Synthetic and computational studies of thiocarbonyl/σ-organyl coupling reactions

Article abstract of DOI:10.1021/om800637y

The reactions of a range of coordinatively unsaturated σ-organyl thiocarbonyl complexes with 1,4,7-trithiacyclononane ([9]aneS₃) have been investigated, leading in some but not all cases to migratory insertive coupling of thiocarbonyl and σ-organyl ligands. Thus, under ambient conditions, the reaction of [RuR-Cl(CS)(PPh₃)₂] (R = C(CO₂Me)=CHCO₂Me, C(C≡CPh)=CHPh, C₆H ₅) with [9]aneS₃ provides σ-organyl complexes [RuR(CS)(PPh₃)([9]aneS₃)]⁺. On heating, the species [Ru(C₆H₅)(CS)(PPh₃)([9]aneS ₃)]⁺ converts to the thiobenzoyl complex [Ru(η²-SCPh)(PPh₃)([9]aneS₃)]⁺. Similarly the silyl complex [RuCl(SiMe₂OEt)-(CS)(PPh ₃)₂] with [9]aneS₃ provides [Ru(SiMe ₂OEt)(CS)(PPh₃)([9]aneS₃)]⁺. However, the styryl and stilbenyl complexes [Ru(CR=CHPh)Cl(CS)(PPh ₃)₂] (R = H, Ph) under similar conditions provide dihapto thioacyl derivatives [Ru(η²-SCCR=CHPh)(PPh₃)([9] aneS₃)]⁺. The osmium species [Os(CH=CHC₆H ₄Me-4)Cl(CS)-(BTD)(PPh₃)₂] (BTD = 2,1,3-benzothiadiazole), however, yields only the nonmigrated product [Os(CH=CHC₆-H₄Me-4)(CS)(PPh₃)([9]aneS ₃)]⁺. Migratory insertion is not induced by other sulfur donor ligands, e.g., Cy₃PCS₂ (Cy = cyclohexyl) and Na[S₂CNMe₂], which provide the complexes [Ru(CH=CH ₂)(S₂CPCy₃)-(CS)(PPh₃) ₂]⁺ and [Ru(CH=CHPh)(S₂CNMe₂)(CS) (PPh₃)₂], respectively. The reactivity of different ligands (R) toward thiocarbonyl migratory insertion in [Ru(R)(CS)(PPh ₃)([9]aneS₃)]⁺ was analyzed through density functional theory. The calculated barriers agree qualitatively with experimental observations. In order to determine the electronic effect of substituents on the migrating ligand, a series of hypothetical systems with phenyl ligands varying only in the para-substituent was considered. A general trend that electron-releasing substituents on the migrating ligand promote reaction was observed. Through symmetry-adapted fragment orbital analysis, this phenomenon is determined to correlate well with the energy of the highest occupied π-orbital of the ligand.

Full text of DOI:10.1021/om800637y

5548
Organometallics 2008, 27, 5548–5558
Synthetic and Computational Studies of Thiocarbonyl/σ-Organyl
Coupling Reactions1
Jennifer C. Green,*,† Andrew L. Hector,‡ Anthony F. Hill,*,§ Sibo Lin,† and
James D. E. T. Wilton-Ely*,†
Chemistry Research Laboratories, UniVersity of Oxford, Mansfield Road, Oxford OX1 3TA, United
Kingdom, School of Chemistry, UniVersity of Southampton, Highfield, Southampton, SO17 1BJ, United
Kingdom, and Research School of Chemistry, Institute of AdVanced Studies, Australian National
UniVersity, Canberra, ACT 0200, Australia
ReceiVed July 7, 2008
The reactions of a range of coordinatively unsaturated σ-organyl thiocarbonyl complexes with 1,4,7-
trithiacyclononane ([9]aneS3) have been investigated, leading in some but not all cases to migratory insertive
coupling of thiocarbonyl and σ-organyl ligands. Thus, under ambient conditions, the reaction of [RuR-
Cl(CS)(PPh3)2] (R ) C(CO2Me)dCHCO2Me, C(Ct CPh)dCHPh, C6H5) with [9]aneS3 provides σ-organyl
complexes [RuR(CS)(PPh3)([9]aneS3)]+. On heating, the species [Ru(C6H5)(CS)(PPh3)([9]aneS3)]+ converts
to the thiobenzoyl complex [Ru(η2-SCPh)(PPh3)([9]aneS3)]+. Similarly the silyl complex [RuCl(SiMe2OEt)-
(CS)(PPh3)2] with [9]aneS3 provides [Ru(SiMe2OEt)(CS)(PPh3)([9]aneS3)]+. However, the styryl and stilbenyl
complexes [Ru(CRdCHPh)Cl(CS)(PPh3)2] (R ) H, Ph) under similar conditions provide dihapto thioacyl
derivatives [Ru(η2-SCCRdCHPh)(PPh3)([9]aneS3)]+. The osmium species [Os(CHdCHC6H4Me-4)Cl(CS)-
(BTD)(PPh3)2] (BTD ) 2,1,3-benzothiadiazole), however, yields only the nonmigrated product [Os(CHdCHC6-
H4Me-4)(CS)(PPh3)([9]aneS3)]+. Migratory insertion is not induced by other sulfur donor ligands, e.g., Cy3PCS2
(Cy ) cyclohexyl) and Na[S2CNMe2], which provide the complexes [Ru(CHdCH2)(S2CPCy3)-
(CS)(PPh3)2]+ and [Ru(CHdCHPh)(S2CNMe2)(CS)(PPh3)2], respectively. The reactivity of different ligands
(R) toward thiocarbonyl migratory insertion in [Ru(R)(CS)(PPh3)([9]aneS3)]+ was analyzed through density
functional theory. The calculated barriers agree qualitatively with experimental observations. In order to
determine the electronic effect of substituents on the migrating ligand, a series of hypothetical systems with
phenyl ligands varying only in the para-substituent was considered. A general trend that electron-releasing
substituents on the migrating ligand promote reaction was observed. Through symmetry-adapted fragment
orbital analysis, this phenomenon is determined to correlate well with the energy of the highest occupied
π-orbital of the ligand.
this situation have focused on 1,4,7-trithiacyclononane ([9]anS3)1,4
Introduction
for the following reasons, each of which should predispose it
Bi- and, to a lesser extent, polydentate phosphines are
prevalent in many metal-mediated catalytic processes. It has
long since been speculated2 that sulfur-based macrocycles might
offer promise as co-ligands in such processes by offering a
combination of multiple soft donors that mimic phosphines in
combination with the robust nature of macrocycle coordination.
The latter might be expected to offset the general lability of
monodentate thioether binding. With very few exceptions1,3 this
potential has yet to be investigated in any detail, and little is
known about how polythiacycloalkanes might effect the reactiv-
ity of organometallic co-ligands. Our own efforts to address
to catalytic applications: (i) It is commercially available, though
somewhat expensive; (ii) in serving as a facially tridentate six-
electron donor, it may be considered as a cyclopentadienyl
mimic; (iii) the remaining sites in its octahedral or five-
coordinate complexes are, by necessity, mutually cis, and
therefore preorganized for co-ligand coupling processes, e.g.,
insertion and migratory insertion reactions. With the exception
of commercial availability, each of these points applies to the
related macrocycle 3,4-benzo-[11]aneS3, the similarly rich
chemistry of which has been investigated Loeb.5 Within the
chemistry of ruthenium, [9]aneS3 has played an increasingly
important role6 including the synthesis of organometallic
complexes.7
* To whom correspondence should be addressed. E-mail: a.hill@
anu.edu.au or james.wilton-ely@chem.ox.ac.uk (synthesis); jennifer.green@
chem.ox.ac.uk (computations).
The results to be described herein relate to the key organo-
metallic process of migratory insertion and, in particular, as it
† University of Oxford.
‡ University of Southampton.
§ Australian National University.
(1) Organometallic Macrocycle Chemistry Part 7. For part 6 see: Hill,
A. F.; Wilton-Ely, J. D. E. T. Organometallics 1997, 16, 4517.
(2) Cooper, S.; Rawle, S. C. Struct. Bonding (Berlin) 1990, 72, 1.
(3) (a) Adams, R. D.; Falloon, S. B. Organometallics 1995, 14, 4594.
(b) Adams, R. D.; Falloon, S. B. Organometallics 1995, 14, 1748. (c)
Adams, R. D.; Falloon, S. B. J. Am. Chem. Soc. 1994, 116, 10540. (d)
Adams, R. D.; Cortopassi, J.; Falloon, S. J. Organomet. Chem. 1993, 463,
C5. (e) Timonen, S.; Pakkanen, T. T.; Pakkanen, T. A. J. Mol. Catal. A
1996, 111, 267.
(4) (a) Cannadine, J.; Hill, A. F.; White, A. J. P.; Williams, D. J.; Wilton-
Ely, J. D. E. T. Organometallics 1996, 15, 5409. (b) Hill, A. F.; Alcock,
N. W.; Cannadine, J. C.; Clark, G. R. J. Organomet. Chem. 1992, 426,
C40. (c) Hill, A. F.; Alcock, N. W.; Cannadine, J. C.; Clark, G. R. J. Chem.
Soc., Dalton Trans. 1993, 1131. (d) Hector, A. L.; Hill, A. F. Inorg. Chem.
1995, 34, 3797. (e) Cannadine, J.; Hector, A. L.; Hill, A. F. Organometallics
1992, 11, 2323. (f) Bedford, R. B.; Hill, A. F.; Jones, C.; White, A. J. P.;
Williams, D. J.; Wilton-Ely, J. D. E. T. Organometallics 1998, 17, 4744.
10.1021/om800637y CCC: $40.75
2008 American Chemical Society
Publication on Web 10/08/2008

Thiocarbonyl/σ-Organyl Coupling Reactions
Organometallics, Vol. 27, No. 21, 2008 5549
relates to thiocarbonyl ligands. In an organometallic context,8
carbon monosulfide is in all respects except its availability9-11
Chart 1. Energies (eV) and Topologies of the Frontier
Orbitals of CO, CS, and CNH
(5) (a) De Groot, B.; Giesbrecht, G. R.; Loeb, S. J.; Shimizu, G. K. H.
Inorg. Chem. 1991, 30, 177. (b) De Groot, B.; Hanan, G. S.; Loeb, S. J.
Inorg. Chem. 1991, 30, 4644. (c) De Groot, B.; Jenkins, H. A.; Loeb, S. J.
Inorg. Chem. 1992, 31, 203. (d) Giesbrecht, G. R.; Hanan, G. S.; Kickham,
J. E.; Loeb, S. J. Inorg. Chem. 1992, 31, 3286. (e) Jenkins, H. A.; Loeb,
S. J. Organometallics 1994, 13, 1840. (f) De Groot, B.; Jenkins, H. A.;
Loeb, S. J.; Murphy, S. L Can. J. Chem. 1995, 73, 1102. (g) Casabo, J.;
Flor, T.; Hill, M. N. S.; Jenkins, H. A.; Lockhart, J. C.; Loeb, S. J.; Romero,
I.; Teixidor, F. Inorg. Chem. 1995, 34, 5410.
(6) (a) Bratsos, I.; Birarda, G.; Jedner, S.; Zangrando, E.; Alessio, E.
Dalton Trans. 2007, 4, 048. (b) Laurenczy, G.; Jedner, S.; Alessio, E.;
Dyson, P. J. Inorg. Chem. Commun. 2007, 10, 558. (c) Shan, N.; Ingram,
J. D.; Easun, T. L.; Vickers, S. J.; Adams, H.; Ward, M. D.; Thomas, J. A.
Dalton Trans. 2006, 2900. (d) Shan, N.; Adams, H.; Thomas, J. A. Inorg.
