Thiocarbamoyl complexes of ruthenium(II), rhodium(III), and iridium(III)

Article abstract of DOI:10.1021/om050514c

The reaction of [Ru(CO)₂(PPh₃)₃] (1) or [Ru(η²-CS₂)(CO)₂(PPh₃) ₂] with N,N-dimethylthio-carbamoyl chloride provides [Ru(η²-SCNMe₂)(CO)₂(PPh₂) ₂]Cl (2·C1), thermolysis of which yields [Ru(η ²-SCNMe₂)Cl(CO)(PPh₂)₂] (3). Treatment of 2·C1 with NaBH₄ leads to carbonyl substitution and formation of [RuH(η²-SCNMe₂)(CO)(PPh ₃)₂] (4), which is readily converted to an alternative isomer of [RuCl(η²-SCNMe₂)(CO)(PPh₃) ₂] (5, Cl trans to S) on treatment with hydrochloric acid. The reaction of 2·PF₆ with Na[S₂CNMe₂] gives [Ru(η²-SCNMe₂)(k²-S₂CNMe ₂)(CO)(PPh₃)] (6), which is also the product of the reaction of 1 with {Me₂NC(S)}₂S. [Ru(η²- SCNMe₂)(CNC₆H₃Me₂-2,6)(CO)(PPh ₃)₂]Cl (7·C1) is isolated from the reaction between [Ru(CNC₆H₃Me₂-2,6)(CO)(PPh₃) ₃] and Me₂NC(S)Cl. [RhCl(CO)(PPh₃) ₂], [RhCl(PPh₃)₃], or [Rh-(cod)(PPh ₃)₂]PF₆ (cod = cycloocta-l,5-diene) react with N,N-dimethylthiocarbamoyl chloride to provide [Rh(η²-SCNMe ₂)Cl₂(PPh₃)₂] (8), while [RhCl(CS)(PPh₃)₂] provides the metallacyclic complex [Rh{k²-=C(NMe₂)SC(=S)}Cl₂(PPh₃) ₂] (9). The complexes [IrCl(CA)(PPh₃)₂] react with Me₂NC(=S)Cl to give the salts [Ir(η²-SCNMe ₂)Cl(CA)(PPh₃)₂]Cl (A = O 10·C1, S 12·C1). Photolysis of 10·C1 or treatment with dimethylamine provides the neutral complex [Ir(η²-SCNMe₂)Cl ₂(PPh₃)₂] (11), which may be obtained directly by reaction of [IrCl(N₂)(PPh₃)₂] with Me ₂NC(S)Cl. Treatment of 10·C1 with NaBH₄ or NaOEt proceeds via attack at the CO ligand to form [Ir(η²-SCNMe ₂){η¹-C(=O)H}Cl(PPh₃)₂] (13) or [Ir(η²-SCNMe₂){η¹-C(=O)OEt}-Cl(PPh ₃)₂] (14), respectively.

Full text of DOI:10.1021/om050514c

5342
Organometallics 2005, 24, 5342-5355
Thiocarbamoyl Complexes of Ruthenium(II),
Rhodium(III), and Iridium(III)
Anthony F. Hill,*,† Derek A. Tocher,‡ Andrew J. P. White,§
David J. Williams,§ and James D. E. T. Wilton-Ely*,‡
Research School of Chemistry, Institute of Advanced Studies, Australian National University,
Canberra, Australian Capital Territory, Australia, Department of Chemistry, University
College London, London WC1H 0AJ, U.K., and Department of Chemistry, Imperial College
London, London SW7 2AZ, U.K.
Received June 22, 2005
The reaction of [Ru(CO)2(PPh3)3] (1) or [Ru(η2-CS2)(CO)2(PPh3)2] with N,N-dimethylthio-
carbamoyl chloride provides [Ru(η2-SCNMe2)(CO)2(PPh2)2]Cl (2‚Cl), thermolysis of which
yields [Ru(η2-SCNMe2)Cl(CO)(PPh2)2] (3). Treatment of 2‚Cl with NaBH4 leads to carbonyl
substitution and formation of [RuH(η2-SCNMe2)(CO)(PPh3)2] (4), which is readily converted
to an alternative isomer of [RuCl(η2-SCNMe2)(CO)(PPh3)2] (5, Cl trans to S) on treatment
with hydrochloric acid. The reaction of 2‚PF6 with Na[S2CNMe2] gives [Ru(η2-SCNMe2)(κ2-
S2CNMe2)(CO)(PPh3)] (6), which is also the product of the reaction of 1 with {Me2NC(S)}2S.
[Ru(η2-SCNMe2)(CNC6H3Me2-2,6)(CO)(PPh3)2]Cl (7‚Cl) is isolated from the reaction between
[Ru(CNC6H3Me2-2,6)(CO)(PPh3)3] and Me2NC(S)Cl. [RhCl(CO)(PPh3)2], [RhCl(PPh3)3], or [Rh-
(cod)(PPh3)2]PF6 (cod ) cycloocta-1,5-diene) react with N,N-dimethylthiocarbamoyl chloride
to provide [Rh(η2-SCNMe2)Cl2(PPh3)2] (8), while [RhCl(CS)(PPh3)2] provides the metallacyclic
complex [Rh{κ2-dC(NMe2)SC(dS)}Cl2(PPh3)2] (9). The complexes [IrCl(CA)(PPh3)2] react with
Me2NC(dS)Cl to give the salts [Ir(η2-SCNMe2)Cl(CA)(PPh3)2]Cl (A ) O 10‚Cl, S 12‚Cl).
Photolysis of 10‚Cl or treatment with dimethylamine provides the neutral complex [Ir(η2-
SCNMe2)Cl2(PPh3)2] (11), which may be obtained directly by reaction of [IrCl(N2)(PPh3)2]
with Me2NC(S)Cl. Treatment of 10‚Cl with NaBH4 or NaOEt proceeds via attack at the CO
ligand to form [Ir(η2-SCNMe2){η1-C(dO)H}Cl(PPh3)2] (13) or [Ir(η2-SCNMe2){η1-C(dO)OEt}-
Cl(PPh3)2] (14), respectively.
Introduction
selenium transfer agents in combination with alkylidyne
complexes. Thioaroyls have been implicated in the
formation of dithiocarboxylatoalkylidene7 and dithio-
carboxylate complexes,6,8-11 and conversely a phospho-
nio-stabilized example has arisen from the abstraction
We have recently been concerned with the organo-
metallic chemistry of what might be termed heteroa-
cyls:1 analogues of the familiar acyl ligand wherein the
oxygen atom is replaced by a heavier chalcogen and/or
the hydrocarbyl substituent is replaced by a heteroatom
group (Scheme 1). The oldest members of this series are
carbamoyl and thiocarbamoyl ligands, the former most
commonly arising from the reactions of metal carbonyls
with amines or amides.2 For thiocarbamoyls, a range
of synthetic strategies is available (Scheme 2) with
varying degrees of general applicability. Mononuclear
chalcoacyls (i.e., LnMC(dS)R; R ) hydrocarbyl) are the
least widely studied, and by far the majority of these
involve metals from groups 8 and 9,3-5 although we have
obtained thioaroyl6 and very recently selenoaroyl1e
complexes of group 6 metals via single-atom sulfur or
(3) (a) Roper, W. R.; Town, K. G. Chem. Commun. 1977, 781. (b)
Collins, T. J.; Roper, W. R. Chem. Commun. 1976, 1044. (c) Collins, T.
J.; Roper, W. R. Chem. Commun. 1977, 901. (d) Collins, T. J.; Roper,
W. R. J. Organomet. Chem. 1978, 159, 73. (e) Clark, G. R.; Collins, T.
J.; Marsden, K.; Roper, W. R. J. Organomet. Chem. 1983, 259, 215. (f)
Clark, G. R.; Collins, T. J.; Marsden, K.; Roper, W. R. J. Organomet.
Chem. 1978, 157, 23. (g) Clark, G. R.; Collins, T. J.; Hall, D.; James,
S. M.; Roper, W. R. J. Organomet. Chem. 1977, 141, C5. (h) Rickard,
C. E. F.; Roper, W. R.; Woodgate, S. D.; Wright, L. J. J. Organomet.
Chem. 2001, 623, 109. (i) Rickard, C. E. F.; Roper, W. R.; Woodgate,
S. D.; Wright, L. J. J. Organomet. Chem. 2000, 607, 27. (j) Elliott, G.
P.; Roper, W. R. J. Organomet. Chem. 1983, 250, C5. (k) Elliott, G. P.;
Roper, W. R.; Waters, J. M. Chem. Commun. 1982, 811. (l) Clark, G.
R.; Collins, T. J.; Marsden, K.; Roper, W. R. J. Organomet. Chem. 1978,
157, C23.
(4) Drews, R.; Edelmann, F.; Behrens, U. J. Organomet. Chem. 1986,
315, 369.
* To whom correspondence should be addressed. E-mail: a.hill@
anu.edu.au; j.wilton-ely@ucl.ac.uk.
(5) (a) Bedford, R. B.; Hill, A. F.; White, A. J. P.; Williams, D. J.
Angew. Chem., Int. Ed. Engl. 1996, 35, 95. (b) Hill, A. F.; White, A. J.
P.; Williams, D. J.; Wilton-Ely, J. D. E. T. Organometallics 1998, 17,
4249. (c) Hill, A. F.; Wilton-Ely, J. D. E. T. J. Chem. Soc., Dalton Trans.
1998, 3501. (d) Cannadine, J. C.; Hector, A.; Hill, A. F. Organometallics
1992, 11, 2323.
† Australian National University.
‡ University College London.
§ Imperial College London.
(1) (a) Anderson, S.; Hill, A. F.; Ng, Y. T. Organometallics 2000,
19, 15. (b) Anderson, S.; Cook, D. J.; Hill, A. F. Organometallics 2001,
20, 2468. (c) Cook, D. J.; Hill, A. F. Organometallics 2003, 22, 3502.
(d) Anderson, A.; Berridge, T. E.; Hill, A. F.; Ng, Y. T.; White, A. J. P.;
Williams, D. J. Organometallics 2004, 23, 2686. (e) Caldwell, L. M.;
Hill, A. F.; Willis, A. C. Chem. Commun. 2005, 221.
(2) Angelici, R. J. Acc. Chem. Res. 1972, 18, 335.
(6) Cook, D. J.; Hill, A. F. Chem. Commun. 1997, 955.
(7) Anderson, S.; Cook, D. J.; Hill, A. F.; Malget, J. M. Organome-
tallics 2004, 23, 2552.
(8) (a) Hill, A. F.; Malget, J. M. J. Chem. Soc., Dalton Trans. 1997,
2003. (b) Anderson, S.; Hill, A. F.; Nasir, B. A. Organometallics 1995,
14, 2987.
10.1021/om050514c CCC: $30.25 © 2005 American Chemical Society
Publication on Web 09/28/2005

