Reactions of binuclear ruthenium-platinum μ-allenyl complexes with nucleophilic and electrophilic reagents. The characterization of two 1:1 adducts of L(PPh3)Pt(μ-η1:η2α,β-C(Ph)=C=CH2)Ru(CO)Cp (L=PPh3, t-BuNC) and p-toluenesulfonyl isocyanate

Article abstract of DOI:10.1016/S0022-328X(99)00613-0

Reactions of (PPh₃)₂Pt(μ-η¹:η²_α,β-C(R)=C=CH₂)Ru(CO)Cp (R=H (1), Ph (2)) with Ph₂PCH₂CH₂CH₂PPh₂, PEt₃ and t-BuNC in THF at -78°C to room temperature afforded the substitution products L₂Pt(μ-η¹:η²_α,β-C(R)=C=CH₂)Ru(CO)Cp (R=H, L₂=Ph₂PCH₂CH₂CH₂PPh₂ (3), R=Ph, L₂=Ph₂PCH₂CH₂CH₂PPh₂ (4), R=H, L₂=2PEt₃ (5), R=Ph, L₂=PPh₃ and t-BuNC (6)). No reaction was observed for 1 with Et₂NH or C₆H₁₁NH₂ and 2 with p-TolS(O)₂NH₂ in THF at reflux temperature. Complex 2 reacted with p-TolS(O)₂NCO (TSI) in toluene at -78°C to room temperature to yield two 1:1 addition products of the reactants: the γ-carbon substituted μ-allenyl (PPh₃)₂Pt(μ-η¹:η²_α,β-C(Ph)=C=CHC(O)NHS(O)₂Tol-p) (7) and the [3+2] cycloadduct (PPh₃)₂Pt(μ-η¹:η²-C=C(Ph)N(S(O)₂Tol-p)C(O)CH₂)Ru(CO)Cp (8). Complexes 4 and 6 afforded with TSI, under essentially similar conditions, only [3+2] cycloadducts, L₂Pt(μ-η¹:η²-C=C(Ph)N(S(O)₂Tol-p)C(O)CH₂)Ru(CO)Cp (L₂=Ph₂PCH₂CH₂CH₂PPh₂ (9), PPh₃ and t-BuNC (10)). All products were characterized by a combination of IR and NMR (¹H, ¹³C{¹H} and ³¹P{¹H}) spectroscopy, FAB MS and elemental analysis. The structures of 7 (as 7·C₃H₆O) and 10 were determined by single-crystal X-ray diffraction analysis. Reactions of 2 with trans-NCCH=CHCN (L) and of 1 with the alkynes MeO₂CC?CCO₂Me, MeO₂CC?CMe, PhC?CH and PhC?CPh (L) resulted in the formation of the mononuclear metal complexes Cp(CO)₂RuC(R)=C=CH₂ (R=H, Ph) and (PPh₃)₂PtL. The reverse of this fragmentation reaction occurred when Cp(CO)₂RuCH=C=CH₂ was treated with (PPh₃)₂Pt(PhC?CPh). No reaction was observed between 2 and each (CN)₂C=CPh₂ and MeS(O)₂NSO in benzene or toluene on heating. The η¹-allenyl Cp(CO)₂RuC(Ph)=C=CH₂, obtained in this study, is a new compound.

Full text of DOI:10.1016/S0022-328X(99)00613-0

www.elsevier.nl/locate/jorganchem
Journal of Organometallic Chemistry 593–594 (2000) 465–478
Reactions of binuclear ruthenium–platinum m-allenyl complexes
with nucleophilic and electrophilic reagents. The characterization
of two 1:1 adducts of
L(PPh3)Pt(m-h1:ha2,b-C(Ph)ꢀCꢀCH2)Ru(CO)Cp (L=PPh3, t-BuNC)
and p-toluenesulfonyl isocyanate
Richard R. Willis a, Mario Calligaris b,1, Paolo Faleschini b, Judith C. Gallucci1 a,
Andrew Wojcicki a,*
a Department of Chemistry, The Ohio State Uni6ersity, Columbus, OH 43210, USA
b Dipartimento di Scienze Chimiche, Uni6ersiteta´ di Trieste, 34127 Trieste, Italy
Received 2 September 1999; accepted 11 October 1999
Dedicated to Professor Fausto Calderazzo on the occasion of his 70th birthday.
Abstract
Reactions of (PPh3)2Pt(m-h1:h2a,b-C(R)ꢀCꢀCH2)Ru(CO)Cp (R=H (1), Ph (2)) with Ph2PCH2CH2CH2PPh2, PEt3 and t-BuNC
in THF at −78°C to room temperature afforded the substitution products L2Pt(m-h1:ha2,b-C(R)ꢀCꢀCH2)Ru(CO)Cp (R=H,
L2=Ph2PCH2CH2CH2PPh2 (3), R=Ph, L2=Ph2PCH2CH2CH2PPh2 (4), R=H, L2=2PEt3 (5), R=Ph, L2=PPh3 and t-BuNC
(6)). No reaction was observed for 1 with Et2NH or C6H11NH2 and 2 with p-TolS(O)2NH2 in THF at reflux temperature.
Complex 2 reacted with p-TolS(O)2NCO (TSI) in toluene at −78°C to room temperature to yield two 1:1 addition products of
the reactants: the g-carbon substituted m-allenyl (PPh3)2Pt(m-h1:ha2,b-C(Ph)ꢀCꢀCHC(O)NHS(O)2Tol-p) (7) and the [3+2] cycload-
duct (PPh3)2Pt(m-h1:h2-CꢀC(Ph)N(S(O)2Tol-p)C(O)CH2)Ru(CO)Cp (8). Complexes 4 and 6 afforded with TSI, under essentially
similar
conditions,
only
[3+2]
cycloadducts,
L2Pt(m-h1:h2-CꢀC(Ph)N(S(O)2Tol-p)C(O)CH2)Ru(CO)Cp
(L2=
Ph2PCH2CH2CH2PPh2 (9), PPh3 and t-BuNC (10)). All products were characterized by a combination of IR and NMR (1H,
13C{1H} and 31P{1H}) spectroscopy, FAB MS and elemental analysis. The structures of 7 (as 7·C3H6O) and 10 were determined
by single-crystal X-ray diffraction analysis. Reactions of 2 with trans-NCCHꢀCHCN (L) and of 1 with the alkynes
MeO2CCꢁCCO2Me, MeO2CCꢁCMe, PhCꢁCH and PhCꢁCPh (L) resulted in the formation of the mononuclear metal complexes
Cp(CO)2RuC(R)ꢀCꢀCH2 (R=H, Ph) and (PPh3)2PtL. The reverse of this fragmentation reaction occurred when
Cp(CO)2RuCHꢀCꢀCH2 was treated with (PPh3)2Pt(PhCꢁCPh). No reaction was observed between 2 and each (CN)2CꢀCPh2 and
MeS(O)2NSO in benzene or toluene on heating. The h1-allenyl Cp(CO)2RuC(Ph)ꢀCꢀCH2, obtained in this study, is a new
compound. © 2000 Elsevier Science S.A. All rights reserved.
Keywords: Mixed-metal complexes; Platinum; Ruthenium; m-h1:ha2,b-Allenyl; Cycloaddition; X-ray structures
1. Introduction
research activity [1–3]. In particular, homobinuclear
m-h1:h2-allenyl complexes of the general formula
(CO)3M(m-PPh2)(m-h1:h2-allenyl)M(CO)3 (M=Fe or
Ru) have received recent attention [3–9]. Reactions of
these complexes with a variety of nucleophilic reagents
have been found to proceed by addition of the latter to
the m-allenyl fragment, to one of the carbonyl ligands
or to the metal.
Reaction chemistry of binuclear and trinuclear transi-
tion-metal m-allenyl complexes is an expanding area of
* Corresponding author.
E-mail address: wojcicki.1@osu.edu (A. Wojcicki)
1 Inquiries concerning X-ray crystallographic studies should be
addressed to M.C. (7·C3H6O) and J.C.G. (10).
0022-328X/00/$ - see front matter © 2000 Elsevier Science S.A. All rights reserved.
PII: S0022-328X(99)00613-0

