Reactions of ruthenium acetylide complexes with isothiocyanate

Article abstract of DOI:10.1021/om971056d

Treatment of Cp(PPh₃)[P(OMe)₃]RuC≡CPh (2; Cp = η⁵-C₅H₅) with PhN=C=S at room temperature affords the [2 + 2] cycloaddition product Cp(PPh₃)[P(OMe)₃]RuC=C(Ph)C-(=NPh)S (3a), containing a four-membered ring, and the neutral vinylidene phosphonate complex Cp(PPh₃)[P(=O)(OMe)₂]Ru=C=C(Ph)C(SH)=NPh (4a) in a 9:1 ratio. Formation of 4a results from an Arbuzov-like dealkylation reaction possibly after addition of PhN=C=S. The same reaction at 40 °C affords a higher yield of 4a and Cp(PPh₃)[P(OMe)₃]RuC=C-(Ph)C(=S)N(R)C(=NR)S (5a; R = Ph) which results from addition of a second isothiocyanate to the four-membered ring of 3a. The reaction of 2 with PhCH₂N=C=S at room temperature directly affords the six-membered-ring product 5b (R = CH₂Ph). Trimerization of phenyl isothiocyanate is catalyzed by Cp(dppe)RuC=CPh (1′; dppe = Ph₂PCH₂CH₂PPh₂) in refluxing CH₂Cl₂. This catalytic reaction proceeds through a pathway in which the first two steps are the same as those observed in the reaction of 2a. An attempt to purify the precursor of the trimerization product gave the cocrystallization of 1′ and (PhNCS)₃ (8). The structures of 3a, 4a, 5b, and the cocrystallization product of 1′ and 8 have been determined by single-crystal X-ray diffraction analysis.

Full text of DOI:10.1021/om971056d

2534
Organometallics 1998, 17, 2534-2542
Rea ction s of Ru th en iu m Acetylid e Com p lexes w ith
Isoth iocya n a te
Chao-Wan Chang, Ying-Chih Lin,* Gene-Hsiang Lee, Shou-Ling Huang, and
Yu Wang
Department of Chemistry, National Taiwan University, Taipei, Taiwan 106, Republic of China
Received December 2, 1997
Treatment of Cp(PPh3)[P(OMe)3]RuCtCPh (2; Cp ) η5-C5H5) with PhNdCdS at room
temperature affords the [2 + 2] cycloaddition product Cp(PPh3)[P(OMe)3]RuCdC(Ph)C-
(dNPh)S (3a ), containing a four-membered ring, and the neutral vinylidene phosphonate
complex Cp(PPh3)[P(dO)(OMe)2]RudCdC(Ph)C(SH)dNPh (4a ) in a 9:1 ratio. Formation
of 4a results from an Arbuzov-like dealkylation reaction possibly after addition of PhNdCdS.
The same reaction at 40 °C affords a higher yield of 4a and Cp(PPh3)[P(OMe)3]RuCdC-
(Ph)C(dS)N(R)C(dNR)S (5a ; R ) Ph) which results from addition of a second isothiocyanate
to the four-membered ring of 3a . The reaction of 2 with PhCH2NdCdS at room temperature
directly affords the six-membered-ring product 5b (R ) CH2Ph). Trimerization of phenyl
isothiocyanate is catalyzed by Cp(dppe)RuCtCPh (1′; dppe ) Ph2PCH2CH2PPh2) in refluxing
CH2Cl2. This catalytic reaction proceeds through a pathway in which the first two steps
are the same as those observed in the reaction of 2a . An attempt to purify the precursor of
the trimerization product gave the cocrystallization of 1′ and (PhNCS)3 (8). The structures
of 3a , 4a , 5b, and the cocrystallization product of 1′ and 8 have been determined by single-
crystal X-ray diffraction analysis.
In tr od u ction
a metallacycle in which one alkyne and one isocyanate
have been coupled. Herein we report that the reaction
of isocyanate and isothiocyanate with two ruthenium
acetylide complexes results in sequential additions of
the organic substrate to the acetylide ligand to produce
novel heterocyclic ligands. With Cp(dppe)RuCtCPh, [2
+ 2] cycloaddition is the first step and is followed by
further addition of two isothiocyanate molecules to give
a trimerization product. When a trimethyl phosphite
ligand is present, the cycloaddition is accompanied by
an Arbuzov-like dealkylation reaction to give a useful
side product from which the mechanism of the trimer-
ization reaction could be delineated. Structural char-
acterization of several relevant complexes is reported
herein.
Metal acetylide complexes have been the focus of
recent study due to their application in organometallic1
and materials2 chemistry. The acetylide ligand is quite
reactive toward electrophiles, undergoing either alky-
lation or protonation at the â-carbon to give stable
vinylidene complexes. Another common reaction ob-
served for this ligand is the [2 + 2] cycloaddition of the
triple bond with unsaturated organic substrates.3 Cy-
cloadditions of organic substrates such as CS2,4
(NC)2CdC(CF3)2, and (NC)2CdC(CN)25 to the acetylide
ligand in various metal complexes have been reported.
Nickel(0) complexes promote the cyclocoupling of alkynes
with isocyanates.6 This reaction may proceed through
(1) (a) Beck, W.; Niemer, B.; Wieser, M. Angew. Chem., Int. Ed. Engl.
1993, 32, 923. (b) Hegedus, L. S. In Organometallics in Synthesis;
Schlosser, M., Ed.; Wiley: New York, 1994; p 383. (c) Bartik, T.; Bartik,
B.; Brady, M.; Dembinski, R.; Gladysz, J . A. Angew. Chem., Int. Ed.
Engl. 1996, 35, 414. (d) Ting, P. C.; Lin, Y. C.; Lee, G. H.; Cheng, M.
C.; Wang, Y. J . Am. Chem. Soc. 1996, 118, 6433.
(2) (a) Myers, L. K.; Langhoff, C.; Thompson, M. E. J . Am. Chem.
Soc. 1992, 114, 7560. (b) Kaharu, T.; Matsubara, H.; Takahashi, S. J .
Mater. Chem. 1992, 2, 43. (c) Lavastre, O.; Even, M.; Dixneuf, P. H.;
Pacreau, A.; Vairon, J . P. Organometallics 1996, 15, 1530. (d) Wu, I.
Y.; Lin, J . T.; Luo, J .; Sun, S. S.; Li, C. S.; Lin, K. J .; Tsai, C.; Hsu, C.
C.; Lin, J . L. Organometallics 1997, 16, 2038.
(3) Bruce, M. I.; Hambley, T. W.; Leddell, M. J .; Snow, M. R.;
Swincer, A. G.; Tiekink, E. R. T. Organometallics 1990, 9, 96.
(4) (a) Selegue, J . P. J . Am. Chem. Soc. 1982, 104, 119. (b)
Birdwhistell, K. R.; Templeton, J . L. Organometallics 1985, 4, 2062.
(c) Selegue, J . P.; Young, B. A.; Logan, S. L. Organometallics 1991,
10, 1972.
Resu lts a n d Discu ssion
Syn th esis of Acetylid e Com p lexes. Treatment of
Cp(PPh3)2RuCtCPh (1)7 with P(OMe)3 in n-decane at
reflux temperature affords a racemic mixture of Cp-
(PPh3)[P(OMe)3]RuCtCPh (2) in high yield.8 Complex
2 is soluble in polar solvents such as CH2Cl2, CHCl3,
acetone, and THF. In the 31P NMR spectrum, two
doublet resonances at δ 158.3 and 56.6 are assigned to
the phosphite and phosphine ligands, respectively.
Complex 2 could also be prepared in lower yield from
(5) (a) Davison, A.; Solar, J . P. J . Organomet. Chem. 1979, 166, C13.
