Multifunctional dithiocarbamates: Synthesis and ring-closing metathesis of diallyldithiocarbamate complexes

Article abstract of DOI:10.1021/om1002123

The complex cis-[RuCl₂(dppm)₂] reacts with the diallyldithiocarbamate KS₂CN(CH₂CH=CH₂) ₂ to form [Ru{S₂CN(CH₂CH=CH₂) ₂}(dppm)₂]⁺. The same ligand was also used to prepare the alkenyl complexes [RuR{S₂CN(CH₂CH=CH ₂)₂}(CO)(PPh₃)₂] (R = CH=CHBu ^t, CH=CHC₆H₄Me-4, C(C≡CBu ^t)=CHBu^t) from the corresponding precursors [RuRCl(CO)(BTD)(PPh₃)₂] (BTD = 2,1,3-benzothiadiazole) and [Ru(C(C≡CBu^t)=CHBu^t)Cl(CO)(PPh₃) ₂]. The complexes [Ni{S₂CN(CH₂CH=CH ₂)₂}(dppp)]⁺ (dppp =1,3-bis(diphenylphosphino) propane) and [M{S₂CN(CH₂CH=CH₂) ₂}(dppf)]⁺ (M = Ni, Pd, Pt; dppf = 1,1′- bis(diphenylphosphino)ferrocene) were prepared from the respective precursors [MCl₂(L₂)] (L₂ = dppp, dppf) and KS ₂CN(CH₂CH=CH₂)₂ in the presence of NH₄PF₆. In a similar manner, treatment of the cyclometalated dimer [Pd(C,N-CH₂C₆H₄NMe ₂)Cl]₂ with the dithiocarbamate ligand yielded [Pd(C,N-CH₂C₆H₄NMe₂){S ₂CN(CH₂CH=CH₂)₂}]. The homoleptic literature complexes [Ni{S₂CN(CH₂CH=CH₂) ₂}₂] and [Co{S₂CN(CH₂CH=CH ₂)₂}₃] were also prepared and characterized. Ring-closing metathesis catalyzed by [Ru(=CHPh)Cl₂(SIMes)(PCy ₃)] converted [Ni{S₂CN(CH₂CH=CH ₂)₂}₂], [Pd(C,N-CH₂C ₆H₄NMe₂){S₂CN(CH₂CH= CH₂)₂}], [Ni{S₂CN(CH₂CH=CH ₂)₂}(dppp)]⁺, [Pt{S₂CN(CH ₂CH=CH₂)₂}(dppf)]⁺, [Ru{S ₂CN(CH₂CH=CH₂)₂}(dppm) ₂]⁺, and [Ru(CH=CHC₆H₄Me-4){S ₂CN(CH₂CH=CH₂)₂}(CO)(PPh ₃)₂] into the corresponding 3-pyrroline dithiocarbamate compounds [Ni(S₂CNC₄H₆)₂], [Pd(C,N-CH₂C₆H₄NMe₂)(S ₂CNC₄H₆)], [Ni(S₂CNC ₄H₆)(dppp)]⁺, [Pt(S₂CNC ₄H₆)(dppf)]⁺, [Ru(S₂CNC ₄H₆)(dppm)₂]⁺, and [Ru(CH=CHC ₆H₄Me-4)(S₂CNC₄H₆)(CO) (PPh₃)₂], respectively. These complexes were also directly prepared from the reaction of the appropriate starting materials with preformed KS₂CNC₄H₆. The more sterically crowded complex [Co{S₂CN(CH₂CH=CH₂)₂}₃] failed to give a reaction with the metathesis catalyst, although it could be prepared directly from KS₂CNC₄H₆ and cobalt acetate. The compounds [Ru(CH=CHC₆H₄Me-4){S ₂CN(CH₂CH=CH₂)₂}(CO)(PPh ₃)₂], [Ni{S₂CN(CH₂CH=CH ₂)₂}(dppp)]PF₆, and [Ni(S₂CNC ₄H₆)(dppp)]PF₆ were characterized crystallographically.

Full text of DOI:10.1021/om1002123

Organometallics 2010, 29, 2547–2556 2547
DOI: 10.1021/om1002123
Multifunctional Dithiocarbamates: Synthesis and Ring-Closing
Metathesis of Diallyldithiocarbamate Complexes
Saira Naeem,† Andrew J. P. White,† Graeme Hogarth,‡ and James D. E. T. Wilton-Ely*,†
†Department of Chemistry, Imperial College London, South Kensington Campus,
London SW7 2AZ, U.K., and ‡Department of Chemistry, University College London,
20 Gordon Street, London WC1H 0AJ, U.K.
Received March 18, 2010
The complex cis-[RuCl2(dppm)2] reacts with the diallyldithiocarbamate KS2CN(CH2CHdCH2)2 to
form [Ru{S2CN(CH2CHdCH2)2}(dppm)2]þ. The same ligand was also used to prepare the alkenyl
complexes [RuR{S2CN(CH2CHdCH2)2}(CO)(PPh3)2] (R = CHdCHBut, CHdCHC6H4Me-4,
C(CtCBut)dCHBut) from the corresponding precursors [RuRCl(CO)(BTD)(PPh3)2] (BTD = 2,1,3-
benzothiadiazole) and [Ru(C(CtCBut)dCHBut)Cl(CO)(PPh3)2]. The complexes [Ni{S2CN(CH2-
CHdCH2)2}(dppp)]þ (dppp =1,3-bis(diphenylphosphino)propane) and [M{S2CN(CH2CHdCH2)2}-
(dppf)]þ (M = Ni, Pd, Pt; dppf = 1,10-bis(diphenylphosphino)ferrocene) were prepared from the
respective precursors [MCl2(L2)] (L2 = dppp, dppf) and KS2CN(CH2CHdCH2)2 in the presence of
NH4PF6. In a similar manner, treatment of the cyclometalated dimer [Pd(C,N-CH2C6H4NMe2)Cl]2 with
the dithiocarbamate ligand yielded [Pd(C,N-CH2C6H4NMe2){S2CN(CH2CHdCH2)2}]. The homolep-
tic literature complexes [Ni{S2CN(CH2CHdCH2)2}2] and [Co{S2CN(CH2CHdCH2)2}3] were also
prepared and characterized. Ring-closing metathesis catalyzed by [Ru(dCHPh)Cl2(SIMes)(PCy3)] con-
verted [Ni{S2CN(CH2CHdCH2)2}2], [Pd(C,N-CH2C6H4NMe2){S2CN(CH2CHdCH2)2}], [Ni{S2CN-
(CH2CHdCH2)2}(dppp)]þ, [Pt{S2CN(CH2CHdCH2)2}(dppf)]þ, [Ru{S2CN(CH2CHdCH2)2}-
(dppm)2]þ, and [Ru(CHdCHC6H4Me-4){S2CN(CH2CHdCH2)2}(CO)(PPh3)2] into the corresponding
3-pyrroline dithiocarbamate compounds [Ni(S2CNC4H6)2], [Pd(C,N-CH2C6H4NMe2)(S2CNC4H6)],
[Ni(S2CNC4H6)(dppp)]þ, [Pt(S2CNC4H6)(dppf)]þ, [Ru(S2CNC4H6)(dppm)2]þ, and [Ru(CHdCHC6-
H4Me-4)(S2CNC4H6)(CO)(PPh3)2], respectively. These complexes were also directly prepared from the
reaction of the appropriate starting materials with preformed KS2CNC4H6. The more sterically crowded
complex [Co{S2CN(CH2CHdCH2)2}3] failed to give a reaction with the metathesis catalyst, although it
could be prepared directly from KS2CNC4H6 and cobalt acetate. The compounds [Ru(CHdCHC6-
H4Me-4){S2CN(CH2CHdCH2)2}(CO)(PPh3)2], [Ni{S2CN(CH2CHdCH2)2}(dppp)]PF6, and [Ni(S2-
CNC4H6)(dppp)]PF6 were characterized crystallographically.
Introduction
use of electron-withdrawing substituents on the amine to tip
the balance in favor of alkene coordination.3a,b Another
approach is to coordinate the amine lone pair to a Lewis
acid such as Ti(OPri)4 before metathesis is carried out.3c
Our interest in secondary amines stems largely from their
reaction with carbon disulfide to yield dithiocarbamate com-
pounds, which have been widely used to coordinate transition-
metal ions. Indeed, dithiocarbamate complexes of transition
metals have been known for over a century,4 but only rarely
have the NR2 substituents been exploited chemically.5 Cou-
pling this potential to the well established attributes of dithio-
carbamates (e.g., stabilization of a wide range of oxidation
states6) provides a versatile class of ligand. In an attempt to
exploit the potential of the substituents on nitrogen, we have
Since the advent of highly active catalysts with good
functional group tolerance, alkene metathesis has rapidly
become one of the most powerful tools in synthetic organic
chemistry.1 In particular, ring-closing metathesis (RCM)
under mild conditions has provided easy access to small- or
medium-sized rings and heterocycles, making it an invalu-
able tool in natural product synthesis.2 However, the co-
ordinatively unsaturated nature of the precatalysts used
renders substrates which are capable of binding to the metal
center problematic. For example, the metathesis of unsatu-
rated molecules bearing unprotected amines can be under-
mined by coordination of the amine lone pair to the metal in
competition with the alkene. A strategy often employed is the
(3) (a) Connon, S. J.; Rivard, M.; Zaja, M.; Blechert, S. Adv. Synth.
Catal. 2003, 345, 572–575. (b) Yang, Q.; Xiao, W.-J.; Yu, Z. Org. Lett. 2005,
7, 871–874. (c) Binder, J. B.; Blank, J. J.; Raines, R. T. Org. Lett. 2007, 9,
4885–4888.
(4) Delepine, M. C. R. Seances Acad. Sci. 1907, 144, 1125–1127.
(5) Hogarth, G. Prog. Inorg. Chem. 2005, 53, 71–561.
*To whom correspondence should be addressed. E-mail: j.wilton-ely@
imperial.ac.uk.
(1) Samojlowicz, C.; Bieniek, M.; Grela, K. Chem. Rev. 2009, 109,
3708–3742.
(2) Nicolaou, K. C.; Bulger, P. G.; Sarlah, D. Angew. Chem., Int. Ed.
ꢀ
2005, 44, 4490–4527.