466
R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
We have recently reported [10] that the complexes
THF solution (5 ml) of Ph2PCH2CH2CH2PPh2 (0.12 g,
0.29 mmol). The resulting solution was allowed to
warm to room temperature (r.t.) over 6 h, and solvent
was removed under reduced pressure. The residue was
dissolved in THF (3 ml), treated with hexane (7 ml),
and cooled at ca. −10°C for 18 h. The yellow precipi-
tate of (Ph2PCH2CH2CH2PPh2)Pt(m-h1:ha2,b-CHꢀCꢀ
CH2)Ru(CO)Cp (3) was collected on a frit. Yield, 0.12
g (49%). M.p. 165°C dec. Selected data for 3: IR
(PPh3)2Pt(m-h1:ha2,b-C(R)ꢀCꢀCH2)Ru(CO)Cp(R=H (1),
Ph (2)) react with the electrophilic species (PPh3)Au+ to
afford trimetallic h3-allyl complexes, [(PPh3)2Pt(m2-
CO)RuCpAu(PPh3)(m3-h1:h3:h1-CH2-CCR)]+ (Eq. (1)).
(MeCN): w(CO) 1902 (s), w(CꢀCꢀC) 1714 (m) cm−1
1H-NMR (CDCl3): l 7.7–7.0 (m, 20H, Ph), 6.70 (s, br,
PtH=37 Hz, 1H, ꢀCH), 5.59 (s, br, JPtH=27 Hz, 1H
.
J
(1)
of ꢀCH2), 4.77 (s, br, JPtH=18 Hz, 1H of ꢀCH2), 4.58
(s, 5H, Cp). 13C{1H}-NMR (CD2Cl2): l 206.5 (s, CO),
168.9 (s, ꢀCꢀ), 112.4 (d, JPC=85 Hz, JPtC=722 Hz,
ꢀCH), 94.5 (s, ꢀCH2), 82.3 (s, Cp), 27.2, 20.6 (2s, CH2).
31P{1H} (CD2Cl2): l 5.4 (d, JPP=20 Hz, JPtP=2564
Hz), 1.5 (d, JPP=20 Hz, JPtP=3406 Hz). FAB MS:
102Ru, 195Pt, m/z (ion, relative intensity) 841 (M+,
19.2), 813 (M+–CO, 3.7), (Pt(Ph2P(CH2)3PPh2)+,
10.3). Anal. Found: C, 51.66; H, 4.26. C36H34OP2PtRu.
Calc.: C, 51.43; H, 4.08.
The present paper is concerned with reactions of 1, 2
and related ruthenium–platinum binuclear m-h1:ha2,b-al-
lenyl complexes with other electrophilic reagents, as well
as with some nucleophilic reagents. The chemistry is
highlighted by [3+2] cycloaddition of p-toluenesulfonyl
isocyanate to the m-allenyl ligand and by fragmentation
of 1 and 2 into mononuclear ruthenium h1-allenyl and
(PPh3)2Pt(alkene or alkyne) complexes upon reaction
with alkenes and alkynes.
2.2.2. Reaction of 2 with Ph2PCH2CH2CH2PPh2
A stirred solution of 2 (0.22 g, 0.21 mmol) in THF
(15 ml) at −78°C was treated dropwise over 10 min
with a solution of Ph2PCH2CH2CH2PPh2 (0.068 g, 0.21
mmol) in THF (5 ml). The resulting solution was
allowed to warm to r.t. over 6 h and was stirred for an
additional 18 h. The solvent was removed under re-
duced pressure, the residue was dissolved in THF (2
ml), and hexane (7 ml) was added with stirring. Cooling
at ca. −10°C for 18 h produced a yellow precipitate of
(Ph2PCH2CH2CH2PPh2)Pt(m - h1:ha2,b - C(Ph)ꢀCꢀCH2)-
Ru(CO)Cp (4), which was collected by filtration. Yield,
0.077 g (40%). Selected data for 4: IR (CH2Cl2): w(CO)
1901 (s), w(CꢀCꢀC) 1712 (m) cm−1. 1H-NMR (C6D6): l
7.7–7.1 (m, 25H, Ph), 6.12 (d, JHH=2.2 Hz, JPtH=24
Hz, 1H of ꢀCH2), 5.56 (d, JHH=2.2 Hz, JPtH=15 Hz,
1H of ꢀCH2), 4.46 (s, 5H, Cp). 31P{1H}-NMR (C6D6):
l 4.0 (d, JPP=22.5 Hz, JPtP=2526 Hz), −1.1 (d,
2. Experimental
2.1. General procedures
All reactions and manipulations were conducted under
an atmosphere of Ar using standard procedures [11].
Solvents were dried, distilled under an Ar atmosphere and
degassed before use [12]. Elemental analyses were per-
formed by M-H-W Laboratories, Phoenix, AZ. Melting
points were measured on a Thomas–Hoover melting
point apparatus and are uncorrected. 1H-, 13C- and
31P-NMR spectra were recorded on a Bruker AM-300
spectrometer, and IR spectra were obtained on a Perkin–
Elmer model 283B spectrophotometer. Mass spectra
(FAB) were recorded on a Kratos VG70-250S spectrom-
eter by Mr David C. Chang.
Reagents were obtained from various commercial
sources and used as received with the exception of TCNE,
which was sublimed, and p-TolS(O)2NCO and
C6H11NH2, which were distilled, the former from P4O10.
Literature procedures were followed to synthesize
MeS(O)2NSO [13], (PPh3)2Pt(C2H4) [14], (PPh3)2Pt(PhCꢁ
CPh) [15], Cp(CO)2RuCHꢀCꢀCH2 [16], and (PPh3)2Pt(m-
h1:h2a,b-C(R)ꢀCꢀCH2)Ru(CO)Cp (R=H, Ph) [17].
J
PP=22.5 Hz, JPtP=3427 Hz). FAB MS: 102Ru, 195Pt,
m/z (ion, relative intensity) 918 (M++1, 31.3), 890
(M++1-CO, 3.7), 607 (Pt(Ph2P(CH2)3PPh2)+, 9.2).
2.2.3. Reaction of 1 with PEt3
A stirred solution of 1 (0.10 g, 0.11 mmol) in THF
(20 ml) at −78°C was treated dropwise with PEt3
(0.050 ml, 0.34 mmol). The resulting solution was then
allowed to warm to r.t. over 6 h, and the solvent was
freed under vacuum. THF (2 ml) was added to the
residue and the orange solution/suspended white solid
was passed through a layer of Celite, which was washed
with additional (8 ml) THF. The filtrate was concen-
trated to 2 ml and hexane (10 ml) was carefully layered
on top of the orange THF solution. After slow diffu-
2.2. Reactions of (PPh3)2Pt(v-p1:ph2,i-C(R)ꢀCꢀCH2)-
Ru(CO)Cp (R=H (1), Ph (2)) with nucleophilic
reagents
2.2.1. Reaction of 1 with Ph2PCH2CH2CH2PPh2
To a stirred solution of 1 (0.28 g, 0.29 mmol) in THF
(15 ml) at −78°C was added dropwise over 3 min a