Thiocarbamoyl Complexes of Ru(II), Rh(III), Ir(III)
Organometallics, Vol. 24, No. 22, 2005 5343
Scheme 1. Inter-relationship of Heteroacyl
Coordination Modes
Scheme 3a
Scheme 2. Synthetic Approaches to
Thiocarbamoyl Complexes
a L ) PPh3. (i) hν, Ph2CdO, CHCl3; (ii) XC(S)NMe2, X ) Cl,
PhNC(S)NMe2; (iii) NaAH, A ) S, Se, Te.
bridges the metal-metal bond. The sporadic nature of
research into chalcoacyls has provided few situations
where comparisons of structural and spectroscopic data
are possible for a wide cohort of variations with all other
factors held constant. The existence of a number of
suitable species within groups 8 and 9 provides a basis
for our investigations in this area. We have now
addressed the synthesis of thiocarbamoyl (thiocarboxa-
mido) complexes of ruthenium, iridium, and rhodium,
some of which (or their isomers) were previously known
but lacked structural and/or spectroscopic data.
Results and Discussion
Ruthenium Complexes. Previous approaches to the
synthesis of thiocarbamoyl complexes of ruthenium
(Scheme 3) have involved (i) photolytic sulfur abstrac-
tion from dithiocarbamato ligands;18 oxidative addition
of Me2NC(dS)Cl or PhN{C(dS)NMe2}2 to [RuCl(NO)-
(PPh3)2];19 or nucleophilic attack by hydrosulfide on a
chloroaminocarbene complex [RuCl2{dC(NMe2)Cl}(CO)-
(PPh3)2].20 This last approach offers the advantage that
it could be extended to all the heavier chalcogens to
provide the first complete series of complexes [Ru(η2-
ACNMe2)Cl(CO)(PPh3)2] (A ) S, Se, Te) and mirrors the
reactions of the chlorotoluidene complex [OsCl2(dCClR)-
(CO)(PPh3)2] (R ) C6H4Me-4), which similarly provided
the first (and only) complete series of chalcoaroyls [Os-
(η2-ACR)Cl(CO)(PPh3)2].21 Mononuclear carbamoyl com-
plexes of ruthenium have a long if somewhat sparse
of sulfur from a dithiobenzoate by trimethylphosphine.12
Bimetallic complexes with thioacyl,4,8b,13-16 selenoa-
cyl,13,14 and recently telluroacyl17 ligands have been
reported wherein the C-chalcogen unit transversely
(15) (a) Umland, H.; Behrens, U. J. Organomet. Chem. 1985, 287,
109. (b) Ziegler, W.; Umland, H.; Behrens, U. J. Organomet. Chem.
1988, 344, 235.
(16) (a) Seyferth, D.; Womack, G. B.; Cowie, M.; Hames, B. W.
Organometallics 1983, 2, 1696. (b) Seyferth, D.; Womack, G. B.;
Gallagher, M. K.; Cowie, M.; Hames, B. W.; Fackler, J. P. Jnr; Mazany,
A. M. Organometallics, 1987, 6, 283.
(17) Hulkes, A. J.; Hill, A. F.; Nasir, B. A.; White, A. J. P.; Williams,
D. J. Organometallics 2004, 23, 679.
(18) Miessler, G. L.; Pignolet, L. H. Inorg. Chem. 1979, 18, 210.
(19) Dean, W. K. J. Organomet. Chem. 1980, 190, 353.
(20) Roper, W. R.; Wright, A. H. J. Organomet. Chem. 1982, 233,
C59.
(21) (a) Clark, G. R.; Marsden, K.; Roper, W. R.; Wright, L. J. J.
Am. Chem. Soc. 1980, 102, 6570. (b) Roper, W. R. J. Organomet. Chem.
1986, 300, 167.
(9) Gill, D. S.; Green, M.; Marsden, K.; Moore, K.; Orpen, A. G.;
Stone, F. G. A.; Williams, I. D.; Woodward, P. J. Chem. Soc., Dalton
Trans. 1984, 1343.
(10) Mercando, L. A.; Handwerker, B. M.; MacMillan, H. J.; Geoffroy,
G. L.; Rheingold, A. L.; Owens-Waltermire, B. E. Organometallics 1993,
12, 1559.
(11) Kreissl, F. R.; Ullrich, N. J. Organomet. Chem. 1989, 361, C30.
(12) Kreissl, F. R.; Ullrich, N.; Wirsing, A.; Thewalt, U. Organome-
tallics 1991, 10, 3275.
(13) (a) Byrne, P. G.; Garcia, M. E.; Jeffery, J. C.; Sherwood, P.;
Stone, F. G. A. J. Chem. Soc., Dalton Trans. 1987, 1215. (b) Ellis, D.
D.; Farmer, J. M.; Malget, J. M.; Mullica, D. F.; Stone, F. G. A.
Organometallics 1998, 17, 5540.
(14) Hill, A. F.; Nasir, B. A.; Stone, F. G. A. Polyhedron 1989, 8,
179.

5344 Organometallics, Vol. 24, No. 22, 2005
Hill et al.
Scheme 4a
Chart 1. Canonical Forms for Dihapto
Thiocarbamoyl Coordination
reactions with electrophiles, the product of this complex
with Me2NC(S)Cl is also 2‚Cl. It is not clear whether
this involves a simple dissociation of the CS2 ligand or
if initial electrophilic attack is followed by extrusion of
CS2 from a metallacyclic dithiocarbamatothioacyl since
no intermediates were detected. Given that the CS2
ligand in the precursor is not considered labile under
these conditions, we are inclined to suspect the latter
process and note that one example of such a metalla-
cycle has been identified previously, albeit in a bimetal-
lic context.30 The presence of the thiocarbamoyl group
in 2+ is indicated by the appearance of absorptions at
1599 (νCN), 1219 and 916 (νCS) cm-1 in the infrared
spectrum (Nujol). From a comparison of these data with
those for a range of thiocarbamoyl complexes of molyb-
denum1 and the iridium complex [Ir(η2-SCNMe2)Cl(CO)-
(PPh3)2]+ (1615, 995, 915 cm-1, vide infra)19 it may be
surmised that the thiocarbamoyl ligand adopts a di-
hapto mode of coordination, with a noncoordinated
chloride counteranion. In contrast, the monohapto thio-
carbamoyl complex [Fe{C(dS)NHMe}(CO)2(η-C5H5)] is
reported to give rise to a νCS-associated absorption at
1158 cm-1 31
The νCO infrared absorptions at 2055 and
.
1995 cm-1 for the related dithiomethoxycarbonyl com-
plex [Ru(η2-SCSMe)(CO)2(PPh3)2]+ 29 also compare well
with those at 2052 and 1989 cm-1 (Nujol) for the
complex 2+. The geometry at ruthenium involves trans
phosphine ligands, as indicated by a singlet resonance
(δP ) 33.7) in the 31P{1H} NMR spectrum. The 13C{1H}
NMR spectrum shows three low-field resonances at-
a L ) PPh3, R ) C6H3Me2-2,6, (i) S(CSNMe2)2; (ii) ClC(S-
)NMe2; (iii) Na[S2CNMe2]; (iv) NaBH4; (v) HCl; (vi) EtOH, ∆.
history,22-27 which includes their implications in cata-
lytic processes26,27 and the structural characteriza-
tion of three examples.22a,26 The only mononuclear
ruthenium thiocarbamoyl complex to have been struc-
turally characterized, however, is the complex
[Ru(η2-SCNMe2)Cl(S2CNMe2)2].18
2
tributable to the thiocarbonyl carbon (δC ) 231.1, JCP
) 8.9 Hz) and the two chemically distinct carbonyl
1
ligands (δC ) 199.4, 199.9 ppm). In both the H (2.42,
The synthesis and reactivity of the new ruthenium
thiocarbamoyl complexes to be described in this paper
are summarized in Scheme 4. The reaction of [Ru(CO)2-
(PPh3)3]28 (1) with N,N-dimethylthiocarbamoyl chloride,
Me2NC(S)Cl, in dichloromethane or tetrahydrofuran
leads at room temperature to the formation of the salt
[Ru(η2-SCNMe2)(CO)2(PPh3)2]Cl (2‚Cl), which may be
isolated in yields of 90-95% by crystallization with
ethanol or hexane. Despite the propensity of the exo-
cyclic sulfur group of [Ru(η2-SCS)(CO)2(PPh3)2]29 for
2.83 ppm) and 13C{1H} (48.0, 49.1 ppm) NMR spectra,
the resonances associated with the methyl groups
indicate inequivalence, consistent with rotation around
the N-C bond being arrested by the partial multiple
character of this bond (Chart 1), a common observation
in carbamoyl chemistry and a recurrent feature of the
further complexes discussed below. The virtual triplet
resonances due to the ipso, ortho, and meta carbon
nuclei of the PPh3 ligands confirm the trans geometry
of the RuP2 unit in complex 2a+. The FAB mass
spectrum shows a molecular ion corresponding to [Ru-
(η2-SCNMe2)(CO)2(PPh3)2]+, with no peaks attributable
to [RuCl(η1-CSNMe2)(CO)(PPh3)2]. Spectroscopic data
associated with the metal complex are not affected by
metathesis of the counteranion, and the formulation was
subsequently confirmed by X-ray crystallography of the
hexafluorophosphate salt (2‚PF6) obtained as a chloro-
form monosolvate by diffusion of ethanol into a chloro-
form solution. The molecular structure of the cation 2+
is depicted in Figure 1 and approximates to a distorted
(22) (a) Wagner, H.; Jungbaur, A.; Thiele, G.; Behrens, H. Z.
Naturforsch. 1979, 34b, 1487. (b) Behrens, H.; Jungbaur, A. Z.
Naturforsch. 1979, 34b, 1477. (c) Jungbaur, A.; Behrens, H. Z.
Naturforsch. 1979, 34b, 1641.
(23) Nonoyama, M. Inorg. Chim. Acta 1986, 115, 169.
(24) Ishida, H.; Tanaka, H.; Tanaka, K.; Tanaka, T. Chem. Lett.
1987, 597.
(25) Ozawa, F.; Chikaoka, S.; Cao, X.; Yamamoto, A. J. Organomet.
Chem. 1992, 424, 173.
(26) Gargulak, J. D.; Gladfelter, W. L. Inorg. Chem. 1994, 33, 253.
(27) Tsuji, Y.; Ohsumi, T.; Kondo, T.; Watanabe, Y. J. Organomet.
Chem. 1986, 309, 333.
(28) Cavit, B. E.; Grundy, K. R.; Roper, W. R. Chem. Commun. 1972,
60.
(29) (a) Grundy, K. R.; Harris, R. O.; Roper, W. R. J. Organomet.
Chem. 1975, 90, C34. (b) Clark, G. R.; Collins, T. J.; James, S. M.;
Roper, W. R. J. Organomet. Chem. 1977, 125, C23. (c) Boniface, S. M.;
Clark, G. R. J. Organomet. Chem. 1980, 184, 125.
(30) Burgmayer, S. J. N.; Templeton, J. L. Inorg. Chem. 1986, 24,
3939.
(31) Busetto, L.; Graziani, M.; Belluco, U. Inorg. Chem. 1971, 10,
78.

Thiocarbamoyl Complexes of Ru(II), Rh(III), Ir(III)
Organometallics, Vol. 24, No. 22, 2005 5345
Table 1. IR Data for the Complexes
[Ru(L)(CO)2(PPh3)2]+a
L
νCO/cm-1
kCK/N m-1
ref
NO
2065, 2014
2055, 1995
1978, 2064
2048, 1988
2020, 1960
16.80
16.56
16.50
16.45
16.00
61
29b
62
SCSMe
NNPh
SCNMe2 (2+)
CPh
60
2
a kCK ) 2.0191 × 10-6 N m-1 × (ν1 + ν22).
angle of the thiocarbamoyl [C2-Ru-S1 42.45(15)°]. The
ruthenium carbonyl separations do however fall toward
the short end of the range (consistent with their thermal
inertness) despite the cationic charge on the complex,
and this might be indicative of a net donor role for the
bidentate thiocarbamoyl ligand. The bond lengths and
angles of the thiirene unit are very similar to those for
the related complex [Ru(η2-SCSMe)(CO)2(PPh3)2]+ (see
Table 1).7 The elongation of the Ru-C8 bond relative
to Ru-C6 might suggest that it is this carbonyl ligand
that is lost in subsequent reactions (e.g., with NaBH4
to form 4).
On heating 2‚Cl for 6 h in ethanol under reflux,
decarbonylation occurs to give the neutral species [Ru-
(η2-SCNMe2)Cl(CO)(PPh3)2] (3) in good yield. This com-
plex has been previously prepared by a different route.20
A more facile decarbonylation process has been seen to
ensue readily on reaction of [Ru(η2-CS2)(CO)2(PPh3)2]
with iodomethane to provide [Ru(η2-SCSMe)I(CO)-
(PPh3)2].29 That the solvent plays a part in this process
was clearly shown by the lack of any spectroscopic (IR)
change upon heating the salt 2‚Cl in refluxing tetrahy-
drofuran for 48 h. Pale yellow blocks of 3 suitable for
an X-ray study were obtained by diffusion of a chloro-
form solution of the complex into ethanol, and the
results of this study are summarized in Figure 2. As
with 2+, the distorted octahedral geometry at ruthenium
involves trans coordination of phosphine ligands with
the remaining ligands lying in the equatorial plane. The
complex displays cis-interligand angles in the range
88.44(10)° to 109.71(8)°, the larger of these lying in the
equatorial plane. The carbonyl-ruthenium separation
is shorter [1.828(10) Å] than those for 2+, consistent
with complex 3 being neutral. Again the thiocarbamoyl
unit is planar, indicating sp2 hybridization of the
nitrogen atom and a short C2-N3 bond length reflecting
multiple bond character. The dimensions of the thio-
carbamoyl ligand are also included in Table S1 for
comparison with those for 2+ and other ruthena- and
osmathiirenes.
Figure 1. Molecular structure of the cation [Ru(η2-
SCNMe2)(CO)2(PPh3)2]+ (2+) in a crystal of 2‚PF6‚CHCl3.
(Phenyl groups simplified, 50% displacement ellipsoids.)
Selected bond lengths (Å) and angles (deg): Ru-C6 )
1.884(6), Ru-C7 ) 1.919(6), Ru-C2 ) 2.047(5), Ru-P1 )
2.4003(16), Ru-P2 ) 2.4107(16), Ru-S1 ) 2.4547(19), S1-
C2 ) 1.674(5), C2-N3 ) 1.301(7), C6-Ru-C7 ) 96.6(2),
C6-Ru-C2 ) 107.2(2), C6-Ru-P1 ) 92.10(18), C7-Ru-
P1 ) 87.23(17), C2-Ru-P1 ) 90.10(16), C6-Ru-P2 )
92.55(18), C7-Ru-P2 ) 87.44(17), C2-Ru-P2 ) 93.14-
(16), C7-Ru-S1 ) 113.72(18), C2-Ru-S1 ) 42.45(15),
P1-Ru-S1 ) 88.25(6), P2-Ru-S1 ) 90.18(6), P1-Ru-
P2 ) 173.29(5), C7-Ru-C2 156.1(2), C6-Ru-S1 149.65-
(17), C2-S1-Ru ) 55.63(19), S1-C2-Ru ) 81.9(2), C2-
N3-C5 ) 122.9(5), C2-N3-C4 ) 121.7(5), C5-N3-C4 )
115.4(5).
octahedral geometry with the mutually trans phosphine
ligands displaying an angle of 173.29(5)° between
ruthenium-phosphorus vectors. The most informative
structural features are associated with the equatorial
plane containing carbonyl and thiocarbamoyl ligands.
The ruthenium atom, the carbonyl ligands, and the
heavy atoms of the thiocarbamoyl ligand are all ap-
proximately coplanar, consistent with electronic delo-
calization throughout the π-system involving these
atoms. The C2-N3 distance of 1.301(7) Å is typical of a
N(sp2)-C(sp2) bond involving conjugation, and the Ru-
C2 bond length of 2.047(5) Å suggests a degree of
multiple bond character. The carbon atom of bidentate
thioacyl ligands might be expected to show a modest
degree of π-acidity, while the sulfur would be expected
to have π-donor character. This appears to be reflected
in the difference between the ruthenium carbonyl bond
lengths, with that trans to the π-competitive thiocar-
bamoyl carbon [Ru-C7 1.919(6) Å] being somewhat
longer than that trans to the π-basic sulfur donor [Ru-
C6 1.884(6) Å]. These effects are presumably reduced
as a result of the requisite distortion from octahedral
geometry of C2, S1, C6, and C8 caused by the small bite
The reaction of 2‚Cl with an ethanolic solution of
sodium borohydride leads to a clean reaction, in which
the RuSC metallacycle is retained, that provides the
neutral complex [RuH(η2-SCNMe2)(CO)(PPh3)2] (4). The
formulation of this colorless compound rests on spec-
troscopic observations. The presence of a hydride ligand
is apparent as a triplet resonance (δH ) -14.30, JHP
)
1
22.1 Hz) in the H NMR spectrum due to coupling to
two mutually trans phosphorus nuclei, a geometry also
indicated by a singlet resonance (δP ) 48.9) in the 31P-
{1H} NMR spectrum. While 13C{1H} NMR data (δC
)
210.6, JCP ) 15.2 Hz) for the carbonyl ligand do not
exclude the possibility of an alternative trans-dicarbonyl
formulation ttt-[RuH{η1-C(dS)NMe2}(CO)2(PPh3)2], the
observation that the ν(CO) absorption at 1912 cm-1 in

