Organometallic macrocycle chemistry. 5.1 σ-vinyl and σ-aryl complexes of ruthenium(II) ligated by 1,4,7-trithiacyclononane: X-ray crystal structure of [Ru(CH=CH2)(CO)(PPh3)([9]aneS 3)]PF6·2CH2Cl2

Article abstract of DOI:10.1021/om960129a

The reaction of coordinatively unsaturated σ-vinyl complexes [Ru(CR=CHR′)Cl(CO)(PPh₃)₂] with 1,4,7-trithiacyclononane ([9]aneS₃) provides chiral salts of the half-sandwich complexes [Ru(CR=CHR′)(CO)(PPh₃)([9]aneS₃)]⁺. The synthesis of the σ-aryl complex [Ru(C₆H₄Me-4)(CO)(PPh₃)([9]aneS ₃)]⁺ is also described. A representative NMR study of one example allowed the assignment of individual chemical shifts for the 12 diastereotopic proton environments of the macrocycle. The crystal structure of [Ru(CH=CH₂)(CO)(PPh₃)-([9]aneS₃)]PF ₆·2CH₂Cl₂ is also reported.

Full text of DOI:10.1021/om960129a

Organometallics 1996, 15, 5409-5415
5409
Or ga n om eta llic Ma cr ocycle Ch em istr y. 5.1 σ-Vin yl a n d
σ-Ar yl Com p lexes of Ru th en iu m (II) Liga ted by
1,4,7-Tr ith ia cyclon on a n e: X-r a y Cr ysta l Str u ctu r e of
[Ru (CHdCH2)(CO)(P P h 3)([9]a n eS3)]P F 6‚2CH2Cl2
J ason C. Cannadine, Anthony F. Hill,* Andrew J . P. White,
David J . Williams, and J ames D. E. T. Wilton-Ely
Department of Chemistry, Imperial College of Science, Technology and Medicine,
South Kensington, London, U.K.
Received February 20, 1996X
The reaction of coordinatively unsaturated σ-vinyl complexes [Ru(CRdCHR′)Cl(CO)(PPh3)2]
with 1,4,7-trithiacyclononane ([9]aneS3) provides chiral salts of the “half-sandwich” complexes
[Ru(CRdCHR′)(CO)(PPh3)([9]aneS3)]+. The synthesis of the σ-aryl complex [Ru(C6H4Me-
4)(CO)(PPh3)([9]aneS3)]+ is also described. A representative NMR study of one example
allowed the assignment of individual chemical shifts for the 12 diastereotopic proton
environments of the macrocycle. The crystal structure of [Ru(CHdCH2)(CO)(PPh3)-
.
([9]aneS3)]PF6 2CH2Cl2 is also reported.
In tr od u ction
add dihalomethanes to provide σ-halomethyl deriva-
tives, these being rare examples of σ-alkyl complexes
ligated by thioether macrocycles. We have been
prompted to investigate the organometallic chemistry
of sulfur-based macrocycles7 by a suggestion2a that these
ligands might emulate the properties associated with
phosphine ligands, while offering the advantage of
coordination sphere robustness typical of macrocycle
complexes. Thus, while phosphines characteristically
break down under more extreme conditions of industrial
catalysis via P-C bond cleavage reactions, it was
suggested that this problem would not arise with crown
thioethers. We report herein the synthesis of a range
of σ-vinyl and σ-aryl complexes ligated by 1,4,7-trithia-
cyclononane as representatives of species that might
serve as model compounds in the subsequent develop-
ment of alkene-modification and C1 coupling catalysts.
Aspects of the work have been communicated in pre-
liminary form.8
The coordination chemistry of crown thioethers has
previously been preoccupied with simple 1:1 or 2:1
adducts with metal halides or oxo halides.2 Scattered
reports have dealt with organometallic complexes li-
gated by the facially coordinating tridentate thioether
1,4,7-trithiacyclononane ([9]aneS3); however, these have
involved typically “innocent” ligands, e.g., CO,3 ben-
zene,4 cyclopentadienyl,5 and recently olefins.6 The
series of rhodium(I) complexes described by Schro¨der6
are of interest in that they are reported to oxidatively
* To whom correspondence should be addressed. E-mail:
a.hill@ic.ac.uk.
X Abstract published in Advance ACS Abstracts, October 15, 1996.
(1) Part 4: Hector, A. L.; Hill, A. F. Inorg. Chem. 1995, 34, 3797.
(2) Cooper, S.; Rawle, S. C. Struct. Bond. 1990, 72, 1. Blake, A. J .;
Schro¨der, M. Adv. Inorg. Chem. 1990, 35, 1.
(3) Adams, R. D.; Yamamoto, J . H. Organometallics 1995, 14, 3704.
Adams, R. D.; Falloon, S. B.; McBride, K. T.; Yamamoto, J . H.
Organometallics 1995, 14, 1739. Smith R. J .; Salek, S. N.; Went, M.
J .; Blower, P. J .; Barnard, N. J . J . Chem. Soc., Dalton Trans. 1994,
3165. Mohmand, G. F.; Thiele, K.; Went, M. J . J . Organomet. Chem.
1994, 471,.241. Laurenczy, G.; Merbach, A. E.; Moullet, B.; Roulet, R.;
Hoferkamp, L.; Suss-Fink, G. Helv. Chim. Acta 1993, 76, 2936. Blake,
A. J .; Halcrow, M. A.; Schro¨der, M. Acta Crystallogr., Sect. C 1993,
49, 85. Rossi, S.; Kallinen, K.; Pursiainen, J .; Pakkanen, T. T.;
Pakkanen, T. A., J . Organomet. Chem. 1992, 440, 367. Hoferkamp,
L.; Rheinwald, G.; Stoeklievans, H.; Suss-Fink, G. Helv. Chim. Acta
1992, 75, 2227. Castro, H. H. K.; Hissink, C. E.; Teuben, J . H.;
Vaalburg, W.; Panek, K. Rec. Trav. Chim. Pays-Bas 1992, 111, 105.
Haefner, S. C.; Dunbar, K. R.; Bender, C. J . Am. Chem. Soc. 1991,
113, 9540. Kim, H. J .; Do, Y. K.; Lee, H. W. J eong, J . H.; Sohn, Y. S.
Bull. Kor. Chem. Soc. 1991, 12, 257. Smith, R. J .; Admans, G. D.;
Richardson, A. P.; Kuppers, H. J .; Blower, P. J . J . Chem. Soc., Chem.
Commun. 1991, 475. Sellmann, D.; Neuner, H. P.; Moll, M.; Knoch, F.