(6) Bond, A. M.; Martin, R. L. Coord. Chem. Rev. 1984, 54, 23–98.
r
2010 American Chemical Society
Published on Web 05/11/2010
pubs.acs.org/Organometallics

2548 Organometallics, Vol. 29, No. 11, 2010
Naeem et al.
investigated cyclic diamines, such as piperazine, to construct
multimetallic compounds in a controlled, stepwise manner.7,8
This methodology has even been extended to the surface
functionalization of nanoparticles.8 While functionalized
dithiocarbamates can be used to incorporate different metals
into the same system, they can also be used to modify the
physical properties of the ligand, such as the protonation of
amino groups to form water-soluble complexes.9
Scheme 1. The Dithiocarbamate Ligand Employed in This
Work, Showing the Numbering Scheme Used for Spectroscopic
Purposes
In the context of alkene metathesis, dithiocarbamates allow
the delocalization of the lone pair of the parent amine, render-
ing the nitrogen nonbasic and thus enabling metathesis to
occur. Herein we explore this potential in the context of our
ongoing investigation of the reactivity of coordinated, func-
tionalized dithiocarbamate ligands. Sporadic reports of com-
plexes bearing the diallyldithiocarbamate ligand (Scheme 1)
have appeared, mostly in the 1980s. These centered on homo-
leptic examples using simple metal salt precursors of iron,10a,b
cobalt,10a nickel,10c copper,10d silver,11 and gold.12 Complexes
bearing other coligands have received little attention. The work
described here explores the synthesis and reactivity of such
compounds and demonstrates that, once ligated to the metal
center, the diallyl unit can enter into organic transformations
such as alkene metathesis. This approach of using metathesis
within the coordination sphere of a metal to create new ligand
architectures has been elegantly demonstrated by Gladysz and
co-workers over the past decade.13
Results and Discussion
Synthesis of Diallyldithiocarbamate Complexes. The bis-
(dppm) compound cis-[RuCl2(dppm)2]14 is a versatile start-
ing material for the addition of bidentate chelates,7,15 and
dithiocarbamates in particular.7,16 The facile removal of the
chloride ligands allows the coordination of the new ligand,
while the lack of lability of the dppm ligands inhibits further
reactivity. The ligand KS2CN(CH2CHdCH2)2 was gener-
ated in situ by treatment of an aqueous solution of diallyla-
mine with carbon disulfide in the presence of potassium
hydroxide. Addition of an excess of this ligand to cis-[RuCl2-
(dppm)2] (dppm = bis(diphenylphosphino)methane) in the
presence of NH4PF6 provided the pale yellow cation
[Ru{S2CN(CH2CHdCH2)2}(dppm)2]PF6 (1) in 69% yield
(Scheme 2). Two new pseudotriplets were observed in the 31P
NMR spectrum at -18.4 and -5.3 ppm, showing coupling of
34.3 Hz. Further evidence for the retention of the dppm
ligands was provided by the multiplet resonances for the
(7) (a) Wilton-Ely, J. D. E. T.; Solanki, D.; Hogarth, G. Eur. J. Inorg.
Chem. 2005, 4027–4030. (b) Knight, E. R.; Solanki, D.; Hogarth, G.; Holt, K.
B.; Thompson, A. L.; Wilton-Ely, J. D. E. T. Inorg. Chem. 2008, 47, 9642–
9653. (c) Macgregor, M. J.; Hogarth, G.; Thompson, A. L.; Wilton-Ely, J. D.
E. T. Organometallics 2009, 28, 197–208.
1
methylene protons at 4.50 and 4.94 ppm in the H NMR
spectrum. The presence of the dithiocarbamate unit was
confirmed by a multiplet at 4.09 ppm for the NCH2 moiety,
while the alkene protons were observed as resonances to
lower field at 5.24 (dCHA), 5.31 (dCHB), and 5.61 (dCHC)
ppm. The overall composition was supported by a molecular
ion in the electrospray mass spectrum (positive mode) at m/z
1042 and good agreement of elemental analysis with calcu-
lated values.
Having established that the chelation chemistry of [S2CN-
(CH2CHdCH2)2]- is shared with simple dithiocarbamates
(e.g., coordination through sulfur), its reactivity was explored
with group 8 alkenyl complexes.17 These compounds have
experienced sustained interest based mainly on the complexes
[Ru(CR1dCHR2)Cl(CO)L2] (L=PPri3,18 PPh319). Their po-
pularity stems from the twin reactive sites of the alkenyl
group and the metal center, making them ideal for the
(8) (a) Knight, E. R.;Cowley, A. R.;Hogarth, G.;Wilton-Ely, J. D. E. T.
Dalton Trans. 2009, 607–609. (b) Knight, E. R.; Leung, N. H.; Lin, Y. H.;
Cowley, A. R.; Watkin, D. J.; Thompson, A. L.; Hogarth, G.; Wilton-Ely, J. D. E.
T. Dalton Trans. 2009, 3688–3697. (c) Knight, E. R.; Leung, N. H.; Thompson,
A. L.; Hogarth, G.; Wilton-Ely, J. D. E. T. Inorg. Chem. 2009, 48, 3866–3874.
(9) (a) McCormick, B. J.; Stormer, B. P.; Kaplan, R. I. Inorg. Chem.
1969, 8, 2522–2524. (b) McCormick, B. J.; Stormer, B. P.; Kaplan, R. I. Can.
J. Chem. 1970, 48, 1876–1880. (c) Calabro, D. C.; Burmeister, J. L. Inorg.
Chim. Acta 1981, 53, L47–L48. (d) Hogarth, G.; Rainford-Brent, E.-J. C.-R.
C. R.; Kabir, S. E.; Richards, I.; Wilton-Ely, J. D. E. T.; Zhang, Q. Inorg.
Chim. Acta 2009, 362, 2020–2026. (e) Naeem, S.; Ogilvie, E.; White, A. J.
P.; Hogarth, G.; Wilton-Ely, J. D. E. T. Dalton Trans. 2010, 39, 4080–4089.
(10) (a) Kello, E.; Lokaj, J.; Vrabel, V. Collect. Czech. Chem. Commun.
1992, 57, 332–338. (b) Lokaj, J.; Kettmann, V.; Pavelcik, F.; Vrabel, V.; Garaj, J.
Collect. Czech. Chem. Commun. 1982, 47, 2633–2638. (c) Lokaj, J.; Pavelcik,
F.; Kettmann, V.; Masaryk, J.; Vrabel, V.; Garaj, J. Acta Crystallogr., Sect. B:
Struct. Sci. 1981, 37, 926–928. (d) Kello, E.; Kettmann, V.; Garaj, J. Collect.
Czech. Chem. Commun. 1984, 49, 2210–2221.
(11) Okumura, K.; Kouyama, S. J. Photopolym. Sci. Technol. 1995, 8,
365–368.
(12) Miller, J. B.; Burmeister, J. L. Synth. React. Inorg. Met.-Org.
Chem. 1985, 15, 223–233.
(13) (a) Martı
´
n-Alvarez, J. M.; Hampel, F.; Arif, A. M.; Gladysz, J.
(14) (a) Sullivan, B. P.; Meyer, T. J. Inorg. Chem. 1982, 21, 1037–1040.
(b) Keller, A.; Jasionka, B.; Glowiak, T.; Ershov, A.; Matusiak, R. Inorg.
Chim. Acta 2003, 344, 49–60.
(15) (a) Lin, Y. H.; Leung, N. H.; Holt, K. B.; Thompson, A. L.;
Wilton-Ely, J. D. E. T. Dalton Trans. 2009, 7891–7901. (b) Lin, Y. H.;
Thompson, A. L.; Tocher, D. A.; Wilton-Ely, J. D. E. T. Manuscript in
preparation.
(16) (a) Dobson, A.; Moore, D. S.; Robinson, S. D. J. Organomet.
Chem. 1979, 177, C8–C12. (b) Dobson, A.; Moore, D. S.; Robinson, S. D.;
Hursthouse, M. B.; New, L. Polyhedron 1985, 4, 1119–1130.
(17) For an overview of alkenyl chemistry of ruthenium(II), see: (a)
Whittlesey, M. K. In Comprehensive Organometallic Chemistry III;
Crabtree, R. H., Mingos, D. M. P., Bruce, M. I., Eds.; Elsevier: Oxford, U.
K., 2006; Vol. 6. (b) Hill, A. F. In Comprehensive Organometallic
Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson, G., Eds.; Pergamon
Press: Oxford, U.K., 1995; Vol. 7.
A. Organometallics 1999, 18, 955–957. (b) Bauer, E. B.; Ruwwe, J.; Martín-
Alvarez, J. M.; Peters, T. B.; Bohling, J. C.; Hampel, F. A.; Szafert, S.; Lis, T.;
Gladysz, J. A. Chem. Commun. 2000, 2261–2262. (c) Ruwwe, J.; Martín-
Alvarez, J. M.; Horn, C. R.; Bauer, E. B.; Szafert, S.; Lis, T.; Hampel, F.;
Cagle, P. C.; Gladysz, J. A. Chem. Eur. J. 2001, 7, 3931–3950. (d) Horn, C.
R.; Martín-Alvarez, J. M.; Gladysz, J. A. Organometallics 2002, 21, 5386–
5393. (e) Bauer, E. B.; Hampel, F.; Gladysz, J. A. Organometallics 2003, 22,
5567–5580. (f) Shima, T.; Hampel, F.; Gladysz, J. A. Angew. Chem., Int. Ed.
2004, 43, 5537–5540. (g) Shima, T.; Bauer, E. B.; Hampel, F.; Gladysz, J. A.
Dalton Trans. 2004, 1012–1028. (h) Wang, L.; Hampel, F.; Gladysz, J. A.
Angew. Chem., Int. Ed. 2006, 45, 4372–4375. (i) Wang, L.; Shima, T.;
Hampel, F.; Gladysz, J. A. Chem. Commun. 2006, 4075–4077. (j) Nawara,
A. J.; Shima, T.; Hampel, F.; Gladysz, J. A. J. Am. Chem. Soc. 2006, 128,
4962–4963. (k) Hess, G. D.; Hampel, F.; Gladysz, J. A. Organometallics
2007, 26, 5129–5131. (l) Skopek, K.; Gladysz, J. A. J. Organomet. Chem.
2008, 693, 857–866. (m) Skopek, K.; Barbasiewicz, M.; Hampel, F.;
Gladysz, J. A. Inorg. Chem. 2008, 47, 3474–3476. (n) de Quadras, L.;
Bauer, E. B.; Stahl, J.; Zhuravlev, F.; Hampel, F.; Gladysz, J. A. New J.
Chem. 2007, 31, 1594–1604.
(18) Werner, H.; Esteruelas, M. A.; Otto, H. Organometallics 1986, 5,
2295–2299.
(19) Torres, M. R.; Vegas, A.; Santos, A.; Ros, J. J. Organomet.
Chem. 1986, 309, 169–177.

Article
Organometallics, Vol. 29, No. 11, 2010 2549
Scheme 2. Preparation of Diallyldithiocarbamate Complexesa
a R = But (2), C6H4Me-4 (3); BTD = 2,1,3-benzothiadiazole.
exploration of new ligands and bimetallic systems.18-27
The most convenient triphenylphosphine-stabilized alkenyl
complexes to use as starting materials are [Ru(CR1dCHR2)Cl-
(CO)(PPh3)2]19 and [Ru(CR1dCHR2)Cl(CO)(BTD)(PPh3)2]
(BTD = 2,1,3-benzothiadiazole),24c where BTD is a labile
ligand. Although many ruthenium dithiocarbamates are
known, no examples are known with the allyl-terminated
ligands used here.
Addition of a slight excess of KS2CN(CH2CHdCH2)2 to an
orange solution of [Ru(CHdCHBut)Cl(CO)(BTD)(PPh3)2] in
dichloromethane led to rapid decolorization and formation of a
yellow solution. Workup yielded a pale yellow product, which
gave rise to a new singlet in the 31P NMR spectrum at 39.7 ppm.
Evidence for the retention of the alkenyl ligand was provided by
(20) (a) Jung, S.; Ilg, K.; Brandt, C. D.; Wolf, J.; Werner, H. Eur. J.
Inorg. Chem. 2004, 469–480. (b) Jung, S.; Brandt, C. D.; Wolf, J.; Werner, H.
Dalton Trans. 2004, 375–383. (c) Werner, H.; Jung, S.; Gonzalez-Herrero,
P.; Ilg, K.; Wolf, J. Eur. J. Inorg. Chem. 2001, 1957–1961. (d) Jung, S.; Ilg,
K.; Wolf, J.; Werner, H. Organometallics 2001, 20, 2121–2123. (e) Werner,
€
H.; St€uer, W.; Jung, S.; Weberndorfer, B.; Wolf, J. Eur. J. Inorg. Chem. 2002,
1076–1080. (f) Werner, H.; Stark, A.; Steinert, P.; Grunwald, C.; Wolf, J.
