1
(CH2Cl2): λmax ca. 360, 286 nm. H NMR (250 MHz, CDCl3):
nm. 1H MNR (250 MHz, CDCl3): δ 1.54 (d, JPH = 2.5 Hz, Cp*,
δ 1.35 (d, JPH = 2.5 Hz, Cp*, 15H), 3.30 (s, OMe, 3H), 6.3–7.6
15H), 3.16 (s, OMe, 3H), 3.76 (s, OMe, 3H), 6.7–7.8 (c, ArH,
(m, CH᎐ and ArH, 25H). 31P{1H} NMR (100 MHz, CDCl3):
13H), 7.96 (s, CH᎐, 1H). 31P{1H} NMR (100 MHz, CDCl3):
᎐
᎐
δ 36.9 (d, JRhP = 157.5 Hz), Ϫ143.8 (septet, JPF = 717 Hz, PF6Ϫ).
FAB mass (m/z of cationic part): 749 (749.7). Anal. Calc. for
C45H43O2P2F6Rh: C, 60.41; H, 4.84. Found C, 60.12; H, 4.83%.
Reddish brown complex 5b (26 mg, 30%) was prepared by the
reaction of 1a (54.5 mg, 0.095 mmol) with ethynyltoluene (0.2
mL) in the presence an excess of NaPF6 by a procedure similar
to that for 5a. IR (Nujol): 1591, 1568, 837 cmϪ1. UV (CH2Cl2):
λmax 344 nm. 1H NMR (250 MHz, CDCl3): δ 1.34 (d, JPH = 2.5
Hz, Cp*, 15H), 2.16 (s, Me, 3H), 2.43 (s, Me, 3H), 3.32 (s, OMe,
3H), 6.31 (s, –CH, 1H), 6.42 (s, –CH, 1H), 6.5–7.5 (m, ArH,
13H). 31P{1H} NMR (100 MHz, CDCl3): δ 36.8 (d, JRhP = 162
Hz), Ϫ143.8 (septet, JPF = 712 Hz, PF6Ϫ). FAB mass (m/z of
cationic part): 777 (Mϩ). Anal. Calc. for C47H47O2P2F6Rh: C,
61.18; H, 5.13. Found C, 60.94; H, 5.05%.
δ 3.12 (d, JRhP = 122 Hz), Ϫ143.9 Hz (septet. JPF = 712 Hz,
PF6Ϫ). FAB mass (m/z of cation part): 658 (675.4). Anal. Calc.
for C34H35O5P2F6Rh: C, 51.14; H, 4.31. Found C, 50.89; H,
4.40%. Yellow complex 8b (32%) was obtained from 1 with
᎐
HC᎐CCOOEt by a procedure similar to that for 8a. IR (Nujol):
᎐
2060 (C᎐O), 1695 (C᎐O), 837 (PF ) cmϪ1. UV (CH2Cl2): λmax
᎐
᎐
᎐
6
1
310 nm. H NMR (250 MHz, CDCl3): δ 1.28 (t, JHH = 7.5 Hz,
Me, 3H), 1.54 (d, JPH = 2.5 Hz, Cp*, 15H), 3.16 (s, OMe, 3H),
4.22 (q, JHH = 7.5 Hz, OCH2, 2H), 6.7–7.8 (m, ArH, 13H), 7.96
(s, CH᎐, 1H). 31P{1H} NMR (100 MHz, CDCl3): δ 3.15 (d,
᎐
JRhP = 125 Hz), Ϫ143.9 (septet, JPF = 711.0 Hz, PF6Ϫ). Anal.
Calc. for C35H37O5P2F6Rh: C, 51.80; H, 4.51. Found C, 51.48;
H, 4.57%.
᎐
Reaction of 1a with EtOOCC᎐CCOOEt
᎐
Reaction of 1a with 1-hexyne
Reddish orange crystals 9b (45 mg, 63%) were obtained from 1a
᎐
(55 mg, 0.095 mmol), EtOOCC᎐CCOOEt (0.1 mL) and an
᎐
A solution of 1a (50 mg, 0.086 mmol), 1-hexyne (0.1 mL) and
an excess of NaPF6 in CH2Cl2–acetone (15 mL/10 mL) was
stirred for 4 h. The solvent was evaporated and the residue was
extracted with CH2Cl2. After the solution was concentrated to 3
mL, diethyl ether was added to give orange crystals of 6 (24 mg,
32%). IR (Nujol): 1660, 1593, 837 cmϪ1. UV (CH2Cl2): λmax ca.
excess of NaPF6 by a procedure similar to that for 8a. IR
(Nujol): 1705 (C᎐O), 1589 (C᎐C) cmϪ1. UV (CH2Cl2): λmax ca.