Z. Naturforsch. 1991, 46b, 303. Elias, H.; Schmidt, G.; Kuppers, H. J .;
Saher, M.; Wieghardt, K.; Nuber, B.; Weiss, J . Inorg. Chem. 1989, 28,
3021. Pomp, C.; Brueke, S.; Kuppers, H. J .; Wieghardt, K.; Kruger,
C.; Nuber, B.; Weiss, J . Z. Naturforsch. 1988, 43b, 299. Ashby, M. T.;
Lichtenberger, D. L. Inorg. Chem. 1985, 24, 636. Sellmann, D.; Zapf,
L. Angew. Chem., Int. Ed. Engl. 1984, 23, 807.
Exp er im en ta l Section
Gen er a l P r oced u r es. All manipulations were carried out
under aerobic conditions. Solvents, alkynes, and the ligand
[9]aneS3 were used as received from commercial sources. 1H,
13C, and 31P-{1H} NMR spectra were recorded on a Bruker
WH-400 or J EOL GX-270 NMR spectrometer and referenced
against internal Me4Si (1H), CDCl3 (13C) or external H3PO4
(31P). For the purposes of NMR assignments the vinyl sub-
stituents are designated according to Figure 1. In some
instances, the poor solubility of the [RuR(CO)(PPh3)([9]-
aneS3)]+ (2+) salts precluded the convenient obtention of 13C
NMR data; however, representative examples [R ) CHdCH2,
C6H4Me, and C(CtCPh)dCHPh] are included. Infrared spec-
tra were recorded using a Perkin-Elmer 1720-X FT-IR spec-
trometer. Characteristic infrared absorbances for PPh3 are
(4) Bell, M. N.; Blake, A. J .; Christie, R. M.; Gould, R. O.; Holder,
A. J .; Hyde, T. I.; Schro¨der, M.; Yellowlees, L. J . J . Chem. Soc., Dalton
Trans. 1992, 2977. Bennett, M. A.; Goh, L. Y.; Willis, A. C. J . Chem.
Soc., Chem. Commun. 1992, 1180.
(5) Blake, A. J .; Crofts, R. D.; Reid, G.; Schro¨der, M. J . Organomet.
Chem. 1989, 359, 371.
(6) Blake, A. J .; Halcrow, M. A.; Schro¨der, M. J . Chem. Soc., Dalton
Trans. 1994, 1631. Blake, A. J .; Gould, R. O.; Halcrow, M. A.; Schro¨der,
M. Ibid. 1994, 2197.
(7) Alcock, N. W.; Cannadine, J . C.; Clark, G. R.; Hill, A. F. J . Chem.
Soc., Dalton Trans. 1993, 1131. Hill, A. F.; Alcock, N. W.; Cannadine,
J . C.; Clark, G. R. J . Organomet. Chem. 1992, 426, C40.
(8) Cannadine, J .; Hector, A. L.; Hill, A. F. Organometallics 1992,
11, 2323.
S0276-7333(96)00129-X CCC: $12.00 © 1996 American Chemical Society

5410 Organometallics, Vol. 15, No. 25, 1996
Cannadine et al.
C2,6(C6H5), J (PC) ) 10.8 Hz], 127.6 [s, dCH2], 35.9, 34.8, 34.3,
34.2, 32.9, 32.7 [s × 6, SCH2] ppm. Anal. Found: C, 43.3; H,
4.0.
C27H30F6OP2RuS3 requires: C, 43.6; H, 4.1. FAB-MS:
m/ z (abundance) [assignment] ) 599 (100) [M]+, 571 (4) [M
- vinyl]+, 542 (4) [M - vinyl - CO]+, 515 (16) [M - vinyl -
CO - C2H4]+, 459 (6) [M - vinyl - CO - 3(C2H4)]+.
F igu r e 1. Vinyl substituent designation.
Syn t h esis of [R u (CH dCH C6H 4Me-4)(CO)(P P h 3)([9]-
a n eS3)]X [X ) Cl (2b‚Cl), AsF 6,(2b‚AsF 6), BF 4 (2b‚BF 4)].
(a) A dark red solution of 1,4,7-trithiacyclononane (0.04 g, 0.22
mmol) and [Ru(CHdCHC6H4Me-4)Cl(CO)(PPh3)2] (1b) (0.20 g,
0.22 mmol) in dichloromethane (20 mL) was stirred for 90 m
during which time the solution decolorized to pale yellow.
Addition of a solution of Na[AsF6] (0.10 g, 0.47 mmol) in water
(1.0 mL) and ethanol (30 mL) followed by concentration (rotary
evaporator) of the solution to ca. 15 mL provided pale yellow
crystals of the desired product. Yield: 0.14 g (80%). The
corresponding chloride salt was obtained by omitting the
addition of Na[AsF6] and had all spectroscopic data associated
with the complex identical to those for the less soluble AsF6
salt.
(b) A solution of [RuH(NCMe)2(CO)(PPh3)2]BF4 (0.41 g, 0.50
mmol) in dichloromethane (30 mL) was treated with 4-ethynyl-
toluene (0.3 mL) and warmed gently for 2 min. The colorless
solution was then treated with 1,4,7-trithiacyclononane (0.10
g, 0.55 mmol), stirred for 20 min, and then diluted with ethanol
(30 mL). Concentration of the mixture afforded pale cream
crystals of the salt (2b‚BF 4). Yield: 0.32 g (83%).
not listed. FAB mass spectrometry was carried out using an
Autospec-Q mass spectrometer employing nitrobenzyl alcohol
as matrix. Assignments are based on “M” representing the
complex cation of the salts. Synthetic procedures for the
complexes [Ru(CRdCHR′)Cl(CO)(PPh3)2],9,10 [Ru(C6H4Me-4)-
Cl(CO)(PPh3)2],11 [RuHCl(CO)(PPh3)3],12 [RuH(NCMe)2(CO)-
(PPh3)2]BF4,13 and [Ru{C(CtCPh)dCHPh}Cl(CO)(PPh3)2]14
have been described elsewhere.
Syn th esis of [Ru (CHdCH2)Cl(CO)(P P h 3)2] (1a ). [Ru-
HCl(CO)(PPh3)3] (0.40 g, 0.42 mmol) was suspended in dichlo-
romethane (50 mL) and a stream of acetylene passed through
the suspension for 30 s resulting in a deep orange solution.
The color darkened over a period of 15 min of stirring. Ethanol
(20 mL) was added, and the mixture concentrated under
reduced pressure to provide orange crystals. These were
isolated by filtration, washed with ethanol (10 mL) and
petroleum ether (10 mL), and dried. Yield: 0.30 g (quantita-
tive). IR (Nujol): 1918vs [ν(CO)], 1566m [ν(CdC)], 1215m,
851w cm-1; (CH2Cl2) 1933vs [ν(CO)], 1559w [ν(CdC)] cm-1
.
NMR (CDCl3, 25 °C): 1H δ 4.51 [dd, 1 H, Hâ, J (HRâ) ) 13.9
Hz, J (Hââ′) ) 2.0 Hz], 5.11 [m, 1 H, Hâ′], 7.41, 7.60 [m × 2,
30 H, C6H5], 7.83 [ddt, 1 H, HR, J (PHR) ) 1.8 Hz, J (HRHâ) )
13.8 Hz, J (HRHâ′) ) 6.3 Hz] ppm; 31P-{1H} 31.2 ppm. Anal.
Found: C,65.5; H, 4.6. C39H33ClOP2Ru requires: C, 65.4; H,
4.6. FAB-MS m/ z (abundance) [assignment] ) 689 (8) [M -
CO]+, 654 (12) [M - Cl - CO]+, 625 [Ru(PPh3)2]+, 363 (14)
[RuPPh3]+, 262 (100) [HPPh3]+.
