Behavior of (ether-phosphine)ruthenium(II) complexes [(η6-C6Me6)RuH(PO)][BF4] containing reactive Ru-O and Ru-H bonds toward various small molecules and their application in ring-opening metathesis polymerization

Article abstract of DOI:10.1021/om980001o

The ruthenium(II) complexes [(η⁶-C₆Me₆)RuH(PO)][BF₄] (5a-c; PO = η²-(O,P)-chelated ether-phosphine; a, Ph₂PCH₂CH₂OCH₃; b, Ph₂PCH₂C₄H₇O₂ (C₄H₇O₂ = 1,3-dioxanyl); c, Ph₂-PCH₂C₃H₅O₂ (C₃H₅O₂ = 1,3-dioxolanyl)), each having a Ru-O and Ru-H functionality, were obtained by hydride abstraction from (n⁶-C₆Me₆)RuH₂(P～O) (4a-c, P～O = η¹-(P)-coordinated ligand) with Ph₃CBF₄. A facile Ru-O bond cleavage occurs when 5a-c are reacted with a variety of small molecules. Carbon monoxide, acetonitrile, tert-butyl isocyanide, and ethene were readily added to 5a-c, leading to the corresponding adducts [(η⁶-C₆Me₆)RuH(P～O)L]-[BF₄] (6a-c, 7a-c, 8a-c, 10a-c; L = CO, CH₃CN, t-BuNC, C₂H₄). π/σ rearrangements with incorporation of the Ru-H bonds in 10a-c were not observed. If 5a-c were treated with carbon disulfide, both functionalities were required. Rupture of the Ru-O contact resulted in a π-CS₂-coordinated intermediate followed by an insertion of CS₂ into the Ru-H bond to give the dithioformato complexes [(η⁶-C₆Me₆)RuH(P～O)(S ₂CH)][BF₄] (9a-c). All compounds were obtained in excellent yields under mild conditions. The structures of 5a, 7c, 8c, and 9a were determined by single-crystal X-ray diffraction methods. Ring-opening metathesis polymerization of norbornene was achieved using complexes 5a-c as the catalyst precursors.

Full text of DOI:10.1021/om980001o

3006
Organometallics 1998, 17, 3006-3014
Beh a vior of (Eth er -p h osp h in e)r u th en iu m (II) Com p lexes
[(η6-C6Me6)Ru H(P kO)][BF 4] Con ta in in g Rea ctive Ru -O
a n d Ru -H Bon d s tow a r d Va r iou s Sm a ll Molecu les a n d
Th eir Ap p lica tion in Rin g-Op en in g Meta th esis
P olym er iza tion
Ekkehard Lindner,* Stefan Pautz, Riad Fawzi, and Manfred Steimann
Institut fu¨r Anorganische Chemie der Universita¨t, Auf der Morgenstelle 18,
D-72076 Tu¨bingen, Germany
Received J anuary 2, 1998
The ruthenium(II) complexes [(η6-C6Me6)RuH(PkO)][BF4] (5a -c; PkO ) η2-(O,P)-chelated
ether-phosphine; a , Ph2PCH2CH2OCH3; b, Ph2PCH2C4H7O2 (C4H7O2 ) 1,3-dioxanyl); c, Ph2-
PCH2C3H5O2 (C3H5O2 ) 1,3-dioxolanyl)), each having a Ru-O and Ru-H functionality, were
obtained by hydride abstraction from (η6-C6Me6)RuH2(P∼O) (4a -c, P∼O ) η1-(P)-coordinated
ligand) with Ph3CBF4. A facile Ru-O bond cleavage occurs when 5a -c are reacted with a
variety of small molecules. Carbon monoxide, acetonitrile, tert-butyl isocyanide, and ethene
were readily added to 5a -c, leading to the corresponding adducts [(η6-C6Me6)RuH(P∼O)L]-
[BF4] (6a -c, 7a -c, 8a -c, 10a -c; L ) CO, CH3CN, t-BuNC, C2H4). π/σ rearrangements
with incorporation of the Ru-H bonds in 10a -c were not observed. If 5a -c were treated
with carbon disulfide, both functionalities were required. Rupture of the Ru-O contact
resulted in a π-CS2-coordinated intermediate followed by an insertion of CS2 into the Ru-H
bond to give the dithioformato complexes [(η6-C6Me6)RuH(P∼O)(S2CH)][BF4] (9a -c). All
compounds were obtained in excellent yields under mild conditions. The structures of 5a ,
7c, 8c, and 9a were determined by single-crystal X-ray diffraction methods. Ring-opening
metathesis polymerization of norbornene was achieved using complexes 5a -c as the catalyst
precursors.
In tr od u ction
nucleophilicity of the ether moiety, the ring size of the
cyclic ether, the number and position of the oxygen
atoms in the ring, and the basicity at the ruthenium.
These results were established from investigations of
the fluxional behavior by VT 31P NMR spectroscopy of
octahedrally coordinated and half-sandwich ruthenium-
(II) complexes containing ether-phosphines as ligands.5
According to these studies, complexes with Ph2-
PCH2C4H7O2 (C4H7O2 ) 1,3-dioxanyl) (2b) have by far
the lowest ∆Hq values while those with Ph2PCH2C3H5O2
(C3H5O2 ) 1,3-dioxolanyl) (2c) and Ph2PCH2CH2OCH3
(2a ) show nearly equal bond strengths.
In recent years there has been considerable interest
in the design and use of so-called hemilabile ligands.1-3
They contain a soft donor (e.g., phosphorus) closely coor-
dinated to the transition metal with a hard donor (e.g.,
oxygen) forming only a weak contact to the metal center.
Due to this feature, the (ether)oxygen atom can easily
be displaced by an incoming substrate. In addition, the
oxygen function, which may be regarded as an intramo-
lecular solvent, is able to stabilize a transition-metal
fragment after substrate dissociation, and therefore,
decomposition is suppressed.2 Thus, ether-phosphines
are capable of making available and protecting vacant
coordination sites and lead to an improvement in both
catalytic and stoichiometric reactions.2,4
This article reports the synthesis and reactivity of the
complexes [(η6-C6Me6)-RuH(PkO)][BF4] (5a -c) (PkO,
η2-(O,P)-coordinated ether-phosphine) containing two
concomitant functionalities.6 Besides a metal-hydride
The strength of the metal-oxygen bond in (ether-
phosphine)ruthenium complexes depends on the O
(4) (a) Lindner, E.; Haustein, M.; Fawzi, R.; Steimann, M.; Wegner,
P. Organometallics 1994, 13, 5021. (b) Lindner, E.; Haustein, M.;
Mayer, H. A.; Gierling, K.; Fawzi, R.; Steimann, M. Organometallics
1995, 14, 2246. (c) Lindner, E.; Gepra¨gs, M.; Gierling, K.; Fawzi, R.;
Steimann, M. Inorg. Chem. 1995, 34, 6106. (d) Lindner, E.; Pautz, S.;
Haustein, M. J . Organomet. Chem. 1996, 509, 215. (e) Lindner, E.;
Keppeler, B.; Mayer, H. A.; Gierling, K.; Fawzi, R.; Steimann, M. J .
Organomet. Chem. 1996, 526, 175. (f) Lindner, E.; Keppeler, B.;
Wegner, P. Inorg. Chim. Acta 1997, 258, 97. (g) Lindner, E.; Dettinger,
J .; Mayer, H. A.; Ku¨hbauch, H.; Fawzi, R.; Steimann, M. Chem. Ber.
1993, 126, 1317.
(1) J effrey, J . C.; Rauchfuss, T. B. Inorg. Chem. 1979, 18, 2658.
(2) (a) Bader, A.; Lindner, E. Coord. Chem. Rev. 1991, 108, 27. (b)
Lindner, E.; Pautz, S.; Haustein, M. Coord. Chem. Rev. 1996, 155, 145.
(3) (a) Yang, H.; Alvarez-Gressier, M.; Lugan, N.; Mathieu, R.
Organometallics 1997, 16, 1401. (b) Braunstein, P.; Chauvin, Y.;
Nahring, J .; Decian, A.; Fischer, J .; Tiripicchio, A.; Ugozzoli, F.
Organometallics 1996, 15, 5551. (c) Chadwell, S. J .; Coles, S. J .;
Edwards, P. G.; Hursthouse, M. B. J . Chem. Soc., Dalton Trans. 1996,
1105. (d) Higgins, T. B.; Mirkin, C. A. Inorg. Chim. Acta 1995, 240,
347. (e) Braun, T.; Steinert, P.; Werner, H. J . Organomet. Chem. 1995,
488, 169. (f) Werner, H.; Stark, A.; Steinert, P.; Gru¨nwald, G.; Wolf, J .
Chem. Ber. 1995, 128, 49.
(5) (a) Lindner, E.; Mo¨ckel, A.; Mayer, H. A.; Ku¨hbauch, H.; Fawzi,
R.; Steimann, M. Inorg. Chem. 1993, 32, 1266. (b) Lindner, E.;
Haustein, M.; Mayer, H. A.; Ku¨hbauch, H.; Vrieze, K.; de Klerk-Engels,
B. Inorg. Chim. Acta 1994, 215, 165.
S0276-7333(98)00001-6 CCC: $15.00 © 1998 American Chemical Society
Publication on Web 06/13/1998

(Ether-phosphine)ruthenium(II) Complexes
Organometallics, Vol. 17, No. 14, 1998 3007
not otherwise noted, the 1H NMR measurements were per-
formed with a Bruker DRX 250 spectrometer at 250.13 MHz.
