Synthesis and characterization of [(η6-arene)RuCl2(R2AsCH=CH2)] and tethered arsinopropylarene-ruthenium(II) complexes

Article abstract of DOI:10.1021/om011092j

The complexes [(η⁶-arene)RuCl₂(R₂AsCH=CH₂)] [arene = MeC₆H₅, R = Ph (1a), R = Cy (1b); p-MeC₆H₄Me, R = Ph (2a), R = Cy (2b); o-MeC₆H₄Me, R = Ph (

Full text of DOI:10.1021/om011092j

Organometallics 2002, 21, 1727-1733
1727
Syn th esis a n d Ch a r a cter iza tion of
[(η6-a r en e)Ru Cl2(R2AsCHdCH2)] a n d Teth er ed
Ar sin op r op yla r en e-Ru th en iu m (II) Com p lexes
J ohn H. Nelson* and Kesete Y. Ghebreyessus
Department of Chemistry/ 216, University of Nevada-Reno, Reno, Nevada 89557-0020
Vernon C. Cook, Alison J . Edwards, Wolfram Wielandt, S. Bruce Wild,* and
Anthony C. Willis
Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia
Received December 27, 2001
The complexes [(η6-arene)RuCl2(R2AsCHdCH2)] [arene ) MeC6H5, R ) Ph (1a ), R ) Cy
(1b); p-MeC6H4Me, R ) Ph (2a ), R ) Cy (2b); o-MeC6H4Me, R ) Ph (3a ), R ) Cy (3b); 1,3,5-
Me3C6H3, R ) Ph (4a ); p-MeC6H4CHMe2, R ) Ph (5a ), R ) Cy (5b); 1,2,4,5-Me4C6H2, R )
Ph (6a ), R ) Cy (6b); C6Me6, R ) Ph (7a )] have been synthesized by reacting [(η6-arene)-
RuCl2]2 with the respective vinyl arsine. The compounds [(η6-MeC6H5)RuCl2(Ph2AsCHdCH2)]
(1a ) and [(η6-1,3,5-Me3C6H3)RuCl2(Ph2AsCHdCH2)] (4a ) undergo KOBut-promoted intramo-
lecular hydroalkylation in boiling acetonitrile to produce tethered arsinopropylarene-
ruthenium(II) complexes 1c and 4c, respectively. The complexes have been characterized
by 1H and 13C{1H} NMR spectroscopy, elemental analyses, cyclic voltammetry, and in several
cases by X-ray crystallography.
In tr od u ction
containing unsaturated phosphines, such as diphenylvi-
nylphosphine (DPVP), divinylphenylphosphine, allyl-
diphenylphosphine, and 1-phenyl-3,4-dimethylphos-
phole.16 In addition, we have shown that the complexes
[(η6-arene)RuCl2(DPVP)] undergo a novel KOBut-pro-
moted hydroalkylation in boiling acetonitrile to produce
tethered phosphinopropylarene-ruthenium(II) com-
pounds, as shown in eq 1.17
In the past decade the chemistry of [(η6-arene)RuCl2-
(PR3)] complexes has attracted a great deal of atten-
tion.1-3 Reports indicate that they are useful precursors
for a variety of catalytic and stoichiometric organic
transformations.3 For example, they react with terminal
alkynes to form novel vinylidene,4-7 allenylidene7,8 and
cumulenylidene7,8 complexes. Although the phosphine
complexes [(η6-arene)RuCl2(PR3)] have been widely
investigated, few arsine complexes of this type are
available for comparative study.9-15
We recently reported the synthesis and characteriza-
tion of a number of [(η6-arene)RuCl2(PR3)] complexes
(1) LeBozec, H.; Touchard, D.; Dixneuf, P. H. Adv. Organomet.
Chem. 1989, 29, 163.
(2) Noyori, R.; Hashiguchi, S. Acc. Chem. Res. 1997, 30, 97.
(3) Naota, T.; Taka, H.; Murahashi, S. C. Chem. Rev. 1998, 98,
2599.
(4) Hansen, H. D.; Nelson, J . H. Organometallics 2000, 19, 4740.
(5) Lebozec, H.; Ouzzine, K.; Dixneuf, P. H. Organometallics 1991,
10, 2768.
(6) Bruneau, C.; Dixneuf, P. H. Acc. Chem. Res. 1999, 32, 311.
(7) Cadierno, V.; Gamasa, M. P.; Gimeno, J . Eur. J . Inorg. Chem.
2001, 571.
(8) Bruce, M. I. Chem. Rev. 1998, 98, 2797.
(9) Fries, G.; Weberndo¨rfer, B.; Ilg, K.; Werner, H. Eur. J . Inorg.
Chem. 2000, 1651.
During the course of this work, a number of reports
on tethered arene-ruthenium(II) complexes have ap-
peared. Smith and Wright,18 Noels and co-workers,11,19
and Fu¨rstner et al.20 have synthesized related complexes
by thermal displacement of p-cymene (1,4-MeC6H4-
CHMe2) from the p-cymene κ-P-γ-arylpropylphosphine
complexes. Therrien et al.21 had previously employed a
(16) Redwine, K. D.; Hansen, H. D.; Bowley, S.; Isbell, J .; Sanchez,
(10) Wolf, J .; Pfeiffer, M.; Stalke, D.; Werner, H. Angew. Chem., Int.
Ed. 2000, 39, 564.
(11) J an, D.; Delaude, L.; Simal, F.; Demonceau, A.; Noels, A. F. J .
Organomet. Chem. 2000, 606, 55.
M.; Vodak, D.; Nelson, J . H. Synth. React. Inorg. Met-Org. Chem. 2000,
30, 379.
(17) Ghebreyessus, K. Y.; Nelson, J . H. Organometallics 2000, 19,
3387.
(12) Butenscho¨n, H. Chem. Rev. 2000, 100, 1527.
(13) Kim, J .-Y.; Lee, W.-Y.; J un, M.-J . Polyhedron 1996, 15, 3793.
(14) Holmes, N. J .; Levason, W.; Webster, M. J . Chem. Soc., Dalton
Trans. 1997, 4223.
(15) Batista, A. A.; Zukerman-Schpector, J .; Porcu, O. M.; Queiroz,
S. L.; Araujo, M. P.; Oliva, G.; Souza, D. H. F. Polyhedron 1994, 13,
689.
(18) Smith, P. D.; Wright, A. H. J . Organomet. Chem. 1998, 559,
141.
(19) Simal, F.; J an, D.; Demonceau, A.; Noels, A. F. Tetrahedron
Lett. 1999, 40, 1653.
