Nucleophilic addition reactions to the allenylidene complex [Cp*Ru=C=C=CPh2iPr2)]+: X-ray crystal structures of Cp*Ru{C(N=CPh2) CH=CPh2}(CO)(PMeiPr2)] [BAr4′]

Article abstract of DOI:10.1016/j.jorganchem.2004.06.002

The allenylidene complex [Cp* Ru=C=C=CPh₂(CO) (PMeⁱPr₂)][BAr₄′] (1) reacts with benzophenoneimine yielding the azaallenyl derivative [Cp* Ru{C(N=CPh₂)CH=CPh₂}(CO) (PMeⁱ Pr₂)][BAr₄′] (2). The addition of primary or secondary amines to 1 yields vinylaminocarbenes, which are better formulated as azoniabutadienyl complexes [Cp* Ru{C(NRR′)CH=CPh₂}(CO), (PMeⁱPr₂)][BAr₄′] (R = H, R′ = CH₂C≡CH (3), R = H, R′ = Me (4), R = R′ = ⁱPr (5)). Tertiary phosphines add to the C_a atom of the allenylidene chain furnishing allenylphosphonio species [Cp* Ru{C(PR₃) C=CPh₂} (CO)(PMeⁱPr₂)][BAr₄ ′] (PR₃ = PMe₃ (6), PMeⁱ Pr₂ (7)). The reaction of 1 with propanethiol afforded the thiocarbene [Cp* Ru{C(SⁿPr) CH=CPh₂} (CO) (PMeⁱPr₂)][BAr₄′] (8), which can be treated as a η¹-thiabutadienyl.

Full text of DOI:10.1016/j.jorganchem.2004.06.002

Journal of Organometallic Chemistry 689 (2004) 2776–2785
www.elsevier.com/locate/jorganchem
Nucleophilic addition reactions to the allenylidene complex
i
+
*
[Cp Ru‚C‚C‚CPh2(CO)(PMe Pr2)] : X-ray crystal structures of
½CpꢀRufCðN@CPh2ÞCH@CPh2gðCOÞðPMeiPr2Þꢁ½BAr04ꢁ,
½CpꢀRufCðNHCH2CBCHÞCH@CPh2gðCOÞðPMeiPr2Þꢁ½BAr04ꢁ,
½CpꢀRufCðPMeiPr2ÞC@CPh2gðCOÞðPMeiPr2Þꢁ½BAr04ꢁ and
½CpꢀRufCðSn PrÞCH@CPh2gðCOÞðPMeiPr2Þꢁ½BAr04ꢁ
*
´
Manuel Jimenez-Tenorio, M. Dolores Palacios, M. Carmen Puerta, Pedro Valerga
´ ´ ´ ´
Departamento de Ciencia de los Materiales e Ingenierıa Metalurgica y Quımica Inorganica, Facultad de Ciencias,
´ ´
Universidad de Cadiz, Apartado 40, 11510 Puerto Real (Cadiz), Spain
Received 23 April 2004; accepted 1 June 2004
In memoriam of Dr. Juan Carlos del Amo Agua do, 28 years old, researcher of the Universidad Complutense,
who was killed in 11 March bombing in Madrid
Abstract
The allenylidene complex ½CpꢀRu@C@C@CPh2ðCOÞðPMeiPr2Þꢁ½BAr04ꢁ (1) reacts with benzophenoneimine yielding the azaallenyl
derivative ½CpꢀRufCðN@CPh2ÞCH@CPh2gðCOÞðPMeiPr2Þꢁ½BAr04ꢁ (2).The addition of primary or secondary amines to 1 yields vi-
nylaminocarbenes, which are better formulated as azoniabutadienyl complexes ½CpꢀRufCðNRR0ÞCH@CPh2gðCOÞ
ðPMeiPr2Þꢁ½BAr40 ꢁ (R=H, R0 =CH2C„CH (3), R=H, R0 =Me (4), R=R0 =iPr (5)).Tertiary phosphines add to the Ca atom of
the allenylidene chain furnishing allenylphosphonio species ½CpꢀRufCðPR3ÞC@CPh2gðCOÞðPMeiPr2Þꢁ½BAr04ꢁ (PR3 =PMe3 (60),
PMeiPr2 (7)). The reaction of 1 with propanethiol afforded the thiocarbene ½CpꢀRufCðSn PrÞCH@CPh2gðCOÞðPMeiPr2Þꢁ½BAr ꢁ
4
(8), which can be treated as a g1-thiabutadienyl.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Allenylidene; Azaallenyl; Azoniabutadienyl; Thiocarbene
1. Introduction
ruthenium fragments such as {[(g5-C9H7)Ru(PPh3)2]+}
[5–7], {[(g5-C9H7)Ru(CO)(PPh3)]+} [5–7], {[CpRu-
(CO)(PiPr3)]+} [8–17] or {[(g6-arene)RuCl(PR3)]+} [18–
21] has been studied by several research groups.
Although the reactivity of cationic allenylidene com-
plexes is governed by the electron deficiency of both
the Ca and Cc atoms of the unsaturated chain, its is
known that regioselective nucleophilic additions at Cc
take place when bulky, electron-rich metallic fragments
are used, leading to r-alkynyl complexes [2,5]. The
The involvement of transition metal allenylidene
complexes in the stoichiometric and catalytic transfor-
mations of alkynes is well established [1–4]. The reactiv-
ity of allenylidene ligands attached to different cationic
*
Corresponding author. Tel.: +34-956-016340; fax: +34-956-
016288.