31P{1H} and 13C{1H} NMR spectra were recorded on a Bruker
DRX 250 spectrometer at 101.25 and 62.90 MHz. 1H and 13C
chemical shifts were measured relative to partially deuterated
solvent peaks and to deuterated solvent peaks, respectively.
31P chemical shifts were measured relative to 85% H3PO4 (δ
) 0). If not otherwise mentioned, the NMR spectra were
recorded at a temperature of 22 °C. The starting complex [{-
(η6-C6Me6)RuCl2}2] (1) was synthesized according to Bennett
et al.12 with a modification described by Crochet et al.6c The
ether-phosphines 2a -c were prepared as previously de-
scribed.13
Sch em e 1
Dich lor o(η6-h e xa m e t h ylb e n ze n e )[(m e t h oxye t h yl)-
d ip h en ylp h osp h in e-P ]r u th en iu m (II) (3a ). A mixture of
1.40 g (2.09 mmol) of [{(η6-C6Me6)RuCl2}2] (1) and 1.02 g (4.18
mmol) of the phosphine 2a was stirred overnight in 50 mL of
CH2Cl2. The reaction mixture was filtered (G3), and the
filtrate was evaporated to dryness under reduced pressure. The
residue was stirred in 100 mL of diethyl ether to give an orange
powder, which was collected by filtration (G3) and dried in
vacuo: yield 2.20 g (91%); mp 212 °C (dec); MS (FD, 60 °C)
m/e 579 [M+]. Anal. Calcd (Found) for C27H35Cl2OPRu: C,
56.06 (55.79); H, 6.10 (6.02); Cl, 12.27 (12.30); Ru, 17.47
(17.39). 31P{1H} NMR (CDCl3): δ 22.7 (s). 13C{1H} NMR
2
(CDCl3): δ 134.3-128.3 (m, Ph), 96.6 (d, J PC ) 2.7 Hz, C6-
1
Me6), 68.9 (s, CH2O), 58.2 (s, OCH3), 30.0 (d, J PC ) 29.6 Hz,
PCH2), 15.5 (s, C6Me6).
Dich lor o[(1,3-d ioxa n -2-ylm eth yl)d ip h en ylp h osp h in e-
P ](η6-h exa m eth ylben zen e)r u th en iu m (II) (3b). 3b was
similarly obtained by reacting 1.00 g (1.5 mmol) of 1 with 857
mg (3.0 mmol) of 2b in 50 mL of CH2Cl2: yield 1.66 g (89%);
mp 206 °C (dec); MS (FAB, 50 °C) m/e 620 [M+]. Anal. Calcd
(Found) for C29H37Cl2O2PRu: C, 56.13 (56.37); H, 6.01 (6.01);
Cl, 11.43 (11.52); Ru, 16.29 (16.50). 31P{1H} NMR (CDCl3): δ
20.9 (s). 13C{1H} NMR (CDCl3): δ 134.1-127.5 (m, Ph), 99.6
(s, CH), 96.0 (s, C6Me6), 66.1 (s, OCH2CH2) 34.5 (d, 1J PC ) 37.7
Hz, PCH2), 25.1 (s, OCH2CH2), 14.9 (s, C6Me6).
bond, 5a -c reveal each one reactive ruthenium-oxygen
bond which is destabilized by the electron-donating
properties of the π-coordinated hexamethylbenzene ring.
By this means, two different types of reactions are
discernible with small molecules. Carbon monoxide,
acetonitrile, and tert-butyl isocyanide are activated
under mild conditions just by cleavage of the ruthenium-
oxygen function, whereas using carbon disulfide and
olefins, both functionalities may be required. To inves-
tigate the dependence of the reactivity on the ether
moieties employed, three different phosphines were
introduced (Scheme 1). Complexes 5a -c show also
considerable activity in the ring-opening metathesis
polymerization (ROMP) of norbornene.
Dich lor o[(1,3-dioxolan -2-ylm eth yl)diph en ylph osph in e-
P ](η6-h exa m eth ylben zen e)r u th en iu m (II) (3c). 3c was
similarly obtained by reacting 1.10 g (1.64 mmol) of 1 with
896 mg (3.28 mmol) of 2c in 50 mL of CH2Cl2: yield 1.80 g
(90%); mp 209 °C (dec); MS (FD, 60 °C) m/e 606 [M+]. Anal.
Calcd (Found) for C28H35Cl2O2PRu: C, 55.45 (55.24); H, 5.82
(5.69); Cl, 11.69 (11.73); Ru, 16.66 (16.68). 31P{1H} NMR
(CDCl3): δ 21.5 (s). 13C{1H} NMR (CDCl3): δ 134.3-127.6 (m,
Exp er im en ta l Section
2
2
Ph), 101.8 (d, J PC ) 6.1 Hz, CH), 96.0 (d, J PC ) 2.7 Hz, C6-
1
Me6), 64.1 (s, OCH2), 32.1 (d, J PC ) 28.3 Hz, PCH2), 15.1 (s,
Gen er a l Com m en ts. All manipulations were carried out
under an atmosphere of argon using standard Schlenk tech-
niques. Solvents were dried over the appropriate reagents and
stored under argon. IR data were obtained with a Bruker IFS
48 FT-IR instrument. FD mass spectra were taken on a
Finnigan MAT 711 A instrument (8 kV, 60 °C), modified by
AMD; FAB mass spectra were recorded on a Finnigan MAT
TSQ 70 (10 kV, 50 °C). Elemental analyses were performed
with a Carlo Erba 1106 analyzer; Cl, F, and S analyses were
carried out according to Scho¨niger7 and determined as de-
scribed by Dirscherl and Erne,8 Brunisholz and Michot,9 and
Wagner.10 Ru was analyzed according to the literature.11 If
C6Me6).
(η6-H exa m et h ylb en zen e)d ih yd r id o[(m et h oxyet h yl)-
d ip h en ylp h osp h in e-P ]r u th en iu m (II) (4a ). A mixture of
2.00 g (3.46 mmol) of 3a and 980 mg (25.95 mmol) of NaBH4
in 50 mL of 2-propanol was heated under reflux for 45 min.
The brown suspension was allowed to cool to room temperature
and was evaporated to dryness under reduced pressure. The
brown residue was extracted with 80 mL of toluene, and the
solution was then filtered (G3). The filtrate was reduced to a
volume of 15 mL, transferred to a neutral alumina column
(length of column 5 cm), and finally eluted with toluene. The
yellow eluate was evaporated to dryness, and the residue was
washed with 20 mL of n-hexane to give a pale yellow
precipitate, which was collected by filtration (G3) and dried
under reduced pressure to yield 1.16 g (66%) of 4a ; mp 92 °C
(dec); MS (FD, 60 °C) m/e 508 [M+ - 2H]. Anal. Calcd (Found)
for C27H37OPRu: C, 63.63 (63.45); H, 7.32 (7.32); Ru, 19.83
(20.01). IR (KBr, cm-1): ν(RuH) 1949 (s). 31P{1H} NMR
(6) (a) Demerseman, B.; Le Lagadec, R.; Guilbert, B.; Renouard, C.;
Crochet, P.; Dixneuf, P. H. Organometallics 1994, 13, 2269. (b)
Demerseman, B.; Renouard, C.; Le Lagadec, R.; Gonzalez, M.; Crochet,
P.; Dixneuf, P. H. J . Organomet. Chem. 1994, 471, 229. (c) Crochet,
P.; Demerseman, B.; Rocaboy, C.; Schleyer, D. Organometallics 1996,
15, 3048.
(7) (a) Scho¨niger, W. Microchim. Acta 1955, 123. (b) Scho¨niger, W.
Microchim. Acta 1956, 869.
(8) Dirscherl, A.; Erne, F. Microchim. Acta 1961, 866.
(9) Brunisholz, G.; Michot, J . Helv. Chim. Acta 1954, 37, 598.
(10) Wagner, S. Microchim. Acta 1957, 19.
(11) Lindner, E.; Bader, A.; Mayer, H. A. Z. Anorg. Allg. Chem. 1991,
598/ 599, 235.
(12) Bennett, M. A.; Huang, T. N.; Matheson, T. W.; Smith, A. K.
Inorg. Synth. 1982, 21, 74.
(13) Lindner, E.; Dettinger, J .; Mo¨ckel, A. Z. Naturforsch., Teil B
1991, 46, 1519.

3008 Organometallics, Vol. 17, No. 14, 1998
Lindner et al.
2
2
(C6D6): δ 53.1 (s). 13C{1H} NMR (C6D6): δ 141.9-128.0 (m,
diastereomer, δ 110.1 (d, J PC ) 8.1 Hz, CH), 99.0 (d, J PC
)
2
2
Ph), 97.1 (d, J PC ) 2.7 Hz, C6Me6), 71.2 (d, J PC ) 12.1 Hz,
2.7 Hz, C6Me6), 75.7 (s, Ru-OCH2), 66.1 (s, OCH2), 36.0 (d,
CH2O), 58.6 (s, OCH3), 36.0 (d, 1J PC ) 30.3 Hz, PCH2), 18.2 (s,
1J PC ) 26.3 Hz, PCH2), 16.5 (s, C6Me6); minor diastereomer, δ
2
2
2
C6Me6). 1H NMR (C6D6): δ -11.0 (d, J PH ) 45.3 Hz, 2H,
109.5 (d, J PC ) 10.1 Hz, CH), 98.6 (d, J PC ) 2.7 Hz, C6Me6),
1
RuH).