Chem. Ber. 1995, 128, 49–62.
ꢀ
~
(21) (a) Esteruelas, M. A.; Lopez, A. M.; Onate, E. Organometallics
~
2007, 26, 3260–3263. (b) Bolano, T.; Castarlenas, R.; Esteruelas, M. A.; Onate,
E. J. Am. Chem. Soc. 2006, 128, 3965–3973. (c) Eguillor, B.; Esteruelas, M. A.;
ꢀ
~
Olivan, M.; Onate, E. Organometallics 2005, 24, 1428–1438. (d) Castarlenas,
~
R.; Esteruelas, M. A.; Onate, E. Organometallics 2001, 20, 3283–3292. (e)
~
Castarlenas, R.; Esteruelas, M. A.; Onate, E. Organometallics 2001, 20, 2294–
(23) (a) Huang, D. J.; Renkema, K. B.; Caulton, K. G. Polyhedron
ꢀ
ꢀ
~
2302. (f) Esteruelas, M. A.; García-Yebra, C.; Olivan, M.; Onate, E.; Tajada, M.
2006, 25, 459–468. (b) Marchenko, A. V.; Gerard, H.; Eisenstein, O.;
Organometallics 2000, 19, 5098–5106. (g) Castarlenas, R.; Esteruelas, M. A.;
Caulton, K. G. New J. Chem. 2001, 25, 1382–1388. (c) Marchenko, A. V.;
~
ꢀ
Onate, E. Organometallics 2000, 19, 5454–5463. (h) Buil, M. L.; Esteruelas, M.
Gerard, H.; Eisenstein, O.; Caulton, K. G. New J. Chem. 2001, 25, 1244–
ꢀ
ꢀ
A.; García-Yebra, C.; Gutierrez-Puebla, E.; Olivan, M. Organometallics 2000,
1255. (d) Coalter, J. N.; Streib, W. E.; Caulton, K. G. Inorg. Chem. 2000, 39,
3749–3756. (e) Pedersen, A.; Tilset, M.; Folting, K.; Caulton, K. G.
Organometallics 1995, 14, 875–888.
~
19, 2184–2193. (i) Bohanna, C.; Buil, M. L.; Esteruelas, M. A.; Onate, E.;
Valero, C. Organometallics 1999, 18, 5176–5179. (j) Bohanna, C.; Callejas, B.;
Edwards, A.; Esteruelas, M. A.; Lahoz, F. J.; Oro, L. A.; Ruiz, N.; Valero, C.
(24) (a) Hill, A. F.; Melling, R. P. J. Organomet. Chem. 1990, 396,
C22–C24. (b) Hill, A. F.; Harris, M. C. J.; Melling, R. P. Polyhedron 1992,
11, 781–787. (c) Harris, M. C. J.; Hill, A. F. Organometallics 1991, 10,
3903–3906. (d) Bedford, R. B.; Hill, A. F.; Thompsett, A. R.; White, A. J. P.;
Williams, D. J. Chem. Commun. 1996, 1059–1060. (e) Hill, A. F.; White, A.
J. P.; Williams, D. J.; Wilton-Ely, J. D. E. T. Organometallics 1998, 17, 4249–
4258. (f) Cannadine, J. C.; Hill, A. F.; White, A. J. P.; Williams, D. J.; Wilton-
Ely, J. D. E. T. Organometallics 1996, 15, 5409–5415. (g) Hill, A. F.; Ho, C.
T.; Wilton-Ely, J. D. E. T. Chem. Commun. 1997, 2207–2208. (h) Hill, A. F.;
Wilton-Ely, J. D. E. T. J. Chem. Soc., Dalton Trans. 1999, 3501–3510. (i)
Cowley, A. R.; Hector, A. L.; Hill, A. F.; White, A. J. P.; Williams, D. J.;
Wilton-Ely, J. D. E. T. Organometallics 2007, 26, 6114–6125. (j) Bedford, R.
B.; Hill, A. F.; Jones, C.; White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E.
T. Organometallics 1998, 17, 4744–4753. (k) Bedford, R. B.; Hill, A. F.;
Jones, C.; White, A. J. P.; Wilton-Ely, J. D. E. T. J. Chem. Soc., Dalton
Trans. 1997, 139–140.
ꢀ
Organometallics 1998, 17, 373–381. (k) Esteruelas, M. A.; Gomez, A. V.;
ꢀ
~
Lopez, A. M.; Onate, E. Organometallics 1998, 17, 3567–3573. (l) Esteruelas,
~
M. A.; Liu, F.; Onate, E.; Sola, E.; Zeier, B. Organometallics 1997, 16, 2919–
~
2928. (m) Buil, M. L.; Elipe, S.; Esteruelas, M. A.; Onate, E.; Peinado, E.; Ruiz,
N. Organometallics 1997, 16, 5748–5755. (n) Esteruelas, M. A.; Lahoz, F. J.;
~
Onate, E.; Oro, L. A.; Sola, E. J. Am. Chem. Soc. 1996, 118, 89–99. (o)
ꢀ
Bohanna, C.; Esteruelas, M. A.; Herrero, J.; Lopez, A. M.; Oro, L. A. J.
Organomet. Chem. 1995, 498, 199–206. (p) Bohanna, C.; Esteruelas, M. A.;
~
Lahoz, F. J.; Onate, E.; Oro, L. A.; Sola, E. Organometallics 1995, 14, 4825–
~
4831. (q) Bohanna, C.; Esteruelas, M. A.; Lahoz, F. J.; Onate, E.; Oro, L. A.
ꢀ
Organometallics 1995, 14, 4685–4696. (r) Crochet, P.; Esteruelas, M. A.; Lopez,
ꢀ
~
A. M.; Martínez, M.-P.; Olivan, M.; Onate, E.; Ruiz, N. Organometallics 1998,
17, 4500–4509.
ꢀ
(22) (a) Gomez-Lor, B.; Santos, A.; Ruiz, M.; Echavarren, A. M. Eur.
~
J. Inorg. Chem. 2001, 2305–2310. (b) Castano, A. M.; Echavarren, A. M.;
ꢀ
´
Lopez, J.; Santos, A. J. Organomet. Chem. 1989, 379, 171–175. (c)
(25) (a) El Guaouzi, M.; Ros, J.; Solans, X.; Font-Bardıa, M. Inorg.
Chim. Acta 1995, 231, 181–186. (b) Matas, L.; Muniente, J.; Ros, J.;
Alvarez-Larena, A.; Piniella, J. F. Inorg. Chem. Commun. 1999, 2, 364–
Montoya, J.; Santos, A.; Echavarren, A. M.; Ros, J. J. Organomet. Chem.
1990, 390, C57–C60. (d) Loumrhari, H.; Ros, J.; Torres, M. R.; Santos, A.;
Echavarren, A. M. J. Organomet. Chem. 1991, 411, 255–261. (e) Montoya,
ꢀ~
367. (c) El Guaouzi, M.; Yanez, R.; Ros, J.; Alvarez-Larena, A.; Piniella, J. F.
ꢀ
J.; Santos, A.; Lopez, J.; Echavarren, A. M.; Ros, J.; Romero, A. J.
Inorg. Chem. Commun. 1999, 2, 288–291. (d) Torres, M. R.; Perales, A.;
Loumrhari, H.; Ros, J. J. Organomet. Chem. 1990, 385, 379–386. (e) Matas,
L.; Moldes, I.; Soler, J.; Ros, J.; Alvarez-Larena, A.; Piniella, J. F. Organo-
metallics 1998, 17, 4551–4555. (f) Loumrhari, H.; Ros, J.; Torres, M. R.;
Perales, A. Polyhedron 1990, 9, 907–911. (g) Maddock, S. M.; Rickard, C. E.
F.; Roper, W. R.; Wright, L. J. Organometallics 1996, 15, 1793–1803. (h)
Deshpande, S. S.; Gopinathan, S.; Gopinathan, C. J. Organomet. Chem.
1991, 415, 265–270. (i) Bedford, R. B.; Cazin, C. S. J. J. Organomet. Chem.
2000, 598, 20–23.
ꢀ
Organomet. Chem. 1992, 426, 383–398. (f) Lopez, J.; Romero, A.; Santos,
A.; Vegas, A.; Echavarren, A. M.; Noheda, P. J. Organomet. Chem. 1989,
373, 249–258. (g) Echavarren, A. M.; Lopez, J.; Santos, A.; Montoya, J. J.
Organomet. Chem. 1991, 414, 393–400. (h) Torres, M. R.; Vegas, A.;
Santos, A.; Ros, J. J. Organomet. Chem. 1987, 326, 413–421. (i) Torres, M.
R.; Santos, A.; Ros, J.; Solans, X. Organometallics 1987, 6, 1091–1095. (j)
Santos, A.; Lopez, J.; Matas, L.; Ros, J.; Galan, A.; Echavarren, A. M.
Organometallics 1993, 12, 4215–4218.
ꢀ

2550 Organometallics, Vol. 29, No. 11, 2010
Naeem et al.
a singlet at 0.39 ppm in the 1H NMR spectrum and resonances
at 4.58 (JHP = 1.8 Hz) and 6.30 ppm (JHP = 2.7 Hz) showing
mutual coupling of 16.4 Hz as well as coupling to the phos-
phorus nuclei. In addition, doublets at 3.31 and 3.79 ppm were
observed for the inequivalent NCH2 protons, while doublets
for the allylic protons were noted at 4.74, 4.87, and 5.01 ppm
as well as a multiplet for the dCHC protons at 5.37 ppm.
Infrared data displayed features typical of dithiocarbamate
(νCN at 1479 cm-1) and triphenylphosphine ligands as well as
an intense absorption at 1901 cm-1 attributed to the carbonyl
ligand. The overall formulation of [Ru(CHdCHBut){S2CN-
(CH2CHdCH2)2}(CO)(PPh3)2] (2) was confirmed by an abun-
dant molecular ion in the electrospray (positive ion) mass
spectrum at m/z 909 and good agreement of elemental analysis
with calculated values (Scheme 2).
In a similar fashion, the compounds [Ru(CHdCHC6H4-
Me-4){S2CN(CH2CHdCH2)2}(CO)(PPh3)2] (3) and [Ru{C-
(CtCBut)dCHBut}{S2CN(CH2CHdCH2)2}(CO)(PPh3)2] (4)
were prepared in moderate yield. Spectroscopic and ana-
lytical data confirmed their formulations. Single crystals of
3 were grown and a structural study undertaken (Figure 1),
the results of which are presented in the Structural Discussion.
In order to broaden the range of metals and coordination
geometries investigated, a selection of group 10 compounds
was chosen for reaction with the diallyldithiocarbamate
ligand. The square-planar nickel complex [NiCl2(dppp)]
(dppp = 1,3-bis(diphenylphosphino)propane) was treated
with an excess of KS2CN(CH2CHdCH2)2 in the presence of
NH4PF6 to yield an orange complex, which was formulated
as [Ni{S2CN(CH2CHdCH2)2}(dppp)]PF6 (5). The dipho-
Figure 1. Molecular structure of 3. Selected bond lengths (A)
and angles (deg): Ru-S(1) = 2.4999(5), Ru-S(3) = 2.4619(4),
Ru-P(1) = 2.3689(5), Ru-P(2) = 2.3607(5), Ru-C(11) =
2.088(2), Ru-C(20) = 1.845(2), S(1)-C(2) = 1.713(2), C(2)-
N(4) = 1.328(3), C(2)-S(3) = 1.707(2), C(6)-C(7) = 1.311(5),
C(9)-C(10) = 1.308(4), C(11)-C(12) = 1.336(3); S(1)-Ru-
S(3) = 70.296(16), P(1)-Ru-P(2) = 174.402(17), S(1)-C(2)-
S(3) = 113.29(11), Ru-C(11)-C(12) = 125.77(15).