E-mail address: pedro.valerga@uca.es (P. Valerga).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.06.002

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M. Jimenez-Tenorio et al. / Journal of Organometallic Chemistry 689 (2004) 2776–2785
2777
substituents of the allenylidene ligand also play an im-
portant role in determining the final product of the nu-
cleophilic addition. Thus, some alkynyl complexes
resulting from the addition to the Cc undergo an isom-
erization reaction leading to more stable allenyl deriva-
tives [11,13,16,17]. The addition of electrophiles to the
Cb of the allenylidene chain is less frequent. Following
the report by Werner and co-workers [22] of the prepa-
ration of carbyne complexes of ruthenium by proton-
ation of vinylidene complexes, we have recently
2.2. Synthesis of [CpꢀRu{CðN@CPh2)CH@CPh2}(CO)
(PMeiPr2)][BAr04] (2)
A dark purple solution of 1 (500 mg, 0.35 mmol) in 8
ml of dichloromethane was treated with benzophenonei-
mine (0.1 ml, 0.55 mmol, 80% excess). The mixture was
stirred for 30 min. The solution became orange-brown
and the volume was then reduced to 1 ml. The solution
was layered with petroleum ether, yielding orange crys-
tals which were filtered off, washed with petroleum ether
and dried. Recrystallization from diethyl ether/petro-
leum ether afforded crystals suitable for single-crystal
X-ray diffraction. Yield: 450 mg, 60%. Anal. Calc. for
C78H65NBF24OPRu: C, 57.4; H, 4.02. Found: C, 57.2;
described the dicationic vinylcarbyne derivatives
2+
0
[Cp Ru„CCH‚CRR (dippe)]
(R=R0 =Ph; R=H,
*
R0 =Ph; dippe=1,2-bis(diisopropylphosphino)ethane)
[23] by protonation of the respective allenylidene com-
+
plexes [Cp Ru‚C‚C‚CRR (dippe)] . The reactions
of addition of nucleophiles to these complexes were also
studied. In all cases addition to the Cc was observed.
The introduction of a strong p-acceptor ligand such as
CO modifies both the electronic and the steric properties
of the metallic fragment, modifying the reactivity of the
allenylidene ligand accordingly. In the context of our
studies in the chemistry of pentamethylcyclo-
pentadienylruthenium complexes, we have recently
reported the preparation and characterization of the
electron-deficient allenylidene complex ½CpꢀRu@C@
H, 4.10%. IR (Nujol): m(CO) 1948 (s) cmꢂ1
,
0
*
1
m(C‚N‚C) 1796 cmꢂ1. H NMR (400 MHz, CDCl3,
298 K): d 0.96 and 1.19 (m, 12H, PCH(CH3)2), 1.24
(d, 3H, JHP =7.1 Hz, PCH3), 2.01 and 2.15 (m, 2H,
2
4
PCH(CH3)2), 1.85 (d, 15H, JHP =1.3 Hz, C5(CH3)5),
6.75 (s, 1H, CH‚), 6.76–7.59 (m, 20H, Ph); 31P{1H}
NMR (161.89 MHz, CDCl3, 298 K): d 42.50 (s);
13C{1H} NMR (75.4 MHz, CDCl3, 298 K) d: 8.10 (d,
1JCP =29.1 Hz, PCH3), 10.44 (s, C5(CH3)5,), 17.12 (d,
2
2JCP =3.6 Hz, PCH(CH3)2), 18.46 (d, JCP =3.6 Hz,
1
PCH(CH3)2), 27.04 (d, JCP =27.4 Hz, PCH(CH3)2),
C@CPh2ðCOÞðPMeiPr2Þꢁ½BAr0 ꢁ (Ar0 =3,5-C6H3(CF3)2)
28.24 (d, JCP =24.6 Hz, PCH(CH3)2), 99.64 (s,
C5(CH3)5), 127–133 (s, Ph+Cb), 148.67 (s, C‚N‚
1
4
[24]. In this work, we focus on the study of the reactivity
of this complex towards a variety of nucleophiles con-
taining N-, P- or S-donor atoms. In all cases, and at var-
iance with the systems containing two phosphine
ligands, products derived from the regioselective addi-
tion to the Ca of the allenylidene ligand have been
isolated and characterized.
2
CPh2), 140 (s, Cc), 195.35 (d, JCP =11.8 Hz, C‚N‚
CPh2), 204.9 (d, CO, JCP =17.6 Hz).
2
2.3. Synthesis of [CpꢀRu{C(NHCHcHd CBCHb)CHa@
CPh2}(CO)(PMeiPr2)][BAr04] (3)
Propargylamine (0.017 ml, 0.38 mmol) was added to
a solution of the allenylidene compound 1 (500 mg, 0.35
mmol) in 8 ml of dichloromethane. The mixture was stir-
red for 5 h. The volume was reduced to 1 ml. The solu-
tion was layered with petroleum ether, yielding orange
crystals which were recrystallized from dichlorome-
thane/petroleum ether. Yield: 310 mg, 60%. Anal. Calc.
for C68H59NBF24OPRu: C, 54.3; H, 3.95. Found: C,
2. Experimental
2.1. General consideration
All synthetic operations were performed under a dry
dinitrogen or argon atmosphere, using conventional
Schlenk techniques. Tetrahydrofuran, diethyl ether and
petroleum ether (boiling point range 40–60 ꢁC) were dis-
tilled from the appropriate drying agents. Fluoroben-
zene was purchased from Aldrich (0.01% water
maximum). All solvents were deoxygenated immediately
before use. The complex ½CpꢀRu@C@C@CPh2ðCOÞ
ðPMeiPr2Þꢁ½BAr04ꢁ (1) was prepared according to a re-
cently reported procedure [24]. IR spectra were recorder
in Nujol mulls on a Perkin–Elmer Spectrum 1000 spec-
trophotometer. NMR spectra were taken on a Varian
Unity 400 MHz or a Varian Gemini 300 MHz spectrom-
eter. Chemical shifts are given in ppm from SiMe4 (1H
and 13C{1H}), or 85% H3PO4 (31P{1H}). Microanalysis
54.4; H, 4.08%. IR (Nujol): m(CO) 1967 (s) cmꢂ1
,
1
m(NH) 3304 cmꢂ1, m(C„C) 3406 cmꢂ1. H NMR (400
MHz, C2D2Cl4, 343 K): d 0.86 and 1.08 (m, 12H,
PCH(CH3)2), 1.40 (d, 3H, JHP =7.9 Hz, PCH3), 1.97
(m, 1H, PCH(CH3)2), 2.11 (m, 1H, PCH (CH3)2), 1.64
2
4
(br, 15H, C5(CH3)5), 2.56 (t, JHbHc =2.6 Hz,
4JHbHd =2.6 Hz, 1H, Hb), 4.20 and 4.25 (dd, 2JHcHd =5.9
4
4
Hz, JHbHc =2.6 Hz, JHbHd =2.6 Hz, 2H, Hc and Hd),
6.38 (s, 1H, Ha), 7.03 (m, 2H, Ph), 7.16 (m, 2H, Ph),
7.38 (m, 6H, Ph), 7.63 (br, 1H, NH ); 31P{1H} NMR
(161.89 MHz, C2D2Cl4, 343 K): d 37.99 (s); 13C{1H}
NMR (75.4 MHz, C2D2Cl4, 343 K) d: 9.76 (d,
1JCP =24.1 Hz, PCH3), 9.64 (s, C5(CH3)5), 18.88 (d,
2
2JCP =12.6 Hz, PCH(CH3)2), 17.32 (d, JCP =12.6 Hz,
´
`
were performed by the Serveis Cientıfico-Tecnics, Uni-
versitat de Barcelona.