(c) A suspension of [RuHCl(CO)(PPh3)3] (0.58 g, 0.50 mmol)
in dichloromethane (20 mL) was treated with 4-ethynyltoluene
(0.3 mL, excess) and heated under reflux for 1 min. The
resulting red solution was then treated with 1,4,7-trithia-
cyclononane (0.10 g, 0.55 mmol) followed by a solution of
NH4[PF6] (0.16 g, 1.0 mmol) in water (0.5 mL) and ethanol 15
mL. Following decolorization, the mixture was concentrated
(rotary evaporator) to afford pale yellow crystals of the salt
(2b‚P F 6). Yield: 0.32 g (76%). IR: (Nujol) 1970vs [ν(CO)],
936w cm-1; (CH2Cl2) 1976vs [ν(CO)] cm-1. NMR (CDCl3, 25
°C): 1H δ 1.70, 2.10, 2.59, 2.82, 2.96, 3.13 [m × 6, 12 H, SCH2],
2.27 [s, 3 H, CH3], 6.54 [d, 1 H, Hâ, J (HRHâ) ) 16.9 Hz], 6.96,
6.78 [(AB)2, 4 H, C6H4, J (AB) ) 8.0 Hz], 7.29 [dd, 1 H, HR,
J (HRHâ) ) 16.9 Hz, J (PHR) ) 6.8 Hz], 7.51-7.40 [m, 15 H,
C6H5] ppm; 13C-{1H} not sufficiently soluble; 31P-{1H} 40.6
Syn t h esis of [R u (CHdCH 2)(CO)(P P h 3)([9]a n eS3)]P F 6
(2a ‚P F 6). [Ru(CHdCH2)Cl(CO)(PPh3)2] (1a ) (0.25 g, 0.35
mmol) was dissolved in dichloromethane (25 mL) and then
1,4,7-trithiacyclononane (0.07 g, 0.40 mmol) added. The
solution was stirred for 20 min, during which time the color
of the solution became progressively paler. All solvent was
then removed and diethyl ether (20 mL) added followed by
ultrasonic trituration to give off-white crystals. These were
isolated by filtration, washed with diethyl ether (10 mL) and
petroleum ether (10 mL), and then dried in vacuo. The
material thus obtained was shown to be spectroscopically pure;
however, metathesis of the chloride counteranion for PF6- can
be carried out by recrystallizing the crude material from a
mixture of dichloromethane, ethanol, and water containing
2-3 equiv of K[PF6]. IR: (Nujol) 1970vs [ν(CO)], 1556w
[ν(CdC)], 1312vw, 1300vw, 1255w, 840vs [ν(PF)] cm-1; (CH2Cl2)
1978vs [ν(CO)], 1559w [ν(CdC)] cm-1. NMR (CDCl3, 25 °C):
1H δ 1.84, 2.18, 2.43, 2.80, 3.15 [m × 5, 12 H, SCH2], 5.45 [dd,
1 H, Hâ, J (HRHâ) ) 17.8 Hz, J (Hââ′) ) 1.7 Hz], 5.90 [ddd, 1
H, Hâ′, J (HRHâ′) ) 10.2 Hz, J (PHâ′) ≈ J (HâHâ′) ) 1.7 Hz],
6.95 [ddd, 1 H, HR, J (PHR) ) 6.9 Hz, J (HRHâ) ) 17.5 Hz,
J (HRHâ′) ) 10.2 Hz]; 31P-{1H} 40.3 ppm; 13C-{1H} (CDCl3:
CH2Cl2 1:4) 198.7 [d, CO, J (PC) ) 16.1 Hz], 148.0 [d, RuCH,
J (PC) ) 10.7 Hz], 133.8 [d, C3,5(C6H5), J (PC) ) 9.0 Hz], 131.7
[d, C1(C6H5), J (PC) ) 46.4 Hz], 131.0 [s, C4(C6H5)], 128.6 [d,
ppm. Anal. Found: C, 46.0, H, 4.0.
C34H36AsF6OPRuS3
requires: C, 46.5; H, 4.1. FAB-MS: m/ z (abundance) [as-
signment] ) 689 (40) [M]+, 515 (10) [M - [9]aneS3]+.
Syn th esis of [Ru (CP h dCHP h )(CO)(P P h 3)([9]a n eS3)]-
P F 6 (2c‚P F 6). (a) A suspension of [RuHCl(CO)(PPh3)3] (0.47
g, 0.50 mmol) and diphenylacetylene (0.30 g, 1.70 mmol) in
tetrahydrofuran (25 mL) was heated under reflux for 20 m.
The solution was allowed to cool, treated with 1,4,7-trithia-
cyclononane (0.09 g, 0.50 mmol), and heated to reflux for 5 m.
The solution was allowed to cool and then treated with a
solution of NH4[PF6] (0.20, 1.22 mmol) in water (1.0 mL) and
ethanol (20 mL). Concentration of the mixture under reduced
pressure provided pale green crystals of the title complex. Yield
0.30 g (63%). This material was spectroscopically pure;
however, an analytically pure sample of a dichloromethane
disolvate was obtained by recrystallization twice from
mixture of dichloromethane and ethanol.
a
(b) 2c‚AsF 6. A suspension of [Ru(CPhdCHPh)Cl(CO)-
(PPh3)2] (1c) (0.20 g, 0.25 mmol) and 1,4,7-trithiacyclononane
(0.05 g, 0.28 mmol) in tetrahydrofuran (20 mL) was heated
under reflux for 2 h during which time the solution turned
pale yellow. A solution of Na[AsF6] (0.10 g, 1.3 mmol) in water
(1.0 mL) and ethanol (20 mL) was added to the hot solution,
which was then concentrated under reduced pressure to ca.
15 mL and cooled to 0 °C to effect the formation of cream
microcrystals. Yield: 0.19 g (80%). IR: (Nujol) 1975sh,
1956vs [ν(CO)], 1592w [ν(CdC)], 1310w, 1299w, 836 [ν(PF)]
cm-1; (CH2Cl2) 1975vs [ν(CO)], 1594w [ν(CdC)] cm-1. NMR
(CDCl3, 25 °C): 1H δ 0.86, 1.23, 1.60, 2.36, 2.61, 2.83, 3.08,
3.22 [m × 8, 12 H, SCH2], 6.03 [s(br), 1 H, dCHPh], 6.30 [d, 2
(9) Torres, M. R.; Vegas, A.; Santos, A. J . Organomet. Chem. 1986,
309 169. Harris, M. C. J .; Hill, A. F. Ibid. 1992, 438, 209.