5346 Organometallics, Vol. 24, No. 22, 2005
Hill et al.
cm-1, 20 cm-1 higher than for 3, suggesting an alterna-
tive isomer with the carbonyl ligand trans to the
thiocarbamoyl carbon. The crystal structure determi-
nation of 3 demonstrated the intuitive trans arrange-
ment for the thiocarbamoyl sulfur (π-donor) and carbo-
nyl (π-acid). The geometry of 5 would therefore appear
to have these atoms in a mutually cis arrangement. The
retention of the bidentate coordination mode for the
thiocarbamoyl ligand in this and the above reaction with
NaBH4 is noteworthy and indicates a considerable
preference for such coordination, at least for low-valent
(“soft”) ruthenium(II). The contrasting geometries of 3
and 5 further support the intermediacy of a formyl
complex in the reaction of 2+ with borohydride. Were
hydride addition to occur at a coordinatively unsatur-
ated intermediate (either from decarbonylation or mon-
odentate thiocarbamoyl coordination), the same regio-
chemistry would be expected for 4 as for 3. However,
direct addition of hydride to 2+ would be expected to
occur at the carbonyl ligand trans to the thiocarbamoyl
carbon. Loss of the remaining carbonyl ligand must
therefore be followed by a regioselective migration of
the hydride to the site adjacent to the thiocarbamoyl
carbon, consistent with the facility of Me2NC(S)H
elimination observed in the mass spectrum.
The reaction of 2‚PF6 with sodium dimethyldithio-
carbamate in refluxing ethanol resulted in the loss of a
carbonyl and one phosphine ligand to give [Ru(η2-
SCNMe2)(κ2-S2CNMe2)(CO)(PPh3)] (6). This neutral com-
plex exhibits a single νCO absorption at 1909 cm-1
(CH2Cl2) in addition to absorbances at 1553, 1529 (νNC),
1232 and 922 (νCS) cm-1 typical of the dihapto thiocar-
bamoyl ligand. The 1H NMR has two singlets attributed
to the thiocarbamoyl methyl groups at 2.95 and 3.07
ppm, whereas those assigned to the dimethyldithiocar-
bamate ligand appear at 3.28 and 3.41 ppm. The
complex shows a singlet at 50.3 ppm in the 31P{1H}
NMR spectrum. The 13C{1H} NMR spectrum has dou-
blet resonances for both the thiocarbamoyl and carbonyl
carbons (243.9 and 205.2 ppm, respectively), confirming
the coordination of only one phosphine. The dithiocar-
bamate carbon resonance occurs at 212.9 ppm and is a
singlet, as are the four methyl groups. FAB-MS analysis
reveals a significant molecular ion and also indicates
that the dimethyldithiocarbamate unit is lost as a major
fragment (much more readily than the bidentate thio-
carbamoyl unit) along with the carbonyl and phosphine.
The displacement of a phosphine in preference to the
adoption of a monohapto thiocarbamoyl coordination is
notable, given that the reaction of [Ru(SCSMe)(CO)2-
(PPh3)2]+ with Na[S2CNEt2] does indeed provide [Ru-
{η1-C(S)SMe}(S2CNEt2)(CO)(PPh3)2], a bis(phosphine)
complex with a monohapto dithiomethoxycarbonyl
ligand.29b However, the reaction of the thioaroyl complex
[Os(η2-SCR)Cl(CO)(PPh3)2] (R ) C6H4Me-4) with Na-
[S2CNEt2] does provide [Os(η2-SCR)(κ2-S2CNEt2)(CO)-
(PPh3)], albeit under forcing conditions (15 h, refluxing
xylene and 2-methoxyethanol mixture).3e The complex
6 is formally isoelectronic with the salt [Ru(η2-SC-
NMe2)(κ2-S2CNMe2)(NO)(PPh3)]PF6 obtained via the
oxidative addition of bis(dimethylthiocarbamoyl)sulfide
to [RuCl(NO)(PPh3)2].19 Accordingly, an alternative
route to 6 is provided by the reaction of [Ru(CO)2(PPh3)3]
and (Me2NCS)2S in refluxing ethanol. The overall yield
Figure 2. Molecular geometry of [Ru(η2-SCNMe2)Cl(CO)-
(PPh2)3] (3) (Phenyl groups simplified, 50% displacement
ellipsoids.) Selected bond lengths (Å) and angles (deg): Ru-
C6 ) 1.828(10), Ru-C2 ) 1.959(8), Ru-P2 ) 2.374(3), Ru-
P1 ) 2.379(3), Ru-Cl ) 2.468(2), Ru-S1 ) 2.548(2), S1-
C2 ) 1.687(9), C2-N3 ) 1.292(10), C6-Ru-C2 ) 103.5(4),
C6-Ru-P2 ) 89.4(3), C2-Ru-P2 ) 92.0(3), C6-Ru-P1
) 89.5(3), C2-Ru-P1 ) 90.5(3), C6-Ru-Cl ) 105.4(3),
P2-Ru-Cl ) 88.44(10), P1-Ru-Cl ) 89.67(10), C2-Ru-
S1 ) 41.4(3), P2-Ru-S1 ) 91.35(9), P1-Ru-S1 ) 90.90-
(8), Cl-Ru-S1 ) 109.71(8), P2-Ru-P1 ) 177.44(9), C2-
Ru-Cl 151.1(3), C6-Ru-S1 144.9(3), C2-S1-Ru ) 50.2(3),
S1-C2-Ru ) 88.3(4), C2-N3-C4 ) 122.8(8), C2-N3-
C5 ) 121.0(8), C4-N3-C5 ) 116.2(8).
the infrared spectrum is also the only ν(CO)-associated
absorption in the FT-Raman spectrum would appear to
discount this possibility. The proposed formulation is
also supported by the appearance of a molecular ion
isotope cluster in the FAB mass spectrum, assigned to
[RuH(η2-CSNMe2)(CO)(PPh3)2]+; none was observed
corresponding to a dicarbonyl derivative. While loss of
the thiocarbamoyl fragment is not a major feature of
the FAB-MS of 2, this fragment is readily lost from 4,
suggesting a facile reductive elimination of Me2NC(S)H.
The replacement of one carbonyl ligand by a hydride,
with ultimate retention of the bidentate thiocarbamoyl
coordination, perhaps implicates the intermediacy of a
formyl complex, e.g., [Ru(η2-SCNMe2)(η1-CHO)(CO)-
(PPh3)2]. This possibility is supported by the iridium
chemistry described below. To further confirm the
identity of 4, its reaction with hydrochloric acid was
investigated on the assumption that it would provide
3. However, while the yellow product isolated, 5, gave
consistent 1H and 31P{1H} NMR and FAB-MS data, the
infrared data included a carbonyl absorption at 1940

Thiocarbamoyl Complexes of Ru(II), Rh(III), Ir(III)
Organometallics, Vol. 24, No. 22, 2005 5347
Scheme 5a
for this method is superior to that for the two-step route
as well as requiring a much shorter reaction time.
The isonitrile analogue of 2‚Cl, [Ru(η2-SCNMe2)-
(CNC6H3Me2-2,6)(CO)(PPh3)2]Cl (7‚Cl), was prepared
via the rapid reaction of [Ru(CNC6H3Me2-2,6)(CO)-
(PPh3)3]32 with N,N-dimethylthiocarbamoyl chloride.
Absorptions due to the isocyanide, carbonyl, and thio-
carbamoyl ligands are all clearly visible in the infrared
spectrum [CH2Cl2: 2130 νCN, 1963 νCO, and 1590 νNC
]
cm-1. All three groups give rise to triplet resonances in
the 13C{1H} NMR spectrum at 236.3 (SC, 2JCP ) 8.9 Hz),
2
203.5 (CO, JCP ) 12.5 Hz), and 158.5 (NC, JCP unre-
solved) ppm. In contrast to the carbonyl analogue, 7‚Cl
does not undergo reaction with sodium borohydride. The
reaction of [Ru(CNC6H3Me2-2,6)(CO)(PPh3)3] with bis-
(thiocarbamoyl)sulfide led only to the isolation of 7‚
S2CNMe2 with [S2CNMe2]- as the counteranion, rather
than ejection of a carbonyl ligand and formation of [Ru-
(η2-SCNMe2)(κ2-S2CNMe2)(CNC6H3Me2-2,6)(PPh3)]. The
less π-acidic isonitrile ligand (cf. CO in 2+) presumably
allows stronger coordination of the single CO in 7+ than
those in 2+.
Rhodium Complexes. Known or claimed thiocar-
bamoyl complexes of rhodium19,34-39 are summarized in
Scheme 5, including the structurally characterized
examples [Rh(η2-SCNMe2)(PPh3){HB(pz)3}]Cl,35 [Rh2-
Cl2(CO)(SCNMe2)(dppm)2]BF4,36 [RhCl(SCNMe2){SC-
(NMe2)NPh}(PPh3)],37 and [RhCl(SCNMe2)(S2CNMe2)-
(PPh3)],38 for which pertinent data are reproduced in
Table S1 (Supporting Information). All result from the
oxidative addition of C-X bonds of Me2NC(S)X (X ) Cl,
SMe, S2CNMe2, NPhCSNMe2). The reaction of [RhCl-
(CO)(PPh3)2] with Me2NC(S)Cl (6 h, 80 °C) has been
reported to provide a red binuclear complex [Rh2(µ-Cl)2-
(η2-SCNMe2)2Cl2(PPh3)4],34 while a later report suggests
a mononuclear structure.39 We find that the reaction of
[RhCl(CO)(PPh3)2] with Me2NCSCl does indeed provide
a neutral mononuclear red complex, [Rh(η2-SCNMe2)-
Cl2(PPh3)2] (8), the mononuclear formulation being
confirmed by FAB mass spectrometry. In contrast with
the iridium chemistry described below, it appears
impossible to isolate a salt of the form [Rh(η2-SCNMe2)-
Cl(CO)(PPh3)2]Cl under the conditions necessary for any
reaction to occur (refluxing tetrahydrofuran), as the
carbonyl ligand is ejected thermally to give 8. The same
complex may be prepared by treating Me2NC(S)Cl with
the carbonyl-free precursor complex [RhCl(PPh3)3] or
[Rh(cod)(PPh3)2]+ in good yields (Scheme 6). With these
more reactive substrates, the reactions proceed readily
at room temperature and 8 may be isolated in high
yields (90-95%). Spectroscopic data for 8 are essentially
a
L ) PPh3. (i) ClC(S)NMe2; (ii) S(CSNMe2)2; (iii) Et3N.
analogous to those for the structurally characterized
iridium analogue described below with the exceptions
that the resonances in the 31P{1H} NMR spectra appear
as doublets due to coupling to rhodium.
The difference in reactivity of the rhodium and
iridium analogues extends also to the reactions of the
species [MCl(CS)(PPh3)2] (M ) Rh, Ir) with Me2NCSCl
(Scheme 4). Due to the strength of the M-CS bond, the
formation of 8 by ejection of the thiocarbonyl ligand was
considered unlikely. However, instead of providing the
thiocarbonyl analogue of the elusive rhodium carbonyl
complex, [Rh(η2-SCNMe2)Cl(CO)(PPh3)2]Cl, a neutral
yellow complex was isolated that did not display a
characteristic νCS IR absorption for a terminal thiocar-
bonyl ligand (typically 1180-1380vs cm-1). A νNC stretch
in the infrared spectrum (Nujol) at 1586 cm-1 and the
(32) This complex is an analogue of the known complex [Ru(CO)-
(CNC6H4Me-4)(PPh3)3].33 It may be prepared using the analogous
procedure by substituting CNC6H4Me-4 with the commercially avail-
able CNC6H3Me2-2,6 (Aldrich).
(33) (a) Christian, D. F.; Roper, W. R. J. Chem. Soc., Chem.
Commun. 1971, 1271. (b) Grundy, K. R. Inorg. Chim. Acta 1981, 53,
L225.
(34) Corain, B.; Martelli, M. Inorg. Nucl. Chem. Lett. 1972, 8, 39.
(35) Hill, A. F.; White, A. J. P.; Williams, D. J.; Wilton-Ely, J. D. E.
T. Organometallics 1998, 17, 3152.
(36) Gibson, J. A. E.; Cowie, M. Organometallics 1984, 3, 722.
(37) (a) Gal, A. W.; van der Ploeg, A. F. M. J.; Vollenbroek, F. A.;
Bosman, W. J. Organomet. Chem. 1975, 96, 123. (b) Bosman, W. P.;
Gal, A. W. Cryst. Struct. Commun. 1976, 5, 703.
(38) Bosman, W. P.; Gal, A. W. Cryst. Struct. Commun. 1975, 4, 465.
(39) Gal, A. W.; Ambrosius, H. P. M. M.; van der Ploeg, A. F. M. J.;
Bosman, W. P. J. Organomet. Chem. 1978, 149, 81.
1
presence of two methyl singlets in the H NMR spec-

