128.8, 128.6,
125.2, 125.3, and 125.2 (all s, Ph), 117.2 (d, J (PC) ) 13.2, RuC),
101.2 (s, CPh2), 86.4 (s, Cp), 45.9 (s, NCH2), 27.2 (d, J (PC) )
22.0, PCHCH3), 20.0 and 19.4 (both s, PCHCH3), 12.6 (s,
NCH2CH3). MS (FAB+): m/z 618 (M+).
In conclusion, if the coligands are selected in such a
way that the metallic fragment is poorly basic, the
allenylidene ligand of diarylallenylidene complexes of
the iron triad shows a strong electrophilic character. As
a result, the reactions of these compounds with second-
ary and primary amines are a useful strategy to obtain
tertiary and secondary azoniabutadienyl complexes,
which are the entry to the synthesis of aminoallenyl and
azabutadienyl derivatives, respectively.
Exp er im en ta l Section
All reactions were carried out with rigorous exclusion of air
using Schlenk-tube techniques. Solvents were dried by the
usual procedures and distilled under argon prior to use. The
starting material [Ru(η5-C5H5)(CdCdCPh2)(CO)(PiPr3)]BF4 (1)
was prepared by the published method.19a
In the NMR spectra, chemical shifts are expressed in ppm
downfield from Me4Si (1H and 13C) and 85% H3PO4 (31P).
Coupling constants, J , are given in hertz.
P r ep a r a tion of [Ru (η5-C5H5){C(CHdCP h 2)dNEt2}(CO)-
(P iP r 3)]BF 4 (2). A dark red solution of 1 (150 mg, 0.24 mmol)
in 5 mL of dichloromethane was treated with diethylamine
(15 mg, 0.26 mmol), and the mixture was stirred for 5 min.
The solution became yellow, and the solvent was removed in
vacuo. The residue was washed with diethyl ether to afford a
yellow solid. Yield: 160 mg (95%). Anal. Calcd for C34H47BF4-
NOPRu: C, 57.96; H, 6.74; N, 1.99. Found: C, 57.86; H, 6.73;
N, 2.04. IR (Nujol, cm-1): ν(CO) 1926 (vs), ν(CdN) 1499 (m),
ν(BF4) 1048 (vs, br). 1H NMR (300 MHz, 293 K, CDCl3): δ
7.50-6.90 (m, 10H, Ph), 6.69 (s, 1H, dCH), 4.68 (s, 5H, Cp),
4.32, 4.21, 4.05, and 3.88 (all m, 4H, NCH2), 2.28 (m, 3H,
PCHCH3), 1.49, (t, 6H, J (HH) ) 7.1, NCH2CH3), 1.28 (dd, 9H,
J (HH) ) 7.1, J (PH) ) 14.6, PCHCH3), 1.26 (dd, 9H, J (HH) )
6.8, J (PH) ) 13.6, PCHCH3). 31P{1H} NMR (121.4 MHz, 293K,
CDCl3): δ 62.4 (s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3):
δ 240.8 (d, J (PC) ) 9.7, RuC), 204.4 (d, J (PC) ) 18.0, CO),
141.4 (s, HCd), 138.8 and 137.5 (both s, Cipso), 137.4 (s, CPh2),
130.0, 129.1, 128.5, and 128.2 (all s, Ph), 86.0 (s, Cp), 55.5 and
P r ep a r a tion of [Ru (η5-C5H5){C(NCH2(CH2)3CH2}dCd
CP h 2}(CO)(P iP r 3) (5). A yellow suspension of 3 (185 mg, 0.26
mmol) in 10 mL of tetrahydrofuran was treated with sodium
methoxide (29 mg, 0.54 mmol) and stirred for 1 h. The solvent
was removed in vacuo. Toluene (10 mL) was added, and the
suspension was filtered to eliminate sodium tetrafluoroborate.
Solvent was evaporated, and the residue was washed with
pentane to afford a yellow solid. Yield: 132 mg (80%). Anal.