Chim. Acta 2006, 359, 759. (e) Serli, B.; Zangrando, E.; Gianferrara, T.;
Scolaro, S.; Dyson, P. J.; Bergamo, A.; Alessio, E. Eur. J. Inorg. Chem.
2005, 3423. (f) Iengo, E.; Zangrando, E.; Baiutti, E.; Munini, F.; Alessio,
E. Eur. J. Inorg. Chem. 2005, 1019. (g) Maurer, P.; Magistrato, A.;
Rothlisberger, U J. Phys. Chem. A 2004, 108, 11494. (h) Shan, N.; Vickers,
S. J.; Adams, H.; Ward, M. D.; Thomas, J. A. Angew. Chem., Int. Ed. 2004,
43, 3938. (i) Sala, X.; Romero, I.; Rodriguez, M.; Llobet, A.; Gonzalez,
G.; Martinez, M.; Benet-Buchholz, J. Inorg. Chem. 2004, 43, 5403. (j)
Adams, H.; Shan, N.; Thomas, J. Acta Crystallograph., Sect. E: Struct.
Rep. Online 2004, E60, m662. (k) Sala, X.; Poater, A.; Romero, I.;
Rodriguez, M.; Llobet, A.; Solans, X.; Parella, T.; Santos, T. M. Eur.
J. Inorg. Chem. 2004, 612. (l) Araujo, C. S.; Drew, M. G. B.; Felix, V.;
Jack, L.; Madureira, J.; Newell, M.; Roche, S.; Santos, T. M.; Thomas,
J. A.; Yellowlees, L. Inorg. Chem. 2002, 41, 2250. (m) Santos, T. M.;
Madureira, J.; Goodfellow, B. J.; Drew, M. G. B.; Pedrosa de Jesus, J.;
Felix, V. Metal-Based Drugs 2001, 8, 125. (n) Roche, S.; Spey, S. E.;
Adams, H.; Thomas, J. A. Inorg. Chim. Acta 2001, 323, 157. (o) Santana-
Marques, M. G. O.; Amado, F. M. L.; Correia, A. J. F.; Lucena, M.;
Madureira, J.; Goodfellow, B. J.; Felix, V.; Santos, T. M. J. Mass Spectrom.
2001, 36, 529. (p) Madureira, J.; Santos, T. M.; Goodfellow, B. J.; Lucena,
M.; Pedrosa de Jesus, J.; Santana-Marques, M. G.; Drew, M. G. B.; Felix,
V. Dalton Trans. 2000, 4422. (q) Roche, S.; Adams, H.; Spey, S. E.;
Thomas, J. A. Inorg. Chem. 2000, 39, 2385. (r) Roche, S.; Haslam, C.;
Heath, S. L.; Thomas, J. A. Chem. Commun. 1998, 1681. (s) Roche, S.;
Thomas, J. A.; Yellowlees, L. J. Chem. Commun. 1998, 1429. (t)
Goodfellow, B. J.; Felix, V.; Pacheco, S. M. D.; Pedrosa de Jesus, J.; Drew,
M. G. B. Polyhedron 1996, 16, 393. (u) Landgrafe, C.; Sheldrick, W. S.
J. Chem. Soc., Dalton Trans. 1996, 989. (v) Landgrafe, C.; Sheldrick, W. S.
J. Chem. Soc., Dalton Trans. 1994, 1885. (w) Blake, A. J.; Christie, R. M.;
Roberts, Y. V.; Sullivan, M. J.; Schro¨der, M.; Yellowlees, L. J. J. Chem.
Soc., Chem. Commun. 1992, 848. (x) Setzer, W. N.; Guo, Q.; Grant, G. J.;
Hubbard, J. L.; Glass, R. S.; Van der Veer, D. G. Heteroat. Chem. 1990,
317. (y) Bell, M. N.; Blake, A. J.; Holder, A. J.; Hyde, T. I.; Schro¨der, M.
J. Chem. Soc., Dalton Trans. 1990, 3841. (z) Rawle, S. C.; Sewell, T. J.;
Cooper, S. R. Inorg. Chem. 1987, 26, 3769. (aa) Rawle, S. C.; Cooper,
S. R. J. Chem. Soc., Chem. Commun. 1987, 308. (ab) Bell, M. N.; Blake,
A. J.; Kueppers, H. J.; Schro¨der, M.; Wieghardt, K. Angew. Chem. 1987,
99, 253.
(7) (a) Shin, R. Y. C.; Bennett, M. A.; Goh, L. Y.; Chen, W.; Hockless,
D. C. R.; Leong, W. K.; Mashima, K.; Willis, A. C. Inorg. Chem. 2003,
42, 96. (b) Goh, L. Y.; Teo, M. E.; Khoo, S. B.; Leong, W. K.; Vittal, J. J.
J. Organomet. Chem. 2002, 664, 161. (c) Shin, R. Y. C.; Teo, M. E.; Leong,
W. K.; Vittal, J. J.; Yip, J. H. K.; Goh, L. Y.; Webster, R. D.
Organometallics 2005, 24, 1483. (d) Edwards, A. J.; Willis, A. C.; Wenger,
E. Organometallics 2002, 21, 1654. (e) Eckermann, A. L.; Fenske, D.;
Rauchfuss, T. B. Inorg. Chem. 2001, 40, 1459. (f) Leung, W.-H.; Lau, K.-
K.; Zhang, Q.-F.; Wong, W.-T.; Tang, B. Organometallics 2000, 19, 2084.
(g) Grant, G. J.; Salupo-Bryant, T.; Holt, L. A.; Morrissey, D. Y.; Gray,
M. J.; Zubkowski, J. D.; Valente, E. J.; Mehne, L. F. J. Organomet. Chem.
1999, 587, 207. (h) Green, M.; Draganjac, M.; Jiang, Y.; Cordes, A. W.
J. Chem. Crystallogr. 1999, 29, 273. (i) Birri, A.; Steed, J. W.; Tocher,
D. A. J. Organomet. Chem. 1999, 575, 242. (j) Harlow, K. J.; Hill, A. F.;
Wilton-Ely, J. D. E. T. J. Chem. Soc., Dalton Trans. 1999, 285. (k) Bennett,
M. A.; Willis, A. C.; Goh, L. Y.; Chen, W. Polyhedron 1996, 15, 3559. (l)
Welch, A. J.; Weller, A. S. Inorg. Chem. 1996, 35, 4548. (m) Bennett,
M. A.; Goh, L. Y.; Willis, A. C. J. Am. Chem. Soc. 1996, 118, 4984. (n)
Adams, R. D.; Yamamoto, J. H. Organometallics 1995, 14, 3704. (o)
Adams, R. D.; Falloon, S. B.; McBride, K. T.; Yamamoto, J. H.
Organometallics 1995, 14, 1739. (p) Bennett, M. A.; Goh, L. Y.; Willis,
A. C. J. Chem. Soc., Chem. Commun. 1992, 1180. (q) Bell, M. N.; Blake,
A. J.; Schro¨der, M.; Stephenson, T. A. J. Chem. Soc., Chem. Commun 1986,
471. (r) Hill, A. F.; Rae, A. D.; Schultz, M.; Willis, A. C. Organometallics
2004, 23, 81.
Chart 2. Supposed Competitive Retrodonation to [9]aneS3
(adapted from ref 36)
a superlative isosteric surrogate for carbon monoxide. The
frontier orbitals of CS12 are topologically similar to those of
CO; however the energetics are significantly different (Chart
1). Thus replacement of oxygen by sulfur stabilizes the π-acidic
orbitals and destabilizes the σ-donor orbital used for binding to
a transition metal; that is, CS is both a stronger σ-donor and
π-acid ligand than CO. The chemical implications, beyond
stronger binding to the metal, are as follows: (i) Transfer of
electron density out onto the sulfur makes it more prone to
electrophilic attack than CO, providing a route to thiolatocarbyne
complexes.13 (ii) For metal centers of only modest π-basicity
where retrodonation fails to satisfy the electrophilicity of the
π* orbitals, the CS ligand is more prone to nucleophilic attack
than CO. (iii) In binuclear carbonyl/thiocarbonyl complexes, it
is always the thiocarbonyl ligand that assumes a bridging role.
It is perhaps in the area of migratory insertion (Scheme 1)
that thiocarbonyls present the most dramatic reactivity. In
addition to conventional σ-organyls,16 a range of co-ligands not
normally associated with migration to CO have been shown to
(9) CS is not isolable under laboratory conditions but has been
spectroscopically observed when CS2 is subjected to high-frequency electric
discharge at-190 °C10 and in the insterstellar medium.11
,
(10) Steudel, R. Angew. Chem., Int. Ed. Engl. 1967, 6, 635. (b) Steudel,
R. Z. Naturforsch. 1966, 21B, 1106.
(11) Bull, D. Sky Telescope 1973, 156. (b) Oppenheimer, M.; Delgars,
A. Astrophys. J. 1974, 187, 231. (c) Liszt, H. S.; Links, R. A. Astrophys.
J. 1975, 196, 709.
(12) (a) Saillard, J. Y.; Grandjean, D.; Caillet, P.; Le Beuze, A. J.
Organomet. Chem. 1980, 190, 371. (b) Richards, W. G. Trans. Faraday
Soc. 1967, 63, 257.
(13) (a) Doyle, R. A.; Angelici, R. J. J. Am. Chem. Soc. 1990, 112,
194. (b) Doyle, R. A.; Angelici, R. J. Organometallics 1989, 8, 2207. (c)
Kim, H. P.; Kim, S.; Jacobson, R. A.; Angelici, R. J. Organometallics 1984,
3, 1124. (d) Greaves, W. W.; Angelici, R. J. Inorg. Chem. 1981, 20, 2983.
(e) Greaves, W. W.; Angelici, R. J.; Helland, B. J.; Klima, R.; Jacobson,
R. A. J. Am. Chem. Soc. 1979, 101, 7618. (f) Dombek, B. D.; Angelici,
R. J. Inorg. Chem. 1976, 15, 2397. (g) Dombek, B. D.; Angelici, R. J.
J. Am. Chem. Soc. 1975, 97, 1261. (h) Desmond, T.; Lalor, F. J.; Ferguson,
G.; Parvez, M. J. Chem. Soc., Chem. Commun. 1984, 75.
(8) For an early review of the coordination chemistry of carbon
monosulfide see: Broadhurst, P. V. Polyhedron 1985, 4, 1801.

5550 Organometallics, Vol. 27, No. 21, 2008
Green et al.
insertion, provided the archetypal metallacyclobutadiene25 and
metallabenzenes,26 the latter being implicated in the formation
of cyclopentadiene-thione complexes.27 Herein we describe the
reactions of the recently reported σ-organyl/thiocarbonyl com-
plexes [Ru(R)Cl(CS)(PPh3)2] (R ) vinyl,28 aryl29) with [9]aneS3,
which lead in some but not all cases to migratory insertion.
