Reactions of Rh(SbPh3)3(CO)X (X=Cl, Br) with organic propargyl compounds. Synthesis, structure and reactivity of rhodiacyclopent-3-ene-2-one complexes

Article abstract of DOI:10.1016/S0022-328X(01)00879-8

The five-coordinate rhodium(I) stibine complexes Rh(SbPh₃)₃(CO)X (X=Cl (1), Br (2)) react with HCCCH₂Y (Y=Cl, Br, OTs, OBs) in CH₂Cl₂ at ambient temperature to afford the η¹-allenyl Rh(SbPh₃)₂(CO)X(Y)(η¹-CH=C=CH₂) (X=Cl, Y=OTs (3a), OBs (3b); X=Y=Br (3c)) and the rhodiacyclopent-3-ene-2-one Rh(SbPh₃)₃Cl(η²-C(O)CH=C(Cl)CH₂) (5a) and Rh(SbPh₃)₃Br(η²-C(O)CH=C(X or Y)CH₂) (X or Y=Cl (5b), Br (5c)) products. The corresponding reactions of Rh(SbPh₃)₃(CO)X with MeCCCH₂Y yield the η¹-propargyl Rh(SbPh₃)₂(CO)Cl(OTs)(η¹-CH ₂CCMe) (4) and the rhodiacyclic Rh(SbPh₃)₃(X or Y)(η²-C(O)C(Me)=C(Y or X)CH₂) (6) complexes. The rhodiacycles 5a and 5c were converted to the η¹-allenyls Rh(SbPh₃)₂(CO)Cl₂(η ¹-CH=C=CH₂) (3d) and 3c, respectively, upon heating at 60°C in THF, with the relative rates being 5c>5a. Treatment of 5a and 5b with one equivalent of AgOTf or AgOTs results in replacement of the halide bonded to Rh and formation of Rh(SbPh₃)₃(OTf)(η²-C(O)CH=C(Cl)CH ₂) (5d) and Rh(SbPh₃)₃(OTs)(η²-C(O)CH=C(Cl)CH ₂) (5e), respectively. The structure of 5d (as 5d·0.5C₇H₈) was determined by single-crystal X-ray diffraction analysis. Addition of two equivalents of AgOTf to 5a and 5b, or of one equivalent of AgOTf to 5d, leads to the replacement of the remaining halide to afford the η¹-allenyl Rh(SbPh₃)₂(CO)(OTf)₂(η ¹-CH=C=CH₂) (3e). The reverse of the 5a to 3e conversion can be effected with chloride and SbPh₃; however, without added SbPh₃, the reaction affords the substitution product 3d instead. Addition of excess pyridine or PPh₃ to 5a yields the substitution products Rh(SbPh₃)₂(py)Cl(η²-C(O)CH=C(Cl)CH ₂) (9) and five-coordinate, 16-electron Rh(PPh₃)₂Cl(η²-C(O)CH=C(Cl)CH₂) (7), respectively. A mechanism is proposed for the conversion of 1 and 2 to 5 and for the transformations between 5 and 3.

Full text of DOI:10.1016/S0022-328X(01)00879-8

Journal of Organometallic Chemistry 630 (2001) 44–56
www.elsevier.com/locate/jorganchem
Reactions of Rh(SbPh3)3(CO)X (X=Cl, Br) with organic
propargyl compounds. Synthesis, structure and reactivity of
rhodiacyclopent-3-ene-2-one complexes
Asgar Kayan 1, Judith C. Gallucci 2, Andrew Wojcicki *
Department of Chemistry, The Ohio State Uni6ersity, 100 West 18th A6enue, Columbus, OH 43210-1185, USA
Received 3 January 2001; received in revised form 8 March 2001; accepted 8 March 2001
Abstract
The five-coordinate rhodium(I) stibine complexes Rh(SbPh3)3(CO)X (X=Cl (1), Br (2)) react with HCꢀCCH2Y (Y=Cl, Br,
OTs, OBs) in CH2Cl2 at ambient temperature to afford the h1-allenyl Rh(SbPh3)2(CO)X(Y)(h1-CHꢁCꢁCH2) (X=Cl, Y=OTs
(3a), OBs (3b); X=Y=Br (3c)) and the rhodiacyclopent-3-ene-2-one Rh(SbPh3)3Cl(h2-C(O)CHꢁC(Cl)CH2) (5a) and
Rh(SbPh3)3Br(h2-C(O)CHꢁC(X or Y)CH2) (X or Y=Cl (5b), Br (5c)) products. The corresponding reactions of
Rh(SbPh3)3(CO)X with MeCꢀCCH2Y yield the h1-propargyl Rh(SbPh3)2(CO)Cl(OTs)(h1-CH2CꢀCMe) (4) and the rhodiacyclic
Rh(SbPh3)3(X or Y)(h2-C(O)C(Me)ꢁC(Y or X)CH2) (6) complexes. The rhodiacycles 5a and 5c were converted to the h1-allenyls
Rh(SbPh3)2(CO)Cl2(h1-CHꢁCꢁCH2) (3d) and 3c, respectively, upon heating at 60 °C in THF, with the relative rates being
5c\5a. Treatment of 5a and 5b with one equivalent of AgOTf or AgOTs results in replacement of the halide bonded to Rh and
formation of Rh(SbPh3)3(OTf)(h2-C(O)CHꢁC(Cl)CH2) (5d) and Rh(SbPh3)3(OTs)(h2-C(O)CHꢁC(Cl)CH2) (5e), respectively. The
structure of 5d (as 5d·0.5C7H8) was determined by single-crystal X-ray diffraction analysis. Addition of two equivalents of AgOTf
to 5a and 5b, or of one equivalent of AgOTf to 5d, leads to the replacement of the remaining halide to afford the h1-allenyl
Rh(SbPh3)2(CO)(OTf)2(h1-CHꢁCꢁCH2) (3e). The reverse of the 5a to 3e conversion can be effected with chloride and SbPh3;
however, without added SbPh3, the reaction affords the substitution product 3d instead. Addition of excess pyridine or PPh3 to
5a yields the substitution products Rh(SbPh3)2(py)Cl(h2-C(O)CHꢁC(Cl)CH2) (9) and five-coordinate, 16-electron Rh(PPh3)2Cl(h2-
C(O)CHꢁC(Cl)CH2) (7), respectively. A mechanism is proposed for the conversion of 1 and 2 to 5 and for the transformations
between 5 and 3. © 2001 Elsevier Science B.V. All rights reserved.
Keywords: Rhodium complexes; h1-Allenyl; h1-Propargyl; Rhodiacyclopent-3-ene-2-one; Cycloaddition; X-ray structure
1. Introduction
and allenyls [4–8]. The latter methodology has been
successfully employed in the preparation of appropriate
platinum(II), palladium(II), iridium(III) [4–7] and, to a
lesser extent, rhodium(III) [8] complexes.
Propargyl halides and tosylates react with transition
metal carbonyl anions to afford metal h1-propargyl and
h1-allenyl complexes [1–3]. They also undergo oxida-
tive addition to various d8 and d10 metal centers, espe-
cially those in phosphine complexes, to provide another
general synthetic route to organometallic propargyls
In order to further explore this chemistry of
rhodium, we undertook a study of reactions of rhodi-
um(I) complexes with propargyl halides and tosylates.
Since the only reported preparative reactions of rhodi-
um(I) with organic propargyls had utilized phosphine
complexes as starting materials [8], we decided to ex-
pand the range of ligands to include stibines. Metal
stibine complexes have not been much investigated in
oxidative addition reactions, even though they are read-
ily available for rhodium(I) [9]. For example, both
Rh(SbR3)2(CO)X and Rh(SbR3)3(CO)X (X=Cl, Br;
R=aryl) have been reported [10–15], with the latter
* Corresponding author. Tel.: +1-614-2924750; fax: +1-614-
2921685.
E-mail address: wojcicki.1@osu.edu (A. Wojcicki).
1 Present address: Kocaeli Universitesi, Fen.-Ed. Fak., Kimya
Bolumu, 41300 Izmit, Turkey.
2 To whom inquiries concerning the crystallographic studies should
be addressed.
0022-328X/01/$ - see front matter © 2001 Elsevier Science B.V. All rights reserved.
PII: S0022-328X(01)00879-8