᎐
᎐
400(sh), 328 nm. 1H NMR (250 MHz, CDCl3): δ 1.03 (t, JHH
7.0 Hz, Me, 3H), 1.27 (t, JHH = 7.0 Hz, Me, 3H), 1.26 (d, JPH
=
=
3.0 Hz, Cp*, 15H), 3.03 (s, OMe, 3H), 4.03 (m, CH2, 2H), 4.18
(m, CH2, 2H), 7.0–7.9 (m, Ph, 13H). 31P{1H} NMR (100 MHz,
CDCl3): δ 10.3 (d, JRhP = 137 Hz, 1P). FAB mass (m/z of cation
part): 737 ([M Ϫ CO]ϩ). Anal. Calc. for C37H41O6PClRhؒ
0.5CH2Cl2: C, 56.76; H, 5.34. Found C, 56.56; H, 5.22%. 9a
390 (sh), 283 nm. 1H NMR (250 MHz, CDCl3): δ 0.68 (t, JHH
=
6.8 Hz, CH3, 3H), 1.03 (t, JHH = 6.8 Hz, CH3, 3H), 1.39 (d, JHH
= 2.5 Hz, Cp*, 15H), 1.2–2.8 (m, (CH2)3, 12H), 3.38 (s, OMe,
3H), 5.56 (s, CH᎐, 1H), 5.69 (d, JRhH = 15.0 Hz, 1H), 6.6–7.8 (m,
᎐
ArH, 13H). 31P{1H} NMR (100 MHz, CDCl3): δ 44.8 (d, JRhP
=
(57%) was obtained from the reaction between 1a (30 mg, 0.052
157.5 Hz), Ϫ143.8 (septet, JPF = 712 Hz, PF6Ϫ). Anal. Calc. for
6
᎐
mmol), MeOOCC᎐CCOOMe (0.15 mL) and NaPF (24 mg,
᎐
0.14 mmol). IR (Nujol): 1705 (C᎐O), 1581 (C᎐C) cmϪ1. UV
᎐
᎐
C41H51O2P2F6Rh: C, 57.62; H, 6.01. Found C, 57.65; H, 5.85%.
(CH2Cl2): λmax 364, 266 nm. 1H NMR (250 MHz, CDCl3):
δ 1.25 (d, JPH = 3.0 Hz, Cp*, 15H), 3.04 (s, OMe, 3H), 3.53 (s,
OMe, 3H), 3.74 (s, OMe, 3H), 5.28 (s, CH2Cl2, 2H), 6.6–7.7 (m,
Reaction of 1a with 1-ethynyl-4-methoxycarbonylbenzene
᎐
A solution of 1a (139 mg, 0.24 mmol), HC᎐CC H COOMe-4
᎐
6
4
Ph, 13H). 31P{1H} NMR (100 MHz, CDCl3): δ 10.3 (d, JRhP
=
(107.4 mg, 0.67 mmol) and KPF6 (144 mg, 0.78 mmol) in
CH2Cl2 (5 mL) and acetone (20 mL) was stirred at room
temperature. After 25 h, the solvent was removed and the
residue was extracted with CH2Cl2 and a solution of CH2Cl2
was filtered with a glass filter (G4). The solvent was removed
under reduced pressure. The residue was washed with diethyl
ether and crystallized from CH2Cl2 and diethyl ether to give red
crystals of 5c (39 mg, 20%) and black brown crystals of 7 (57
137.5 Hz, 1P). FAB mass (m/z of cation part): 709 ([M Ϫ
CO]ϩ). Anal. Calc. for C35H37O6PClRhؒ0.5CH2Cl2: C, 55.70; H,
5.00. Found C, 55.20; H, 4.75%.
Reaction of 2a with 1-ethynyl-4-methoxycarbonylbenzene
᎐
A solution of 2a (45.7 mg, 0.071 mmol), HC᎐CC H COOMe-4
᎐
6
4
(37.6 mg, 0.235 mmol) and KPF6 (37.2 mg, 0.202 mmol) in
CH2Cl2 (5 mL) and acetone (20 mL) was stirred at room tem-
perature. After 8 h, the solvent was removed and the residue
was extracted with CH2Cl2 and a solution of CH2Cl2 was
filtered with a glass filter (G4). The solvent was removed under
reduced pressure. The residue was washed with diethyl ether
and crystallized from CH2Cl2 and diethyl ether to give yellow
mg, 24%). 5c: IR (Nujol): 1717(C᎐O), 839 (P–F) cmϪ1. UV
᎐
1
(CH2Cl2): λmax 387, 290 (sh), 239 nm. H NMR (250 MHz,
CD2Cl2): δ 1.36 (d, JPH = 2.5 Hz, Cp*, 15H), 3.35 (s, OMe, 3H),
3.88 (s, COOMe, 3H), 3.95 (s, COOMe, 3H), 6.49 (d, JHH
=
8.5Hz, ᎐CH, 1H), 8.19 (d, J = 8.5 Hz, ᎐CH, 1H), 6.5–7.7 (m,
᎐
᎐
HH
ArH, 21H). 31P{1H} NMR (100 MHz, CD2Cl2): δ 35.8 (d, JRhP
= 157.5 Hz), Ϫ144.8 (sept, JPF = 712 Hz). Anal. Calc. for
C49H47O6P2F6Rh: C, 58.22; H, 4.69. Found C, 58.14; H, 4.58%.