These phenomena have been interpreted with recourse to
theoretical methods. Aspects of this work have contributed to
a preliminary communication.4e
Scheme 1. Valence Electron Counts (nVE) Associated with
Migratory Insertion (A ) O, S)
Results and Discussion
The σ-organyl/thiocarbonyl starting complexes for this study
are available via two routes. The reaction of [RuHCl(CS)(P-
Ph3)3]30 with diphenylmercury provides the coordinatively
unsaturated σ-aryl complex [Ru(C6H5)Cl(CS)(PPh3)2]29 by anal-
ogy with that described for the related osmium complex
[Os(C6H4Me-4)Cl(CS)(PPh3)2].16a The series of coordinatively
unsaturated σ-vinyl complexes (Scheme 2) arises from the facile
hydroruthenation of alkynes by the same hydrido complex,28
while the 18-electron complex [Os(CHdCHC6H4Me)Cl-
(CS)(BTD)(PPh3)2] (BTD ) 2,1,3-benzothiadiazole),32b by
virtue of the labile BTD ligand, is synthetically equivalent to a
16-electron species.
migrate to CS with ease, including hydrides,17-21 silyls,22
boryls,23 and boranes.24 Furthermore, CS/alkyne coupling of
alkynes, which might be viewed as a special case of migratory
(14) (a) Busetto, L.; Graziani, M.; Belluco, U. Inorg. Chem. 1971, 10,
78. (b) Brothers, P. J.; Headford, C. E. L.; Roper, W. R. J. Organomet.
Chem. 1980, 195, C29. (c) Herberhold, M.; Hill, A. F.; McAuley, N.; Roper,
W. R. J. Organomet. Chem. 1986, 310, 95. (d) Clark, G. R.; Collins, T. J.;
Hall, D.; James, S. M.; Roper, W. R. J. Organomet. Chem. 1977, 141, C5.
(e) Collins, T. J.; Roper, W. R. J. Organomet. Chem. 1977, 139, C9. (f)
Singh, M. M.; Angelici, R. J. Inorg. Chem. 1984, 23, 2691. (g) Singh, M. M.;
Angelici, R. J. Angew. Chem. 1983, 95, 160. (h) Faraone, F.; Piraino, P.;
Marsala, V.; Sergi, S. J. Chem. Soc., Dalton Trans. 1977; Chim. l’Indust.
1976, 58, 654. (i) Wnuk, T. A.; Angelici, R. J. Inorg. Chem. 1977, 16,
1173.
(15) (a) Dunker, J. W.; Finer, J.; Clardy, J.; Angelici, R. J. J. Organomet.
Chem. 1976, 114, C49. (b) Kim, H. P.; Kim, S.; Jacobson, R. A.; Angelici,
R. J. J. Am. Chem. Soc. 1986, 108, 5154. (c) Doyle, R. A.; Daniels, L. M.;
Angelici, R. J.; Stone, F. G. A. J. Am. Chem. Soc. 1989, 111, 4995. (d)
Dombeck, B. D.; Angelici, R. J. J. Am. Chem. Soc. 1974, 96, 7568. (e)
Johnson, A. R.; Davis, W. M.; Cummins, C. C.; Serron, S.; Nolan, S. P.;
Musaev, D. G.; Morokuma, K. J. Am. Chem. Soc. 1998, 120, 2071. (f)
Jeffrey, J. C.; Razay, H.; Stone, F. G. A. J. Chem. Soc., Dalton Trans.
1982, 1733. (g) Jeffery, J. C.; Razay, H.; Stone, F. G. A. J. Chem. Soc.,
Chem. Commun. 1981, 243. (h) Werner, H.; Kolb, O.; Thometzek, P. J.
Organomet. Chem. 1988, 347, 137. (i) Kolb, O.; Werner, H. Angew. Chem.
1982, 94, 207. (k) Choi, M. G.; Daniels, L. M.; Angelici, R. J. J. Organomet.
Chem. 1990, 383, 321. (l) Albano, V. G.; Monari, M.; Busetto, L.; Carlucci,
L.; Zanotti, V. Gazz. Chim. Ital. 1992, 122, 201. (m) Busetto, L.; Monari,
M.; Palazzi, A.; Albano, V.; Demartin, F. J. Chem. Soc., Dalton Trans.
1983, 1849.
Vinyl Complexes. Four representative examples were chosen
to illustrate various features: monosubstituted, disubstituted,
R-carbomethoxy, and R-alkynyl substituted. The metallacyclic
complex [Ru{C(CO2Me)dCHCO2Me}Cl(CS)(PPh3)2] is coor-
dinatively saturated as a result of the ꢀ-ester group; however
this coordination appears to be hemilabile. Thus treating the
complex with [9]aneS3 in the presence of a salt of a noncoor-
-
dinating anion (ClO4 or PF6-) results in the formation of the
octahedral vinyl complex [Ru{C(CO2Me)dCHCO2Me}(CS)-
(PPh3)([9]aneS3)]PF6 (1 · PF6) via opening of the metallacycle
and substitution of the chloride and one phosphine ligand
(Scheme 3). The facial coordination of the macrocycle follows
from the complex 1H NMR data associated with the ligand. In
an octahedral complex of the form [ML1L2L3([9]aneS3)], the
chirality at the metal center renders each of the 12 macrocyclic
protons chemically distinct. We have in one instance shown
that NOESY and COSY techniques allow the identification of
each of these resonances;4a however detailed analyses were not
attempted in the present study. The gross formulation of the
cation follows from positive ion FAB-mass spectrometry, which
reveals an abundant molecular ion in addition to fragmentations
due to loss of vinyl and phosphine ligands. A further feature of
complexes of [9]aneS3 is the appearance of fragmentations
attributable to ethylene elimination from the macrocycle. A
singlet resonance is observed in the 31P{1H} NMR spectrum
that further confirms tridentate coordination of the macrocycle.
(16) (a) Clark, G. R.; Collins, T. J.; Marsden, K.; Roper, W. R. J.
Organomet. Chem. 1983, 259, 215. (b) Clark, G. R.; Collins, T. J.; Marsden,
K.; Roper, W. R. J. Organomet. Chem. 1978, 157, C23. (c) Rickard, C. E. F.;
Roper, W. R.; Woodgate, S. D.; Wright, L. J. J. Organomet. Chem. 2001,
623, 109. (d) Rickard, C. E. F.; Roper, W. R.; Woodgate, S. D.; Wright,
L. J. J. Organomet. Chem. 2000, 607, 27.
(17) (c) Although migratory coupling of CO and hydrides is on occasion
inferred and believed to be kinetically feasible, thermodynamically the
hydride-carbonyl tautomer is generally favored over the formyl.18 An
exception is when the formyl may be trapped via formation of a strong
metal-oxygenbond16orproceedirreversiblyviasubsequenttransformations.19,20
,
(18) Koga, N.; Morokuma, K. New J. Chem. 1991, 15, 749.
(19) Fagan, P. J.; Moloy, K. G.; Marks, T. J. J. Am. Chem. Soc. 1981,
103, 6959.
(20) (a) Fryzuk, M. D.; Mylvaganam, M.; Zaworotko, M. J.; MacGillivray,
L. R. Organometallics 1996, 15, 1134. (b) Manriquez, J. M.; McAlister,
D. R.; Sanner, R. D.; Bercaw, J. E. J. Am. Chem. Soc. 1976, 98, 6733. (c)
Manriquez, J. M.; McAlister, D. R.; Sanner, R. D.; Bercaw, J. E. J. Am.
Chem. Soc. 1978, 100, 2716. (d) Wolczanski, P. T.; Bercaw, J. E. Acc.
Chem. Res. 1980, 13, 121. (e) Barger, P. T.; Bercaw, J. E. Organometallics
1984, 3, 278.
(21) Roper, W. R.; Town, K. G. J. Chem. Soc., Chem. Commun. 1977,
781. (b) Collins, T. J.; Roper, W. R. J. Organomet. Chem. 1978, 159, 73.
(c) Collins, T. J.; Roper, W. R. J. Organomet. Chem. 1977, 139, C9. (d)
Collins, T. J.; Roper, W. R. J. Chem. Soc., Chem. Commun. 1976, 1044.
(22) (a) Rickard, C. E. F.; Roper, W. R.; Salter, D. M.; Wright, L. J.
Organometallics 1992, 11, 3931. (b) Attar-Bashi, M. T.; Rickard, C. E. F.;
Roper, W. R.; Wright, L. J.; Woodgate, S. D. Organometallics 1998, 17,
504.
(24) Crossley, I. R.; Hill, A. F.; Willis, A. C. Organometallics 2007,
26, 3891.
(25) Elliot, G. P.; Roper, W. R. J. Organomet. Chem. 1983, 250, C5.
(26) (a) Elliott, G. P.; Roper, W. R.; Waters, J. M. Chem. Commun.
1982, 811. (b) Clark, G. R.; Johns, P. M.; Roper, W. R.; Wright, L. J.
Organometallics 2008, 27, 451. (c) Clark, G. R.; Johns, P. M.; Roper, W. R.;
Wright, L. J. Organometallics 2006, 25, 1771. (d) Clark, G. R.; Lu, G.-L.;
Roper, W. R.; Wright, L. J. Organometallics 2007, 26, 2167. (e) For a
review of metallabenzenes derived from thiocarbonyl ligands see: Wright
L. J. Dalton Trans. 2006, 1821.
(27) Hill, A. F.; Schultz, M.; Willis, A. C Organometallics 2005, 24–
2027.
(28) Cowley, A. R. C.; Hill, A. F.; White, A. J. P.; Williams, D. J.;
Wilton-Ely, J. D. E. T. Organometallics 2007, 26, 6114.
(29) Bedford, R. B.; Hill, A. F.; White, A. J. P.; Williams, D. J. Angew.
Chem., Int. Ed. Engl. 1996, 35, 95.
(23) Irvine, G. J.; Lesley, M. J. G.; Marder, T. B.; Norman, N. C.; Rice,
C. R.; Robins, E. G.; Roper, W. R.; Whittell, G. R.; Wright, L. J. Chem.
ReV. 1998, 98, 2685.
(30) Brothers, P. J.; Roper, W. R. J. Organomet. Chem. 1983, 258, 73.

Thiocarbonyl/σ-Organyl Coupling Reactions
Organometallics, Vol. 27, No. 21, 2008 5551
Scheme 2. Synthesis of Starting Thiocarbonyl Complexes (L
) PPh3): (i) MeO2CCt CCO2Me;26 (ii) R1Ct CR2;26 (iii)
HgPh2;27 (iv) SiHClMe2;20 (v) EtOH20
Scheme 4. Reactions of 1,4,7-Trithiacyclononane with
Ruthenium Thiocarbonyl Styryl and Stilbenyl Complexes (L
) PPh3): (i) [9]aneS3, LiClO4
coordinates to the metal center31 may be ruled out on the basis
of both infrared (νCt C ) 2157 cm-1) and 13C NMR data (δCt
C
) 101.5, 98.6 ppm). The macrocyclic ligand gives rise to four
singlet resonances (37.2, 35.2, 34.1, 30.4 ppm), one broadened
singlet (34.3 ppm), and a doublet (33.8 ppm, JCP ) 5.3 Hz),
these latter two resonances arising from the two methylene
carbons bound to the sulfur trans to the phosphine ligand. The
simple vinyl complexes [Ru(CRdCHPh)Cl(CS)(PPh3)2] (R )
H, Ph) both react with [9]aneS3 to provide salts with similar
FAB-MS data to the previous examples, confirming the gross
composition. The remaining data however indicate that the
products involve migratory insertion of the vinyl and thiocar-
bonyl ligands (Scheme 3), to provide the thioacyl salts [Ru(η2-
SCCRdCHPh)(PPh3)([9]aneS3)]+ (R ) H, 3 · ClO4; R ) Ph,
4 · ClO4). The bidentate thioacyl (metallathiirene) group is an
intense visible chromophore,14-16 and hence these salts are deep
purple. We have so far been unsuccessful in obtaining crystal-
lographic confirmation of the thioacyl formulations; however
this follows unambiguously from the following spectroscopic
data: Immediate indication that the thiocarbonyl component is
no longer terminal in nature follows from the absence of a
characteristically intense νCS absorption in the infrared spectrum
of either derivative. In the case of 4 · ClO4, for which carbon-
13 NMR data are available, the thiocarbonyl resonance is
observed as a doublet at 312.8 ppm (JCP ) 9.7 Hz) in a region
typical of metallathiirenes.11,32 For the thiocinnamoyl example
(3 · ClO4), only one of the vinylic protons (HR) was observed
in the 1H NMR spectrum due to the second being obscured by
phenyl resonances. This signal, which appears at 7.64 ppm,
shows coupling to Hꢀ (11.9 Hz) in addition to a very small
coupling (1.7 Hz) to the now more remote (4J) phosphorus
nucleus. The absence of coupling to phosphorus and the change
in shift of the HR resonance to higher field (8.65 ppm, dt, JHH
) 14.1, JHP ) 2.9 Hz in the alkenyl precursor) indicate that the
Scheme 3. Reaction of 1,4,7-Trithiacyclononane ([9]aneS3)
with Ruthenium and Osmium Thiocarbonyl Alkenyl
Complexes (L ) PPh3): (i) [9]aneS3, NH4PF6, or NaClO4
(31) (a) Gotzig, J.; Otto, H.; Werner, H. J. Organomet. Chem. 1985,
287, 247. (b) Jia, G.; Rheingold, A. L.; Meek, D. W. Organometallics 1989,
8, 1378. (c) Jia, G.; Gallucci, J. C.; Rheningold, A. L.; Haggerty, B. S.;
Meek, D. W. Organometallics 1991, 10, 3459. (d) Jia, G.; Meek, D. W.