(10) For a recent review of the hydroruthenation of alkynes and
σ-vinyl complexes of ruthenium see: Hill, A. F. In Comprehensive
Organometallic Chemistry II; Abel, E. W., Stone, F. G. A., Wilkinson,
G., Eds.; Pergamon Press: Oxford, 1995; Vol. 7.
(11) Roper, W. R.; Wright, L. J . J . Organomet. Chem. 1977, 142,
C1. Rickard, C. E. F.; Roper, W. R.; Taylor, G. E.; Waters, J . M.; Wright,
L. J . Ibid. 1990, 389, 375.
(12) Laing, K. R.; Roper, W. R. J . Chem. Soc. A 1970, 2149.
(13) Cavit, B. E.; Grundy, K. R.; Roper, W. R. J . Chem. Soc., Chem.
Commun. 1972, 60.
(14) (a) Hill, A. F.; Melling, R. P. J . Organomet. Chem. 1990, 396,
C22. (b) Hill, A. F.; Harris, M. C. J .; Melling, R. P. Polyhedron 1992,
11, 781.

Organometallic Macrocycle Chemistry
Organometallics, Vol. 15, No. 25, 1996 5411
H, H2,6(CC6H5), J (HH) ) 6.6 Hz], 6.88, 7.11, 7.21, 7.48 [m ×
4, 23 H, C6H5] ppm; 31P-{1H} 38.7 ppm; 13C-{1H} not
sufficiently soluble. Anal. Found for chloride salt: C, 51.7;
{1H} 40.4 ppm. Anal. Found: C, 46.8; H, 4.2. C32H34F6OP2-
RuS3 0.25CH2Cl2 requires: C, 46.7; H, 4.2.
.
Cr ysta llogr a p h ic An a lysis. Crystals of (2a ‚P F 6)‚2CH2-
Cl2 suitable for diffraction analysis were grown by slow
diffusion of a solution of the complex in dichloromethane into
ethanol.
Crystal data for (2a ‚P F 6).2CH2Cl2, C27H30F6OP2RuS3‚
2CH2Cl2: M ) 913.6, triclinic, space group P1h, a ) 10.208(3)
Å, b ) 11.685(3) Å, c ) 16.162(3) Å, R ) 99.61(2)°, â )
104.01(2)°, γ ) 93.32(2)°, V ) 1834.5(7) Å3, Z ) 2, Dc ) 1.654
g cm-1, µ(Mo-KR) ) 10.3 cm-1, F(000) ) 920. A pale yellow
prismatic block of dimensions 0.50 × 0.43 × 0.27 mm was used,
coated with epoxy resin to inhibit desolvation.
Da ta Collection a n d P r ocessin g. Data were measured
on a Siemens P4/PC diffractometer with Mo KR radiation
(graphite monochromator) using ω-scans. A total of 4760
independent reflections were measured (2θ e 45°), of which
4163 had |Fo| > 4σ(|Fo|) and were considered to be observed.
These data were corrected for Lorentz and polarization factors,
but not for absorption.
.
H, 4.5. C39H38ClOPRuS3 2CH2Cl2 requires: C, 51.5; H, 4.4.
Solvent of crystallization by NMR integration. Anal. Found
for hexafluoroarsenate salt: C, 49.9; H, 4.1. C39H38AsF6-
OPRuS3 requires: C49.8; H, 4.1. FAB-MS: m/ z (abundance)
[assignment] ) 751 (100) [M]+, 571 (5) [M - vinyl]+, 543 (3)
[M - vinyl - CO]+, 515 (11) [M - CO - vinyl - C2H4]+, 461
(8) [M - CO - PPh3]+, 433 (32) [M - CO - C2H4 - PPh3]+,
263 (8) [HPPh3]+.
Syn th esis of [Ru {C(CtCP h )dCHP h }(CO)(P P h 3)([9]-
a n eS3)]P F 6 (2d ‚P F 6). [Ru{C(CtCPh)dCHPh}Cl(CO)(PPh3)2]
(1d ) (0.30 g, 0.337 mmol) and 1,4,7-trithiacyclononane (0.07
g, 0.40 mmol) were dissolved in dichloromethane (20 mL) and
the mixture stirred for 24 h. During this period the solution
became much lighter in color, and all solvent was then
removed. Ultrasonic trituration in diethyl ether (25 mL)
provided a cream-colored solid that was filtered, washed with
diethyl ether (20 mL) and petroleum ether (10 mL), and dried.
Yield: 0.25 g (92%). The material thus obtained was shown
to be spectroscopically pure; however, metathesis of the
chloride counteranion for PF6- can be carried out by recrystal-
lizing the crude material from a mixture of dichloromethane,
ethanol, and water containing 2-3 equiv of NH4[PF6]. IR:
(Nujol) 2157w [ν(CtC)], 1973vs [ν(CO)] 1593 [ν(CdC)], 1298w,
915w, 838vs [ν(PF)] cm-1; (CH2Cl2) 2162vw [ν(CtC)], 1982vs
Str u ctu r e An a lysis a n d Refin em en t. The structure was
solved by the heavy atom method. All the non-hydrogen atoms
were refined anisotropically, all phenyl rings being treated as
-
idealized rigid bodies. The PF6 counteranion was found to
be disordered: Two discrete 50% occupancy orientations with
a common F-P-F axis were identified. The positions of all
the hydrogen atoms were located from a ∆F map; all of these
positions were subsequently idealized, assigned isotropic
thermal parameters [U(H) ) 1.2 Ueq(C)] and allowed to ride
on their parent carbon atoms. Refinement was by full-matrix
least-squares methods based on F2 to give for the observed data
R1 ) 0.038, wR2 ) 0.094 for 415 parameters. The maximum
and minimum residual electron densities in the final ∆F map
were 0.50 and -0.43 eÅ-3, respectively. The mean and
maximum shift/error ratios in the final refinement cycle were
0.002 and 0.033, respectively. Computations were carried out
on a 90 MHz Pentium PC using the SHELXTL PC program
system (Version 5.03, Siemens Analytical X-ray Instruments,
Inc., Madison, WI, 1994). Additional material available from
the Cambridge Crystallographic Data Centre comprises H-
atom coordinates, thermal parameters and remaining bond
lengths and angles.
[ν(CO)] , 1594w [ν(CdC)] cm-1
.