1
PCH(CH3)2), 26.91 (d, JCP =29.9 Hz, PCH(CH3)2),

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M. Jimenez-Tenorio et al. / Journal of Organometallic Chemistry 689 (2004) 2776–2785
2778
1
28.55 (d, JCP =26.84 Hz, PCH(CH3)2), 40.99 (s, HNC
mixture was stirred at 60 ꢁC for 3 h and it was filtered
through celite. The solvent was almost completely re-
moved in vacuo. Addition of petroleum ether gave an
orange crystalline solid which was filtered, washed with
petroleum ether and dried. Yield: 310 mg, 60%. Anal.
Calc. for C68H63BF24OP2Ru: C, 53.5; H, 4.16. Found:
H2), 74.47 (s, C„CH), 76.73 (s, C„CH), 100.0 (s,
C5(CH3)5), 120–142 (Cb, Cc Ph), 205.22 (d, JCP =17.7
2
2
Hz, CO), 248.5 (d, JCP =11.5 Hz, Ca).
2.4. Synthesis 0 of [CpꢀRu{C(NRR0)CH@CPh2}(CO)
(PMeiPr2)][BAr4] (R=H, R0 =CH3 (4); R=R0 =CH
(CH3)2 (5))
C, 53.4; H, 4.05%. IR (Nujol): m(CO) 1888 (s) cmꢂ1
,
1
m(C‚C‚C) 1856 cmꢂ1. H NMR (400 MHz, CDCl3,
298 K): d 0.84, 0.97 and 1.13 (m, 12H, PCH(CH3)2),
1.18 (d, JHP =8.5 Hz, 3H, PCH3), 1.84 (m, 2H,
2
A procedure similar to that for 3 was followed for the
preparation of these complexes, using 0.35 mmol of me-
thylamine (4) or diisopropylamine (5), respectively.
These compounds were also recrystallized from dichlo-
romethane/petroleum ether.
4
PCH(CH3)2), 1.59 (d, JHP =1.6 Hz, 15H, C5(CH3)5),
2
1.73 (d, JHP =12.3 Hz, 9H, P(CH3)3), 7.04–7.36 (m,
10H, Ph); 31P{1H} NMR (161.89 MHz, CDCl3, 298
K): d 22.6 (s, PMe3), 43.8 (s, PMeiPr2); 13C{1H}
NMR (161.89 MHz, CDCl3, 298 K): d 10.82 (m,
P(CH3)3), 10.50 (s, C5(CH3)5), 18.68, 19.11 (m,
Compound 4. Yield: 280 mg, 55%. Anal. Calc. for
C66H59NBF24OPRu: C, 53.5; H, 4.02. Found: C, 53.4;
H, 4.08%. IR (Nujol): m(CO) 1958 (s) cmꢂ1, m(NH)
1
PCH(CH3)2), 29.00 (d, JCP =23.6 Hz, PCH(CH3)2),
1
29.94 (d, JCP =25.7 Hz, PCH(CH3)2), 97.94 (d,
1
3387 cmꢂ1. H NMR (400 MHz, C2D2Cl4, 343 K): d
1
3JCP =1.6 Hz, C5(CH3)5), 102.28 (d, JCP =23.2 Hz,
2
0.95 (m, 12H, PCH(CH3)2), 1.45 (d, 3H, JHP =8.0 Hz,
3
Ca), 115.50 (d, JCP =21.0 Hz, Cc), 120–130 (all s, Ph),
PCH3), 2.05 (m, 1H, PCH(CH3)2), 2.14 (m, 1H,
PCH(CH3)2), 1.72 (br, 15H, C5(CH3)5), 2.62 (s, 3H,
NHCH3), 6.12–7.50 (m, 10H, Ph), 8.04 (br, 1H, NH);
31P{1H} NMR (161.89 MHz, C2D2Cl4, 343 K): d
40.36 (s); 13C{1H} NMR (75.4 MHz, C2D2Cl4, 343 K)
2
209.17 (d, JCP =6.2 Hz, Cb), 210.39 (dd, JCP =17.9
2
3
Hz, JCP =8.2 Hz, CO).
2.6. Synthesis of [CpꢀRu{C(P0MeiPr2)@C@CPh2}(CO)
(PMeiPr2)][BAr04] (7)
1
d : 8.96 (d, JCP =23.6 Hz, PCH3), 10.02 (s, C5(CH3)5),
17.74 (d, JCP =13.6 Hz, PCH(CH3)2), 17.96 (d,
2
1
2JCP =14.0 Hz, PCH(CH3)2), 25.96 (d, JCP =28.6 Hz,
This compound was obtained following a similar pro-
cedure to that for 6. It was also isolated as secondary
product in the nucleophilic addition of propanethiol to
1. Yield: 400 mg, 60%. Anal. Calc. for C72H71BF24O-
P2Ru: C, 54.6; H, 4.52. Found: C, 54.4; H, 4.55%. IR
1
PCH(CH3)2), 27.39 (d, JCP =26.2 Hz, PCH(CH3)2),
35.65 (s, HNCH3), 102.1 (s, C5(CH3)5), 121–146 (Cb,
2
Cc, Ph), 203.75 (d, JCP =18.26 Hz, CO), 255.32 (d,
2JCP =10.7 Hz, Ca).
Compound 5. Yield: 320 mg, 60%. Anal. Calc. for
C71H69NBF24OPRu: C, 54.9; H, 4.48. Found: C, 54.7;
(Nujol): m(CO) 1897 (s) cmꢂ1, m(C‚C‚C) 1850 cmꢂ1
.