(b) Bruce, M. I.; Hambley, T. W.; Snow, M. R.; Swincer, A. G.
Organometallics 1985, 4, 501. (c) Barrett, A. G. M.; Carpenter, N. E.;
Mortier, J .; Sabat, M. Organometallics 1990, 9, 151.
(6) Hoberg, H.; Oster, B. W. J . Organomet. Chem. 1983, 252, 359.
(7) (a) Bruce, M. I.; Windsor, N. J . Aust. J . Chem. 1977, 32, 1471.
(b) Bruce, M. I.; Humphrey, M. G. Aust. J . Chem. 1989, 42, 1067.
(8) Bruce, M. I. Aust. J . Chem. 1977, 30, 1602.
S0276-7333(97)01056-X CCC: $15.00 © 1998 American Chemical Society
Publication on Web 05/20/1998

Reactions of Ru Acetylides with Isothiocyanate
Organometallics, Vol. 17, No. 12, 1998 2535
Sch em e 1
treatment of Cp(PPh3)2RuCl with P(OMe)3 followed by
the reaction with HCtCPh. Treatment of 1 with dppe
affords Cp(dppe)RuCtCPh (1′) in high yield.
[2 + 2] Cycloa d d ition a n d Ar bu zov-lik e Dea lk y-
la t ion . Treatment of 2 with a 10-fold excess of
PhNdCdS in CH2Cl2 at room temperature for 3 days
affords the yellow [2 + 2] cycloaddition product Cp-
by reductive elimination.10 Other organic compounds
with similar heterocyclic ring structures have been
reported.11 By treatment of complex 2 with excess
PhCH2NdCdS in CH2Cl2 at room temperature, the
analogous red-orange complex Cp(PPh3)[P(OMe)3]-
RuCdC(Ph)C(dS)N(CH2Ph)C(dNCH2Ph)S (5b) was di-
rectly obtained. Spectroscopic data for 5b are consistent
with this formulation and are comparable with those
for 5a . This reaction also yields the corresponding
phosphonate complex 4b. For PhCH2NdCdS, the
analogous four-membered-ring compound Cp(PPh 3)-
(PPh3)[P(OMe)3]RuCdC(Ph)C(dNPh)S (3a ) and the
neutral red-orange phosphonate vinylidene complex Cp-
(PPh3)[P(dO)(OMe)2]RudCdC(Ph)C(SH)dNPh (4a ) in
a 9:1 ratio (75% total yield). The two complexes can be
separated by column chromatography. Complex 3a is
derived from a [2 + 2] cycloaddition of the CtC triple
bond with the CdS double bond. This neutral complex
is stable in air but, in CHCl3 solution, decomposes to
give 2. The 31P NMR spectrum has two doublet reso-
nances at δ 56.2 and 151.7 with J P-P ) 68.8 Hz, which
are assigned to the PPh3 and the P(OMe)3 ligands,
respectively. The air-stable complex 4a is formed by
an Arbuzov-like dealkylation reaction of the phosphite
ligand.9 The two OMe groups in 4a are diastereotopic
[P(OMe)3]RuCdC(Ph)C(dNCH2Ph)S (3b), a precursor
of 5b, is obtained at 5 °C but transforms, in the presence
of PhCH2NCS, to 5b over 20 min at room temperature.
Isolation of the phosphonate complex indicates that
the CR-S bond is labile. Thus, 3 may easily form the
zwitterionic vinylidene complex A (Scheme 1). Struc-
ture A has a negative charge localized on the N atom,
which may attack the carbon atom of a second isothio-
cyanate to give B. Subsequent ring closure gives the
six-membered-ring complex 5.
Str u ctu r e Deter m in a tion . Complex 3a was char-
acterized by a single-crystal X-ray diffraction analysis;
an ORTEP drawing is shown in Figure 1. Crystal and
intensity collection data are given in Table 1, and
selected bond distances and angles are given in Table
2. The central coordination sphere of the ruthenium
atom contains an η5-cyclopentadienyl ring, the phos-
phorus atoms of phosphite and phosphine ligands, and
the carbon atom (C1) of the organic ligand. The four
atoms of the four-membered ring formed by the [2 + 2]
cycloaddition are essentially planar with the C1-C2
distance of 1.388(10) Å typical of a CdC double bond.
The bond distances for C1-S and C9-S (1.868(7) and
1.823(8) Å) are typical of C-S single bonds.12 The
1
and occur in the H NMR spectrum at δ 3.18 and 3.03
with J P-H ) 11.5 Hz. The 31P NMR spectrum of 4a has
resonances at δ 48.0 and 93.4, the latter due to the
phosphonate.
Interestingly, if the reaction is carried out at 40 °C
in the presence of excess PhNdCdS, the yield of 4a
increases and the new product Cp(PPh3)[P(OMe)3]-
RuCdC(Ph)C(dS)N(Ph)C(dNPh)S (5a ) could be isolated
in moderate yield. Complex 5a was also prepared
directly from the reaction of 3a with excess PhNCS at
40 °C. In 5a two PhNCS molecules and the acetylide
ligand are incorporated to form a six-membered ring.
In analogy to this, we note that the heterocyclic com-
pound 2-thiopyridone can be prepared by the addition
of MeNCS to a cobaltacyclopentadiene complex, possibly
through CdN bond insertion into a Co-C bond followed
(10) Wakatsuki, Y.; Yamazaki, H. J . Chem. Soc., Chem. Commun.
1973, 280.
(11) Wagner, G.; Richter, P. Pharmazie 1967, 22, 610.
(12) Frank, G. W.; Degen, P. J . Acta Crystallogr., Sect. B 1973, B29,
1815.
(9) (a) Brill, T. B.; Landon, S. Chem. Rev. 1984, 84, 577. (b)
Nakazawa, H.; Miyoshi, K. Trends Organomet. Chem. 1994, 1, 295.

2536 Organometallics, Vol. 17, No. 12, 1998
Chang et al.
