A.M. McDonagh et al. / Journal of Organometallic Chemistry 610 (2000) 71–79
77
ether. The solvent was removed on a rotary evaporator
to give a purple powder identified as 2 (31 mg, 54%).
Anal. Calc. for C48H44ClNO2P4Ru: C 65.36, H 5.03, N
1.59. Found: C 64.41, H 5.39, N 1.78%. MS: 881 ([M]+,
100), 846 ([M−Cl]+, 15), 735 ([FeCl(diph)2]+, 20), 700
([Fe(diph)2]+, 5), 559 ([M−diph]+, 35), 413 ([Fe-
Cl(diph)]+, 50). UV–vis (umax, nm [m, 104 M−1 cm−1)]:
543 [1.7], 340 [1.1], 275 [2.3], 268 [2.4]. IR (cm−1): 2043
Anal. Calc. for C48H45ClP4Ru: C 65.34, H 5.14. Found:
C 65.69, H 5.00%. MS: 882 ([M]+, 85), 847 ([M−Cl]+,
14), 783 ([M−CꢀCPh]+, 14), 745 ([Ru(diph)2]+, 16),
423 ([Ru(diph)]+, 12). IR (KBr, cm−1): 2077 (m)
w(CꢀC). UV–vis (umax, nm [m, 104 M−1 cm−1)]: 292
1
[1.8]. H-NMR: l 1.62 (m, 12H, Me), 6.56 (d, JHH=7
Hz, 2H, H4), 6.84 (t, JHH=7 Hz, 1H, H6), 6.98 (t,
J
HH=7 Hz, 2H, H5), 7.23 to 7.55 (m, 28H, Ph).
1
(w) w(CꢀC). H-NMR: l 1.52 (t, JHH=4 Hz, 6H, Me),
31P-NMR: l 52.2 (t, JPP=26 Hz, 2P), 54.1 (t, JPP=26
Hz, 2P). [h]578(Hg)= −261 (c 0.91).
1.59 (t, JHH=4 Hz, 6H, Me), 6.23 (d, JHH=9 Hz, 2H,
H4), 7.23 to 7.53 (m, 28H, Ph), 7.78 (d, JHH=9 Hz, 2H,
H5). 31P-NMR: l 72.3 (t, JPP=43 Hz, 2P), 77.0 (t,
3.2.5. (−)589-trans-[Ru(4-CꢀCC6H4NO2)Cl{(R,R)-
diph}2] (5)
JPP=43 Hz, 2P). [h]436= −3200 (c 0.022).
A
mixture of
3
(50 mg, 0.061 mmol), 4-
3.2.3. (−)589-cis-[RuCl2{(R,R)-diph}2] (3)
HCꢀCC6H4NO2 (20 mg, 0. 14 mmol) and sodium hexa-
fluorophosphate (25 mg, 0.15 mmol) in toluene (5 ml)
was stirred at reflux for 2 h to afford a light brown
precipitate which was collected by filtration in air and
then dissolved in dichloromethane. Sodium methoxide
(1 ml, 0.2 M solution in methanol) was added with
stirring. The solvent was then removed on a rotary
A mixture of [RuCl2(DMSO)4] (375 mg, 0.77 mmol)
and (S,S)-diph (500 mg, 1.56 mmol) was stirred in
methanol (15 ml) for 30 min at reflux. The mixture was
allowed to cool to r.t. to afford a yellow precipitate
which was removed by filtration. The filtrate was re-
duced to a viscous oil on a rotary evaporator and water
(5 ml) added. A yellow precipitate formed and was
collected by filtration, dissolved in dichloromethane
and dried over anhydrous magnesium sulfate. This
mixture was filtered and the yellow solution reduced to
dryness on a rotary evaporator to give a yellow powder.