(20) Fu¨rstner, A.; Liebl, M.; Lehmann, C. W.; Picquent, M.; Kunz,
R.; Bruneau, C.; Touchard, D.; Dixneuf, P. H. Chem. Eur. J . 2000, 6,
1847.
10.1021/om011092j CCC: $22.00 © 2002 American Chemical Society
Publication on Web 03/20/2002

1728 Organometallics, Vol. 21, No. 8, 2002
Nelson et al.
Sch em e 1
spectra contain in each case three multiplets in the
olefinic region. The integrated ratios of these resonances
to those of the η6-arene protons indicated one DPVAs
or DCVAs ligand per ruthenium and confirmed that the
vinyl group had not undergone hydroalkylation with the
η6-arene ligands. The proton chemical shifts for the
DPVAs complexes, except for the protons HC, are similar
to those of the analogous DPVP complexes.17 The
average chemical shift of HC for the DPVAs complexes
occurs about 0.2 ppm downfield of the corresponding
average value for the DPVP complexes. The carbon
chemical shifts for the two series of complexes are also
similar, except for those of the vinyl carbon atoms. The
vinyl carbon resonances were conclusively assigned by
a combination of APT and HETCOR (Figure 1) spec-
troscopies. For the DPVP complexes the chemical shift
for CR is greater than that for Câ; for the DPVAs
complexes the reverse is true.
more reactive ethyl benzoate complex in a similar
synthesis. Bennett et al.22 have recently used an o-
toluate precursor to prepare tethered arene-ruthenium-
(II) complexes, as shown eq 2.
Rea ction s of 1a -7a , 1b-3b, 5b, a n d 6b w ith
KOBu t . We have recently shown that the complexes
[(η6-arene)RuCl2(DPVP)] undergo novel base promoted
hydroalkylations with KOBut in boiling acetonitrile17 (eq
1). To explore the application of this synthetic method-
ology further, we have attempted to prepare analogous
hydroalkylated compounds from the vinyl arsine com-
plexes. As our first attempt we investigated the reaction
of [(η6-arene)RuCl2(DPVAs)] with KOBut in boiling
acetonitrile (Scheme 2).
As a continuation of our work in this area, we now
report the synthesis and characterization of a series of
complexes of the type [(η6-arene)RuCl2(R2AsCHdCH2)],
where R ) phenyl and cyclohexyl. Hydroalkylation
reactions of these arsine complexes have been investi-
gated in order to probe the generality of base-promoted
synthesis of tethered arene complexes.
Complexes 1a and 4a undergo base-promoted hy-
droalkylation with 1 equiv of KOBut to produce 1c and
4c, in 20-25% yields. The conversion was accompanied
by a change in the color of the solution from a clear red
to a dark red. Excess base caused excessive decomposi-
tion. The precursors 2a , 3a , 5a -7a , 1b-3b, 5b, and 6b
underwent extensive decomposition under the same
reaction conditions.
Resu lts a n d Discu ssion
Syn th esis a n d Ch a r a cter iza tion of 1a -7a , 1b-
3b, 5b, a n d 6b. The [(η6-arene)RuCl2(R2AsCHdCH2)]
complexes [arene ) MeC6H5, R ) Ph (1a ), R ) Cy (1b);
p-MeC6H4Me, R ) Ph (2a ), R ) Cy (2b); o-MeC6H4Me,
R ) Ph (3a ), R ) Cy (3b); 1,3,5-Me3C6H3, R ) Ph (4a );
p-MeC6H4CHMe2, R ) Ph (5a ), R ) Cy (5b); 1,2,4,5-
Me4C6H2, R ) Ph (6a ), R ) Cy (6b); C6Me6, R ) Ph (7a )]
were prepared by reacting the [(η6-arene)RuCl2]2 com-
plexes with 2.2 equiv of diphenylvinylarsine (DPVAs)
or dicyclohexylvinylarsine (DCVAs)] in dichloromethane
at ambient temperature (Scheme 1).
Following workup, both 1c and 4c were isolated as
air stable microcrystalline red solids by precipita-
tion with n-hexane. Their 1H and 13C{1H} NMR spec-
tral data are consistent with the structures proposed.
1
In the H NMR spectra, in both cases the three vinyl
resonances and one methyl resonance are replaced by
three multiplets in the aliphatic region due to the
three sets of methylene protons. In the 13C{1H} NMR
spectra, the CR, Câ, and one methyl resonance dis-
appear and are replaced by three new resonances in the
aliphatic region. The proton and carbon chemical
shifts are similar to those of their phosphine ana-
logues.17
After of stirring for 4 h, the solution was layered with
n-hexane and left overnight to crystallize. The product
separated and was isolated by filtration and recrystal-
lized from dichloromethane/n-hexane. The products
were obtained in almost quantitative yields as orange-
red-brown solids. They are air and moisture stable solids
that are soluble in halocarbons, methanol, acetone, and
acetonitrile. They slowly decompose in solution, how-
ever, apparently by dissociation and subsequent polym-
erization and/or oxidation of the arsine. The DCVAs
complexes are less stable in solution than the DPVAs
complexes, and complexes 4b and 7b could not be
isolated in an analytically pure state. Attempts to
X-ray crystallographic analyses confirmed the struc-
tures of the precursors 2a , 4a -6a , 1b, 3b, 5b, and 6b.
The structures of 4a and 5b are shown in Figures 2 and
3; the structures of the remaining compounds are given
in the Supporting Information. Crystallographic data
are summarized in Tables 1 and 3, and selected bond
distances and angles are given in Tables 2 and 4. The
coordination sphere around the ruthenium center in
each case is that of a pseudo-octahedral half-sandwich
with the η6-arene ligand, the vinyl arsine, and the two
chlorine atoms occupying the six coordination sites. The
average Ru-As bond length observed for the DPVAs
complexes 1a , 2a , and 4a -6a [2.4485(2) Å] is slightly
shorter than that observed for the complexes 1b, 3b,
5b, and 6b [2.4707(4) Å], which contain the larger and
prepare the more bulky But AsCHdCH2 derivatives
2
ultimately led to the recovery of the [(η6-arene)RuCl2]2
starting materials and the arsine oxide.
The compounds were characterized by elemental
analyses, melting point determination, 1H and 13C{1H}
spectroscopy, and cyclic voltammetry. The 1H NMR
(21) Therrien, B.; Ward, T. R.; Pilkington, M.; Hoffmann, C.;
Gilardoni, F.; Weber, J . Organometallics 1998, 17, 330.
(22) Bennett, M. A.; Edwards, A. J .; Harper, J . R.; Khimyak, T.;
Willis, A. C. J . Organomet. Chem. 2001, 629, 7.