5348 Organometallics, Vol. 24, No. 22, 2005
Hill et al.
Scheme 6a
Scheme 7a
a
L ) PPh3, cod ) 1,5-cyclooctadiene. (i) ClC(S)NMe2.
trum at 2.33 and 2.43 ppm confirmed the presence of
the thiocarbamoyl ligand. Due to the poor solubility of
the complex in all available deuterated solvents, the 13C-
{1H} NMR spectrum could not be adequately recorded.
The most diagnostic spectroscopic technique was found
to be FAB mass spectrometry, which showed a series
of fragmentations for a metallacycle formed by coupling
of the thiocarbamoyl and thiocarbonyl ligands. We have
found that the observation of the loss of a thiocarbonyl
ligand in FAB mass spectrometry is very rare. Accord-
ingly, isotopic distributions corresponding to [M - Cl
- CS]+, [M - Cl - CS2]+, [M - Cl - S2CNMe2]+, and
[M - Cl - SCSCNMe2]+ suggest the fragmentation of
a metallacycle. Interestingly no molecular ion was seen,
only a peak for [M - Cl]+ (m/z ) 793); however the
possibility of the complex being a chloride salt was
rejected, as attempts to metathesize the chloride coun-
teranion with KPF6 failed. The formulation was further
supported by elemental microanalysis. On the basis of
this evidence, the product is tentatively formulated as
[RhCl2{κ2-C(NMe2)SC(dS)}(PPh3)2] (9), as depicted in
Scheme 6. There is a structural precedent for this class
of metallacycle in the complex [OsH{κ2-C(NRMe)SC(S)}-
(PPh3)2] (R ) C6H4CH3-4), which was also obtained via
the coupling of thiocarbamoyl and thiocarbonyl ligands,
upon reaction of the complex [Os(η2-SCNRMe)(CO)(CS)-
(PPh3)2]+ with Na[BH4].40 Unfortunately, we were un-
successful in obtaining crystals suitable for crystallo-
graphic analysis.
aL ) PPh3, coe ) cyclooctene. (i) CHCl3, EtOH; (ii) ClCS-
NMe2; (iii) PPh3; (iv) Et3N; (v) HBF4; (vi) S(CSNMe2)2.
mates to Vaska’s complex en route to the thiocarbonyl
analogue of Vaska’s complex [IrCl(CS)(PPh3)2].42a Thus
both [IrCl(CA)(PPh3)2] (A ) O, S) react with ClCS2Ph
to provide the neutral dithiophenoxycarbonyl complexes
[Ir{C(dS)SPh)Cl2(CA)(PPh3)2], which on treatment with
K[PF6] provide the salts [Ir(η2-SCSPh)Cl(CA)(PPh3)2]-
PF6. In the preceding discussion, no evidence for the
formation of monodentate thiocarbamoyl complexes had
been obtained. We have therefore reinvestigated the
reaction of [IrCl(CO)(PPh3)2] with Me2NCSCl and ex-
tended it to the related reaction of [IrCl(CS)(PPh3)2] for
comparison with the unexpected formation of 9 above.
The reaction of Vaska’s complex with Me2NCSCl in
refluxing benzene has been previously reported39 to
provide the salt [Ir(η2-SCNMe2)Cl(CO)(PPh3)2]Cl (10‚
Cl), although the limited spectroscopic data do not
unequivocally differentiate between this formulation
and the neutral species [Ir{η1-C(dS)NMe2}Cl2(CO)-
(PPh3)2], akin to [Ir{η1-C(dS)SPh}Cl2(CA)(PPh3)2].
A slow reaction ensues between [IrCl(CO)(PPh3)2] and
Me2NCSCl in dichloromethane at ambient temperatures
(cf. that with ClCS2Ph which is complete within 1 h).
Iridium Complexes. Scheme 7 summarizes syn-
thetic routes to known thiocarbamoyl complexes of
iridium, which (as for rhodium) mainly rely on the
oxidative addition of thiocarbamoyl chlorides or thi-
irams. We have previously discussed the oxidative
addition of chlorothionoformate and chlorodithiofor-
(41) (a) Lu, G.-L.; Roper, W. R.; Wright, L. J.; Clark, G. R. J.
Organomet. Chem. 2005, 690, 972. (b) Collins, T. J.; Roper, W. R.;
Town, K. G. J. Organomet. Chem. 1976, 121, C41. (c) Kubota, K.;
Carey, C. R. J. Organomet. Chem. 1970, 29, 491.
(42) (a) Hill, A. F.; Wilton-Ely, J. D. E. T. Organometallics 1996,
15, 5, 3791. (b) Hill, A. F.; Wilton-Ely, J. D. E. T. Inorg. Synth. 2002,
33, 244.
(40) Boniface, S. M.; Clark, G. R. J. Organomet. Chem. 1981, 208,
253.

Thiocarbamoyl Complexes of Ru(II), Rh(III), Ir(III)
Organometallics, Vol. 24, No. 22, 2005 5349
Scheme 8a
a
L ) PPh3. (i) ClC(S)NMe2; (ii) hν; (iii) HNMe2; (iv) NaBH4;
(v) NaOEt.
Figure 3. Molecular structure of [Ir(η2-SCNMe2)Cl2-
(PPh3)2] (11). (Phenyl groups simplified, 50% displacement
ellipsoids.) Selected bond lengths (Å) and angles (deg): Ir-
C2 ) 1.971(6), Ir-P2 ) 2.3594(19), Ir-P1 ) 2.3652(19),
Ir-Cl(2) ) 2.3791(17), Ir-S1 ) 2.4265(17), Ir-Cl(1) )
2.4823(17), S1-C2 ) 1.704(7), C2-N3 ) 1.279(8), P2-Ir-
P1 ) 177.49(7), C2-Ir-P2 ) 90.3(2), C2-Ir-P1 ) 90.4-
(2), C2-Ir-Cl(2) ) 106.59(19), C2-Ir-S1 ) 44.10(19), P2-
Ir-Cl(1) ) 88.97(6), P1-Ir-Cl(1) ) 89.53(6), P2-Ir-Cl(2)
) 90.52(7), P1-Ir-Cl(2) ) 91.57(7), Cl(2)-Ir-Cl(1) ) 93.19-
(6), P2-Ir-S1 ) 88.71(6), P1-Ir-S1 ) 90.14(6), S1-Ir-
Cl(1) ) 116.12(6), C2-S1-Ir ) 53.6(2), S1-C2-Ir )
82.3(3), Cl(2)-Ir-S1 150.65(7), C2-Ir-Cl(1) 160.21(19),
C2-N3-C4 ) 122.1(6), C2-N3-C5 ) 122.2(6), C4-N3-
C5 ) 115.7(6).
However, heating the reagents in refluxing tetrahydro-
furan under reflux leads to the spontaneous crystalliza-
tion of the colorless product 10‚Cl (Scheme 8). The ionic
formulation is further supported by the following ob-
servations: Metathesis of the counteranion (Cl-) with
(NH4)[PF6] does not effect the solution spectroscopic
data associated with the complex cation, excluding the
alternative neutral formulation of [Ir{η1-C(dS)NMe2}-
Cl2(CO)(PPh3)2]. The gross molecular composition is also
indicated by the appearance of a molecular ion at m/z
) 868 showing the correct isotope distributions for the
proposed formulation (although metal halide ionization
is not uncommon in FAB mass spectrometry). In con-
trast to the proposed rhodium analogue which sponta-
neously decarbonylates, the salt 10‚Cl is thermally
stable (thf or benzene reflux). However, it slowly
converts (3-5 days) in bright sunlight at room temper-
ature to give a neutral red species (Scheme 8), which
shows no νCO-associated infrared absorption and gives
rise to a molecular ion at m/z ) 875 corresponding to
[Ir(η2-SCNMe2)Cl2(PPh3)2] (11). Two isomers of this
formulation have been suggested39 as resulting from the
subsequent treatment of [Ir2(µ-Cl)2(C8H14)4] with triph-
enylphosphine and Me2NCSCl. This species is however
most conveniently prepared via the reaction of [IrCl-
(N2)(PPh3)2] with Me2NCSCl. In contrast to the reaction
with [IrCl(CO)(PPh3)2], that with the dinitrogen complex
is considerably more facile (30 min, CH2Cl2, 25 °C). It
therefore seems likely that the mechanism is distinct,
i.e., that the Me2NCSCl displaces dinitrogen followed
by oxidative addition rather than formation of the salt
[Ir(η2-SCNMe2)Cl(N2)(PPh3)2]Cl. A third route to this
complex is provided, somewhat surprisingly, by the slow
reaction (16 h) of [Ir(η2-SCNMe2)(CO)Cl(PPh3)2]Cl with
HNMe2 at room temperature. Given that two isomers
have been reported for this complex on the basis of
spectroscopic data, a crystal structure determination
was carried out. Yellow platelike needles of [Ir(η2-
SCNMe2)Cl2(PPh3)2]‚2CH2Cl2 (11) were grown by layer-
ing ethanol on a saturated solution of the complex in
dichloromethane. The results of the crystallographic
study are summarized in Figure 3 and confirm (i) the
trans bis(phosphine) arrangement and (ii) the dihapto
coordination of the thiocarbamoyl ligand. The complex
exhibits essentially an octahedral geometry with cis-
interligand angles in the range 88.71(6)° to 116.12(6)°.
As for 2‚PF6 and 3, the thiocarbamoyl ligand, the metal,
and the two remaining equatorial ligands are essentially
coplanar. The two Ir-Cl bond lengths offer an internal
comparison of the respective trans influences of the two