70.6 (s, Ru-OCH2), 66.7 (s, OCH2), 33.6 (d, J PC ) 27.6 Hz,
PCH2), 16.7 (s, C6Me6). 1H NMR (400.14 MHz, CD2Cl2): major
[(1,3-Dioxa n -2-ylm eth yl)d ip h en ylp h osp h in e-P ](η6-h ex-
a m eth ylben zen e)d ih yd r id or u th en iu m (II) (4b). 4b was
synthesized and worked up in the same way as 4a by using
1.50 g (2.42 mmol) of 3b and 686 mg (18.1 mmol) of NaBH4 in
50 mL of 2-propanol: yield 907 mg (68%); mp 115 °C (dec);
MS (FD, 60 °C) m/e 551 [M+]. Anal. Calcd (Found) for
2
diastereomer, δ -8.2 (d, J PH ) 46.1 Hz, RuH); minor diaste-
reomer, δ -8.4 (d, J PH ) 48.0 Hz, RuH).
2
Ca r b on yl(η6-h exa m et h ylb en zen e)h yd r id o[(m et h oxy-
et h yl)d ip h en ylp h osp h in e-P ]r u t h en iu m (II) Tet r a flu o-
r obor a te (6a ). A solution of 5a (120 mg, 0.20 mmol) in 10
mL of CH2Cl2 was treated with carbon monoxide (1 bar) at
ambient temperature. After 1 h, the orange solution changed
to bright yellow. The reaction mixture was reduced to a
volume of 1 mL and was layered with diethyl ether (3 mL) to
afford bright yellow crystals of 6a : yield 81 mg (65%); mp 148
°C (dec); MS (FD, 60 °C) m/e 537 [M+ - BF4]. Anal. Calcd
(Found) for C28H36BF4O2PRu: C, 53.94 (54.07); H, 5.82 (5.77);
F, 12.19 (12.10); Ru, 16.21 (15.86). IR (KBr, cm-1): ν(RuH)
2059 (s), ν(CO) 1973 (vs). 31P{1H} NMR (CD2Cl2): δ 47.6 (s).
C
29H39O2PRu: C, 63.14 (62.98); H, 7.13 (7.03); Ru, 18.32
(18.18). IR (KBr, cm-1): ν(RuH) 1931 (s). 31P{1H} NMR
(toluene-d8): δ 55.3 (s). 13C{1H} NMR (toluene-d8): δ 141.6-
2
2
127.1 (m, Ph), 102.4 (d, J PC ) 11.5 Hz, CH), 96.5 (d, J PC
)
1
3.4 Hz, C6Me6), 66.6 (s, OCH2CH2), 40.8 (d, J PC ) 29.6 Hz,
PCH2), 25.9 (s, OCH2CH2), 17.6 (s, C6Me6). 1H NMR (toluene-
2
d8): δ -11.0 (d, J PH ) 45.3 Hz, 2H, RuH).
[(1,3-Dioxola n -2-ylm et h yl)d ip h en ylp h osp h in e-P ](η6-
h exa m eth ylben zen e)d ih yd r id or u th en iu m (II) (4c). 4c
was synthesized and worked up in the same way as 4a by
using 1.50 g (2.47 mmol) of 3c and 702 mg (18.5 mmol) of
NaBH4 in 50 mL of 2-propanol: yield 864 mg (65%); mp 119
°C (dec); MS (FD, 60 °C) m/e 536 [M+ - 2H]. Anal. Calcd
(Found) for C28H37O2PRu: C, 62.55 (62.76); H, 6.94 (6.84); Ru,
18.80 (18.97). IR (KBr, cm-1): ν(RuH) 1946 (s). 31P{1H} NMR
(C6D6): δ 54.6 (s). 13C{1H} NMR (C6D6): δ 133.4-127.2 (m,
13C{1H} NMR (CD2Cl2): δ 198.7 (d, J PC ) 18.9 Hz, CO),
2
132.5-127.2 (m, Ph), 113.3 (s, C6Me6), 67.5 (s, CH2O), 58.5 (s,
OCH3), 31.2 (d, J PC ) 34.6 Hz, PCH2), 16.5 (s, C6Me6). 1H
1
2
NMR (CD2Cl2): δ -11.0 (d, J PH ) 31.3 Hz, 1H, RuH).
Ca r bon yl[(1,3-d ioxa n -2-ylm eth yl)d ip h en ylp h osp h in e-
P ](η6-h exa m et h ylb en zen e)h yd r id or u t h en iu m (II) Tet -
r a flu or obor a te (6b). 6b was synthesized and worked up in
the same way as 6a by reacting a solution of 150 mg (0.24
mmol) of 5b in 10 mL of CH2Cl2 with carbon monoxide (1 bar)
for 30 min: yield 109 mg (68%); mp 142 °C (dec); MS (FD,
60 °C) m/e 579 [M+ - BF4]. Anal. Calcd (Found) for
2
2
Ph), 104.3 (d, J PC ) 10.1 Hz, CH), 96.8 (d, J PC ) 2.7 Hz, C6-
1
Me6), 64.4 (s, OCH2), 40.6 (d, J PC ) 30.3 Hz, PCH2), 17.7 (s,
C6Me6). 1H NMR (C6D6): δ -10.8 (d, J PH ) 45.7 Hz, 2H,
2
RuH).
(η6-H e xa m e t h y lb e n ze n e )h yd r id o [(m e t h o x y e t h y l)-
d ip h en ylp h osp h in e-O,P ]r u th en iu m (II) Tetr a flu or obo-
r a te (5a ). A mixture of 1.30 g (2.55 mmol) of 4a and 842 mg
(2.55 mmol) of Ph3CBF4 in 50 mL of THF was stirred overnight
at room temperature. The yellow solution was evaporated to
dryness under reduced pressure, and the residue was extracted
with n-hexane in a Soxhlet apparatus. The resulting yellow
powder was dried in vacuo: yield 1.44 g (95%): mp 107 °C
(dec); MS (FD, 60 °C) m/e 508 [M+ - BF4]. Anal. Calcd
(Found) for C27H36BF4OPRu: C, 54.46 (54.47); H, 6.09 (5.76);
F, 12.76 (13.17); Ru, 16.96 (16.73). IR (KBr, cm-1): ν(RuH)
1943 (m). 31P{1H} NMR (CD2Cl2): δ 67.5 (s). 13C{1H} NMR
C
30H38BF4O3PRu: C, 54.15 (54.22); H, 5.76 (5.61); F, 11.42
(11.79); Ru, 15.19 (14.87). IR (KBr, cm-1): ν(RuH) 2068 (m),
ν(CO) 1974 (s). 31P{1H} NMR (CD2Cl2): δ 45.5 (s). 13C{1H}
2
NMR (CD2Cl2): δ 199.3 (d, J PC ) 20.6 Hz, CO), 134.9-127.5
2
2
(m, Ph), 113.7 (d, J PC ) 1.4 Hz, C6Me6), 99.0 (d, J PC ) 4.3
4
1
Hz, CH), 67.1 (d, J PC ) 6.4 Hz, OCH2CH2), 36.0 (d, J PC
)
34.9 Hz, PCH2), 22.9 (s, OCH2CH2), 17.2 (s, C6Me6). 1H NMR
2
(CD2Cl2): δ -11.0 (d, J PH ) 31.0 Hz, 1H, RuH).
Car bon yl[(1,3-dioxolan -2-ylm eth yl)diph en ylph osph in e-
P ](η6-h exa m et h ylb en zen e)h yd r id or u t h en iu m (II) Tet -
r a flu or obor a te (6c). 6c was synthesized and worked up in
the same way as 6a by reacting a solution of 130 mg (0.21
mmol) of 5c in 10 mL of CH2Cl2 with carbon monoxide (1 bar)
for 3 h: yield 84 mg (62%); mp 124 °C (dec); MS (FAB 50 °C)
m/e 565 [M+ - BF4]. Anal. Calcd (Found) for C29H36BF4O3-
PRu: C, 53.47 (53.22); H, 5.57 (5.62); F, 11.67 (11.53); Ru,
15.51 (15.32). IR (KBr, cm-1): ν(RuH) 2060 (m), ν(CO) 1973
(s). 31P{1H} NMR (CD2Cl2): δ 45.2 (s). 13C{1H} NMR (CD2-
2
(CD2Cl2): δ 134.2-127.1 (m, Ph), 98.6 (d, J PC ) 2.7 Hz, C6-
1
Me6), 79.3 (s, CH2O), 72.4 (s, OCH3), 30.5 (d, J PC ) 27.6 Hz,
2
PCH2), 16.4 (s, C6Me6). 1H NMR (CD2Cl2): δ -8.3 (d, J PH
)
46.3 Hz, 1H, RuH).
[(1,3-Dioxa n -2-ylm et h yl)d ip h en ylp h osp h in e-O,P ](η6-
h exa m et h ylb en zen e)h yd r id or u t h en iu m (II) Tet r a flu o-
r obor a te (5b). 5b was prepared and worked up analogously
to 5a by using 820 mg (1.48 mmol) of 4b and 491 mg (1.48
mmol) of Ph3CBF4 in 50 mL of THF: yield 830 mg (88%); mp
111 °C (dec); MS (FD, 60 °C) m/e 551 [M+ - BF4]. Anal. Calcd
(Found) for C29H38BF4O2PRu: C, 54.64 (54.82); H, 6.01 (6.19);
F, 11.92 (12.18); Ru, 15.85 (16.12). IR (KBr, cm-1): ν(RuH)
2001 (m, br). 31P{1H} NMR (CD2Cl2): δ 65.8, 49.9 (both s).