A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
45
undergoing conversion to the former on repeated crys-
tallization [15]. Square-planar Rh(SbPh3)2(CO)Cl was
successfully used by Chin [16] in the synthesis of rhodi-
um(III) allyl complexes.
lization, which causes loss of SbPh3 and formation of
Rh(SbPh3)2(CO)Cl [15]. The analogous bromide
Rh(SbPh3)3(CO)Br (2) was obtained by reaction of 1
(1.2 g, 0.98 mmol) with LiBr (0.096 g, 1.1 mmol) in 30
ml of acetone at reflux temperature for 45 min, cooling
to r.t. and removal of the solvent. Extraction of the
solid residue with 40 ml of C6H6, filtration of the
mixture to remove LiCl and excess LiBr, and evapora-
tion to dryness of the filtrate yielded a red solid, which
was dried under reduced pressure for 2 days. The
product was characterized by comparison of its spectro-
scopic properties with those reported in the literature
for 2 [15].
In this paper, we report on reactions of
Rh(SbPh3)3(CO)X (X=Cl (1), Br (2)) with propargyl
halides and tosylates. Whereas reactions of 1 and 2 with
the tosylates generally give the expected rhodium(III)
h1-allenyl and h1-propargyl complexes, those with
propargyl halides surprisingly afford rhodiacyclopent-
3-ene-2-one products (I). Some h1-allenyl and rhodia-
cyclic complexes were found to interconvert under
appropriate experimental conditions. Part of this inves-
tigation was the subject of a preliminary communica-
tion [17].
2.3. Reactions of Rh(SbPh3)3(CO)X (X=Cl (1), Br
(2)) with organic propargyl compounds
2.3.1. Reaction of 1 with HCꢀCCH2OTs
A stirred red solution of 1 (0.31 g, 0.25 mmol) in 15
ml of CH2Cl2 at r.t. was treated with solid
HCꢀCCH2OTs (0.22 g, 1.1 mmol). The solution imme-
diately changed color to pale yellow and was stirred for
an additional 30 min. The volume was then reduced to
ca. 2 ml, and 25 ml of hexane was added to precipitate
a
yellow solid, Rh(SbPh3)2(CO)Cl(OTs)(h1-CHꢁCꢁ
2. Experimental
CH2) (3a). The product was collected by filtration,
washed with hexane (2×10 ml) and dried in vacuo for
2 days. Yield: 0.22 g (80%). IR (CHCl3, cm−1): w(CO)
2073. 1H-NMR (CDCl3): l 8.0–6.9 (m, 34H, Ph,
2.1. General procedures and measurements
C6H4), 5.71 (q, 1H, JHH=2JRhH=6.0 Hz, CH), 4.17
4
All reactions and manipulations of air-sensitive com-
pounds were carried out under an atmosphere of argon
by using standard procedures [18]. Solvents were dried,
distilled under argon and degassed before use. Hexane,
benzene, THF and Et2O were distilled from Na/K alloy
and benzophenone, and CH2Cl2 from P4O10. Elemental
analyses were performed by M-H-W Laboratories,
Phoenix, AZ. 1H-, 13C- and 31P-NMR spectra were
recorded on a Bruker AM-250, AC-300 and AC-200
spectrometers. IR spectra were obtained on a Perkin–
Elmer 1600 Fourier transform spectrometer. Mass spec-
tra (FAB) were recorded on a Kratos VG70-250S
spectrometer by Mr David C. Chang. Conductance
measurements on ca. 1 mM solutions of rhodium com-
plexes in CH2Cl2 were carried out at room temperature
with a YSI Model 35 conductivity apparatus.
4
4
(dd, 2H, JHH=6.0 Hz, JRhH=1.3 Hz, CH2), 2.31 (s,
3H, Me). 13C{1H}-NMR (CDCl3): l 206.0 (s, ꢁCꢁ),
1
182.6 (d, JRhC=62.6 Hz, CO), 140.1–126.0 (m, Ph,
1
C6H4), 72.1 (s, CH2), 67.6 (d, JRhC=24.4 Hz, CH),
21.3 (s, Me). Anal. Found: C, 52.19; H, 3.76. Calc. for
C47H40ClO4RhSSb2: C, 52.14; H, 3.72%.
2.3.2. Reaction of 1 with HCꢀCCH2OBs
Reaction between
1 (0.20 g, 0.16 mmol) and
HCꢀCCH2OBs (0.12 g, 0.61 mmol) was conducted sim-
ilarly to that described above. Yield of Rh(SbPh3)2-
(CO)Cl(OBs)(h1-CH=C=CH2) (3b), a yellow solid:
0.146 g (84%). IR (CHCl3, cm−1): w(CO) 2078. 1H-
NMR (CDCl3): l 7.8–7.1 (m, 35H, Ph), 5.72 (q, 1H,
4JHH=2JRhH=6.0 Hz, CH), 4.19 (dd, 2H, JHH=6.0
4
Hz, JRhH=1.3 Hz, CH2). 13C{1H}-NMR (CDCl3): l
4
1
2.2. Materials
206.0 (s, ꢁCꢁ), 182.7 (d, JRhC=62.2 Hz, CO), 141.5–
1
126.6 (m, Ph), 72.3 (s, CH2), 67.6 (d, JRhC=24.4 Hz,
Reagents were obtained from various commercial
sources and used as received, except as noted below.
Procedures reported in the literature were used to syn-
thesize the organic propargyl compounds RCꢀCCH2-
OTs (Ts=p-MeC6H4SO2; R=H, Me) [19], HCꢀCCH2-
OBs (Bs=PhSO2) [19] and MeCꢀCCH2Cl [4]. The
complex Rh(SbPh3)3(CO)Cl (1) [11–15] was prepared
by the method of Vallarino [10], but without recrystal-
CH). FAB MS; m/z 1064 (M+−2), 910 (M++2−
OBs),
V
883
(M++2−OBs−CO).
\m=1.01
−1 cm2 mol−1. Anal. Found: C, 51.50; H, 3.80. Calc.
for C46H38ClO4RhSSb2: C, 51.70; H, 3.58%.
2.3.3. Reaction of 1 with MeCꢀCCH2OTs
Reaction between
1 (0.42 g, 0.34 mmol) and
MeCꢀCCH2OTs (0.10 g, 0.45 mmol) in CH2Cl2 (15 ml)