Ta ble 1. Cr ysta l a n d In ten sity Collection Da ta for Cp (P P h 3)[P (OMe)3]Ru CdC(P h )C(S)dNP h (3a ),
Cp (P P h 3)[P (dO)(OMe)2]Ru dCdC(P h )C(SH)dNP h (4a ), Cp (P P h 3)[P (OMe)3]Ru CdC(P h )C(S)NP h C(NP h )S (5b),
a n d Cp (d p p e)Ru CtCP h ‚(P h NCS)3
mol formula
space group
a, Å
b, Å
C41H38NO3P2SRuCl3 (3a )
P1h
10.316(3)
11.237(6)
18.010(4)
100.64(3)
94.02(2)
93.59(3)
1040.6(13)
2
C41H39NO3P2SRu (4a )
P1h
10.970(3)
12.064(5)
14.595(3)
90.39(4)
101.59(2)
100.51(4)
1858.5(10)
2
C52H53N2O3.5P2S2Ru (5b)
P21/c
C60H49N3SRu
Cc
18.904(5)
15.951(2)
35.173(8)
90.00
94.82(2)
90.00
10 568(4)
8
18.798(8)
13.714(3)
19.934(4)
90.00
114.76(4)
90.00
c, Å
R, deg
â, deg
γ, deg
V, Å3
4666.5(24)
4
Z
cryst dimens, mm
radiation
2θ range, deg
scan type
total no. of rflns
no. of unique reflns, I > 2σ(I)
R
0.20 × 0.20 × 0.30
0.25 × 0.25 × 0.30
0.50 × 0.40 × 0.20
0.20 × 0.20 × 0.30
Mo KR, λ ) 0.7107 Å
2-45
2-45
2-45
2-60
θ-2θ
5303
3077
0.042
0.040
4848
2958
0.041
0.042
6069
3685
0.051
0.047
8099
4983
0.054
0.052
Rw
dihedral angle between the planes of the four-membered
ring and the phenyl substituent in the imino group, are
similar to that in 3a . The [2 + 2] cycloaddition of a CtC
bond of an iron acetylide with CS2, yielding 2H-thiete-
2-thione (â-dithiolactone), has been reported.4 A similar
process has been proposed for the first stage of the
reaction of alkynes with CS2.4 The reaction of phos-
phenium complexes with isocyanates leading to [2 + 2]
addition via the NdC bond to give four-membered
phosphametallacycles has been reported.14 Interest-
ingly, such a reaction does not take place with the bis-
(triphenylphosphine) analogue of 2. The reaction of
vinylidene complexes with metal acetylide leading to [2
+ 2] addition via the terminal CdC bond of the vin-
ylidene to give unusual cyclic C4 bridging has also been
reported.15
The molecular structure of 4a was determined by an
X-ray diffraction study; an ORTEP drawing is shown
in Figure 2. Crystal and intensity collection data are
given in Table 1, and selected bond distances and angles
are given in Table 3. With the formation of the
phosphonate ligand, the two ruthenium-phosphorus
bonds (Ru-P1(phosphite) ) 2.303(2) Å and Ru-P2 )
2.323(2) Å) are now comparable. The ruthenium-
carbon bond has a formal bond order of 2, consistent
with a short Ru-C1 bond (1.798(6) Å). The carbon-
carbon double bond of the vinylidene ligand is 1.337(9)
Å, typical for a C(sp2)-C(sp) allene bond.16 The ruthe-
nium-vinylidene linkage is very nearly linear (Ru-C1-
C2 ) 175.2(5)°). The N-C9 and S-C9 bond lengths of
1.344(8) and 1.641(6) Å, respectively, both display
partial double-bond character, indicative of several
resonance contributions.
The molecular structure of 5b was determined by an
X-ray diffraction study; an ORTEP drawing which
emphasizes the heterocyclic six-membered ring is shown
in Figure 3. Crystal and intensity collection data are
given in Table 1, and selected bond distances and angles
are given in Table 4. As observed in 3a , the Ru-P1-
(phosphite) bond length of 2.239(3) Å is shorter than
F igu r e 1. ORTEP drawing (50% thermal ellipsoids) of 3a .
Three phenyl groups on the triphenylphosphine ligand and
all hydrogen atoms are eliminated for clarity.
Ta ble 2. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) of Cp (P P h 3)[P (OMe)3]Ru CdC(P h )C(dNP h )S
(3a )
Ru-P1
Ru-P2
Ru-C1
S-C1
2.2263(23)
2.3095(21)
2.025(7)
1.868(7)
1.823(8)
N-C9
1.271(10)
1.418(9)
1.388(11)
1.459(10)
1.439(10)
N-C10
C1-C2
C2-C3
C2-C9
S-C9
P1-Ru-P2
P1-Ru-C1
P2-Ru-C1
C1-S-C9
C9-N-C10
Ru-C1-S
Ru-C1-C2
93.94(8)
90.50(21)
94.81(20)
72.6(3)
122.2(6)
129.1(4)
138.0(5)
S-C1-C2
C1-C2-C3
C1-C2-C9
C3-C2-C9
S-C9-N
S-C9-C2
N-C9-C2
92.9(5)
132.3(6)
101.3(6)
126.4(7)
135.5(6)
93.1(5)
131.3(7)
C9dN bond distance of 1.271(10) Å confirms an imino
group. The dihedral angle between the phenyl plane
(C10-C15) on the imino group and the plane (S, C1,
C2, C9) formed by the four-membered ring is 37.8(3)°.
The two ruthenium-phosphorus bonds in 3a are Ru-
P1 ) 2.226(2) Å and Ru-P2 ) 2.310(2) Å, with the
shorter distance belonging to the phosphite ligand.
Organic compounds containing similar four-membered
rings with an imino group have been observed as stable
products from the phosphine-induced elimination of a
sulfur atom from 1,2-dithio 3-imines.13 The structural
features of the 2-imino-2H-thiete portion, including the
(13) Goerdeler, J .; Yunis, M.; Puff, H.; Roloff, A. Chem. Ber. 1986,
119, 162.
(14) Malisch, W.; Hahner, C.; Gru¨n, K.; Reising, J .; Goddard, R.;
Kru¨ger, C. Inorg. Chim. Acta 1996, 244, 147.
(15) Fischer, H.; Leroux, F.; Roth, G.; Stumpf, R. Organometallics
1996, 15, 3723.
(16) Maki, A. G.; Toth, R. A. J . Mol. Spectrosc. 1965, 17, 136.

Reactions of Ru Acetylides with Isothiocyanate
Organometallics, Vol. 17, No. 12, 1998 2537
Ta ble 4. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) of Cp (P P h 3)[P (OMe)3]-
Ru CdC(P h )C(dS)N(CH2P h )C(dNCH2P h )S (5b)
Ru-P1
Ru-P2
Ru-C
2.2389(24)
2.341(3)
2.105(7)
1.635(8)
1.749(8)
1.750(8)
1.594(6)
1.596(6)
1.595(6)
1.863(8)
1.864(8)
1.825(8)
1.430(11)
1.409(11)
1.446(11)
N1-C9
1.410(10)
1.487(9)
1.399(9)
N1-C10
N1-C17
N2-C17
N2-C18
C1-C2
S1-C9
S2-C1
S2-C17
P1-O1
P1-O2
P1-O3
P2-C28
P2-C34
P2-C40
O1-C25
O2-C26
O3-C27
1.272(10)
1.456(10)
1.356(10)
1.514(10)
1.477(10)
1.510(12)
1.498(11)
1.443(12)
1.415(12)
1.384(12)
1.397(11)
1.357(12)
C2-C3
C2-C9
C10-C11
C18-C19
C46-C47
C46-C50
C47-C48
C48-C49
C49-C50
P1-Ru-P2
P1-Ru-C1
P2-Ru-C1
C1-S2-C17
Ru-P1-O1
Ru-P1-O2
Ru-P1-O3
O1-P1-O2
O1-P1-O3
O2-P1-O3
Ru-P2-C28
Ru-P2-C34
Ru-P2-C40
C28-P2-C34
C28-P2-C40
C34-P2-C40
P1-O1-C25
P1-O2-C26
P1-O3-C27
C9-N1-C10
C9-N1-C17
94.61(9)
94.84(21)
96.78(21)
108.6(4)
116.75(24)
121.81(24)
108.70(24)
97.6(3)
106.8(3)
103.6(3)
122.0(3)
117.1(3)
115.7(3)
100.2(4)
99.7(4)
C10-N1-C17
C17-N2-C18
Ru-C1-S2
113.9(6)
118.8(6)
106.2(4)
135.6(6)
117.5(6)
120.4(7)
128.0(7)
111.5(6)
120.0(6)
121.1(6)
118.9(6)
114.2(6)
118.1(5)
124.3(6)
117.6(6)
113.3(7)
106.6(7)
106.8(7)
108.6(7)
109.5(7)
108.4(7)
F igu r e 2. ORTEP drawing (50% thermal ellipsoids) of 4a .
Three phenyl groups on the triphenylphosphine ligand and
all hydrogen atoms are eliminated for clarity.
Ru-C1-C2
S2-C1-C2
C1-C2-C3
C1-C2-C9
C3-C2-C9
S1-C9-N1
S1-C9-C2
N1-C9-C2
N1-C10-C11
S2-C17-N1
S2-C17-N2
N1-C17-N2
N2-C18-C19
C47-C46-C50
C46-C47-C48
C47-C48-C49
C48-C49-C50
C46-C50-C49
98.0(4)
126.0(6)
121.9(6)
125.3(7)
118.8(6)
126.9(6)
) 1.750(8) Å) in the six-membered ring are short enough
to reflect some double-bond character.18 The hetero-
cyclic six-membered ring is essentially planar.
