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4955
isotopes): 804, [M]; 748, [M ꢁ 2CO]; 720, [M ꢁ 3CO];
3.4. Preparation of mer-[ReH(CO)3L1] (3a)
725, [M ꢁ Br]. IR(mCO): 2022, 1954, 1888 cmꢁ1
.
1H
NMR (400 MHz, CDCl3): d 1.15–2.55 (m, 44H, Cy), d
A solution of [ReH(CO)5] (0.1 mL, 0.7 mmol) in THF
(10 mL) was added to a solution of L1 in toluene (10 mL,
0.22 M), the mixture was stirred for 24 h, and the white so-
lid formed was filtered out. This product was a mixture of
mer and fac isomers. Washing with THF removed the more
soluble fac-isomer, leaving the mer-isomer, which was
washed with 2 mL of ethanol and recrystallized from 2:10
(v/v) CH2Cl2/EtOH by slow evaporation. Yield: 39%
(0.2 g). Anal. Calc. for C30H27O5P2Re: C, 50.72; H,
3.80%. Found: C, 50.35; H, 3.80%. MS (m/z, referred to
the most abundant isotopes): 716, [M]; 688, [M ꢁ CO].
3.84–4.46 (m, 4H, –OCH2CH2O–). 31P{1H} NMR
(161 MHz, CDCl3):
d
129.7 (s). 13C{1H} NMR
(100 MHz, CDCl3): d 23.8–28.9(m, C2–C6 of Cy), d
37.9–43.1 (m, C1 of Cy), d 64.6 (s, a, –OCH2), d 64.9
(s, a, –OCH2), d 188.1 (m, CO cis to Br), d 189.0 (t,
2JCP = 7 Hz, CO trans to Br).
3.3. Preparation of fac-[Re(O3SCF3)(CO)3L] (2) [L = L1
(2a), L2 (2b), L3 (2c)]
A mixture of the appropriate compound 1 (0.13 mmol)
and Ag(O3SCF3) (0.1 mmol) in CH2Cl2 (20 mL) was
heated under reflux for 1 h and filtered to remove AgBr.
The solvent was removed under vacuum, and the residue
was treated with ethanol (2 mL), affording a brown prod-
uct that was filtered out, washed with ethanol and dried un-
der vacuum.
IR(mCO): 2035, 1954, 1917 cmꢁ1 1H NMR (400 MHz,
.
CD2Cl2): d ꢁ6.09 (d, 1H, JPH = 36 Hz, ReH), d 2.02 (m,
2H, –CH2–), d 3.91 (m, 4H, –OCH2–), d 7.50–7.95 (m,
20H, Ph). 31P{1H} NMR (161 MHz, CD2Cl2): d 120.8 (d,
JPP = 23 Hz); 124.4 (d, JPP = 23 Hz). 13C{1H} NMR
3
(100 MHz, CDCl3): d 32.7 (t, JCP = 4 Hz, –CH2–), d
59.8 (s, –OCH2–), d 61.0 (s, –OCH2–), d 127.7–132.5 (m,
ortho-C, meta-C, para-C of Ph), d 141.8 (d, JCP = 55 Hz,
ipso-C of Ph), d 143.7 (d, JCP = 49 Hz, ipso-C of Ph), d
193.2 (t, JCP = 12 Hz, cis CO), d 196.9 (m, trans CO).
Compound 2a. Yield: 67% (0.02 g). Anal. Calc. for
C31H26F3O8P2ReS: C, 43.05; H, 3.03%. Found: C, 42.98;
H, 2.96%. MS (m/z, referred to the most abundant iso-
topes): 864, [M]. IR(mCO): 2042, 1960, 1940 cmꢁ1
.
1H
NMR (400 MHz, CDCl3):
d
1.72–2.16 (m, 2H,
3.5. Preparation of fac-[ReH(CO)3L2] (3b)
–CH2CH2–), d 3.66–3.86 (m, 4H, –OCH2–), d 7.19–7.70
(m, 20H, Ph). 31P{1H} NMR (161 MHz, CDCl3): d 112.7
(s). 13C{1H} NMR (100 MHz, CDCl3): d 30.2 (s, –CH2),
d 64.8 (s, –OCH2), d 118.8 (s, –CF3), d 128.2–134.9 (m,
A solution of [ReH(CO)5] (0.1 mL, 0.7 mmol) in THF
(10 mL) was added to a solution of [1,2-bis(diisopropyl-
phosphinoxy)ethane] (7.5 mL, 0.29 M) in toluene (Re:L
mole ratio 1:3), and the mixture was heated at 60 ꢁC for
6 h. After cooling to room temperature, the solvent was re-
moved under vacuum, and the residual oil was chromato-
graphed on a silica gel column (length 70 cm, diameter
4 cm) using a 10:1 mixture of light petroleum (40–60 ꢁC)
and diethyl ether as eluent. The first fraction eluted
(25 mL) was concentrated to dryness, leaving an oil that
was treated with ethanol (2 mL). Cooling the resulting
solution to –25 ꢁC afforded white crystals of complex 3b.