5350 Organometallics, Vol. 24, No. 22, 2005
Hill et al.
“ends” of the thiocarbamoyl ligand. The Ir-Cl2 bond
which is “trans” to the sulfur is significantly (61σ)
shorter than that “trans” to C2, which is somewhat
surprising for a pseudo-octahedral d6-center, if C2 and
S1 are expected to have π-acid and π-dative character,
respectively. Similarly, on steric grounds it might also
be expected that Ir-Cl1 would be shorter.
The thiocarbonyl analogue of Vaska’s complex, [Ir-
(CS)Cl(PPh3)2],41,42 behaved in a straightforward man-
ner with Me2NC(S)Cl, reacting to give [Ir(η2-SCNMe2)-
Cl(CS)(PPh3)2]Cl (12‚Cl), with no indication of coupling
of the thiocarbonyl and thiocarbamoyl ligands, in con-
trast to the formation of 9. The thiocarbonyl ligand gave
rise to a νCS absorption at 1349 cm-1 in the infrared
spectrum (Nujol), consistent with coordination to irid-
ium(III), and a triplet at 254.5 (2JCP ) 8.1 Hz) ppm in
the 13C{1H} NMR spectrum. The thiocarbamoyl ligand
exhibited a νNC band at 1616 cm-1 in the IR spectrum
(Nujol) and a triplet at 195.2 (2JCP ) 3.6 Hz) in the 13C-
{1H} NMR spectrum further upfield from that of the
thiocarbonyl carbon. The reaction of [IrCl(CS)(PPh3)2]
with PhSC(dS)Cl has been reported to give the neutral
complex [Ir{η1-C(dS)SPh}Cl2(CS)(PPh3)2] if carried out
in benzene,42a but the salt [Ir(η2-SCSPh)Cl2(CS)(PPh3)2]-
PF6 is obtained if the reaction is carried out in a mixture
of CH2Cl2 and EtOH in the presence of KPF6. Spectro-
scopic data for the latter are generally similar to those
for 12‚Cl with the exception of the 13C resonance
attributable to the dithioalkoxycarbonyl carbon, which
appears at 250.9 ppm. The other feature that distin-
guishes these two reactions is the enhanced preference
for dihapto coordination demonstrated by the thiocar-
bamoyl ligand relative to the dithioalkoxycarbonyl
ligand in that no evidence for the formation of neutral
complex [IrCl2{η1-CdS)NMe2}(CS)(PPh3)2] was ob-
tained.
Colorless crystals of 12‚Cl(CHCl3)6 suitable for crys-
tallography were grown from chloroform as a chlorofom
hexasolvate. The results of a crystallographic analysis
are summarized in Figure 4. The geometry at the metal
center is distorted octahedral (Figure 4) with cis-
interligand angles ranging from 86.38(9)° to 111.92(11)°.
An unusual feature of the crystal structure was the
octahedral arrangement of the six chloroform molecules
around the chloride counteranion (Figure 4b, average
Cl3CH‚‚‚Cl ) 2.55 Å).
The complex [IrH(η2-SCNMe2)(CO)(PPh3)2]Cl has been
previously prepared from the reaction of Me2NC(S)Cl
with [IrH(CO)(PPh3)3],39 while the reaction of [Ir-
(SCSMe)Cl(CO)(PPh3)2]OTf with Na[BH4] provides [IrH-
{C(dS)SMe}Cl(CO)(PPh3)2].41 It might therefore be
expected that the reaction of 10‚Cl with ethanolic
sodium borohydride would provide one or both of [IrH-
(η2-SCNMe2)(CO)(PPh3)2]Cl and [IrHCl{C(dS)NMe2}-
(CO)(PPh3)2]. In practice, neither is obtained; instead
the reaction led to the isolation of the formyl complex
[Ir(η2-SCNMe2){η1-C(dO)H}Cl(PPh3)2] (13). The pres-
ence of the formyl ligand was clearly indicated in the
IR spectrum (Nujol) by a characteristic absorption at
2572 cm-1 as well as the conspicuous absence of an
absorption due to a terminal carbonyl ligand. A triplet
resonance was observed at 14.67 (3JHP ) 6.6 Hz) ppm
Figure 4. (a) Molecular structure of the cationic complex
[Ir(η2-SCNMe2)Cl(CS)(PPh3)2]+ (12+) in a crystal of 12‚Cl-
(CHCl3)6. (Phenyl groups simplified, 50% displacement
ellipsoids). Selected bond lengths (Å) and angles (deg): Ir-
C6 ) 1.864(11), Ir-C2 ) 1.994(11), Ir-P2 ) 2.399(2), Ir-
P1 ) 2.402(2), Ir-Cl ) 2.429(3), Ir-S1 ) 2.491(3), S1-C2
) 1.669(11), C2-N3 ) 1.288(13), P2-Ir-P1 ) 173.42(10),
C6-Ir-C2 ) 109.3(5), C6-Ir-P2 ) 93.0(3), C2-Ir-P2 )
90.9(3), C6-Ir-P1 ) 92.4(3), C2-Ir-P1 ) 90.7(3), C6-
Ir-Cl ) 96.9(4), P2-Ir-Cl ) 86.38(9), P1-Ir-Cl ) 89.33-
(10), C2-Ir-S1 ) 41.9(3), P2-Ir-S1 ) 88.79(9), P1-Ir-
S1 ) 88.19(9), Cl-Ir-S1 ) 111.92(11), C2-Ir-Cl 153.8(3),
C6-Ir-S1 151.2(4), C2-S1-Ir ) 52.9(4), S1-C2-Ir )
85.2(5), C2-N3-C5 ) 123.9(10), C2-N3-C4 ) 119.9(11),
C5-N3-C4 ) 116.2(10). (b) Structure of the anionic
complex [Cl(HCCl3)6]- in a crystal of 12‚Cl(CHCl3)6.
(Chloroform molecules exhibit disorder; one orientation
shown for each.)
1
in the H NMR spectrum, while a proton-coupled 13C
NMR spectrum revealed the formyl resonance to be split

Thiocarbamoyl Complexes of Ru(II), Rh(III), Ir(III)
Organometallics, Vol. 24, No. 22, 2005 5351
into a doublet of triplets at 215.2 [JHC ) 164.2, JCP
)
5.4 Hz] ppm due to coupling to both the formyl proton
and the mutually trans phosphorus nuclei. The thio-
carbamoyl resonance in this spectrum appears as a
somewhat broadened singlet at 205.3 ppm. The FAB
mass spectrum showed fragmentations for the molecu-
lar ion at 868 (100), [M - HCO - PPh3]+ at 578 (41)
and [M - Cl - HCO - PPh3]+ at 542 (33). Unfortu-
nately, crystals of suitable quality for a crystallographic
analysis were not obtained. Although formyl complexes
of group 8 metals have been well-studied,43-47 very few
formyl complexes of group 9 metals are known,47,48 but
do include a rare example of a thioformyl complex [Ir-
{C(dS)H}Cl2(CO)(PPh3)2]3a and the structurally char-
acterized salt [IrH{C(dO)H}(PMe3)4]PF6.48
The carbonyl ligand in 10+ has νCO 2042 cm-1 (CH2-
Cl2), and accordingly it is perhaps not surprising that
this ligand would be prone toward nucleophilic attack.
What is unexpected, however, is that the formyl complex
is stable and does not decompose via transfer of the
hydrogen to the metal, as is generally the case for
formyls. Such an R-Ir-H elimination would require a
vacant coordination site on iridium, and thus the
stability of 13 may be taken as testament to the tenacity
of the dihapto thiocarbamoyl coordination.
Figure 5. Superposition of the equatorial planar sections
of the molecular structures of the complexes 2+, 3, 11, and
12+ (50% displacement ellipsoids).
indicate that the bidentate-C,S coordination mode is
strongly favored and ultimately retained in co-ligand
modification reactions. In the case of the salt [Ir(η2-
SCNMe2)Cl(CO)(PPh3)2]Cl (10‚Cl), the reactivity of the
species is centered on the carbonyl ligand (CH2Cl2: νCO
2042 cm-1), thus providing compounds bearing both
thiocarbamoyl and formyl or alkoxycarbonyl ligands. A
representative series of examples has been investigated
crystallographically. Table S1 (Supporting Information)
collates pertinent geometrical parameters for the 22
structurally characterized “metallathiirenes” of ruthe-
nium, osmium, and iridium,3,5,18,29,35-38,49-51 including
the complexes 2+, 3, 11, and 12+. Remarkably, there is
very little obvious correlation between the geometric
parameters M-C, M-S, C-S, and M-C-S. Further-
more, Figure 5 depicts a superposition of the equatorial
planes of the complexes 2+, 3, 11, and 12+ and again,
to the naked eye, there is little notable variation in the
orientations of either the thiocarbamoyl or the two
remaining ligands. This comparative lack of geometric
flexibility coupled with the paucity of reactions involving
the thiocarbamoyl ligand itself might point to such
ligands serving as useful three-electron spectator ligands,
were it not for the observation of a novel coupling of
thiocarbamoyl and thiocarbonyl ligands observed in the
formation of 9. In the context of other more common
three-electron ligands, consideration of the IR data in
Table 1 leads to the conclusion that the thiocarbamoyl
ligand is a comparatively strong net donor, given the
popular convention of describing the metal centers in
the nitrosyl and alkylidyne complexes as formally
zerovalent.
To investigate further the reaction of nucleophiles at
the carbonyl ligand, 10‚Cl was treated with sodium
ethoxide in ethanolic solution to provide rapidly the
ethoxycarbonyl species [Ir(η2-SCNMe2){η1-C(dO)OEt}-
Cl(PPh3)2] (14). The ethyl group was observed in the 1H
NMR spectrum as a triplet resonance at 0.66 (JHH
)
7.3 Hz) ppm and a quartet at 3.57 (JHH ) 7.3 Hz) ppm.
The ethoxycarbonyl group gave rise to a νOCO absorption
at 1618 cm-1 in the IR spectrum (Nujol) and resonances
in the 13C{1H} NMR spectrum: a triplet at 168.3 (JCP
) 6.3 Hz) and singlets at 59.8 and 14.1 ppm for the ethyl
carbons, respectively. Attempts at preparing a carbam-
oyl thiocarbamoyl species by nucleophilic attack of
lithium diisopropylamide and secondary amines proved
unsuccessful. As noted above, dimethylamine leads to
slow decarbonylation to provide 11, and since this
reaction does not proceed in the absence of amine, it
may be surmised that the amine does indeed attack the
carbonyl but that the resulting carbamoyl complex is
unstable.
Concluding Remarks
Convenient general synthetic routes to thiocarbamoyl
complexes of divalent ruthenium and trivalent rhodium
and iridium have been illustrated, and reactivity studies
(43) Collman, J. P.; Winter, S. R. J. Am. Chem. Soc. 1973, 95, 4089.
(44) (a) Casey, C. P.; Meszaros, M. W.; Neumann, S. M.; Gennick-
Cesa, I.; Haller, K. J. Organometallics 1985, 4, 143. (b) Casey, C. P.;
McAlister, D. R.; Calabrese, J. C.; Neumann, S. M.; Andrews, M. A.;
Meszaros, M. W.; Haller, K. J. Cryst. Struct. Commun. 1982, 11, 1015;
(45) (a) Clark, G. R.; Headford, C. E. L.; Marsden, K.; Roper, W. R.
J. Organomet. Chem. 1982, 231, 335. (b) Brown, K. L.; Clark, G. R.;
Headford, C. E. L.; Marsden, K.; Roper, W. R. J. Am. Chem. Soc. 1979,
101, 503. (c) Collins, T. J.; Roper, W. R. J. Organomet. Chem. 1978,
159, 73.
Experimental Section
General Comments. Unless otherwise stated, all manipu-
lations were carried out under aerobic conditions using com-
mercially available solvents and reagents as received. Infrared
and NMR spectroscopy was carried out at 25 °C using Perkin-
Elmer 1720-X and JEOL JNM EX270 spectrometers, respec-
tively. “tv” implies a virtual triplet, taken as evidence of
mutually trans-coordinated phosphine ligands. Generally the
resonances for the ortho and meta carbon nuclei of PPh3
ligands were not unequivocally distinguished, having compa-
rable JPC values. FAB mass spectra (nitrobenzyl alcohol
matrixes) were measured using an Autospec Q instrument;
for salts, “M” refers to the cationic complex. All solid-state
(46) (a) Smith, G.; Cole-Hamilton, D. J.; Thornton-Pett, M.; Hurst-
house, M. B. J. Chem. Soc., Dalton Trans. 1985, 387. (b) Nelson, G.
O.; Sumner, C. E. Organometallics 1986, 5, 1983.
(47) (a) Wayland, B. B.; Woods, B. A.; Pierce, R. J. Am. Chem. Soc.
1982, 104, 302. (b) Wayland, B. B.; Woods, B. A. Chem. Commun. 1981,
700.
(48) Thorn, D. L. J. Am. Chem. Soc. 1980, 102, 7109.