Tethered Arsinopropylarene-Ru(II) Complexes
Organometallics, Vol. 21, No. 8, 2002 1729
F igu r e 1. (a) Expansion of the 13C/1H HECTOR spectrum of 2b in the aliphatic region; (b) expansion of the 13C/1H HECTOR
spectrum of 2b in the vinyl region.
Sch em e 2
more basic DCVAs. The global average Ru-As bond
length for these complexes is slightly shorter than the
Ru-As bond distance reported9 for [(p-Cy)RuCl{(As,O)-
Ph2P(O)CH2CH2AstBu2}]PF6. The Ru-Cl distances in
all of the complexes are similar to those observed in the
related phosphine complexes.16,17
The electrochemistry of the complexes was investi-
gated by cyclic voltammetry (Table 5). The compounds
exhibit chemically reversible one-electron oxidations
with the Ru(II/III) potentials ranging from 0.48 to 0.76
V for 1a -7a , 1c, and 4c and 0.50-0.67 V for 1b-3b,
5b, and 6b. Oxidations of the DPVP complexes17 and
the DPVAs complexes occur at essentially the same
potentials, indicating that these two ligands have
equivalent donor properties toward ruthenium(II). Oxi-
dations of the DCVAs complexes occur about 0.1 V less
than for the DPVAs complexes, suggesting that DCVAs
F igu r e 2. Structural drawing of 4a showing the atom-
numbering scheme (30% probability ellipsoids). Hydrogen
is a slightly better donor than either DPVAs or DPVP.
As observed for the DPVP complexes and their hy-
droalkylation products, the oxidations of 1a and 1c
(0.76/0.77 V) and 4a and 4c (0.66/0.65 V) occur at the
same potentials within experimental error. For all
complexes, the trends in the Ru(II/III) potentials as a
atoms are omitted for clarity.
function of the arene follow the expected decrease in the
donating ability of the arene ligands: the addition of
each methyl group to the arene ring lowers the oxidation
potential by about 60 mV.

1730 Organometallics, Vol. 21, No. 8, 2002
Nelson et al.
voltammetric analyzer. A three-electrode system was used. The
working electrode was a glassy carbon disk, the auxiliary
electrode was a platinum electrode, and the reference electrode
was an aqueous Ag+/AgCl electrode separated from the cell
by a Luggin capillary. The Fc/Fc+ couple occurred at 497 mV
under the same conditions.28 Carbon atoms and the attached
hydrogen atoms are numbered as shown in I and II below.
Syn th esis. P r ep a r a tion of Bu t2AsCHdCH2. Since reac-
tion of But AsCl with excess vinylmagnesium chloride afforded
2
only a 20% conversion with But AsCl and But AsCHdCH2 not
2
2
being separable by distillation, But AsCl was converted to
2
But AsI. A solution of But AsCl (27.10 g ) 120.7 mmol) in
2
2
acetone (25 mL) was added to a solution of sodium iodide
(28.60 g ) 190.8 mmol) in acetone (175 mL). A white
precipitate formed instantly, and the solution became yellow.
The suspension was heated at reflux for 22 h and filtered, and
the filtrate was concentrated under vacuum. The residue was
extracted with ether (200 mL) and filtered. After removal of
the solvent, under reduced pressure, the yellow residue was
distilled, affording a pale yellow oil, bp 79 °C/1 mm, yield 82%.
Anal. Calcd for C8H18AsI: C, 30.40; H, 5.74. Found: C, 30.72;
H, 5.79. 1H NMR (300.1 MHz, C6D6, 25 °C): δ 1.21 (s, 18H,
CH3). 13C{1H} NMR (75.5 MHz, C6D6, 25 °C): δ 35.4 (s, Cq),
29.6 (s, CH3).
F igu r e 3. Structural drawing of 5b showing the atom-
numbering scheme (30% probability ellipsoids). Hydrogen
atoms are omitted for clarity.
Con clu sion
To a solution of 21.50 g (68.03 mmol) of But AsI in 120 mL
2
of tetrahydofuran was slowly added 200.0 mL of a 1.6 M
tetrahydrofuran solution of vinylmagnesium chloride at ambi-
ent temperature under dry nitrogen. The mixture was then
heated at reflux for 22 h, cooled to 0 °C, and hydrolyzed with
degassed 2 M aqueous NH4Cl solution (50 mL). The organic
layer was separated and the aqueous layer extracted with
ether (3 × 50 mL). The combined organic fractions were
concentrated under vacuum, and the residue was distilled
under reduced pressure to afford a pale yellow oil, bp 78
°C/10 mm, yield 41%. Anal. Calcd for C10H21As: C, 55.56; H,
A series of Ru(II) vinylarsine complexes of the type
[(η6-arene)RuCl2(R2AsCHdCH2)] were prepared and the
compounds characterized. They are air stable in the
solid state but decompose in solution at ambient tem-
perature. The complexes show reversible Ru(II/III) redox
couples. The Ru-As distances are sensitive to the
substituent (R) on the vinylarsine. 1a and 4a underwent
intramolecular base-promoted hydroalkylation. The novel
products of these reactions contain a tethered arsino-
propyl-η6-arene ligand. The new complexes are stable
and are electronically similar to their precursors.
1
9.79. Found: C, 54.48; H, 9.47. H NMR (300.1 MHz, CD2Cl2,
25 °C): δ 6.51 (dd, 3J (HaHc) ) 18.5 Hz, 3J (HaHb) )11.4 Hz,
3
2
1H, Ha), 5.92 (dd, J (HaHb) ) 11.4 Hz, J (HbHc) ) 2.7 Hz, 1H,
3
2
Hb), 5.78 (dd, J (HaHc) ) 18.5 Hz, J (HbHc) ) 2.7 Hz, 1H, Hc),
1.13 (s, 18H, CH3). 13C{1H} NMR (75.5 MHz, CD2Cl2, 25 °C):
δ 138.6 (s, CR), 131.4 (s, Câ), 32.7 (Cq), 29.9 (CH3).