Organometallics 1991, 10, 1444. (e) Field, L. D.; George, A. V.; Hambley,
T. W. Inorg. Chem. 1990, 29, 4565. (f) McKullen, A. K.; Selegue, J. P.;
Wang, J.-G. Organometallics 1991, 10, 3421. (g) Bianchini, C.; Peruzzini,
M.; Zanobini, F.; Frediani, P.; Albinati, A. J. Am. Chem. Soc. 1991, 113,
5453. (h) Alcock, N. W.; Hill, A. F.; Melling, R. P.; Thompsett, A. R.
Organometallics 1993, 12, 641. (i) Hill, A. F.; Melling, R. P.; Thompsett,
A. R. J. Organomet. Chem. 1991, 402, C8. (j) Hill, A. F.; Melling, R. P. J.
Organomet. Chem. 1990, 396, C22.
(32) (a) Anderson, S.; Cook, D. J.; Hill, A. F. Organometallics 2001,
20, 2468. (b) Hill, A. F.; Wilton-Ely, J. D. E. T. J. Chem. Soc., Dalton
Trans. 1998, 3501. (c) Andon, W.; Ohtaki, T.; Suzuki, T.; Kabe, Y. J. Am.
Chem. Soc. 1991, 113, 7782. (d) Drews, R.; Edelmann, F.; Behrens, U. J.
Organomet. Chem. 1986, 315, 369. (e) Faraone, F.; Tresoldi, G.; Loprete,
G. A. J. Chem. Soc., Dalton Trans. 1979, 933. (f) Tresoldi, G.; Faraone,
F.; Piraino, P. J. Chem. Soc., Dalton Trans. 1979, 1053. (g) Hill, A. F.;
Malget, J. M. J. Chem. Soc., Dalton Trans. 1997, 2003. (h) Cook, D. J.;
Hill, A. F. Organometallics 2003, 22, 3502. (i) Cook, D. J.; Hill, A. F.
J. Chem. Soc., Chem. Commun. 1997, 955.
Clear evidence that migratory insertion has not ensued is
provided by the appearance of an intense absorption at 1290
cm-1 due to the terminal thiocarbonyl ligand.
A similar result is obtained for the R-alkynyl-substituted vinyl
complex [Ru{C(Ct CPh)dCHPh}Cl(CS)(PPh3)2], which pro-
vides the salt [Ru{C(Ct CPh)dCHPh}(CS)(PPh3)([9]aneS3)]PF6
(2 · PF6) in high yield (83%). Spectroscopic data for this salt
are immediately comparable to those for (1 · PF6) and are
unremarkable other than to confirm that once again migratory
13
insertion has not occurred (νCS ) 1294 cm-1
;
C
(CS)
) 297.2
(d), JCP ) 19.7 Hz). The possibility that the R-alkynyl group

5552 Organometallics, Vol. 27, No. 21, 2008
Green et al.
Scheme 5. Reaction of 1,4,7-Trithiacyclononane with
Ruthenium Aryl and Silyl Compounds (L ) PPh3): (i)
[9]aneS3, NH4PF6; (ii) heat (R ) Ph only)
CHdCHPh moiety is no longer directly bonded to the ruthenium
center. We have also reported the preparation of the osmium
species [Os(CHdCHC6H4Me-4)Cl(CS)(BTD)(PPh3)2], which
reacts with carbon monoxide to yield the thioacyl complex
[Os(η2-SCCHdCHC6H4Me-4)Cl(CO)(PPh3)2].32b However, treat-
ment of [Os(CHdCHC6H4Me-4)Cl(CS)(BTD)(PPh3)2] with
[9]aneS3 in the presence of NH4PF6 provides the nonmigrated
product
[Os(CHdCHC6H4Me-4)(CS)(PPh3)([9]aneS3)]PF6
(5 · PF6) in 69% yield. This complex gives rise to an intense
νCS absorption at 1298 cm-1, and the remainder of the data
compare well with those of the carbonyl analogue [Os(CHd
CHC6H4Me-4)(CO)(PPh3)([9]aneS3)]PF6.32b
Aryl and Silyl Complexes. Given that the vinyl complexes
discussed above led to different products upon reaction with
[9]aneS3, we have briefly investigated the reactions of the
complexes [Ru(C6H5)Cl(CS)(PPh3)2]29 and [Ru(SiMe2OEt)-
Cl(CS)(PPh3)2]22 with [9]aneS3. While both of these species
react with carbon monoxide to provide thioacyl complexes, the
latter example described by Roper22 is remarkable in that silyl
groups are characteristically not prone to such processes. With
the exception of early transition metal (d0) sila-acyl complexes
reported by Tilley that result from the carbonylation of the
corresponding silyl complexes,33 sila-acyls are in general only
accessible via external nucleophilic attack by silyl anions on
coordinated CO,34,35 typically as intermediates en route to
silylcarbenes and carbynes.35 Thus the high propensity of
thiocarbonyl ligands for migratory insertion processes is em-
phatically illustrated, though the formation of a Ru-S bond in
adopting the bidentate coordination mode no doubt contributes
to the thermodynamic impetus.
Treating both [Ru(C6H5)Cl(CS)(PPh3)2] and [Ru(SiMe2OEt)-
Cl(CS)(PPh3)2] with [9]aneS3 leads to tridentate coordination
of the macrocycle, as for the vinyl complexes above; however
there is no indication of migratory insertion of either the phenyl
or silyl ligands with the thiocarbonyl under ambient conditions.
Thus the salts [Ru(C6H5)(CS)(PPh3)([9]aneS3)]PF6 (6 · PF6) and
[Ru(SiMe2OEt)(CS)(PPh3)([9]aneS3)]PF6 (7 · PF6) are readily
obtained in 72% and 83% yield, respectively (Scheme 5). The
formulations follow unambiguously from spectroscopic data.
The presence of intense infrared absorptions at 1293 (R ) Ph)
and 1275 cm-1 (R ) SiMe2OEt) confirms that the terminal
thiocarbonyl retains its integrity in both products. However, on
heating in tetrahydrofuran for 4 h, 6 · PF6 was found to convert
smoothly into the thiotoluoyl complex [Ru(η2-SCC6H5)-
(PPh3)([9]aneS3)]PF6 (8 · PF6), which displays no terminal
thiocarbonyl absorption. The products 6 · PF6 and 8 · PF6 give
similar FAB-MS spectra and microanalytical data, indicating
an identical empirical composition but differ in 1H and 31P NMR
chemical shift (39.4 ppm for 6 · PF6 and 35.9 ppm for 8 · PF6)
and the presence of a coordinated terminal νCS absorption. The
data for 8 · PF6 associated with the SCR ligand also compare
well to those for [Ru(η2-SCC6H5)(CA)(PPh3)2] (A ) O, S).29
The nature of [9]aneS3 bonding to a metal is a matter for
debate2 in that while phosphines PR3 are often supposed to
involve a variable degree of retrodonation into π-acidic P(d) or
P-R (σ*) orbitals, such interactions for thioethers are less clear-
cut. In general macrocycle C-S bonds become elongated in
metal complexes relative to free [9]aneS3, and calculations
indicate that for the complexes [M([9]aneS3)2]n+ (Mn ) Tc1,
RuII, RhIII) there is considerable population of C-S σ*
orbitals.36 A π-acidic component to the bonding of [9]aneS3
complexes would certainly be in concert with the observed
ability of this ligand to induce migratory insertion, given that
migratory insertion is generally favored by any factor that
reduces retrodonation to the (thio)carbonyl ligand. We have
addressed this qualitative interpretation in two ways. Experi-
mentally, we have investigated the reactions of the model
σ-organyl/thiocarbonyl precursors with sulfur chelates that have
π-basic character in the expectation that migratory insertion
would not be favored. Second (Vide infra) we have computa-
tionally interrogated the electronic nature of species on the
migratory insertion reaction coordinate.
Reactions with π-Basic Sulfur Chelates. In contrast to
[9]aneS3 which is primarily a σ-donor ligand with at best a
modest degree of π-acidity,36 dithiocarbamates are strongly
π-basic.37 The reaction of [Ru(CHdCHPh)Cl(CS)(PPh3)2] with
Na[S2CNMe2] was investigated and found to provide the
noninserted vinyl complex [Ru(CHdCHPh)(S2CNMe2)(CS)-
(PPh3)2] (9), as indicated by the appearance of an intense
thiocarbonyl absorption (Nujol: 1251 cm-1) and also by the
double-triplet multiplicity of the low-field 1H NMR reso-
nance (δH ) 8.00 ppm, dt, JHH ) 17.2, JHP ) 2.3 Hz) due to
the R-proton of the vinyl group that remains bound to rutheni-
um (Scheme 6).
In a similar manner, the reaction of [Ru(CHdCH2)-
Cl(CS)(PPh3)2] with tricyclohexylphosphonio dithiocarboxylate
(Cy3PCS2) was investigated and found, in the presence of
NH4[PF6], to provide the salt [Ru(CHdCH2)(S2CPCy3)-
(CS)(PPh3)2]PF6 (10 · PF6). We have previously described the
analogous carbonyl salt [Ru(CHdCHC6H4Me-4)(S2CPCy3)-
(CO)(PPh3)2]Cl and also noted that the hydride-thiocarbonyl
complex [RuHCl(CS)(PPh3)3] is not converted to a thioformyl
derivative by Cy3PCS2, but rather provides the complex
[RuH(S2CPCy3)(CS)(PPh3)2]Cl, while [RuHCl(CO)(PPh3)3] pro-
(33) (a) Camion, B. K.; Falk, J.; Tilley, T. D. J. Am. Chem. Soc. 1987,
109, 2049. (b) Woo, H.-G.; Freeman, W. P.; Tilley, T. D. Organometallics
1992, 11, 2198.
(34) Anglin, J. R.; Calhoun, H. P.; Graham, W. A. G. Inorg. Chem.