Rea ction s of 2 w ith Isocya n a te. Treatment of 2
with PhNCO at -20 °C for 7 days afforded the two
F igu r e 3. ORTEP drawing (50% thermal ellipsoids) of 5b.
Three phenyl groups on the triphenylphosphine ligand and
all hydrogen atoms are eliminated for clarity.
Ta ble 3. Selected Bon d Dista n ces (Å) a n d An gles
(d eg) of Cp (P P h 3)[P (dO)(OMe)2]Ru dCdC(P h )-
C(SH)dNP h (4a )
products Cp(PPh3)[P(OMe)3]RuCdC(Ph)C(dNPh)O (6)
and
Cp(PPh3)[P(OMe)3]RuCdC(Ph)C(dO)N(Ph)C-
Ru-P1
Ru-P2
Ru-C1
P1-O1
P1-O2
P1-O3
2.3027(20)
2.3234(20)
1.799(6)
1.582(4)
1.617(5)
1.491(4)
N-C9
1.344(8)
1.417(8)
1.336(8)
1.503(9)
1.478(8)
1.641(6)
1
(dNPh)O (7) in a 1:1 ratio, as indicated by H and 31P
NMR spectra. These products are unstable at room
temperature and were only characterized by spectro-
scopic methods. In the 31P NMR spectrum of the crude
mixture, the two doublet resonances at δ 155.3 and 56.9
with J P-P ) 66.9 Hz are assigned to the P(OMe)3 and
PPh3 ligands of 6 and another set of 31P resonances at
δ 151.7 and 55.0 with J P-P ) 69.1 Hz are assigned to 7.
The FAB mass spectrum of the crude mixture displayed
parent peaks at m/e 774.2 and 893.2 for 6 and 7,
respectively. By comparing the spectroscopic data for
the two products with those for 3 and 5, it is plausible
to conclude that 3 and 6 have similar structures, as do
complexes 5 and 7. The dealkylation phosphonate
product was not observed at -20 °C. However, when
the reaction was carried out at room temperature, more
than three phosphonate complexes were observed by the
31P NMR spectra. Separation of these complexes by
chromatography caused decomposition, and no further
characterization was attempted.
N-C10
C1-C2
C2-C3
C2-C9
C9-S
P1-Ru-P2
P1-Ru-C1
P2-Ru-C1
Ru-P1-O1
Ru-P1-O2
Ru-P1-O3
O1-P1-O2
O1-P1-O3
O2-P1-O3
P1-O1-C16
92.95(7)
91.13(19)
90.57(21)
107.81(19)
110.00(19)
119.06(19)
96.8(3)
112.8(3)
108.0(3)
122.8(5)
P1-O2-C17
C9-N-C10
Ru-C1-C2
C1-C2-C3
C1-C2-C9
C3-C2-C9
N-C9-C2
N-C9-S
120.0(4)
129.2(5)
175.2(5)
116.8(5)
124.2(6)
119.0(5)
114.0(5)
125.4(5)
120.5(5)
C2-C9-S
that of Ru-P2(phosphine) (2.341(3) Å). The Ru-C1
bond length of 2.105(7) Å is typical of a Ru-C single
bond, and the C1-C2 bond length of 1.356(10) Å is
typical of a double bond. The carbon-sulfur double
bond in 5b is 1.635(8) Å, which is comparable to that in
ethylene trithiocarbonate (1.652(2) Å).17 The two
C(sp2)-S single bonds (C1-S2 ) 1.749(8) and C17-S2
(17) Klewe, F.; Seip, H. M. Acta Chem. Scand. 1972, 26, 1860.
(18) Waters, J . M.; Ibers, J . A. Inorg. Chem. 1977, 12, 3273.

2538 Organometallics, Vol. 17, No. 12, 1998
Chang et al.
Sch em e 2
Tr im er iza tion of Isoth iocya n a te. Our efforts to
prepare the dppe analogues of 3 and 5 by reacting Cp-
(dppe)RuCtCPh (1′) with PhNCS led to isolation of a
cocrystallization product of 1′ and 1,3,5-triphenyl-1,3,5-
triazinane-2,4,6-trithione (PhNCS)3 (8),19 a trimeriza-
tion product of isothiocyanate. In the reaction, the [2
+ 2] cycloaddition product Cp(dppe)RuCdC(Ph)C(dNPh)-
S (9a ) and Cp(dppe)RuCdC(Ph)C(dS)N(Ph)C(dNPh)S
(10a ) were also isolated and identified. The reaction of
1′ with a 10-fold excess of PhNCS at room temperature
for 3 days afforded the orange-yellow complex 9a in 72%
yield. When the reaction was carried out for 7 days at
room temperature, the brown complex 10a was isolated
in 65% yield. This transformation was monitored by
31P NMR spectroscopy. At the beginning of the reaction,
the 31P resonance of 1′ appeared at δ 86.0; within 3 days
the resonance attributed to 9a appeared at δ 94.1, and
after 4 more days the resonance of 10a appeared at δ
99.3. With longer reaction time at room temperature,
a complex mixture containing several organometallic
compounds was obtained. When the reaction was
carried out at 40 °C for 2 days, a mixture composed of
the major organometallic product 11, which showed a
resonance at δ 79.4 in the 31P NMR spectrum, and 8
were obtained. Compounds 11 and 8 were separated
by column chromatography. Complex 11 is dark brown
and stable in air. Attempts to obtain single crystals of
11 by recrystallization led to the yellow cocrystallization
product of 1′ and 8. The mass spectrum of 11 displays
only the parent peaks attributed to 1′. However, the
31P NMR resonance of 11 (δ 79.6) is different from those
of 1′ and 10a . On the basis of these data, we believe
that 11 is a precursor of the trimerization product. The
31P NMR chemical shift of 11 falls in the region for that
F igu r e 4. ORTEP drawing (50% thermal ellipsoids) of the
cocrystallization product of 1′ and 8. Four phenyl groups
on the dppe ligand and all hydrogen atoms are eliminated
for clarity.
of a ruthenium vinylidene dppe complex. A possible
structure of 11 is depicted in Scheme 2. The formation
of 11 may be initiated by opening of the six-membered
ring of 10a to give the zwitterionic vinylidene complex
C, with the anionic charge localized at the N atom. The
nucleophilic attack of this N atom on a free isothio-
cyanate molecule followed by ring closure regenerates
1′ and releases the six-membered trimerization product
8. It is less likely that the N atom will attack the CR
atom because of the lower stability of an eight-
membered ring.
The crystal structure of the cocrystallization product
of 1′ and 8 is shown in Figure 4. Crystal and intensity
collection data are given in Table 1, and selected bond
distances and angles are given in Table 5. The two
molecules are packed together with no significant
(19) Tripolt, R.; Nachbaur, E. Phosphorus, Sulfur Silicon Relat.
Elem. 1992, 65, 173.

Reactions of Ru Acetylides with Isothiocyanate
Organometallics, Vol. 17, No. 12, 1998 2539
Ta ble 5. Selected Bon d Dista n ces (Å) a n d An gles
ably a vinylidene complex with a trimer unit bound to
the acetylide ligand. The acetylide complex is a catalyst
in this reaction. Without this catalyst, the thermolysis
of phenyl isocyanate in CH2Cl2 yields diphenylurea,
(PhNH)2CO.