Exp er im en ta l Section
All chemicals were reagent grade and were used as received
or synthesized as described below. Acetonitrile was dried over
CaH2 and distilled immediately before use. Diethyl ether and
tetrahydrofuran were distilled from sodium/benzophenone
ketyl under nitrogen. Acetone was dried over potassium car-
bonate and distilled from P2O5 under nitrogen. Cyclohexylmag-
nesium chloride, tert-butylmagnesium chloride, and vinylmag-
nesium chloride were purchased from Aldrich and were used
as received. 1,3,5-Trimethylcyclohexa-1,4-diene, 3,6-dimeth-
ylcyclohexa-1,4-diene,23 [(η6-arene)RuCl2]2,24 Ph2AsCHdCH2,25
P r ep a r a tion s of 1a -7a , 1b-3b, 5b, a n d 6b. The com-
plexes were synthesized from the appropriate [(η6-arene)-
RuCl2]2 as follows. A suspension of 1.0 mmol of the dimer in
40 mL of dichloromethane was treated with 2.2 equiv of
diphenylvinylarsine or dicyclohexylvinylarsine via syringe. The
mixture was stirred at ambient temperature for 4 h. The
volume of the solution was reduced to about 10 mL on a rotary
evaporator, and n-hexane was added. The products were
isolated by filtration, washed with n-hexane, and dried under
vacuum to give the pure products as microcrystalline orange-
Cy2AsCHdCH2,26 and But AsCl27 were synthesized by litera-
2
red-brown solids. Similar reactions with But AsCHdCH2 led
2
ture procedures. Elemental analyses were performed by Gal-
braith Laboratories, Knoxville, TN. Melting points were ob-
tained using a Mel-Temp apparatus and are uncorrected. NMR
spectra were recorded on CDCl3 solutions with a Varian Inova
500-FT NMR spectrometer operating at 500 MHz for 1H and
125 MHz for 13C for the compounds 1a -7a , 1b-3b, 5b, and
6b, and on a Varian Unity plus-500 FT-NMR spectrometer
operating at 500 MHz for 1H and 125.7 MHz for 13C for 1c
and 4c. Proton and carbon chemical shifts are quoted rela-
tive to internal Me4Si, with positive values being downfield of
the reference. Cyclic voltammograms were recorded at 25 °C
in freshly distilled CH2Cl2 solutions containing 0.1 M tetrabu-
tylammonium hexafluorophosphate using a BAS CV50-W
to inseparable mixtures of [(η6-arene)RuCl2]2, [(η6-arene)Ru-
(But AsCHdCH2)Cl2], But AsdO(CHdCH2), and polymeric
2
2
But AsCHdCH2.
2
(23) Birch, A. J . Adv. Org. Chem. 1972, 8, 1.
(24) Bennett, M. A.; Smith, A. K. J . Chem. Soc., Dalton Trans. 1974,
233.
(25) Cook, V. C. Ph.D. Dissertation, Australian National University,
2000.
(26) Gugger, P. A.; Willis, A. C.; Wild, S. B.; Heath, G. A.; Webster,
R. D.; Nelson, J . H. J . Organomet. Chem. 2002, 643-644, 136.
(27) Tzschach, A.; Deylig, W. Z. Anorg. Allg. Chem. 1965, 336, 36.
(28) Gagne, R. R.; Koval, C. A.; Lisensky, G. C. Inorg. Chem. 1980,
19, 2854.

Tethered Arsinopropylarene-Ru(II) Complexes
Organometallics, Vol. 21, No. 8, 2002 1731
Ta ble 1. Cr ysta llogr a p h ic Da ta a n d Str u ctu r e Refin em en t for 1a , 2a , a n d 4a -6a
1a
2a
4a
5a c
6a
formula
Mw
cryst syst
space group
a (Å)
b (Å)
c (Å)
C
21H21AsCl2Ru
C22H23AsCl2Ru
534.32
monoclinic
P21/n
16.9549(2)
7.1927(1)
17.4522(2)
4
C23H25AsCl2Ru
608.04
triclinic
P1h
8.2468(1)
8.6891(2)
18.8657(3)
2
C24H27AsCl2Ru
562.38
monoclinic
P21/n
17.2658(2)
7.32020(10)
18.9833(2)
4
C24H27AsCl2Ru
562.37
triclinic
P1h
8.8486(1)
15.0305(3)
17.5860(3)
2
520.29
monoclinic
P21/n
16.6943(1)
7.2377(1)
16.9808(3)
4
Z
R (deg)
â (deg)
γ (deg)
volume (Å3)
90
90
99.543(1)
95.976(1)
112.9407(9)
1206.34(4)
1.674
34 020
7036
0.0346
0.0464
1.810
90
89.384(1)
83.995(1)
77.814(1)
2273.52(6)
1.643
60 968
13 219
0.0438
0.0381
1.559
105.453(1)
90
1977.59(1)
1.747
46 382
5765
0.0330
0.0343
1.756
100.1886(8)
90
2094.76(4)
1.694
54 987
6180
0.0336
0.0331
1.677
105.4484(8)
90
2312.60(5)
1.62
53 512
6744
0.0338
0.0354
1.0152
F
calcd (Mg/m3)
no. of reflns collcd
no. of ind reflns
R1a
wR2b
GOF
a
The data were refined by the method of full-matrix least squares on F2, with the final R indices having I > 2.00σ(I), R1 ) ∑||Fo| -
|Fc||/∑Fo. bwR2(F2) ) {∑[w(Fo - Fc2)]/∑[w(Fo2)2]}1/2
.
c I > 3.00σ(I).
2
Ta ble 2. Selected Bon d Dista n ces (Å) a n d Bon d An gles (d eg) for 1a , 2a , a n d 4a -6a
1a
2a
4a
5a
6a
Ru-As
2.4490(3)
2.4090(5)
2.4070(5)
2.195(2)
85.26(1)
80.21(1)
88.23(2)
2.45389(2)
2.4183(5)
2.4080(5)
2.200(2)
80.07(1)
86.08(1)
88.05(2)
2.4471(3)
2.4076(6)
2.4046(6)
2.212(2)
82.42(2)
81.70(2)
88.63(2)
2.4441(1)
2.4193(5)
2.4144(5)
2.207(8)
82.583(14)
82.148(15)
88.77(2)
2.4486(3)
2.4121(7)
2.4067(6)
2.215(3)
84.82(2)
84.31(2)
88.03(3)
Ru-Cl(1)
Ru-Cl(2)
Ru-(C1-C6)a
As-Ru-Cl(1)
As-Ru-Cl(2)
Cl(1)-Ru-Cl(2)
a
(C1-C6) denotes the average Ru-C distances.