1H NMR (400 MHz, CDCl3, 298 K): d 0.71, 1.16 and
1.35 (m, 27H, PCH(CH3)2, P0CH(CH3)2, P0CH3), 1.63
1
H, 4.38%. IR (Nujol): m(CO) 1968 (s) cmꢂ1. H NMR
2
(d, JHP =11.1 Hz, 3H, PCH3), 1.85 (m, 2H,
(400 MHz, C2D2Cl4, 343 K): d 0.87 (m, 12H,
PCH(CH3)2), 1.20 (d, 3JHH =3.7 Hz, 12H, NCH(CH3)2),
PCH(CH3)2), 1.77 (d, JHP =1.3 Hz, 15H, C5(CH3)5),
4
2
1.39 (d, 3H, JHP =8.0 Hz, PCH3), 1.98 (m, 1H,
2.57 (m, 1H, P0CH(CH3)2), 2.79 (m, 1H, P0CH(CH3)2),
7.16–7.40 (m, 10H, Ph); 31P{1H} NMR (161.89 MHz,
CDCl3, 298 K): d 43.76 (s), 41.52 (s); 13C{1H} NMR
PCH(CH3)2), 2.06 (m, 1H, PCH(CH3)2), 1.72 (br, 15H,
C5(CH3)5), 3.05 (m, 2H, NCH(CH3)2), 6.20–7.40 (m,
10H, Ph); 31P{1H} NMR (161.89 MHz, C2D2Cl4, 343
K): d 39.65 (s); 13C{1H} NMR (75.4 MHz, C2D2Cl4,
1
(75.4 MHz, CDCl3, 298 K) d: 4.64 (d, JCP =57.7 Hz,
P0CH3), 10.62 (s, C5(C H3)5), 15.82, 16.95, 17.37,
17.74, 18.62 and 19.60 (m, PCH(CH3)2 and
1
343 K) d: 8.74 (d, JCP =25.6 Hz, PCH3), 10.15 (s,
C5(CH3)5), 18.23 (d, JCP =13.0 Hz, PCH(CH3)2),
2
1
P0CH(CH3)2), 22.68 (d, JCP =42.7 Hz, P0CH(CH3)2),
2
18.67 (d, JCP =15.0 Hz, PCH(CH3)2), 25.32 (d,
1
23.59 (d, JCP =45.9 Hz, P0CH(CH3)2), 29.77 (d,
1
1
1JCP =27.9 Hz, PCH(CH3)2), 27.86 (d, JCP =26.0 Hz,
1JCP =25.7 Hz, PCH(CH3)2), 30.26 (d, JCP =24.4 Hz,
3
PCH(CH3)2), 98.02 (d, JCP =1.7 Hz, C5(CH3)5),
PCH(CH3)2), 28.94 (s, NCH(CH3)2), 47.56 (s,
NCH(CH3)2), 100.36 (s, C5(CH3)5), 125–148 (Cb, Cc,
1
101.01 (d, JCP =23.2 Hz, Ca), 115.49 (d, JCP =21.0
3
0
0
2
Ph), 201.59 (d, JCP =17.9 Hz, CO), 246.37, (d,
2
Hz, Cc), 120–130 (all s, Ph), 206.96 (d, JCP =4.2 Hz,
0
2JCP =11.1 Hz, Ca).
2
Cb), 210.99 (dd, JCP =19.9 Hz, JCP =6.7 Hz, CO).
3
0
2.5. Synthesis 0 of [CpꢀRu{CðPMe3Þ@C@CPh2}(CO)
(PMeiPr2)][BAr4] (6)
2.7. Synthesis 0 of [CpꢀRu{C(SnPr)CH@CPh2}(CO)
(PMeiPr2)][BAr4] (8)
PMe3 (0.043 ml, 0.50 mmol) was added to a solution
of the allenylidene complex 1 (500 mg, 0.35 mmol). The
A deep purple solution of 1 (500 mg, 0.35 mmol) in
10 ml of dichloromethane was treated with propanethiol

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M. Jimenez-Tenorio et al. / Journal of Organometallic Chemistry 689 (2004) 2776–2785
2779
2
(0.05 ml, 0.70 mmol) and stirred for 6 h. The solvent was
removed in vacuo. Petroleum ether was added, and the
suspension was filtered off in order to remove the excess
of propanethiol. The solution was concentrated and lay-
ered with petroleum ether. After two days an orange mi-
crocrystalline solid was obtained. It was filtered off,
washed with petroleum ether and dried in vacuo. Re-
crystallization from diethyl ether/petroleum ether affor-
ded crystals suitable for single-crystal X-ray
diffraction. Yield: 240 mg, 45%. Anal. Calc. for
C68H62BF24OPSRu: C, 53.5; H, 4.09. Found: C, 53.4;
H, 4.05%. IR (Nujol): m(CO) 1898 (s) cmꢂ1, m(C‚C)
142.46 (s, Cb), 203.72 (d, JCP =17.9, Hz, CO), 309.70
(br, RuCa).
2.8. X-ray structure determinations
Crystals of 2, 7 and 8 were obtained by recrystalli-
zation from diethyl ether/petroleum ether, and 3 from
dichloromethane/petroleum ether. Crystal data and ex-
perimental details are given in Table 1. X-ray diffrac-
tion data were collected on
APEX 3-circle diffractometer with CCD area detector
a Bruker SMART
´
at the Servicio Central de Ciencia y Tecnologıa de la
Universidad de Cadiz. Hemispheres of the reciprocal
1590 cmꢂ1
.
0.98 (t, JHH =7.5 Hz, 3H, SCH2CH2CH3), 1.13 (m,
1H NMR (400 MHz, CDCl3, 298 K): d
´
3
space were measured by omega scan frames with
d(x) 0.30ꢁ. Correction for absorption and crystal de-
cay (insignificant) were applied by semi-empirical
method from equivalents using program SADABS [25].