Various metal-promoted coupling modes of isothio-
cyanates have been studied using a dirhenium com-
plex21 and a dirhodium complex.22 In our system,
transformation of isothiocyanates uses a metal-coordi-
nated acetylide ligand. However, as can been seen in
Schemes 1 and 2, the other ligands, such as dppe and a
combination of P(OMe)3 and PPh3, play a crucial role
in differentiating the conversion of 10 to 8.
Con clu sion . The reactions of ruthenium acetylide
complexes with isothiocyanate or isocyanate yielded a
series of addition products. Addition of one RNCS
molecule to the acetylide ligand via a [2 + 2] cycload-
dition gave a four-membered-ring product. Addition of
a second RNCS molecule generated a complex with a
heterocyclic six-membered ring. For the cationic vin-
ylidene complex with a P(OMe)3 ligand, an Arbuzov-
like dealkylation of P(OMe)3 resulted in the formation
of a neutral vinylidene complex with a phosphonate
ligand. Complete characterization of this phosphonate
complex assisted in elucidating the mechanism of the
sequential addition processes. For the acetylide com-
plex with a bidentate dppe ligand, other than the two
addition processes mentioned above, a third addition led
to an organic trimerization product and regenerated the
acetylide complex.
(d eg) of Cp (d p p e)Ru CCP h ‚(P h NCS)3
Ru-P1
Ru-P2
Ru-C3
Ru-C5
Ru-C6
Ru-C7
Ru-C8
Ru-C9
S1-C40
S2-C41
S3-C42
2.286(5)
2.288(5)
N1-C40
N1-C41
N1-C43
N2-C41
N2-C42
N2-C49
N3-C40
N3-C42
N3-C55
C3-C4
1.417(21)
1.437(19)
1.491(21)
1.433(21)
1.406(21)
1.527(20)
1.415(20)
1.373(20)
1.519(23)
1.183(22)
1.395(19)
1.893(18)
2.224(17)
2.185(16)
2.210(15)
2.247(17)
2.238(16)
1.644(15)
1.627(16)
1.687(19)
C4-C10
P1-Ru-P2
84.81(17)
88.5(5)
88.6(5)
Ru-C3-C4
C3-C4-C10
S1-C40-N1
S1-C40-N3
N1-C40-N3
S2-C41-N1
S2-C41-N2
N1-C41-N2
S3-C42-N2
S3-C42-N3
N2-C42-N3
170.9(15)
170.5(16)
123.7(11)
119.3(11)
116.9(12)
125.7(12)
119.4(10)
114.8(13)
119.3(12)
122.7(13)
117.6(15)
P1-Ru-C3
P2-Ru-C3
C40-N1-C41
C40-N1-C43
C41-N1-C43
C41-N2-C42
C41-N2-C49
C42-N2-C49
C40-N3-C42
C40-N3-C55
C42-N3-C55
123.0(13)
120.3(12)
116.7(13)
123.8(12)
118.0(12)
117.9(13)
123.6(13)
118.3(12)
117.9(13)
intermolecular contacts. The two bonds Ru-P1 and
Ru-P2 are 2.286(5) and 2.288(5) Å, respectively. The
Ru-C3 bond length of 1.89(2) Å is typical for a Ru-
C(sp) single bond, and the C3-C4 bond length of
1.186(2) Å is that of a triple bond. In the organic
portion, all three carbon-sulfur double bonds are
comparable in length: 1.64(2), 1.63(2), and 1.69(2) Å.
The heterocyclic six-membered ring is essentially planar
(the distances of all constituent atoms to the plane are
within the 0.029(10) and -0.038(22) Å range), with a
slight double-bond character for all C-N bonds.
Exp er im en ta l Section
Gen er a l P r oced u r es. All manipulations were performed
under nitrogen using vacuum-line, drybox, and standard
Schlenk techniques. CH3CN and CH2Cl2 were distilled from
CaH2 and diethyl ether and THF from Na/ketyl. All other
solvents and reagents were of reagent grade and were used
without further purification. NMR spectra were recorded on
Bruker AC-200 and AM-300WB FT-NMR spectrometers and
are reported in units of δ with residual protons in the solvent
as an internal standard (CDCl3, δ 7.24; CD3CN, δ 1.93; C2D6-
CO, δ 2.04). FAB mass spectra were recorded on a J EOL SX-
102A spectrometer and are reported in m/ z units. Complexes
Cp(dppe)RuCtCPh (1′) and Cp(PPh3)2RuCtCPh23 were pre-
pared by following the methods reported in the literature.
Elemental analyses and X-ray diffraction studies were carried
out at the Regional Center of Analytical Instrument located
at the National Taiwan University.
P r ep a r a tion of Cp (P P h 3)[P (OMe)3]Ru CtCP h (2). In
a Schlenk flask charged with P(OMe)3 (7.70 mL, 63.30 mmol)
and Cp(PPh3)2RuCtCPh (1; 10.00 g, 12.66 mmol), n-decane
(80 mL) was added. The resulting solution was heated to
reflux for 1 h to give a yellow solution. The solvent was
reduced in volume to about 5 mL under vacuum, and a yellow
precipitate formed. After filtration, the precipitate was washed
with 2 × 20 mL of pentane to give the product Cp(PPh3)-
[P(OMe)3]RuCtCPh (2; 7.60 g, 11.64 mmol, 92% yield).
Spectroscopic data for 2 are as follows. 1H NMR: 7.69-6.86
(m, 20 H, Ph); 4.64 (s, 5H, Cp); 3.37 (d, J P-H ) 11.6 Hz, 9 H,
P(OMe)3). 31P NMR: 158.3 (d, J P-P ) 64.5 Hz, P(OMe)3); 56.6
(d, J P-P ) 64.5 Hz, PPh3). 13C NMR: 139.2-122.9 (Ph); 130.3
(CR); 112.6 (Câ); 84.2 (Cp); 51.9 (P(OMe)3). Mass: 654.0 (M+),
553.1 (M+ - C2Ph); 428.9 (M+ - C2Ph,P(OMe)3). Anal. Calcd
for C34H34O3P2Ru: C, 62.47; H, 5.24. Found: C, 62.68; H, 5.32.
The reaction of 1′ with PhCH2NCS at room temper-
ature afforded Cp(dppe)RuCdC(Ph)C(dS)N(CH2Ph)C-
(dNCH2Ph)S (10b) in moderate yield. At 5 °C, the
product was Cp(dppe)RuCdC(Ph)C(dNCH2Ph)S (9b),
which resulted from [2 + 2] cycloaddition of PhCH2NCS
with the acetylide ligand. Like 2, 1′ can differentiate
phenyl isothiocyanate and benzyl isothiocyanate. In-
terestingly, no trimerization product was observed in
this reaction. Decomposition of 10b under thermal
conditions gave a complex mixture from which no
isolable product was obtained.
When the reaction of 1′ with PhNCO was carried out
at 5 °C, the yellow six-membered-ring complex Cp-
(dppe)RuCdC(Ph)C(dO)N(Ph)C(dNPh)O (12) was iso-
lated in moderate yield. Complex 12 is stable at 5 °C
but decomposes at room temperature. The 31P NMR
resonance of 12 appears at δ 96.4, and a weak resonance
at δ 98.2, assignable to the precursor of 12, appears in
the initial stage of the reaction and disappears at the
end of the reaction. We believe that this species is the
[2 + 2] cycloaddition product. In CH2Cl2, trimerization
of phenyl isocyanate occurs in the presence of 1′, giving
(PhNCO)3.20 After 2 days, a 31P NMR resonance at δ
76.0 indicates a major organometallic product, presum-
(20) (a) Hong, P.; Sonogashira, K.; Hagihara, N. Tetrahedron Lett.
1970, 1633. (b) Schwetlick, K.; Noack, R. J . Chem. Soc., Perkin Trans.