5352 Organometallics, Vol. 24, No. 22, 2005
Hill et al.
infrared samples were measured as Nujol mulls between KBr
plates. Elemental microanalytical data were provided by SACS
at London Metropolitan University. The FT-Raman spectrum
of 4 was provided by Dr. E. Coleyshaw. Petroleum ether refers
to the fraction that boils between 40 and 60 °C. The complex
[Ru(CO)2(PPh3)3] was prepared as described below, with minor
modifications to the method described by Roper28 that avoid
the use of silver salts, residual traces of which compromise
the storage properties. The complex [Ru(CNC6H3Me2-2,6)(CO)-
(PPh2)3]52 is an analogue of [Ru(CNC6H4Me-4)(CO)(PPh3)3]
described previously33 and may be prepared using either of
the reported multistep procedures, substituting CNC6H4Me-4
with commercially available CNC6H3Me2-2,6. The remaining
complexes [Ru(η2-CS2)(CO)2(PPh3)2],29 [RhCl(PPh3)3],53 [RhCl-
(CO)(PPh3)2],54 [RhCl(CS)(PPh3)2],55 [Rh(cod)(PPh3)2]PF6,56
[IrCl(CO)(PPh3)2],57 [IrCl(N2)(PPh3)2],58 and [RuHCl(CO)-
(PPh3)3]59 were prepared according to published procedures.
Various procedures are available for the preparation of [IrCl-
(CS)(PPh3)2],41,42,55 of which we used that described in ref 42b,
with the modification that the amount of hydrochloric acid
used in the penultimate step was doubled. All other reagents
were used as received from commercial sources.
Preparation of [Ru(CO)2(PPh3)3] (1). A mixture of [Ru-
HCl(CO)(PPh3)3] (2.00 g, 2.10 mmol) and sodium tetrafluo-
roborate (1.84 g) was heated in refluxing acetonitrile (60 mL)
for 40 min. The hot solution was filtered through diatomaceous
earth and the filtrate transferred to a 250 mL round-bottomed
flask and freed of volatiles (rotary evaporator). Dichlo-
romethane (100 mL) was added to the residue, and carbon
monoxide was then bubbled through the mixture for 5 min.
The flask was sealed under an atmosphere of carbon monoxide,
and the contents were stirred vigorously for 1 h. After this
time the extent of the conversion to [RuH(CO)2(NCMe)(PPh3)2]-
BF4 was determined by solution infrared spectroscopy (CH2-
Cl2), and if necessary, further carbon monoxide was passed
through the mixture. The dichloromethane was then removed
(rotary evaporator) and to the residue were added triph-
enylphosphine (1.00 g) and potassium hydroxide pellets (0.7
g). Dry, degassed methanol (50 mL) was added and the
suspension heated anaerobically under reflux for 20 min and
then filtered while hot. The bright yellow precipitate was
washed with methanol (2 × 50 mL) and then dried under
vacuum. Yield: 1.55 g (78%). The material obtained by this
method was suitable for subsequent synthetic applications,
although it can be recrystallized from dichloromethane and
ethanol under strictly anaerobic conditions in the event that
traces of KBF4 (IR) remain. Note: Extended reflux times or
the use of ethanol in the final step results in appreciable
contamination with RuH2(CO)(PPh3)3. Carbonyl-associated
infrared data for [RuHCl(CO)(PPh3)3], [RuH2(CO)(PPh3)3], and
1 are sufficiently similar that these alone are insufficient to
determine purity. 31P{1H} NMR data are, however, definitive.
Preparation of [Ru(η2-SCNMe2)(CO)2(PPh3)2]Cl (2‚Cl).
(a) This reaction must be carried out under strictly anaerobic
conditions due to the air-sensitivity of 1; however the subse-
quent workup may be carried out aerobically. N,N-Dimeth-
ylthiocarbamoyl chloride (0.27 g, 2.15 mmol) and [Ru(CO)2-
(PPh3)3] (1: 1.00 g, 1.06 mmol) were combined in a Schlenk
tube under nitrogen. To this was added thoroughly dried and
degassed tetrahydrofuran (50 mL) and the mixture stirred for
1 h. Addition of petroleum ether (80 mL) completed precipita-
tion of the colorless product, which may be recrystallized from
a mixture of dichloromethane and ethanol. Yield: 0.80 g (94%).
(b) [Ru(η2-CS2)(CO)2(PPh3)2] (0.20 g, 0.26 mmol) and N,N-
dimethylthiocarbamoyl chloride (0.07 g, 0.57 mmol) were dried
under vacuum and dissolved in dried and degassed tetrahy-
drofuran (30 mL), and the mixture was stirred for 2 h. Addition
of petroleum ether (50 mL) completed precipitation of the
colorless product. Yield: 0.16 g (75%). The less soluble
hexafluorophosphate salt (2‚PF6) was prepared by metathesis
of 2‚Cl in dichloromethane with a solution of [NH4]PF6 in
water and ethanol. IR CH2Cl2: 2048, 1988 νCO, 1602 νNC cm-1
.
.
Nujol: 2052, 1989 νCO, 1599 νNC, 1309, 1219, 916 νCS, 816 cm-1
1
NMR (CDCl3, 25 °C) H: 2.42, 2.83 (s × 2, 6 H, CH3), 7.25-
7.60 (m, 30 H, C6H5) ppm. 13C{1H}: 231.1 (t, CS, JCP ) 8.9),
2
199.9 (t, CO, 2JCP ) 11.6), 199.4 (t, CO, 2JCP ) 12.5), 133.5 (tv,
o/m-C6H5, JCP ) 5.4), 131.8 (p-C6H5), 129.8 (tv, i-C6H5, JCP
)
25.0), 129.1 (tv, o/m-C6H5, JCP ) 5.4 Hz), 49.1, 48.0 (CH3) ppm.
31P{1H}: 33.7 ppm. FAB-MS m/z (% abundance): 770 (75)
[M]+, 742 (100) [M - CO]+, 480 (23) [M - CO - PPh3]+, 452
(15) [M - 2CO - PPh3]+, 407 (3) [M - 2CO - PPh3 - NMe2]+.
Anal. (2‚PF6) Found: C, 50.3; H, 4.0; N, 1.4. C41H36F6NO2P3-
RuS requires: C, 50.5; H, 3.8; N, 1.4. Crystal data for 2‚PF6:
C42H37Cl3F6NO2P3RuS, Mw ) 1034.12, triclinic, P1h (#2), a )
13.062(4) Å, b ) 14.194(7) Å, c ) 15.229(4) Å, R ) 66.88(3)°, â
) 70.28(2)°, γ ) 63.82(3)°, V ) 2283.8(14) Å3, Z ) 2, µ(Cu KR)
) 6.340 mm-1, Dcalc ) 1.504 Mg m-3, T ) 293(2) K, colorless
plate, 6343 independent measured reflections, R1 ) 0.0473,
wR2 ) 0.1203, 5045 absorption-corrected reflections [I > 2σ-
(I), 2θ e 116°], 555 parameters, CCDC 275850.
Preparation of [Ru(η2-SCNMe2)Cl(CO)(PPh3)2] (3) (CO
trans to S). A suspension of [Ru(η2-SCNMe2)(CO)2(PPh3)2]Cl
(2‚Cl: 0.20 g, 0.25 mmol) in ethanol (20 mL) was heated under
reflux for 6 h and then allowed to cool to room temperature.
The product was isolated by filtration, washed with petroleum
ether (20 mL), and dried under vacuum. Yield: 0.19 g (95%).
The complex was identified by comparison of spectroscopic data
with those previously published for 3, prepared via an alterna-
tive route.20 A sample for crystallographic analysis was grown
from chloroform as a monosolvate. Crystal data for 3‚CHCl3:
C41H37Cl4NOP2RuS, Mw ) 896.59, monoclinic, P21/n, a )
17.314(2) Å, b ) 9.4199(10) Å, c ) 25.059(3) Å, â ) 92.716-
(8)°, V ) 4082.5(8) Å3, Z ) 4, µ(Mo KR) ) 0.808 mm-1, Dcalc
)
1.459 Mg m-3, T ) 293(2) K, pale yellow block, 7178 indepen-
dent measured reflections, R1 ) 0.0792, wR2 ) 0.1692, 3231
independent absorption-corrected reflections [I > 2σ(I), 2θ e
50°], 450 parameters, CCDC 275851.
(49) Rickard, C. E. F.; Roper, W. R.; Salter, D. M.; Wright, L. J.
Organometallics 1992, 11, 3931.
(50) Attar-Bashi, M. T.; Rickard, C. E. F.; Roper, W. R.; Wright, L.
J.; Woodgate, S. D. Organometallics 1998, 17, 504.
(51) Dean, W. K. Cryst. Struct. Commun. 1979, 8, 335.
(52) Herberhold, M.; Hill, A. F. J. Organomet. Chem. 1989, 368, 111.
(53) Osborn, J. A.; Wilkinson, G. Inorg. Synth. 1990, 28, 77.
(54) Evans, D.; Osborn, J. A.; Wilkinson, G. Inorg. Synth. 1990, 28,
79.
Preparation of [RuH(η2-SCNMe2)(CO)(PPh3)2] (4). A
solution of [Ru(η2-SCNMe2)(CO)2(PPh3)2]Cl (2‚Cl: 1.00 g, 1.24
mmol) in a mixture of dichloromethane (100 mL) and ethanol
(60 mL) was treated with a filtered solution of sodium
borohydride (0.50 g, 13.2 mmol, excess) in ethanol (50 mL).
The resulting suspension was stirred for 1 h and then filtered
to provide the pale green product, which was washed succes-
sively with water (40 mL), ethanol (40 mL), and petroleum
ether (40 mL) and then dried under vacuum. Yield: 0.90 g
(98%). The crude product could be recrystallized from a
(55) Kubota, M.; Ho, C. O. M. Inorg Synth. 1979, 19, 204.
(56) Shapley, J. R.; Schrock, R. R.; Osborn, J. A. J. Am. Chem. Soc.
1969, 91, 2816.
(57) Collman, J. P.; Sears, C. T., Jr.; Kubota, M. Inorg. Synth. 1990,
28, 92.
(58) Collman, J. P.; Hoffman, N. W.; Hosking, J. W. Inorg. Synth.
1970, 12, 8.
mixture of dichloromethane and ethanol. IR CH2Cl2: 1912 νCO
,
,
(59) Laing, K. R.; Roper, W. R. J. Chem. Soc. A 1970, 2149.
(60) Roper, W. R. In Transition Metal Carbyne Complexes; Kreissl,
F. R., Ed.; NATO ASI Series C, Vol. 392; Kluwer Academic Publish-
ers: Dordrecht, The Netherlands, 1993.
1561 νNC cm-1. Nujol: 1905 νCO, 1557 νNC, 1308, 1230, 920 νCS
832 cm-1 (νRuH not unambiguously identified). Raman: 1913
1
2
νCO cm-1. NMR (CDCl3, 25 °C) H: -14.27 (t, 1 H, RuH, JHP
(61) Johnson, B. F. G.; Segal, J. A. J. Chem. Soc., Dalton Trans.
1973, 478.
(62) Haymore, B. L.; Ibers, J. A. Inorg. Chem. 1975, 14, 2748.
) 22.1 Hz), 1.77, 2.64 (s × 2, 6 H, CH3), 7.20-7.65 (m, 30 H,
2
C6H5) ppm. 13C{1H}: 256.7 (t, CS, JCP ) 11.6), 210.6 (t, CO,