NMR (CDCl3, 25 °C): 1H δ
1.80, 2.12, 2.84, 3.22, 3.59, 3.77 [m × 6, 12 H, SCH2], 6.62
[s(br), 1 H, Hâ ], 7.08-7.6 [m, 25 H, PC6H5 and CC6H5] ppm;
31P-{1H} 38.8 ppm; 13C-{1H} 198.2 [d, CO, J (PC) ) 17.9 Hz],
146.6 [s, RuCdC], 139.6 [C1(tCC6H5)], 133.7 [d, C3,5(PC6H5),
J (PC) ) 8.9 Hz], 131.8 [d, C1(PC6H5), J (PC) ) 46.4 Hz], 130.9
[C4(PC6H5)], 128.6 [d, C2,6(PC6H5), J (PC) ) 10.7 Hz], 128.4,
127.8, 127.4 [C2,3,5,6(CC6H5)], 127.6 [RuCdCH], 126.2
[C1(dCHC6H5)], 126.2, 124.7 [C4(C6H5)], 101.3, 99.4 [CtC],
37.5, 36.9, [s × 2, SCH2], 35.7[s(br), SCH2, S trans to P], 35.3
[d, SCH2, S trans to P, J (PC) ) 7.7 Hz], 34.3, 32.1 [s × 2, SCH2]
ppm. Anal. Found: C, 52.6; H, 4.1. C41H38F6OP2RuS3‚0.25CH2-
Cl2 requires: C, 52.6; H, 4.1. Solvent of crystallization by NMR
integration. FAB-MS: m/ z (abundance) [assignment] ) 775
(100) [M]+, 571 (3) [M - vinyl]+, 516 (9) [M - PPh3]+, 486 (4)
[M - CO - PPh3]+, 457 (28) [M - CO - PPh3 - C2H4]+.
Syn th esis of [Ru (C6H4Me-4)(CO)(P P h 3)([9]a n eS3)]P F 6
(2e‚P F 6). A suspension of [Ru(C6H4Me-4)Cl(CO)(PPh3)2] (1e)
(0.40 g, 0.51 mmol) in dichloromethane (40 mL) and ethanol
(20 mL) was treated with 1,4,7-trithiacyclononane (0.10 g, 0.57
mmol) and K[PF6] (0.19 g, 1.0 mmol) dissolved in water (1.0
mL) and ethanol (5 mL). The mixture was stirred for 2 h,
during which time a cloudy precipitate (KCl) formed from the
yellow solution. The solvent was removed under reduced
pressure and the residue triturated ultrasonically with diethyl
ether. The ether washings were discarded, and the residue
was dissolved in dichloromethane (30 mL) . The solution was
filtered through diatomaceous earth and the filtrate diluted
with ethanol (30 mL). The solution was concentrated under
reduced pressure to ca. 10 mL to effect the formation of
colorless microcrystals of the desired salt, which were isolated
by filtration, washed with ethanol (5 mL) and light petroleum
(2 × 10 mL), and dried in vacuo. Yield: 0.25 g (61%). Further
material could be obtained by concentration of the filtrate.
IR: (Nujol) 1974vs [ν(CO)], 840 [ν(PF)] cm-1; (CH2Cl2) 1976vs
Resu lts a n d Discu ssion
The σ-vinyl complexes [Ru(CRdCHR′)Cl(CO)(PPh3)2]10
are readily prepared for a wide range of substituents
R and R′ by reaction of [RuHCl(CO)(PPh3)3] with
alkynes RCtCR′,9 diynes (R ) CtCR′),14 vinyl [Hg-
(CRdCHR′)2],11 or dialkynyl mercurials (R ) CtCR′).14
These complexes, and the σ-aryl analogue [Ru(C6H4Me-
4)Cl(CO)(PPh3)2],11 by virtue of their coordinative un-
saturation, readily coordinate a wide range of mono-
dentate,15 bidentate,16 and tridentate17 ligands as well
as being intermediates in the hydrosulfination of alkynes
(15) Harris, M. C. J .; Hill, A. F. Organometallics 1991, 10, 3903.
Hill, A. F.; Melling, R. P.; Thompsett, A. R. J . Organomet. Chem. 1991,
402, C8. Herberhold, M.; Hill, A. F. Ibid. 1986, 315, 105. Herberhold,
M.; Hill, A. F. Ibid. 1988, 353, 249. Herberhold, M.; Hill, A. F. Ibid.
1989, 377, 151. Herberhold, M.; Hill, A. F. Ibid. 1990, 395, 327. Hill,
A. F. J . Chem. Soc., Chem. Commun. 1995, 741. Alcock, N. W.;
Cartwright, J .; Hill, A. F.; Marcellin, M.; Rawles, H. M. Ibid. 1995,
369. Gieren, A.; Ruiz-Perez, C.; Hu¨bner, T.; Herberhold, M.; Hill, A.
F. J . Chem. Soc., Dalton Trans. 1988, 1693. Torres, M. R.; Vegas, A.;
Santos, A.; Ros, J . J . Organomet. Chem. 1987, 326, 413. Torres, M. R.;
Santos, A.; Perales, A.; Ros, J . Ibid. 1988, 353, 221. Torres, M. R.;
Perales, A.; Loumrhari, H.; Ros, J . Ibid. 1990, 384, C61. Montoya, J .;
Santos, A.; Echavarren, A. M.; Ros, J . Ibid. 1990, 390, C57. Loumrhari,
H.; Ros, J .; Yanez, R.; Torres, M. R. Ibid. 1991, 408, 233. Loumrhari,
H.; Ros, J .; Torres, M. R.; Santos, A.; Echavarren, A. M. Ibid. 1991,
411, 255. Montoya, J .; Santos, A.; Lopez, J .; Echavarren, A. M.; Ros,
J .; Romero, A. Ibid. 1992, 426, 383. Torres, M. R.; Perales, A. Ros, J .
Organometallics 1988, 7, 1223.
[ν(CO)] cm-1
.
NMR (CDCl3, 25 °C): 1H δ 1.64, 2.17, 2.56-
3.37 [m × 3] 12 H, SCH2], 2.15 [s, 3 H, CH3], 6.58, 6.92 [m(br)
× 2, 4 H, C6H4-fluxional], 7.17-7.68 [m × 4, 30 H, C6H5] ppm;
13C-{1H} 198.6 [d, CO, J (PC) ) 17.8 Hz], 143.6 [d, C1(C6H4),
J (PC) ) 10.7 Hz], 142.0 [s(br), C2,6(C6H4)], 133.8 [d, C3,5(C6H5),
J (PC) ) 8.9 Hz], 132.1 [s, C4(C6H4)], 131.7 [d, C1(C6H5), J (PC)
) 46.6 Hz], 130.9 [s, C4(C6H5)], 129.0 [s, C3,5(C6H4)], 128.6 [d,
C2,6(C6H5), J (PC) ) 10.8 Hz], 38.0, 36.9, 31.8, 31.5 [s × 4,
SCH2], 35.6 [d, SCH2,S-trans to P, J (PC) ) 7.9 Hz], 32.5 [d,
SCH2, S trans to P, J (PC) ) 3.6 Hz], 20.6 [CH3] ppm; 31P-

5412 Organometallics, Vol. 15, No. 25, 1996
Cannadine et al.