2 1995, 395. (c) Verardo, G.; Giumanini, A. G.; Gorassini, F.; Straz-
zolini, P.; Benetollo, F.; Bombieri, G. J . Heterocycl. Chem. 1995, 32,
995.
(21) Adams, R. D.; Huang, M. Organometallics 1996, 15, 3644.
(22) Gibson, J . A. E.; Cowie, M. Organometallics 1984, 3, 984.
(23) Bruce, M. I.; Humphrey, M. G. Aust. J . Chem. 1989, 42, 1067.

2540 Organometallics, Vol. 17, No. 12, 1998
Chang et al.
Rea ction of 2 w ith P h NCS. To a Schlenk flask charged
with 2 (0.50 g, 0.76 mmol) was added CH2Cl2 (20 mL), and
PhNCS (0.92 mL, 7.66 mmol) was injected by a syringe. The
resulting mixture was stirred at room temperature for 3 days
while the color changed from bright yellow to brown. The
solvent was removed under vacuum. The residue was redis-
solved in ether and passed through a silica gel packed column.
Hexane eluted the starting material, ether eluted an orange-
yellow band, and methanol eluted a brown band. The solvent
of the orange-yellow band was removed to give a yellow oil
which was washed with hexane to give a yellow powder and
further washed with 20 mL of pentane to give the product Cp-
) 12.7 Hz, 1H, CH2Ph); 4.34 (s, 5H, Cp); 3.92 (d, J H-H ) 16.9
Hz, 1H, CH2Ph); 3.84 (d, J H-H ) 16.9 Hz, 1H, CH2Ph); 3.35
(d, J P-H ) 10.9 Hz, 9 H, P(OMe)3). 31P NMR: 148.6 (d, J P-P
)
73.3 Hz, P(OMe)3); 57.9 (d, J P-P ) 73.3 Hz, PPh3). 13C NMR:
134.1-122.7 (Ph, Câ, Cγ); 84.8 (Cp); 52.3 (d, J C-P ) 7.5 Hz,
P(OMe)3). Mass: 790.2 (M+), 553.1 (M+ - organic ligand);
429.1 (M+ - organic ligand, P(OMe)3). Anal. Calcd for
C
50H48N2O3P2S2Ru: C, 63.08; H, 5.08; N, 2.94. Found: C,
62.95; H, 5.04; N, 3.12. Spectroscopic data for 4b are as
follows. 1H NMR: 10.86 (s, 1H, SH); 7.63-6.67 (m, 20 H, Ph);
5.19 (s, 5H, Cp); 3.07 (d, J P-H ) 11.2 Hz, 3 H, OMe); 2.97 (d,
J P-H ) 11.5 Hz, 3 H, OMe); 2.44 (d, J H-H ) 7.3 Hz, 1H, -NCH2-
Ph); 2.39 (d, J H-H ) 7.3 Hz, 1H, -NCH2Ph). 13C NMR: 343.5
(t, J C-P ) 17.0 Hz, CR); 142.4-126.8 (Ph, Câ, Cγ); 92.9 (Cp);
50.5 (d, J C-P ) 9.4 Hz, OMe); 50.1 (d, J C-P ) 8.4 Hz, OMe).
(PPh3)[P(OMe)3]RuCdC(Ph)C(dNPh)S (3a ). The yield of 3a
after recrystallization from hexane/CH2Cl2 (1:1) is 0.38 g (63%
yield). After a similar workup procedure, the brown band gave
the orange-red phosphonate complex Cp(PPh3)[P(dO)(OMe)2]-
RudCdC(Ph)C(SH)dNPh (4a ; 0.030 g, 5% yield). Spectro-
scopic data for 3a are as follows. 1H NMR: 7.29-7.00 (m, 20
H, Ph); 4.75 (s, 5H, Cp); 3.37 (d, J P-H ) 11.0 Hz, 9 H, P(OMe)3).
31P NMR: 95.2 (d, J P-P ) 45.8 Hz, P(OMe)2); 49.3 (d, J P-P
)
45.8 Hz, PPh3). Mass: 790.0 (M+), 758.0 (M+ - S), 539.0 (M+
- organic ligand); 428.9 (M+ - organic ligand, P(OMe)3). Anal.
Calcd for
C41H39NO3P2SRu: C, 62.42; H, 4.98; N, 1.78.
Found: C, 62.57; H, 4.64; N, 1.95.
The [2 + 2] cycloaddition product Cp(PPh3)[P(OMe)3]-
31P NMR: 151.7 (d, J P-P ) 68.9 Hz, P(OMe)3); 56.2 (d, J P-P
)
68.9 Hz, PPh3). 13C NMR: 134.1-122.7 (Ph, Câ, Cγ); 84.8 (Cp);
52.3 (d, J C-P ) 7.5 Hz, P(OMe)3). Mass: 790.2 (M+), 553.1
(M+ - C2Ph); 429.1 (M+ - C2Ph, P(OMe)3). Anal. Calcd for
RuCdC(Ph)C(dNCH2Ph)S (3b) could be observed when the
same reaction was carried out in CDCl3 at 5 °C for 5 days and
monitored by NMR spectra. Complexes 3b and 5b formed
simultaneously in a 1:3 ratio at this temperature and at room
temperature 3b transformed to 5b in ca. 2 h. Spectroscopic
data for 3b are as follows. 1H NMR: 7.73-6.85 (m, 25 H, Ph);
4.73 (s, 5H, Cp); 4.49, 4.39 (two d, J H-H ) 13.6 Hz, 2H,
-NCH2); 3.42 (d, J P-H ) 11.0 Hz, 9 H, OMe). 31P NMR: 151.8
(d, J P-P ) 67.8 Hz, P(OMe)2); 56.0 (d, J P-P ) 67.8 Hz, PPh3).
Mass: 804.1 (M+ + 1), 553.1 (M+ - organic ligand); 429.1 (M+
- organic ligand, P(OMe)3).
C
41H39NO3P2SRu: C, 62.42; H, 4.98; N, 1.78. Found: C, 61.99;
1
H, 5.12; N, 1.73. Spectroscopic data for 4a are as follows. H
NMR: 7.70-6.70 (m, 20 H, Ph); 5.26 (s, 5H, Cp); 3.18 (d, J P-H
) 11.5 Hz, 3 H, OMe); 3.03 (d, J P-H ) 11.5 Hz, 3 H, OMe). 13
C
NMR: 345.2 (t, J C-P ) 17.1 Hz, CR); 137.9-123.4 (Ph, Câ, Cγ);
93.0 (Cp); 52.2 (d, J C-P ) 8.6 Hz, OMe); 51.8 (d, J C-P ) 8.4
Hz, OMe). 31P NMR: 95.3 (d, J P-P ) 45.9 Hz, P(OMe)2); 48.0
(d, J P-P ) 45.9 Hz, PPh3). Mass: 776.0 (M+), 744.0 (M+ - S);
539.0 (M+
- CdC(Ph)C(SH)CdNPh). Anal. Calcd for
Rea ction of 2 w ith P h NCO. This reaction was monitored
by NMR spectroscopy. Complex 2 (0.05 g, 0.08 mmol) and
PhNCO (0.10 mL, 0.76 mmol) were dissolved in CDCl3 (1 mL)
in an NMR tube under nitrogen. The resulting mixture was
C
40H37NO3P2SRu: C, 62.00; H, 4.81; N, 1.81. Found: C, 61.74;
H, 5.01; N, 1.70. The 31P NMR spectrum of the crude product
(after 3 days of reaction time) displayed the resonances
attributed to 3a and 4a in a 9:1 ratio.