1
sphine ligand gave rise to two multiplets in the H NMR
spectrum at 2.18 and 2.68 ppm alongside doublets at 4.15 ppm
(JHH = 6.2 Hz), 5.23 (JHH = 17.1 Hz), and 5.33 ppm (JHH=
10.2 Hz) and a multiplet at 5.67 ppm for the diallyldithiocar-
bamate ligand. The overall composition was supported by a
molecular ion at m/z 642 and good agreement of elemental
analysis with calculated values (Scheme 2). Single crystals
of 5 were grown and a structural investigation undertaken
(Figure 2 and Structural Discussion).
In a similar manner, the dppf (1,10-bis(diphenylphosphino)-
ferrocene) complexes of all three congeners of group 10, [M-
{S2CN(CH2CHdCH2)2}(dppf)]PF6 (M = Ni, 6; M = Pd, 7;
M = Pt, 8) were prepared from [MCl2(dppf)]. These complexes
shared similar spectroscopic features, with two broad singlets
observed in each case for the cyclopentadienyl protons at 4.59
(26) (a) Jia, G.; Wu, W. F.; Yeung, R. C. Y.; Xia, H. P. J. Organomet.
Chem. 1997, 539, 53–59. (b) Liu, S. H.; Chen, Y.; Wan, K. L.; Wen, T. B.;
Zhou, Z.; Lo, M. F.; Williams, I. D.; Jia, G. Organometallics 2002, 21, 4984–
4992. (c) Liu, S. H.; Xia, H.; Wen, T. B.; Zhou, Z.; Jia, G. Organometallics
2003, 22, 737–743. (d) Liu, S. H.; Hu, Q. Y.; Xue, P.; Wen, T. B.; Williams, I.
D.; Jia, G. Organometallics 2005, 24, 769–772. (e) Liu, S. H.; Xia, H.; Wan,
K. L.; Yeung, R. C. Y.; Hu, Q. Y.; Jia, G. J. Organomet. Chem. 2003, 683,
331–336. (f) Xia, H.; Wen, T. B.; Hu, Q. Y.; Wang, X.; Chen, X.; Shek, L. Y.;
Williams, I. D.; Wong, K. S.; Wong, G. K. L.; Jia, G. Organometallics 2005,
24, 562–569. (g) Maurer, J.; Sarkar, B.; Schwederski, B.; Kaim, W.; Winter,
Figure 2. Molecular structure of the cation present in the crys-
tals of 5. Selected bond lengths (A) and angles (deg): Ni-S(1) =
2.2089(17), Ni-S(3) = 2.2097(17), Ni-P(11) = 2.1747(17), Ni-
P(15) = 2.1788(17), S(1)-C(2) =1.723(7),C(2)-N(4) = 1.314(8),
C(2)-S(3) = 1.728(7), C(6)-C(7) = 1.304(11), C(9)-C(10) =
1.271(15); S(1)-Ni-S(3) = 79.24(6), P(11)-Ni-P(15) =
94.56(6), S(1)-C(2)-S(3) = 109.5(4).
ꢀ ꢁ
R. F.; Zalis, S. Organometallics 2006, 25, 3701–3712. (h) Xia, H.; Wen, T.
B.; Hu, Q. Y.; Wang, X.; Chen, X. X.; Shek, L. Y.; Williams, I. D.; Wong, K.
S.; Wong, G. K. L.; Jia, G. Organometallics 2005, 24, 562–569. (i) Xia, H.;
Wen, T. B.; Hu, Q. Y.; Wang, X.; Chen, X.; Shek, L. Y.; Williams, I. D.; Wong,
K. S.; Wong, G. K. L.; Jia, G. Organometallics 2005, 24, 562–569. (j)
Loumrhari, H.; Ros, J.; Torres, M. R. Polyhedron 1991, 10, 421–427.
(27) (a) Wilton-Ely, J. D. E. T.; Wang, M.; Benoit, D.; Tocher, D. A.
Eur. J. Inorg. Chem. 2006, 3068–3078. (b) Wilton-Ely, J. D. E. T.;
Pogorzelec, P. J.; Honarkhah, S. J.; Tocher, D. A. Organometallics 2005,
24, 2862–2874. (c) Wilton-Ely, J. D. E. T.; Honarkhah, S. J.; Wang, M.;
Tocher, D. A. Dalton Trans. 2005, 1930–1939. (d) Wilton-Ely, J. D. E. T.;
Wang, M.; Honarkhah, S. J.; Tocher, D. A. Inorg. Chim. Acta 2005, 358,
3218–3226.
and 4.69 ppm (6). The only unique feature was the JPtP coupling
of 3367 Hz observed in the 31P NMR spectrum for 8. An
organometallic palladium example, [Pd(C,N-CH2C6H4NMe2)-
{S2CN(CH2CHdCH2)2}] (9), was prepared from the [Pd(C,N-
CH2C6H4NMe2)Cl]2 dimer. In addition to resonances for the

Article
Organometallics, Vol. 29, No. 11, 2010 2551
Figure 3. Steric profiles of coligand sets in the complexes chosen to investigate ring-closing metathesis (R = C6H4Me-4).
[S2CN(CH2CHdCH2)2]- chelate, the cyclometalated ligand
gave rise to singlets at 2.93 and 4.02 ppm in the H NMR
spectrum for the methyl and methylene groups, respectively,
and a multiplet for the aromatic protons.
those observed for 12. As a further means to confirm the for-
mulation, 12 was prepared through a different route, by direct
reaction of Ni(OAc)2 with an excess of preformed KS2CNC4-
H6.28 Identical data were recorded for the compounds pre-
pared by this alternative route.
1
Ring Closing of Diallyldithiocarbamate Complexes. As
detailed in earlier work,7,8 our interest in introducing func-
tionality into the pendant arms of dithiocarbamates is aimed
at utilizing this additional center of reactivity within the
complex. Having prepared a range of diallyl-substituted
dithiocarbamate complexes, we sought to probe the chemi-
stry of the pendant unsaturated units toward ring-closing
metathesis.
In order to commence the investigation using relatively
simple systems, the homoleptic compounds [Ni{S2CN(CH2-
CHdCH2)2}2] (10) and [Co{S2CN(CH2CHdCH2)2}3] (11)
were prepared by literature methods10a,c and (hitherto un-
available) NMR data recorded.
In the complexes described here, the nitrogen lone pair is
involved in bonding within the dithiocarbamate unit, leading
to multiple-bond character in the N-C bond. This arrests
free rotation around this linkage, meaning that the steric
effects of the coligands could prove a significant factor in the
ring-closing metathesis activity of the complexes described
here. Figure 3 depicts the steric environment of the metal
centers in this study (minus the diallydithiocarbamate ligand
undergoing metathesis).
The palladium compound [Pd(C,N-CH2C6H4NMe2)-
{S2CN(CH2CHdCH2)2}] (9) was also treated in the same
way and resulted in complete conversion to the ring-closed
product [Pd(C,N-CH2C6H4NMe2)(S2CNC4H6)] (13). A more
complicated 1H NMR spectrum was observed for 13, due to
the unsymmetrical nature of the complex. A doublet and a
multiplet at 4.56 (JHH = 13.5 Hz) and 5.97 ppm, respectively,
were observed for the methylene and alkene protons, along
with resonances for the cyclometalated ligand. A molecular
ion was observed in the mass spectrum (ES positive mode) at
m/z 385. The same product was also prepared using the direct
method described above (Scheme 3). These successful reac-
tions both involved sterically undemanding square-planar
substrates; therefore, attention turned to the complex [Co{S2-
CN(CH2CHdCH2)2}3] (11). After 2 h, no reaction was ob-
served with 5 mol % catalyst loading per dithiocarbamate
ligand. Higher loadings did not improve the situation. This
remained the case after 24 h of stirring in dichloromethane at
room temperature. The modest steric profile of the octahedral
arrangement of three diallyldithiocarbamateligandsappeared
sufficient to prevent coordination and subsequent metathesis
of the alkene units by the ruthenium alkylidene catalyst. In
order to test whether the product was unstable in some way,
[Co(S2CNC4H6)3] (14) was prepared directly from cobalt
The square-planar complex 10 was treated with 5 mol % of
the catalyst [Ru(dCHPh)Cl2(SIMes)(PCy3)] per dithiocar-
bamate ligand (hence 10 mol % overall) under nitrogen in
dry, degassed dichloromethane. The reaction was monitored
by 1H NMR spectroscopy and, after 2 h, only trace amounts
of the starting material were observed. Instead, a much
simpler spectrum was revealed in which singlets at 4.36 and
5.91 ppm were observed for the methylene and alkene
protons, respectively. The mass spectrum (ES positive mode)
did not display a simple molecular ion but instead exhibited a
peak for 2[M]þ at m/z 696. However, the formulation of the
3-pyrroline dithiocarbamate complex [Ni(S2CNC4H6)2] (12),
shown in Scheme 3, was supported by elemental analysis.
Although the [S2CNC4H6]- ligand has been prepared before,
it has found most use in main-group compounds such as
1
acetate and KS2CNC4H6. H NMR analysis of the product
showed resonances for the 3-pyrrolinedithiocarbamate ligand
at 4.48 and 5.91 ppm, similar to the other complexes of this
ligand prepared in this work. Mass spectrometry and elemental
analysis data confirmed the formulation.
This result did not bode well for the other diallyldithiocarba-
mate complexes discussed earlier. After 2 h, no clear spectro-
1
scopic change (31P, H NMR spectroscopy) was observed in
the attempted ring-closing metathesis of [Ni{S2CN(CH2CHd
CH2)2}(dppp)] (5) with 10 mol % of [Ru(dCHPh)Cl2(SIMes)-
(PCy3)]; however, after the reaction was continued in dichlor-
omethane at room temperature overnight, the resonances for
the diallyldithiocarbamate ligand were replaced with singlets at
4.33 and 5.89 ppm. A very minor change in the chemical shift
of the 31P NMR resonance to 12.5 ppm was discernible, despite
the remoteness of the transformation from the phosphorus
nuclei. Further spectroscopic and analytical data supported the
formulation of the product as [Ni(S2CNC4H6)(dppp)]PF6 (15).
Single crystals of this compound were grown and a structural
1
[O(SiMe2CH2)2TeI(S2CNC4H6)].28 The H NMR data for
this compound consist of a broadened singlet at 4.50 ppm and
a singlet at 5.92 ppm, values which are in good agreement with
ꢀ
~
(28) Fuentes-Aleman, D.; Toscano, R.-A.; Munoz-Hernandez, M.;
a y Garcıa, P.; Cea-Olivares, R. J. Organo-
´ ´
ꢀ
ꢀ
Lopez-Cardoso, M.; Garcı
met. Chem. 2008, 693, 3166–3170.