The structures were solved by direct methods, com-
pleted by subsequent difference Fourier synthesis and
refined on F2 by full-matrix least-squares procedures
using the program SHELXTL [26]. All non-hydrogen at-
oms were refined with anisotropic displacement coeffi-
cients. CF3 groups of the ½BAr04ꢁꢂ anion showed
orientation disorder in all these compounds. 6 of 8
of the CF3 groups were refined as pairs of CF3 with
complementary orientations for compounds 2, 7 and
8. In addition for compound 3, one other CF3 was
partially splitted. All the remaining hydrogen atoms
2
12H, PCH(CH3)2), 1.54 (d, JHP =8.7 Hz, 3H, PCH3),
1.70 (m, 2H, SCH2CH2CH3), 1.99 (m, 1H, PCH(CH3)2),
2.20 (m, 1H, PCH(CH3)2), 1.59 (s, 15H, C5(CH3)5), 3.11
(m, 2H, SCH2CH2CH3), 6.62 (s, 1H, ‚CH), 6.92, 7.16
and 7.34 (m, 10H, Ph); 31P{1H} NMR (161.89 MHz,
CDCl3, 298 K): d 36.37 (s); 13C{1H} NMR (75.4
1
MHz, CDCl3, 298 K) d: 7.56 (d, JCP =32.8 Hz,
PCH3), 10.04 (s, C5(CH3)5), 13.23 (s, SCH2CH2C H3),
2
18.11 (d, JCP =8.7 Hz, PCH(CH3)2), 17.68 (d,
2JCP =4.4 Hz, PCH(CH3)2), 20.90 (s, SCH2CH2CH3),
1
27.48 (d, JCP =26.3 Hz, PCH(CH3)2), 29.34 (d,
1JCP =24.0 Hz, PCH(CH3)2), 47.07 (s, SCH2CH2CH3),
103.41 (s, C5(CH3)5), 128.28, 128.51, 128.79 and
130.50 (all s, Ph), 138.08, 139.62, 141.39 (all s, Cc, Ph),
Table 1
Crystal data and details of structure determination for compounds 2, 3, 7 and 8
Compound
2
3
7
8
Formula
C78H65BF24NOPRu
1631.16
Triclinic
C68H59BF24NOPRu
1505.01
Triclinic
C76H81BF24O2P2Ru
1656.23
Monoclinic
C68H62BF24OPRuS
1526.09
Triclinic
Formula weight
Crystal system
Space group
ꢀ
ꢀ
ꢀ
P1 (No. 2)
P1 (No. 2)
P21/c (No. 14)
P1 (No. 2)
Unit cell dimensions
˚
a (A)
˚
13.5058(8)
15.6887(9)
18.784(1)
96.103(1)
102.117(1)
94.997(1)
3844.9(4)
2
13.7633(5)
15.0298(5)
18.0297(6)
79.344(1)
82.689(1)
82.125(1)
3610.8(2)
2
22.472(2)
22.123(2)
17.030(2)
90
12.6098(6)
13.9079(7)
19.822(1)
90.008(1)
91.813(1)
91.813(1)
3473.7(3)
2
b (A)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
110.405(2)
90
7935(1)
3
˚
V (A )
Z
4
1.386
dcalc (g/cm3)
1.409
0.327
1.384
0.341
1.459
0.384
l (Mo Ka) (mmꢂ1
F(000)
)
0.337
3392
1656
0.71073
1524
0.71073
1548
0.71073
˚
k (Mo Ka) (A)
0.71073
2.4–24.1
62030, 12448, 0.044
11869
hmin–hmax (ꢁ)
1.7–25.0
25451, 13189, 0.023
12065
2.0–25.1
33503, 12657, 0.049
9915
1.0–25.0
26479, 10700, 0.050
8728
Total, unique, Rint
Observed (I>2r(I))
Reflections, parameters
R, wR2 (I>2r(I))
R, wR2 (all)
13189, 1114
0.0679, 0.1500
0.0748, 0.1549
1.08
12657,1071
0.0699, 0.1534
0.0927, 0.1662
1.08
12448, 1183
0.0789, 0.1545
0.0841, 0.1575
1.09
10700, 1055
0.0868, 0.1603
0.1079, 0.1717
1.08
Goodness-of-fit
3
Residuals (e/A )
˚
ꢂ0.64, 0.73
ꢂ0.64, 0.71
ꢂ0.91, 0.69
ꢂ0.37, 0.69

´
M. Jimenez-Tenorio et al. / Journal of Organometallic Chemistry 689 (2004) 2776–2785
2780
C31
in both compounds were refined using the SHELX rid-
ing model. The program ORTEP-3 [27] was used for
plotting.
C30
C29
C32
C7
C36
C35
C37
C28
C8
C3
C34
C2
C38
C33
C1
3. Results and discussion
C18
C19
C27
C13
C12
C39
C4
C9
C17
We have previously studied the reactivity of the elec-
*
C6
C16
C5
tron-rich allenylidene complex [Cp Ru‚C‚C‚
Ru1
CPh2(dippe)]+ towards nucleophiles and electrophiles
[23]. In that system, nucleophilic additions take place
at the Cc atom of the allenylidene chain, whereas elec-
trophiles such as H+ enter in the Cb position. At vari-
ance with this behaviour, the addition of nucleophiles
to the electron-poor allenylidene complex 1 occur at
the Ca. Scheme 1 summarizes the nucleophilic addition
reactions studied in the present work.
C15
N1
C20
C10
C11
O1
C14
C45
C44
C41
C21
C22
C26
C25
C46
P1
C42
C43
C23
C24
C40
*
Fig. 1. ORTEP diagram of the cation [Cp Ru{C(N‚CPh2)-
Thus, the reaction of 1 with benzophenoneimine
yields the azaallenyl derivative ½CpꢀRufCðN@CPh2Þ
CH@CPh2gðCOÞðPMeiPr2Þꢁ½BAr04ꢁ (2). Although Cr or
W azaallenyl complexes are known [28], ruthenium de-
rivatives of this kind are rather scarce. The first isolated
and characterized azaallenyl ruthenium complex was
[CpRu{C(N‚CPh2)CH‚CPh2}(CO)(PiPr3)][BF4] [29],
similarly prepared by addition of benzophenoneimine
to the allenylidene complex [CpRu‚C‚C‚CPh2
(CO)(PiPr3)][BF4]. The X-ray crystal structure of 2 was
CH‚CPh2}(CO)(PMeiPr2)]+ in compound 2. Selected bond distances
˚
(A) and angles (ꢁ): Ru1–2.338(1); Ru1–C11 1.850(5); Ru1–C12
2.057(4); C12–C13 1.467(6); C13–C27 1.345(6); C12–N1 1.272(5);
C14–N1 1.262(6); C11–O1 1.1.47(5); Ru1–C12–N1 122.8(3); N1–C14–
C15 120.7(5); N1–C14–C21 1117.4(5); N1–C12–Ru1 122.8(3);
N1–C12–C13 118.8(4); C14–N1–C12 168.7(5); C12–Ru1–P1 89.9(1);
C11–Ru1–P1 87.0(1); Ru1–C12–C13 118.4(3).
bonds. The angle C12–N1–C14 has
a value of
168.7(5)ꢁ, which indicates an essentially linear C‚N‚C
C assembly. In the related complex [CpRu{C(N‚CPh2)
CH‚CPh2}(CO)(PiPr3)]+ [29], this angle has a value of
149.9(6)ꢁ, being therefore more deviated from linearity.