R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
467
sion of the two solvents at 0°C for 24 h, a yellow solid
of (PEt3)2Pt(m-h1:ha2,b-CHꢀCꢀCH2)Ru(CO)Cp (5) was
isolated by filtration. Yield, 0.062 g (85%). Selected
was stirred for an additional 10 h. A yellow solid of
(PPh3)2Pt(m-h1:ha2,b-C(Ph)ꢀCꢀCHC(O)NHS(O)2Tol-p)-
Ru(CO)Cp (7) was then separated from an orange
solution by filtration. Yield, 0.10 g (54%). Selected data
data for 5: IR (CH2Cl2): w(CO) 1892 (s) cm−1 1H-
.
for 7: IR (CH2Cl2): w(CO) 1924 (s), 1670 (s) cm−1
.
NMR (CDCl3): l 6.42 (m, JPtH=31 Hz, 1H, ꢀCH),
5.41 (m, JPtH=20 Hz, 1H of ꢀCH2), 5.00 (s, 5H, Cp),
4.70 (m, JPtH=13 Hz, 1H of ꢀCH2), 2.1–0.75 (several
m, 30H, Et). 31P{1H}-NMR (CDCl3): l 23.9 (s, br,
1H-NMR (CDCl3): l 12.1 (s, 1H, NH), 8.1–6.8 (m,
39H, Ph and C6H4), 5.96 (s, JPtH=10 Hz, 1H, ꢀCH),
4.48 (s, 5H, Cp), 2.43 (s, 3H, Me). 13C{1H}-NMR
(CDCl3): l 201.9 (s, RuCO), 178.1 (s, NCO), 164.5
(s, ꢀCꢀ), 146.2 (s, ꢀCPh), 108.4 (s, ꢀCH), 86.6 (s, Cp),
J
PtP=3681 Hz), 12.4 (s, br, JPtP=2733 Hz). FAB MS:
102Ru, 195Pt, m/z (ion, relative intensity) 665 (M+, 6.1),
547 (M+–PEt3, 6.0), 429 (M+–2PEt3, 12.1).
21.5 (s, Me). 31P{1H}-NMR (CDCl3): l 21.6 (d, JPP
11 Hz, JPtP=2789 Hz), 20.9 (d, JPP=11 Hz, JPtP
=
=
3923 Hz). FAB MS: 102Ru, 195Pt, m/z (ion, relative
intensity) 1226 (M+, 16.3), 1198 (M+–CO, 9.8), 964
(M+–PPh3, 21.6), 719 (Pt(PPh3)2+, 100). Anal. Found:
C, 57.64; H, 4.12. C59H49NO4P2PtRuS Calc.: C, 57.79;
H, 4.03.
2.2.4. Reaction of 2 with t-BuNC
A stirred orange–red solution of 2 (0.20 g, 0.19
mmol) in THF (10 ml) at −78°C was treated dropwise
over 5 min with t-BuNC (0.10 ml, 0.89 mmol). The
color of the solution immediately turned yellow al-
though the reaction was not complete at this point, as
ascertained by NMR spectroscopy. The solution was
allowed to warm to r.t. over 8 h and was stirred for an
additional 8 h. The solvent was removed under reduced
pressure and the yellow residue was treated with 5 ml of
4:1 hexane–THF. Filtration afforded (0.12 g, 67%
yield) (t-BuNC)(PPh3)Pt(m-h1:ha2,b-C(Ph)ꢀCꢀCH2)Ru-
(CO)Cp (6) as a yellow solid. M.p. 98°C. Selected data
The orange filtrate was evaporated to dryness, and
the residue was extracted with 3:1 hexane–toluene (3×
9 ml). The solvent was removed from the combined
extracts to leave a small amount (B0.020 g, B11%
yield) of (PPh3)2Pt(m-h1:h2-CꢀC(Ph)N(S(O)2Tol-p)C-
(O)CH2)Ru(CO)Cp (8). Selected data for 8: IR
(CH2Cl2): w(CO) 1899 (s), 1724 (s) cm−1 1H-NMR
.
(C6D6): l 8.5–6.5 (m, 39H, Ph and C6H4), 4.84 (s, 5H,
Cp), 3.71 (d, JHH=21.3 Hz, JPtH=17.2 Hz, 1H of
CH2), 2.72 (dt, JHH=21.3 Hz, JPH=14.5 Hz, 1H of
CH2), 1.88 (s, 3H, Me). 13C{1H}-NMR (C6D6): l 206.2
(s, RuCO), 174.5 (d, JPC=8.5 Hz, JPtC=120 Hz,
ꢀCPt), 153.1 (s, ꢀCPh), 151.5 (s, NCO?), 86.3 (s, Cp),
52.5 (s, JPtC=54.7 Hz, CH2), 20.6 (s, Me). 31P{1H}-
NMR (C6D6): l 22.7 (d, JPP=11.3 Hz, JPtP=2643 Hz),
16.3 (d, JPP=11.3 Hz, JPtP=3621 Hz). FAB MS:
102Ru, 195Pt, m/z (ion, relative intensity) 1226 (M+,
25.4), 719 (Pt(PPh3)2+, 100). Anal. Found: C, 57.88; H,
4.43. C59H49NO4P2PtRuS Calc.: C, 57.79; H, 4.03.
1
for 6: IR (CH2Cl2): 1901 (s) cm−1. H-NMR (CDCl3):
l 7.8–6.7 (m, 20H, Ph), 5.62 (s, JPtH=17 Hz, 1H of
ꢀCH2), 4.98 (s, JPtH=13 Hz, 1H of ꢀCH2), 4.74 (s, 5H,
Cp), 1.29 (s, 9H, Me). 13C{1H}-NMR (CD2Cl2): l 205.0
(s, JPtC=50.4 Hz, CO), 166.5 (s, ꢀCꢀ), 150.1 (s, ꢀCPh),
143.8 (s, br, CN?), 97.0 (s, JPtC=32.2 Hz, ꢀCH2), 84.1
(s, Cp), 57.0 (s, C of t-Bu), 29.9 (s, Me). 31P{1H}-NMR
(CDCl3): l 25.6 (s, JPtP=3544 Hz). FAB MS: 102Ru,
195Pt, m/z (ion, relative intensity) 850 (M+, 68.0), 767
(M+–BuNC, 9.4). Anal. Found: C, 54.01; H, 4.51.
C38H36NOPPtRu Calc.: C, 53.71; H, 4.27.
2.2.5. Reactions of 1 and 2 with nitrogen nucleophiles
In a typical experiment, a solution of 1 (0.20 g, 0.21
mmol) and Et2NH (0.050 ml, 0.49 mmol) in THF (30
ml) first at r.t. and then at reflux temperature was
monitored by 1H- and 31P-NMR spectroscopy. No
changes were noted over 1 h of reaction time. Similar
results were obtained for reactions of 1 with C6H11NH2
and 2 with p-TolS(O)2NH2.
2.3.2. Reaction of 4 with TSI
A stirred solution of 4 (0.27 g, 0.29 mmol) in benzene
(10 ml) at r.t. was treated with TSI (0.075 ml, 0.49
mmol). After 15 h of stirring, the solvent was removed
under vacuum and the orange residue was thoroughly
washed with hexane (2×15 ml) to yield (0.17 g, 53%) a
yellow powder of (Ph2PCH2CH2CH2PPh2)Pt(m-h1:h2-
CꢀC(Ph)NS(O)2Tol-p)C(O)CH2)Ru(CO)Cp (9). Se-
lected data for 9: IR (CH2Cl2) w(CO) 1894 (s), 1708 (m)
2.3. Reactions of L2Pt(v-p1:ph2,i-C(Ph)ꢀCꢀCH2)-
Ru(CO)Cp (L2=2PPh3 (2), Ph2PCH2CH2CH2PPh2
(4), PPh3 and t-BuNC (6)) with p-TolS(O)2NCO (TSI)
1
cm−1. H-NMR (CDCl3): l 8.0–6.8 (m, 29H, Ph and
C6H4), 4.55 (s, 5H, Cp), 3.41 (d, JPH=23 Hz, JPtH=21
Hz, 1H of CH2), 2.82 (m, 1H of CH2). 31P{1H}-NMR
(CDCl3): l 0.47 (d, JPP=26.5 Hz, JPtP=2362 Hz),
−6.6 (d, JPP=26.5 Hz, JPtP=3468 Hz). FAB MS:
102Ru, 195Pt, m/z (ion, relative intensity) 1114 (M+,
24.2), 1086 (M+–CO, 20.3), 607 (Pt(Ph2P(CH2)3PPh2)+,
61.6).
2.3.1. Reaction of 2 with TSI
A stirred solution of 2 (0.15 g, 0.15 mmol) in toluene
(7 ml) at −78°C was treated with 3.0 ml of a 0.079 M
solution of TSI (0.24 mmol) in toluene. The resulting
red solution was allowed to warm to r.t. over 8 h and

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R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
2.3.3. Reaction of 6 with TSI
Hz), 19.7 (d, JPP=7.0 Hz, JPtP=3248 Hz), 14.5 (s,
PtP=3748 Hz), among a host of other signals. After
the solution was allowed to warm to r.t., the above
A stirred solution of 6 (0.10 g, 0.12 mmol) in toluene
(7 ml) at −78°C was treated dropwise over 5 min with
3.0 ml of a 0.079 M solution of TSI (0.24 mmol) in
toluene. The resulting solution was allowed to warm to
r.t. over 6 h and was stirred for an additional 12 h. The
volume was reduced to about 1 ml, and hexane (10 ml)
was added with vigorous stirring to induce the precipi-
tation of a yellow solid of (t-BuNC)(PPh3)Pt(m-h1:h2-
CꢀC(Ph)NS(O)2Tol-p)C(O)CH2)Ru(CO)Cp (10). Yield,
0.075 g (60%). Selected data for 10: IR (CH2Cl2) w(CO)
J
signals disappeared except for the signal at l 14.5.
2.4.4. Reaction of 2 with ClS(O)2NCO
To a stirred solution of 2 (0.16 g, 0.16 mmol) in THF
(10 ml) at −78°C was added dropwise over 1 min
ClS(O)2NCO (0.060 ml, 0.68 mmol). The resulting solu-
tion was stirred for 1 h, during which time its color
changed from orange to dark red. Warming to r.t. over
6 h and stirring for an additional 12 h yielded a cloudy
brown solution. This solution was filtered and the
solvent was removed from the filtrate to yield a brown
tar. Attempted purification of the tar by crystallization
or chromatography resulted in decomposition.
1
1908 (s), 1714 (m) cm−1. H-NMR (C6D6): l 8.3–6.5
(m, 24H, Ph and C6H4), 5.38 (s, 5H, Cp), 3.66 (dd,
JHH=21.6 Hz, JPH=1.8 Hz, JPtH=50 Hz, 1H of
CH2), 3.29 (dd, JHH=21.6 Hz, JPH=6.6 Hz, 1H of
CH2). 13C{1H}-NMR (C6D6): l 203.1 (s, RuCO), 167.7
(s, ꢀCPt), 141.1 (s, ꢀCPh), 85.3 (s, Cp), 52.7 (s, CH2),
21.1 (s, Me). 31P{1H}-NMR (C6D6): l 14.6 (s, JPtP
=
2.5. Reaction of (PPh3)2Pt(v-p1:ph2,i-C(Ph)ꢀCꢀCH2)-
Ru(CO)Cp (2) with CO followed by p-TolS(O)2NCO
(TSI)
3538 Hz). FAB MS: 102Ru, 195Pt, m/z (ion, relative
intensity) 1047 (M+, 14.0), 1019 (M+–CO, 9.3), 850
(M+–TolSO2NCO, 100). Anal. Found: C, 52.51; H,
4.27. C46H43N2O4PPtRuS Calc.: C, 52.77; H, 4.14.
Carbon monoxide was bubbled through a solution of
2 (0.10 g, 0.10 mmol) in toluene (10 ml) at r.t. for 18 h
to ensure conversion of the latter to Cp(CO)2-
RuC(Ph)ꢀCꢀCH2 and (PPh3)2Pt(CO)2. The reaction so-
lution was then placed under an Ar atmosphere, cooled
to −78°C, and treated with two equivalents of TSI
(0.079 M solution, 0.20 mmol) in toluene (2.5 ml). The
resulting solution was allowed to warm to r.t. over 1 h,
during which time a white precipitate had formed. A
31P{1H}-NMR spectrum (CDCl3) of the solid showed a
singlet resonance at l 5.10 (JPtP=3698 Hz). A 1H-
NMR spectrum (CDCl3) of the material remaining in
solution revealed resonances of Cp(CO)2RuC-
(Ph)ꢀCꢀCH2 (l 5.28 (s, 5H, Cp), 4.14 (s, 2H, ꢀCH2))
and of another Ru compound (l 5.00 (s, 5H, Cp), 3.16
(s, 2H, CH2)). The reaction solution was filtered to
remove the precipitate, the solvent was removed under
reduced pressure from the filtrate and hexane (10 ml)
was added to the red residue. After the mixture had
been stirred for 18 h, an orange powder was isolated by
filtration. FAB MS: 102Ru, m/z (ion, relative intensity)
339 (M++1, 20.6), 311 (M++1-CO, 7.8), 283 (M++
1-2CO, 21.9) (M=Cp(CO)2RuC3H2Ph). No satisfac-
tory FAB MS data were obtained for the other Ru
compound. Attempts at separation/purification of the
orange powder by chromatography on alumina were
unsuccessful.
2.4. Reactions of (PPh3)2Pt(v-p1:ph2,i-C(R)ꢀCꢀCH2)-
Ru(CO)Cp (R=H (1), Ph (2)) with other unsaturated
organic compounds
2.4.1. Reactions of 1 with alkynes
A stirred solution of 1 (0.10–0.20 g, 0.11–0.21
mmol) in THF (5–10 ml) at −78°C or r.t. was treated
with
1–2
equivalents
of
MeO2CCꢁCCO2Me,
MeO2CCꢁCMe, PhCꢁCH or PhCꢁCPh. The solutions
at −78°C were allowed to warm to r.t. and all solu-
tions were stirred at ca. 25°C for 3–12 h. Aliquots were
withdrawn, freed of the solvent, and the residue was
1
dissolved in a deuteriated solvent and examined by H
and/or 13P-NMR spectroscopy.
2.4.2. Reactions of 2 with (CN)2CꢀCPh2,
trans-NCCHꢀCHCN and MeS(O)2NSO
A stirred solution of 2 (0.15–0.20 g, 0.15–0.19
mmol) in benzene or toluene (ca. 10 ml) at r.t. was
treated with 1–2 equivalents of (CN)2CꢀCPh2, trans-
NCCHꢀCHCN or MeS(O)2NSO. No reaction was ob-
served by 31P-NMR spectroscopy in 2–6 h. The
solution was then maintained at reflux temperature for
1
2–4 h, cooled, and examined by H and/or 31P-NMR
spectroscopy as described for the preceding experiments
(Section 2.4.1).
2.6. Crystallographic analyses
2.4.3. Reactions of 1 with (CN)2CꢀC(CN)2
To a stirred solution of 1 (0.20 g, 0.21 mmol) in
CH2Cl2 (10 ml) at −78°C was added solid
(CN)2CꢀC(CN)2 (0.030 g, 0.23 mmol). After 1 h of
reaction time the solution was examined by 31P{1H}-
NMR spectroscopy: l 26.6 (d, JPP=7.0 Hz, JPtP=2891
2.6.1. (PPh3)2Pt(v-p1:ph2,i-C(Ph)ꢀCꢀCHC-
(O)NHS(O)2Tol-p)Ru(CO)Cp·C3H6O (7·C3H6O)
Crystals of 7·C3H6O were grown from dichloro-
methane–acetone. Lattice constants were determined