13C{1H} NMR (CD2Cl2): δ 134.6-127.4 (m, Ph), 107.8, 105.1
(s, CH), 98.9, 98.6 (s, C6Me6), 80.8, 76.9 (s, Ru-OCH2CH2),
2
Cl2): δ 199.2 (d, J PC ) 21.6 Hz, CO), 132.7-129.1 (m, Ph),
113.7 (s, C6Me6), 100.9 (s, CH), 65.2 (d, 4J PC ) 12.8 Hz, OCH2),
35.7 (d, 1J PC ) 30.7 Hz, PCH2), 17.2 (s, C6Me6). 1H NMR (CD2-
2
Cl2): δ -11.0 (d, J PH ) 31.9 Hz, 1H, RuH).
Ac e t o n i t r i l e ( η6 -h e x a m e t h y l b e n z e n e ) h y d r i d o -
[(m eth oxyeth yl)diph en ylph osph in e-P ]r u th en iu m (II) Tet-
r a flu or obor a te (7a ). A solution of 5a (150 mg, 0.25 mmol)
in 10 mL of CH2Cl2 was treated with 10.3 mg (0.25 mmol) of
acetonitrile at room temperature. The orange solution spon-
taneously brightens to yellow. After 5 min of stirring, the
solvent was removed under vacuum. The residue was washed
with 10 mL of n-hexane to give a pale yellow precipitate, which
was collected by filtration (G3) and dried in vacuo: yield 159
1
67.6, 66.9 (s, OCH2CH2), 37.5, 36.6 (d, J PC ) 24.5 and 28.9
Hz, PCH2), 26.9, 22.0 (s, OCH2CH2), 16.6 (s, C6Me6).
[(1,3-Dioxola n -2-ylm eth yl)d ip h en ylp h osp h in e-O,P ](η6-
h exa m et h ylb en zen e)h yd r id or u t h en iu m (II) Tet r a flu o-
r obor a te (5c). 5c was prepared and worked up analogously
to 5a by using 850 mg (1.58 mmol) of 4c and 522 mg (1.58
mmol) of Ph3CBF4 in 50 mL of THF: yield 867 mg (90%); mp
94 °C (dec); MS (FD, 60 °C) m/e 537 [M+ - BF4]. Anal. Calcd
(Found) for C28H36BF4O2PRu: C, 53.94 (54.06); H, 5.82 (5.72);
F, 12.19 (12.34); Ru, 16.21 (16.19). IR (KBr, cm-1): ν(RuH)
1978 (w, br). 31P{1H} NMR (CD2Cl2): major diastereomer, δ
60.2 (s); minor diastereomer, δ 55.7 (s). 13C{1H} NMR (CD2-
Cl2): δ 135.8-127.8 (m, Ph of both diastereomers); major
mg (100%); mp 148 °C (dec); MS (FD, 60 °C) m/e 548 [M+
-
BF4]. Anal. Calcd (Found) for C29H39BF4NOPRu: C, 54.73
(54.41); H, 6.18 (6.03); F, 11.94 (12.06); N, 2.20 (2.22); Ru, 15.88
(16.05). IR (KBr, cm-1): ν(CN) 2278 (w), ν(RuH) 1946 (m).
31P{1H} NMR (CD2Cl2): δ 47.9 (s). 13C{1H} NMR (CD2Cl2): δ
134.4-127.8 (m, Ph), 123.6 (s, NCMe), 101.6 (d, 2J PC ) 2.7 Hz,
C6Me6), 68.3 (d, 2J PC ) 6.1 Hz, CH2O), 58.3 (s, OCH3), 29.6 (d,
1J PC ) 32.3 Hz, PCH2), 16.4 (s, C6Me6), 3.4 (s, NCMe). 1H NMR
2
(CD2Cl2): δ -9.6 (d, J PH ) 45.3 Hz, 1H, RuH).

(Ether-phosphine)ruthenium(II) Complexes
Organometallics, Vol. 17, No. 14, 1998 3009
Aceton itr ile[(1,3-dioxan -2-ylm eth yl)diph en ylph osph in e-
P ](η6-h exa m et h ylb en zen e)h yd r id or u t h en iu m (II) Tet -
r a flu or obor a te (7b). 7b was prepared and worked up
analogously to 7a by treating a solution of 180 mg (0.28 mmol)
of 5b in 10 mL of CH2Cl2 with 11.6 mg (0.28 mmol) of CH3-
CN: yield 190 mg (100%); mp 83 °C (dec); MS (FD, 60 °C) m/e
593 [M+ - BF4]. Anal. Calcd (Found) for C31H42BF4NO2PRu:
C, 54.88 (55.10); H, 6.09 (5.79); F, 11.20 (11.08); N, 2.06 (2.10);
Ru, 14.90 (15.09). IR (KBr, cm-1): ν(CN) 2275 (w), ν(RuH)
1948 (m). 31P{1H} NMR (CD2Cl2): δ 48.2 (s). 13C{1H} NMR
(CD2Cl2): δ 133.1-127.2 (m, Ph), 123.5 (s, NCMe), 101.6 (d,
mmol) of t-BuNC: yield 215 mg (100%); mp 201 °C (dec); MS
(FD, 60 °C) m/e 620 [M+ - BF4]. Anal. Calcd (Found) for
C
33H45BF4NO2PRu: C, 56.10 (55.80); H, 6.42 (6.31); F, 10.76
(11.03); N, 1.98 (2.07); Ru, 14.30 (14.19). IR (KBr, cm-1): ν-
(CN) 2139 (vs), ν(RuH) 1983 (w). 31P{1H} NMR (CD2Cl2): δ
2
48.4 (s). 13C{1H} NMR (CD2Cl2): δ 148.6 (d, J PC ) 18.2 Hz,
2
CNCMe3), 133.1-128.2 (m, Ph), 107.4 (d, J PC ) 2.0 Hz, C6-
2
4
Me6), 101.6 (d, J PC ) 5.4 Hz, CH), 64.8 (d, J PC ) 6.0 Hz,
OCH2), 57.5 (s, CNCMe3), 35.3 (d, 1J PC ) 31.7 Hz, PCH2), 30.1
(s, CNCMe3), 16.6 (s, C6Me6). 1H NMR (CD2Cl2): δ -11.1 (d,
2J PH ) 36.5 Hz, 1H, RuH).
2
2J PC ) 2.9 Hz, C6Me6), 99.8 (d, J PC ) 5.0 Hz, CH), 66.9 (d,
η2-Dit h iofor m a t o(η6-h exa m et h ylb en zen e)[(m et h oxy-
et h yl)d ip h en ylp h osp h in e-P ]r u t h en iu m (II) Tet r a flu o-
r obor a te (9a ). A solution of 5a (200 mg, 0.36 mmol) in 10
mL of CH2Cl2 was treated with 51.1 mg (0.72 mmol) of carbon
disulfide at room temperature. Within 60 min the solution
turned from orange to dark red. After the solution was stirred
overnight, the solvent was removed under reduced pressure.
The residue was washed with 10 mL of n-hexane and dried in
vacuo: yield 225 mg (100%); mp 78 °C (dec); MS (FAB, 50 °C)
m/e 585 [M+ - BF4]. Anal. Calcd (Found) for C28H36BF4-
OPRuS2: C, 50.08 (49.92); H, 5.40 (5.21); F, 11.32 (11.03); Ru,
15.05 (14.99); S, 9.55 (9.73). IR (KBr, cm-1): δ (HCS2) 1288
(s). 31P{1H} NMR (CD2Cl2): δ 33.5 (s). 13C{1H} NMR (CD2-
2J PC ) 3.4 Hz, OCH2CH2), 35.8 (d, 1J PC ) 32.7 Hz, PCH2), 25.1
(s, OCH2CH2), 16.6 (s, C6Me6), 3.3 (s, NCMe).1H NMR (CD2-
2
Cl2): δ -9.6 (d, J PH ) 35.5 Hz, 1H, RuH).
Acet on it r ile[(1,3-d ioxola n -2-ylm et h yl)d ip h en ylp h os-
p h in e -P ](η6-h e xa m e t h ylb e n ze n e )h yd r id or u t h e n iu m -
(II) Tetr a flu or obor a te (7c). 7c was prepared and worked
up analogously to 7a by treating a solution of 160 mg (0.26
mmol) of 5c in 10 mL of CH2Cl2 with 10.5 mg (0.26 mmol)
of CH3CN: yield 170 mg (100%); mp 165 °C (dec); MS (FD,
60 °C) m/e 579 [M+ - BF4]. Anal. Calcd (Found) for
C
30H39BF4NO2PRu: C, 54.23 (54.16); H, 5.92 (5.60); F, 11.44
(11.63); N, 2.11 (2.00); Ru, 15.21 (14.98). IR (KBr, cm-1): ν-
(CN) 2278 (w), ν(RuH) 1949 (m). 31P{1H} NMR (CD2Cl2): δ
46.5 (s). 13C{1H} NMR (CD2Cl2): δ 133.0-128.4 (m, Ph), 124.2
3
Cl2): δ 242.5 (d, J PC ) 7.4 Hz, CS2), 134.2-127.2 (m, Ph),
102.6 (d, 2J PC ) 2.0 Hz, C6Me6), 68.3 (d, 2J PC ) 2.7 Hz, CH2O),
58.3 (s, OCH3), 25.9 (d, 1J PC ) 29.6 Hz, PCH2), 16.6 (s, C6Me6).