Calcd for C35H46NOPRu: C, 66.86; H, 7.37; N, 2.23. Found:
C, 66.45; H, 7.42, N, 2.12. IR (Nujol, cm-1): ν(CdCdC) 1934
(m), ν(CO) 1929 (m). 1H NMR (300 MHz, 293 K, CDCl3): δ
7.80-7.00 (m, 10H, Ph), 4.87 (s, 5H, Cp), 3.39 and 2.96 (both
m, 4H, NCH2), 2.06 (m, 3H, PCHCH3), 1.67 (m, 4H, NCH2CH2),
1.50-1.10 (m, 2H, NCH2CH2CH2), 1.00 (dd, 9H, J (HH) ) 6.6,
J (PH) ) 15.0, PCHCH3), 0.84 (dd, 9H, J (HH) ) 6.6, J (PH) )
15.8, PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, CDCl3): δ
71.0 (s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3): δ 207.9 (d,
J (PC) ) 20.4, CO), 198.1 (d, J (PC) ) 2.7, CdCdC), 142.6 and
141.3 (both s, Cipso), 128.6, 128.5, 125.5, and 125.4 (all s, Ph),
120.8 (d, J (PC) ) 12.0, RuC), 101.5 (s, CPh2), 86.6 (s, Cp), 55.8

5002 Organometallics, Vol. 18, No. 24, 1999
Bernad et al.
Ta ble 3. Su m m a r y for Cr ysta l Da ta Collection a n d
Str u ctu r e An a lysis of [Ru (η5-C5H5)-
(s, NCH2), 27.3 (s, NCH2CH2), 27.1 (d, J (PC) ) 19.4, PCHCH3),
25.1 (s, NCH2CH2CH2), 19.6 and 19.5 (both s, PCHCH3). MS
(FAB+): m/z 630 (M+).
{C(CHdCP h 2)dNEt2}(CO)(P iP r 3)]BF 4 (2)
P r ep a r a tion of [Ru (η5-C5H5){C(CHdCP h 2)dNHn P r }-
(CO)(P iP r 3)]BF 4 (6). A dark red solution of 1 (150 mg, 0.24
mmol) in 5 mL of dichloromethane was treated with n-
propylamine (15 mg, 0.26 mmol), and the mixture was stirred
for 5 min. The solution became brown, and the solvent was
removed in vacuo. The residue was washed with diethyl ether
to afford a brown solid, which was crystallized from dichlo-
romethane/diethyl ether to give yellow crystals. Yield: 150 mg
(90%). Anal. Calcd for C33H45BF4NOPRu: C, 57.39; H, 6.57;
N, 2.03. Found: C, 57.02; H, 6.63; N, 1.91. IR (Nujol, cm-1):
ν(NH) 3321 (m), ν(CO) 1948 (vs), ν(CdN) 1529 (m), ν(BF4) 1077
(vs, br). 1H NMR (300 MHz, 293 K, CDCl3): δ 9.75 (s, 1H, NH),
7.50-7.00 (m, 10H, Ph), 6.45 (s, 1H, dCH), 4.82 (s, 5H, Cp),
3.66 (m, 2H, NCH2), 2.19 (m, 3H, PCHCH3), 1.77 and 1.42
(both m, 2H, CH2CH2), 1.23 (dd, 9H, J (HH) ) 6.9, J (PH) )
14.4, PCHCH3), 1.22 (dd, 9H, J (HH) ) 6.9, J (PH) ) 14.1,
PCHCH3), 0.85 (t, 3H, J (HH) ) 7.5, CH2CH2CH3). 31P{1H}
NMR (121.4 MHz, 293 K, CDCl3): δ 64.5 (s). 13C{1H} NMR
(75.4 MHz, 293 K, CDCl3): δ 242.2 (d, J (PC) ) 10.6, RuC),
204.5 (d, J (PC) ) 16.5, CO), 141.3 and 140.7 (both s, Cipso),
138.8 (s, CPh2), 133.7 (s, HCd), 130.3, 128.9, 128.5, 128.4,
and 128.3 (all s, Ph), 86.8 (s, Cp), 54.6 (s, NCH2), 28.9 (d, J (PC)
) 23.4, PCHCH3), 21.5 (s, CH2CH2), 19.8 and 19.3 (both s,
PCHCH3), 11.03 (s, CH2CH2CH3). MS (FAB+): m/z 604
(M+).