46
A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
was carried out similarly to the preceding reactions.
After 90 min of stirring at r.t., the reaction solution was
filtered through Celite, and the filtrate was concentrated
to ca. 1.5 ml. Addition of 20 ml of hexane to the filtrate
afforded a yellow solid, which was washed with hexane
(2×10 ml) and dried in vacuo. Yield: 0.29 g. The solid
was shown by NMR spectroscopy to be a mixture of
2.3.6. Reaction of 2 with HCꢀCCH2Cl
This reaction was conducted analogously to the im-
mediately preceding one. The IR and NMR spectra of
the product were identical with those of 5b obtained
from 1 and HCꢀCCH2Br.
2.3.7. Reaction of 2 with HCꢀCCH2Br
three
products:
Rh(SbPh3)2(CO)Cl(OTs)(h1-CH2-
Propargyl bromide (0.240 g, 2.03 mmol) was added
to a solution of 2 (0.31 g, 0.24 mmol) in 10 ml of
CH2Cl2 at r.t. The resulting solution was stirred for 1 h
and then treated the same as for the other reactions.
Yield: 0.25 g of a yellow solid, which was shown
CꢀCMe) (4), Rh(SbPh3)3Cl(h2-C(O)C(Me)ꢁ(OTs)CH2)
(6a) and Rh(SbPh3)3(OTs)(h2-C(O)C(Me)ꢁC(Cl)CH2)
(6b), in ca. 1:1:1 ratio, respectively. IR (CHCl3, cm−1):
1
w(CO) 2069 (4). H-NMR (CD2Cl2): l 7.8–6.8 (m, Ph,
C6H4), 4.09 (br s, CH2, 6b), 3.45 (br s, CH2, 6a), 2.84
(m, CH2, 4), 2.46 (s, OTs Me, 6b), 2.38 (s, OTs Me, 6a),
2.30 (s, OTs Me, 4), 1.48 (s, ꢁCMe, 6b), 1.11 (s, ꢁCMe,
spectroscopically to be
a
ca. 1:1 mixture of
Rh(SbPh3)3Br(h2-C(O)CHꢁC(Br)CH2)
(5c)
and
Rh(SbPh3)2(CO)Br2(h1-CHꢁCꢁCH2) (3c). IR (CHCl3,
5
6a), 1.04 (t, JHH=2.7 Hz, ꢀCMe, 4). 13C{1H}-NMR
cm−1): w(CO) 2066 (3c), w(C=O) 1596 (5c). H-NMR
1
1
(CDCl3): l 227.8 (d, JRhC=21.4 Hz, CꢁO, 6a), 220.5
3
1
1
(CDCl3): l 7.9–6.6 (m, Ph), 5.75 (d, JRhH=0.8 Hz,
(d, JRhC=24.5 Hz, CꢁO, 6b), 183.4 (d, JRhC=67.1
Hz, CO, 4), 173.8 (s, ꢁCOTs, 6a), 165.1 (s, ꢁCCl, 6b),
144.5 (s, ꢁCMe, 6b), 144.1 (s, ꢁCMe, 6a), 141.8–126.5
(m, Ph, C6H4), 89.6 (s, ꢀCMe, 4), 87.3 (s, ꢀCCH2, 4),
4
CH, 5c), 5.65 (q, JHH=2JRhH=5.9 Hz, CH, 3c), 3.91
4
4
(dd, JHH=5.9 Hz, JRhH=1.3 Hz, CH2, 3c), 3.88 (d,
2JRhH=1.2 Hz, CH2, 5c). 13C{1H}-NMR (CDCl3): l
1
1
29.8 (d, JRhC=19.6 Hz, CH2, 6b), 21.7 (s, OTs Me,
231.1 (d, JRhC=23.6 Hz, CꢁO, 5c), 206.2 (s, ꢁCꢁ, 3c),
1
182.8 (d, 1JRhC=62.4 Hz, CO, 5c), 161.3 (s, ꢁCBr),
6a,b), 21.4 (s, OTs Me, 4), 20.4 (d, JRhC=19.8 Hz,
2
CH2, 6a), 11.2 (s, ꢁCMe, 6b), 10.8 (s, ꢁCMe, 6a), 3.8 (s,
144.5 (d, JRhC=5.2 Hz, CH, 5c), 137.1–128.3 (m, Ph),
71.6 (d, JRhC=24.0 Hz, CH, 3c), 69.0 (s, CH2, 3c),
35.7 (d, JRhC=21.6 Hz, CH2, 5c).
1
1
ꢀCMe, 4), −5.4 (d, JRhC=19.8 Hz (CH2, 4). FAB
MS; m/z: 925 (M++2−OTs) (4).
1
2.3.4. Reaction of 1 with HCꢀCCH2Cl
2.3.8. Reaction of 1 with MeCꢀCCH2Cl
A solution of 1 (0.20 g, 0.16 mmol) in 10 ml of
CH2Cl2 was treated with HCꢀCCH2Cl (0.101 g, 1.35
mmol), and the mixture was stirred at r.t. for 1 h.
Work-up was as described for the initial reaction in this
section. Yield of Rh(SbPh3)3Cl(h2-C(O)CHꢁC(Cl)CH2)
(5a), a green solid: 0.166 g (78%). IR (CHCl3, cm−1):
Reaction of 1 (1.0 g, 0.82 mmol) with MeCꢀCCH2Cl
(0.41 g, 4.6 mmol) was carried out similarly to the
preceding reactions and utilized the same work-up.
Yield, 1.0 g (93%) of a beige solid, Rh(SbPh3)3Cl(h2-
C(O)C(Me)ꢁC(Cl)CH2) (6c). IR (Nujol, cm−1): w(C=
1
1
O) 1600. H-NMR (CDCl3): l 7.4–6.9 (m, 45H, Ph),
w(CꢁO) 1596. H-NMR (CDCl3): l 7.4–6.9 (m, 45H,
3.78 (br s, 2H, CH2), 1.31 (br s, 3H, Me). 13C{1H}-
Ph), 5.64 (s, 1H, CH), 3.71 (s, 2H, CH2). 13C{1H}-
NMR (CDCl3): l 230.0 (d, 1JRhC=23.1 Hz, CꢁO),
170.2 (s, ꢁCCl), 140.4 (s, CH), 136.7–128.3 (m, Ph),
32.4 (d, 1JRhC=21.4 Hz, CH2). FAB MS: m/z: 911
NMR (CDCl3): l 163.4 (s, ꢁCCl), 146.4 (s, CMe),
1
136.7–128.2 (m, Ph), 30.4 (d, JRhC=22.9 Hz, CH2),
12.9 (s, Me) (CꢁO signal was not observed because of
low solubility of 6c). FAB MS; m/z: 925 (M++2−
Cl−SbPh3). Anal. Found: C, 54.07; H, 4.02. Calc. for
C59H50Cl2ORhSb3: C, 53.93; H, 3.84%.
(M++2−Cl−SbPh3). \m=0.07
V .
−1 cm2 mol−1
Anal. Found: C, 53.58; H, 3.92. Calc. for
C58H48Cl2ORhSb3: C, 53.58; H, 3.72%.
2.3.5. Reaction of 1 with HCꢀCCH2Br
2.3.9. Reaction of 2 with MeCꢀCCH2OTs
A similarly conducted reaction between 1 (0.22 g,
0.18 mmol) and HCꢀCCH2Br (0.160 g, 1.35 mmol)
yielded 0.183 g (76%) of yellow Rh(SbPh3)3Br(h2-
C(O)CHꢁC(Cl)CH2) (5b) after work-up. IR (CHCl3,
Reaction of
2
(0.365 g, 0.287 mmol) with
MeCꢀCCH2OTs (0.10 g, 0.45 mmol), conducted simi-
larly to the other reactions, yielded 0.275 g (64%) of
Rh(SbPh3)3Br(h2-C(O)C(Me)ꢁC(OTs)CH2) (6d) as a
pale orange solid. 1H-NMR (CDCl3): l 7.8–6.9 (m,
49H, Ph, C6H4), 3.49 (d, 2JRhH=1.9 Hz, 2H, CH2),
2.37 (s, 3H, OTs Me), 1.28 (s, 3H, ꢁCMe). 13C{1H}-
NMR (CDCl3): l 228.1 (d, 1JRhC=25.0 Hz, CꢁO),
174.2 (s, ꢁCOTs), 144.1 (s,ꢁCMe), 140.6–127.3 (m, Ph,
C6H4), 21.6 (s, OTs Me), 20.3 (d, 1JRhC=21.7 Hz,
CH2), 10.8 (s, ꢁCMe).
1
cm−1): w(C=O) 1599. H-NMR (CDCl3): l 7.4–6.9
(m, 45H, Ph), 5.65 (s, 1H, CH), 3.68 (s, 2H, CH2).
1
13C{1H}-NMR (CDCl3): l 230.4 (d, JRhC=23.2 Hz,
CꢁO), 170.8 (s, ꢁCCl), 140.6 (s, CH), 136.7–128.3 (m,
Ph), 32.3 (d, 1JRhC=21.5 Hz, CH2). FAB MS; m/z: 911
(M++2−Br−SbPh3). \m=0.068 V−1 cm2 mol−1
.
Anal. Found: C, 51.94; H, 3.49. Calc. for
C58H48BrClORhSb3: C, 51.81; H, 3.60%.