2
2
(s, NCMe), 102.1 (d, J PC ) 5.4 Hz, CH), 102.0 (d, J PC ) 2.7
Hz, C6Me6), 65.1 (d, 2J PC ) 5.4 Hz, OCH2), 35.2 (d, 1J PC ) 31.0
Hz, PCH2), 16.5 (s, C6Me6), 3.7 (s, NCMe).1H NMR (CD2Cl2,):
4
1H NMR (CD2Cl2): δ 11.7 (d, J PH ) 6.3 Hz, 1H, HCS2).
[(1,3-Dioxa n -2-ylm e t h yl)d ip h e n ylp h osp h in e -P ](η2-
dith iofor m ato)(η6-h exam eth ylben zen e)r u th en iu m (II) Tet-
r a flu or obor a te (9b). 9b was obtained analogously as 9a by
using a solution of 5b (200 mg, 0.31 mmol) in 10 mL of CH2-
Cl2 and 47.8 mg (0.62 mmol) of CS2: yield 224 mg (100%); mp
79 °C (dec); MS (FD, 60 °C) m/e 626 [M+ - BF4]. Anal. Calcd
(Found) for C30H38BF4O2PRuS2: C, 50.49 (50.64); H, 5.67
(5.37); F, 10.65 (10.91); Ru, 14.16 (14.34); S, 8.99 (9.32).
31P{1H} NMR (CD2Cl2): δ 32.2 (s). 13C{1H} NMR (CD2Cl2): δ
2
δ -9.6 (d, J PH ) 45.3 Hz, 1H, RuH).
ter t-Bu tyl Isocya n id e(η6-h exa m eth ylben zen e)h yd r id o-
[(m eth oxyeth yl)diph en ylph osph in e-P ]r u th en iu m (II) Tet-
r a flu or obor a te (8a ). Addition of t-BuNC (27.9 mg, 0.35
mmol) to a solution of 5a (200 mg, 0.35 mmol) in 10 mL of
dichloromethane, followed by 5 min of stirring at room
temperature, gave a yellow solution, which was evaporated
to dryness. The residue was washed with 10 mL of n-hexane
to give a bright yellow precipitate. The precipitate was
collected by filtration (G3), washed with 10 mL of n-hexane,
and dried in vacuo: yield 228 mg (100%); mp 207 °C (dec);
MS (FD, 60 °C) m/e 592 [M+ - BF4]. Anal. Calcd (Found) for
3
242.6 (d, J PC ) 6.7 Hz, CS2), 135.6-124.4 (m, Ph), 102.9 (s,
1
C6Me6), 99.6 (s, CH), 66.5 (s, OCH2CH2), 33.2 (d, J PC ) 30.3
Hz, PCH2), 23.5 (s, OCH2CH2), 16.0 (s, C6Me6). 1H NMR (CD2-
4
Cl2): δ 11.6 (d, J PH ) 6.3 Hz, 1H, HCS2).
[(1,3-Dioxola n -2-ylm et h yl)d ip h en ylp h osp h in e-P ](η2-
dith iofor m ato)(η6-h exam eth ylben zen e)r u th en iu m (II) Tet-
r a flu or obor a te (9c). 9c was obtained analogously by using
a solution of 5c (180 mg, 0.29 mmol) in 10 mL of CH2Cl2 and
44.0 mg (0.58 mmol) of CS2: yield 202 mg (100%); mp 76 °C
(dec); MS (FD, 60 °C) m/e 613 [M+ - BF4]. Anal. Calcd
(Found) for C29H36BF4O2PRuS2: C, 49.79 (50.07); H, 5.19
(5.40); F, 10.86 (10.64); Ru, 14.47 (14.70); S, 9.17 (9.02).
31P{1H} NMR (CD2Cl2): δ 30.9 (s). 13C{1H} NMR (CD2Cl2): δ
C
32H45BF4NOPRu: C, 56.64 (56.27); H, 6.68 (6.56); F, 11.20
(11.08); N, 2.06 (2.30); Ru, 14.89 (14.92). IR (KBr, cm-1): ν-
(CN) 2138 (vs), ν(RuH) 1974 (m). 31P{1H} NMR (CD2Cl2): δ
49.5 (s). 13C{1H} NMR (CD2Cl2): δ 148.8 (d, J PC ) 18.9 Hz,
2
2
CNCMe3), 134.1-127.8 (m, Ph), 107.2 (d, J PC ) 2.8 Hz, C6-
2
Me6), 68.3 (d, J PC ) 7.1 Hz, CH2O), 58.4 (s, OCH3), 57.6 (s,
1
CNCMe3), 30.3 (d, J PC ) 32.7 Hz, PCH2), 30.1 (s, CNCMe3),
16.4 (s, C6Me6). 1H NMR (CD2Cl2): δ -11.2 (d, J PH ) 36.1
2
Hz, 1H, RuH).
3
ter t-Bu t yl Isocya n id e[(1,3-d ioxa n -2-ylm et h yl)d ip h e-
n ylp h osp h in e-P ](η6-h exa m eth ylben zen e)h yd r id or u th e-
n iu m (II) Tetr a flu or obor a te (8b). 8b was prepared and
worked up analogously to 8a by using a solution of 180 mg
(0.28 mmol) of 5b in 10 mL of CH2Cl2 and 23.5 mg (0.28
mmol) of t-BuNC: yield 201 mg (100%); mp 193 °C (dec); MS
(FD, 60 °C) m/e 635 [M+ - BF4]. Anal. Calcd (Found) for
C34H47BF4NO2PRu: C, 56.67 (56.89); H, 6.57 (6.45); F, 10.54
(10.84); N, 1.94 (2.05); Ru, 14.03 (14.12). IR (KBr, cm-1): ν-
(CN) 2142 (s), ν(RuH) 1985 (w). 31P{1H} NMR (CD2Cl2): δ
50.0 (s). 13C{1H} NMR (CD2Cl2): δ 142.9 (s, CNCMe3), 133.9-
243.0 (d, J PC ) 8.0 Hz, CS2), 133.9-127.8 (m, Ph), 117.1 (d,
2
2J PC ) 2.0 Hz, C6Me6), 103.0 (d, J PC ) 2.0 Hz, CH), 65.2 (s,
1
OCH2), 31.1 (d, J PC ) 30.0 Hz, PCH2), 16.4 (s, C6Me6). 1H
4
NMR (CD2Cl2): δ 11.7 (d, J PH ) 6.3 Hz, 1H, HCS2).
( η2 -E t h e n e ) ( η6 -h e x a m e t h y l b e n z e n e ) h y d r i d o -
[(m eth oxyeth yl)diph en ylph osph in e-P ]r u th en iu m (II) Tet-
r a flu or obor a te (10a ). A solution of 140 mg (0.24 mmol) of
5a in 10 mL of CH2Cl2 was treated with ethene (1 bar) at
ambient temperature. After 8 h of stirring, the solvent was
removed under reduced pressure. The residue was washed
with 10 mL of n-hexane to give a pale beige precipitate, which
was collected by filtration (G3) and dried in vacuo: yield 146
2
2
127.2 (m, Ph), 107.3 (d, J PC ) 2.1 Hz, C6Me6), 99.6 (d, J PC
)
4
mg (100%); mp 73 °C (dec); MS (FD, 60 °C) m/e 537 [M+
-
4.3 Hz, CH), 66.9 (d, J PC ) 13.5 Hz, OCH2CH2), 57.6 (s,
1
CNCMe3), 36.5 (d, J PC ) 32.7 Hz, PCH2), 30.1 (s, CNCMe3),
BF4]. Anal. Calcd (Found) for C29H40BF4OPRu: C, 55.87
(55.78); H, 6.47 (6.26); F, 12.19 (12.07); Ru, 16.21 (16.40). IR
(KBr, cm-1): ν(RuH) 2029 (w). 31P{1H} NMR (CD2Cl2): δ 53.4
(s). 13C{1H} NMR (CD2Cl2, -30 °C): δ 131.9-127.0 (m, Ph),
108.9 (d, 2J PC ) 2.0 Hz, C6Me6), 67.9 (s, CH2O), 58.3 (s, OCH3),
25.1 (s, OCH2CH2), 16.6 (s, C6Me6). 1H NMR (CD2Cl2): δ -11.2
2
(d, J PH ) 35.6 Hz, 1H, RuH).
ter t-Bu tyl Isocya n id e[(1,3-d ioxola n -2-ylm eth yl)d ip h e-
n ylp h osp h in e-P ](η6-h exa m eth ylben zen e)h yd r id or u th e-
n iu m (II) Tetr a flu or obor a te (8c). 8c was prepared and
worked up analogously to 8a by using a solution of 190
mg (0.30 mmol) of 5c in 10 mL of CH2Cl2 and 25.3 mg (0.30
1
41.0, 37.6 (s, C2H4), 29.1 (d, J PC ) 37.1 Hz, PCH2), 15.9 (s,
2
C6Me6). 1H NMR (CD2Cl2): δ -10.9 (d, J PH ) 36.9 Hz, 1H,
RuH).

3010 Organometallics, Vol. 17, No. 14, 1998
Lindner et al.