Thiocarbamoyl Complexes of Ru(II), Rh(III), Ir(III)
Organometallics, Vol. 24, No. 22, 2005 5353
2
2JCP ) 15.2), 136.8 (tv, i-C6H5, JCP ) 20.6), 134.3 (tv, o/m-C6H5,
JCP ) 6.3), 129.1 (p-C6H5), 127.5 (tv, o/m-C6H5, JCP ) 4.5 Hz),
45.7, 43.7 (CH3) ppm. 31P{1H}: 48.9 ppm. FAB-MS m/z (%
abundance): 742 (5) [M]+, 655 (3) [M - SCHNMe2]+, 625 (2)
[M - SCHNMe2 - CO)]+, 480 (3) [M - PPh3]+, 452 (3) [M -
CO - PPh3]+, 363 (4) [RuPPh3]+. Anal. Found: C, 59.7; H, 4.9;
N, 1.7. C40H37NOP2RuS‚CH2Cl2 requires: C, 59.5; H, 4.8; N,
30 H, C6H5) ppm. 13C{1H}: 236.3 (t, CS, JCP ) 8.9), 203.5 (t,
CO, 2JCP ) 12.5), 158.5 (t, CN, JCP not resolved), 135.4-126.5
(C6H5 + C6H3), 47.7, 46.2 (NCH3), 17.87 (CCH3) ppm. 31P-
{1H}: 34.7 ppm. FAB-MS m/z (% abundance): 873 (79) [M]+,
611 (73) [M - PPh3]+, 583 (100) [M - CO - PPh3]+, 452 (35)
[M - CO - isonitrile - PPh3]+, 363 (13) [RuPPh3]+. The
corresponding hexafluorophosphate salt 7‚PF6 was prepared
by anion metathesis of 7‚Cl with NH4[PF6] in a mixture of
dichloromethane, ethanol, and water and recrystallized from
a mixture of chloroform and ethanol. Anal. Found: C, 53.9;
H, 4.0; N, 2.5. C49H45F6N2OP3RuS‚0.75CHCl3 requires: C, 54.0;
H, 4.2; N, 2.5.
Preparation of [Rh(η2-SCNMe2)Cl2(PPh3)2] (8). (a) [RhCl-
(PPh3)3] (1.00 g, 1.08 mmol) and Me2NC(S)Cl (0.27 g, 2.19
mmol) were dried under vacuum and dissolved in degassed
dichloromethane (30 mL), and the mixture was stirred for 2
h. On reduction of solvent volume (rotary evaporator) after
addition of ethanol (30 mL), red crystals of the product formed.
These were washed with ethanol (20 mL) and petroleum ether
(20 mL), and dried in vacuo. Yield: 0.75 g (88%). (b) A
suspension of [Rh(cod)(PPh3)2]PF6 (0.50 g, 0.57 mmol) and Me2-
NC(S)Cl (0.14 g, 1.14 mmol) in tetrahydrofuran (15 mL) was
stirred for 10 h under nitrogen. The red precipitate was
filtered, washed with petroleum ether (25 mL), and dried. A
further crop of product was obtained by addition of petroleum
ether (50 mL) to the filtrate. Combined yield: 0.28 g (63%).
IR CH2Cl2: 1607 νNC cm-1. Nujol: 1608 νNC, 1311, 1223, 920
νCS, 826, 328, 300, 273 νRhCl/νRhS cm-1. NMR (CDCl3, 25 °C)
1H: 2.16, 2.37 (s × 2, 6 H, CH3), 7.20-8.10 (m, 30 H, C6H5)
ppm. 31P{1H}: 18.6 (JRhP ) 95.0 Hz) ppm. FAB-MS m/z (%
abundance): 750 (65) [M]+, 715 (4) [M - Cl]+, 488 (81) [M -
PPh3]+, 453 (20) [M - Cl - PPh3]+, 409 (3) [M - Cl - NMe2 -
PPh3]+. Anal. Found: C, 58.2; H, 4.4; N, 1.7. C39H36Cl2NP2-
RhS‚0.25CH2Cl2 requires: C, 58.4; H, 4.6; N, 1.7 (CH2Cl2 by
1H NMR integration).
Preparation of [RhCl2{K2-C(NMe2)SC(dS)}(PPh3)2] (9).
[RhCl(CS)(PPh3)2] (0.50 g, 0.71 mmol) and Me2NC(S)Cl (0.17
g, 1.38 mmol) were dried under vacuum, and dry, degassed
tetrahydrofuran (30 mL) was added under nitrogen. The
resulting orange suspension was heated under reflux for 24 h
to give a yellow-orange solid, which was filtered off (the filtrate
was found to contain unreacted starting material) and then
dissolved in dichloromethane (250 mL) and passed through
diatomaceous earth to remove insoluble impurities. Pale
orange crystals precipitated on reduction in solvent volume
of this dichloromethane solution. These were isolated by
filtration and washed with petroleum ether (30 mL) and dried.
Yield: 0.35 g (60%). IR CH2Cl2: 1605 νNC cm-1. Nujol: 1586
νNC, 1315, 1267, 1231, 1221, 1109, 973, 879, 855 cm-1. NMR
(CDCl3, 25 °C) 1H: 2.33, 2.43 (s × 2, 6 H, CH3), 7.20-8.15 (m,
30 H, C6H5) ppm. Poor solubility precluded the successful
acquisition of 13C{1H} or 31P{1H} NMR data. FAB-MS m/z (%
abundance): 793 (29) [M - Cl]+, 750 (9) [M - Cl - {C(dS)}]+,
718 (3) [M - Cl - {C(dS)S}]+, 671 (13) [M - Cl - {C(dS)S}
- NMe2]+, 663 (10) [M - Cl - {C(dS)SC(NMe2)}]+, 627 (15)
[M - 2Cl - {C(dS)SC(NMe2)}]+, 532 (26) [M - Cl - PPh3]+,
497 (18) [M - 2Cl - PPh3]+, 488 (22) [M - Cl - {C(dS)} -
PPh3]+, 456 (4) [M - Cl - {C(dS)S} - PPh3]+, 453 (11) [M -
2Cl - {C(dS)} - PPh3]+, 414 (24) [M - Cl - {C(dS)S} - NMe2
- PPh3]+, 400 (4) [M - Cl - {C(dS)SC(NMe2)} - PPh3]+, 377
(4) [M - 2Cl - {C(dS)S} - NMe2 - PPh3]+, 364 (5) [M - Cl2
- {C(dS)SC(NMe2)} - PPh2]+. Anal. Found: C, 56.5; H, 4.3;
N, 1.6. C40H36Cl2NP2RhS2 requires: C, 56.4; H, 4.3; N, 1.6.
Preparation of [Ir(η2-SCNMe2)Cl(CO)(PPh3)2]Cl (10‚
Cl). [IrCl(CO)(PPh3)2] (0.50 g, 0.64 mmol) and Me2NC(S)Cl
(0.16 g, 1.30 mmol) were dried under vacuum, and then dry,
degassed tetrahydrofuran (20 mL) was added under nitrogen.
This suspension was heated under reflux for 1 h. After cooling,
the colorless crystals that formed were filtered off and washed
with petroleum ether (30 mL). Yield: 0.55 g (95%). IR CH2-
Cl2: 2042 νCO, 1623 νNC cm-1. Nujol: 2014 νCO, 1622 νNC, 1315,
1
1.7 (CH2Cl2 by H NMR integration).
Preparation of [Ru(η2-SCNMe2)Cl(CO)(PPh3)2] (5) (CO
cis to S). To a solution of [RuH(η2-SCNMe2)(CO)(PPh3)2] (4:
0.30 g, 0.40 mmol) in dichloromethane (20 mL) and ethanol
(15 mL) was added a solution of concentrated hydrochloric acid
(3 drops) in ethanol (10 mL). The mixture was stirred for 1 h.
Concentration of the solution (rotary evaporator) provided a
yellow product, which was isolated by filtration and washed
with water (10 mL), ethanol (20 mL), and petroleum ether (20
mL). Yield: 0.20 g (64%). The product could be recrystallized
from a mixture of dichloromethane and ethanol. IR CH2Cl2:
1957 νCO, 1560 νNC cm-1. Nujol: 1940 νCO, 1562 νNC, 1313, 941
νCS, 830 cm-1. NMR (CDCl3, 25 °C) 1H: 2.49, 2.65 (2 × s, 6 H,
CH3), 7.10-8.00 (m, 30 H, C6H5) ppm. 31P{1H}: 22.0 ppm.
FAB-MS m/z (% abundance): 778 (28) [M]+, 749 (4) [M - CO]+,
742 (4) [M - Cl]+, 689 (82) [M - SCNMe2]+, 654 (8) [M -
SCNMe2 - Cl]+, 625 (20) [Ru(PPh3)2]+, 487 (8) [M - CO -
PPh3]+, 452 (20) [M - Cl - CO - PPh3]+, 363 (26) [RuPPh3]+.
Anal. Found: C, 56.3; H, 4.4; N, 1.6. C40H36ClNOP2RuS‚
1.25CH2Cl2 requires: C, 56.1; H, 4.4; N, 1.6 (CH2Cl2 by 1H
NMR integration).
Preparation of [Ru(η2-SCNMe2)(K2-S2CNMe2)(CO)-
(PPh3)] (6). (a) [Ru(η2-SCNMe2)(CO)2(PPh3)2]PF6 (2‚PF6) (0.20
g, 0.22 mmol) was suspended in ethanol (30 mL) and NaS2-
CNMe2 (0.13 g, 0.91 mmol, excess) added as a solution in water
(2 mL) and ethanol (10 mL). The reaction mixture was then
heated under reflux for 24 h. The solvent was removed under
reduced pressure and the residue extracted into toluene (50
mL) and filtered through diatomaceous earth to remove any
ionic contaminants. The toluene was then removed from the
filtrate and the residue crystallized from dichloromethane (20
mL) and ethanol (20 mL) by slow concentration (rotary
evaporator) to provide pale yellow crystals. Yield: 0.12 g (92%).
(b) A suspension of [Ru(CO)2(PPh3)3] (1: 0.15 g, 0.16 mmol)
and [S(SCNMe2)2] (0.04 g, 0.19 mmol) in degassed ethanol (20
mL) was heated at reflux for 3 h under nitrogen. The resultant
pale yellow product was filtered, washed with ethanol (20 mL)
and hexane (20 mL), and dried. Yield: 0.09 g (95%). IR CH2-
Cl2: 1909 νCO, 1561, 1520 νNC cm-1. Nujol: 1908 νCO, 1553,
1529 νNC, 1393, 1307, 1257, 1232, 1181, 1152, 922 νCS, 842
1
cm-1. NMR (CDCl3, 25 °C) H: 2.95, 3.07 [s × 2, 6 H, SCN-
(CH3)2], 3.28, 3.41 [s × 2, 6 H, S2CN(CH3)2], 7.25-7.80 (m, 15
H, C6H5) ppm. 13C{1H}: 243.9 (d, SCNMe2, 2JCP ) 8.9), 212.9
2
1
(S2CNMe2), 205.2 (d, CO, JCP ) 14.2), 134.3 (d, i-C6H5, JCP
) 44.6), 133.7 (d, o/m-C6H5, JCP ) 10.7), 129.9 (p-C6H5), 128.0
(d, o/m-C6H5, JCP ) 9.0 Hz), 46.9, 45.6 [(SCN(CH3)2], 38.9 [S2-
CN(CH3)2] ppm. 31P{1H}: 50.3 ppm FAB-MS m/z (% abun-
dance): 600 (7) [M]+, 572 (11) [M - CO]+, 482 (4) [M -
SCNMe2 - CO]+, 309 (17) [M - CO - PPh3]+. Anal. Found:
C, 49.9; H, 4.0; N, 4.4. C25H27N2OPRuS3 requires: C, 50.1; H,
4.5; N, 4.7.
Preparation of [Ru(η2-SCNMe2)(CNC6H3Me2-2,6)(CO)-
(PPh3)2]Cl (7‚Cl). [Ru(CNC6H3Me2-2,6)(CO)(PPh3)3] (0.30 g,
0.29 mmol) and Me2NC(S)Cl (0.07 g, 0.57 mmol) were dried
under vacuum and dissolved in degassed tetrahydrofuran (25
mL). The orange suspension was stirred for 3 h at room
temperature, resulting in the formation of a colorless product.
This was filtered and washed with petroleum ether (35 mL)
and dried. Yield: 0.23 g (88%). The product can be recrystal-
lized from chloroform and ethanol. IR CH2Cl2: 2130 νCtN, 1963
νCO, 1590 νNC cm-1. Nujol: 2125 νCtN, 1947 νCO, 1592 νNC, 1311,
1222, 1172, 917, 827 cm-1. NMR (CDCl3, 25 °C) 1H: 1.77 (s, 6
H, CCH3), 2.40, 2.52 (s × 2, 6 H, NCH3), 6.92 (d, 2 H, m-C6H3,
3
3JHH ) 7.3), 7.09 (t, 1 H, p-C6H3, JHH ) 7.6), 7.38-7.55 (m,