A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
47
2.5.2. Reaction of Rh(SbPh3)3Br(p2-C(O)CHꢁ
C(Cl)CH2) (5b) with sil6er triflate
2.4. Thermolysis of rhodiacyclic complexes 5
Reaction between 5b (0.15 g, 0.11 mmol) and AgOTf
(0.029 g, 0.11 mmol, one equivalent) was conducted
very similarly to that between 5a and AgOTf. The
precipitated AgBr was qualitatively analyzed for bro-
mide by treatment with nitric acid, 1,2-dichloroethane
and 3% H2O2 to afford bromine in the organic layer.
The product Rh(SbPh3)3(OTf)(h2-C(O)CHꢁC(Cl)CH2)
(5d) was isolated in 95% yield (0.15 g) and characterized
by comparison of its spectroscopic properties with
those of the 5d obtained from the immediately preced-
ing reaction.
2.4.1. Thermolysis of
Rh(SbPh3)3Br(p2-C(O)CHꢁC(Br)CH2) (5c)
A
mixture of 5c and Rh(SbPh3)2(CO)Br2(h1-
CHꢁCꢁCH2) (3c) (0.250 g), obtained from 2 and
HCꢀCCH2Br (vide supra), was dissolved in 10 ml of
THF, and the resulting solution was stirred at 60 °C
for 1 h. After cooling to r.t. and concentration of the
solution to ca. 2 ml, hexane (20 ml) was added to
induce the precipitation of an orange solid. The solid
was washed with 10 ml of hexane and dried in vacuo
1
for 2 days. The IR and H-NMR spectra showed the
presence of pure 3c.
2.5.3. Reaction of Rh(SbPh3)3(OTf )(p2-C(O)CHꢁ
C(Cl)CH2) (5d) with sil6er triflate
A solution containing 5d (0.297 g, 0.210 mmol) and
AgOTf (0.055 g, 0.21 mmol, one equivalent) in 10 ml of
CH2Cl2 was stirred at r.t. for 75 min, filtered, concen-
trated and treated with 20 ml of hexane. The precipi-
tated green solid was filtered off, washed with hexane
2.4.2. Thermolysis of
Rh(SbPh3)3Cl(p2-C(O)CHꢁC(Cl)CH2) (5a)
A solution of 5a (0.22 g, 0.17 mmol) in 15 ml of THF
was maintained at 60 °C with stirring for 16 h. The
work-up was identical with that in the immediately
preceding experiment and resulted in the isolation of a
(10
ml)
and
dried
in
vacuo.
Yield
of
1
yellow solid. A H-NMR spectrum of this solid showed
Rh(SbPh3)2(CO)(OTf)2(h1-CHꢁCꢁCH2) (3e), 0.212 g
ca. 3:1 mixture of 5a and Rh(SbPh3)2(CO)Cl2(h1-
CHꢁCꢁCH2) (3d). The solid was then extracted with a
mixture of methanol (2 ml) and Et2O (3 ml), and a
green residue (pure 5a) was removed by filtration. The
filtrate was evaporated to dryness to leave a yellow
solid, 3d. Yield: 0.048 g (30%). IR (CD2Cl2, cm−1):
(86%). IR (CHCl3, cm−1): w(CO) 2080, w(CꢁCꢁC)
1
2012. H-NMR (CDCl3): l 7.8–6.9 (m, 30H, Ph), 5.70
(q, 1H, 4JHH=2JRhH=5.8 Hz, CH), 4.38 (d, 2H,
4JHH=5.8 Hz, CH2). 13C{1H}-NMR (CDCl3): l 207.2
1
(s, ꢁCꢁ), 179.5 (d, JRhC=68.5 Hz, CO), 136.7–126.0
(m, Ph), 76.9 (s, CH2), 71.4 (d, JRhC=24.6 Hz, CH).
1
1
w(CO) 2066. H-NMR (CD2Cl2): l 7.7–7.0 (m, 30H,
3e was also obtained, in comparable yield, directly
from either Rh(SbPh3)3Cl(h2-C(O)CHꢁC(Cl)CH2) (5a)
or Rh(SbPh3)3Br(h2-C(O)CHꢁC(Cl)CH2) (5b) by reac-
tion with two equivalents of AgOTf in CH2Cl2 at r.t.
The experimental procedures were very similar to those
of the two immediately preceding reactions.
4
Ph), 5.49 (q, 1H, JHH=2JRhH=5.9 Hz, CH), 3.95 (dd,
4
4
2H, JHH=5.9 Hz, JRhH=1.2 Hz, CH2).
2.5. Reactions of rhodiacyclic complexes 5 with
sil6er(I) salts
2.5.1. Reaction of Rh(SbPh3)3Cl(p2-C(O)CHꢁ
C(Cl)CH2) (5a) with sil6er triflate
2.5.4. Reaction of Rh(SbPh3)3Br(p2-C(O)CHꢁ
C(Cl)CH2) (5b) with sil6er tosylate
Silver triflate (AgOTf, Tf=CF3SO2; 0.037 g, 0.14
mmol, one equivalent) was added to a solution of 5a
(0.18 g, 0.14 mmol) in 10 ml of CH2Cl2, and the
mixture was stirred at r.t. for 75 min. AgCl was filtered
off, the filtrate was concentrated to ca. 5 ml, and 5 ml
of hexane was added with stirring. The resulting mix-
ture was filtered again, and the filtrate was evaporated
to dryness. Crystallization of the residue from CH2Cl2–
hexane afforded a green solid (0.19 g, 97% yield),
Rh(SbPh3)3(OTf)(h2-C(O)CHꢁC(Cl)CH2) (5d), which
was dried in vacuo for 2 days. IR (CHCl3, cm−1):
Silver tosylate (0.028 g, 0.10 mmol, one equivalent)
was added to a solution of 5b (0.135 g, 0.10 mmol) in
10 ml of CH2Cl2, and the mixture was stirred at r.t. for
90 min. The solution was then filtered to remove AgBr,
which was qualitatively analyzed for bromide by oxida-
tion to bromine with H2O2–HNO3 in the presence of
1,2-dichloroethane (vide supra). The filtrate was con-
centrated to ca. 5 ml, and 5 ml of hexane was added.
After another filtration, the solvent was evaporated
from the filtrate, and the solid residue was dried in
vacuo. Yield of pale green Rh(SbPh3)3(OTs)(h2-
C(O)CHꢁC(Cl)CH2) (5e): 0.14 g (97%). IR (CHCl3,
1
w(CꢁO) 1613. H-NMR (CDCl3): l 7.3–6.9 (m, 45H,
Ph), 5.82 (s, 1H, CH), 3.93 (s, 2H, CH2). 13C{1H}-
NMR (CDCl3): l 217.7 (d, 1JRhC=22.7 Hz, CꢁO),
172.3 (s, ꢁCCl), 137.6 (s, CH), 136.6–128.2 (m, Ph),
1
cm−1): w(CꢁO) 1607. H-NMR (CDCl3): l 7.8–6.7 (m,
49H, Ph, C6H4), 5.82 (s, 1H, CH), 4.13 (s, 2H, CH2),
2.44 (s, 3H, Me). 13C{1H}-NMR (CDCl3): l 222.7 (d,
1JRhC=22.2 Hz, CꢁO), 172.5 (s, ꢁCCl), 139.5 (s, CH),
32.1
−1 cm2 mol−1. Anal. Found: C, 50.62; H, 3.70. Calc.
for C59H48ClF3O4RhSSb3: C, 50.13; H, 3.42%.
(d,
1JRhC=22.4
Hz,
CH2).
\m=5.13
1
V
141.7–126.6 (m, Ph, C6H4), 31.9 (d, JRhC=21.3 Hz,
CH2), 21.4 (s, Me). \m=0.61 V−1 cm2 mol−1. Anal.

48
A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
Found: C, 54.96; H, 3.99. Calc. for C65H55ClO4RhSSb3:
C, 54.37; H, 3.86%.
solid was filtered off, washed with 5 ml of hexane and
dried in vacuo. Yield, 0.10 g (68%) of Rh(SbPh3)3Br(h2-
C(O)C(Me)ꢁC(Cl)CH2) (6e). IR (CHCl3, cm−1):
1
w(CꢁO) 1586. H-NMR (CDCl3): l 7.5–6.9 (m, 45H,
2.6. Reactions of rhodium complexes 3 and 5 with
chloride salts
Ph), 3.77 (s, 2H, CH2), 1.32 (s, 3H, Me). 13C{1H}-NMR
1
(CDCl3): l 228.9 (d, JRhC=26.4 Hz, CꢁO), 163.9 (s,
ꢁCCl), 146.5 (s, ꢁCMe), 136.9–128.2 (m, Ph), 30.3 (d,
2.6.1. Reaction of Rh(SbPh3)2(CO)(OTf )2-
1JRhC=21.1 Hz, CH2), 12.9 (s, Me).
(p1-CHꢁCꢁCH2) (3e) with [(n-Bu)4N]Cl
A solution of 3e (0.20 g, 0.17 mmol) and [(n-
Bu)4N]Cl (0.096 g, 0.34 mmol, two equivalents) in 10
ml of CH2Cl2 was stirred at r.t. for 4 h. The solvent was
then evaporated, and the solid residue was extracted
with cold methanol (3×3 ml). The extracts containing
[(n-Bu)4N]OTf were separated from the solid by decan-
tation and discarded. The remaining solid was dissolved
in 3 ml of Et2O, and the solution was filtered. The
filtrate was evaporated to dryness under reduced pres-
sure to leave a yellow solid (0.064 g, 40% yield), which
2.7. Reactions of rhodiacyclic complexes 5 and 6 with
triphenylphosphine
2.7.1. Reaction of Rh(SbPh3)3Cl(p2-C(O)CHꢁ
C(Cl)CH2) (5a) with PPh3
A solution of 5a (0.42 g, 0.32 mmol) and PPh3 (0.25
g, 0.96 mmol) in 15 ml of CH2Cl2 was stirred at r.t. for
3 h and then concentrated to 3 ml under reduced
pressure. Addition of 20 ml of hexane induced the
1
precipitation of
a
green solid, Rh(PPh3)2Cl(h2-
was dried in vacuo. Its IR and H-NMR spectra were
C(O)CHꢁC(Cl)CH2) (7), which was collected on a filter
frit, washed with hexane (2×15 ml) and dried in
vacuo. Yield: 0.18 g (75%). IR (CHCl3, cm−1): w(CꢁO)
identical with those of the Rh(SbPh3)2(CO)Cl2(h1-
CHꢁCꢁCH2) (3d) obtained by thermolysis of
Rh(SbPh3)3Cl(h2-C(O)CHꢁC(Cl)CH2) (5a).
1
1648. H-NMR (CDCl3): l 7.5–7.2 (m, 30H, Ph), 4.84
(s, 1H, CH), 2.64 (m, 2H, CH2). 31P{1H}-NMR
2.6.2. Reaction of Rh(SbPh3)2(CO)(OTf )2-
1
(CDCl3): l 29.56 (d, JRhP=123.8 Hz). FAB MS; m/z:
(p1-CHꢁCꢁCH2) (3e) with [(n-Bu)4N]Cl and SbPh3
A solution containing 3e (0.20 g, 0.17 mmol), [(n-
Bu)4N]Cl (0.096 g, 0.34 mmol, two equivalents) and
SbPh3 (0.060 g, 0.17 mmol) in 10 ml of CH2Cl2 was
stirred at r.t. for 4 h and then evaporated to dryness.
The residue was extracted with MeOH (3×3 ml), and
the mixture was filtered. The extracts were discarded,
and the remaining solid was recrystallized from
CH2Cl2–hexane and dried in vacuo. Yield: 0.15 g (68%)
of Rh(SbPh3)3Cl(h2-C(O)CHꢁC(Cl)CH2) (5a). The
product was characterized by the comparison of its
spectroscopic properties with those of an authentic 5a.
729 (M+−Cl), 701 (M+−Cl−CO), 662 (M+−Cl−
C4H3O), 627 (M+−2Cl−C4H3O). Anal. Found: C,
62.58; H, 4.50. Calc. for C40H33Cl2OP2Rh: C, 62.76; H,
4.35%.
2.7.2. Reaction of Rh(SbPh3)3Cl(p2-C(O)C(Me)ꢁ
C(Cl)CH2) (6c) with PPh3
The procedure employed was very similar to that for
the immediately preceding reaction. By using 0.20 g
(0.15 mmol) of 6c and 0.11 g (0.42 mmol) of PPh3,
0.087 g (73% yield) of a beige solid, Rh(PPh3)2Cl(h2-
C(O)C(Me)ꢁC(Cl)CH2) (8), was obtained after recrys-
tallization from CH2Cl2–hexane. IR (CHCl3, cm−1):
2.6.3. Reaction of Rh(SbPh3)3(OTf )(p2-C(O)-
CHꢁC(Cl)CH2) (5d) with [(n-Bu)4N]Cl
1
w(CꢁO) 1631. H-NMR (CDCl3): l 7.7–7.3 (m, 30H,
Ph), 2.81 (br s, 2H, CH2), 0.85 (s, 3H, Me). 31P{1H}-
NMR (CDCl3): l 29.12 (d, 1JRhP=124.2 Hz). FAB
MS; m/z: 743 (M+−Cl), 662 (M+−Cl−C5H5O), 627
(M+−2Cl−C5H5O).
Reaction between 5d (0.235 g, 0.166 mmol) and
[(n-Bu)4N]Cl (0.047 g, 0.17 mmol, one equivalent) was
conducted similarly to the immediately preceding reac-
tion. The solid product was recrystallized from
CH2Cl2–hexane to afford 0.098 g (45% yield) of
Rh(SbPh3)3Cl(h2-C(O)CHꢁC(Cl)CH2) (5a), which was
2.8. Reaction of Rh(SbPh3)3Cl(p2-C(O)CHꢁC(Cl)CH2)
(5a) with pyridine
1
characterized by comparison of its IR and H-NMR
spectra with those of the 5a obtained from 1 and
propargyl chloride.
Pyridine (0.073 g, 0.93 mmol) was added to a solu-
tion of 5a (0.20 g, 0.15 mmol) in 10 ml of CH2Cl2, and
the resulting solution was stirred at r.t. for 30 min and
then concentrated to ca. 1.5 ml under reduced pressure.
Addition of hexane (20 ml) induced the precipitation of
a light green solid, which was collected on a filter frit
and washed with hexane (2×5 ml). After recrystalliza-
tion from CH2Cl2–hexane, the product was dried in
vacuo. Yield: 0.12 g, (76%) of Rh(SbPh3)2(py)Cl(h2-
C(O)CHꢁC(Cl)CH2) (9). IR (CHCl3, cm−1): w(CꢁO)
2.6.4. Reaction of Rh(SbPh3)3Br(p2-C(O)C(Me)ꢁ
C(OTs)CH2) (6d) with [(n-Bu)4N]Cl
A solution of 6d (0.163 g, 0.109 mmol) and [(n-
Bu)4N]Cl (0.031 g, 0.11 mmol, one equivalent) in 10 ml
of CH2Cl2 was stirred at r.t. for 4 h. It was then filtered,
the filtrate was concentrated to ca. 1.5 ml, and a pale
orange solid was precipitated with 10 ml of MeOH. The