Ta ble 1. Cr ysta l Da ta a n d Refin em en t Deta ils for Com p ou n d s 5a , 7c, 8c, a n d 9a
compound
5a
7c
8c
9a
formula
fw
C
595.4
27H36BF4OPRu
C30H39BF4NO2PRu
664.5
C33H45BF4NO2PRu
706.6
C28H36BF4OPRuS2
671.5
color
yellow cubes
0.25 × 0.20 × 0.15
monoclinic
P21/c
11.714(3)
13.097(3)
18.019(3)
90
108.03(1)
90
2628.7(10)
4
pale yellow cubes
0.35 × 0.20 × 0.20
triclinic
P1h
9.883(3)
12.773(3)
12.924(3)
76.65(2)
69.51(2)
87.70(2)
1485.5(7)
2
yellow cubes
0.25 × 0.20 × 0.20
triclinic
P1h
9.768(2)
12.018(2)
14.577(2)
105.28(3)
90.66(3)
90.50(3)
1650.5(6)
2
red cubes
0.40 × 0.30 × 0.30
monoclinic
P21
8.632(2)
15.857(4)
10.622(3)
90
96.38(2)
90
1444.9(7)
2
cryst dimens
cryst syst
space group
a, Å
b, Å
c, Å
R, deg
â, deg
γ, deg
V, Å3
Z
d
calcd, g cm-3
1.504
1.486
1.422
1.543
T, °C
F(000), e
-100
1224
-100
684
-100
732
-100
688
µ(Mo KR), mm-1
2θ limits, deg
no. of reflns measd
no. of unique data with I g 2σ(I)
no. of variables
S
0.704
4-50
10 078
3266
321
1.67
0.042
0.105
0.635
4-50
10 386
5000
378
1.67
0.032
0.576
4-50
11 490
5218
389
1.59
0.050
0.79
4-50
10 186
4984
343
0.94
0.020
0.055
a
R1
b
wR2
0.081
0.130
R1 ) ∑||F0| - |Fc||/∑|F0|. wR2 ) [∑[w(F0 - Fc2)2]/∑[w(Fo2)2]]0.5
.
a
b
2
[(1,3-Dioxa n -2-ylm e t h yl)d ip h e n ylp h osp h in e -P ](η2-
et h en e)(η6-h exa m et h ylb en zen e)h yd r id or u t h en iu m (II)
Tetr a flu or obor a te (10b). 10b was prepared and worked up
analogously by reacting a solution of 5b (150 mg, 0.24 mmol)
in 10 mL of CH2Cl2 with ethene (1 bar) for 1 h: yield 156 mg
(100%); mp 178 °C (dec); MS (FD, 60 °C) m/e 579 [M+ - BF4].
Anal. Calcd (Found) for C31H42BF4O2PRu: C, 55.95 (55.73);
H, 6.36 (6.12); F, 11.42 (11.79); Ru, 15.87 (16.08). IR (KBr,
cm-1): ν(RuH) 2032 (w). 31P{1H} NMR (CD2Cl2): δ 52.3 (s).
13C{1H} NMR (CD2Cl2): δ 133.0-126.2 (m, Ph), 109.7 (d, 2J PC
concentrated solutions of 5a , 7c, 8c, and 9a in CH2Cl2. The
crystals were mounted on a glass fiber and transferred to a
P4 Siemens diffractometer, using graphite-monochromated Mo
KR radiation. Rotation photographs were taken, and a photo
search was performed to find a suitable reduced cell. The
lattice constants were determined with 25 precisely centered
high-angle reflections and refined by least-squares methods.
The final cell parameters for 5a , 7c, 8c, and 9a are sum-
marized in Table 1. Intensities were collected with the ω-scan
technique with the scan speed varying from 6 to 60 deg/min
in ω. Scan ranges for 5a , 7c, 8c, and 9a were 1.0, 1.2, 1.2,
and 1.0, respectively. For compounds 8c and 9a , an absorption
correction was applied (Ψ-scan, maximum and minimum
transmission 8c, 0.547, 0.480; 9a , 0.563, 0.520). All structures
were solved by Patterson methods14 and refined by least
squares with anisotropic thermal parameters for all non-
hydrogen atoms (based on F2). The hydride atoms of com-
pounds 5a and 7c were located from a final Fourier map and
refined with isotropic thermal parameters, while all other
hydrogen atoms were included in calculated positions (riding
model). Maximum and minimum peaks in the final difference
syntheses were 1.124 and -0.625 (5a ), 1.492 and -0.503 (7c),
1.343 and -0.723 (8c), and 0.328 and -0.340 e Å3 (9a ).
2
) 3.1 Hz, C6Me6), 99.4 (s, CH), 67.1 (d, J PC ) 6.3 Hz, OCH2-
1
CH2), 40.8, 37.7 (s, br, C2H4), 36.3 (d, J PC ) 25.1 Hz, PCH2),
25.0 (s, OCH2CH2), 16.0 (s, C6Me6).1H NMR (CD2Cl2): δ -10.8
2
(d, J PH ) 36.5 Hz, 1H, RuH).
[(1,3-Dioxola n -2-ylm et h yl)d ip h en ylp h osp h in e-P ](η2-
et h en e)(η6-h exa m et h ylb en zen e)h yd r id or u t h en iu m (II)
Tetr a flu or obor a te (10c). 10c was prepared and worked up
analogously by reacting a solution of 5c (140 mg, 0.22 mmol)
in 10 mL of CH2Cl2 with ethene (1 bar) for 16 h: yield 146 mg
(100%); mp 130 °C (dec); MS (FD, 60 °C) m/e 564 [M+ - BF4].
Anal. Calcd (Found) for C30H40BF4O2PRu: C, 55.31 (55.03);
H, 6.19 (5.87); F, 11.66 (11.31); Ru, 15.51 (15.83). IR (KBr,
cm-1): ν(RuH) 2029 (w, br). 31P{1H} NMR (CD2Cl2): δ 51.7
(s). 13C{1H} NMR (CD2Cl2): δ 132.9-128.0 (m, Ph), 109.9 (d,
2
2J PC ) 2.0 Hz, C6Me6), 101.7 (s, CH), 65.2 (d, J PC ) 4.0 Hz,
Resu lts a n d Discu ssion
OCH2), 41.5, 38.5 (s, br, C2H4), 34.6 (d, 1J PC ) 34.4 Hz, PCH2),
16.4 (s, C6Me6).1H NMR (CD2Cl2): δ -10.8 (d, 2J PH ) 34.8 Hz,
1H, RuH).
The dihydrido complexes 4a -c were obtained upon
replacing both chlorides by hydrides in the intermedi-
ates 3a -c with NaBH415 which result from the reaction
of [{(η6-C6Me6)RuCl2}2] (1) with the ligands 2a -c
(Scheme 1).16 The pale yellow, air-sensitive compounds
ROMP of Nor bor n en e w ith Com p lexes 5a -c a s Ca ta -
lyst P r ecu r scor s. In a typical experiment, a solution of
approximately 1 wt % (referring to the weight of norbornene)
of the corresponding complex 5a -c in 2 mL of CH2Cl2 was
added to a solution of norbornene in CH2Cl2 (10 mg of
monomer/1 mL of solvent), and the solution was stirred at
room temperature. Within 60 min the solution became
viscous. After the corresponding reaction time (Table 6) the
mixture was added to 500 mL of methanol and the resulting
mixture was vigorously stirred for 2 h. The colorless precipi-
tate was collected by filtration (G3), washed with methanol,
and dried in vacuo.
1
4a -c were characterized by their H, 31P{1H}, and 13C-
{1H} NMR and mass spectra (Experimental Section).
Moreover, the structure of 4b was determined by an
X-ray structural analysis.17
(14) Sheldrick, G. M. SHELXTL V5.03 program; University of
Go¨ttingen: Go¨ttingen, Germany, 1995.
(15) Bennett, M. A.; Latten, J . Aust. J . Chem. 1987, 40, 841.
(16) (a) Comprehensive Organometallic Chemistry II; Able, E. W.;
Stone, F. G. A.; Wilkinson, G., Eds.; Pergamon Press: Oxford, U.K.,
1995; Vol. 7, Chapter 9. (b) Le Bozec, H.; Touchard, D.; Dixneuf, P. H.
Adv. Organomet. Chem. 1989, 29, 163.
Cr ysta llogr a p h ic An a lyses. Single crystals of 5a , 7c, 8c,
and 9a were obtained by slow diffusion of n-hexane into

(Ether-phosphine)ruthenium(II) Complexes
Organometallics, Vol. 17, No. 14, 1998 3011
Syn th esis of th e η2(O,P )-Ch ela ted Hyd r id or u -
th en iu m (II) Com plexes [(η6-C6Me6)Ru H(P kO)][BF4]
(5a -c). Intramolecular coordination of the ether oxy-
gen donors succeeded by treating 4a -c with Ph3CBF4
in THF, leading to the bifunctionalized, yellow com-
plexes [(η6-C6Me6)RuH(PkO)][BF4] (5a -c), which are
easily soluble in CH2Cl2 but insoluble in nonpolar
solvents (Scheme 1).
Because of the ring contribution ∆R,18 the 31P reso-
nance (δ 67.5) of 5a is shifted to lower field compared
to the corresponding signal of 4a . The η2-(O,P)-
coordination mode of the phosphines in complexes 5b,c
is responsible for a center of chirality at the carbon atom
of the CH unit of the ether moiety. Since ruthenium
represents an additional center of chirality, complexes
5b ,c may exist in diastereomeric forms. Whereas in
similar examples only one diastereomeric form was
observed,19,20 the 31P{1H} NMR spectra of 5b,c in CD2-
Cl2 show two singlets at 65.8 and 49.9 ppm for 5b and
at 60.2 and 55.7 ppm for 5c in an approximately 1:1
and 3:1 ratio, which is consistent with the existence of
two diastereomers. In contrast to the remarkable low-
field shift in case of 5a , the ring contribution ∆R in 5b,c
is obviously compensated by steric contributions to the
chemical shift.20,21
F igu r e 1. ORTEP plot of 5a .