R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
469
by a least-squares refinement of 25 reflections, accu-
rately centered on an Enraf–Nonius CAD4 diffrac-
tometer. A summary of the crystal data and refinement
is presented in Table 1. No significant change in intensi-
ties of control reflections was observed over the course
of data collection. The data were corrected for Lorentz
polarization effects, as well as for absorption, through
an empirical correction based on the c scans of four
close-to-axial reflections [18]. The structure was solved
by Patterson and Fourier methods [18] and refined on
F2 by least-squares methods [19]. A difference Fourier
map revealed the presence of one acetone molecule
disordered over two positions (occupancy factor 50%).
Hydrogen atoms were located in calculated positions
and refined as riding, including free torsion of the
methyl groups. Uiso values for H atoms were set to
1.2Ueq values of the parent carbon or nitrogen atoms.
The hydrogen atoms of the solvent molecules were not
included in the calculations. Final full-matrix least-
squares refinement converged to R=0.059. Anisotropic
temperature factors were assigned to all non-hydrogen
atoms, with exclusion of the acetone molecules, which
were refined isotropically with distance constraints.
2.6.2. (t-BuNC)(PPh3)Pt(v-p1:p2-CꢀC(Ph)N-
(S(O)2Tol-p)C(O)CH2)Ru(CO)Cp (10)
Table 1
Crystal data and experimental details for (PPh3)2Pt(m-h1:ha2,b
-
Crystals of 10 were grown from dichloromethane–
hexane. The data collection crystal, a yellow plate, was
glued to the inside surface of a glass capillary. A small
amount of a dichloromethane–hexane mixture was also
sealed inside the capillary. The unit cell constants were
determined by a least-squares fit of the diffractometer
setting angles for 25 reflections in the 2q range 29–30°
C(Ph)ꢀCꢀCHC(O)NHS(O)2Tol-p)Ru(CO)Cp·C3H6O (7·C3H6O) and
(t-BuNC)(PPh3)Pt(m-h1:h2-CꢀC(Ph)N(S(O)2Tol-p)C(O)CH2)Ru(CO)-
Cp (10)
7·C3H6O
10
Molecular formula
C59H49NO4P2PtRuS· C46H43N2O4PPtRuS
C3H6O
Formula weight
Crystal system
Space group
1284.31
Triclinic
1047.05
Monoclinic
P21/n
11.502(3)
16.518(4)
23.008(5)
with Mo–Ka radiation on
diffractometer.
a
Rigaku AFC5S
(
P1
Six standard reflections were measured after every
150 reflections during data collection and indicated that
the crystal was undergoing decay. Four of the stan-
dards were low angle reflections (2qB10°) and showed
a percentage decrease in intensity in the range 5.3–
8.2%. The other two standards were high angle (2q#
30°) and exhibited much larger decreases in intensity,
28.1–30.7%. Data reduction was done with the TEXSAN
package [20]. A decay correction was applied based on
an average decrease in intensity of 14.3%. The data was
also corrected for absorption by the empirical c scan
method [21].
,
a (A)
10.797(6)
12.050(10)
22.809(20)
78.64(5)
89.72(5)
86.82(5)
2904.8(8)
2
,
b (A)
,
c (A)
h (°)
i (°)
k (°)
102.50(2)
3
,
V (A )
4268(2)
4
1.63
Z
Dcalc. (g cm−3
)
1.47
Temperature (°C)
Ambient
28.2
23
37.8
v (cm−1
)
Crystal size (mm)
Radiation
Scan type
Scan angle (°)
2q range (°)
0.30×0.33×0.40
Mo–Ka, graphite (u=0.71073 A)
ꢀ/2q
0.60+0.35 tan q
4–54
0.19×0.31×0.31
,
ꢀ
a
The Pt and Ru atoms were located by the Patterson
method. The rest of the molecule was elucidated by use
of the DIRDIF procedure [22] and standard Fourier
methods. Full-matrix least-squares refinements on F
were performed in TEXSAN [20]. The Cp ring appeared
to be disordered and was modeled in terms of two
orientations within a common plane: C(37), C(38),
C(39), C(40) and C(41) label one ring, while C(37A),
C(38A), C(39A), C(40A) and C(41A) label the other.
Each ring has a fixed occupancy factor of 0.5. The t-Bu
group also appeared to be disordered with respect to
rotation about the N(2)ꢂC(36) bond, and was modeled
with two sets of Me carbons: C(44), C(45) and C(46)
define one set, and C(47), C(48) and C(49) define the
second set. Each set has an occupancy factor fixed at
0.5. Both the Cp ring and the Me carbons of the t-Bu
group were refined isotropically, while all the other
non-hydrogen atoms were refined anisotropically. Hy-
drogen atoms were included in the model as fixed
contributions based on calculated positions at CꢂH=
1.30+0.35 tan q
4–55
Transmission factors
No. of unique
reflections measured
0.84–1.00
12638
0.71–1.00
10155
No. of reflections with 9282
4763
I\2|(I)
No. of parameters
Minimized function
w
654
497
ꢀw(Fo2−Fc2)2
1/[|2(Fo2)
+(0.1083P)2
ꢀw(ꢁFoꢁ−ꢁFcꢁ)2
1/|2(Fo)
+22.0586P] where
P=(Fo2+2Fc2)/3
0.059
R (I\2|(I)) b
wR2 (for 7·C3H6O)
0.051
0.045
c
0.155
and wR (for 10)
GOF
1.04
1.19
Residuals in final
2.90, −2.86
0.70, −1.19
difference map
−3
,
(e A
)
a Extended by 25% on both sides for background measurements.
b R=ꢀꢂFoꢁ−ꢁFcꢂ/ꢀꢁFoꢁ.
c wR2={ꢀ[w(Fo2−Fc2)2]/ꢀ(wFo2)2}1/2 and wR={ꢀw(ꢁFoꢁ−ꢁFcꢁ)2/
ꢀwFo2}1/2
.
,
0.98 A and BH=1.2Beq (attached carbon atom).