1977, 16, 2281.
vides
a
mixture of the two complexes [RuH(S2-
CPCy3)(CO)(PPh3)2]+ and [Ru(S2CHPCy3)(CO)(PPh3)2]+.38
(35) (a) Fischer, E. O.; Hollfelder, H.; Friedrich, P.; Kreibl, F. R.;
Huttner, G. Angew. Chem., Int. Ed. 1977, 16, 401. (b) Jamison, G. M.;
Bruce, A. E.; White, P. S.; Templeton, L. J. J. Am. Chem. Soc. 1991, 113,
5057. (c) Jeffery, J. C.; Ruiz, M. A.; Stone, F. G. A. J. Organomet. Chem.
1988, 355, 231. (d) Wadepohl, H.; Arnold, U.; Pritzkow, H.; Calhorda,
M. J.; Veiros, L. F. J. Organomet. Chem. 1999, 587, 233.
(36) Mullen, G. E. D.; Fassler, T. F.; Went, M. J.; Howland, K.; Stein,
B.; Blower, P. J. J. Chem. Soc., Dalton Trans. 1999, 3759.
(37) For a recent comprehensive review of dithiocarbamate coordination
chemistry see: Hogarth, G. Prog. Inorg. Chem. 2005, 53, 71.
(38) Hector, A. L.; Hill, A. F. J. Organomet. Chem. 1993, 447, C7.

Thiocarbonyl/σ-Organyl Coupling Reactions
Organometallics, Vol. 27, No. 21, 2008 5553
Table 2. Migrated and Nonmigrated [9]aneS3 (*not observed)
Scheme 6. Reactions of Vinyl-thiocarbonyl Complexes with
π-Basic Chelates (L ) PPh3): (i) Na[S2CNMe2]; (ii) Cy3PCS2,
[NH4]PF6
Scheme 7. Reaction Pathway for Migratory Insertion (L )
in THF of 1f does not yield 3f. By modeling 2, 2TS (the
transition state between 1 and 2) and 3, several questions may
be answered: Can formation of 3a,b occur stepwise through
1a,b at room temperature? Why does 1c need heat to react?
Why does 1f not react further on heating, and why do 1d,e not
proceed to 3d,e at room temperature and will heat induce
reaction?
PPh3, for R see Tables 1 and 2)
The Gibbs’ free energy of 1TS relative to 1 can be interpreted
as the reaction barrier (Figure 1). 1TSa,b are only +62.52 and
+60.64 kJ/mol relative to their respective reactants, and reaction
is expected to occur easily. 1TSc-e give reasonable reaction
barriers (95.17, 84.12, and 101.24 kJ/mol) for a heated reaction.
(Note: alternative structures for 1TSd with the alkynyl moiety
syn to the phosphine are precluded by the cone angle of PPh3,
and another alternative with the phenyl rings in-plane with each
other results in a higher barrier). Systems a-e are exergonic,
and equilibrium favors formation of product if the reaction
barrier is surmountable. 1TSa-e structures (Figure 2) match
well with previously reported transition states for CO insertion
Table 1. Experimental Reactivity of an Array of Ligands Towards
Migratory Insertion with Coordinated CS
R
reactive conditions
a
b
c
d
e
f
CHdCHPh
CPhdCHPh
Ph
C(Ct CPh)dCHPh
C(CO2Me)dCHCO2Me
SiMe2OEt
rt
rt
reflux in THF (339 K), 4 h
unreactive at rt; reflux untried
unreactive at rt; reflux untried
unreactive upon reflux in THF
Thus, neither dithiocarbamate nor phosphonio dithiocarboxylate
ligands induce migratory insertive coupling of vinyl and
thiocarbonyl ligands, consistent with the above arguments that
π-donor ligands disfavor such processes.
Computational Studies. The variation in propensity of the
migratory insertion reactions for vinyl, aryl, and silyl ligands
with coordinated CS described above and summarized in Table
1 calls for more insight, which we expected might follow from
computational studies. The key points of interest along the
reaction coordinate (Scheme 7) are the 16-electron precursors
(Pa-f), which with [9]aneS3 convert to the pseudo-octahedral
cationic “half-sandwich” complexes 1 (isolable for R ) Ph,
C(Ct CPh)dCHPh, C(CO2Me)dCHCO2Me, SiMe2OEt), which
in some but not all cases either spontaneously (R ) CHdCHPh,
CPhdCHPh) or with heating (R ) Ph) evolve to the thioacyls
3 presumably via a three-center-two-electron bonded reactive
intermediate 2. Thus at room temperature, [9]aneS3 displaces
chloride and a phosphine from precursors [Ru(R)Cl(CS)(PPh3)2]
(Pa-f) to yield 3a,b and 1c-f. Upon reflux in THF (bp ) 66
°C), 1c presumably rearranges via 2c to 3c. Heating under reflux
Figure 1. Relative reaction profiles for systems a-e. Intermediates
2a-e are not shown for clarity, and ensuing transition states toward
3a-e, while not found, are not expected to affect the overall reaction
barrier.

5554 Organometallics, Vol. 27, No. 21, 2008
Green et al.
Table 3. Substituent Effects on Ligand Binding Energy of Reactant
and Relative SCF Energy of Transition State and Product
R
LBE1 (kJ mol-1
)
∆E1TS (kJ mol-1
)
∆E3 (kJ mol-1
)
g
h
i
c
j
k
m
p-NH2C6H4
p-OHC6H4
p-CH3C6H4
Ph
p-FC6H4
p-CHOC6H4
p-NO2C6H4
-385.53
-376.77
-374.78
-371.51
-372.87
-366.91
-366.75
69.27
79.14
92.25
93.58
95.26
97.64
102.96
-87.19
-72.51
-62.14
-55.33
-59.14
-47.76
-41.24
Scheme 8. Ligand Binding Energy (fragment charges are
consistent with homolytic cleavage of the Ru-R bond)
Table 4. Frontier Symmetry-Adapted Fragment Orbital Gross
Populationsa
ligand ligand ligand ligand metal metal metal metal
HO-2 HO-1 HOFO LUFO HO-1 HOFO LUFO LU+1
1g
1TSg
3g
1h
1TSh
3h
1i
1TSi
3i
1c
1TSc
3c
1j
1TSj
3j
1k
1TSk
3k
1.99
1.99
2.00
1.99
1.99
2.00
1.99
1.99
2.00
1.99
1.99
2.00
1.99
1.99
2.00
1.97
1.85
1.82
1.99
1.20
1.78
1.68
1.96
1.82
1.74
1.96
1.81
1.76
1.97
1.84
1.78
1.97
1.82
1.77
2.00
2.00
2.00
2.00
2.00
2.00
1.96
1.76
1.70
1.94
1.73
1.67
1.97
1.79
1.78
1.96
1.93
1.91
1.94
1.22
0.90
1.20
1.21
0.92
1.20
1.16
0.93
1.21
1.18
0.93
1.22
1.17
0.92
1.23
1.17
0.93
1.24
1.18
0.93
1.19
1.21
0.94
1.30
1.34
1.05
1.31
1.30
1.05
1.41
1.33
1.12
0.00
0.01
0.00
0.01
0.01
0.00
0.01
0.02
0.01
0.01
0.01
0.00
0.01
0.01
0.00
0.03
0.05
0.03
0.02
0.04
0.02
0.03
0.07
0.05
0.03
0.07
0.06
0.02
0.05
0.03
0.05
0.09
0.06
1.96
1.99
1.98
1.96
2.00
1.98
1.96
1.97
1.98
1.96
1.99
1.98
1.96
1.98
1.98
1.96
1.99
1.98
1.96
1.99
1.98
1.95
1.99
1.98
1.97
1.99
1.97
1.96
1.99
1.97
1.94
1.99
1.97
0.80
0.98
1.38
0.79
0.99
1.37
0.79
1.10
1.38
0.78
1.05
1.37
0.77
1.08
1.37
0.76
1.07
1.36
0.74
1.05
1.35
0.80
0.95
1.37
0.77
0.97
1.36
0.74
0.94
1.35
0.67
0.98
1.31
0.02
0.05
0.31
0.01
0.05
0.26
0.01
0.04
0.23
0.01
0.04
0.21
0.01
0.04
0.23
0.01
0.05
0.19
0.01
0.04
0.17
0.01
0.09
0.29
0.01
0.02
0.29
0.01
0.07
0.28
0.00
0.07
0.13
0.01
0.07
0.02
0.01
0.07
0.02
0.01
0.08
0.02
0.01
0.06
0.02
0.01
0.07
0.01
0.01
0.06
0.02
0.01
0.05
0.02
0.01
0.07
0.01
0.01
0.14
0.02
0.01
0.09
0.01
0.01
0.06
0.04
Figure 2. Transition states 1TSa-e and the ground-state geometry
for [Ru(CHdCH2)(CO)(PPh3)([9]aneS3)]+ (11, taken from ref 4a.
Hydrogens have been omitted for clarity.
into Co-vinyl bonds; the π-system of the group R is aligned
with the newly forming C-C bond.39
The overall reaction 1f to 3f is endergonic (∆G ) +32.98
kJmol-1). This difference from the other systems can be
rationalized as being due to the weakness of the Si-C bond
and the lack of π-conjugation in the product. Even if the reaction
barrier were very low (unlikely, given the presumed five-
coordinate nature of silicon at 1TSf), thermodynamics would
prohibit a significant yield of 3f. Thus, no attempt was made to
find 1TSf or 2f.
1m
1TSm 1.86
3m
1a
1TSa
3a
1b
1TSb
3b
1d
1TSd
3d
1e
1.82
2.00
2.00
2.00
2.00
2.00
2.00
2.00
2.00
1.99
1.94
1.94
1.90
Previous carbonylation studies have observed that electron-
withdrawing (EW) substituents on the migrating ligand inhibit
reaction or that electron-donating (ED) ones promote it.8-11
Such trends are difficult to observe in a-e because of the widely
varying steric profiles of the ligands. To determine the electronic
effect of substituents on thiocarbonyl insertion, a series of
hypothetical systems g-k and m, employing sterically consis-
tent, para-substituted phenyls, have been modeled and compared
1TSe
3e
with c (Table 3). Indeed, EW substituents do increase ∆E1TS
,
a HOFO and LUFO stand for “highest occupied fragment orbital” and
“lowest unoccupied fragment orbital”, respectively. Bold entries denote
the highest occupied π orbital of the ligand fragment.
inhibiting reaction. Does this effect stem from stabilization of
1 or from destabilization of 1TS? To find out, the structures
are partitioned into ligand and metal fragments. Single-point
calculations are run on the fragments of systems c and g-j. By
comparing the energies of the sum of the fragments versus the
energy of the whole system, ligand binding energies (LBEs)
may be determined (Scheme 8).
to bonding favors a negative charge on the R-carbon (next to
the positively charged metal), which EW substituents inhibit.
Further, gross populations of the symmetry-adapted fragment
orbitals (SFOs) reveal that π-back-bonding is minimal, presum-
ably due to the formal +1 charge of the ruthenium, the
competitively π-acidic thiocarbonyl ligand, and the low-
symmetry environment (Table 4). This result discounts the
possibility that EW-substituted ligands are inert due to a greater
M-R bond strength. Instead, the inhibitory effect of EW
substituents lies in 1TS. The difference in Hirshfeld charge44
between the metal fragment and the ligand decreases by
0.39-0.45 going from 1 to 1TS. Approximately 0.2 electron is
transferred from the ligand to the metal fragment (Table 5).
Surprisingly, it is found that EW substituents correlate with
weaker bonding in 1 (Table 3). The electrostatic contribution
(39) Luo, X. L.; Tang, D. Y.; Ming, L. J. Mol. Struct. 2006, 765, 21.