2552 Organometallics, Vol. 29, No. 11, 2010
Scheme 3. Ring-Closing Metathesis and Direct Routes to 3-Pyrroline Dithiocarbamate Complexesa
Naeem et al.
a [Ru] catalyst = [Ru(dCHPh)Cl2(SIMes)(PCy3)]; BTD = 2,1,3-benzothiadiazole; L = PPh3.
investigation undertaken (Figure 4 and Table 1). The salient
features of this structure are discussed in the Structural Discus-
sion.
Thus, it was proved that metathesis of the coordinated
diallyldithiocarbamate ligand was possible despite the steric
encumbrance introduced by the dppp ligand.
organic functionality in the form of the alkenyl ligand. After
2 h, some evidence of transformation was present and, after
a further 22 h, complete conversion had taken place to
yield [Ru(CHdCHC6H4Me-4)(S2CNC4H6)(CO)(PPh3)2] (18).
1
This species displayed a more complex H NMR spectrum
for the cyclized ligand due to the lack of symmetry in the
molecule as a whole. Two broadened singlets were observed
for the NCH2 protons at 3.50 and 3.77 ppm, while the
protons of the (Z)-alkene gave rise to a singlet resonance at
5.62 ppm. Infrared spectroscopy exhibited a νCO absorption
at 1912 cm-1, and these data in favor of the given formula-
tion were further corroborated by a molecular ion in the (ES
positive mode) mass spectrum at m/z 915 and good agree-
ment of elemental analysis with calculated values. To pro-
vide further chemical confirmation for compounds 12-18,
they were all prepared directly from 3-pyrroline dithiocar-
bamate and an appropriate precursor. Spectroscopic data
were found to be identical. It is worth noting that, for larger
scale preparations, the RCM method is significantly cheaper
due to the relative expense of 3-pyrroline.
The same reactivity was found with [Pt{S2CN(CH2CHd
CH2)2}(dppf)]PF6 (8), which underwent ring-closing meta-
thesis with 10 mol % [Ru(dCHPh)Cl2(SIMes)(PCy3)] over-
night to give [Pt(S2CNC4H6)(dppf)]PF6 (16) in 89% yield.
The ease with which this reaction proceeded illustrated that
there appears to be no difference between the reactivity of first-
and third-row transition-metal complexes. On steric grounds,
the bis(dppm) complex [Ru{S2CN(CH2CHdCH2)2}(dppm)2]-
PF6 (1) appeared to be a much greater challenge, yet, after 24 h,
conversion to [Ru(S2CNC4H6)(dppm)2]PF6 (17) was shown to
be complete (again with little evidence after 2 h) using 10 mol %
of the catalyst. These results indicate that steric factors may
slow the reaction but need not prevent RCM from taking place.
The previous examples all contain bidentate chelates
(diphosphines or cyclometalated ligands), which confer sub-
stantial robustness on the substrates. Thus, the metathesis
reaction was next investigated with [Ru(CHdCHC6H4Me-4)-
{S2CN(CH2CHdCH2)2}(CO)(PPh3)2] (3), which only has
monodentate ligands and bears an additional unsaturated
Structural Discussion
A distorted-octahedral geometry is found for the ruthe-
nium center in [Ru(CHdCHC6H4Me-4){S2CN(CH2CHd
CH2)2}(CO)(PPh3)2] (3) with cis-interligand angles in the

Article
Organometallics, Vol. 29, No. 11, 2010 2553
planar, and thus the steric bulk of the phosphine ligand is
distal to the dithiocarbamate moiety (in contrast to the
structure of 3). The coordination plane is markedly dis-
torted, with S(1) lying ca. 0.51 A out of the {Ni,S(3),P(11),
P(15)} plane, the atoms of which are coplanar to within ca.
0.03 A. Other data are similar to previous examples of nickel
dithiocarbamate compounds in the literature, such as
[Ni(S2CNC4H8NH2)(dppp)]2þ 7b
.
[Ni(S2CNC4H6)(dppp)]PF6 (15) crystallized with two in-
dependent cation:anion pairs (A and B) in the asymmetric
unit. Complex cation A is shown in Figure 4, while B is
shown in Figure S4 in the Supporting Information. The
geometry at the nickel center is distorted square planar, with
P(13) lying ca. 0.22 A [0.25 A] out of the {Ni,S(1),S(3),P(9)}
plane, the atoms of which are coplanar to within ca. 0.04 A
[0.01 A] (the values in brackets refer to cation B). One
interesting oddity of the two independent cations is that in
15-B the two Ni-S bonds are the same [2.2286(7) and
2.2277(7) A], but in 15-A they are statistically significantly
different [2.2158(7) and 2.2300(7) A]; it is the bond to S(1)
that is anomalously short. There is no obvious reason the
bonding should be different between the two independent
complexes. The bite angle of the dithiocarbamate ligand,
S(1)-Ni(1)-S(3), is 79.45(3) and 79.21(3)° for the two
independent molecules in the structure, which are close to
Figure 4. Molecular structure of one (A) of the two crystal-
lographically independent cationic complexes present in the
crystals of 15.
˚
Table 1. Selected Bond Lengths (A) and Angles (deg) for the Two
Crystallographically Independent Cationic Complexes (A and B)
Present in the Crystals of 15
that of 79.68(7)° for [Ni(S2CNC4H8NH2)(dppp)]2þ 7b
.
The
C(6)-C(7) distances of 1.305(5) and 1.311(5) A are con-
sistent with the presence of a double bond.
The C-S bonds across all three structures are in the range
1.707(2)-1.728(7) A, while the C(2)-N(4) bonds show a
greater deviation, ranging between 1.300(3) and 1.328(3) A.
A
B
Ni(1)-S(1)
Ni(1)-P(9)
S(1)-C(2)
C(2)-S(3)
Ni(1)-S(3)
Ni(1)-P(13)
C(2)-N(4)
C(6)-C(7)
2.2158(7)
2.1740(7)
1.722(3)
1.721(3)
2.2300(7)
2.1654(7)
1.300(3)
1.305(5)
2.2286(7)
2.1697(7)
1.716(3)
1.717(3)
2.2277(7)
2.1775(7)
1.309(3)
1.311(5)
Conclusion
The diallyldithiocarbamate complexes described here ably
demonstrate the potential of dithiocarbamates to introduce a
further reactive site into metal complexes. Previously, only
simple, homoleptic compounds of this dithiocarbamate li-
gand have been reported, but this work demonstrates its
coordination to octahedral ruthenium σ-alkenyl and bis-
(dppm) compounds as well as examples of all three group
10 metals. The potential of the pendant allyl units to allow
further modification of the compounds has been shown in
the ring-closing metathesis of six examples of Ru, Ni, Pd, and
Pt to generate cyclic dithiocarbamate ligands in situ. These
reactions proceeded cleanly (and in some cases rapidly)
under mild conditions, showing surprisingly limited depen-
dence on the steric environment. The failure of the cobalt-
(III) complex 10 to undergo reaction will be examined
further, both by experiment and computation, to probe the
contribution of steric and electronic effects. Having demon-
strated the viability of this approach, work is underway to
investigate the cross-metathesis of metal dithiocarbamate
units.
S(1)-Ni(1)-S(3)
S(1)-Ni(1)-P(13)
S(3)-Ni(1)-P(13)
S(1)-C(2)-S(3)
S(1)-Ni(1)-P(9)
S(3)-Ni(1)-P(9)
P(9)-Ni(1)-P(13)
79.45(3)
92.47(3)
169.03(3)
111.22(14)
172.64(3)
93.81(3)
93.81(3)
79.21(3)
93.26(3)
169.67(3)
111.65(15)
172.16(3)
93.01(3)
94.33(3)
range 70.296(16)-102.77(6)°. The Ru-S distances of
2.4619(4) and 2.4999(5) A are marginally shorter than those
of 2.466(1) and 2.508(1) A found in [Ru{C(CtCPh)d
CHPh}(S2CNC4H8NH2)(CO)(PPh3)2]Cl,7c though in both
compounds the greater trans influence of the alkenyl ligand
over that of the carbonyl is reflected in the elongation of the
Ru-S bond trans to it. The S(3)-C(2)-S(1) angle of
113.29(11)° is slightly smaller than that of 114.6(3)° observed
for the literature complex, while the S(3)-Ru-S(1) angle of
70.296(16)° is the same as that of 70.33(4)° found in the
enynyl compound. The C(2)-N(4) distance of 1.328(3) A
indicates significant double-bond character,29 restricting
rotation and causing near-planarity of the RuS2CNR2 unit.
The bond data for the alkenyl ligand itself are unremarkable
and compare well with previous examples in the literature.24i
The geometry at the nickel center in the structure of [Ni-
{S2CN(CH2CHdCH2)2}(dppp)]PF6 (5) is distorted square
Experimental Section
General Comments. Experiments to form 1-11 and all reac-
tions using KS2CNC4H6 were carried out under aerobic condi-
tions, while the metathesis reactions were conducted under
nitrogen using degassed dichloromethane. All the complexes
appear indefinitely stable toward the atmosphere in solution
and in the solid state. The compounds [Ru(CHdCHBut)-
Cl(CO)(BTD)(PPh3)2], [Ru(CHdCHC6H4Me-4)Cl(BTD)(CO)-
(PPh3)2], and [Ru(CHdCHCPh2OH)Cl(BTD)(CO)(PPh3)2]
(29) Allen, F. H.; Kennard, O.; Watson, D. G.; Brammer, L.; Orpen,
A. G.; Taylor, R. J. Chem. Soc., Perkin Trans. 1987, S1–S19.

2554 Organometallics, Vol. 29, No. 11, 2010
Naeem et al.
were prepared in a manner identical with that for the corres-
ponding BSD (2,1,3-benzoselanadiazole) complexes.24c The
following complexes have been described elsewhere: [Ru{C(Ct
CBut)dCHBut}Cl(CO)(PPh3)2],30 cis-[RuCl2(dppm)2],14b [MCl2-
(dppf)] (M = Ni,31 Pd,32 Pt33), [NiCl2(dppp)],34 [Pd(C,N-CH2C6-
H4NMe2)Cl]2,35 and [Ru(dCHPh)Cl2(SIMes)(PCy3)].36 Solu-
diethyl ether (10 mL) and dried under vacuum. Yield: 175 mg
(69%). IR (solid state): 1482, 1435, 1414, 1244, 1098, 999, 928,
833 (νPF), 739, 727, 694 cm-1 31P NMR (CD2Cl2): -18.4, -5.3
.
(t ꢀ 2, dppm, JHH = 34.3 Hz). 1H NMR (CD2Cl2): 4.09 (m, 4H,
NCH2); 4.50, 4.94 (m ꢀ 2, 2 ꢀ 2H, PCH2P); 5.24 (d, 2H, dCHA,
J
HH = 17.0 Hz); 5.31 (d, 2H, dCHB, JHH = 10.1 Hz); 5.61 (m,
10
tions (4.0 mmol) of the ligand KS2CN(CH2CHdCH2)2 were
2H, dCHC); 6.49, 6.99, 7.11, 7.27-7.51, 7.71 (m ꢀ 5, 40H,
C6H5) ppm. MS (ES positive): m/z (abundance) 1042 (100) [M]þ.