The IR spectrum of 2 displays one strong band at
1796 cmꢂ1 ascribed to the C‚N‚C group. The reso-
nance for the ruthenium-bound Ca atom of the azaalle-
nyl ligand appears as one doublet at 195.35 ppm in the
13C{1H} NMR spectrum.
*
determined. An ORTEP view of the cation [Cp Ru
{C(N‚CPh2)CH‚CPh2}(CO)(PMeiPr2)]+ is shown in
Fig. 1, together with a listing of selected bond lengths
and angles.
The complex has a three-legged piano stool structure.
˚
The Ru1–C12 separation of 2.057(4) A is consistent with
a single bond, whereas the C12–N1 and N1–C14 bond
˚
lengths, 1.272(5) and 1.262(6) A indicate double C‚N
+
+
R'
CPh2
Ru
N
Ru
N
R
C
C
Pri2MeP
Pri2MeP
Ph
Ph
HC
HC
OC
OC
C
C
+
HN=CPh2
Ph
Ph
HNRR'
2
R = CH2CCH; R' = H 3
R = Me; R' = H 4
Ru
R = R' = iPr
5
C
Pri2MeP
C
Ph
+
C
OC
nPrSH
+
PR3
1
Ph
Ru
PR3
Ph
C
Pri2MeP
S
Ru
nPr
Ph
C
C
Pri2MeP
OC
HC
OC
C
C
Ph
PR3 = PMe3 6, PMeiPr2
8
Ph
7
Scheme 1. Summary of nucleophilic addition reactions to the allenylidene complex 1.

´
M. Jimenez-Tenorio et al. / Journal of Organometallic Chemistry 689 (2004) 2776–2785
2781
Primary and secondary amines such as HC„
CCH2NH2, MeNH2 or iPr2NH also react with the alleny-
lidene complex 1 adding to the Ca–Cb bond furnishing
the corresponding derivatives ½CpꢀRufCðNRR0ÞCH@
3; R=H, R0 =Me 4; R=R0 =iPr 5). In general, the
addition of amines to the Ca–Cb of allenylidenes yields
vinylaminocarbenes, for which the following main
resonance structures must be considered [11]:
COOMe(dippe)]+ (Tp=hidrotris(pyrazolyl)borate) [30],
˚
but very similar to the value of 2.063(6) A reported
for the azoniabutadienyl complex [CpRu{C(NEt2)
CH‚CPh2}(CO)(PiPr3)]+ [11]. The C11–N1 separation
CPh2gðCOÞðPMeiPr2Þꢁ½BAr0 ꢁ (R=H, R0 =CH2C„CH
˚
of 1.329(5) A is intermediate between a single and a dou-
4
ble carbon–nitrogen bond. These data suggest that for
compound 3 there is a contribution of the azoniabuta-
dienyl resonance structure B which seems more impor-
tant than the vinylaminocarbene structure A. The Ru–
˚
˚
Ca (2.063(6) A) and Ca–N (1.306(7) A) bond distances
in [CpRu{C(NEt2)CH‚CPh2}(CO)(PiPr3)]+ indicate
that for this compound the contribution of the azoniab-
utadienyl resonance structure is even more important
than for 3. One possible explanation for this comes from
R
R
R
N
R'
N
R'
N
R'
[Ru]
[Ru]
[Ru]
Ph
Ph
Ph
Ph
Ph
Ph
*
the fact that Cp is a better p-donor than Cp, and hence
*
the metal centre results more electron-rich in Cp com-
A
B
C
plexes when compared to their Cp counterparts. As a
result, the resonance structure with one negative charge
at the ruthenium is more favoured in the complex con-
Structure A corresponds to a vinylaminocarbene,
whereas B corresponds to an g1-azoniabutadienyl com-
plex. The X-ray crystal structure of compound 3 was
*
taining Cp than in the Cp case. Thus, complexes 3–5
are more properly referred to as azoniabutadienyl deriv-
*
determined. An ORTEP view of the cation [Cp Ru-
{C(NHCH2C„CH)CH‚CPh2}(CO)(PMeiPr2)]+
is
shown in Fig. 2, together with a listing of selected bond
lengths and angles.
˚
The Ru1–C11 bond length of 2.020(4) A is longer
than the value expected for a Ru‚C bond, i.e. 1.86(2)
˚
A
in the alkoxycarbene [TpRu‚C(OMe)CH2CO-
C17
C10
C9
C18
C19
C16
C5
C1
C4
C6
C15
C14
O1
C3
C2
C8
C29
Ru1
C21
C13
C20
C11
C22
C7
C36
P1
N1
C12
C34
C35
C26
C27
C28
C25
C30
C23
C31
C24
C32
C33
*
Fig. 2. ORTEP diagram of the cation [Cp Ru{C(NHCH2C„CH)-
CH‚CPh2}(CO)(PMeiPr2)]+ in compound 3. Selected bond distances
˚
(A) and angles (ꢁ): Ru1–P1 2.346(1); Ru1–C29 1.853(5); Ru1–C11
2.020(4); C11–C12 1.472(6); C12–C13 1.345(6); N1–C11 1.329(5); N1–
C26 1.469(6); C13–C14 1.481(7); C13–C20 1.484(6); Ru1–C11–N1
120.1(3); N1–C11–C12 112.5(4); C11–C12–C13 132.9(4); Ru1–C11–
C12 127.3(3); C12–C13–C14 122.9(4); C12–C13–C20 199.5(4); C11–
N1–C26 127.5(4); C11–Ru1–P1 97.7(1).