solid 10a (27.8 mg, 43%). IR (Nujol): 1715 (C᎐O), 1630 (C᎐O)
᎐
᎐
and 839 (P–F) cmϪ1. UV (CH2Cl2): λmax 405, 284 nm. 1H NMR
(250 MHz, CDCl3): δ 1.74 (d, JPH = 3.5 Hz, Cp*, 15H), 2.97 (s,
OMe, 3H), 3.06 (bs, OMe, 6H), 3.48 (bs, OMe, 3H), 3.84 (s,
7: IR (Nujol): 3285 (O–H), 1717 (C᎐O), 1605 (C᎐C), 839 (P–F)
᎐
᎐
1
cmϪ1. UV (CH2Cl2): λmax 404, 279 nm. H NMR (250 MHz,
CD2Cl2): δ 1.41 (d, JPH = 3.5 Hz, Cp*, 15H), 3.44 (s, OMe, 3H),
3.83 (s, COOMe, 3H), 6.74 (s, OH, 1H), 5.8–8.0 (m, ArH, 17H).
31P{1H} NMR (100 MHz, CD2Cl2): δ 29.7 (d, JRhP = 136.5 Hz).
Anal. Calc. for C39H40O4PCl2RhؒCH2Cl2: C, 55.71; H, 4.91.
Found C, 55.10; H, 4.92%.
COOMe, 3H), 5.59 (d, JRhH = 7.0 Hz, CH᎐, 1H) 5.6–7.2
᎐
(m, ArH, 15H). 31P{1H} NMR (100 MHz, CDCl3): δ 138.7 (d,
JRhP = 153 Hz), Ϫ143.7 (septet, JPF = 712 Hz, PF6Ϫ). FAB
mass (m/z of cation part): 765 ([M Ϫ 1]ϩ), 605 ([M Ϫ (HC᎐
᎐
C6H5COOMe)]ϩ). Anal. Calc. for C41H43O6P2F6Rh: C, 54.08;
H, 4.76. Found C, 53.82; H, 4.81%. Brown complex 10b (18%)
᎐
was obtained from the reaction of 2a and HC᎐CC H NO -4.
᎐
6
4
2
Reaction of 1a with methylpropiolate
IR (Nujol): 1628 (C᎐O), 835 (PF ) cmϪ1. H NMR (CD2Cl2):
1
᎐
6
A solution of 1a (110 mg, 0.189 mmol), HC᎐CCOOMe
δ 1.74 (d, JPH = 3.5 Hz, Cp*, 15H), 2.99 (s, MeO, 3H), 3.08 (br,
᎐
(0.1 mL) and an excess of NaPF6 in CH2Cl2 (5 mL) and acetone
(10 mL) was stirred at room temperature. After 5 h, the solvent
was removed under reduced pressure and the residue extracted
with CH2Cl2. The solvent was removed. The residue was
washed with diethyl ether and crystallized from CH2Cl2 and
diethyl ether to give yellow orange crystals of 8a (61 mg, 40%).
IR (Nujol): 2060, 1699, 1583, 839 cmϪ1. UV (CH2Cl2): λmax 293
MeO, 3H), 3.52 (br, MeO, 3H), 5.68 (d, JRhH = 7.5 Hz, CH᎐,
᎐
1H), 6.4–8.2 (m, Ph and ring Protons). 31P{1H} NMR (CDCl3):
δ 140.4 (d, JRhH = 153 Hz), Ϫ143.7 (septet, JPF = 712 Hz, PF6Ϫ).
FAB mass (m/z of cation part): 752 ([M Ϫ PF6]ϩ), 605 ([M Ϫ
PF Ϫ HC᎐CC H NO ]ϩ). Anal. Calc. for C H NO P F Rhؒ
᎐
6
6
4
2
39 40
6
2
6
CH2Cl2: C, 48.90; H, 4.31; N, 1.43. Found C, 49.19; H, 4.40; N,
1.52%.
J. Chem. Soc., Dalton Trans., 2002, 195–211
207