Anal. Calcd for C57H54F6NP5RuS2 (Mw = 1187.11): C, 57.7; H,
4.6; N, 1.2. Found: C, 57.7; H, 4.5; N, 1.1.
prepared in water. Other reagents and solvents were used as
received from commercial sources. Petroleum ether refers to the
fraction boiling at 40-60 °C. Electrospray mass spectrometry data
were obtained using a Micromass LCT Premier instrument, and
infrared data were measured using a Perkin-Elmer Spectrum 100
FT-IR spectrometer. Characteristic phosphine-associated infrared
data were observed in all relevant complexes but have been omitted
for reasons of brevity. NMR spectroscopy was performed at 25 °C
using a Bruker AV400 spectrometer. All couplings are in hertz, and
31P NMR spectra are proton-decoupled. Resonances for the
hexafluorophosphate anion are not reported. Elemental analysis
data were obtained from London Metropolitan University. For
the ring-closed products, further purification to remove remaining
ruthenium catalyst was achieved by careful recrystallization from
dichloromethane and diethyl ether to provide materials of suffi-
cient purity for synthetic and spectroscopic purposes.
[Ru(CHdCHBut){S2CN(CH2CHdCH2)2}(CO)(PPh3)2] (2).
[Ru(CHdCHBut)Cl(CO)(BTD)(PPh3)2] (100 mg, 0.110 mmol)
gave 63 mg of pale yellow product (63%). IR (solid state): 1901
(νCO), 1642, 1479, 1410, 1358, 1227, 982, 916 cm-1 31P NMR
.
(CDCl3): 39.7 (s, PPh3). 1H NMR (CDCl3): 0.39 (s, 9H, CCH3);
3.31 (d, 2H, NCH2, JHH = 6.2 Hz); 3.79 (d, 2H, NCH2, JHH
=
6.0 Hz); 4.58 (dt, 1H, Hβ, JHH = 16.4 Hz, JHP = 1.8 Hz); 4.74
(d, 1H, dCHA, JHH = 17.0 Hz); 4.87 (d, 1H, dCHA, JHH = 17.1
Hz); 5.01 (d, 2H, dCHB, JHH = 10.2 Hz); 5.37 (m, 2H, dCHC);
6.29 (dt, 1H, HR, JHH = 16.4 Hz, JHP = 2.7 Hz); 7.29-7.36,
7.56-7.61 (m ꢀ 2, 30H, C6H5) ppm. MS (ES positive): m/z
(abundance) 909 (71) [M]þ; 826 (58) [M - alkenyl]þ. Anal.
Calcd for C50H51NOP2RuS2 (Mw = 909.10): C, 66.1; H, 5.7; N,
1.5. Found: C, 65.9; H, 5.6; N, 1.6.
General Procedure for Reactions of Metal Complexes with
KS2CN(CH2CHdCH2)2. A fresh solution of KS2CN(CH2CHd
CH2)2 in water (30 mL) was prepared by stirring diallylamine
(1.00 mL, 6.371 mmol) and CS2 (0.42 mL, 6.984 mmol) in the
presence of KOH (393 mg, 7.004 mmol) for 40 min.9 Assuming
complete conversion, appropriate portions of this solution were
added by syringe to a solution of the metal complex in acetone
and dichloromethane (20 mL/10 mL). The reaction mixture was
stirred for 20 min. All solvent was removed, the crude product
was dissolved in dichloromethane (15 mL), and this solution was
filtered through diatomaceous earth (Celite) to remove KCl
and excess ligand. All solvent was again removed, diethyl ether
(20 mL) was added, and the crude product was triturated ultra-
sonically. The pale yellow precipitate was filtered and washed with
water (5 mL) and diethyl ether (10 mL). The product was dried
under vacuum. Note: the preparation of the ligand as a methanolic
solution led to substantial contamination of the alkenyl complexes
with the corresponding methyl xanthate species [Ru(alkenyl)-
(S2COMe)(CO)(PPh3)2], through attack of deprotonated solvent
on CS2 and subsequent coordination.
[Ru{S2CN(CH2CHdCH2)2}(dppm)2]PF6 (1). A solution of
cis-[RuCl2(dppm)2] (200 mg, 0.213 mmol) in acetone (20 mL)
and dichloromethane (10 mL) was treated with 2 equiv of the
dithiocarbamate ligand and NH4PF6 (69 mg, 0.423 mmol) in
water (5 mL), and the reaction mixture was stirred for 30 min.
All solvent was removed, the residue was dissolved in the
minimum volume of dichloromethane, and this solution was
filtered through diatomaceous earth (Celite) to remove KCl and
excess ligand. All solvent was again removed, diethyl ether
(30 mL) was added, and the solid was triturated ultrasonically.
The pale yellow product was washed with water (10 mL) and
[Ru(CHdCHC6H4Me-4){S2CN(CH2CHdCH2)2}(CO)(PPh3)2]
(3). [Ru(CHdCHC6H4Me-4)Cl(CO)(BTD)(PPh3)2] (100 mg, 0.106
mmol) gave 61 mg of pale yellow product (61%). IR (solid state):
1094 (νCO), 1710, 1643, 1548, 1410, 1277, 1230, 1127, 981, 968, 935,
920, 827 cm-1 31P NMR (CDCl3): 39.3 (s, PPh3). 1H NMR
.
(CDCl3): 2.24 (s, 3H, CCH3); 3.53 (d, 2H, NCH2, JHH = 5.3 Hz);
3.80 (d, 2H, NCH2, JHH = 6.0 Hz);4.81 (d, 1H, dCHA, JHH = 17.1
Hz); 4.86 (d, 1H, dCHA, JHH = 17.4 Hz); 5.00 (d, 2H, dCHB,
JHH = 10.2 Hz); 5.25 (m, 2H, dCHC); 5.53 (d, 1H, Hβ, JHH
=
16.7 Hz); 6.38, 6.83 (AB, 4H, C6H4, JAB = 8.0 Hz); 7.28-7.36,
7.55-7.59 (m ꢀ 2, 30H, C6H5); 7.71 (dt, 1H, HR, JHH = 16.7 Hz,
JHP = 3.2 Hz) ppm. MS (ES positive): m/z (abundance) 943 (5)
[M]þ; 826 (32) [M - alkenyl]þ. Anal. Calcd for C53H49NOP2RuS2
(Mw = 943.11): C, 67.5; H, 5.2; N, 1.5. Found: C, 67.4; H, 5.2; N, 1.6.
[Ru(C(CtCBut)dCHBut){S2CN(CH2CHdCH2)2}(CO)-
(PPh3)2] (4). [Ru(C(CtCBut)dCHBut)Cl(CO)(PPh3)2] (100 mg,
0.117 mmol) gave 32 mg of pale yellow product (28%). IR (solid
state): 2162 (νCtC), 1921 (νCO), 1640, 1464, 1410, 1356, 1228, 1186,
992, 920, 828 cm-1
.
31P NMR (CDCl3): 38.3 (s, PPh3). 1H NMR
(CDCl3): 0.61 (s, 9H, But); 1.59 (s, 9H, But); 3.48 (m, 2H, NCH2);
3.59 (d, 2H, NCH2, JHH = 6.2 Hz); 4.81 (d, 1H, dCHA, JHH
=
17.0 Hz); 4.86 (d, 1H, dCHA, JHH = 17.0 Hz); 4.98 (d, 2H, dCHB,
JHH = 10.1 Hz); 5.17 (m, 2H, dCHC); 5.22 (s, 1H, Hβ); 7.26-7.36,
7.60 (m ꢀ 2, 30H, C6H5) ppm. MS (ES positive): m/z (abundance)
990 (32) [M]þ; 826 (20) [M - alkenyl]þ. Anal. Calcd for C56H59-
NOP2RuS2 3.25CH2Cl2 (Mw = 989.22): C, 56.2; H, 5.2; N, 1.1.
3
Found: C, 56.0; H, 4.8; N, 1.5.
[Ni{S2CN(CH2CHdCH2)2}(dppp)]PF6 (5). A solution of
[NiCl2(dppp)] (200 mg, 0.369 mmol) in acetone (20 mL) and
dichloromethane (10 mL) was treated with 1.5 equiv of KS2CN-
(CH2CHdCH2)2 and NH4PF6 (120 mg, 0.736 mmol) in water
(5 mL), and the reaction mixture was stirred for 30 min. All
solvent was removed, the residue was dissolved in the minimum
volume of dichloromethane, and this solution was filtered
through diatomaceous earth (Celite) to remove KCl, excess
NH4PF6, and ligand. All solvent was again removed, petroleum
ether (30 mL) was added, and the solid was triturated ultra-
sonically. The orange product was washed with water (10 mL)
and petroleum ether (10 mL) and dried under vacuum. Yield:
212 mg (73%). IR (solid state): 1515, 1435, 1418, 1242, 1177,
(30) (a) Wakatsuki, Y.; Yamazaki, H.; Kumegawa, N.; Satoh, T.;
ꢀ
Satoh, J. Y. J. Am. Chem. Soc. 1991, 13, 9604–9610. (b) Santos, A.; Lopez,
ꢀ
J.; Matas, L.; Ros, J.; Galan, A.; Echavarren, A. M. Organometallics 1993,
12, 4215–4218. (c) Prepared in this work in a manner analogous to that used
for [Ru{C(CtCBut)dCHBut}Cl(CO)(PPh3)2] in ref 22c.
(31) Rudie, A. W.; Lichtenberg, D. W.; Katcher, M. L.; Davison, A.
Inorg. Chem. 1978, 17, 2859–2863.
(32) Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi, T.;
Hirotsu, K. J. Am. Chem. Soc. 1984, 106, 158–163.
(33) Whitesides, G. M.; Gaasch, J. F.; Stedronsky, E. R. J. Am.
Chem. Soc. 1972, 94, 5258–5270.
(34) Bomfim, J. A. S.; de Souza, F. P.; Filgueiras, C. A. L.; de Sousa,
A. G.; Gambardella, M. T. P. Polyhedron 2003, 22, 1567–1573.
(35) Cope, A. C.; Friedrich, E. C. J. Am. Chem. Soc. 1968, 90, 909–
913.
(36) Scholl, M.; Ding, S.; Lee, C. W.; Grubbs, R. H. Org. Lett. 1999,
1, 953–956.
1100, 971, 938, 824 (νPF), 742, 691 cm-1 31P NMR (CDCl3):
.
12.8 (s, dppp). 1H NMR (CDCl3): 2.18 (m, 2H, dppp-CH2); 2.68
(m, 4H, dppp-PCH2); 4.15 (d, 4H, NCH2, JHH = 6.2 Hz); 5.23
(d, 2H, dCHA, JHH = 17.1 Hz); 5.33 (d, 2H, dCHB, JHH = 10.2
Hz); 5.67 (m, 2H, dCHC); 7.40 - 7.62 (m, 20H, C6H5) ppm. MS
(ES þpositive): m/z (abundance) 642 (100) [M]þ. Anal. Calcd

Article
Organometallics, Vol. 29, No. 11, 2010 2555
for C34H36F6NNiP3S2 (Mw = 788.39): C, 51.8; H, 4.6; N, 1.8.
Found: C, 52.0; H, 4.7; N, 1.8.
residue was dissolved in the minimum volume of dichloro-
methane, and this solution was filtered through diatomaceous
earth (Celite) to remove KCl and excess ligand. All solvent was
again removed, petroleum ether (30 mL) was added, and the solid
was triturated ultrasonically. The orange product was washed with
water (10 mL) and petroleum ether (10 mL) and dried under
vacuum. Yield: 258 mg (86%). IR (solid state): 1488, 1407, 1343,
1329, 1280, 1249, 1177, 1139, 1112, 1044, 1022, 992, 973, 926, 870,
852, 750 cm-1. 1H NMR (CDCl3): 2.93 (s, 6H, NMe2); 4.02 (s, 2H,
CH2Pd);4.43 (m, 4H, NCH2);5.26(d, 2H, dCHB, JHH = 10.2 Hz);
5.29-5.34 (m, 2H, dCHA); 5.84 (m, 2H, dCHC); 6.94-7.05 (m,
4H, C6H4) ppm. MS (ES positive): m/z(abundance) 413 (100) [M]þ.