A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
49
1606. 1H-NMR (CDCl3): l 9.1–8.9, 7.7–7.0 (dd, m,
35H, py, Ph), 5.69 (s, 1H, CH), 3.56 (d, 2JHH=17.4 Hz,
1H of CH2), 2.77 (d, 2JHH=17.4 Hz, 1H of CH2).
„ scan absorption correction [21] was applied to the
data with transmission factors of 0.899–1.0. The data
set was truncated at 45° in 2q because of two factors:
the non-uniform decay of the standards mentioned
above and the fact that reflections in the 45–50° shell
were very weak.
The structure was solved by starting with the direct
methods procedure in SHELXS-86 [22] and then using
several cycles of structure factor/Fourier calculations to
elucidate the whole molecule. Full-matrix least-squares
refinements based on F2 were performed in SHELXL-93
[23]. There is also a molecule of toluene in the asym-
metric unit, which appears to be disordered. The phenyl
ring portion of the toluene was modeled as a rigid
group and the occupancy factor for this molecule was
set to 0.5. The Rh complex was refined anisotropically
and the toluene molecule was refined isotropically. The
hydrogen atoms were included in the model at calcu-
1
13C{1H}-NMR (CDCl3): l 234.4 (d, JRhC=26.6 Hz,
CꢁO), 170.2 (s, ꢁCCl), 153.9–151.7 (2s, py), 137.6–
1
124.1 (m, Ph, py), 28.1 (d, JRhC=24.2 Hz, CH2) (CH
signal was not identified). FAB MS; m/z: 911 (M++
2−Cl−py). Anal. Found: C, 51.98; H, 4.02. Calc. for
C45H38Cl2NORhSb2: C, 52.67; H, 3.73%.
2.9. Crystallographic analysis of Rh(SbPh3)3-
(OTf )(p2-C(O)CHꢁC(Cl)CH2)·0.5C7H8 (5d·0.5C7H8)
Crystals of 5d·0.5C7H8 were grown by slow diffusion
of hexane into a solution of 5d in toluene. The crystal
used for data collection was a rectangular rod in shape.
Examination of the diffraction pattern on a Rigaku
AFC5S diffractometer indicated a monoclinic crystal
system. Based on the systematic absences, 0k0, k"2n,
and h0l, h+l"2n, the space group was uniquely deter-
mined as P21/n. Unit cell constants were obtained by a
least-squares fit of the setting angles for 25 reflections in
the 2q range 21–30° with Mo–Ka radiation (u(Ka1)=
,
lated positions with CꢂH=0.98 A and fixed. The final
refinement cycle was based on the 6923 intensities with
I\0 and 666 variables and resulted in agreement fac-
tors of R1=0.053 and wR2=0.140 for the 4989 reflec-
tions with I\2|(I). The final difference electron
density map contains maximum and minimum peak
,
0.70930 A). Six standard reflections were measured
heights of 0.96 and −0.75 e A−3. Neutral atom scat-
,
during data collection and showed a non-uniform de-
crease in intensity, especially above 2q of 45°. Data
reduction was done with the TEXSAN package [20]. No
decay correction was applied to the data. An empirical
tering factors were used and include terms for anoma-
lous dispersion [24]. A summary of the crystal data and
the details of the intensity data collection and refine-
ment are provided in Table 1.
Table 1
Crystal data and structure refinement parameters for 5d·0.5C7H8
3. Results and discussion
Empirical formula
Formula weight
Crystal system
C59H48ClF3O4RhSSb3·0.5C7H8
3.1. Reaction chemistry
1459.71
Monoclinic
P21/n
Space group
Reactions of the five-coordinate rhodium(I) com-
plexes Rh(SbPh3)3(CO)X (X=Cl (1), Br (2)) with or-
ganic propargyl compounds HCꢀCCH2Y as well as the
chemistry of the resultant products are set out in
Scheme 1. The corresponding reaction chemistry start-
ing with 1 or 2 and organic methylpropargyl com-
pounds MeCꢀCCH2Y is presented in Scheme 2.
Unit cell dimensions
,
a (A)
17.518(4)
16.588(4)
21.962(4)
99.47(2)
6295(2)
4
1.540
,
b (A)
,
c (A)
i (°)
3
,
V (A )
Z
Dcalc (g cm−3
)
Treatment of 1 in CH2Cl2 at room temperature with
an excess of HCꢀCCH2OTs or HCꢀCCH2OBs affords
the rhodium(III) h1-allenyl complexes Rh(SbPh3)2-
(CO)Cl(OTs)(h1-CHꢁCꢁCH2) (3a) and Rh(SbPh3)2-
(CO)Cl(OBs)(h1-CHꢁCꢁCH2) (3b), respectively, as yel-
low solids in 80–84% yield. This behavior parallels that
generally observed for reactions of metal complexes
with the unsubstituted propargyl compounds which
yield h1-allenyl oxidative addition products [1,4,6–
8,25]. In contrast to the foregoing, reaction of 1 with an
excess of HCꢀCCH2Cl or HCꢀCCH2Br under com-
parable conditions surprisingly leads to the formation
of the rhodiacyclopent-3-ene-2-one complexes Rh-
(SbPh3)3Cl(h2-C(O)CHꢁC(Cl)CH2) (5a) and Rh
Crystal size (mm)
0.19×0.19×0.31
1.658
2.04–22.50
05h518, 05k517,
−235l523
8948
8619 [Rint=0.054]
Full-matrix least squares on
F2
Absorption coefficient (mm−1
Data collection range in q (°)
Index ranges
)
Reflections collected
Independent reflections (Rint
Refinement method
)
Data/restraints/parameters
Final R indices [I\2|(I)]
R indices (all data)
6923/0/666
R1=0.053, wR2=0.140
R1=0.085, wR2=0.152
1.032
Goodness-of-fit on F2
Largest difference peak and hole 0.956 and −0.753
−3
,
(e A
)