Ch a r t 1. Coor d in a tion of 1,4,7-Tr ith ia cyclon on a n e
[9]a n eS3 a n d Rela ted F a cia lly Tr id en ta te Liga n d s
Sch em e 1. Syn th esis of σ-Hyd r oca r byl [9]a n eS3
Com p lexes
by [RuHCl(CO)(PPh3)3].18 We have recently been con-
cerned with the addition of polydentate ligands and
found that they provided a facile access to a range of
σ-organylhydrotris(pyrazolyl)borato complexes of ruthe-
nium(II), [Ru(CRdCHR′)(CO)(PPh3){HB(pz)3] (pz ) pyr-
azol-1-yl).17 The facial tridentate coordination of 1,4,7-
trithiacyclononane ([9]aneS3) to a metal is in some ways
reminiscent of the coordination of cyclopentadienyl,
arene, or hydrotris(pyrazolyl)borate ligands (Chart 1).
The reactions of [Ru(CRdCHR′)Cl(CO)(PPh3)2] (1)
with [9]aneS3 were therefore investigated. For these
purposes we chose three representative vinyl ligands:
unsubstituted (1a ), trans-â-monosubstituted (1b), and
R,â-disubstituted (1c). The parent vinyl complex
[Ru(CHdCH2)Cl(CO)(PPh3)2] (1a ) has been described as
forming in a mixture with poly-unsaturated vinyl
derivatives [Ru{(CHdCH)nCHdCH2}Cl(CO)(PPh3)2] from
the reaction of [RuHCl(CO)(PPh3)3] with ethyne. In our
hands this was not observed to be the case, and high
yields of pure (1a ) are obtained by judicious control of
reaction time and the amount of ethyne used (see
Experimental Section).
Addition of [9]aneS3 to a bright red solution of
[Ru(CHdCHC6H4Me-4)Cl(CO)(PPh3)2] (1b) leads to de-
colorization and the formation of a product formulated
as the salt [Ru(CHdCHC6H4Me-4)(CO)(PPh3)([9]aneS3)]-
Cl (2b‚Cl). Spectroscopic data for this material are
essentially identical to those of the more crystalline
compounds obtained by counterion metathesis with
Li[ClO4], NH4[PF6], or Na[AsF6]. In a similar manner
the reactions of [RuRCl(CO)(PPh3)2] [R ) CHdCH2 (1a ),
CPhdCHPh (1c)] with [9]aneS3 and NH4[PF6] provide
the salts [RuR(CO)(PPh3)([9]aneS3)]PF6 (R ) CHdCH2
(2a ‚P F 6), CPhdCHPh (2c‚P F 6)] (Scheme 1). The com-
plexes are thermally and aerobically stable as solids or
briefly stable in solution. The formulations rest on
spectroscopic data and an X-ray diffraction analysis of
the bis(dichloromethane) solvate of 2a ‚P F 6 (vide in-
fra): The gross molecular composition follows from
elemental microanalytical and FAB-MS data. These
include, in addition to a correctly distributed isotope
cluster for the molecular ion, fragmentations attribut-
able to loss of the macrocyclic, carbonyl, vinyl, and
phosphine ligands. The appearance of one ν(CO)-
associated infrared absorption [(Nujol) 1970 cm-1
(2b‚P F 6)] indicates that migratory insertion of the
alkenyl and carbonyl ligands has not occurred. 1H NMR
data associated with the macrocycle ligand in the
complexes are complicated (up to nine multiplets) due
to the chirality at ruthenium rendering all 12 macro-
cycle proton environments chemically inequivalent.
These data will be dealt with in more detail later (vide
infra), however, data associated with the vinyl ligand
are typical for such a ligand being bound trans to a good
donor ligand: The proton R to ruthenium in 2b+ appears
as a double-doublet (δ 7.29 ppm) showing trans coupling
to one proton (16.9 Hz) and one phosphorus (6.8 Hz).
The â-proton, however only shows resolvable coupling
to the R-proton. The 13C NMR data for the complexes
further confirm the formulations: The carbonyl ligand
in 2a + gives rise to a doublet (198.7 ppm) showing a
typical cis PRuCO coupling of 16.1 Hz, while the CR
resonance for the vinyl ligand appears as a doublet
[J (PC) ) 10.7 Hz] at 148.0 ppm. The six carbon atoms
of the macrocycle are chemically distinct and give rise
to six peaks in the region 10-40 ppm. For 2a + these
appear as singlets; however, in this and related ex-
amples two of these are either broad or resolved into
doublets. For example, in the case of the 4-tolyl
derivative [Ru(C6H4Me-4)(CO)(PPh3)([9]aneS3)]PF6
(2e‚P F 6) (vide infra) two doublets are clearly seen with
couplings to phosphorus of 7.9 and 3.6 Hz. In all the
spectra the two broadened or split resonances are
therefore attributed to the (diastereotopic) methylene
carbons bound to the sulfur atom trans to phosphorus.
We have recently been concerned with the coordina-
tion chemistry of R-alkynyl vinyl ligands bound to
ruthenium, osmium, and rhodium and have prepared
the complex [Ru{C(CtCPh)dCHPh}(CO)(PPh3){κ3-HB-
(pz)3}]PF6 via the reaction of [Ru{C(C≡CPh)dCHPh}-
Cl(CO)(PPh3)2] (1d ) with K[HB(pz)3].17 In a similar
manner to the synthesis of 2a -2c, the reaction of
(16) Cartwright, J .; Hill, A. F. J . Organomet. Chem. 1992, 429, 229.
Hector, A. L.; Hill, A. F. Ibid. 1993, 447, C7. Cartwright, J .; Harman,
A.; Hill, A. F. Ibid. 1990, 396, C31. Burns, I. D.; Hill, A. F.; Thompsett,
A. R.; Alcock, N. W.; Claire, K. S. Ibid. 1992, 425, C8. Torres, M. R.;
Perales, A.; Loumrhari, H.; Ros, J . Ibid. 1990, 385, 379. Loumrhari,
H.; Matas, L.; Ros, J .; Torres, M. R.; Perales, A. Ibid. 1991, 403, 373.
Santos, A.; Lopez, J .; Montoya, J .; Noheda, P.; Romero, A.; Echavarren,
A. M. Organometallics 1994, 13, 3605. Loumrhari, H.; Ros, J .; Torres,
M. R. Polyhedron 1991, 10, 421. Loumrhari, H.; Ros, J .; Torres, M. R.;
Perales, A. Ibid. 1990, 9, 907.
(17) Alcock, N. W.; Hill, A. F.; Melling, R. P. Organometallics 1991,
10, 3898. Hill, A. F. J . Organomet. Chem. 1990, 385, C35.
(18) Hill, A. F. J . Chem. Soc., Chem. Commun. 1995, 741.

Organometallic Macrocycle Chemistry
Organometallics, Vol. 15, No. 25, 1996 5413
F igu r e 2. NMR spectroscopic analysis of [Ru(CHdCHC6H4Me-4)CO)(PPh3)([9]aneS3)]Cl. (a) 1-D 1H NMR spectrum in
the region δ 1.6-3.8 ppm (CH3 resonance augmented). (b) 2D-(1H-1H) COSY NMR spectrum in the region δ 1.6-3.8 ppm.