Fig. 3. VT 31P{1H} NMR spectra of compound
3 in CD2Cl2
(temperature range 193–293 K) and in C2D2Cl4 (temperature range
303–333 K).

´
M. Jimenez-Tenorio et al. / Journal of Organometallic Chemistry 689 (2004) 2776–2785
2782
atives than vinylaminocarbenes. The 31P{1H} NMR
spectra of these compounds display broad resonances
at 25 ꢁC (Fig. 3).
temperature it was possible to determine the values of
the equilibrium constant for compound 3. Fig. 5 shows
a plot of lnKeq versus 1/T for this equilibrium.
The difference in energy DH0 between the two iso-
mers, calculated from the slope of the least-square best
fit line to these data, is of the order of only 1 0.1 kcal
molꢂ1, whereas the activation energy barrier DG„ has
been estimated to be ca. 13 kcal molꢂ1. The latter value
was derived from the separation dm of the exchanging
resonances in the slow-exchanging NMR spectrum,
and the observed coalescence temperature Tc for each
set of resonances, using the following approximate
equation [31]:
As the temperature is lowered, the broad resonances
decoalesce to two peaks, which get progressively sharp-
er. If the temperature is raised, the original spectra are
restored, and at higher temperatures the broad features
give rise to one single resonance. A similar behaviour
is observed in the 1H NMR spectra of these com-
pounds (Fig. 4), which clearly indicate the occurrence
of an equilibrium between two rapidly interconverting
species.
We have interpreted this behaviour in terms of the re-
stricted rotation around the C–N bond which originates
two possible diastereoisomers for complexes 3 and 4.
¼
DG ¼ RTc½22:96 þ lnðTc=ð2:2dmÞÞꢁ:
Complex 1 reacts with tertiary phosphines such as
PMe3 or PMeiPr yielding allenylphosphonio deriva-
tives ½CpꢀRufCðPR3Þ@C@CPh2gðCOÞðPMeiPr2Þꢁ½BAr04ꢁ
(PR3 =PMe3 (6), PMeiPr2 (7)). These compounds result
apparently from the attack of the phosphine at the Ca
atom of the allenylidene group [7,13]. However, its has
been observed that the reaction of 1 with one equivalent
of PMe3 at room temperature affords one mixture con-
taining the allenylphosphonio derivative 6 plus another
species, identified as the alkynylphosphonio complex
½CpꢀRuðCBCCðPMe3ÞPh2ÞðCOÞðPMeiPr2Þꢁ½BAr04ꢁ [32].
The latter results from the addition of the PMe3 at the
Cc of the allenylidene, as we have previously observed
+
+
H
N
R
N
Ru
Ru
R
C
Pri2MeP
H
C
Pri2MeP
OC
OC
Ph
Ph
Ph
Ph
i
This also holds in case of 5, since the two Pr groups
attached to the nitrogen atom are not equivalent and un-
dergo rapid exchange in the NMR timescale. By integra-
tion of the H NMR resonances corresponding to the
protons of each of the species in equilibrium at each
1
*
in the complex [Cp Ru(C„CC(PEt3)Me2)(PEt3)2]-
[BPh4] [33]. However, when the mixture is heated up
to 60 ꢁC for 6 h, the alkynylphosphonio disappears,
and only the allenylphosphonio 6 remains. This suggests
that the product resulting from the attack of the phos-
phine at Cc is kinetic, and that the thermodynamically
stable final product is always the allenylphosphonio de-
rivative. Furthermore, it has been reported that the
complex [(g5-Indenyl)Ru{C„CC(PMe3)Ph2}(dppm)]
[PF6] (dppm=1,1-bis(diphenylphosphino)methane) un-
dergoes an isomerization process to yield the thermody-
namically more stable allenylphosphonio complex
[(g5-Indenyl)Ru{C(PMe3)‚C‚CPh2}(dppm)][PF6] [34].
1
0.8
0.6
0.4
0.2
0
0.0035
0.004
0.0045
0.005
0.0055
1/T
Fig. 4. VT 1H NMR spectra of compound 3 in CD2Cl2 (temperature
range 193–293 K) and in C2D2Cl4 (temperature range 303–333 K).
Fig. 5. Plot of lnKeq vs. 1/T (Kꢂl) for the equilibrium in solution
between the two isomers of compound 3.

´
M. Jimenez-Tenorio et al. / Journal of Organometallic Chemistry 689 (2004) 2776–2785
2783
The structure is comparable to that of the allenyl-
phosphonio derivative [CpRu{C(PHPh2)CH‚CPh2}-
(CO)(PiPr3)]+ [13]. The Ru1–C12 separation of
+
+
+
Ph
PMe
3
+
Ru
Ru
C
3
Ph
C
Ru
i
C
i
Pr MeP
Pr MeP
2
PMe
2
Ph
i
C
C
3
C
Pr MeP
˚
2
OC
2.168(5) A suggests a single Ru–C bond, as expected,
whereas the C12–C13–C14 angle of 176.9(5)ꢁ indicates
the linearity of the allenyl moiety.
C
OC
Ph
OC
PMe
Ph
Ph
60˚C, 6 h
+
The addition of propanethiol to the Ca–Cb bond
of the allenylidene ligand in 7 yields formally the thio-
carbene complex ½CpꢀRufCðSn PrÞCH@CPh2gðCOÞ
ðPMeiPr2Þꢁ½BAr04ꢁ (8). This compound was structurally
characterized by single-crystal X-ray diffraction. An
Ph
+
C
3
Ph
Ru
C
i
Pr MeP
2
OC
PMe
As it has been previously observed for the alkynyl-
*
n
*
ORTEP view of the cation [Cp Ru{C(S Pr) CH‚
phosphonio complex [Cp Ru(C„CC(PEt3)Me2)(PEt3)]-
CPh2}(CO)(PMeiPr2)]+ is shown in Fig. 7, together with
a listing of selected bond lengths and angles.