Anal. Calcd for C16H22N2PdS2 (Mw = 412.91): C, 46.5; H, 5.4; N,
6.8. Found: C, 46.5; H, 5.3; N, 6.8.
[Ni{S2CN(CH2CHdCH2)2}2] (10). This compound was pre-
pared using the literature procedure.8 1H NMR (CDCl3): 4.19 (d,
8H, NCH2, JHH = 5.6 Hz); 5.25 (d, 4H, dCHA, JHH = 17.1 Hz);
5.31 (d, 4H, dCHB, JHH = 10.1 Hz); 5.76 (m, 4H, dCHC) ppm.
[Co{S2CN(CH2CHdCH2)2}3] (11). This compound was pre-
pared using the literature procedure.9 1H NMR (CDCl3): 4.19,
4.44 (dd ꢀ 2, 2 ꢀ 6H, NCH2, JHH = 15.0, 5.1 Hz); 5.25-5.29 (m,
12H, dCHA/B); 5.82 (m, 6H, dCHC) ppm.
Preparation of KS2CNC4H6. An aqueous solution (30 mL) of
3-pyrroline (40 mg, 0.579 mmol) and KOH (32.5 mg, 0.579 mmol)
was stirred for 10 min and then treated with carbon disulfide (52.8
mg, 0.693 mmol). After it was stirred for a further 40 min, the
solution was used for the additions to the metal complexes.
[Ni(S2CNC4H6)2] (12). (a) Compound 10 (40 mg, 0.099
mmol) and [Ru(dCHPh)Cl2(SIMes)(PCy3)] (8.4 mg, 0.010
mmol) were dissolved in dry, degassed dichloromethane (20
mL) and stirred for 2 h. All solvent was then removed, and the
residue was triturated in diethyl ether (20 mL) to yield a green-
brown product, which was washed with diethyl ether (20 mL)
and dried under vacuum. Yield: 28 mg (81%).
(b) [Ni(OAc)2] (20 mg, 0.113 mmol) was dissolved in dichlor-
omethane (10 mL) and acetone (20 mL) and treated with an aqueous
solution of KS2CNC4H6 (0.170 mmol). The reaction mixture was
stirred for 1 h and all solvent removed. The crude product was
dissolved in dichloromethane, and this solution was filtered through
diatomaceous earth (Celite) to remove KCl and excess ligand. All
solvent was again removed and ultrasonic trituration in diethyl ether
(20 mL) used to obtain a green-brown product. Yield: 30 mg (77%).
IR (solid state): 1625, 1497, 1434, 1351, 1326, 1187, 995, 930, 895, 755
cm-1.1HNMR(CDCl3):4.36(s,8H,NCH2); 5.91 (s, 4H, HCdCH)
ppm. MS (ES positive): m/z (abundance) 696 (100) 2[M]þ. Anal.
Calcd for C10H12N2NiS4 (Mw = 347.17): C, 34.6; H, 3.5; N, 8.1.
Found: C, 34.8; H, 3.5; N, 8.0.
[Ni{S2CN(CH2CHdCH2)2}(dppf)]PF6 (6). A solution of
[NiCl2(dppf)] (100 mg, 0.146 mmol) in acetone (20 mL) and
dichloromethane (10 mL) was treated with 1.5 equiv of KS2CN-
(CH2CHdCH2)2 and NH4PF6 (48 mg, 0.295 mmol) in water
(5 mL), and the reaction mixture was stirred for 30 min. All
solvent was removed, the residue was dissolved in the minimum
volume of dichloromethane, and this solution was filtered
through diatomaceous earth (Celite) to remove KCl, excess
NH4PF6, and ligand. All solvent was again removed, petroleum
ether (30 mL) was added, and the solid was triturated ultra-
sonically. The orange product was washed with water (10 mL)
and petroleum ether (10 mL) and dried under vacuum. Yield:
130 mg (96%). IR (solid state): 1528, 1500, 1481, 1434, 1240,
1164, 1094, 1025, 976, 932, 830 (νPF), 742, 697 cm-1 31P NMR
.
(d6-acetone): 31.1 (s, dppp). 1H NMR (d6-acetone): 4.25 (d, 4H,
NCH2, JHH = 6.0 Hz); 4.59, 4.69 (s(br) ꢀ 2, 2 ꢀ 4H, C5H4); 5.23
(d, 2H, dCHA, JHH = 17.2 Hz); 5.29 (d, 2H, dCHB, JHH = 10.0
Hz); 5.73 (m, 2H, dCHC); 7.35-7.96 (m, 20H, C6H5) ppm. MS
(ES positive): m/z (abundance) 785 (100) [M]þ. Anal. Calcd for
C41H38F6FeNNiP3S2 (Mw = 930.33): C, 52.9; H, 4.1; N, 1.5.
Found: C, 52.8; H, 4.0; N, 1.5.
[Pd{S2CN(CH2CHdCH2)2}(dppf)]PF6 (7). A solution of
[PdCl2(dppf)] (50 mg, 0.068 mmol) in acetone (20 mL) and
dichloromethane (10 mL) was treated with 1.5 equiv of KS2CN-
(CH2CHdCH2)2 and NH4PF6 (22.4 mg, 0.137 mmol) in water
(5 mL), and the reaction mixture was stirred for 30 min. All
solvent was removed, the residue was dissolved in the minimum
volume of dichloromethane, and this solution was filtered
through diatomaceous earth (Celite) to remove KCl, excess
NH4PF6, and ligand. All solvent was again removed, petroleum
ether (30 mL) was added, and the solid was triturated ultra-
sonically. The orange product was washed with water (10 mL)
and petroleum ether (10 mL) and dried under vacuum. Yield: 60
mg (90%). IR (solid state): 1522, 1482, 1436, 1309, 1243, 1168,
1096, 997, 984, 830 (νPF), 757, 742, 698 cm-1 31P NMR (d6-
.
acetone): 32.3 (dppf). 1H NMR (d6-acetone): 4.33 (d, 4H,
NCH2,, JHH = 6.0 Hz); 4.59, 4.74 (s(br) ꢀ 2, 2 ꢀ 4H, C5H4);
5.27 (d, 2H, dCHA, JHH = 17.2 Hz); 5.31 (d, 2H, dCHB, JHH
=
10.5 Hz); 5.77 (m, 2H, dCHC); 7.59-7.82 (m, 20H, C6H5) ppm.
MS (ES positive): m/z (abundance) 832 (100) [M]þ. Anal. Calcd
for C41H38F6FeNP3S2 (Mw = 978.06): C, 50.3; H, 3.9; N, 1.4.
Found: C, 50.4; H, 4.0; N, 1.5.
[Pt{S2CN(CH2CHdCH2)2}(dppf)]PF6 (8). A solution of
[PtCl2(dppf)] (100 mg, 0.122 mmol) in acetone (20 mL) and
dichloromethane (10 mL) was treated with 1.5 equiv of KS2CN-
(CH2CHdCH2)2 and NH4PF6 (40 mg, 0.245 mmol) in water
(5 mL), and the reaction mixture was stirred for 30 min. All solvent
was removed, the residue was dissolved in the minimum volume
of dichloromethane, and this solution was filtered through
diatomaceous earth (Celite) to remove KCl, excess NH4PF6,
and ligand. All solvent was again removed, petroleum ether
(30 mL) was added, and the solid was triturated ultrasonically.
The orange product was washed with water (10 mL) and petro-
leum ether (10 mL) and dried under vacuum. Yield: 125 mg
(96%). IR (solid state): 1528, 1483, 1436, 1411, 1245, 1194, 1168,
[Pd(C,N-CH2C6H4NMe2)(S2CNC4H6)] (13). (a) Compound
9 (40 mg, 0.097 mmol) and [Ru(dCHPh)Cl2(SIMes)(PCy3)] (4.1
mg, 0.005 mmol) were dissolved in dry, degassed dichloromethane
(20 mL), and this solution was stirred for 2 h. All solvent was then
removed, and the residue was triturated in diethyl ether (20 mL) to
yield a pale brown product, which was washed with petroleum
ether (20 mL) and dried under vacuum. Yield: 26 mg (70%).
(b) The same procedure as for 12 was employed using [Pd(C,N-
CH2C6H4NMe2)Cl]2 (20 mg, 0.036 mmol) and KS2CNC4H6 (0.109
mmol) with trituration in petroleum ether (20 mL) to yield a pale
brown product. Yield: 19 mg (69%). IR (solid state): 1577, 1501,
1449, 1354, 1188, 1105, 1045, 1027, 989, 929, 869, 849, 737 cm-1. 1H
NMR (CDCl3): 2.94 (s, 6H, NMe2); 4.03 (s, 2H, CH2Pd); 4.56 (d,
4H, NCH2, JHH = 13.5 Hz); 5.97 (m, 2H, HCdCH); 6.94-7.04 (m,
4H, C6H4) ppm. MS (ES positive): m/z(abundance) 385 (100) [M]þ.
Anal. Calcd for C14H18N2PdS2 (Mw = 384.86): C, 43.7; H, 4.7; N,
7.3. Found: C, 43.8; H, 4.7; N, 7.2.
1098, 1026, 997, 942, 829 (νPF), 757, 699, 690 cm-1 31P NMR
.
(CDCl3): 15.9 (dppf, JPtP = 3367 Hz). 1H NMR (CDCl3): 4.11
(d, 4H, NCH2, JHH = 6.2 Hz); 4.41, 4.60 (s(br) ꢀ 2, 2 ꢀ 4H,
C5H4); 5.24 (d, 2H, dCHA, JHH = 17.1 Hz); 5.34 (d, 2H, dCHB,
JHH = 10.0 Hz); 5.67 (m, 2H, dCHC); 7.49-7.69 (m, 20H,
C6H5) ppm. MS (ES positive): m/z (abundance) 921 (100) [M]þ.
Anal. Calcd for C41H38F6FeNP3PtS2 (Mw = 1066.71): C, 46.2;
H, 3.6; N, 1.3. Found: C, 46.0; H, 3.6; N, 1.3.
[Co(S2CNC4H6)3] (14). [Co(O2CMe)2] 4H2O (100 mg, 0.401
3
[Pd(C,N-CH2C6H4NMe2){S2CN(CH2CHdCH2)2}] (9).
A
mmol) was dissolved in water (20 mL) and treated with an aqueous
solution of KS2CNC4H6 (1.606 mmol). The reaction mixture was
stirred for 3 h and all solvent removed. The crude product was
dissolved in dichloromethane, and this solution was filtered through
diatomaceous earth (Celite). All solvent was again removed and
solution of [Pd(C,N-CH2C6H4NMe2)Cl]2 (200 mg, 0.362 mmol)
in acetone (20 mL) and dichloromethane (10 mL) was treated
with 3 equiv of KS2CN(CH2CHdCH2)2, and the reaction
mixture was stirred for 30 min. All solvent was removed, the

2556 Organometallics, Vol. 29, No. 11, 2010
Naeem et al.
ultrasonic trituration in diethyl ether (20 mL) used to obtain a green
product. Yield: 192 mg (97%). IR (solid state): 1572, 1475, 1428,
1351, 1193, 1171, 1102, 1008, 990, 930, 761 cm-1. 1H NMR
(CDCl3): 4.48 (s(br), 12H, NCH2); 5.91 (s(br), 6H, HCdCH) ppm.