1
stored at -20 °C for 7 days. The H and 31P NMR spectra of
The reaction of 2 with PhNCS in refluxing CH2Cl2 was
carried out under nitrogen for 4 days. The workup procedure
was similar to that mentioned above. The reaction gave 4a
the mixture indicated formation of the two major products Cp-
(PPh3)[P(OMe)3]RuCdC(Ph)C(dNPh)O (6) and Cp(PPh3)-
and Cp(PPh3)[P(OMe)3]RuCdC(Ph)C(dS)N(Ph)C(dNPh)S (5a )
after purification in 40% total yield. The 31P NMR spectrum
of the crude product (after 4 days of reaction time) displayed
[P(OMe)3]RuCdC(Ph)C(dO)N(Ph)C(dNPh)O (7). The total
NMR yield of 6 and 7 is estimated to be about 70%, on the
basis of the integration of the Cp resonances and the 31P
resonances. Since these two complexes are unstable at room
temperature, no attempt was made to isolate the products. The
31P NMR spectrum of the crude product (after 7 days of
reaction time) displayed the resonances attributed to 6 and 7
in a 1:1 ratio. Spectroscopic data for 6 are as follows. 1H
NMR: 8.03-6.84 (m, 25 H, Ph); 4.63 (s, 5H, Cp); 3.62 (d, J P-H
) 11.1 Hz, 9 H, P(OMe)3). 31P NMR: 155.4 (d, J P-P ) 66.9
Hz, P(OMe)3); 56.9 (d, J P-P ) 66.9 Hz, PPh3). Mass: 774.2
(M+ + 1), 654.1 (M+ - C(O)CdNPh); 429.1 (M+ - CdC(Ph)C-
(O)CdNPh, P(OMe)3). Spectroscopic data for 7 are as follows.
1H NMR: 7.85-6.83 (m, 30 H, Ph); 4.43 (s, 5H, Cp); 3.14 (d,
the resonances attributed to 5a and 4a in
a 3:2 ratio.
Spectroscopic data for 5a are as follows. 1H NMR: 7.84-6.52
(m, 30 H, Ph); 4.40 (s, 5H, Cp); 3.06 (d, J P-H ) 11.0 Hz, 9 H,
P(OMe)3). 31P NMR: 148.6 (d, J P-P ) 72.5 Hz, P(OMe)3); 53.9
(d, J P-P ) 72.5 Hz, PPh3). Mass: 925.1 (M+ + 1), 553.1 (M+
- C2Ph); 429.1 (M+ - C2Ph, P(OMe)3). Anal. Calcd for
C
48H44N2O3P2S2Ru: C, 62.39; H, 4.80; N, 3.03. Found: C,
62.52; H, 4.95; N, 3.11. Complex 5a can also be prepared from
the reaction of 3a with PhNCS in refluxing CH2Cl2 for 3 days.
In the crude mixture, a small amount of 4a was observed.
Rea ction of 2 w ith P h CH2NCS. In a Schlenk flask
charged with 2 (0.50 g, 0.76 mmol), PhCH2NCS (1.01 mL, 766
mmol) and CH2Cl2 (20 mL) were added and the mixture was
stirred at room temperature for 3 days with the color changing
from bright yellow to brown. The solvent was removed under
vacuum and the residue was subjected to a silica gel packed
column chromatograph. Hexane eluted the organic com-
pounds, a 1:1 hexane/ether solution eluted a brown band, and
methanol eluted an orange band. The brown band was dried
under vacuum and the residue washed with 2 × 15 mL of
hexane to give the solid product Cp(PPh3)[P(OMe)3]-
J P-H ) 11.0 Hz, 9 H, P(OMe)3). 31P NMR: 151.7 (d, J P-P
)
69.1 Hz, P(OMe)3); 54.6 (d, J P-P ) 69.1 Hz, PPh3). Mass: 893.2
(M+ + 1), 654.1 (M+ - organic ligand + C2Ph); 553.1 (M+
organic ligand); 429.1 (M+ - organic ligand, P(OMe)3).
-
Rea ction of Cp (d p p e)Ru CtCP h (1′) w ith P h NCS. In
a Schlenk flask charged with 1′ (0.30 g, 0.46 mmol), PhNCS
(0.55 mL, 4.59 mmol) and CH2Cl2 (20 mL) were added; the
mixture was stirred at room temperature for 4 days and the
color of the solution changed from bright yellow to brown. The
solvent was removed under vacuum and the residue was
washed with 2 × 30 mL of hexane to give the product. After
filtration, the solid was further washed with 20 mL of pentane,
RuCdC(Ph)C(S)N(CH2Ph)C(dNCH2Ph)S (5b; 0.42 g, 58%
yield). The orange band, after the same treatment, gave the
orange phosphonate complex Cp(PPh3)[P(dO)(OMe)2]-
RudCdC(Ph)C(SH)dNCH2Ph (4b; 0.06 g, 10% yield). Spec-
troscopic data for 5b are as follows. 1H NMR: 7.35-6.99 (m,
30 H, Ph); 6.19 (d, J H-H ) 12.7 Hz, 1H, CH2Ph); 6.02 (d, J H-H
giving the product Cp(dppe)RuCdC(Ph)C(dNPh)S (9a ; 0.26
g, 72% yield). Spectroscopic data for 9a are as follows. 1H
NMR: 7.80-6.30 (m, 30 H, Ph); 4.50 (s, 5H, Cp); 2.60-2.47
(m, 4 H, PCH2). 13C NMR: 133.7-122.6 (Ph, Câ, Cγ); 84.6 (Cp);

Reactions of Ru Acetylides with Isothiocyanate
Organometallics, Vol. 17, No. 12, 1998 2541
29.3 (t, J C-P ) 21.5 Hz, CH2). 31P NMR: 93.9 (PPh2). FAB
mass: 801.0 (M+), 565.0 (M+ - organic ligand). Anal. Calcd
for C46H39NP2SRu: C, 68.98; H, 4.91; N, 1.75. Found: C,
68.99; H, 4.79; N, 1.88. If the same reaction was carried out
C2Ph). Anal. Calcd for C53H44N2O2P2Ru: C, 70.42; H, 4.91;
N, 3.10. Found: C, 70.63; H, 4.78; N, 3.34.
A Schlenk flask was charged with 1′ (0.20 g, 0.31 mmol),
and the atmosphere was replaced with nitrogen; then PhNCO
(1.00 mL, 9.21 mmol) and CH2Cl2 (20 mL) were introduced
and the mixture was heated to reflux for 2 days. The 31P NMR
spectrum revealed a complex mixture at the initial stage of
the reaction, but after 1 day, only a single product was
obtained. The mixture was heated for 2 days and the color of
the solution changed from bright yellow to brown. The solvent
was removed under vacuum, and the residue was subjected
to silica gel packed column chromatography. Hexane eluted
the starting material, ether eluted the organometallic complex
12, and methanol eluted the trimer. Removal of methanol
under vacuum followed by addition of hexane gave a light
yellow precipitate. After filtration, the solid was further
washed with 20 mL of pentane, giving the product (PhNCO)3
(8a ; 0.45 g, 41% yield). Spectroscopic data for 8a are consistent
with those in the literature.14
for 7 days at room temperature, the complex Cp(dppe)RuCdC-
(Ph)C(S)N(Ph)C(dNPh)S (10a ; 0.28 g, 65% yield) was isolated.
Spectroscopic data for 10a are as follows. 1H NMR: 7.75-
6.94 (m, 35 H, Ph); 3.68 (s, 5H, Cp); 2.65-2.30 (m, 4 H, PCH2).
13C NMR: 151.0-121.5 (Ph, Câ, Cγ); 85.1 (Cp); 30.7 (t, J C-P
)
+
22.0 Hz, CH2). 31P NMR: 99.3 (PPh2). Mass: 936.0 (M+
1), 565.0 (M+ - organic ligand). Anal. Calcd for C53H44N2P2S2-
Ru: C, 68.00; H, 4.74; N, 2.99. Found: C, 67.79; H, 5.01; N,
2.85.