(c) Illustration of the three distinct ethylene coupling systems as a result of coordination of [9]aneS3 to a chiral ruthenium
centre.
1d with [9]aneS3 and NH4[PF6] provides [Ru-
{C(CtCPh)dCHPh}(CO)(PPh3)([9]aneS3)]PF6 (2d ‚P F 6).
In contrast to the simple vinyl derivatives, this complex
is yellow; however, all spectroscopic data indicate that
it is of the same general structure. The possibility that
the sulfur macrocycle is bidentate with the enynyl
ligand adopting a trihapto coordination may be excluded
by the observation of a peak at 2157 cm-1 in the infrared
spectrum that is attributable to the free alkynyl group.
Furthermore, the acetylenic carbons give rise to singlet
resonances in the 13C-{1H} NMR spectrum at 101.3 and
99.4 ppm. The absence of coupling to phosphorus would
therefore appear to also preclude coordination to the
ruthenium centre.
The reactions of [RuHCl(CO)(PPh3)3] with alkynes are
in many cases sufficiently clean that it is not necessary
to preisolate the coordinatively unsaturated σ-vinyl
complexes. Thus, treating [RuHCl(CO)(PPh3)3] with a
terminal alkyne (RCtCH: R ) H, C6H4Me-4; 2-3
equiv) in dichloromethane followed by [9]aneS3 and Cl/
PF6 metathesis provides the salts 2a ‚P F 6 and 2b‚P F 6
in overall yields comparable to those obtained from the
isolated σ-vinyl complexes 1a and 1b. In the case of
internal alkynes (PhCtCPh, PhCtCCtCPh), the same
approach is successful with the exception that hydro-
ruthenation is normally less facile and refluxing tetra-
hydrofuran is required prior to addition of [9]aneS3 and
NH4[PF6] to provide 2c‚P F 6 and 2d ‚P F 6. The salt
[RuH(CO)(NCMe)2(PPh3)2]BF4 has been shown19 to
provide σ-vinyl complexes [Ru(CHdCHR)(CO)(NCMe)2-
(PPh3)2]+ the nitrile ligands of which are labile and
readily replaced by bidentate ligands.16 These com-
plexes can be generated in situ and also serve as
precursors for [9]aneS3 coordination. Thus, treating
[RuH(CO)(NCMe)2(PPh3)2]BF4 with 2 equiv of a termi-
nal alkyne followed by [9]aneS3 provides the salts
2a ‚BF 4 and 2b‚BF 4 and precludes the requirement of
counteranion metathesis.
The 16-electron σ-aryl complex [Ru(C6H4Me-4)Cl(CO)-
(PPh3)2] (1e) is readily available from the reaction of
[RuHCl(CO)(PPh3)3] with [Hg(C6H4Me-4)2].10 Treating
1e with [9]aneS3 and NH4[PF6] provides the air-stable
colorless salt [Ru(C6H4Me-4)(CO)(PPh3)([9]aneS3)]PF6 in
61% yield. In contrast to the precursor complex, the
salt shows no tendency to react with carbon monoxide
via migratory insertion, consistent with the coordinative
saturation at ruthenium. This observation, while not
surprising, does confirm that the macrocyclic ligand,
once coordinated, does not dissociate any of its sulfur
donors to an extent sufficient to allow CO coordination.
Spectroscopic data for 2e+ are essentially comparable
(19) Lo´pez, J .; Romero, A.; Santos, A.; Vegas, A.; Echavarren, A.
M.; Noheda, P. J . Organomet. Chem. 1989, 373, 249.

5414 Organometallics, Vol. 15, No. 25, 1996
Cannadine et al.
to those for the σ-vinyl derivatives 2a +-2d + with two
Ta ble 1. Cr ysta l Da ta a n d Da ta Collection a n d
Solu tion a n d Refin em en t Deta ils for
exceptions: Firstly, both the tolyl (AB)2 “quartet” reso-
[Ru (CHdCH2)(CO)(P P h 3)([9]a n eS3)]P F 6
1
nance in the H NMR spectrum and the resonance due
to the o-tolyl carbons in the 13C NMR spectrum are
broad, indicating presumably that the molecule is
fluxional. The nature of this fluxionality is therefore
associated with rotation of the tolyl group about the
Ru-C bond. Secondly, the resonances due to the
(diastereotopic) methylene carbons bound to sulfur trans
to phosphorus are clearly resolved into two doublets
with different couplings to phosphorus.
Crystal Data
emp formula
Mr
C
27H30OPS3Ru.PF6‚2(CH2Cl2)
913.55
a, b, c (Å)
R, â, γ (deg)
V (Å3)
10.208(3), 11.685(3), 16.162(3)
99.61(2), 104.01(2), 93.32(2)
1834.5(7)
space grp
Z
P1h
2
Dcalcd (g cm-3
crystallizn
)
1.654
diffusion of ethanol into a
dichloromethane solution
0.50 × 0.43 × 0.27
F u r th er NMR Stu d ies. As noted above, the NMR
data associated with the macrocycle in salts of the
complexes 2+, while indicating the low symmetry of the
ruthenium coordination sphere, are not particularly
informative. The data do, however, indicate that the
macrocycle does not dissociate on the 1H-NMR time
scale. It is, however, noteworthy that the various
multiplets associated with the [9]aneS3 ring span a
range of over 2 ppm as shown in the representative
spectrum of 2b‚Cl shown in Figure 2a. We therefore
chose to investigate one example in more detail using
two-dimensional 1H-1H COSY-45 techniques. For this
purpose, the chloride salt 2b‚Cl was used as the salts
of the noncoordinating anions were insufficiently soluble.
The 2D-COSY-45 spectrum in the range 1.6-3.7 ppm
is shown in Figure 2b. Using both the occurrence of
off-diagonal peaks and the direction of the contour lines
of each of the peaks it is possible to identify and to
cryst size (mm)
Data Collection
T (K)
293(2)
diffractometer
scan type
abs cor
Siemens P4/PC
ω-scans (3.56 e 2θ e 45.0°)
none
no. of data
4760 unique; 4163 with F g 4σ(F ) retained
Solution and Refinement
method
program
residuals
heavy atom and difference Fourier
SHELXTL PC Version 5.03
R1 ) 0.038, wR2 ) 0.0943
e density max ) 0.504, min ) -0.425 e Å-3
Ta ble 2. Selected Bon d Len gth s (Å) a n d An gles
(d eg) for 2a +
Ru-C(30)
Ru-P
1.858(5)
2.3469(13)
2.4156(13)
1.833(2)
1.848(2)
1.827(6)
1.826(5)
1.471(8)
1.832(5)
1.292(7)
Ru-C(28)
Ru-S(1)
2.097(5)
2.3747(13)
2.4370(12)
1.846(2)
1.806(6)
1.478(8)
1.832(6)
1.798(5)
1.462(8)
1.137(6)
Ru-S(4)
P-C(27)
P-C(21)
S(1)-C(9)
C(3)-S(4)
C(5)-C(6)
S(7)-C(8)
C(28)-C(29)
Ru-S(7)
P-C(15)
S(1)-C(2)
C(2)-C(3)
S(4)-C(5)
C(6)-S(7)
C(8)-C(9)
C(30)-O(31)
2
3
distinguish J and J couplings. Thus, it is possible to
divide the spectrum into three sets of mutually coupled
ABCD spin systems corresponding to the three ethylene
bridges of the macrocycle. This subdivision is illus-
trated in Figure 2c. Thus, for example, the protons Hc,
He, Hh, and Hj can be seen to all be mutually coupled
by the appearance of the off-diagonal peaks indicated.