Ta ble 2. Selected In ter a tom ic Dista n ces (Å) a n d
An gles (d eg) for 5a
Bond Lengths
Ru(1)-O(1)
Ru(1)-P(1)
O(1)-C(27)
2.188(3)
2.2656(12)
1.450(6)
P(1)-C(25)
C(25)-C(26)
C(26)-O(1)
1.847(5)
1.509(8)
1.448(6)
Compared to 4a -c in the 13C{1H} NMR spectra of
5a -c, the signals (doubled sets in the case 5b,c because
of diastereomers!) of the carbon atoms adjacent to the
ether oxygen function are shifted to lower field,22 which
is a further hint for the η2-(O,P)-coordination mode. In
the high-field region (ca. -8 ppm) of the 1H NMR
spectra of 5a and 5c, one doublet (2J PH) and two
doublets (diasteromers!), respectively, are assigned to
Bond Angles
82.77(10) O(1)-C(26)-C(25) 111.6(4)
C(25)-P(1)-Ru(1) 102.9(2)
C(26)-C(25)-P(1) 108.9(3)
O(1)-Ru(1)-P(1)
C(26)-O(1)-Ru(1) 115.3(3)
C(26)-O(1)-C(27) 112.0(4)
is formed by the atoms P(1), Ru(1), and O(1). Compared
to the mesitylene and half-sandwich complexes [(η6-
C6H3Me3)RuCl(PkO)][BPh4]23 and [(η5-C5Me5)Ru(PkO)L]-
[BPh4] (L ) CO, 2.231 (3) Å; P∼O, 2.262 (6) Å),4b,20
respectively, the distance between ruthenium and oxy-
gen (Ru(1)-O(1) ) 2.188 (3) Å) is shorter.
1
the hydrides. However, even in the 400 MHz H NMR
spectrum of 5b only two broad resonances occur, con-
sistent with two superimposed doublets.
Cr ysta l Str u ctu r e of 5a . For a full characterization
of the chelates 5a -c, an X-ray structural analysis has
been performed with the example of complex 5a . The
ORTEP drawing of the cation of 5a is depicted in Figure
1. A listing of selected bond distances and angles is
compiled in Table 2. 5a adopts a three-legged piano-
stool configuration with an O(1)-Ru(1)-P(1) bond angle
of 82.77(10)°. The Ru(1)-P(1) bond length (2.266(1) Å)
corresponds well with the Ru-P distance of the η2-(O,P)-
coordinated ether-phosphine in [(η5-C5Me5)Ru(P∼O)-
(PkO)][BPh4], 2.258(3) Å.20 However, in contrast to the
related complex [(η6-C6H3Me3)RuCl(PkO)][BPh4] (O,P )
Ph2PCH2CH2OCH3)23 in which the five-membered che-
late ring prefers an envelope conformation, 5a reveals
a twisted chelate ring. The atoms C(25) and C(26) are
located -0.25 Å below and 0.38 Å above the plane that
Utiliza tion of On ly On e F u n ction a lity: Clea va ge
of th e Ru -O Bon d in 5a -c by Rea ction w ith CO,
CH3CN, a n d t-Bu NC. If the complexes [(η6-C6Me6)-
RuH(PkO)][BF4] (5a -c) are reacted with carbon mon-
oxide, acetonitrile, and tert-butyl isocyanide, a facile
Ru-O bond dissociation takes place, resulting in the
formation of the yellow adducts [(η6-C6Me6)RuH(P∼O)L]-
[BF4] (L ) CO (6a -c), CH3CN (7a -c), t-BuNC (8a -c),
Scheme 2).
Compared to 5a -c, in the 31P{1H} and 13C{1H} NMR
spectra of 5-8 the 31P signals and 13C resonances of the
carbon atoms in the R-position of the ether oxygen
function are shifted to higher field, confirming the η1-
(P)-coordination of the O,P ligands. The 31P signals split
into doublets if the non-hydride protons are selectively
decoupled, corroborating the presence of one hydride.
The IR spectra of 6-8 reveal typical absorptions for the
CtO and CtN stretching vibrations (Experimental
Section).24,25
Cr ysta l Str u ctu r es of 7c a n d 8c. Complexes 7c
and 8c were characterized by crystal structure deter-
minations as well (Figures 2 and 3). Selected bond
distances and angles are summarized in Tables 3 and
4. The overall geometry is similar to that of other three-
(17) Pautz, S. Ph.D. Thesis, University of Tu¨bingen, 1997. Triclinic,
space group P1h, unit cell dimensions a ) 9.095(2) Å, b ) 17.293(5) Å,
c ) 17.613(4) Å, R ) 98.02(2)°, â ) 101.77(2)°, γ ) 98.67(2)°; Z ) 4, V
) 2638.9(11) Å3, dcalc ) 1.388 g cm-3
.
(18) Garrou, P. E. Chem. Rev. 1981, 81, 229.
(19) Werner, H.; Daniel, T.; Nu¨rnberg, O.; Knaup, W.; Meyer, U. J .
Organomet. Chem. 1993, 445, 229.
(20) Lindner, E.; Haustein, M.; Mayer, H. A.; Schneller, T.; Fawzi,
R.; Steimann, M. Inorg. Chim. Acta 1994, 231, 201.
(21) Lindner, E.; Fawzi, R.; Mayer, H. A.; Eichele, K.; Hiller, W.
Organometallics 1992, 11, 1033.
(22) The assignment of the 13C NMR resonances was supported by
13C DEPT 135 NMR spectroscopy: Gu¨nther, H. NMR-Spektroskopie;
Thieme Verlag: Stuttgart, 1992.
(24) (a) Werner, H.; Werner, R. J . Organomet. Chem. 1979, 174, C67.
(b) Werner, R.; Werner, H. Chem. Ber. 1982, 115, 3781.
(25) Colthup, N. B.; Daly, L. H.; Wiberley, S. E. Introduction to
Infrared and Raman Spectroscopy; Academic Press: San Diego, CA,
1990.
(23) Lindner, E.; Pautz, S.; Fawzi, R.; Steimann, M. J . Organomet.
Chem. 1998, 555, 247.

3012 Organometallics, Vol. 17, No. 14, 1998
Lindner et al.
Sch em e 2
F igu r e 3. ORTEP plot of 8c.
NCCH3 and Ru-CN-t-Bu arrangements in 7c and 8c
deviate only slightly from a stretched geometry. The
bond lengths N(1)-C(13) (1.145(4) Å), C(13)-C(14)
(1.461(4) Å) and Ru(1)-C(13) (1.925(4) Å), C(13)-N(1)
(1.160(6) Å) are similar to those established in the
above-mentioned ruthenium complexes27,28 and in [(η5-
C5H5)Ru(PPh3)(CN-t-Bu)(ICH3)][PF6], respectively.29
F igu r e 2. ORTEP plot of 7c.
legged piano-stool analogues.26 The Ru(1)-N(1) dis-
tance in 7c (2.032(2) Å) is slightly shorter than that in
[(η6-C6H6)Ru(CH3CN)2Cl][BF4] (2.062(5) Å)27 and [(η6-
C6H6)Ru(CH3CN)3][PF6]2 (2.055(4) Å).28 The Ru-
(27) McCormick, F. B.; Cox, D. D.; Gleason, W. B. Organometallics
1993, 12, 610.
(26) Elschenbroich, C.; Salzer, A. Organometallchemie; B. G. Teub-
ner: Stuttgart; Germany, 1990.
(28) Luginbu¨hl, W.; Zbinden, P.; Pittet, P. A.; Armbruster, T.; Bu¨rgi,
H.-B.; Merbach, A. E.; Ludi, A. Inorg. Chem. 1991, 30, 2350.

(Ether-phosphine)ruthenium(II) Complexes
Organometallics, Vol. 17, No. 14, 1998 3013
Ta ble 3. Selected In ter a tom ic Dista n ces (Å) a n d
An gles (d eg) for 7c
Bond Lengths
Ru(1)-N(1)
Ru(1)-P(1)
2.032(2)
2.2895(9)
N(1)-C(13)
C(13)-C(14)
1.145(4)
1.461(4)
Bond Angles
86.45(6) N(1)-C(13)-C(14) 178.3(3)
N(1)-Ru(1)-P(1)
C(13)-N(1)-Ru(1) 172.4(2)
Ta ble 4. Selected In ter a tom ic Dista n ces (Å) a n d
An gles (d eg) for 8c
Bond Lengths
Ru(1)-C(13)
Ru(1)-P(1)
1.925(4)
2.2810(11)
N(1)-C(13)
N(1)-C(14)
1.160(6)
1.448(6)
Bond Angles
86.60(11) N(1)-C(13)-Ru(1) 177.5(3)
C(13)-Ru(1)-P(1)
C(13)-N(1)-C(14) 177.6(5)
Utiliza tion of Tw o F u n ction a lities: Rea ction s
w ith Ca r bon Disu lfid e a n d Olefin s. Five minutes
after an excess of CS2 was reacted with 5a -c in CH2-
Cl2 at ambient temperature, the 31P signals of the
chelates disappeared and two new single peaks ap-
peared between 32 and 36 ppm. The low-field signal is
indicative of an intermediary π-coordinated carbon
disulfide being formed by rupture of the weak Ru-O
bond.30 This was also evidenced by an IR absorption
at 1306 cm-1 (5a /CS2, CH2Cl2), pointing to the CdS
vibration.31 Finally, in the 1H NMR spectrum of a
mixture of 5a /CS2, a doublet at - 1.7 ppm is still
ascertained, belonging to the Ru-H proton of the
intermediate.
F igu r e 4. ORTEP plot of 9a .