470
R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
Methyl group hydrogen atoms were idealized to sp3
geometry based on positions located on various differ-
ence electron density maps. There are no hydrogens on
the Me carbon C(46), as no reasonable positions for
defining hydrogen atoms could be located on a DF
map. The final refinement cycle was based on the
4763 intensities with I\2|(I). Scattering factors for
the non-hydrogen atoms, including terms for anoma-
lous dispersion [23], and the scattering factor for
the hydrogen atom [24] are from the literature. A
summary of the crystal data and the details of the
intensity data collection and refinement are provided in
Table 1.
are inequivalent, as they are for 1 and 2, and couple
differently to 195Pt (JPtP=2564 and 3406 Hz for 3,
JPtP=2526 and 3427 Hz for 4). Again these features are
very reminiscent of those of the m-allenyl precursors.
The appearance in the FAB mass spectra of a peak
corresponding to Pt(Ph2P(CH2)3PPh2)+, as well as the
1
presence in the H- and 13C{1H}-NMR spectra of the
appropriate resonances of CH2CH2CH2, indicate that
phosphine substitution indeed occurred at platinum.
Complexes 3 and 4 are much less reactive than 1 and
2. For example, neither 3 nor 4 reacts with CO in
benzene at ca. 70°C in 2–4 days. Likewise, no reaction
was observed between 3 and t-BuNC in THF at reflux
temperature for 18 h. In contrast, under less forcing
conditions, reactions do occur for 1 and/or 2 with CO
and t-BuNC and lead to replacement of PPh3 by the
reacting ligand or to fragmentation of the binuclear
complex [17].
3. Results and discussion
3.1. Reactions of (PPh3)2Pt(v-p1:ph2,i-C(R)ꢀCꢀCH2)-
Ru(CO)Cp (R=H (1), Ph (2)) with nucleophilic
reagents
Treatment of 1 with PEt3 (either two equivalents or
an excess) in THF under conditions comparable with
those for the reactions of
1
and
2
with
Ph2PCH2CH2CH2PPh2 leads to the formation of
(PEt3)2Pt(m-h1:ha2,b-CHꢀCꢀCH2)Ru(CO)Cp (5) (Eq.
(3)), isolated in 85% yield as a yellow solid.
Reaction of 1 and 2 with Ph2PCH2CH2CH2PPh2 in
THF first at −78°C and then at r.t. afforded the
substitution products (Ph2PCH2CH2CH2PPh2)Pt(m-
h1:h2a,b-C(R)ꢀCꢀCH2)Ru(CO)Cp (R=H (3), Ph (4)) as
yellow solids (Eq. (2)).
(3)
The product exhibits spectroscopic properties that are
very similar to those of 1–4. Accordingly, the IR w(CO)
absorption at 1892 cm−1 reflects stronger basicity of
PEt3 than of PPh3 or Ph2PCH2CH2CH2PPh2. In the
1H-NMR spectrum of 5 the ꢀCH resonance is observed
at l 6.42 as a multiplet, while the inequivalent ꢀCH2
protons are seen at l 5.41 and 4.70, also as multiplets
owing to spin–spin coupling with phosphorus. All
three protons are coupled to 195Pt (JPtH=31, 20 and
13 Hz, respectively). The two PEt3 ligands are, as
expected [17], inequivalent in the 31P{1H}-NMR spec-
trum, giving rise to signals at l 23.9 and 12.4 with
JPPB1 Hz and JPtP=3681 and 2733 Hz, respectively.
A parent mass peak, m/z 665, is observed in the FAB
spectrum.
(2)
The substitution was shown to proceed cleanly by
NMR spectroscopy; however, the yields of isolated
products are only 40–50% owing to the difficulty in
complete removal of triphenylphosphine.
Complexes 3 and 4 were characterized by a combina-
tion of IR and NMR (1H, 13C{1H} and 31P{1H})
spectroscopy, FAB mass spectrometry and chemical
analysis. The IR w(CO) absorption at 1902–1901 cm−1
is about 10 cm−1 lower than that of 1 or 2, consistent
with replacement of two PPh3 ligands with a stronger
base Ph2PCH2CH2CH2PPh2. The 1H- and 13C{1H}-
NMR spectra (cf. Section 2) show that the Ru(CO)Cp
fragment remained intact. The m-h1:ha2,b-allenyl also
retains its integrity in the reaction, as reflected by its
The reaction of 2 with an excess of t-BuNC in THF,
first at −78°C and then at r.t., afforded the monosub-
stitution
product
(t-BuNC)(PPh3)Pt(m-h1:ha2,b
-
C(Ph)ꢀCꢀCH2)Ru(CO)Cp (6) (Eq. (4)) as a yellow solid
in 67% yield.
characteristic H- and 13C{1H}-NMR signals. Thus, the
1
ꢀCH2 protons are inequivalent and resonate at l 5.59
and 4.77 for 3 and l 6.12 and 5.56 (2JHH=2.2 Hz) for
4. The ꢀCH proton of 3 occurs at l 6.70. The 13C{1H}
signals are observed at l 168.9 (ꢀCꢀ), 112.4 (ꢀCH,
J
PtC=722 Hz) and 94.5 (ꢀCH2). These data are very
similar to those of the parent complexes 1 and 2 [17]. In
the 31P{1H}-NMR spectra of 3 and 4, the two P nuclei
(4)

R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
471
The second PPh3 ligand could not be replaced even
upon heating for several hours at ca. 67°C. Complex 6
is rather unusual in that all of its ligands and the two
metals are different. It was unambiguously character-
ized by IR and NMR (1H, 13C{1H} and 31P{1H})
spectroscopy, FAB mass spectrometry and elemental
analysis. The IR w(CO) absorption at 1901 cm−1 shows
higher electron density at ruthenium in 6 than in 2, as
a result of replacement of PPh3 with the more basic
t-BuNC at platinum. The ꢀCH2 protons observed at l
5.62 and 4.98 are not discernibly coupled to each other
or to phosphorus, but are coupled to 195Pt (JPtH=17
and 13 Hz, respectively). The 13C{1H}-NMR spectrum
displays rather typical resonances for the three m-allenyl
carbons at l 166.5 (ꢀCꢀ), 150.1 (ꢀCPh) and 97.0 (ꢀCH2,
results discussed in the next section reinforce this gener-
alization further.
3.2. Reactions of L2Pt(v-p1:ph2,i-C(R)ꢀCꢀCH2)-
Ru(CO)Cp (L2=2PPh3, R=H (1), Ph (2);
L2=Ph2PCH2CH2CH2PPh2, R=H (3), Ph (4);
L2=PPh3 and t-BuNC, R=Ph (6)) with electrophilic
reagents
As was stated in Section 1, complexes 1 and 2 react
with the electrophilic species (PPh3)Au+ to afford
trimetallic h3-allyl cations by addition of gold phos-
phine to the b-carbon atom of the m-allenyl ligand [10].
To explore the generality and scope of the electrophilic
reactions of 1, 2 and related complexes, we have ex-
tended our investigation to various unsaturated elec-
trophiles, especially isocyanates, alkenes and alkynes.
We begin our presentation with reactions between com-
plexes 1–4, 6 and p-TolS(O)2NCO. p-Toluenesulfonyl
isocyanate was previously shown to react with mononu-
clear transition-metal h1-allyls, propargyls and allenyls
(Eq. (5)) to afford [3+2] cycloaddition products
[16,25,26].
J
PtH=32.2 Hz). The lone 31P{1H}-NMR signal is ob-
served at l 25.6 with JPtP=3544 Hz; the magnitude of
the latter suggests that the Ph3PꢂPt bond is positioned
trans to RuꢂPt [10,17]. Additional evidence for this
stereochemical feature comes from the structural analy-
sis of complex 10, which will be presented in Section
3.2.1. The FAB mass spectrum of 6 shows a strong
molecular ion peak at m/z 850.
Unlike Ph2PCH2CH2CH2PPh2, PEt3 and t-BuNC,
which reacted with substitution at the Pt center of 1
and 2, the nitrogen-donor ligands Et2NH, C6H11NH2
and p-TolS(O)2NH2 failed to react with 1 or 2 in THF
or benzene solution even at elevated temperatures. This
selectivity reflects a greater preference of platinum for
the softer ligands phosphine and isocyanide than for
the harder amines.
(5)
Furthermore, cycloaddition reactions with the h1-allyl
and propargyl complexes were found to proceed suffi-
ciently cleanly to be amenable to kinetic studies [16,26].
The results obtained here may be contrasted with
those of Carty [4,5] and Doherty [6–9], who have
reported a number of reactions of (CO)3Ru(m-PPh2)-
(m-h1:ha2,b-C(Ph)ꢀCꢀCH2)Ru(CO)3, (CO)3Ru(m-PPh2)-
(m-h1:ha2,b-C(Ph)ꢀCꢀCPh2)Ru(CO)3, (CO)3Fe(m-PPh2)-
(m-h1:ha2,b-C(R)ꢀCꢀCH2)Fe(CO)3 (R=H, Ph) and
(CO)3Fe(m-SBu-t)(m-h1:ha2,b-CHꢀCꢀCH2)Fe(CO)3 with
nucleophilic reagents. They found that the aforemen-
tioned m-allenyl complexes are quite electrophilic and
readily react with primary amines [4a,7], alcohols [8],
organolithium reagents [9a], isocyanides [4a,9b], phos-
phite esters [4a,6b] and monodentate and bidentate
phosphines [4–6]. In most cases, the nucleophile adds
to the allenyl ligand; however, addition to carbon
monoxide and metal also has been noted. By way of
contrast, complexes 1 and 2 do not display such elec-
trophilic properties, and their reactions with nucle-
ophilic reagents appear to be limited to substitution at
the relatively labile platinum center. The much more
pronounced electrophilic properties of the Carty–Do-
herty m-allenyls may be attributed to the presence of six
good p-acid CO ligands in those complexes. The pres-
ence of only one CO in conjunction with the consider-
ably weaker p-acceptor Cp and PPh3 ligands renders
complexes 1 and 2 appreciably more nucleophilic. The
3.2.1. Reactions of 2, 4 and 6 with p-TolS(O)2NCO
(TSI)
Reaction of 2 with an excess of TSI in toluene first at
−78°C and then at r.t. afforded two bimetallic products:
yellow (PPh3)2Pt(m - h1:ha2,b - C(Ph)ꢀCꢀCHC(O)NHS-
(O)2Tol-p)Ru(CO)Cp (7), isolated in 54% yield, and or-
ange (PPh3)2Pt(m - h1:h2 - CꢀC(Ph)N(S(O)2Tol - p)C(O)-
CH2)Ru(CO)Cp (8), obtained in ca. 11% yield (Eq. (6)).
(6)