50
A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
Scheme 1. (i) HCꢀCCH2OTs; (ii) HCꢀCCH2OBs; (iii) HCꢀCCH2Cl; (iv) HCꢀCCH2Br; (v) thermolysis at 60 °C; (vi) one equivalent AgOTf; (vii)
two equivalents AgOTf; (viii) one equivalent AgOTs; (ix) one equivalent [(n-Bu)4N]Cl; (x) two equivalents [(n-Bu)4N]Cl; (xi) two equivalents
[(n-Bu)4N]Cl, SbPh3; (xii) PPh3; (xiii) pyridine.
(SbPh3)3Br(h2-C(O)CHꢁC(Cl)CH2) (5b) as green and
yellow solids, respectively, in ca. 75% yield. A similar
oxidative addition reaction of 2 with HCꢀCCH2Cl also
affords 5b in comparable yield. However, reaction of 2
with HCꢀCCH2Br generates a mixture (ca. 1:1) of the
rhodiacyclopent-3-ene-2-one complex Rh(SbPh3)3Br-
(h2-C(O)CHꢁC(Br)CH2) (5c) and the h1-allenyl
The rhodiacyclic complex 5a also undergoes substitu-
tion of SbPh3 by pyridine or PPh3. Accordingly, reac-
tion of 5a with an excess of pyridine in CH2Cl2 at room
temperature
affords
76%
Rh(SbPh3)2(py)Cl(h2-
C(O)CHꢁC(Cl)CH2) (9) in which one of the trans
SbPh3 ligands of 5a was replaced with pyridine. In
contrast, reaction of 5a with a threefold excess of PPh3
in CH2Cl2 at ambient temperature yields a five-coordi-
nate, 16-electron rhodiacyclic complex, Rh(PPh3)2Cl-
(h2-C(O)CHꢁC(Cl)CH2) (7), which contains two trans
phosphines. Related rhodiacyclopent-3-ene-2-one com-
plexes of the general formula Rh(PPh3)2Cl(h2-
C(O)C(R)ꢁC(R%)CH2) were synthesized by Liebeskind
and co-workers [29,30] by the application of other
methodologies.
Thermolysis of rhodiacyclic complexes 5 results in
the formation of the corresponding h1-allenyls 3. When
a ca. 1:1 mixture of 3c and 5c, obtained from 2 and
HCꢀCCH2Br (vide supra), was heated in THF solution
at 60 °C for 1 h, all of 5c converted to 3c. A similar
treatment of 5a for 16 h afforded a 30% conversion to
the h1-allenyl Rh(SbPh3)2(CO)Cl2(h1-CHꢁCꢁCH2) (3d),
with the rest of the rhodiacyclopent-3-ene-2-one com-
plex remaining unchanged.
Rh(SbPh3)2(CO)Br2(h1-CHꢁCꢁCH2)
(3c).
Several
metallacyclopent-3-ene-2-one complexes, including
those of rhodium(III), have been reported; however,
they were all obtained by methods very different from
those for 5a–5c [26–31].
The new rhodiacyclics 5a and 5b undergo a number
of substitution reactions at rhodium. Thus, coordinated
chloride or bromide can be replaced with triflate or
tosylate by use of the soluble salts AgOTf or AgOTs. In
this manner, each of 5a and 5b was converted to
Rh(SbPh3)3(OTf)(h2-C(O)CHꢁC(Cl)CH2) (5d), and 5b
was transformed to Rh(SbPh3)3(OTs)(h2-C(O)CHꢁ
C(Cl)CH2) (5e), with one equivalent of AgOTf and
AgOTs, respectively. The two products were isolated in
high (86–97%) yield. The substitution reaction was
shown to be reversible by conversion of 5d back to 5a
with one equivalent of [(n-Bu)4N]Cl in CH2Cl2.

A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
51
Scheme 2. (i) MeCꢀCCH2OTs; (ii) MeCꢀCCH2Cl; (iii) PPh3, (iv) [(n-Bu)4N]Cl.
(CO)Cl(OTs)(h1-CH2CꢀCMe) (4) and what appear to
be two regioisomers of rhodiacyclopent-3-ene-2-one
that differ in the location of Cl and OTs—
Rh(SbPh3)3Cl(h2-C(O)C(Me)ꢁC(OTs)CH2) (6a) and
Rh(SbPh3)3(OTs)(h2-C(O)C(Me)ꢁC(Cl)CH2) (6b)—in
an approximate 1:1:1 ratio. Crystallization of this mix-
ture from CH2Cl2–hexane increases the relative amount
of 4. The formation of the h1-propargyl 4 rather than a
corresponding rhodium(III) h1-allenyl conforms to the
generally observed outcome of reactions of metal com-
plexes with organic propargyl compounds upon alkyl
or aryl substitution at the latter’s carbon [2,32,33]. In
contrast to the aforementioned reaction, the bromide
complex 2 and MeCꢀCCH2OTs afford under compara-
ble conditions only the rhodiacycle Rh(SbPh3)3Br(h2-
C(O)C(Me)ꢁC(OTs)CH2) (6d), where tosylate is a
substituent on the ring and bromide remains bonded to
rhodium. Treatment of 6d with [(n-Bu)4N]Cl gives
Rh(SbPh3)3Br(h2-C(O)C(Me)ꢁC(Cl)CH2) (6e) by re-
placement of OTs with Cl.
Conversion of 5 to 3 has also been effected by use of
AgOTf. Accordingly, reaction of 5a or 5b with two
equivalents of AgOTf, or of 5d with one equivalent of
AgOTf, all in CH2Cl2 solution at ambient temperature,
results in a loss of one SbPh3 ligand, replacement of all
halide with triflate, and rearrangement to the six-coor-
dinate h1-allenyl complex Rh(SbPh3)2(CO)(OTf)2(h1-
CHꢁCꢁCH2) (3e), which was isolated as a green solid in
85–90% yield. Stirring a solution of 3e and two equiva-
lents of [(n-Bu)4N]Cl in THF at room temperature
afforded complete substitution of triflate by chloride to
give 3d, which is also accessible directly from 5a by
thermolysis (vide supra). The reverse of the thermolysis
reaction of 5, viz., transformation of the h1-allenyl
complexes 3 to the rhodiacycles 5, was accomplished in
68% yield for 3e to 5a by treatment with two equiva-
lents of [(n-Bu)4N]Cl and one equivalent of SbPh3 in
CH2Cl2 solution at room temperature for 4 h.
Reactions of 1 and 2 with methylpropargyl chloride
and tosylate (MeCꢀCCH2Y) are similar to those with
the corresponding unsubstituted propargyl compounds
HCꢀCCH2Y; nevertheless, some differences have been
noted. Thus, treatment of 1 with an excess of
MeCꢀCCH2OTs in CH2Cl2 at room temperature af-
fords a mixture of the h1-propargyl Rh(SbPh3)2-
Reaction of 1 with MeCꢀCCH2Cl, like that of 1 with
HCꢀCCH2Cl, yields
a rhodiacyclic product, now
Rh(SbPh3)3Cl(h2-C(O)C(Me)ꢁC(Cl)CH2) (6c). Complex
6c reacts with a ca. threefold excess of PPh3 to form
five-coordinate Rh(PPh3)2Cl(h2-C(O)C(Me)ꢁC(Cl)CH2)
(8), in which two PPh3 ligands replace three SbPh3