Ta ble 3. Cr ysta llogr a p h ic Da ta a n d Str u ctu r e Refin em en t for 1b, 3b, 5b, a n d 6b
1b
3bc
5b
6b
formula
Mw
C
21H33AsCl2Ru
C22H35AsCl2Ru
546.42
C24H39AsCl2Ru
574.47
C24H39AsCl2Ru
574.47
532.39
cryst syst
space group
a (Å)
b (Å)
c (Å)
triclinic
P1h
6.8817(2)
12.3822(3)
13.3182(4)
2
monoclinic
P21/c
6.8884(1)
10.8798(2)
30.8497(6)
4
monoclinic
P21/a
12.9473(1)
9.9644(1)
19.0128(2)
4
monoclinic
P21/c
7.5720(1)
17.7649(2)
18.49849(2)
4
Z
R (deg)
â (deg)
γ (deg)
volume (Å3)
84.7614(9)
81.8110(9)
83.394(1)
1112.58(5)
1.589
90
90
90
91.6770(6)
90
2311.02(6)
1.570
90.9678(5)
90
2452.53(4)
1.556
100.5395(5)
90
2446.35(5)
1.560
F
calcd (mg/m3)
no. of reflns collcd
17 968
30 220
56 694
59 722
no. of ind reflns
3925
0.0400
0.0377
1.309
5198
0.0598
0.1092
2.872
7152
0.0435
0.0449
1.727
7164
0.0418
0.0422
1.578
R1a
wR2b
GOF
a
The data were refined by the method of full-matrix least squares on F2, with the final R indices having I > 2.00σ(I). R1 ) ∑||Fo| -
|Fc ||/∑Fo. wR2(F2) ) {∑[w(Fo - Fc2)]/∑[w(Fo2)2]}1/2
.
c I > 3.00σ(I).
b
2
1a : mp 200-202 °C (97% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 7.67 (m, 4H, Ho), 7.43 (m, 6H, Hm,p), 6.84
MHz, CDCl3, 25 °C): δ 133.80 (Câ), 133.17 (Co), 131.17 (CR),
130.18 (Cp), 130.13 (Ci), 128.07 (Cm ), 95.67 (Cq, arene), 86.34
(CH, arene), 17.72 (CH3, arene). Anal. Calcd for C22H23AsCl2-
Ru: C, 49.47; H, 4.31; Cl, 13.27. Found: C, 49.28; H, 4.32; Cl,
13.19.
3
(dd, 3J (HaHc) ) 18.5 Hz, J (HaHb) ) 11.3 Hz, 1H, Ha), 6.06 (d,
3
3J (HaHb) ) 11.3 Hz, 1H, Hb), 5.55 (d, J (HaHc) ) 18.5 Hz, 1H,
Hc), 5.42 (apparent t, 3J (HH) ) 5.8 Hz, 2H, Hm), 5.26 (d, 3J (HH)
3
3a : mp 282-284 °C (93% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 7.70 (m, 4H, Ho), 7.40 (m, 6H, Hm,p), 6.84
) 5.8 Hz, 1H, Hp), 4.98 (apparent t, J (HH) ) 5.8 Hz, 1H, Ho)
2.16 (s, 3H, CH3). 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C):
δ 133.77 (Câ), 132.98 (Co), 130.94 (CR), 130.46 (Ci), 130.17 (Cp),
128.75 (Cm), (104.48, 86.10, 85.31, 78.63, (C, arene), 18.05 (CH3,
arene). Anal. Calcd for C21H21AsCl2Ru: C, 48.49; H, 4.04; Cl,
13.63. Found: C, 48.46; H, 3.87; Cl, 13.47.
3
(dd, 3J (HaHc) ) 18.5 Hz, J (HaHb) ) 11.5 Hz, 1H, Ha), 6.04 (d,
3
3J (HaHb) ) 11.5 Hz, 1H, Hb), 5.57 (d, J (HaHc) ) 18.5 Hz, 1H,
Hc), 5.11 (m, [AX]2, 2H, arene), 5.07 (m, [AX]2, 2H, arene), 2.02
(s, 6H, 2CH3). 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C): δ
134.19 (Câ), 133.07 (Co), 131.48 (CR), 130.37 (Cp), 130.07 (Ci),
128.67 (Cm), 100.82 (Cq, arene), 86.45 (CH, arene), 80.53
(CH, arene), 16.45 (CH3, arene). Anal. Calcd for C22H23AsCl2-
Ru: C, 49.47; H, 4.31; Cl, 13.27. Found: C, 49.28; H, 4.32; Cl,
13.19.
2a : mp >300 °C dec (95% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 7.70 (m, 4H, Ho), 7.44 (m, 6H, Hm,p), 6.90
3
(dd, 3J (HaHc) ) 18.5 Hz, J (HaHb) ) 11.5 Hz, 1H, Ha), 6.04 (d,
3
3J (HaHb) ) 11.5 Hz, 1H, Hb), 5.53 (d, J (HaHc) ) 18.5 Hz, 1H,
Hc), 5.24 (s, 4H, arene) 1.92 (s, 6H, 2CH3). 13C{1H} NMR (125.7

1732 Organometallics, Vol. 21, No. 8, 2002
Nelson et al.
Ta ble 4. Selected Bon d Dista n ces (Å) a n d Bon d
An gles (d eg) for 1b, 3b, 5b, a n d 6b
Ta ble 5. Ru (II/III) P oten tia ls for 1a -7a , 1b-3b, 5b,
6b, 1c, a n d 4c
1b
3b
5b
3b
E1/2
Ru(II/III)
(V)a
E1/2
Ru(II/III)
(V)a
∆Ep
∆Ep
(mV)
Ru-As
2.4630(6)) 2.4649(5) 2.4834(3) 2.4713(3)
compound
(mV) compound
Ru-Cl(1)
2.429(1)
2.391(1)
2.187(4)
85.84(3)
86.04(3)
2.436(2)
2.392(2)
2.200(7)
86.11(5)
85.65(5)
87.66(8)
2.4242(7) 2.4166(7)
2.4117(3) 2.4021(7)
2.198(3)
84.47(3)
88.70(2)
87.61(3)
Ru-Cl(2)
1a
2a
3a
4a
5a
6a
7a
0.76
0.70
0.71
0.66
0.70
0.61
0.48
152
122
272
161
174
150
126
1b
2b
3b
5b
6b
1c
4c
0.67
0.60
0.60
0.60
0.51
0.77
0.65
83
145
112
94
133
153
158
Ru-(C1-C6)a
As-Ru-Cl(1)
As-Ru-Cl(2)
2.206(30
84.92(2)
82.74(2)
88.09(2)
Cl(1)-Ru-Cl(2) 86.06(4)
a
(C1-C6) denotes the average Ru-C distances.
a
Measured at 298 K in CH2Cl2 solutions at a glassy carbon
working electrode, 0.1 M tetrabutylammonium hexafluorophos-
phate as supporting electrolyte. All potentials are vs Fc/Fc+. Scan
rate 100 mV/s.