472
R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
Fig. 1. ORTEP plot of 7 in 7·C3H6O. The non-hydrogen atoms are drawn at the 50% probability level. For clarity only the P-bonded carbon atoms
of the PPh3 groups are shown, and the hydrogen atoms are omitted.
Complex
7
precipitated from the reaction solu-
C(Ph)ꢀCꢀCH2. The addition was accompanied by a
proton transfer from the ꢀCH2 carbon of 2 to the
isocyanate nitrogen. The connectivity of m-allenyl to
tion, whereas 8 was isolated from the mother liquor.
That the PtꢂRu bond remains intact in 7 is evident
upon examination of the w(CO) region of the IR spec-
trum (1924 (s), 1670 (s) cm−1) and the signals in the
31P{1H}-NMR spectrum (21.6, JPP=11 Hz, JPtP=2789
Hz and 20.9, JPP=11 Hz, JPtP=3923 Hz). The former
shows CO groups bonded to ruthenium and nitrogen,
respectively, and the latter indicate that the phosphorus
atoms of PPh3 on platinum are inequivalent and res-
onate with the appropriate coupling constants. The
1H-NMR spectrum reveals NH (l 12.1) and CH (l
5.96, JPtH=10 Hz) protons and the Me group of the
p-TolS(O)2 substituent (l 2.43), all as singlets, to sug-
gest an interaction between m-allenyl and a TSI-derived
fragment. The 13C{1H}-NMR signals at l 164.5, 146.2
and 108.4 are very similar to those for the parent
complex 2 (l 165.3, 149.1 and 97.2). Further evidence
for the formulation of 7 comes from the FAB mass
spectrum, which shows a molecular ion peak at m/z
1226, and from elemental analysis.
Table 2
,
Selected bond distances (A), bond angles (°) and torsion angles (°) for
(PPh3)2Pt(m-h1:ha2,b-C(Ph)ꢀCꢀCHC(O)NHS(O)2Tol-p)Ru(CO)
Cp·C3H6O (7·C3H6O)
Bond distances
PtꢂRu
2.7009(8)
2.260(2)
2.296(2)
2.028(9)
1.854(11)
2.147(9)
2.053(9)
CO
C(4)ꢂO(3)
C(4)ꢂN
C(1)ꢂC(2)
C(1)ꢂC(5)
C(2)ꢂC(3)
C(3)ꢂC(4)
1.137(13)
1.210(14)
1.37(2)
1.378(12)
1.490(12)
1.354(13)
1.45(2)
PtꢂP(1)
PtꢂP(2)
PtꢂC(1)
RuꢂC
RuꢂC(1)
RuꢂC(2)
Bond angles
C(1)ꢂPtꢂP(1)
C(1)ꢂPtꢂP(2)
P(1)ꢂPtꢂP(2)
C(1)ꢂPtꢂRu
P(1)ꢂPtꢂRu
P(2)ꢂPtꢂRu
CꢂRuꢂC(1)
CꢂRuꢂC(2)
CꢂRuꢂPt
98.0(3)
159.2(3)
102.15(8)
51.6(2)
147.86(6)
109.24(6)
98.6(4)
85.5(4)
70.6(3)
47.8(2)
74.8(3)
C(2)ꢂC(1)ꢂC(5) 123.3(8)
C(2)ꢂC(1)ꢂPt
C(5)ꢂC(1)ꢂPt
C(2)ꢂC(1)ꢂRu
C(5)ꢂC(1)ꢂRu
117.6(6)
119.1(6)
67.2(5)
123.9(6)
C(1)ꢂC(2)ꢂC(3) 140.6(9)
However, to unequivocally establish the structure of
7 an X-ray diffraction analysis was carried out. The
crystal consists of PtRu binuclear molecules (7) and
acetone of crystallization in a 1:1 ratio. The molecular
structure of 7 appears in Fig. 1, and selected bond
distances and angles are provided in Table 2.
C(3)ꢂC(2)ꢂRu
C(1)ꢂC(2)ꢂRu
144.6(7)
74.6(6)
C(2)ꢂC(3)ꢂC(4) 126(1)
O(3)ꢂC(4)ꢂN 121(1)
O(3)ꢂC(4)ꢂC(3) 123(1)
NꢂC(4)ꢂC(3) 115.4(9)
C(1)ꢂRuꢂPt
C(2)ꢂRuꢂPt
OꢂCꢂRu
174(1)
Torsion angles
Molecules of 7 are comprised of Ru(CO)Cp and
Pt(PPh3)2 fragments joined by a PtꢂRu single bond that
is supported by a bridging m-h1:ha2,b-C(Ph)ꢀCꢀCHC(O)
NHS(O)2Tol-p ligand. This new m-allenyl ligand re-
sulted from the addition of p-TolS(O)2NCO through
C(5)ꢂC(1)ꢂC(2)ꢂC(3)
PtꢂC(1)ꢂC(2)ꢂC(3)
RuꢂC(1)ꢂC(2)ꢂC(3)
C(5)ꢂC(1)ꢂC(2)ꢂRu
67(2)
−111(1)
−176(2)
−116.6(9)
C(1)ꢂC(2)ꢂC(3)ꢂC(4) −179(1)
RuꢂC(2)ꢂC(3)ꢂC(4) 8(2)
the NCO carbon to g-carbon of the parent m-h1:ha2,b
-

R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
473
PtꢂRu remained unchanged and is through C(1) to Pt
and through the internal CꢀC (C(1) and C(2)) to Ru.
The remaining structural features of 7 are remarkably
similar to those found in 1 and/or (PPh3)(CO)Pt(m-
h1:h2a,b-C(Ph)ꢀCꢀCH2)Ru(CO)Cp (I), and its relevant
metrical parameters are also comparable [17].
Complex 4 reacted with excess TSI in benzene at r.t.
to produce (Ph2PCH2CH2CH2PPh2)Pt(m-h1:h2-CꢀC-
(Ph)N(S(O)2Tol-p)C(O)CH2)Ru(CO)Cp (9) (Eq. (7)) as
a yellow solid in 53% yield.
,
The PtꢂRu bond distance of 2.7009(8) A is somewhat
,
shorter than that of 2.718(1) A in 1, but longer than
,
that of 2.668(1) A in I. The RuꢂC(allenyl) bond lengths
,
in 7 are RuꢂC(1)=2.147(9) A and RuꢂC(2)=2.053(9)
,
,
A; for comparison, RuꢂCa=2.116(6) A and RuCb=
,
,
(7)
2.098(7) A in 1, and RuꢂCa=2.162(9) A and RuCb=
,
,
2.107(8) A in I. The PtꢂC(1) bond distance 2.028(9) A
No product structurally analogous to 7 was observed in
this reaction. Salient spectroscopic features of 9 include
,
in 7 may be compared with that of 2.015(6) A in 1 and
1
2
,
2.025(9) A in I. The m-h :ha,b-allenyl ligand displays
IR w(CO) absorptions at 1894 (s) and 1708 (m) cm−1
,
carbonꢂcarbon bond distances (C(1)ꢂC(2)=1.378(12)
inequivalent NMR signals of the CH2 protons at l 3.41
,
and C(2)ꢂC(3)=1.354(13) A) that are in the normal
and 2.82 and two 31P{1H} resonances at l 0.47 (JPtP
=
range for this type of bonding with CaꢂCb\CbꢂCg [2].
The allenyl C(1)ꢂC(2)ꢂC(3) bond angle of 140.6(9)° is
somewhat less obtuse than that observed in similarly
bonded compounds [2,9a].
2362 Hz) and −6.6 (JPtP=3468 Hz) showing mutual
coupling (JPP=26.5 Hz) of the phosphorus nuclei. The
FAB mass spectrum shows a peak at m/z 1114, consis-
tent with the complex being a 1:1 adduct of 4 and TSI.
These data support a structure similar to that of 8.
Treatment of 6 with a two-fold excess of TSI in
toluene at −78°C, followed by warming and continued
reaction at r.t., resulted in the isolation of yellow
(t - BuNC)(PPh3)Pt(m - h1:h2 - CꢀC(Ph)N(S(O)2Tol - p)-
C(O)CH2)Ru(CO)Cp (10) in 60% yield (Eq. (8)).
The atoms P(1), P(2), Ru and C(1) provide a dis-
torted planar coordination environment around the Pt
center, with the bond angles being P(1)ꢂPtꢂP(2)
102.15(8)°, C(1)ꢂPtꢂRu 51.6(2)°, C(1)ꢂPtꢂP(1) 98.0(3)°
and P(2)ꢂPtꢂRu 109.24(6)°. The two PtꢂP bond dis-
tances are slightly different: PtꢂP(1)=2.260(2) and
,
PtꢂP(2)=2.296(2) A. A somewhat longer PtꢂP bond
trans to the bridging hydrocarbyl a-carbon (C(1)) than
that trans to ruthenium appears to be a general phe-
nomenon in these heterobinuclear and heterotrinuclear
RuPt(PPh3)2-fragment containing m-allenyl and related
complexes [10,17]. Significantly, it is the phosphine
approximately trans to that carbon atom (C(1)ꢂPtꢂP(2)
159.2(3)°) that undergoes facile substitution by other
ligands, e.g. CO [17] and t-BuNC.
(8)
Complex 8, the other product of the reaction in Eq.
(6), is assigned a cycloaddition structure on the basis of
spectroscopic similarities to the structurally character-
ized 10 (vide infra). The IR w(CO) bands at 1899 (s)
and 1724 (s) cm−1 are consistent with the presence of a
ruthenium-bonded CO and a butenolactone ring [25b],
Spectroscopic data for 10, furnished in Section 2,
show many similarities to those for 8 and 9. The CH2
protons are inequivalent (l 3.66, JPH=1.8 Hz, JPtH
=
50 Hz and 3.29, JPH=6.6 Hz) and mutually coupled
(2JHH=21.6 Hz). The m-allenyl-derived carbon atoms
resonate at l 167.7 (ꢀCPt), 141.1 (ꢀCPh) and 52.7
(CH2), close to the chemical shift values reported
for [3+2] cycloaddition-derived butenolactone com-
plexes and for products of related cycloaddition reac-
tions [16,27,28]. The FAB mass spectrum features
a parent molecular ion peak at m/z 1047 and, most
interestingly, a peak at m/z 850. The latter corre-
sponds to (M+–TolS(O)2NCO) and occurs with rela-
tive intensity=100 to indicate that the cycloaddition
reaction of 6 with TSI is readily reversed for 10+ in the
gas phase.
1
respectively. The position and the splitting of the H-
and 13C{1H}-NMR signals of the methylene group
indicate that this CH2 is considerably different from the
ꢀCH2 of the precursor 2. Thus, the 13C{1H} resonance
occurs as a singlet at l 52.5 (JPtC=54.7 Hz), shifted
upfield from l 97.2 in 2, in line with the hybridization
changing from sp2 to sp3. An AB/ABX splitting pattern
in the 1H-NMR spectrum (l 3.71, 2JHH=21.3 Hz,
2
J
PtH=17.2 Hz and 2.72 Hz, JHH=21.3 Hz, JPH=14.5
Hz) implicates Csp3-bonded geminal protons that are
rendered inequivalent by the absence of a symmetry
plane in the molecule. The two PPh3 phosphorus nuclei
are predictably inequivalent (l 22.7 and 16.3) and show
JPtP values (2643 and 3621 Hz, respectively) typical for
these PtRu complexes [10,17].
Unequivocal determination of the structure of 10 was
achieved by an X-ray diffraction analysis. The molecu-
lar structure is shown in Fig. 2, and selected bond