formula
fw
C34H47BF4NOPRu
704.60
cryst size (mm)
cell measmts (25 rflns) (deg)
color, shape
cryst syst
space group
a (Å)
0.42 × 0.18 × 0.14
12.7 < 2θ <14.7
yellow green, prism
monoclinic
P21/n (No. 14)
9.084(2)
22.215(4)
17.224(2)
104.24(1)
3369(1)
4
0.71069
1464
Psi
0.98-1.00
3 rflns, 100 rflns
-0.80
290(1)
ω/2θ
4
5 < 2θ < 50.1
5610
3747
388
9.66
full-matrix least squares on F
0.044
0.054
1.722
b (Å)
c (Å)
â (deg)
V (Å3)
Z (formula units)
λ(Mo KR) (Å)
F(000)
abs cor
transmissn factors
stds: no., interval
decay (%)
temp (K)
scan method
scan speed (ω) (deg min-1
2θ interval (deg)
no. of unique rflns
no. of obsd rflns (I > 3σI)
no. of params
)
rfln/param ratio
refinements
Ra
P r ep a r a t ion of [R u (η5-C5H 5){C(CH dCP h 2)dNH P h }-
(CO)(P iP r 3)]BF 4 (7). A dark red solution of 1 (150 mg, 0.24
mmol) in 5 mL of dichloromethane was treated with aniline
(15 mg, 0.26 mmol), and the mixture was stirred for 5 min.
The solution became brown, and the solvent was removed in
vacuo. The residue was washed with diethyl ether to afford a
brown solid, which was crystallized from dichloromethane/
diethyl ether to give yellow crystals. Yield: 157 mg (90%).
Anal. Calcd for C36H43BF4NOPRu: C, 59.67; H, 5.98; N, 1.86.
Found: C, 59.20; H, 5.93; N, 1.84. IR (Nujol, cm-1): ν(NH)
3271 (m), ν(CO) 1947 (vs), ν(CdN) 1592 (m), ν(BF4) 1061 (vs,
-2
b
Rw (w ) σF
)
GOF
residual peaks (e Å-3
)
+0.65, -0.43
a
b
R ) ∑(|Fo| - |Fc|)/∑|Fo|. Rw ) [(∑w(|Fo| - |Fc|)2/∑wFo2)]1/2
.
27.6 (d, J (PC) ) 23.4, PCHCH3), 25.0 (s, CH2CH2), 19.8 and
19.3 (both s, PCHCH3), 12.6 (s, CH2CH2CH3). MS (FAB+): m/z
604 (M+).
P r ep a r a tion of Ru (η5-C5H5){C(CHdCP h 2)dNP h }(CO)-
(P iP r 3) (9). A brown suspension of 7 (185 mg, 0.26 mmol) in
10 mL of tetrahydrofuran was treated with sodium methoxide
(29 mg, 0.54 mmol) and stirred for 1 h. The mixture became
yellow, and the solvent was removed in vacuo. Toluene (10
mL) was added, and the suspension was filtered to eliminate
sodium tetrafluoroborate. Solvent was evaporated, and the
residue was washed with pentane to afford a yellow solid.
Yield: 150 mg (90%). Anal. Calcd for C36H42NOPRu: C, 67.90;
H, 6.66; N, 2.19. Found: C, 67.50; H, 6.63; N, 2.26. IR (Nujol,
cm-1): ν(CO) 1908 (vs), ν(CdN) 1542. 1H NMR (300 MHz, 293
K, CDCl3) δ 7.51-6.70 (m, 15H, Ph), 4.69 (s, 5H, Cp), 2.14 (m,
3H, PCHCH3), 1.07 (dd, 9H, J (HH) ) 6.6, J (PH) ) 13.2,
PCHCH3), 0.94 (dd, 9H, J (HH) ) 6.9, J (PH) ) 12.9, PCHCH3).