4a : mp 211-213 °C (90% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C ): δ 7.71 (m, 4H, Ho), 7.40 (m, 6H, Hm,p), 6.80
3
(dd, 3J (HaHc) ) 18.5 Hz, J (HaHb) ) 11.5 Hz, 1H, Ha), 5.98 (d,
3
3J (HaHb) ) 11.5 Hz, 1H, Hb), 5.47 (d, J (HaHc) ) 18.5 Hz, 1H,
Hc), 4.82 (s, 3H, CH, arene), 1.99 (s, 9H, 3CH3). 13C{1H} NMR
(125.7 MHz, CDCl3, 25 °C): δ 133.41 (Co), 132.66 (Câ), 132.30
(CR), 129.98 (Cp), 129.10 (Ci), 128.48 (Cm), 101.62 (Cq, arene),
81.72 (CH, arene), 18.63 (CH3). Anal. Calcd for C23H25AsCl2-
Ru: C, 50.40; H, 4.56; Cl, 12.94. Found: C, 50.26; H, 4.39; Cl,
12.68.
2b: mp 219-221 °C (85% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.31 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.85 (d, 3J (HaHb) ) 12.0 Hz, 1H, Hb), 5.57 (d,
3J (HaHc) ) 19.0 Hz, 1H, Hc), 5.34 (s, 4H, arene), 2.28 (t, 3J (HH)
2
) 12.0 Hz, 2H HRa) 1.95 (s, 6H, CH3), 1.90 (d, J (HH) ) 13.0
Hz, 2H, Hâe), 1.80 (d, 2J (HH) ) 13.0 Hz, 2H, Hâe), 1.65 (d,
5a : mp 186-189 °C (95% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 7.68 (m, 4H, Ho,), 7.40 (m, 6H, Hm,p), 6.91
2
2J (HH) ) 13.0 Hz, 2H, Hγ e), 1.62 (d, J (HH) ) 13.0 Hz, 2H,
Hγe), 1.54 (d, 3J (HH) ) 10.0 Hz, 2H, Hδ), 1.32 (dt, 2J (HH) )
3
(dd, 3J (HaHc) ) 18.5 Hz, J (HaHb) ) 11.4 Hz, 1H, Ha), 5.98 (d,
3
2
13.0 Hz, J (HH) ) 12.0 Hz, 2H, Hâa), 1.29 (dt, J (HH) ) 13.0
Hz, 3J (HH) ) 12.0 Hz, 2H, Hâa), 1.07 (m, 6H, Hγδ). 13C{1H}
NMR (125.7 MHz, CDCl3, 25 °C): δ 128.97 (CR), 127.77 (Câ),
93.42 (Cq, arene), 84.87 (CH, arene), 36.74 (CR′), 28.70 (Câ′),
28.34 (Câ′), 26.66 (Cγ′), 26.50 (Cγ′), 25.32 (Cδ′), 17.24 (2CH3).
Anal. Calcd for C22H35AsCl2Ru: C, 48.38; H, 6.41; Cl, 12.98.
Found: C, 48.12; H, 6.19; Cl, 12.73.
3
3J (HaHb) ) 11.4 Hz, 1H, Hb), 5.43 (d, J (HaHc) ) 18.5 Hz, 1H,
Hc), 5.28, 5.30 (AB, 3J (HH) ) 6.0 Hz, 4H, CH, arene), 2.63
3
(septet, J (HH) ) 6.9 Hz, 1H, CH), 1.91 (s, 3H, CH3), 0.96 (d,
3J (HH) ) 6.9 Hz, 6H, 2CH3). 13C{1H} NMR (125.7 MHz, CDCl3,
25 °C): δ 133.88 (Câ), 133.15 (Co), 131.14 (CR) 130.03 (Cp),
128.57 (Cm) Ci not observed, 106.84, 95.19, 85.62, 83.25 (C,
arene), 38.26 (CH, arene), 21.48 (2CH3), 17.69 (CH3). Anal.
Calcd for C24H27AsCl2Ru: C, 51.28; H, 4.80; Cl, 12.61. Found:
C, 51.41; H, 4.98; Cl, 12.52.
3b: mp 210-200 °C (87% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.38 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.94 (d, 3J (HaHc) ) 12.0 Hz, 1H, Hc), 5.67 (d,
3J (HaHc) ) 19.0 Hz, 1H, Hb), 5.27 (m, [AX]2, 2H, arene), 5.16
(m, [AX]2, 2H arene) 2.36 (tt, 3J (HH) ) 12.5, 3J (HH) ) 12.5
6a : mp 199-200 °C (85% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 7.71 (m, 4H, Ho), 7.39 (m, 6H, Hm,p), 6.90
3
(dd, 3J (HaHc) ) 18.3 Hz, J (HaHb) ) 11.3 Hz, 1H, Ha), 5.93 (d,
2
Hz, 2H, HRa), 2.05 (s, 6H, 2CH3), 1.95 (d, J (HH) ) 13.0 Hz,
3
3J (HaHb) ) 11.3 Hz, 1H, Hb), 5.46 (d, J (HaHc) ) 18.3 Hz, 1H,
2
2
2H, Hâe), 1.89 (d, J (HH) ) 13.0 Hz, 2H Hâe), 1.77 (d, J (HH)
Hc), 4.98 (s, 2H, arene) 1.82 (s, 12H, 4CH3). 13C{1H} NMR
(125.7 MHz, CDCl3, 25 °C): δ 132.74 (Co), 132.42 (Câ), 131.92
(CR), 129.38 (Cp), 128.59 (Ci), 127.91 (Cm), 94.49 (Cq, arene),
87.49 (CH, arene), 15.64 (CH3). Anal. Calcd for C24H27AsCl2-
Ru: C, 51.28; H, 4.80; Cl, 12.61. Found: C, 51.14; H, 4.63; Cl,
12.49.
2
3
) 19.5 Hz, Hγ), 1.71 (t, J (HH) ) J (HH) ) 12.5 Hz, 2H, Hδ),
1.61 (d, 2J (HH) ) 11.0 Hz, 2H, Hδ), 1.39 (apparent qd, 2J (HH)
) 3J (HH) ) 12.5 Hz,3J (HH) ) 2.5 Hz, 2H, Hâa), 1.36 (apparent
qd, 2J (HH) ) 3J (HH) ) 12.5 Hz,3J (HH) ) 2.5 Hz, 2H, Hâa),
1.15 (m, 6H, 4Hγ , 2Hδ). 13C{1H} NMR (125.7 MHz, CDCl3, 25
°C): δ 130.06 (CR), 128.81 (Câ), 101.29 (Ci, arene), 85.23 (CH,
arene), 77.40 (CH, arene), 37.47 (CR′), 29.32 (Câ′), 29.15 (Câ′),
27.25 (Cγ′′), 27.08 (Cγ′′), 25.84 (Cδ′), 16.26 (2CH3). Anal. Calcd
for C22H35AsCl2Ru: C,48.38; H, 6.41; Cl, 12.98. Found: C,
48.14; H, 6.29; Cl, 12.82.