5354 Organometallics, Vol. 24, No. 22, 2005
Hill et al.
1215, 919 νCS, 844, 292 νIrCl cm-1. NMR (CDCl3, 25 °C) 1H:
1.77, 2.64 (s × 2, 6 H, CH3), 7.20-7.65 (m, 30 H, C6H5) ppm.
31P{1H}: -2.4 ppm. 13C{1H}: 193.7 (t, SCN, 2JCP ) 4.5), 169.8
abundance): 884 (100) [M]+, 622 (47) [M - PPh3]+, 587 (10)
[M - Cl - PPh3]+, 542 (4) [M - Cl - CS - PPh3]+, 497 (10)
[M - Cl - SCNMe2 - CS - PPh3)]+, 360 (4) [M - (PPh3)2]+. A
sample for microanalysis was crystallized from a mixture of
dichloromethane and ethanol. Anal. Found: C, 50.8; H, 4.5;
N, 1.4. C40H36Cl2IrNP2S2‚0.5CH2Cl2 requires: C, 50.6; H, 3.9;
N, 1.5. Crystals of 12‚Cl(CHCl3)6 suitable for diffractometry
were grown by slow evaporation of a chloroform solution of
the salt. Crystal data for 12‚Cl‚(CHCl3)6: C46H42Cl20IrNP2S2,
Mw ) 1636.07, triclinic, P1h (#2), a ) 9.513(2) Å, b ) 14.790(2)
Å, c ) 24.540(2) Å, R ) 73.757(11)°, â ) 87.499(12)°, γ )
2
(t, CO, JCP ) 7.2), 133.7 (tv, o/m-C6H5, JCP ) 5.4), 132.1 (p-
C6H5), 128.8 (tv, o/m-C6H5, JCP ) 5.4), 126.0 (tv, i-C6H5, JCP
)
30.4), 48.9, 46.2 (s × 2, CH3) ppm. FAB-MS m/z (% abun-
dance): 868 (100) [M]+, 840 (8) [M - CO]+, 578 (26) [M - CO
- PPh3]+, 542 (20) [M - Cl - CO - PPh3]+, 497 (2) [M - Cl -
CO - NMe2 - PPh3]+. Anal. Found: C, 50.0; H, 4.2; N, 1.5.
C41H38Cl3IrNOP2S‚0.5CH2Cl2 requires: C, 50.1; H, 4.0; N, 1.4.
Preparation of [Ir(η2-SCNMe2)Cl2(PPh3)2] (11). (a) [IrCl-
(N2)(PPh3)2] (0.22 g, 0.28 mmol) and Me2NC(S)Cl (0.07 g, 0.57
mmol) were dried under vacuum, and dry, degassed dichlo-
romethane (20 mL) was introduced under nitrogen. The
reaction was stirred for 2 h, during which time the solution
color changed to orange. The solvent volume was reduced to
ca. 2 mL and the mixture placed on a silica column. The
column was eluted with a dichloromethane/tetrahydrofuran
(95:5) solvent mixture to give the desired product as the first
bright red fraction. Crystallization was achieved from a
dichloromethane/ethanol mixture to provide red crystals,
which were washed with ethanol (10 mL) and petroleum ether
(10 mL) and dried. Yield: 0.17 g (69%). (b) [Ir(η2-SCNMe2)Cl-
(CO)(PPh3)2]Cl (10‚Cl) (0.15 g, 0.17 mmol) was dissolved in
dichloromethane (20 mL) and then treated with HNMe2 (1.0
mL, 2.0 mmol, 2 M solution in thf, Aldrich). The reaction was
stirred for 40 h, during which the solution color became red.
Ethanol (20 mL) was added and the solvent volume reduced
by rotary evaporation until crystallization had occurred. The
red product was washed with ethanol (10 mL) and petroleum
ether (10 mL) and dried. Yield: 0.10 g (66%). (c) [Ir(η2-
SCNMe2)Cl(CO)(PPh3)2]Cl (10‚Cl) (0.050 g, 0.06 mmol) was
dissolved in chloroform (2 mL) and then left in bright sunlight
for 5 days. After this period deep red crystals had formed.
These were isolated and washed with ethanol (5 mL) and
petroleum ether (5 mL) and dried. Yield: 0.03 g (62%). IR CH2-
Cl2: 1607 νNC cm-1. Nujol: 1603 νNC, 1312, 1226, 916 νCS, 837
87.346(18)°, V ) 3309.7(10) Å3, Z ) 2, µ(Mo KR) ) 2.968 mm-1
,
Dcalc ) 1.642 Mg m-3, T ) 293(2) K, clear platy needles, 6326
independent measured reflections, R1 ) 0.0504, wR2 ) 0.1314,
5306 independent absorption-corrected reflections [I > 2σ(I),
2θ e 45°], 616 parameters, CCDC 275853.
Preparation of [Ir(η2-SCNMe2){η1-C(dO)H}Cl(PPh3)2]
(13). [Ir(η2-SCNMe2)Cl(CO)(PPh3)2]Cl (10: 0.20 g, 0.22 mmol)
was dissolved in dichloromethane (10 mL) and ethanol added
(20 mL). A filtered solution of NaBH4 (0.10 g, 2.63 mmol) in
ethanol (15 mL) was added and the reaction stirred for 30 min.
The colorless precipitate was filtered, washed with ethanol (20
mL) and petroleum ether (30 mL), and dried. Yield: 0.19 g
(99%). The complex could be recrystallized from a mixture of
dichloromethane and ethanol as a dichloromethane hemisol-
vate. IR CH2Cl2: 2720, 2592 νCH, 1618 νCO, 1568 νCN cm-1
.
Nujol: 2700, 2670, 2572 νCH, 1620 νCO, 1562, 1556 νCN, 1342,
1317, 1236, 930 νCS cm-1. NMR (CDCl3, 25 °C) 1H: 2.11, 2.38
(s × 2, 6 H, CH3), 7.73, 7.28 (m × 2, 30 H, C6H5), 14.67 (t, 1 H,
HCO, 3JHP ) 6.6 Hz). 31P{1H}: 2.4 ppm. 13C(1H coupled): 215.2
1
2
2
(dt, HCO, JCH ) 164.2, JCP ) 5.4), 205.3 (s br, CS, JCP not
resolved), 135.0 (dtv, o/m-C6H5, JCP not resolved, 1JCH ) 162.4),
131.4 (s, p-C6H5), 127.7 (dtv, o/m-C6H5, JCP not resolved, JCH
1
) 161.3), 130.6 (ttv, i-C6H5, JPC ) 23.2, 2JCH ) 7.2), 43.4, 42.9
1
(q × 2, CH3, JCH ) 139.2 Hz) ppm. FAB-MS m/z (% abun-
dance): 868 (100) [M]+, 834 (13) [M - Cl]+, 805 (7) [M - Cl -
HCO]+, 752 (3) [M - HCO - SCNMe2]+, 715 (3) [M - Cl -
HCO - SCNMe2]+, 605 (3) [M - PPh3]+, 578 (41) [M - HCO
- PPh3]+, 542 (33) [M - Cl - HCO - PPh3]+. Anal. Found:
C, 52.5; H, 3.6; N, 1.3. C40H37ClIrNOP2S‚0.5CH2Cl2 requires:
1
cm-1. NMR (CDCl3, 25 °C) H: 2.17, 2.20 (s × 2, 6 H, CH3),
7.20-8.10 (m, 30 H, C6H5) ppm. 31P{1H}: -11.9 ppm. FAB-
MS m/z (% abundance): 875 (36) [M]+, 840 (100) [M - Cl]+,
787 (2) [M - SCNMe2]+, 752 (1) [M - Cl - SCNMe2]+, 615 (4)
[M - PPh3]+, 578 (17) [M - Cl - PPh3]+, 542 (25) [M - 2Cl -
PPh3]+, 497 (5) [M - 2Cl - PPh3 - NMe2]+. Anal. Found: C,
52.8; H, 4.2; N, 1.6. C39H36Cl2IrNP2S requires: C, 53.5; H, 4.1;
N, 1.6. Crystals of a bis(dichloromethane) solvate suitable for
crystallographic analysis were grown by layering ethanol on
a dichloromethane solution of the complex. Crystal data for
11‚(CH2Cl2)2: C41H40Cl6IrNP2S, Mw ) 1045.64, triclinic, P1h
(#2), a ) 12.5073(18) Å, b ) 12.9507(16) Å, c ) 13.3127(11) Å,
R ) 85.265(7)°, â ) 87.535(12)°, γ ) 88.242(12)°, V ) 2146.2-
1
C, 52.4; H, 4.1; N, 1.5 (CH2Cl2 by H NMR integration).
Preparation of [Ir(η2-SCNMe2){η1-C(dO)OEt}Cl(PPh3)2]
(14). [Ir(η2-SCNMe2)Cl(CO)(PPh3)2]Cl (10: 0.20 g, 0.22 mmol)
was added to an ethanolic solution of NaOEt [prepared by
dissolving sodium (0.2 g) in ethanol (20 mL)], giving rise to a
rapid reaction involving a brief color change to yellow as the
starting material reacted in solution before precipitating as a
colorless product. After stirring for 30 min to ensure complete
reaction, the crystals were filtered off, washed with ethanol,
and recrystallized from dichloromethane and ethanol. The
colorless product was washed with petroleum ether (20 mL)
and hexane (10 mL) and dried. Yield: 0.18 g (89%). IR CH2-
(4) Å3, Z ) 2, µ(Mo KR) ) 3.638 mm-1, Dcalc ) 1.618 Mg m-3
,
T ) 293(2) K, yellow needles, 7546 independent measured
reflections. R1 ) 0.0456, wR2 ) 0.0980, 5862 independent
absorption-corrected reflections [I > 2σ(I), 2θ e 50°] and 453
parameters, CCDC 275852.
Cl2: 1605 νCO, 1573 νNC cm-1. Nujol: 1618 νCO, 1578, 1572 νNC
,
1315, 1231, 1169, 1041, 914 νCS, 865 cm-1. NMR (CDCl3, 25 °)
3
1H: 0.66 (t, 3 H, CCH3, JHH ) 7.3), 2.14, 2.20 (s × 2, 6 H,
2
NCH3), 3.57 (q, 2 H, OCH2, JHH ) 7.3 Hz), 7.20-8.10 (m, 30
Preparation of [Ir(η2-SCNMe2)Cl(CS)(PPh3)2]Cl (12‚
Cl). [IrCl(CS)(PPh3)2] (0.30 g, 0.38 mmol) and Me2NC(S)Cl
(0.05 g, 0.41 mmol) were dried under vacuum, and dry,
degassed tetrahydrofuran (20 mL) was added under nitrogen.
This suspension was heated under reflux anaerobically for 3
h, leading to a suspension. The product was filtered off, washed
with petroleum ether (30 mL), and dried. Yield: 0.31 g (90%).
The salt could be recrystallized from a mixture of dichlo-
romethane and ethanol as a dichloromethane hemisolvate. IR
CH2Cl2: 1615 νNC cm-1. Nujol: 1616 νNC, 1349 νCS, 1217, 921
νCS, 844 cm-1. NMR (25 °C) 1H (CDCl3): 2.57, 2.77 (s × 2, 6 H,
CH3), 7.40-7.85 (m, 30 H, C6H5) ppm. 13C{1H} (1:2 CDCl3/CH2-
Cl2): 254.5 (t, CS, 2JCP ) 8.1), 195.2 (t, SCN, 2JCP ) 3.6), 134.2
(tv, o/m-C6H5, JCP not resolved), 132.2 (s, p-C6H5), 128.8 (tv,
o/m-C6H5, JCP not resolved), 126.3 (tv, i-C6H5, JCP ) 29.5 Hz),
48.6, 45.3 (CH3) ppm. 31P{1H}: -0.7 ppm. FAB-MS m/z (%
H, C6H5). 13C{1H}: 202.0 (t, SCN, JCP not resolved), 168.3 (t,
2
CO2, JCP ) 6.3), 135.1 (tv, o/m-C6H5, JCP not resolved), 132.3
(tv, i-C6H5, JCP ) 26.8),129.5 (s, p-C6H5), 127.3 (tv, o/m-C6H5,
JCP not resolved), 59.8 (OCH2), 44.8, 42.2 (NCH3), 14.1 (CCH3)
ppm. 31P{1H}: -6.5 ppm. FAB-MS m/z (% abundance): 913
(9) [M]+, 878 (8) [M - Cl]+, 868 (32) [M - OEt]+, 840 (11) [M
- CO2Et]+, 806 (3) [M - Cl - CO2Et]+, 745 (12) [M - Cl -
OEt - SCNMe2]+, 715 (2) [Ir(PPh3)2]+, 651 (2) [M - PPh3]+,
606 (5) [M - OEt - PPh3]+, 578 (25) [M - CO2Et - PPh3]+,
542 (26) [M - Cl - CO2Et - PPh3]+, 497 (6) [IrCS(PPh3)]+.
Anal. Found: C, 54.5; H, 4.4; N, 1.5. C42H41ClIrNO2P2S‚0.25CH2-
Cl2 requires: C, 54.3; H, 4.5; N, 1.5.
Acknowledgment. We are grateful to the EPSRC
(UK) for funding and contributions toward diffraction

Thiocarbamoyl Complexes of Ru(II), Rh(III), Ir(III)
Organometallics, Vol. 24, No. 22, 2005 5355
of 2‚PF6 (CCDC 275850), 3‚CHCl3 (CCDC 275851), 11‚
(CH2Cl2)2 (CCDC 275852), and 12‚(CHCl3)6 (CCDC 275853);
Table S1 collating structural data for metallathiirenes of
ruthenium, rhodium, and iridium. This material is available
free of charge via the Internet at http://pubs.acs.org.
equipment. One of us (J.D.E.T.W.-E.) gratefully ac-
knowledges the Ramsay Memorial Trust for provision
of a Fellowship. We would like to thank Johnson
Matthey Ltd. for the generous loan of ruthenium salts.
Supporting Information Available: X-ray crystallo-
graphic files in CIF format for the structure determinations
OM050514C