Both samples of yellow solid contained cis and trans
isomers and so they were combined to give 572 mg
(90%). The cis/trans isomers were cleanly separated by
fractional crystallization in dichloromethane (10 ml)
with the slow addition of pet. spirit (65 ml). Lemon
yellow crystals were formed on standing which were
identified as 3 (450 mg, 71%). MS: 816 ([M]+, 60), 781
([M−Cl]+, 100), 745 ([Ru(diph)2]+, 25), 423
evaporator
and
the
residue
extracted
into
dichloromethane (ꢀ10 ml). The mixture was filtered,
pet. spirit (about 5 ml) was added and the solution
taken to dryness to give a red powder identified as 5 (36
mg, 63%). Anal. Calc. for C48H44ClNO2P4Ru: C 62.17,
H 4.78, N 1.51. Found: C 61.97, H 4.89, N 1.37%. MS:
927 ([M]+, 100), 892 ([M−Cl]+, 20), 745 ([Ru(diph)2]+,
28), 423 ([Ru(diph)]+, 26). IR (cm−1): 2057 (m)
w(CꢀC). UV–vis (umax, nm [m, 104 M−1 cm−1]: 467
1
[2.1], 251 [4.0], 243 [sh, 4.8]. H-NMR: l 1.62 (d of t,
JHP=15 and 3 Hz, 12H, Me), 6.41 (d, JHH=9 Hz, 2H,
H4), 7.24 to 7.53 (in, 28H, Ph), 7.82 (d, JHH=9 Hz, 2H,
H5). 31P-NMR: l 50.4 (t, JPP=22 Hz, 2P), 54.4 (t,
1
([Ru(diph)]+, 27). H-NMR: l 1.63 (m, 6H, Me), 2.31
J
PP=22 Hz, 2P). 13C-NMR: l 12.4 (t, JCP=16 Hz,
(m, 6H, Me), 6.55 to 7.68 (28H, Ph). 31P-NMR: l 55.1
(t, JPP=22 Hz, 2P), 47.5 (t, JPP=22 Hz, 2P). [h]D=
−26 (c 0.42).
Me), 14.9 (t, JCP=16 Hz, Me), 111.6 (C2), 123.4 to
147.4 (Ph). [h]D= −504 (c 0.145).
The volume of the filtrate was reduced to ꢀ10 ml
and left standing to afford golden yellow microcrystals
identified as the trans isomer of 3 (100 mg, 16%).
1H-NMR: l 1.55 (br s, 12H, Me), 6.60 to 7.49 (28H,
Ph). 31P-NMR: l 52.0 (s).
3.2.6. (−)365-trans-[Ru(4-CꢀCC6H4-(E)-CHꢁCH-4-
C6H4NO2)Cl{(R,R)-diph}2] (6)
A mixture of 3 (50 mg, 0.061 mmol), 4-HCꢀCC6H4-
(E)-CHꢁCH-4-C6H4NO2 (31 mg, 0.12 mmol) and
sodium hexafluorophosphate (20 mg, 0.12 mmol) in
toluene (5 ml) was stirred at reflux for 2 h. On cooling,
the red solution was decanted and the remaining solid
was washed twice with toluene (5 ml). Addition of
dichloromethane (5 ml) and sodium methoxide (1 ml,
0.2 M solution in methanol) afforded a dark purple
solution which was taken to dryness in vacuo.
Dichloromethane (5 ml) was added, and the mixture
was filtered to remove the excess sodium hexa-
fluorophosphate. Addition of pet. spirit (10 ml) and
reduction of the solvent volume afforded a purple solid
which was collected and washed with pet. spirit to
3.2.4. (−)578-trans-[Ru(4-CꢀCPh)Cl{(R,R)-diph}2] (4)
A mixture of (−)589-cis-[RuCl2{(R,R)-diph}2] (220
mg, 0.27 mmol), phenylacetylene (160 ml, 1.5 mmol)
and sodium hexafluorophosphate (95 mg, 0.56 mmol)
was refluxed in toluene (20 ml) for 4 h. The resulting
pink precipitate was collected and dissolved in a mini-
mum of dichloromethane. Triethylamine was added
dropwise to the stirred solution until no pink color
remained. The yellow solution was then passed through
a short alumina column, eluting with dichloromethane.
The solvent was removed on a rotary evaporator to
afford a yellow solid identified as 4 (175 mg, 74%).
afford
6
(36 mg, 57%). Anal. Calc. for
C56H50ClNO2P4Ru: C 65.34, H 4.90, N 1.36. Found: C