7a : mp > 200 dec (92% yield). 1H NMR (500.0 MHz, CDCl3,
25 °C): δ 7.73 (m, 4H, Ho), 7.41 (m, 6H, Hm,p), 6.89 (dd,
3J (HaHc) ) 18.5 Hz, 3J (HaHb) ) 11.5 Hz, 1H, Ha), 5.92 (d,
3
3J (HaHb) ) 11.5 Hz, 1H, Hb), 5.47 (d, J (HaHc) ) 18.5 Hz, 1H,
Hc), 1.85 (s, 18H, 6CH3). 13C{1H} NMR (125.7 MHz, CDCl3,
25 °C): δ 134.10 (Co), 133.99 (CR), 132.34 (Câ), 129.86 (Cp),
128.42 (Cm), 128.07 (Ci), 93.90 (C, arene), 15.49 (CH3, arene).
Anal. Calcd for C26H31AsCl2Ru: C, 52.91; H, 5.25; Cl, 12.01.
Found: C, 52.69; H, 5.31; Cl, 11.94.
5b: mp 173-176 °C (88% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.37 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.95 (d, 3J (HaHb) ) 12.0 Hz, 1H, Hb), 5.65 (d,
3
3J (HaHc) ) 19.0 Hz, 1H, Hc), 5.40, 5.38 (AB, J (HH) ) 6.0 Hz,
4H, ring), 2.79 (sept, 3J (HH) ) 7.0 Hz, 1H, CH) 2.37 (t, 3J (HH)
2
1b: mp 177-179 °C (95% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.31 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.87 (d, 3J (HaHb) ) 12.0 Hz, 1H, Hb), 5.60 (d,
3J (HaHc) ) 19.0 Hz, 1H, Hc), 5.50 (apparent t, 3J (HH) ) 5.0
) 12.5 Hz, 2H, HRa) 2.02 (s, 3H, CH3) 1.95 (d, J (HH) ) 12.5
Hz, 2H, Hâe), 1.87 (d, 2J (HH) ) 12.5 Hz, 2H, Hâe), 1.68 (m,
4H, Hγ ), 1.59 (m, 4H, Hδ), 1.43 (apparent quart., 3J (HH) )
3
12.5 Hz, 2H, Hâa), 1.36 (aparent q, 2J (HH) ) J (HH) ) 12.5
Hz, 2H, Hâa), 1.15 (d, 3J (HH) ) 7.0 Hz, 6H, CH3), 1.14 (m, 6H,
3
3
Hz, 2H, Hm), 5.22 (d, J (HH) ) 5.0 Hz, 2H Ho) 5.16 (t, J (HH)
) 5.0 Hz, 1H, Hp), 2.31 (t, 3J (HH) ) 12.5 Hz, 2H, HRa), 2.09 (s,
3H, CH3), 1.90 (d, 2J (HH) ) 11.5 Hz, 2H, Hâe), 1.82 (d, 2J (HH)
H
γδ). 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C): δ 129.53 (CR),
128.14 (Câ), 105.89 (Cq, arene), 93.69 (Cq, arene), 84.95 (CH,
arene), 81.60 (CH, arene), 36.97 (CR′), 29.84 (CH), 29.02 (Câ′),
28.54 (Câ′), 27.06 (Cγ′), 26.92 (Cγ′), 25.62 (Cδ′), 21.58 (2CH3),
17.66 (CH3). Anal. Calcd for C24H39AsCl2Ru: C, 50.16; H, 6.79;
Cl, 12.35. Found: C, 49.93; H, 6.60; Cl, 12.21.
6b: mp 198-200 °C (93% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 6.40 (dd, 3J (HaHc) ) 19.0 Hz, 3J (HaHb) ) 12.0
Hz, 1H, Ha), 5.95 (d, 3J (HaHb) ) 12.0 Hz, 1H, Hb), 5.65 (d,
3J (HaHc) ) 19.0 Hz, 1H, Hc), 5.25 (s, 2H, arene H), 2.37 (tt,
3J (HH) ) 12.5 Hz, 3J (HH) ) 3.0 Hz, 2H HRa) 1.97 (s, 12H CH3),
1.96 (d, 2J (HH) ) 12.5 Hz, 2H, Hâe), 1.87 (d, 2J (HH) ) 12.5
2
) 12.5 Hz, 2H Hâe), 1.67 (d, J (HH) ) 11.5 Hz, 2H, Hγ e), 1.62
2
3
(d, J (HH) ) 11.0 Hz, 2H, Hγe), 1.54 (d, J (HH) ) 9.5 Hz, 2H,
Hδ), 1.33 (q 2J (HH) ) 3J (HH) ) 12.5 Hz, 2H, Hâa), 1.30 (q,
2J (HH) ) 3J (HH) ) 12.5 Hz, 2H, Hâa), 1.10 (m, 6H, Hγδ).
13C{1H} NMR (125.7 MHz, CDCl3, 25 °C): δ 129.29 (CR), 128.48
(Câ), 105.16 (Ci, arene), 84.24 (Co, arene), 84.20 (Cm, arene),
74.73 (Cp, arene), 32.28 (CR′), 29.94 (Câ′), 28.83 (Câ′), 26.92 (Cγ′′)
26.74 (Cγ′′), 25.48 (Cδ′), 18.04 (CH3). Anal. Calcd for C22H35
-
AsCl2Ru: C, 47.40; H, 6.20; Cl, 13.32. Found: C, 47.16; H, 6.27;
Cl, 13.09.

Tethered Arsinopropylarene-Ru(II) Complexes
Organometallics, Vol. 21, No. 8, 2002 1733
Hz, 2H, Hâe), 1.76 (d, 2J (HH) ) 12.5 Hz, 2H, Hγ), 1.71 (d,
2J (HH) ) 12.0 Hz, 2H, Hγ), 1.64 (d, 3J (HH) ) 10.5 Hz, 2H,
1H, H4), 4.76 (d, 4J (HH) ) 1.5 Hz, 2H, H2,6), 2.54 (t, 3J (HH) )