31P{1H} NMR (121.4 MHz, 293 K, C6D6): δ 67.5 (s). 13C{1H}
NMR (75.4 MHz, 293 K, C6D6): δ 208.2 (d, J (PC) ) 15.0, CO),
204.5 (d, J (PC) ) 9.0, RuC), 154.1 (s, NCipso), 142.0 (s, HCd),
144.6 and 141.2 (both s, Cipso), 130.1 (s, CPh2), 130.9, 128.7,
128.6, 128.4, 127.2, 126.8, 121.8, and 121.0 (all s, Ph), 87.8 (s,
Cp), 29.4 (d, J (PC) ) 23.4, PCHCH3), 19.9 and 19.7 (both s,
PCHCH3). MS (FAB+): m/z 638 (M+).
1
br). H NMR (300 MHz, 293 K, CDCl3): δ 11.13 (s, 1H, NH),
7.41-6.98 (m, 15H, Ph), 6.70 (s, 1H, dCH), 5.18 (s, 5H, Cp),
2.32 (m, 3H, PCHCH3), 1.34 (dd, 9H, J (HH) ) 7.2, J (PH) )
14.4, PCHCH3). 1.32 (dd, 9H, J (HH) ) 7.2, J (PH) ) 14.1,
PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K, CDCl3): δ 62.2
(s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3): δ 248.7 (d, J (PC)
) 11.5, RuC), 204.5 (d, J (PC) ) 17.0, CO), 141.5, 140.6, and
138.8 (all s, Cipso), 139.9 (s, CPh2), 136.8 (s, HCd), 130.53,
129.6, 129.5, 129.1, 128.8, 128.7, 128.4, 128.2, and 123.4 (all
s, Ph), 87.8 (s, Cp), 29.4 (d, J (PC) ) 23.4, PCHCH3), 19.9 and
19.7 (both s, PCHCH3). MS (FAB+): m/z 638 (M+).
P r ep a r a tion of Ru (η5-C5H5){C(CHdCP h 2)dNn P r }(CO)-
(P iP r 3) (8). A brown suspension of 6 (185 mg, 0.27 mmol) in
10 mL of tetrahydrofuran was treated with sodium methoxide
(29 mg, 0.54 mmol) and stirred for 1 h. The mixture became
yellow, and the solvent was removed in vacuo. Toluene (10
mL) was added, and the suspension was filtered to eliminate
sodium tetrafluoroborate. Solvent was evaporated, and the
residue was washed with pentane to afford a yellow solid.
Yield: 145 mg (90%). Anal. Calcd for C33H44NOPRu: C, 65.75;
H, 7.35; N, 2.32. Found: C, 65.62; H, 7.01; N, 2.21. IR (Nujol,
cm-1): ν(CO) 1948 (vs), ν(CdN) 1605 (m). 1H NMR (300 MHz,
293 K, C6D6): δ 7.80-7.00 (m, 10H, Ph), 6.89 (s, 1H, dCH),
4.61 (s, 5H, Cp), 3.71 and 3.59 (both m, 2H, NCH2), 2.16 (m,
3H, PCHCH3) 1.89 and 1.72 (both m, 2H, NCH2CH2), 1.14 (m,
12H, CH2CH2CH3 and PCHCH3), 1.01 (dd, 9H, J (HH) ) 6.9,
J (PH) ) 12.6, PCHCH3). 31P{1H} NMR (121.4 MHz, 293 K,
C6D6): δ 67.55 (s). 13C{1H} NMR (75.4 MHz, 293 K, CDCl3):
δ 208.6 (d, J (PC) ) 17.4, CO), 193.0 (d, J (PC) ) 11.5, RuC),
144.8, (s, 2 Cipso), 141.6 (s, HCd), 132.0 (s, CPh2), 128.7, 128.5,
128.1, 127.5, and 126.5 (all s, Ph), 87.3 (s, Cp), 60.0 (s, CH2N),
Cr ysta l Da ta for 2. A crystal suitable for X-ray diffraction
analysis was mounted onto a glass fiber and transferred to
an AFC6S-Rigaku automatic diffractometer (T ) 290 K, Mo
KR radiation, graphite monochromator, λ ) 0.710 73 Å).