52
A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
ligands in 6c. Product 8 appears to be structurally
analogous to 7.
19.5 Hz) strongly supports the propargyl structure. The
arrangement of ligands in 4 is assigned from the same
considerations as for complexes 3.
3.2. Characterization of products
All rhodiacyclic complexes 5–9 show one IR absorp-
tion at 1648–1586 cm−1, but no terminal w(CO) bands.
With the aid of structure determinations of 5a, 5b and
5d (vide infra), this absorption is assigned to w(CꢁO) of
the rhodiacyclopent-3-ene-2-one ring. In the 13C{1H}-
NMR spectrum, the resonance of this CꢁO occurs at l
234.4–217.7 with coupling to 103Rh (1JRhC=21–27
Hz).
All new complexes were characterized by a combina-
tion of IR and NMR (1H-, 13C{1H}- and 31P{1H}-)
spectroscopy, FAB mass spectrometry, conductance
measurements and elemental analysis. The structures of
5a, 5b (as 5b·0.5CH2Cl2) and 5d (as 5d·0.5C7H8) were
elucidated by X-ray diffraction techniques.
For complexes 3, the presence of an h1-CHꢁCꢁCH2
Complexes 5 reveal H-NMR signals of ring CH at l
1
1
ligand is evidenced in the H-NMR spectrum by the
5.82–5.64 and CH2 at l 4.13–3.68, the latter with the
generally unresolved coupling to 103Rh. In the 13C{1H}-
NMR spectra, the corresponding signals appear at l
144.5–137.6 (CH) and l 35.7–28.1 (1JRhC=20–24 Hz,
CH2). The 13C chemical shift of the rhodiacyclic ꢁCX is
dependent on X and, for 5, occurs in the range l
172.5–170.2 when X=Cl and at l 161.3 when X=Br.
With the exception of 5d, complexes 5 are non-elec-
trolytes in CH2Cl2 solution, in which they show molar
conductivity values of less than 1 V−1 cm2 mol−1. For
5d, a \m of 5.13 V−1 cm2 mol−1 indicates considerable
dissociation of triflate in solution [37,38].
appearance of a quartet at l 5.72–5.56 (4JHH
ꢀ
2JRhH=5.8–6.0 Hz) for the CH proton and of a dou-
blet of doublets at l 4.38–3.91 (4JHH=5.8–6.0 Hz,
4JRhH=1.2–1.3 Hz) for the CH2 protons. The positions
4
of these signals and the values of JHH are in good
agreement with the corresponding data reported for a
number of transition metal h1-allenyl complexes
[2,4,25,34–36]. Further support for this ligand formula-
tion is furnished by the 13C{1H}-NMR spectra, which
show resonances at l 207.2–206.0 (ꢁCꢁ), 76.9–69.0
1
(CH2) and 71.6–67.6 (CH, JRhC=24.0–24.6 Hz), all
consistent with the h1-allenyl assignment [2,25,34–36].
Rhodiacyclic complexes 6, derived from methyl-
propargyl organics and Rh(SbPh3)3(CO)X, show pro-
ton CH2 and carbon-13 ꢁCMe and CH2 chemical shifts
that are similar to those of 5, as well as comparable
1JRhC for the CH2. Their 13C chemical shift of the ring
ꢁCX is also dependent on X, being observed at l
165.1–163.4 for X=Cl and l 174.2–173.8 for X=
OTs. This difference is the basis for the assignment of
structure to the presumably isomeric 6a and 6b as well
as to 6d.
The 13C{1H}-NMR spectra also show a signal at l
1
182.8–179.5 as a doublet with JRhC=62.2–68.5 Hz,
which is assigned to a CO ligand. The presence of CO
is confirmed by a strong IR w(CO) absorption at 2080–
2065 cm−1. The proposed ligand stereochemistry of 3 is
based on the assumed trans oxidative addition of
HCꢁCꢁCH2 and X to a square planar Rh center,
formed by dissociation of one SbPh3 ligand from five-
coordinate 1 or 2. A recent structure determination of a
1
six-coordinate
iridium(III)
h1-allenyl
complex,
The H-NMR spectral features associated with the
Ir(PPh3)2(CO)(NHSO2Ph)Cl(h1-CHꢁCꢁCH2) [36], sup-
ports this assignment. Molar conductivity measure-
ments on complex 3b show it to be essentially unionized
in CH2Cl2 solution (\m=1.01 V−1 cm2 mol−1). Com-
parable \m values were obtained for structurally similar
iridium(III) phosphine h1-allenyl complexes [37]. In
contrast, CH2Cl2 solutions of 1:1 electrolytes give sub-
stantially higher molar conductivities, 10.30–26.8
rhodiacyclic ring of the triphenylphosphine-containing
complexes 7 and 8 are similar to those of 5 and 6, and
their 31P{1H}-NMR spectra consist of a doublet at l
29.5–29.1 with 1JRhP=124 Hz to indicate that the PPh3
ligands are trans. These data as well as elemental
analysis and FAB mass spectra implicate five-coordi-
nate formulations that are analogous to those reported
earlier [29–31].
V
−1 cm2 mol−1 [37,38].
Replacement of one SbPh3 ligand in 5a with pyridine
1
1
The H- and 13C{1H}-NMR spectra of 4 allow as-
affords 9, which shows H- and 13C{1H}-NMR spectra
signment of an h1-propargyl structure to the hydrocar-
byl ligand. Thus, the CH2 proton signal occurs as an
unresolved multiplet at l 2.82, whereas the Me signal is
similar to those of its parent complex with additional
signals of pyridine. However, the CH2 protons of 9,
unlike those of 5–8, are inequivalent and appear in the
spectrum as an AB pattern with l 3.56 and 2.77 and
2JHH=17.4 Hz. This inequivalence is attributed to the
presence of a chiral Rh center that resulted from pyri-
dine entering a position trans to SbPh3.
The structures of three rhodiacyclic complexes 5—
5a, 5b and 5d—were elucidated by X-ray diffraction
analysis. That of 5a was communicated earlier [17]; for
further details see information in Section 5. Crystallo-
5
observed at l 1.04 as a triplet with a JHH=2.7 Hz.
These data are characteristic of those for MCH2CꢀCMe
complexes [25,32,33]. The 13C{1H} resonances at l 89.6,
87.3, 3.8 and −5.4 for the C3H2Me ligand further
support this formulation. The conspicuous absence of a
signal associated with ꢁCꢁ at ca. l 205 [2,25,34–36]
rules out an alternative h1-allenyl tautomeric formula-
1
tion, and the high-field CH2 signal (l −5.4, JRhC
=