Reaction of 1′ (0.30 g, 0.46 mmol) with PhCH2NCS (0.61
mL, 4.58 mmol) was carried out in CH2Cl2 (20 mL) at room
temperature for 3 days. The solvent was reduced under
vacuum to about 1 mL, and the residue was passed through a
silica gel packed column. A brown band was eluted with ether,
and after removal of ether, the product was washed with 2 ×
20 mL of hexane to give the brown-yellow product Cp(dppe)-
X-r a y An a lysis of 3a . Single crystals of 3a suitable for
an X-ray diffraction study were grown as mentioned above. A
single crystal of dimensions 0.20 × 0.20 × 0.30 mm3 was glued
to a glass fiber and mounted on an Enraf-Nonius CAD4
diffractometer. Initial lattice parameters were determined
from a least-squares fit to 25 accurately centered reflections
with 10.0° < 2θ < 25°. Cell constants and other pertinent data
are collected in the Supporting Information. Data were
collected using the θ/2θ scan method. The scan angle was
determined for each reflection according to the expression 0.8
+ 0.35 tan θ. The final scan speed for each reflection was
determined from the net intensity gathered during an initial
RuCdC(Ph)C(S)N(CH2Ph)C(dNCH2Ph)S (10b; 0.27 g, 62%
yield). Spectroscopic data for 10b are as follows. 1H NMR:
7.62-6.75 (m, 35 H, Ph); 5.96 (s, 2H, CH2Ph); 3.56 (s, 2H, CH2-
Ph); 3.84 (s, 5H, Cp); 2.90-2.58 (m, 4 H, PCH2). 13C NMR:
184.8, 151.4, 143.3-125.6 (Ph, Câ, Cγ); 84.8 (Cp); 52.4, 51.6 (2
× CH2Ph); 30.0 (J C-P ) 22.2 Hz, CH2). 31P NMR: 88.4 (s,
PPh2). Mass: 965.1 (M+ + 1), 565.0 (M+ - organic ligand).
Anal. Calcd for C55H48N2P2S2Ru: C, 68.52; H, 5.01; N, 2.91.
Found: C, 68.75; H, 4.84; N, 3.18. If the same reaction is
carried out at 5 °C for 5 days, the two products Cp(dppe)-
prescan and ranged from 2 to 7° min-1
.
RuCdC(Ph)C(dNCH2Ph)S (9b) and 10b in a 1:4 ratio are
observed in the NMR spectrum. 9b is unstable and is
converted to 10b in about 2 h at room temperature. Spectro-
scopic data for 9b are as follows. 1H NMR: 7.69-6.85 (m, 30
H, Ph); 4.43 (s, 2H, CH2Ph); 3.91 (s, 5H, Cp); 2.90-2.60 (m, 4
H, PCH2). 31P NMR: 94.5 (s, PPh2). Mass: 816.1 (M+ + 1),
565.0 (M+ - organic ligand).
The raw intensity data were converted to structure factor
amplitudes and their esd’s by correction for scan speed,
background, and Lorentz-polarization effects. An empirical
correction for absorption based on the azimuthal scan was
applied to the data set. Crystallgraphic computations were
carried out on a Microvax III computer using the NRCC
structure determination package.24 Merging of equivalent and
duplicate reflections gave a total of 5303 unique measured
data, from which 3077 were considered observed (I > 2.0σ(I)).
The structure was first solved by using the heavy-atom method
(Patterson synthesis), which revealed the position of the metal,
and then refined via standard least-squares and difference
Fourier techniques. The quantity minimized by the least-
squares program was w(|Fo| - |Fc|)2. The analytical forms of
the scattering factor tables for the neutral atoms were used.25
All other non-hydrogen atoms were refined by using anisotro-
pic thermal parameters. Hydrogen atoms were included in
the structure factor calculations in their expected positions on
the basis of idealized bonding geometry but were not refined
in least squares. Final refinement using full-matrix least
Tr im er iza tion of P h NCS on Cp (d p p e)Ru CtCP h .
A
Schlenk flask was charged with 1′ (0.07 g, 0.11 mmol), and
the atmosphere was replaced with nitrogen; then PhNCS (0.55
mL, 4.59 mmol) and CH2Cl2 (20 mL) were introduced and the
mixture was heated to reflux. The 31P NMR spectrum revealed
a complex mixture at the initial stage of the reaction, but after
2 days, only a single product was obtained. The mixture was
heated for 4 days, and the color of the solution changed from
bright yellow to brown. The solvent was removed under
vacuum, and the residue was washed with 2 × 30 mL of
hexane to give a brown-black product. After filtration, the
solid was further washed with 20 mL of pentane, giving the
product (PhNCS)3 (8; 0.26 g, 72% yield). Spectroscopic data
are consistent with those in the literature.14
squares converged smoothly to values of R ) 0.042 and Rw
)
Tr im er iza tion of P h NCO on Cp (d p p e)Ru CtCP h .
A
0.040. The procedures for 4a , 5b, and the cocrystallization
product of 1′ and 8 were similar. The final residuals of the
refinement were R ) 0.041 and Rw ) 0.042; R ) 0.051 and Rw
) 0.047, and R ) 0.054 and Rw ) 0.052 for 4b, 5b, and the
cocrystallization product of 1′ and 8, respectively. Final values
of all refined atomic positional parameters (with esd’s) and
tables of thermal parameters are given in the Supporting
Information.
Schlenk flask was charged with 1′ (0.10 g, 0.15 mmol), and
the atmosphere was replaced with nitrogen; then PhNCO (1.00
mL, 1.50 mmol) and CH2Cl2 (20 mL) were introduced and the
mixture was stored at 5 °C for 2 days. The solvent was
removed under vacuum, and the residue was subjected to silica
gel packed column chromatography. The organic portion
(PhNHCONHPh) was eluted with hexane, and the yellow
organometallic compound was eluted with ether. Removal of
ether solvent followed by addition of hexane gave a yellow
precipitate. After filtration, the solid was further washed with
Ack n ow led gm en t. We are grateful for support of
this work by the National Science Council, Taiwan,
Republic of China.
20 mL of pentane, giving the product Cp(dppe)RuCdC(Ph)C-
(O)N(Ph)C(dNPh)O (12; 0.10 g, 73% yield). Spectroscopic data
for 12 are as follows. 1H NMR: 8.10-6.90 (m, 30 H, Ph); 3.94
(s, 5H, Cp); 2.45-2.10 (m, 4 H, PCH2). 13C NMR: 153.3, 140.8,
135.0-121.6 (Ph, Câ, Cγ); 86.2 (Cp); 29.4 (J C-P ) 19.5 Hz, CH2).
(24) Gabe, E. J .; Lee, F. L.; Lepage, Y. In Crystallographic Comput-
ing 3; Sheldrick, G. M., Kruger, C., Goddard, R., Eds.; Clarendon
Press: Oxford, England, 1985; p 167.
(25) International Tables for X-ray Crystallography; Reidel Publish-
ing Co.: Dordrecht, Boston, 1974; Vol. IV.
31P NMR: 96.4 (PPh2). FAB mass: 905.0 (M+), 565.0 (M+
-

2542 Organometallics, Vol. 17, No. 12, 1998
Chang et al.
Su p p or tin g In for m a tion Ava ila ble: Details of the struc-
tural determination for complexes 3a , 4a , and 5b and the
cocrystallization product of 1′ and 8, including tables of crystal
data and structure refinement parameters, positional and
anisotropic thermal parameters, and bond distances and
angles (32 pages). Ordering information is given on any
current masthead page.
OM971056D