(40) Markies, B. A.; Wijkens, P.; Dedieu, A.; Boersma, J.; Spek, A. L.;
Van Koten, G. Organometallics 1995, 14, 5628–5641.
(41) Bassetti, M.; Sunley, G. J.; Fanizzi, F. P.; Maitlis, P. M. J. Chem.
Soc., Dalton Trans. 1990, 1799.
(42) Koga, N.; Morokuma, K. J. Am. Chem. Soc. 1986, 108, 6136.
(43) Sugita, N.; Minkiewicz, J. V.; Heck, R. F. Inorg. Chem. 1978, 17,
2809.

Thiocarbonyl/σ-Organyl Coupling Reactions
Organometallics, Vol. 27, No. 21, 2008 5555
Table 5. Changes in Hirshfeld Charge Differences between Metal and Ligand Fragments from 1 to 1TS and 1 to 3
system
g
h
i
c
j
k
m
a
b
d
e
∆∆Hirshfeld charge1TS
∆∆Hirshfeld charge3
-0.39
-0.88
-0.40
-0.80
-0.45
-0.75
-0.39
-0.72
-0.44
-0.76
-0.43
-0.72
-0.41
-0.71
-0.43
-0.80
-0.41
-0.69
-0.42
-0.88
-0.45
-0.81
According to the SFO populations (Table 4), charge transfer
occurs primarily from the highest occupied π orbital (HOPO)
of the ligand to the metal fragment’s singly occupied fragment
orbital (SOFO). This occurs less readily with EW substituents
and more easily with ED substituents. As the energy of the
SOFO of the metal fragment does not vary much between
systems, the energy of the ligand HOPO inversely correlates
with reaction barrier (Figure 3).
In 3, SFO population analysis shows significant π-donation
from the aryl substituent to the CS unit, evidenced by the partial
population of the thioacyl fragment orbitals. Also, the ligand
SOMO, previously forming a polar Ru-R σ-bond, loses electron
density in forming a more covalent SC-R σ-bond. This explains
why reaction with ED-substituted ligands is more exothermic
than with EW-substituted ligands (and allows j, containing a
π-donating, σ-withdrawing fluoride substituent, to be slightly
more exothermic than c). Conversely, the reverse migration
reaction faces a smaller barrier with EW-substituted ligands.
This agrees with previously reported electronic substituent
effects in decarbonylation reactions.45 An elegant demonstration
of this was provided by Roper and Wright46and involves the
σ-aryl complexes shown in Scheme 9. In solution, the 4-tolyl
derivative is in equilibrium with the corresponding benzoyl
isomer, though the former is favored; The 4-nitrophenyl complex
exists entirely in the σ-aryl-dicarbonyl form, while reduction
to the 4-amino derivative results in exclusive formation of the
benzoyl isomer. However protonation of the amino groups,
which removes its π-donor capacity, results in migration of the
aryl ligand back to ruthenium. It was previously inferred that
the electron-donating nature of the 4-amino substituent weak-
ened the Ru-C bond of the σ-aryl isomer, thereby favoring
migratory insertion. The above results however would suggest
that it is stabilization of the electrophilic benzoyl carbon that is
the more determining factor.
The inverse correlation between HOPO energy and reaction
barrier does not cleanly apply to the substituted vinyl systems
a,b,d,e due to varying steric effects and (in b,d,e) the presence
of multiple high-lying π orbitals. However, because steric forces
vary less among 3a,b,d,e than in 1TSa,b,d,e, the net thermo-
dynamic driving force can still be rationalized as the result of
the electron-donating ability of the ligands. Again, SFO popula-
tion analysis finds that most of the electron donation occurs
from the HOPO and SOFO of the ligand fragments. 3b has the
highest ligand SOFO and is the most thermodynamically
favorable product. 3a, due to the low steric profile of the ligand,
is able to form a shorter SC-R bond to compensate for its
relatively low-lying HOPO and SOFO. 3d is correctly more
favorable than 3e, which has the lowest-lying HOPO and SOFO
of all (Figure 4).
Concluding Remarks
It could be argued that the results described herein do not
necessarily translate in toto to the more general manifold of
migratory insertion. Nevertheless, we have tried both experi-
mentally and computationally to separate the variables that are
contributing factors, and some of these inferences will be more
generally applicable. First, the computational studies indicate
that while the π-basicity of the migrating group may in some
part contribute to a destabilization of the ground-state precursor
through a compromise in the covalent versus ionic character of
Scheme 9. Effect of p-Substituents upon Migratory Insertion
of σ-Aryl Ligands (L ) PPh3)46
Figure 3. Energy of highest occupied π orbitals of ligand fragments
plotted against relative SCF energy of their respective transition
states 1TS(c,g-k,m).
Figure 4. Highest occupied π orbitals and singly occupied orbitals
of substituted vinyl ligand fragments of 3a,b,d,e.

5556 Organometallics, Vol. 27, No. 21, 2008
Green et al.
mg, 0.277 mmol) were dissolved in dichloromethane (40 mL). This
solution was then treated with NH4PF6 (110 mg, 0.675 mmol) in a
mixture of water (20 mL) and ethanol (40 mL) and the mixture
stirred overnight. Ethanol (40 mL) was added and the volume
reduced until crystallization was complete. The resulting yellow
crystals were washed with petroleum ether (20 mL) and dried under
vacuum. The spectroscopically pure crude product can be recrystal-
lized from dichloromethane and ethanol. Yield: 180 mg (87%). IR
(CH2Cl2): 1710 νCdO, 1567 νCdO or νCdC cm-1. IR (Nujol): 1722,
1713 νCdO, 1567 νCdO, 1331, 1290 νCS, 1204, 1155, 947, 907, 855,
the metal-carbon bond, it is the mesomeric stabilization of the
resulting thioacyl (“metallathiirene”) product that appears to
dominate the energetics. This interpretation is of course biased
by the cationic nature of both precursors and products, and
perhaps by the possible π-acid role of the [9]aneS3 ligand, to
which we have previously alluded. For this reason the reactions
of suitable precursors with π-basic sulfur chelates were inves-
tigated, including one example that generates a cationic product
that does not enter into migratory insertion (Cy3PCS2).
In the present system, vinyl ligands appear more prone to
migratory insertion than simple aryls (or silyls), and this result
is consistent with the general observations of Maitlis.47 We have
previously shown that vinyl ligands are capable of irreversibly
migrating onto a transient methylene ligand48 following Roper’s
illustration that aryl groups in analogous complexes preferen-
tially, albeit reversibly, migrate to an adjacent carbonyl.49 Within
the series of vinyl compounds investigated herein it however
becomes apparent that the presence of an electron-withdrawing
substituent (CO2Me or Ct CPh) on the R-carbon of the vinyl
group disfavors migration, presumably by enhancing the
metal-vinyl bond strength, but also by reducing the mesomeric
stabilization of the resulting metallathiirene.
1
852, 833, 820 cm-1. NMR H: δ 2.09, 2.27, 2.83, 3.10 - 3.35,
3.36 (m × 5, 12 H, CH2), 3.52, 3.79 (s × 2, 3 H × 2, OCH3), 5.28
(s, 1 H, CdCH), 7.30-7.85 (m, 15 H, C6H5). 31P{1H}: δ 37.2
ppm. FAB-MS m/z (% abundance): 731 (100) [M]+, 702 (3) [M
- C2H4]+, 469 (6) [M - PPh3]+, 441 (18) [M - C2H4 - PPh3]+,
407 (6) [M - C(CO2Me)dCHCO2Me - [9]aneS3]+. Microana-
lytical data were obtained for the corresponding and more crystalline
perchlorate salt (1 · ClO4) · 2CH2Cl2 prepared in an identical manner
(LiClO4 in place of NH4PF6). Spectroscopic data associated with
the cation are however identical to those for 1 · PF6. Anal. Found:
C, 43.6; H, 3.9. Calcd for C28H34ClO8PRuS4 · 2CH2Cl2: C, 43.3;
H, 4.0. Dichloromethane of solvation confirmed by 1H NMR
integration.
Preparation of [Ru{C(Ct CPh)dCHPh}(CS)(PPh3)([9]-
aneS3)]PF6 (2 · PF6). A solution of [Ru{C(Ct CPh)dCHPh}Cl(CS)-
(PPh3)2] (270 mg, 0.297 mmol) in dichloromethane (30 mL) and
ethanol (10 mL) was treated with [9]aneS3 (60 mg, 0.333 mmol)
and a solution of KPF6 (110 mg, 0.598 mmol) in water (1 mL) and
ethanol (10 mL) and then stirred for 30 h. All solvent was then
removed and the crude product dissolved in dichloromethane and
filtered through diatomaceous earth to remove KCl. Ethanol was
then added, and crystals were obtained by slow rotary evaporation.
The off-white product was filtered off, washed with ethanol (10
mL) and petroleum ether (10 mL), and dried under vacuum. Yield:
230 mg (83%). IR (Nujol): 2157 νCC, 1977, 1715, 1593, 1581, 1572,
1294 νCS, 904, 840 (PF6) cm-1. NMR 1H: δ 1.90-2.10, 2.30-2.50,
2.80-3.45 (m × 3, 12 H, CH2), 6.88 (s br, 1 H, CdCH), 7.10-7.65
Experimental Section
General Procedures. All operations were carried out under
aerobic conditions. All solvents were used as received. Multinuclear
NMR spectra were recorded in CDCl3 (unless otherwise stated) at
25 °C on a Jeol JNM EX270 NMR spectrometer. Infrared spectra
were recorded as both dichloromethane solutions and Nujol mulls
using Perkin-Elmer 1720-X or Mattson Series 1 FT-IR spectrom-
eters. Characteristic “fingerprint” bands for PPh3 are omitted. FAB-
mass spectrometry was carried out using an Autospec Q instrument
with 3-nitrobenzyl alcohol (nba) as a matrix. The elimination of
ethylene was a recurrent feature in the mass spectra, as has been
noted previously for complexes of [9]aneS3.36 Quoted yields take
into account dichloromethane, which was in the majority of cases
found (1H NMR) to form solvates with salts. Elemental analysis
was carried out by the Imperial College Microanalytical Service
and SACS at London Metropolitan University. In the case of
analytical data for partial solvates, the stoichiometry was confirmed,
where possible, by 1H NMR integration. The compounds
(m, 25 H, PC6H5 + CC6H5) ppm. 13C{1H}: δ 297.2 (d, CS, 2JCP
)
19.7 Hz), 145.7 (s, RuC), 139.6 (s, CPh), 133.9 [d, C2,6(PC6H5),
1
2JCP ) 8.9 Hz], 131.0 [C4(PC6H5)], 130.9 [d, C1(PC6H5), JCP
)
45.3 Hz], 130.9 (s, CPh), 128.6 [d, C3,5(PC6H5) JCP obscured],
128.4, 127.8, 127.5 [s × 3, C2,3,5,6(CC6H5)], 127.7 (s, CHPh), 126.3
[C1(CHC6H5)], 124.4 [s, C4(C6H5)], 101.5, 98.6 (Ct C), 37.2, 35.2,
34.1, 30.4 (s × 4, SCH2), 34.3 (s br, SCH2, S trans to P), 33.8 (d,
[Ru(C6H5)Cl(CS)(PPh3)2],29
[Ru(SiMe2OEt)Cl(CS)(PPh3)2],22
[Ru(CRdCHPh)Cl(CS)(PPh3)2] (R ) H, Ph, Ct CPh), [Ru(CHd
SCH2, S trans to P, JCP ) 5.3 Hz) ppm. 31P{1H}: δ 37.0 ppm.