Ta ble 5. Selected In ter a tom ic Dista n ces (Å) a n d
An gles (d eg) for 9a
Bond Lengths
Ru(1)-P(1)
Ru(1)-S(1)
Ru(1)-S(2)
2.3476(9)
2.3814(9)
2.3649(7)
S(1)-C(1)
S(2)-C(1)
1.675(3)
1.672(3)
Bond Angles
P(1)-Ru(1)-S(1)
P(1)-Ru(1)-S(2)
S(2)-Ru(1)-S(1)
91.31(2)
89.46(3)
71.41(2)
S(2)-C(1)-S(1)
C(1)-S(1)-Ru(1)
C(1)-S(2)-Ru(1)
111.71(14)
88.06(9)
88.68(10)
Gradually, the above-mentioned low-field 31P reso-
nance in the spectra of 5a -c/CS2 disappears, because
in a following step CS2 is inserted into the Ru-H bond
of the intermediates to give the red, air-stable products
9a -c (Scheme 2). The intensity of the high-field 31P
signal attributed to the HCS2Ru(P∼O) moiety increases
and remains the only resonance after completion of the
reaction. The IR absorption at 1306 cm-1 is replaced
by a band at 1288 cm-1, which is characteristic for νas
(CS2) of 9a .
Cr ysta l Str u ctu r e of 9a . To confirm the insertion
of carbon disulfide into the Ru-H bond, an X-ray
structural analysis has been performed with the ex-
ample of 9a (Figure 6). Selected bond distances and
angles are summarized in Table 5. Complex 9a is
octahedrally coordinated about the ruthenium with the
C6Me6 ligand occupying three coordination sites. The
distorted octahedral geometry is due to a small S(1)-
Ru(1)-S(2) angle of 71.41(2)°, similar to those in the
corresponding ruthenium and osmium dithioformato
complexes.30,32 Both almost equal Ru-S bonds are
comparable with reported values.32
ature, the 13C{1H} NMR spectra of 10b,c display two
broad resonances at 37 and 42 ppm, corresponding to
the ethene carbon atoms. In the case of 10a , these
signals appear only at -30 °C. Obviously, the rotation
of the olefin in the complexes with the sterically more
demanding ether-phosphines 2b,c is slow on the NMR
time scale at room temperature. The same dynamic
behavior in 10a is already observed at -30 °C, whereas
at room temperature the ethylene signals coalesce into
the baseline.
At about -11 ppm a doublet is observed in the 1H
NMR spectra of 10a -c (2J PH ≈ 35 Hz) which is ascribed
to the hydride ligand.33 Unlike in [(η6-C6H6)RuH(η2-
C2H4)(PMe3)][PF6],34 the Ru-H function in 10a -c is not
involved in a π/σ rearrangement. The results of an
X-ray structural analysis of 10a are in good agreement
with those of a similar complex.35
Because of the remarkable tolerance of ruthenium
complexes toward a variety of functionalized olefins,
ruthenium-based systems play an important role in the
ring-opening metathesis reaction.36,37 It was reported
that the presence of Ru-H bonds in a complex is
Stirring a solution of 5a -c in dichloromethane under
an atmosphere of ethene affords the pale beige adducts
[(η6-C6Me6)RuH(η2-C2H4)(P∼O)][BF4] (10a -c, Scheme
2). In agreement with an η1-(P)-coordination of the O,P
ligands, the 31P{1H} NMR spectra of 10a -c each exhibit
a singlet between 52 and 55 ppm. At ambient temper-
(33) Kletzin, H.; Werner, H.; Serhadli, O.; Ziegler, M. L. Angew.
Chem., Int. Ed. Engl. 1983, 22, 46.
(34) (a) Werner, H.; Werner, R. J . Organomet. Chem. 1979, 174, C
63. (b) Werner, R.; Werner, H. Chem. Ber. 1983, 116, 2074.
(35) Pautz, S. Ph.D. Thesis, University of Tu¨bingen, 1997. Mono-
clinic, space group Cc, unit cell dimensions a ) 18.124(2) Å, b ) 11.059-
(2) Å, c ) 16.052(3) Å, â ) 118.071(12)°; Z ) 4, V ) 2838.8(8) Å3, dcalc
(29) Conroy-Lewis, F. M.; Redhouse, A. D.; Simpson, S. J . J .
Organomet. Chem. 1989, 366, 357.
(30) Werner, H.; Tena, M. A.; Mahr, N.; Peters, K.; von Schnering,
H. G. Chem. Ber. 1995, 128, 41.
) 1.459 g cm-3
.
(36) Ivin, K. J .; Mol, J . C. Olefin Metathesis and Metathesis
Polymerization; Academic Press: London, 1997.
(31) Pandey, K. K. Coord. Chem. Rev. 1995, 140, 37.
(32) Lindner, E.; Lin, Y. C.; Gepra¨gs, M.; Yih, K. H.; Fawzi, R.;
Steimann, M. J . Organomet. Chem. 1996, 512, 101.
(37) (a) Novak, B. M.; Grubbs, R. H. J . Am. Chem. Soc. 1988, 110,
960. (b) Novak, B. M.; Grubbs, R. H. J . Am. Chem. Soc. 1988, 110,
7542. (c) Feast, W. J .; Harrison, D. B. J . Mol. Catal. 1991, 65, 63.

3014 Organometallics, Vol. 17, No. 14, 1998
Lindner et al.
Sch em e 3
which are provided with each one having a functional
Ru-O and Ru-H bond, and their behavior toward small
molecules. With carbon monoxide, acetonitrile, and tert-
butyl isocyanide, only the Ru-O contact is affected. In
the reaction of 5a -c with carbon disulfide, both func-
tionalities participate. In the beginning, a rupture of
the Ru-O linkage takes place with π-coordination of
CS2, subsequently carbon disulfide is inserted into the
Ru-H bond. The second step is favored by an increas-
ing steric demand of the employed ether-phosphine.
Since the basic character of the selected phosphines is
too low,34 no π/σ rearrangement happens when 5a -c
are treated with ethene.
Ta ble 6. P olym er iza tion of Nor bor n en e w ith
Com p ou n d s 5a -c
time mg of norbornene/ yield
transc
(%)
complex
(h)
mL of CH2Cl2
(%)a
activityb
5a
1
10
30
10
30
10
30
10
30
10
30
10
10
14.5
36.5
28.1
45.7
58.4
56.3
78.6
60.2
80.7
74.2
35.2
53.5
82.0
224.7
82.4
134.3
73.4
73.4
52.3
42.9
28.3
25.1
10.0
19.6
78.1
82.1
83.2
82.9
85.2
81.7
83.5
80.9
83.5
78.1
82.6
83.0
5a
5a
5a
5a
2
4
A remarkable dependence of the qualitatively esti-
mated reaction rates on the kind of ether-phosphines
was ascertained in the systems 5a -c/CO and ethene.
In both instances the time required for quantitative
formation of the corresponding adducts 6a -c and
10a -c increases in the order 2b < 2a < 2c (Experi-
mental Section). For 2b, this finding is consistent with
the lowest energy of the Ru-O bond. However, other
influences, e.g., steric factors, are also likely to account
for the different kinetics of the above-mentioned reac-
tions because the ∆Hq values for 2a and 2c are rather
similar.
8
16
5b
5c
16
16
a
b
Methanol-insoluble fraction. Activity ) [g of polymer/(g of
Ru)(h)]. c Cis and trans double bonds of the polymer were quanti-
fied by inverse-gated decoupled 13C NMR spectrospcopy.
advantageous for the generation of active metathesis
catalysts.36 This observation in connection with the
application of (arene)ruthenium complexes in ring-
opening metathesis reactions38 were motivations to
prove the potential of the chelates 5a -c in the ROMP
of norbornene. If a CH2Cl2 solution of norbornene is
treated with catalytic amounts of 5a -c at room tem-
perature, a polymerization is induced and the reaction
mixture becomes viscous within 1 h. Finally, (poly)-
norbornene was isolated by precipitation with methanol
as a white, tacky polymer (Scheme 3). The results of
the ring-opening metathesis polymerization of nor-
bornene with 5a -c are summarized in Table 6.
Complexes 5a -c turned out to be suitable catalyst
precursors for the ring-opening metathesis polymeriza-
tion of norbornene. Their considerable activities in-
crease with a decreasing steric demand of the phosphine
employed in the sequence 2b < 2c < 2a , pointing to
the fact that the Ru-O bond cleavage which happens
in the initiation phase of the reaction is only of minor
significance for the overall catalytic process.
Ack n ow led gm en t. Support of this work by the
Fonds der Chemischen Industrie, Frankfurt/Main, Ger-
many, is gratefully acknowledged. We are also indebted
to Priv.-Doz. Dr. H. A. Mayer, Institut fu¨r Anorganische
Chemie II, University of Tu¨bingen, for helpful discus-
sions.
Con clu sion
The investigations presented describe the synthesis
of the complexes [(η6-C6Me6)RuH(PkO)][BF4] (5a -c),
Su p p or tin g In for m a tion Ava ila ble: Tables of atomic
coordinates, bond lengths and angles, and anisotropic dis-
placement parameters for 5a , 7a , 8c, and 9a (26 pages).
Ordering information is given on any current masthead page.
(38) (a) Stumpf, A. W.; Saive, E.; Demonceau, A.; Noels, A. F. J .
Chem. Soc., Chem. Commun. 1995, 1127. (b) Demonceau, A.; Stumpf,
A. W.; Saive, E.; Noels, A. F. Macromolecules 1997, 30, 3127. (c) Hafner,
A.; Mu¨hlebach, A.; van der Schaaf, P. A. Angew. Chem., Int. Ed. Engl.
1997, 36, 2121.
OM980001O