3
5.0 Hz, 2H, Hc), 2.33 (t, J (HH) ) 5.0 Hz 2H, Ha), 2.28 (s, 6H,
2
3
3
Hδ), 1.38 (qd, J (HH) ) J (HH) ) 12.5 Hz, J (HH) ) 3.0 Hz,
H
7,8), 2.17 (m, 2H, Hb). 13C{1H} NMR (125.7 MHz, CDCl3, 25
2
3
2H, Hâa), 1.37 (qd, J (HH) ) 3J (HH) ) 12.5 Hz, J (HH) ) 3.0
Hz, 2H, Hâa), 1.18 (m, m, 6H, Hγδ). 13C{1H} NMR (125.7 MHz,
CDCl3, 25 °C): δ 129.38 (CR), 128.20 (Câ), 94.56 (Cq, arene),
86.31 (CH, arene), 36.38 (CR′), 29.84 (CH), 29.62 (Câ′), 28.96
(Câ′), 27.45 (Cγ′), 27.26 (Cγ′′), 26.04 (Cδ′), 21.58 (2CH3), 16.46
(CH3). Anal. Calcd for C24H39AsCl2Ru: C, 50.16; H, 6.79; Cl,
12.35. Found: C, 50.01; H, 6.59; Cl, 12.22.
°C): δ 133.81 (Co), 133.12 (Ci), 129.83 (Cp), 128.38 (Cm), 102.76
(C1), 94.52 (C4), 88.90 (C2,6), 79.23 (C3,5), 30.58 (Cc), 20.99 (Ca),
20.18 (Cb), 18.05 (C7,8). Anal. Calcd for C23H25AsCl2Ru: C,
50.40; H, 4.56; Cl, 12.94. Found: C, 50.21; H, 4.43; Cl, 12.60.
X-r a y Da ta Collection a n d P r ocessin g. Crystals of the
compounds were obtained from CHCl3/n-hexane solvent mix-
tures mounted on glass fibers and placed on a Nonius Kappa
CCD diffractometer. Intensity data were taken in the ω-mode
for 1a , 2a , and 4a -6a , and φ- and ω-mode for 1b, 3b, 5b, and
6b at 200 K with Mo KR graphite-monochromated radiation
(λ ) 0.71073 Å). The data were corrected for Lorentz-
polarization effects and absorption by integration using the
Gaussian method.29 Scattering factors and corrections for
anomalous dispersion were taken from a standard source.30
Calculations were performed with the teXsan (MSC 1992-
1997) software package version 1.831 for 1a , 2a , 4a -6a , 1b,
3b, 5b, and 6b and CRYSTALS Issue 1032 for 5a on the Silicon
Graphics Power Challenge computer of the Australian Na-
tional University’s super computer facility. The structures
were solved by Patterson methods, DIRDIF-92,33 for 1a , 2a ,
4a , 6a , 1b, 3b, 5b, and 6b and SIR-9234 for 5a . Anisotropic
thermal parameters were assigned to all non-hydrogen atoms.
Hydrogen atoms were included at calculated positions in which
the C-H vector was fixed at 0.95 Å but not refined. Compound
4a crystallized as a chloroform solvate.
P r ep a r a tion s of 1c a n d 4c. The complexes were prepared
by the following procedure. A solution of [(η6-arene)RuCl2-
(DPVAs)] (0.20 g) in 25 mL of CH3CN was stirred at room
temperature for 15 min under nitrogen. To this solution was
added KOBut (0.02-0.03 g) and 5 mL of CH3CN. The clear
red solution turned dark red upon addition of the base. The
solution was heated at reflux for 48 h. The solvent was
removed on a rotary evaporator. The residue was washed with
ether to remove some decomposition products. The mixture
was then filtered and rotary evaporated to dryness. The
residue was dissolved in a small quantity of dichloromethane,
the solution was layered with n-hexane, and the products were
allowed to crystallize in a freezer. The resulting solid was
isolated by filtration and dried in vacuo to give the pure
products as red powders.
Ack n ow led gm en t. This research was supported by
an award from the Research Corporation and by the
donors of the Petroleum Research Fund Administered
by the American Chemical Society. We are grateful for
this support.
Su p p or tin g In for m a tion Ava ila ble: Structural drawings
of 1a , 2a , 5a , 6a , 1b, 3b, and 6b, tables of crystal data and
structure refinement, atomic coordinates, isotropic and aniso-
tropic displacement parameters, bond lengths and angles, and
hydrogen coordinates for 1a , 2a , 4a -6a , 1b, 3b, 5b, and 6b.
This material is available free of charge via the Internet at
http://pubs.acs.org.
1c: mp 198-200 °C (20% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 7.66 (m, 4H, Ho), 7.36 (m, 6H, Hm,p), 6.29 (t,
3
3
3J (HH) ) 5.5 Hz, 1H, H4), 5.78 (dd, J (HH) ) 6.0 Hz, J (HH)
3
) 5.5 Hz, 2H, H2,6), 5.22 (d, J (HH) ) 6.0 Hz, 2H, H3,5), 2.64
(t, 3J (HH) ) 6.0 Hz, 2H, Hc), 2.43 (t, 3J (HH) ) 6.0 Hz, 2H, Ha)
2.27 (m, 2H, Hb). 13C{1H} NMR (125.7 MHz, CDCl3, 25 °C): δ
133.22 (Co), 132.89 (Ci), 130.10 (Cp), 128.62 (Cm), 96.67 (C1),
88.40 (C4), 87.36 (C2,6), 82.27 (C3,5), 30.68 (Cc), 29.67 (Ca), 20.82
(Cb). Anal. Calcd for C21H21AsCl2Ru: C, 49.49; H, 4.04; Cl,
13.63. Found: C, 49.23; H, 3.88; Cl, 13.46.
OM011092J
(29) Coppens, P. In Crystallographic Computing; Ahmed, R., Hall,
S. R., Huber, C. P., Eds.; Munksgaard: Copenhagen, 1970; pp 255-
270.
(30) International Tables for X-ray Crystallography; D. Reidel
Publishing Co.: Boston, 1992; Vol. C.
(31) TEXSAN, Single-Crystal Structure Analysis Software, Version
1.8; Molecular Structure Corp.: 3200 Research Forest Dr., The
Woodlands, TX 77381, 1997.
(32) Watkin, D. J .; Prout, C. K.; Carruthers, J . R.; Betteridge, P.
W. CRYSTALS Issue 10; Chemical Crystallography Laboratory: Ox-
ford, UK, 1996.
(33) Beurskens, P. T.; Admiraal, G.; Beurskens, G.; Bosman, W. P.;
Gould, R. O.; Smits, J . M.; Smykalla, M. C. The DIRDIF-92 program
system; Technical Report of the Crystallography Laboratory; University
of Nijmegen: The Netherlands, 1992.
(34) Altomare, A.; Cascarano, M.; Giacovazzo, C.; Guagliardi, A.;
Burla, M. C.; Polodori, G.; Camalli, M. J . Appl. Crystallogr. 1994, 27,
435.
4c: mp 212-214 °C (25% yield). 1H NMR (500.0 MHz,
CDCl3, 25 °C): δ 7.66 (m, 4H, Ho), 7.33 (m, 6H, Hm,p), 5.71 (s,