A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
53
graphic analysis of 5b (as 5b·0.5CH2Cl2) established its
molecular structure as depicted in Scheme 1, with
RhꢂBr and CꢂCl bonding; however, the metrical
parameters are of insufficient accuracy for comparison
and discussion. The structure of 5d (as 5d·0.5C7H8)
represents the most accurate of the three structures and
is considered here in some detail. An ORTEP drawing of
5d is shown in Fig. 1, and selected bond distances and
angles are given in Table 2.
The coordination environment around the Rh center
is approximately octahedral, with the three SbPh3 lig-
ands adopting a meridional configuration. The inequiv-
alent SbPh3 is located trans to the CH2 carbon of the
h2-C(O)CHꢁC(Cl)CH2 ligand, and the triflate is posi-
tioned trans to the C(O) carbon. This general stereo-
chemistry—SbPh3 ligands arranged meridionally and
the CH2 trans to SbPh3—was also found in 5a [17] and
5b.
The rhodiacyclic ring is essentially planar, with the
deviations from the least-squares plane being Rh
0.008(1), C(1) −0.005(10), C(2) −0.002(11), C(3) −
,
0.011(11) and C(4) −0.012(11) A. The RhꢂC bond
distances RhꢂC(1)=2.099(9) and RhꢂC(4)=1.962(11)
,
A may be compared with the corresponding distances
of 2.064(9) and 1.973(6)
in Rh(PPh3)2Cl(h2-
,
A
C(O)CHꢁC(C(O)Ph)CH2) [30] and of 2.089(6) and
2
,
2.012(5) A in Cp(PPh3)Rh(h -C(O)C(Et)ꢁC(Et)CH2)
[29]. The bite angle of h2-C(O)CHꢁC(Cl)CH2,
C(1)ꢂRhꢂC(4), measures 83.2(4)° and is somewhat
larger than that of the appropriate analogous ligand in
Rh(PPh3)2Cl(h2-C(O)CHꢁC(C(O)Ph)CH2)
(80.6(3)°
[30])
and
Cp(PPh3)Rh(h2-C(O)C(Et)ꢁC(Et)CH2)
(80.6(2)° [29]). The CꢂC bond distances within the
rhodiacyclic ring (C(1)ꢂC(2)=1.49(2), C(2)ꢂC(3)=
,
1.291(14) and C(3)ꢂC(4)=1.47(2) A) are all in the
range expected for this structure and compare quite
well with the corresponding distances in similar com-
pounds [29,30].
Of the three RhꢂSb bond distances, those for the
trans SbPh3 ligands are essentially equal (RhꢂSb(1)=
Fig. 1. ORTEP plot of 5d in 5d·0.5C7H8. The non-hydrogen atoms are
drawn at the 30% probability level. For clarity the phenyl groups are
omitted.
,
2.602(1), RhꢂSb(2)=2.612(1) A) whereas that for the
remaining SbPh3 (trans to CH2) is longer (RhꢂSb(3)=
,
2.695(1) A). This difference may result from steric
effects associated with the size of SbPh3, since lig-
andꢂligand repulsion would be most pronounced for
the stibine cis to each of the other two stibenes. Indeed,
Table 2
,
Selected bond lengths (A) and bond angles (°) for 5d·0.5C7H8
Bond lengths
the
bond
angles
Sb(1)ꢂRhꢂSb(2)=172.29(4),
RhꢂC(1)
RhꢂC(4)
RhꢂO(2)
RhꢂSb(1)
RhꢂSb(2)
RhꢂSb(3)
2.099(9)
1.962(11)
2.310(8)
2.602(1)
2.612(1)
2.695(1)
C(1)ꢂC(2)
C(2)ꢂC(3)
C(3)ꢂC(4)
ClꢂC(2)
1.49(2)
1.291(14)
1.47(2)
1.753(11)
1.226(11)
Sb(1)ꢂRhꢂSb(3)=93.56(4) and Sb(2)ꢂRhꢂSb(3)=
94.03(3)° reflect distortions that are consistent with
repulsion between large SbPh3 ligands in cis positions.
Furthermore, RhꢂSb bond lengths in octahedral rhodi-
um(III) complexes containing only trans SbPh3 ligands
O(1)ꢂC(4)
Bond angles
,
are shorter than those in 5d: 2.588(1) A in trans-
C(1)ꢂRhꢂC(4)
C(1)ꢂRhꢂO(2)
C(1)ꢂRhꢂSb(1)
C(1)ꢂRhꢂSb(2)
C(1)ꢂRhꢂSb(3)
C(4)ꢂRhꢂO(2)
C(4)ꢂRhꢂSb(1)
C(4)ꢂRhꢂSb(2)
C(4)ꢂRhꢂSb(3)
O(2)ꢂRhꢂSb(1)
O(2)ꢂRhꢂSb(2)
O(2)ꢂRhꢂSb(3)
83.2(4)
92.7(4)
85.7(3)
86.6(3)
176.0(3)
175.7(4)
90.2(3)
88.1(3)
92.9(4)
90.5(2)
90.7(2)
91.2(2)
Sb(1)ꢂRhꢂSb(2)
Sb(1)ꢂRhꢂSb(3)
Sb(2)ꢂRhꢂSb(3)
C(2)ꢂC(1)ꢂRh
C(3)ꢂC(4)ꢂRh
O(1)ꢂC(4)ꢂRh
C(1)ꢂC(2)ꢂC(3)
C(2)ꢂC(3)ꢂC(4)
C(3)ꢂC(4)ꢂO(1)
C(1)ꢂC(2)ꢂCl
172.29(4)
93.56(4)
94.03(3)
105.7(7)
114.4(8)
123.5(8)
122.1(10)
114.5(10)
122.0(10)
117.2(9)
120.6(10)
Rh(SbPh3)2(NCMe)(Ph)Cl2 [39] and 2.551(2) and
,
2.588(2)
A
in trans-Rh(SbPh3)2(DPD)Ph2·2C6H6
(DPD=1,3-diphenyl-1,3-propandionate) [40].
The triflate is bonded to rhodium with RhꢂO=
,
2.310(8) A. This bond length may be compared with
,
other RhꢂOTf distances of 2.37(1)
A
in [Rh2-
(h1-OCMe2)(m-CO)(CO)(OTf)(dppm)2](OTf)·0.5C6H6
(dppm=1,2-bis(diphenylphosphino)methane) [41] and
C(3)ꢂC(2)ꢂCl
,
2.323(6) and 2.332(6) A in [{Rh(m-Pz)(Me)(CNBu-
t)2}2(m-OTf)](OTf) (Pz=pyrazolate) [42].

54
A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
(c) Addition of Y−=OTs− or OBs− to rhodium in
II produces six-coordinate h1-allenyl complexes 3.
Alternatively, the h1-allenyl ligand of II can migrate
onto coordinated CO. Reactions of four-coordinate
rhodium(I) carbonyl complexes with MeI are known
[46] to yield methylrhodium(III) and acetylrhodiu-
m(III) products. The migratory insertion of II may
be promoted by an external ligand—Y− or SbPh3—
to give intermediate III. We favor SbPh3 to be the
assisting ligand, since this would yield a cationic
product, which is expected to be more reactive than
an electrically neutral product to the addition of
nucleophile to coordinated C(O)CHꢁCꢁCH2 (vide
infra).
(d) Intermediate III undergoes coordination of the
allenyl Cb=Cg to rhodium to form IV, which then
adds external X− or Y− to give the rhodiacyclic
product 5. Alternatively, but less likely,3 ligation
occurs through the allenyl Ca=Cb. The latter type of
h3 coordination of C(O)C(R)ꢁCꢁCH2 to one metal
has been documented crystallographically for a binu-
clear FeRu complex [47]. Addition of nucleophile to
Cb of ligated allene is a known reaction [48].
(e) The proposed equilibrium between IIIa and IIIb
which results from exchange of X and Y readily
accounts for the formation of 5b alone from the
reaction of either 1 with HCꢀCCH2Br or 2 with
HCꢀCCH2Cl. (However, this aspect of reactivity can
also be explained by the addition of either ionic Y−
or ligated X to the C(O)CHꢁCꢁCH2 in IV originating
from IIIa.)
Scheme 3. L=Sb(C6H5)3.
The stereochemistry at rhodium of the foregoing
transformations is consistent with the elucidated struc-
tures of 5a, 5b and 5d. Thus, the migratory insertion of
CO (i.e. conversion of II to III) and coordination of
Cb=Cg, both required to proceed with cis stereochem-
istry at metal, lead to the correct isomeric structure of
the rhodiacyclic product.
A number of reactions in Scheme 1 may be rational-
ized on the basis of the relative ease of substitution and
rearrangement of b-halo and b-sulfonato enones [49]
and of the comparative leaving ability of these sub-
stituent groups. For example, the formation of 3a and
3b from 1 and HCꢀCCH2OTs and HCꢀCCH2OBs,
respectively, may be attributed to the excellent leaving
properties of the organic sulfonates compared to chlo-
ride. This would disfavor formation of the rhodiacyclic
structures 5 and instead produce the h1-allenyls 3.
The conversion reactions of 5 to 3 may be explained
similarly. Thus, thermolysis of 5 proceeds more readily
for 5c than for 5a, consistent with Br− being a better
3.3. Mechanistic aspects
A possible mechanism of formation of complexes 3
and 5 from Rh(SbPh3)3(CO)X (X=Cl (1), Br (2)) and
HCꢀCCH2Y (Y=Cl, Br, OTs, OBs) is presented in
Scheme 3. Salient features of this mechanism are:
(a) Complexes 1 and 2 undergo dissociation of SbPh3
to afford square-planar Rh(SbPh3)2(CO)X in solu-
tion [15].
(b) Oxidative addition of HCꢀCCH2Y to the
rhodium center in Rh(SbPh3)2(CO)X generates tran-
sient [Rh(SbPh3)2(CO)X(h1-CHꢁCꢁCH2)]+Y− (II).
Such an ionic process has been proposed on the basis
of kinetic studies of oxidative addition of alkyl
halides, especially MeI, to iridium(I) in various
Ir(PR3)2(CO)X complexes [43,44]. Furthermore,
cationic intermediates have been isolated or detected
in oxidative addition of alkyl and acyl halides to
rhodium(I), iridium(I), palladium(II) and platinu-
m(II) complexes [45]. In the present case, the addition
of HCꢀCCH2Y proceeds by attack of Rh at the CH
carbon (SN2% mechanism) to yield RhCHꢁCꢁCH2.
Again, ample precedent exists for such a behavior of
organic propargyl halides and tosylates toward metal
complexes [1,4,6–8,25].
3 Molecular modeling indicates that Cb=Cg is more likely to
coordinate to the metal than Ca=Cb. We thank an anonymous
reviewer for providing us with this result.

A. Kayan et al. / Journal of Organometallic Chemistry 630 (2001) 44–56
55
leaving group than Cl−. Likewise, substitution of the
Acknowledgements
rhodiacyclic ring Cl in 5a, 5b or 5d with OTf leads to
the formation of the h1-allenyl complex 3e. Presumably
the reaction is driven by the excellent leaving group
properties of triflate.
This study was supported in part by the National
Science Foundation and The Ohio State University.
The reverse reaction, i.e. conversion of 3 to 5, was
effected for 3 with Cl− in the presence of SbPh3 to give
5a. Without added SbPh3, there is only ligand substitu-
tion of chloride for triflate to yield h1-allenyl 3d. The
formation of 5a may occur by intermediacy of II, which
would then proceed to the rhodiacyclic product by the
mechanism in Scheme 3.
The reactions of methylpropargyl organics with 1
and 2, set out in Scheme 2, likely take place by a similar
pathway. Here, however, initial interaction of
MeCꢀCCH2Y with the rhodium(I) center may afford
either an h1-allenyl or a propargyl complex [2,32,33]
analogous to II in Scheme 3, or a mixture of both. This
would account for the formation of 4 as well as of 6a
and 6b from 1 and MeCꢀCCH2OTs.
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