Accurate unit cell parameters and an orientation matrix were
determined by least-squares fitting from the settings of 25
high-angle reflections. Crystal data and details on data col-
lection and refinements are given in Table 3. Data were
collected by the ω/2θ scan method. Lorentz and polarization
corrections were applied. Decay was monitored by measuring
3 standard reflections every 100 measurements. Slight cor-
rections for decay and absorption (semiempirical ψ method)
were also applied.

Butadienyl and Allenyl Derivatives of Ru(II)
Organometallics, Vol. 18, No. 24, 1999 5003
The structure was solved by Patterson methods and sub-
sequent expansion of the model using DIRDIF.32 Reflections
having I > 3σ(I) were used for structure refinement. Non-
hydrogen atoms were anisotropically refined, and the hydrogen
atoms were included at idealized positions and not refined.
All calculations for data reduction, structure solution, and
refinement were carried out on a VAX 3520 computer at the
Servicio Central de Ciencia y Tecnolog´ıa de la Universidad de
Ca´diz, using the TEXSAN33 software system and ORTEP34 for
plotting. Maximum and minimum peaks in the final difference
calculations were carried out at the MP2 level using the
program Gaussian 94.35 The basis sets employed were
LANL2DZ ECP for the Ru atom and 6-31G for the rest
of the atoms.
Ack n ow led gm en t. We thank the DGES (PROJ ECT
PB-95-0806, Programa de Promocio´n General del Cono-
cimiento) for financial support.
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates and equivalent isotropic displacement coefficients,
anisotropic thermal parameters, and bond distances and
angles for 2. This material is available free of charge via the
Internet at http://pubs.acs.org.
Fourier maps were +0.65 and -0.43 e Å-3
.
Ap p en d ix
The theoretical calculations were carried out through
a series of partial optimizations on compounds 10-13.
The ligands Cp, CO, and PH3 were kept frozen. The
OM9904706
(35) Frisch, M. J .; Trucks G. W.; Schlegel, H. B.; Gill, P. M. W.;
J ohnson, B. G.; Robb, M. A.; Cheeseman, J . R.; Keith, T.; Peterson, G.
A.; Montgomery, J . A.; Raghavachari, K.; Al-Laham, M. A.; Zakrzewski,
V. G.; Ortiz, J . V.; Foresman, J . B.; Ciolowski, J .; Stefanov, B. B.;
Nanayakkara, A.; Challacombe, M.; Peng, C. Y.; Ayala, P. Y.; Chen,
W.; Wong, M. W.; Andres, J . L.; Replogle, E. S.; Gomperts, R.; Martin,
R. L.; Fox, D. J .; Binkley, J . S.; Defrees, D. J .; Baker, J .; Stewart, J .
P.; Head-Gordon, M.; Gonzalez, C.; Pople, J . A. Gaussian 94, Revision
D.3; Gaussian, Inc., Pittsburgh, PA, 1995.
(32) Beurskens, P. T.; DIRDIF; Technical Report 1984/1; Crystal-
lography Laboratory, Toernooiveld, 6525 ED Nijmegen, The Nether-
lands, 1984.
(33) TEXSAN Single-Crystal Structure Analysis Software, version
5.0; Molecular Structure Corp., The Woodlands, TX, 1989.
(34) J ohnson, C. K. ORTEP, A Thermal Ellipsoid Plotting Program;
Oak Ridge National Laboratory, Oak Ridge, TN, 1965.