3
CH2)Cl(CS)(PPh3)2],
[Ru{κ2-C(CO2Me)dCHCO2Me)Cl(CS)-
FAB-MS m/z (% abundance): 791 (100) [M]+, 763 (14) [M -
C2H4]+, 587 (5) [M - vinyl]+, 560 (12) [M - C2H4 - vinyl]+,
501 (6) [M - C2H4 - PPh3]+. Anal. Found: C, 49.8; H, 3.9. Calcd
for C41H38F6P2RuS4 · CH2Cl2: C, 49.4; H, 4.0 (dichloromethane of
(PPh3)2],28 and [Os(CHdCHC6H4Me-4)Cl(CS)(BTD)(PPh3)2]32b
were prepared as described elsewhere. All other reagents were used
as received from commercial sources. NB: CAUTION although
no problems were encountered, perchlorate salts should be treated
with care due to the risk of spontaneous detonation.
1
solvation confirmed by H NMR integration).
Preparation of [Ru(η2-SCCHdCHPh)(PPh3)([9]aneS3)]ClO4
(3 · ClO4). [Ru(CHdCHPh)Cl(CS)(PPh3)2] (200 mg, 0.247 mmol)
and [9]aneS3 (50 mg, 0.277 mmol) were dissolved in dichlo-
romethane (15 mL), and a solution of LiClO4 (200 mg, 1.880 mmol)
in water (1 mL) and ethanol (15 mL) was then added. The solution
was stirred for 1 h, after which a purple precipitate that had formed
was filtered off and washed with ethanol (10 mL) and petroleum
ether (10 mL) and dried. Yield: 150 mg (77%). IR (Nujol): 1585,
1565, 1330, 1310, 1279, 1241, 1196, 1089 (ClO4), 969, 929, 918,
905, 823, 816, 803 cm-1. NMR 1H: δ 1.01, 1.43, 2.21, 2.57, 2.84,
3.10 (m × 6, 12 H, SCH2), 7.27-7.55 (m, 22 H, PC6H5 + CHdCH
+ C6H5) ppm. 31P{1H}: δ 37.3 ppm. FAB-MS m/z (% abundance):
691 (86) [M]+, 663 (60) [M - C2H4]+, 516 (8) [M - C2H4 -
SCCHdCHPh]+, 428 (6) [M - PPh3]+, 401 (23) [M - C2H4 -
PPh3]+. Anal. Found: C, 48.5; H, 4.1. Calcd for C33H34-
ClO4PRuS4 · 0.5CH2Cl2: C, 48.3; H, 4.2.
Preparation of [Ru{C(CO2Me)dCHCO2Me}(CS)(PPh3)-
([9]aneS3)]PF6 (1 · PF6). [Ru{κ2-C(CO2Me)dCHCO2Me}Cl(CS)-
(PPh3)2] (200 mg, 0.236 mmol) and 1,4,7-trithiacyclononane (50
(44) Hirshfeld, F. L. Theor. Chim. Acta 1977, 44, 129.
(45) Stille, J. K.; Regan, M. T. J. Am. Chem. Soc. 1974, 96, 1508.
(46) (a) Clark, G. R.; Roper, W. R.; Wright, L. J.; Yap, V. P. D.
Organometallics 1997, 16, 5135. (b) Roper, W. R.; Wright, L. J. J.
Organomet. Chem. 1977, 142, C1. (c) Roper, W. R.; Taylor, G. E.; Waters,
J. M.; Wright, L. J. J. Organomet. Chem. 1979, 182, C46.
(47) (a) Maitlis, P. M.; Long, H. C.; Quyoum, R.; Turner, M. L.; Wang,
Z.-Q. Chem. Commun. 1996, 1. (b) Martinez, J. M.; Adams, H.; Bailey,
N. A.; Maitlis, P. M. Chem. Commun. 1989, 286.
(48) Hill, A. F.; Ho, C. T.; Wilton-Ely, J. D. E. T. Chem. Commun.
1997, 2207.
(49) (a) Bohle, D. S.; Clark, G. R.; Rickard, C. E. F.; Roper, W. R.;
Shepard, W. E. B.; Wright, L. J. Chem. Commun. 1987, 563. (b) Bohle,
D. S.; Clark, G. R.; Rickard, C. E. F.; Roper, W. R.; Wright, L. J. J.
Organomet. Chem. 1989, 358, 411.

Thiocarbonyl/σ-Organyl Coupling Reactions
Organometallics, Vol. 27, No. 21, 2008 5557
Preparation of [Ru(η2-SCCPhdCHPh)(PPh3)([9]aneS3)]ClO4
(4 · ClO4). [Ru(CPhdCHPh)Cl(CS)(PPh3)2] (200 mg, 0.226 mmol)
and 1,4,7-trithiacyclononane (100 mg, 0.554 mmol) were dissolved
in dichloromethane (40 mL) and stirred until all solid had dissolved
(ca. 30 min). NaClO4 (60 mg, 0.490 mmol) dissolved in a mixture
of water (20 mL) and ethanol (40 mL) was added and the solution
stirred for a further 60 min, during which time a purple coloration
appeared. After addition of petroleum ether (30 mL) and subsequent
partial reduction in solvent volume, purple crystals were obtained
and washed with petroleum ether (20 mL) and dried. Yield: 160
mg (82%). IR Nujol: 1581, 1557, 1313, 1258, 1203, 1203, 1143,
1090 (ClO4-), 998, 934, 905, 845 cm-1. NMR (CDCl3) 1H: δ 0.87,
1.44, 1.83, 2.21, 2.29, 2.51, 2.77, 3.08 (m × 8, 12 H, CH2), 5.32
(s, 1 H, CdCH), 6.67 [d, C2,6(C6H5)], 7.10-7.45 (m, 15 H + 8 H,
PC6H5 + CC6H5) ppm. 13C{1H}: δ 312.8 (d, 2JPC ) 9.7 Hz), 149.8,
146.5, 139.1, 135.0, 131.5, 130.8, 129.0, 128.7, 128.6, 128.0
(CPhdCHPh), 134.0 [d, 1JPC ) 9.7 Hz, C2,6(PC6H5)] 130.6 [d, 1JPC
The red crystals were washed with ethanol (1 mL) and hexane (10
mL) and dried. Yield: 150 mg (72%). IR (Nujol): 1709, 1567
(C6H5), 1293 νCS, 1015, 1000, 936, 904, 840 (PF6) cm-1. NMR
(CD2Cl2) 1H: δ 1.49, 2.03, 2.19, 2.36, 2.48, 2.67, 2.92, 3.13, 3.27,
3.38 (m × 10, 12 H, SCH2), 6.82 [s br, H2,6(RuC6H5)], 7.20-7.50
[m, 18 H, PC6H5 and H3-5(RuC6H5)] ppm. 31P{1H} (CH2Cl2/
CDCl3, 3:1): δ 39.4 ppm. FAB-MS m/z (% abundance): 665 (100)
[M]+, 637 (50) [M - C2H4]+, 516 (6) [M - C2H4 - C6H5 - CS]+,
484 (2) [M - [9]aneS3]+, 375 (43) [M - C2H4 - PPh3]+, 347
(10) [M - 2C2H4 - PPh3]+, 319 (14) [M - 3C2H4 - PPh3]+, 279
(34) [Ru[9]aneS3]+. Anal. Found: C, 45.7; H, 3.7. Calcd for
C31H32F6P2RuS4: C, 46.0; H, 4.0.
Preparation of [Ru(SiMe2OEt)(CS)(PPh3)([9]aneS3)]PF6
(7 · PF6). [Ru(SiMe2OEt)(CS)Cl(PPh3)2] (200 mg, 0.247 mmol) and
[9]aneS3 (50 mg, 0.277 mmol) were dissolved in a mixture of
dichloromethane (25 mL) and ethanol (10 mL). KPF6 (100 mg,
0.543 mmol) was added as an ethanolic solution (1 mL). The red
reaction mixture was stirred for 20 h and all solvent removed from
the colorless solution. The crude product was dissolved in dichlo-
romethane (10 mL) and filtered through diatomaceous earth. All
solvent was again removed and the product precipitated by
ultrasonic trituration in diethyl ether (10 mL). The colorless powder
was washed with diethyl ether (10 mL) and hexane (10 mL) and
dried. Yield: 171 mg (83%). IR (Nujol): 1709, 1408, 1275 νCS (1269
1
) 42.1 Hz, C1(PC6H5)], 130.3 [C4(PC6H5)], 128.4 [d, JPC ) 9.7,
3
C3,5(PC6H5)], 38.23 (d, JPC ) 5.4 Hz, SCH2 trans to P), 36.69
(SCH2), 36.21 (d, 3JPC ) 7.5 Hz), 34.12, 32.36, 28.85 (SCH2) ppm.
31P{1H}: δ 37.2 ppm. FAB-MS m/z (% abundance): 767 (100)
[M]+, 739 (85) [M - C2H4]+, 587 (3) [M - CPhdCHPh]+, 516
(13) [M - C2H4 - SCCPhdCHPh]+, 477 (30) [M - C2H4 -
PPh3]+, 324 (12) [M - [9]aneS3 - PPh3]+. Satisfactory microana-
lytical data were not obtained for the perchlorate salt; however
metathesis of the counteranion with NaBPh4 provided the tetraphe-
nylborate salt, which analyzed adequately. Anal. Found: C, 64.5;
H, 5.0. Calcd for C63H58BPRuS4 · 1.25CH2Cl2: C, 64.7; H, 5.1.
1
for 7 · BPh4) 1243, 1064, 930, 840 (PF6) cm-1. NMR H: δ 0.02,
0.40 (s × 2, 2 × 3 H, C(CH3)2), 1.11 (t, 3 H, CH2CH3, JHH ) 6.93
Hz), 2.11, 2.32, 2.54, 2.63, 2.78, 3.01, 3.19-3.43 (m × 7, 12 H,
SCH2), 3.48 (q, 2 H, OCH2, JHH ) 7.04 Hz), 7.4-7.6 (m, 15 H,
PC6H5) ppm. 31P{1H}: δ 36.2 ppm. FAB-MS m/z (% abundance):
691 (100) [M]+, 663 (8) [M - C2H4]+, 588 (3) [M - SiMe2OEt]+,
560 (5) [M - C2H4 - SiMe2OEt]+, 428 (3) [M - PPh3]+, 401 (7)
[M - C2H4 - PPh3]+. Anal. Found: C, 41.7; H, 4.7. Calcd for
C29H38F6OP2RuS4Si: C, 41.7; H, 4.6.
Preparation of [Ru(η2-SCC6H5)(PPh3)([9]aneS3)]PF6 (8 · PF6).
[Ru(C6H5)(CS)(PPh3)([9]aneS3)]PF6 (60 mg, 0.074 mmol) was
dissolved in tetrahydrofuran (10 mL) and stirred at reflux for 4 h.
All solvent was evaporated and the crude product triturated
ultrasonically in hexane (20 mL). The dark red-brown product was
filtered, washed with hexane (20 mL), and dried. Yield: 52 mg
1
Dichloromethane solvate confirmed by H NMR integration. The
corresponding salt [Ru(η2-SCCRdCHR)(PPh3)([9]aneS3)]Cl (R )
C6H4Me-4) was similarly prepared from [Ru(CRdCHR)Cl-
(CS)(PPh3)2] by omitting the halide exchange step. Yield: 86%.