MS (ES positive): m/z (abundance) 1005 (65) [2 M þ Na]þ, 514 (4)
[M þ Na]þ. Anal. Calcd for C15H18CoN3S6 (Mw = 491.65): C,
36.6; H, 3.7; N, 8.6. Found: C, 36.6; H, 3.7; N, 8.5.
[Ni(S2CNC4H6)(dppp)]PF6 (15). (a) Compound 5 (40 mg,
0.051 mmol) and [Ru(dCHPh)Cl2(SIMes)(PCy3)] (4.3 mg, 0.005
mmol) were dissolved in dry, degassed dichloromethane (20 mL),
and this solution was stirred for 24 h. All solvent was then removed,
and the residue was triturated in diethyl ether (20 mL) to yield
a green-brown product, which was washed with diethyl ether
(20 mL) and dried under vacuum. Yield: 26 mg (67%).
(b) [NiCl2(dppp)] (20 mg, 0.037 mmol) was dissolved in
dichloromethane (10 mL) and acetone (20 mL) and treated with
an aqueous solution of KS2CNC4H6 (0.056 mmol) followed by
NH4PF6 (12 mg, 0.074 mmol) in water (0.5 mL). The reaction
mixture was stirred for 1 h and all solvent removed. The crude
product was dissolved in dichloromethane, and this solution
was filtered through diatomaceous earth (Celite) to remove KCl
and excess ligand. All solvent was again removed and ultrasonic
trituration in diethyl ether (20 mL) used to obtain a green-brown
product. Yield: 26 mg (92%). IR (solid state): 1631, 1522, 1485,
degassed dichloromethane (20 mL), and the mixture was stirred
for 24 h. All solvent was then removed, and the residue was
triturated in diethyl ether (20 mL) to yield a colorless product,
which was washed with diethyl ether (20 mL) and dried under
vacuum. Yield: 34 mg (88%).
(b) The same procedure as for 13 was employed using
[Ru(CHdCHC6H4Me-4)Cl(CO)(BTD)(CO)(PPh3)2] (20 mg,
0.021 mmol) and KS2CNC4H6 (0.032 mmol) to give a colorless
product. Yield: 10 mg (52%). IR (solid state): 1912 (νCO), 1477,
1355, 1266, 1185, 1032, 933, 851, 832 cm-1 31P NMR (CDCl3):
.
39.5 (s, PPh3). 1H NMR (CDCl3): 2.25 (s, 3H, CCH3); 3.50, 3.77
(s(br) ꢀ 2, 2 ꢀ 2H, NCH2); 5.58 (d, 1H, Hβ, JHH = 16.7 Hz); 5.62
(s, 2H, HCdCH); 6.45, 6.84 (AB, 4H, C6H4, JAB = 7.9 Hz);
7.28-7.33, 7.57-7.62 (m ꢀ 2, 30H, C6H5); 7.77 (dt, 1H, HR,
JHH = 16.7 Hz, JHP = 3.2 Hz) ppm. MS (ES positive) m/z
(abundance) 915 (8) [M]þ; 798 (62) [M - alkenyl]þ. Anal. Calcd
for C51H45NOP2RuS2 CH2Cl2 (Mw = 999.99): C, 62.5; H, 4.7;
3
N, 1.4. Found: C, 62.7; H, 4.7; N, 1.7.
Crystallography. Single crystals of complex 3 were grown by
slow diffusion of ethanol into a dichloromethane solution of the
compound.
Crystal Data for 3: [C53H49NOP2RuS2] 2CH2Cl2, Mw =
1027.99, triclinic, P1 (No. 2), a=11.9308(4) A, b=13.4909(4)
A, c = 17.5672(5) A, R = 109.806(3)°, β = 109.393(3)°, γ =
3
1452, 1435, 1355, 1264, 1184, 1160, 1100, 998, 972, 931, 831 (νPF
)
93.684(2)°, V = 2459.09(15) A3, Z = 2, Dc = 1.388 g cm-3
,
1
cm-1
.
31P NMR (CDCl3): 12.5 (s, dppp). H NMR (CDCl3):
μ(Cu KR)=5.290 mm-1, T=173 K, pale yellow needles, Oxford
Diffraction Xcalibur PX Ultra diffractometer; 9569 indepen-
dent measured reflections (Rint = 0.0268), F2 refinement, R1-
(obsd)=0.0303, wR2(all)=0.0807, 8384 independent observed
absorption-corrected reflections (|Fo| > 4σ(|Fo|), 2θmax=145°),
583 parameters. CCDC 768226.
2.19 (m, 2H, dppp-CCH2C); 2.70 (m, 4H, dppp-PCH2); 4.33
(s(br), 4H, NCH2); 5.89 (s, 2H, HCdCH); 7.43-7.63 (m, 20H,
C6H5) ppm. MS (ES positive): m/z (abundance) 614 (100) [M]þ.
Anal. Calcd for C32H32F6NNiP3S2 (Mw = 760.34): C, 50.6; H,
4.2; N, 1.8. Found: C, 50.7; H, 4.3; N, 1.9.
[Pt(S2CNC4H6)(dppf)]PF6 (16). (a) Compound 8 (40 mg,
0.038 mmol) and [Ru(dCHPh)Cl2(SIMes)(PCy3)] (3.2 mg,
0.004 mmol) were dissolved in dry, degassed dichloromethane
(20 mL), and the mixture was stirred for 24 h. All solvent was
then removed, and the residue was triturated in diethyl ether (20
mL) to yield a yellow product, which was washed with diethyl
ether (20 mL) and dried under vacuum. Yield: 35 mg (89%).
(b) Thesameprocedureasfor15 wasemployedusing[PtCl2(dppf)]
(20 mg, 0.024 mmol), KS2CNC4H6 (0.036 mmol), and NH4PF6
(8 mg, 0.049 mmol) to give a yellow product. Yield: 22 mg (88%). IR
(solid state): 1632, 1523, 1482, 1453, 1436, 1354, 1307, 1265, 1169,
Single crystals of complex 5 were grown by slow diffusion of
diethyl ether into a dichloromethane solution of the compound.
Crystal Data for 5: [C34H36NNiP2S2](PF6) C4H10O, Mw =
3
862.50, monoclinic, C2/c (No. 15), a = 21.0143(5) A, b =
10.6307(3) A, c=36.8148(15) A, β=97.725(3)°, V=8149.7(5)
A3, Z=8, Dc=1.406 g cm-3, μ(Mo KR)=0.755 mm-1, T=173 K,
orange blocks, Oxford Diffraction Xcalibur 3 diffractometer;
12382 independent measured reflections (Rint = 0.0324), F2
refinement, R1(obsd)=0.1071, wR2(all)=0.2567, 9319 indepen-
dent observed absorption-corrected reflections (|Fo| > 4σ(|Fo|),
2θmax=64°), 469 parameters. CCDC 768227.
1098, 1035, 998, 929, 830 (νPF) cm-1
.
31P NMR (CDCl3): 15.9 (s,
Single crystals of complex 15 were grown by slow diffusion of
ethanol into a chloroform solution of the compound.
Crystal Data for 15: [C32H32NNiP2S2](PF6) 1.75CHCl3,
dppf, JPtP =3374Hz).1HNMR(CDCl3):4.42(s,4Hþ 4H, C5H4 þ
NCH2); 4.61 (s, 4H, C5H4); 5.93 (s, 2H, HCdCH); 7.50-7.71 (m,
20H, C6H5) ppm. MS (ES positive): m/z (abundance) 893 (100)
[M]þ. Anal. Calcd for C39H34F6FeNP3PtS2 (Mw = 1038.66): C,
45.1; H, 3.3; N, 1.4. Found: C, 45.0; H, 3.4; N, 1.3.
3
M
w = 969.22, triclinic, P1 (No. 2), a = 13.7545(4) A, b =
15.2829(3) A, c = 20.3044(4) A, R = 92.0086(14)°, β =
102.8560(19)°, γ = 98.9786(18)°, V = 4099.38(17) A3, Z =
4 (two independent complexes), Dc=1.570 g cm-3, μ(Mo
KR)=1.089 mm-1, T = 173 K, orange prisms, Oxford Dif-
fraction Xcalibur 3 diffractometer; 24 642 independent mea-
sured reflections (Rint=0.0173), F2 refinement, R1(obs)=0.0381,
wR2(all) = 0.0980, 16 353 independent observed absorption-
corrected reflections (|Fo|>4σ(|Fo|), 2θmax = 64°), 1064 para-
meters. CCDC 768228.
[Ru(S2CNC4H6)(dppm)2]PF6 (17). (a) Compound 1 (40 mg,
0.034 mmol) and [Ru(dCHPh)Cl2(SIMes)(PCy3)] (2.9 mg,
0.003 mmol) were dissolved in dry, degassed dichloromethane
(20 mL), and the mixture was stirred for 24 h. All solvent was
then removed, and the residue was triturated in diethyl ether (20
mL) to yield a colorless product, which was washed with diethyl
ether (20 mL) and dried under vacuum. Yield: 34 mg (86%).
(b) The same procedure as for 15 was employed using
cis-[RuCl2(dppm)2] (20 mg, 0.021 mmol), KS2CNC4H6 (0.032
mmol), and NH4PF6 (7 mg, 0.043 mmol) to give a colorless
product. Yield: 19 mg (78%). IR (solid state): 1477, 1449, 1434,
The structures were refined using the SHELXTL and
SHELX-97 program systems.37 Further details can be found
in the Supporting Information.
1355, 1312, 1190, 1097, 1028, 999, 932, 835 (νPF) cm-1 31P
.
Acknowledgment. We gratefully acknowledge Johnson
Matthey Ltd for a generous loan of ruthenium trichloride.
NMR (d6-acetone): -19.5, -3.9 (tv ꢀ 2, dppm, JHH = 34.5 Hz).
1H NMR (d6-acetone): 3.91, 4.36 (d ꢀ 2, 2 ꢀ 2H, NCH2, JHH
=
14.9 Hz); 4.74, 4.35 (m ꢀ 2, 2 ꢀ 2H, PCH2P); 5.96 (s, 2H,
HCdCH); 6.71, 7.02, 7.20-7.39, 7.42-7.59, 7.90 (m ꢀ 5, 40H,
C6H5) ppm. MS (ES positive): m/z (abundance) 1014 (100) [M]þ.
Anal. Calcd for C55H50F6NP5RuS2 (Mw = 1159.05): C, 57.0; H,
4.4; N, 1.2. Found: C, 57.0; H, 4.3; N, 1.2.
Supporting Information Available: Text, figures, and CIF files
giving crystallographic data for the structures of 3, 5, and 15.
This material is available free of charge via the Internet at http://
pubs.acs.org.
[Ru(CHdCHC6H4Me-4)(S2CNC4H6)(CO)(PPh3)2] (18). (a)
Compound 3 (40 mg, 0.042 mmol) and [Ru(dCHPh)Cl2-
(SIMes)(PCy3)] (3.6 mg, 0.004 mmol) were dissolved in dry,
(37) Sheldrick, G. SHELXTL PC version 5.1; Bruker AXS, Madison, WI,
1997. Sheldrick, G. SHELX-97; Institut Anorganische Chemie, Tammannstr. 4,
€
D37077 Gottingen, Germany, 1998.