474
R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
Fig. 2. ORTEP plot of 10. The non-hydrogen atoms are represented by 30% probability thermal ellipsoids. The hydrogen atoms have been omitted
for clarity, except the two hydrogens bonded to C(6). Only one orientation of the disordered Cp ring and one set of methyl carbons on the
disordered t-butyl group are shown.
are PtꢂRu=2.664(1), PtꢂP 2.271(3), PtꢂC(20)=
distances and angles are given in Table 3. The most
striking feature of 10 is the presence of a bridging
butenolactone group, which was formed by [3+2] cy-
cloaddition of TSI to the m-allenyl ligand of 6. The
,
1.964(13) and PtꢂC(5)=1.983(9) A. The PtꢂRu bond
distance may be compared with those in the range
,
2.668(1)–2.718(1) A for the m-allenyl complexes 1, 7
butenolactone is h2 bonded to Ru (RuꢂC(4)=2.150(9)
1
,
and RuꢂC(5)=2.153(10) A) and h bonded to Pt
Table 3
,
,
(PtꢂC(5)=1.983(9) A). These bond distances are
Selected bond distances (A) and angles (°) for (t-BuNC)(PPh3)Pt(m-
h1:h2-CꢀC(Ph)N(S(O)2Tol-p)C(O)CH2)Ru(CO)Cp (10)
unexceptional.
The generated C4N five-membered ring is essentially
planar (deviation from the least-squares plane: N(1)
0.0228, C(4) −0.0368, C(5) 0.0345, C(6) −0.0218,
Bond distances
PtꢂRu
PtꢂP
PtꢂC(5)
PtꢂC(20)
RuꢂC(4)
RuꢂC(5)
RuꢂC(43)
O(4)ꢂC(43)
2.664(1)
2.271(3)
1.983(9)
1.964(13)
2.150(9)
2.153(10)
1.836(12)
1.152(12)
N(1)ꢂC(4)
N(1)ꢂC(7)
N(2)ꢂC(20)
N(2)ꢂC(36)
C(4)ꢂC(5)
C(4)ꢂC(8)
C(5)ꢂC(6)
C(6)ꢂC(7)
1.497(12)
1.390(14)
1.151(13)
1.480(15)
1.447(12)
1.515(13)
1.526(14)
1.518(14)
,
C(7) 0.0128, mean 0.0257 A), and its bond distances are
normal. Thus, C(5)ꢂC(6)=1.526(14) and C(6)ꢂC(7)=
,
1.518(14) A correspond to carbonꢂcarbon single bonds,
,
while C(4)ꢂC(5)=1.447(12) A is in line with a metal-
coordinated carbonꢂcarbon double bond [29]. The car-
bonꢂnitrogen bond distances C(4)ꢂN(1)=1.497(12)
and C(7)ꢂN(1)=1.390(14) A are respectively represen-
Bond angles
RuꢂPtꢂP
RuꢂPtꢂC(5)
RuꢂPtꢂC(20)
PꢂPtꢂC(5)
PꢂPtꢂC(20)
C(5)ꢂPtꢂC(20)
PtꢂRuꢂC(4)
159.34(7)
52.8(3)
RuꢂC(4)ꢂC(5)
N(1)ꢂC(4)ꢂC(5)
PtꢂC(5)ꢂRu
PtꢂC(5)ꢂC(4)
PtꢂC(5)ꢂC(6)
RuꢂC(5)ꢂC(4)
RuꢂC(5)ꢂC(6)
C(4)ꢂC(5)ꢂC(6)
C(5)ꢂC(6)ꢂC(7)
O(3)ꢂC(7)ꢂN(1)
O(3)ꢂC(7)ꢂC(6)
N(1)ꢂC(7)ꢂC(6)
PtꢂC(20)ꢂN(2)
RuꢂC(43)ꢂO(4)
70.5(6)
106.5(8)
80.1(4)
125.0(7)
127.6(7)
70.2(6)
120.5(7)
107.3(8)
106.9(9)
126.4(11)
127.1(11)
106.4(10)
173.8(11)
172.2(11)
,
tative of a single bond [30] and a single bond shortened
by contribution from the resonance representation
N(1)ꢀC(7)ꢂO(3).
The coordination environment around the platinum
center is distorted planar, with C(5) being displaced
100.3(3)
106.7(3)
100.3(3)
152.8(4)
77.9(2)
47.1(2)
75.3(4)
39.3(3)
91.9(4)
102.6(4)
112.5(9)
175.3(13)
114.4(6)
PtꢂRuꢂC(5)
,
−0.154 A from the ‘best’ four-atom plane PtRuPC(20)
PtꢂRuꢂC(43)
C(4)ꢂRuꢂC(5)
C(4)ꢂRuꢂC(43)
C(5)ꢂRuꢂC(43)
C(4)ꢂN(1)ꢂC(7)
C(20)ꢂN(2)ꢂC(36)
RuꢂC(4)ꢂN(1)
,
(mean deviation 0.015 A). This plane makes an angle of
61.6(5)° with the butenolactone ring. The four-coordi-
nate environment of platinum is characterized by the
following
bond
angles:
PꢂPtꢂC(20)
100.3(3),
RuꢂPtꢂC(5) 52.8(3), RuꢂPtꢂC(20) 100.3(3) and
PꢂPtꢂC(5) 106.7(3)°. The corresponding bond distances

R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
475
Scheme 1.
ligands are omitted for clarity in Scheme 1). This
intermediate is similar to that (II) proposed for [3+2]
cycloaddition of TSI to Cp(CO)2FeCHꢀCꢀCH2 (Eq.
(5)) [25b].
and I [17]. The PtꢂP [31], PtꢂCsp [17] and PtꢂCsp [32]
2
bond lengths are normal. Interestingly, the PPh3 ligand
is positioned approximately trans to Ru (RuꢂPtꢂP
159.34(7)°), and t-BuNC is approximately trans to C(5)
(C(5)ꢂPtꢂC(20) 152.8(4)°). If the same stereochemistry
characterizes the precursor complex 6 — and there is
spectroscopic evidence for it (cf. Section 3.1) — then
substitution of t-BuNC for PPh3 in 2 (Eq. (4)) proceeds
stereoselectively at the platinum site trans to the hydro-
carbyl carbon. Studies of ligand substitution reactions
of 1 and 2 suggest that this may be a general phe-
nomenon [17].
Collapse of the PtRu m-alkyne intermediate by attack
of the negative nitrogen terminus at the ꢁCR carbon,
with rearrangement of Pt-h2-C(R)ꢁCCH2 to Pt-h1-
C(ꢀCR)CH2, affords the [3+2] cycloaddition product.
Alternatively, the intermediate undergoes proton trans-
fer to the nitrogen to generate the p-TolS(O)2NHC(O)-
substituted m-h1:ha2,b-allenyl complex. The latter
pathway occurs, together with the cycloaddition route,
in the reaction of 2 with TSI. It is precedented by the
behavior of Cl3CC(O)NCO toward the h1-allyl complex
Cp(CO)2FeCH2CHꢀCH2 resulting in the formation of
Cp(CO)2FeCH2CHꢀCHC(O)NHC(O)CCl3 [25c].
The mechanism in Scheme 1 shows an interesting
example of metal cooperativity in effecting the forma-
tion of products. Platinum appears to be the more
involved metal atom in the reaction by undergoing a
bonding change from the Pt-h1-C mode in the m-allenyl
complex to a Pt+-h2-(CꢁC) attachment in the zwitteri-
onic intermediate. The positive charge that develops on
the platinum as a result of this conversion renders the
CꢁC more vulnerable to addition, and the CH2 protons
more susceptible to abstraction by the negative nitro-
gen. The role of the ruthenium atom in these transfor-
mations may be to help stabilize the Pt+-h2-(CꢁC)
interaction in the intermediate, and thus promote at-
tack by nitrogen.
Reactions of complexes 1 and 3 with TSI under a
variety of conditions were investigated by 1H- and
31P{1H}-NMR spectroscopy and found to yield prod-
ucts strictly analogous to those obtained from the
Ph-substituted PtRu analogs 2 and 4. However, in
addition to the products differing from 7–9 only by
replacement of Ph with H, a number of other, un-
characterized binuclear and mononuclear metal-
containing species were detected in solution. The com-
plexes could not be successfully separated by chro-
matography, and studies on these systems were not
further pursued.
The formation of complexes 7–10 may be rational-
ized by a mechanism similar to that proposed for
reactions of metal h1-allyl, propargyl and allenyl com-
plexes with unsaturated electrophilic reagents [33]. A
suitable adaptation of the latter for the binuclear PtRu
m-h1:h2a,b-allenyl complexes and TSI is depicted in
Scheme 1. Electrophilic attack of TSI, through the
carbonyl carbon, at the uncoordinated CꢀCH2 bond of
m-allenyl leads to the formation of a zwitterionic PtRu
alkyne intermediate, in which the alkyne bonds in a
perpendicular mode to both Ru and Pt (all ancillary