IR (Nujol): 1602, 1573, 1503, 1317, 12611180, 1090, 1026. 938,
908, 838, 814 cm-1. NMR 1H: δ 0.88, 1.44, 2.24, 2.73, 3.02, 3.26,
3.47 (m × 7, 12 H, CH2), 2.27, 2.31 (s × 2, 3 H × 2, CH3), 6.51,
7.04 (d × 2, 8 H, C6H4, 3JHH ) 8.2 Hz), 7.31, 7.53 (m × 2, 15 H,
C6H5), 7.71 (s, 1 H, dCHR) ppm. 31P{1H}: δ 38.0 ppm. Anal.
Found: C, 52.4; H, 4.7. Calcd for C41H41F6P2RuS4: C, 52.4; H, 4.4.
Preparation of [Os(CHdCHC6H4Me-4)(CS)(PPh3)([9]aneS3)]PF6
(5 · PF6). [Os(CHdCHC6H4Me-4)Cl(CS)(BTD)(PPh3)2] (130 mg,
0.124 mmol) and 1,4,7-trithiacyclononane (30 mg, 0.166 mmol)
were dissolved in dichloromethane (10 mL), and an ethanolic
solution (5 mL) of NH4PF6 (40 mg, 0.245 mmol) was added. The
reaction was stirred at reflux for 1 h and all solvent evaporated.
Diethyl ether (15 mL) was added and a cream solid obtained by
ultrasonic trituration. This was filtered, washed with diethyl ether
(20 mL) and hexane (20 mL), and dried. Yield: 80 mg (69%). IR
(87%). IR (Nujol): 1585, 1301, 1170, 977, 934, 905, 838 νPF cm-1
.
NMR 1H: δ 1.10, 1.33, 1.62, 2.03, 2.26, 2.45, 2.63, 2.92, 3.18 (m
× 9, 12 H, SCH2), 6.81, 6.97 (m × 2, 2 H, CC6H5), 7.20-7.70
(m, 18 H, C6H5) ppm. 31P{1H}: δ 35.9 ppm. FAB-MS m/z (%
abundance): 665 (29) [M]+, 637 (24) [M - C2H4]+, 375 (13) [M
- C2H4 - PPh3]+, 263 (10) [PPh3]+. Anal. Found: C, 45.9; H,
3.9. Calcd for C31H32F6P2RuS4: C, 46.0; H, 4.0.
(Nujol): 2135, 1977, 1622, 1588, 1298 νCS, 974, 937, 836 νPF cm-1
.
Preparation of [Ru(CHdCHPh)(K2-S2CNMe2)(CS)(PPh3)2]
(9). A solution of [Ru(CHdCHPh)Cl(CS)(PPh3)2] (160 mg, 0.198
mmol) in dichloromethane (20 mL) was treated with a solution of
sodium dimethyldithiocarbamate (500 mg, 3.491 mmol) in water
(2 mL) and ethanol (10 mL), prompting an immediate color change
(red solution to a yellow one). The solution was stirred for 2 min,
after which ethanol (40 mL) was added to precipitate yellow crystals
from the green solution. These were filtered and washed with
ethanol (10 mL) and petroleum ether (10 mL). Yield: 139 mg
(79%). Stability: Good as solid but less than 1 h in solution. IR
(Nujol): 1914, 1597, 1585, 1575, 1545, 1512, 1504, 1480, 1432,
NMR 1H: δ 1.26, 2.10, 2.38, 2.79, 2.87, 3.19 (m × 6, 12 H, SCH2),
2.28 (s, 3 H, CH3), 6.59 (d, 1 H, dCH, JHH ) 16.8 Hz), 6.84, 7.00
(d × 2, 4 H, C6H4, 3JAB ) 7.92 Hz), 7.16-7.66 (m, 15 H, PC6H5),
7.98 (dd, 1 H, OsCH, JHH ) 16.95 Hz, JHP ) 4.83 Hz) ppm.
31P{1H}: δ 7.4 ppm. FAB-MS m/z (% abundance): 795 (32) [M]+,
767 (4) [M - C2H4]+, 579 (2) [M - CS - vinyl - 2C2H4]+, 503
(2) [M - C2H4 - PPh3]+. Anal. Found: C, 43.7; H, 4.0. Calcd for
C34H36F6OsP2S4: C, 43.5; H, 3.9.
Preparation of [Ru(C6H5)(CS)(PPh3)([9]aneS3)]PF6 (6 · PF6).
[Ru(C6H5)(CS)Cl(PPh3)2] (200 mg, 0.256 mmol) and 1,4,7-trithia-
cyclononane (50 mg, 0.277 mmol) were dissolved in a mixture of
dichloromethane (25 mL) and ethanol (10 mL). KPF6 (100 mg,
0.543 mmol) was added as an ethanolic solution (1 mL). The
reaction mixture was stirred for 15 h at room temperature, after
which all solvent was removed from the red solution. The crude
product was dissolved in dichloromethane (10 mL) and filtered
through diatomaceous earth to remove precipitated KCl. Ethanol
(10 mL) was then added and the solvent volume reduced (rotary
evaporator) until precipitation of the red product was complete.
1
1384, 1281, 1251 νCS, 1141, 1053, 966, 798 cm-1. NMR H: δ
2.36, 2.73 (s × 2, 6 H, CH3), 5.51 (d, 1 H, CHPh, JHH ) 16.7 Hz),
6.61 [d, 2 H, H2,6(C6H5), JHH ) 7.6 Hz], 6.89 [t, 1 H, H4(C6H5),
JHH ) 7.3 Hz], 7.04 [t, 2 H, H3,5(C6H5), JHH ) 7.3 Hz], 7.29-7.67
(m, 30 H, PC6H5), 8.00 (dt, 1 H, RuCH, JHH ) 17.2, JHP ) 2.3 Hz)
ppm. 31P{1H}: δ 36.5 ppm. FAB-MS m/z (% abundance): 894 (13)
[M]+, 789 (22) [M - vinyl]+, 773 (26) [M - S2CNMe2]+. Anal.
Found: C, 61.2; H, 5.0; N, 1.5. Calcd for C48H43NP2-
RuS3 · 0.75CH2Cl2: C, 61.2; H, 4.7; N, 1.5.

5558 Organometallics, Vol. 27, No. 21, 2008
Green et al.
Preparation of [Ru(CHdCH2)(K2-S2CPCy3)(CS)(PPh3)2]PF6
(10 · PF6). [Ru(CHdCH2)Cl(CS)(PPh3)2] (200 mg, 0.273 mmol)
was dissolved in dichloromethane (10 mL), and S2CPCy3 (107 mg,
0.300 mmol) was added, resulting in an immediate deep red color.
Ethanol (5 mL) was added along with NH4PF6 (90 mg, 0.552 mmol)
in water (1 mL) and ethanol (5 mL). The solution was stirred for
2 h and the solvent volume then reduced (rotary evaporator) until
precipitation of a purple solid was observed. This was filtered off
and washed with ethanol (10 mL) and petroleum ether (20 mL)
and dried. Yield: 242 mg (74%). IR (Nujol): 1716, 1586, 1551,
1267 νCS, 1237, 967, 919, 840 (PF6) cm-1. NMR 1H: δ 0.09-2.15
(m, 33 H, Cy), 4.36 (dt, 1 H, Hꢀ, JHRHꢀ ) 17.8, JHꢀ’Hꢀ ) 2.1 Hz),
5.39 (dt, 1 H, Hꢀ′, JHRHꢀ′ ) 10.4, JHꢀHꢀ′ ) 2.5 Hz), 7.32-7.55 (m,
30 H, PC6H5), 7.65 (ddd, 1 H, HR, JHRHꢀ ) 11.8, JHRP ) 6.7, JHRHꢀ′
) 1.5 Hz) ppm. 31P{1H}: δ 36.7, 31.8 ppm. FAB-MS m/z (%
abundance): 1053 (21) [M]+, 791 (72) [M - PPh3]+, 763 (4) [M
- vinyl - PPh3]+, 697 (3) [M - S2CPCy3]+, 433 (5) [M -
S2CPCy3 - PPh3]+. Anal. Found: C, 55.5; H, 5.9. Calcd for
C58H66F6P4RuS3 · CH2Cl2: C, 55.2; H, 5.3.
Computational Details. Models used PH3 in place of PPh3.
Because ligands must rotate 90° from 1 to 1TS so that the π-system
is aligned toward the CS, full phosphines would incur higher
reaction barriers, particularly for 1TSb,d, which bear dCHPh
moieties syn to the phosphine. In this respect, we have previously
identified C-H · · · π interactions between arylphosphine and vinyl
ligands.50 Calculations were performed using density functional
methods of the Amsterdam Density Functional (ADF v2006.01)51-54
with the generalized gradient approximation and the local density
approximation of Vosko, Wilk, and Nusair,55 with Becke8856 and
Perdew8657 electron exchange and correlation corrections. The basis
sets used were uncontracted triple-ꢁ Slater-type orbitals (STOs) with
polarization functions, labeled TZP in ADF. Scalar relativistic
effects were included with the ZORA formalism. The cores of atoms
were frozen: C, N, O, and F up to the 1s level, P and S up to the
2p level, and Ru up to the 3d level. Minima 1a-f and 3a-f have
been verified by full frequency calculations. Although some
possessed an imaginary eigenvector in the Hessian, these were
visually confirmed to correspond with very flat motions on the
potential energy surface; reoptimization at higher convergence
criteria could resolve these, but would not significantly lower any
energies. 1g-m and 3g-m were derived from 1c and 3c and
underwent full geometry optimization. Guess structures for 1TSa-e
were found by reoptimizing 1 while fixing the R-CS distance at
decreasing intervals; the maxima along these linear transits were
used in transition-state searches. Guess structures for 1TSg-m were
derived from 1TSc, and the substituents were optimized prior to
initiating transition-state searches. All transition states possessed
an imaginary frequency vibration corresponding with formation of
the R-CS bond. Some also possessed a second, lower-energy
imaginary frequency. Intermediates 2a-e were determined by
geometry optimization of the extremes of the corresponding
imaginary frequency vibrations of 1TSa-e, but all possessed their
own imaginary frequency vibration, suggesting a nearly barrierless
isomerization to 3. As such, transition states from 2 to 3 were not
found, and 1TS is assumed to determine the overall reaction barrier.
Acknowledgment. We thank the Oxford Supercomputing
Centre for the use of its Zuse cluster, the Indiana University
Wells Scholar Program for undergraduate summer funding
(S.L.), and Merton College (J.D.E.T.W.-E.).
Supporting Information Available: Full symmetry-adapted
fragment orbital gross populations and all Cartesian coordinate files
(.xyz) for the structures. This material is available free of charge
via the Internet at http://pubs.acs.org.
(50) Hill, A. F.; White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T.
Organometallics 1998, 17, 4249.
(51) te Velde, G.; Baerends, E. J. J. Comput. Phys. 1992, 99, 84.
(52) Fonseca Guerra, C.; Snijders, J. G.; Velde, G. T.; Baerends, E. J.
Theor. Chem. Acc. 1998, 99, 391.
(53) (a) te Velde, G.; Bickelhaupt, F. M.; Baerends, E. J.; Fonseca
Guerra, C.; Van Gisbergen, S. J. A.; Snijders, J. G.; Ziegler, T. J. Comput.
Chem. 2001, 22, 931.
OM800637Y
(55) Vosko, S. H.; Wilk, L.; Nusair, M. Can. J. Phys 1980, 58, 1200.
(56) Becke, A. D. Phys. ReV. A 1988, 38, 3098.
(57) Perdew, J. P. Phys. ReV. B 1986, 33, 8822.
(54) SCM, Version 2006 01; Theoretical Chemistry, Vrije Universiteit,
Amsterdam, 2000,