[BPh4] [33], complex 7 is also formed as by-product in
many reactions involving the allenylidene complex 1,
as a degradation product. The 31P{1H} NMR spectra
of 6 and 7 display two singlet resonances, one for the
PMeiPr3 attached to ruthenium and another one for
the phosphine at the Ca. The fact that no resolved cou-
pling 3JPP is observed for these compounds is consistent
with the NMR spectral properties reported for related
compounds such as [CpRu{C(PR3)‚C‚CPh2}(CO)-
(PiPr3)][BF4] (PR3 =PHPh2, PMePh2, PPh3) [13]. The
resonances for the Ca atoms appear as doublets in the
13C{1H}NMR spectra of these complexes at 102.28
and 101.01 ppm for 6 and 7, respectively, whereas the
resonances of the Cb and Cc atoms of the allenyl chain
appear at lower fields. The crystal structure of com-
pound 7 was determined. An ORTEP view of the cation
˚
The Ru1–C11 bond length has a value of 2.065(7) A,
much longer than the separations of 1.829(3) and
˚
1.837(4) A found, respectively, for [Ru‚CHSPhCl2
(PCy3)2] [a] and [Ru‚CHSPhCl2(PiPr3)2] [b], but of
the same order than the Ru–C bond distances found
in the azaallenyl and azoniabutadienyl complexes 2–5
reported in this work. The Ru1–S1 bond length of
˚
1.657(6) A is shorter than the analogous separation in
i
˚
[Ru‚CHSPhCl2(P Pr3)2] (1.706(4) A) [b], and in general
˚
shorter than a standard C–S single bond (1.75–1.79 A).
As it happens with the vinylaminocarbenes, we can con-
sider the following main resonance structures for a
vinylthiocarbene:
i
i
+
*
[Cp Ru{C(PMe Pr2)CH‚CPh2}(CO)(PMe Pr2)]
is
S
R
S
R
S
R
shown in Fig. 6, together with a listing of selected bond
lengths and angles.
[Ru]
[Ru]
[Ru]
Ph
Ph
Ph
Ph
Ph
Ph
A
B
C
*
Fig.
6. ORTEP
diagram
of
the
cation
[Cp Ru{C(P-
*
MeiPr2)‚C‚CPh2}(CO)(PMeiPr2)]+ in compound 7. Selected bond
distances (A) and angles (ꢁ): Ru1–P2 2.227(1); Ru1–C11 1.844(6);
Fig. 7. ORTEP diagram of cation [Cp Ru{C(SCH2CH2CH3)-
CH‚CPh2}(CO)(PMeiPr2)]+ in compound 8. Selected bond distances
˚
˚
(A) and angles (ꢁ): Ru1–P1 2.336(2); Ru1–C29 1.794(8); Ru1–C11
Ru1–C12 2.168(5); C12–C13 1.306(7); C13–C14 1.333(7); C12–P1
1.803(5); Ru1–C12–P1 118.8(2); C12–Ru1–P2 89.7(1); C12–C13–C14
176.9(5); Ru1–C12–C13 128.5(4); C11–Ru1–C12 97.7(2); C11–Ru1–P2
91.9(2).
2.065(7); C11–S1 1.657(6); C11–C12 1.444(8); C12–C13 1.332(8); Ru1–
C11–C12 126.1(4); Ru1–C11–S1 120.5(4); C11–C12–C13 129.1(6);
C12–C11–S1 113.4(5); C11–Ru1–P1 90.4(2); C11–S1–C26 112.2(3).

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M. Jimenez-Tenorio et al. / Journal of Organometallic Chemistry 689 (2004) 2776–2785
2784
The observed sequence of bond lengths suggests
Appendix A. Supplementary material
that the contribution of the structure B is more im-
portant, and hence complex 8 can be better considered
as a g1-thiabutadienyl rather than a thiocarbene. The
resonance for the Ca atom appears as one broad sig-
nal at 309.70 ppm in the 13C{1H}NMR spectrum,
shifted to lower fields with respect to the position of
the resonances for the Ca atoms in the azoniabuta-
dienyl complexes 2–5, which appear in the range
246–255 ppm.
Supplementary data associated with this article can
be found, in the online version, at doi:10.1016/j.jorgan-
chem.2004.06.002.
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4. Conclusion
The allenylidene0 complex ½CpꢀRu@C@C@CPh2
ðCOÞðPMeiPr2Þꢁ½BAr4ꢁ undergoes nucleophilic addition
reactions which take place at the Ca atom of the al-
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complexes. The activation energy barrier has been es-
timated to be ca. 13 kcal molꢂ1 in the case R=H,
R0 =CH2C„CH, the difference in energy between the
stereoisomers being only 1 kcal molꢂ1. The addition
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´
[12] M.A. Esteruelas, A.V. Gomez, A.M. Lopez, E. On˜ate, N. Ruız,
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derivatives
½BAr04ꢁ, whereas the reaction with propanethiol yields
½CpꢀRufCðPR3ÞC@CPh2ðCOÞðPMeiPr2Þꢁ
´ ´
[17] M.A. Esteruelas, A.V. Gomez, A.M. Lopez, J. Modrego, E.
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the
thiocarbene
½CpꢀRufCðSn PrÞCH@CPh2ðCOÞ
ðPMeiPr2Þꢁ½BAr04ꢁ which is better considered as a
thiabutadienyl complex as inferred from its X-ray
crystal structure analysis. In summary, despite of the
well-known differences between systems bearing Cp
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¨
*
or Cp ligands, in this particular case the reactivity
*
Commun. (1998) 1315.
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of
the
complex
[Cp Ru‚C‚C‚CPh2(CO)
(PMeiPr2)]+ towards nucleophiles parallels in general
terms that of the related CpRu system [CpRu‚
C‚C‚CPh2(CO)(PiPr3)]+ [8–17,29].
(b) P. Gonzalez-Herrero, B. Weberndorfer, K. Ilg, J. Wolf, H.
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Acknowledgements
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´
We thank the Ministerio de Ciencia y Tecnologıa
(DGICYT, Project BQU2001 – 4026 and Grant
BES2002-1422 to M. Dolores Palacios) and the Conse-
´
´
´
jerıa de Educacion y Ciencia de la Junta de Andalucıa
(P.A.I. research group FQM188) for financial support,
and Johnson Matthey plc for generous loans of ruthe-
nium trichloride.
(b) R. Aummann, S. Althaus, C. Kruger, P. Betz, Chem. Ber. 122
¨
(1989) 357.
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.
31P{1H} NMR
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¨
5
5
(CDCl3) d 30.4 (d, JPP =4 Hz, PMe3), 48.3 (d, JPP =4 Hz,
PMeiPr2).