476
R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
3.2.2. Reactions of 1 and 2 with other unsaturated
organic compounds
A similar behavior was observed when the phenyl-sub-
stituted alkynes PhCꢁCH and PhCꢁCPh were allowed to
react with 1 in THF solution under comparable condi-
tions. Again, approximately 50% of 1 was consumed, and
Since TSI reacted with each of 2, 4 and 6 to furnish
stable addition products, it was of interest to ascertain
whether other unsaturated electrophilic reagents would
behave similarly. In that vein, reactions were examined
between the electrophiles ClS(O)2NCO and TCNE and
complexes 1 and 2. Both of these electrophilic reagents are
known to react with transition-metal h1-allenyls to afford
[3+2] cycloaddition complexes that are structurally
analogous to the product in Eq. (5) [33]. However, the
reaction of 2 with ClS(O)2NCO afforded only uncharac-
terized decomposition materials. The reaction of 1 with
TCNE in CH2Cl2 at ca. −78°C gave several products as
shown by a 31P{1H}-NMR spectrum; of these, two could
be characterized as a binuclear (PPh3)2PtRu-containing
species and known [15] (PPh3)2Pt(TCNE). Only the latter
remained intact after the solution was allowed to warm to
r.t.
1
the products identified by H- and 31P{1H}-NMR spec-
troscopy were Cp(CO)2RuCHꢀCꢀCH2, (PPh3)2Pt-
(PhCꢁCH) [15] or (PPh3)2Pt(PhCꢁCPh) [15] and
Pt(PPh3)4 [34]. There were, however, other, unassigned
peaks in the NMR spectra.
That the reaction in Eq. (9) can also proceed in the
reverse direction was demonstrated for L=PhCꢁCPh.
When Cp(CO)2RuCHꢀCꢀCH2 in CDCl3 was treated with
a slight deficiency of (PPh3)2Pt(PhCꢁCPh) at r.t., and the
resulting solution was stirred for several hours, unreacted
Cp(CO)2RuCHꢀCꢀCH2 (the excess), 1 (\95%) and a
small amount of (PPh3)2Pt(PhCꢁCPh) (B5%) were de-
tected in solution by 1H- and 31P{1H}-NMR spec-
troscopy. However, the reaction is not truly reversible,
since the forward process is accompanied by some decom-
position of the monocarbonyl 1 in producing the dicar-
bonyl Cp(CO)2RuCHꢀCꢀCH2.
The fragmentation of 1 upon treatment with PhCꢁCPh
may be contrasted with the reaction between (CO)3Ru(m-
PPh2)(m-h1:ha2,b-C(Ph)ꢀCꢀCH2)Ru(CO)3 and PhCꢁCPh,
studied by Carty and co-workers [36]. The latter, con-
ducted in toluene at reflux, resulted in a coupling of the
allenyl and alkyne fragments with retention of both Ru
atoms in the product complex.
The less electrophilic alkene (CN)2CꢀCPh2 was found
to be unreactive toward 2 in benzene solution, even at
reflux temperature. In contrast, the reaction of 2 with a
two-fold excess of fumaronitrile in benzene, also at reflux,
resulted in ca. 75% consumption of 2 after 24 h and the
formation of Cp(CO)2RuC(Ph)ꢀCꢀCH2 (cf. Section 3.2.3
for characterization), known [15] (PPh3)2Pt(trans-
NCCHꢀCHCN) and other unidentified materials (Eq.
(9)): L=trans-NCCHꢀCHCN). The products were char-
1
acterized without separation by H- and 31P{1H}-NMR
3.2.3. Characterization of Cp(CO)2RuC(Ph)ꢀCꢀCH2
The allenyl product of the reaction in Eq. (9) (L=
trans-NCCHꢀCHCN), Cp(CO)2RuC(Ph)ꢀCꢀCH2, rep-
resents a new organometallic compound. It can also be
prepared by a similar reaction of 2 with CO in toluene as
detailed in Section 2. Its isomer Cp(CO)2RuCH2-CꢁCPh
was previously obtained from Cp(CO)2Ru− and
PhCꢁCCH2Cl or PhCꢁCCH2OS(O)2Tol-p [16], and this
propargyl complex has not been observed to undergo
conversion to Cp(CO)2RuC(Ph)ꢀCꢀCH2.
Attempts at isolation and purification of Cp(CO)2-
RuC(Ph)ꢀCꢀCH2 from its reaction mixtures proved to be
unsuccessful. However, NMR data obtained on such
mixtures provided sufficient information for reliable char-
acterization. Thus, the 1H-NMR spectrum of Cp-
(CO)2RuC(Ph)ꢀCꢀCH2 shows the Cp and CH2
resonances at l 5.28 and 4.14, respectively. The position
of these signals may be compared with those of the
corresponding signals at l 5.33 and 2.17 for Cp(CO)2Ru-
CH2CꢁCPh[16],bothrecordedusingCDCl3 solution.The
chemical shift of the CH2 resonance at l 4.14 is consistent
with the presence of an MC(R)ꢀCꢀCH2 fragment [16,35].
In the 13C{1H}-NMR spectrum of Cp(CO)2RuC(Ph)
ꢀCꢀCH2, resonances are observed at l 206.6 for ꢀCꢀ, 68.1
for ꢀCPh and 61.8 for ꢀCH2. These data are in excellent
agreement with those for Cp(CO)2RuCHꢀCꢀCH2, with
the signal at l 206.6 being particularly diagnostic for
mononuclear metal h1-allenyl complexes [16].
spectroscopy.
(9)
The second CO ligand of Cp(CO)2RuC(Ph)ꢀCꢀCH2
must originate from another molecule of 2, and this
transfer of CO is likely to be responsible for the decom-
position observed in the reaction. Redistribution of CO
also accounts for the approximate 2:1 ratio of
(PPh3)2Pt(trans-NCCHꢀCHCN) to Cp(CO)2RuC(Ph)ꢀ
1
CꢀCH2 estimated by H-NMR signal intensities.
Reactions of activated alkynes with 1 are similar to
those of fumaronitrile with 2 (cf. Eq. (9)), except that they
proceed at r.t. Thus,
a 1:1 mixture of 1 and
MeO2CCꢁCCO2Me in THF afforded after 12 h Cp-
(CO)2RuCHꢀCꢀCH2 and (PPh3)2Pt(MeO2CCꢁCCO2-
Me) [15], characterized by 1H- and 31P{1H}-NMR spec-
troscopy, in addition to other unidentified products. The
reaction between 1:1 1 and MeO2CCꢁCMe in THF pro-
ceeded similarly at r.t. to give Cp(CO)2RuCHꢀ
CꢀCH2 and (PPh3)2Pt(MeO2CCꢁCMe) [15], among
other uncharacterized products. Only about 50% of 1 was
consumed in 12 h.

R.R. Willis et al. / Journal of Organometallic Chemistry 593–594 (2000) 465–478
477
5. Supplementary material
Efforts were also made to characterize Cp(CO)2RuC-
(Ph)ꢀCꢀCH2 by conversion to a [3+2] cycloaddition
product with TSI. Toward that goal, a solution of
Cp(CO)2RuC(Ph)ꢀCꢀCH2 and (PPh3)2Pt(CO)2 in
toluene, obtained by reaction of 2 with CO, was treated
with an excess of TSI. The ensuing reaction afforded a
white precipitate, shown by 31P{1H}-NMR spec-
troscopy (l 5.10, JPtP=3698 Hz) to be a mononuclear
platinum phosphine species. One of the two complexes
Crystallographic data for the structural analyses has
been deposited with the Cambridge Crystallographic
Data Centre, CCDC no. 135123 for compound
7·C3H6O and no. 135151 for compound 10. Copies of
this information may be obtained free of charge from
The Director, CCDC, 12 Union Road, Cambridge,
CB2 1EZ, UK (Fax: +44-1223-336033; e-mail: de-
posit@ccdc.cam.ac.uk or http://www.ccdc.cam.ac.uk).
1
remaining in solution was characterized by H-NMR
spectroscopy as unreacted Cp(CO)2RuC(Ph)ꢀCꢀCH2,
while the other displayed singlet resonances at l
5.00 (Cp) and 3.16 (CH2). The position of the l
3.16 signal is consistent with the complex being a
[3+2] cycloaddition product of Cp(CO)2RuC(Ph)ꢀ
CꢀCH2 and TSI of structure analogous to that de-
picted in Eq. (5) [16,25b]. An orange solid isolated
upon subsequent addition of pentane showed a FAB
Acknowledgements
We acknowledge financial support of this investiga-
tion by the National Science Foundation (NSF), The
Ohio State University, and MURST (Rome). Mass
spectra were obtained at The Ohio State University
Chemical Instrument Center (funded in part by NSF
Grant 79-10019). We thank Johnson Matthey Aesar/
Alfa for a loan of ruthenium chloride.
mass spectrum appropriate for
a Cp(CO)2Ru(C3-
H2Ph) complex, but with a different fragmentation
pattern than that for Cp(CO)2RuCH2CꢁCPh [16].
There was no evidence for
a
1:1 adduct of
Cp(CO)2RuC(Ph)ꢀCꢀCH2 and TSI in the spectrum,
possibly owing to a facile loss of TSI by the parent
molecular ion.
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This study has shown that the complexes
(PPh3)2Pt(m-h1:ha2,b-C(R)ꢀCꢀCH2)Ru(CO)Cp (1, 2) and
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