Furthermore, it can be seen that the long axis of the
ovoid contours for the cross-peaks between Hj and Hh
is perpendicular to the diagonal, indicating that the
coupling between these two nuclei is vicinal (3J ). The
direction of the long axis of the countours for the J (HjHe)
off-diagonal peak is, however, parallel to the diagonal,
indicating a geminal relationship (2J ) for these two
protons. More generally, it can be seen that each of the
12 proton resonances is associated with two perpen-
dicular and one parallel off-diagonal peak, i.e., coupling
to one geminal and two vicinal protons.
C(30)-Ru-C(28)
C(28)-Ru-P
C(28)-Ru-S(1)
C(30)-Ru-S(4)
P-Ru-S(4)
C(30)-Ru-S(7)
P-Ru-S(7)
S(4)-Ru-S(7)
C(15)-P-Ru
89.5(2)
C(30)-Ru-P
88.10(14)
89.80(14)
177.65(4)
84.28(14)
86.41(5)
167.82(13)
85.79(5)
114.08(11)
115.49(9)
106.7(2)
91.18(14) C(30)-Ru-S(1)
87.75(14) P-Ru-S(1)
172.9(2)
95.56(4)
100.8(2)
95.64(4)
85.02(4)
C(28)-Ru-S(4)
S(1)-Ru-S(4)
C(28)-Ru-S(7)
S(1)-Ru-S(7)
C(27)-P-Ru
118.33(10) C(21)-P-Ru
C(2)-S(1)-C(9)
C(9)-S(1)-Ru
C(3)-S(4)-Ru
C(6)-S(7)-C(8)
C(8)-S(7)-Ru
101.8(3)
102.6(2)
100.9(2)
102.5(3)
104.8(2)
C(2)-S(1)-Ru
C(3)-S(4)-C(5)
C(5)-S(4)-Ru
C(6)-S(7)-Ru
100.8(3)
106.0(2)
103.5(2)
C(29)-C(28)-Ru 130.3(5)
O(31)-C(30)-Ru 177.2(4)
investigated by NOE experiments, and these point
toward an interaction between the ortho protons of the
phosphine rings and some but not all of the macro-
cycle protons. Specifically, it is the highest field proton,
designated “h”, that shows a through-space inter-
action.
Discu ssion of th e Str u ctu r e of (2a ‚P F 6)‚2CH2Cl2.
The racemic salt forms colorless crystals of a bis-
(dichloromethane) solvate. The results of the X-ray
analysis are summarised in Tables 1 (procedural details)
and 2 (selected bond lengths and angles) and Figures 3
and 4, which depict the geometry of the cationic complex
2a +.
The X-ray analysis shows the ruthenium to have a
slightly distorted octahedral coordination with angles
at ruthenium in the ranges 84.3(1)-100.8(1)° and
167.8(1)-177.7(1)°. The [9]aneS3 macrocycle is in a
conventional facial perching coordination mode with
intersulfur angles of 85.0(1)-86.4(1)°. The conforma-
While this exercise was not carried out with all
complexes, in this case the simplification of the data is
reassuring in regard to the formulation. The facial
“Ru(CO)(PPh3)(σ-vinyl)” moiety causes a surprisingly
wide spread of chemical shift values for the macrocyclic
protons. This could be for two reasons. Firstly, the
three ligands have very different electronic effects on
the metal center. It has on occasion20 been argued that
sulfur-based macrocycles may function as π-acceptor
ligands, and while this will no doubt remain a matter
for debate, any such interaction could be transmitted
to the adjacent CH2 groups if S-C σ* orbitals are
involved in the retrodative process. Alternatively, the
coordination sphere is sterically very irregular (e.g., see
Figure 4), and this might exert variable interligand
nonbonding interactions. This latter possibility may be
(20) Blake, A. J .; Holder, A. J .; Hyde, T. J .; Schro¨der, M. J . Chem.
Soc., Chem. Commun. 1989, 1433.

Organometallic Macrocycle Chemistry
Organometallics, Vol. 15, No. 25, 1996 5415
F igu r e 4. Partial space-filling representation of complex
2a + illustrating the irregularity of the steric profile of the
“Ru(vinyl)(CO)(PPh3)” fragment. The view is along the axis
perpendicular to the plane defined by S(1), S(2), and S(3).
F igu r e 3. Molecular structure of the cation (2a +) of
[Ru(CHdCH2)(CO)(PPh3)([9]aneS3)]PF6 2CH2Cl2 showing
.
40% probability thermal ellipsoids.
tions of each five-membered chelate ring are either all
δ or all λ depending on the enantiomer. The ruthenium-
sulfur distances all differ significantly from each other
with the longest Ru-S linkage [2.437(1) Å] being that
trans to the σ-vinyl group, reflecting the strong trans
influence of σ-organyl groups in general. Of intermedi-
ate length [2.416(1) Å] is the bond trans to the carbonyl
ligand, while the shortest [2.375(1) Å] is that trans to
the bulky phosphine. What is of note is the fact that
all the Ru-S distances are noticeably longer that those
normally observed for [9]aneS3 complexes of divalent
ruthenium. The phosphine to ruthenium distance of
2.347(1) Å is normal for six-coordinate ruthenium(II),
as is the Ru-CO distance of 1.858(5) Å. The bond from
ruthenium to the vinyl carbon, at 2.097(5) Å, is within
the range reported10 for vinyl complexes of divalent
ruthenium. The associated CdC bond distance of
1.292(7) Å indicates a pronounced degree of bond
ordering and an absence of any significant π-retro-
donation from the cationic ruthenium centre. This is
further supported by the ambivalent orientation of the
plane of the vinyl ligand, which is inclined by ca. 32° to
the Ru-P vector. There are no notable intermolecular
interactions.
Ack n ow led gm en t. We are indebted to Dr. Oliver
W. Howarth of the University of Warwick for the
measurement and assistance with the interpretation of
1
the NOE and 2D-COSY H NMR spectra. We wish to
thank J ohnson-Matthey Chemicals for a generous loan
of ruthenium salts and the EPSRC (U.K.) for the
provision of a studentship (to J .D.E.T.W.-E.) and for the
diffractometer.
Su p p or tin g In for m a tion Ava ila ble: Tables of final
atomic positional parameters and anisotropic thermal param-
eters for the structural analysis (7 pages). Ordering informa-
tion is given on any current masthead page.
OM960129A