Yield: 24% (0.09 g). Anal. Calc. for C17H33O5P2Re: C,
36.10; H, 5.88%. Found: C, 36.40; H, 5.96%. MS (m/z, re-
ferred to the most abundant isotopes): 566, [M]; 538,
2
Ph), d 189.2 (t, JCP = 7 Hz, CO trans to OTf), d 189.5
(m, CO cis to OTf). 19F{1H} NMR (376 MHz, CDCl3): d
ꢁ76.9 (s).
Compound 2b. Yield: 50% (0.02 g). Anal. Calc. for
C18H32F3O8P2ReS: C, 30.25; H, 4.52%. Found: C, 30.22;
H, 4.56%. MS (m/z, referred to the most abundant iso-
topes): 714, [M]; 658, [M ꢁ 2CO]. IR(mCO): 2038, 1968,
1
1914 cmꢁ1. H NMR (400 MHz, CDCl3): d 1.16–1.51 (m,
24H, –CH3), d 2.49–2.59 (m, 4H, CH–), d 3.98–4.08 (m,
4H, –CH2CH2–). 31P{1H} NMR (161 MHz, CDCl3): d
145.0 (s). 13C{1H} NMR (100 MHz, CDCl3): d 16.2 (m,
–CH3), d 28.1 (m, CH–), d 62.1 (m, –OCH2CH2O–), d
2
118.2 (s, –CF3), d 188.9 (t, JCP = 8 Hz, CO trans to
[M ꢁ CO]. IR(mCO): 2077, 1964, 1914 cmꢁ1
.
1H NMR
OTf), d 187.2 (m, CO cis to OTf). 19F{1H} NMR
(376 MHz, CDCl3): d ꢁ77.1 (s).
(400 MHz, CD2Cl2): d ꢁ5.69 (t, 1H, JHP = 27 Hz, ReH),
d 1.04–1.20 (m, 24H, –CH3), d 2.16 (m, 2H, CH–), d
2.32 (m, 2H, CH–), d 4.03 (m, 2H, –OCH2–), d 4.23 (m,
2H, –OCH2–). 31P{1H} NMR (161 MHz, CD2Cl2): d
149.5 (s). 13C{1H} NMR (100 MHz, CDCl3): d 17.2,
17.4, 17.8 and 18.6 (all s, CH3), d 33.0 (t, JCP = 15 Hz,
CH–), d 33.4 (t, JCP = 14 Hz, CH–), d 67.0 (m, –OCH2-
CH2O–), d 195.6 (m, CO cis to H), d 196.2 (t, 2JCP = 14 Hz,
CO trans to H).
2
Compound 2c. Yield: 56% (0.01 g). Anal. Calc. for
C30H48F3O8P2ReS: C, 41.18; H, 5.53%. Found: C,
41.12; H, 5.64%. MS (m/z, referred to the most abundant
isotopes): 874, [M]; 846, [M ꢁ CO]; 818, [M ꢁ 2CO]; 790,
[M ꢁ 3CO]. IR(mCO): 2040, 1972, 1918 cmꢁ1
.
1H NMR
(400 MHz, CDCl3): d 1.16–2.32 (m, 44H, Cy), d 3.63–
4.04 (m, 4H, –OCH2CH2O–). 31P{1H} NMR
(161 MHz, CDCl3):
d
138.8 (s). 13C{1H} NMR
(100 MHz, CDCl3): d 26.1–27.4(m, C2–C6 of Cy), d
40.4–43.2 (m, C1 of Cy), d 65.9 (s, a, –OCH2–), d
118.5 (s, –CF3), d 190.2 (m, CO cis to OTf), d 192.1
3.6. Preparation of fac-[ReH(CO)3L3] (3c) and
[Re2H2(CO)8-l-L3] (3c0)
2
(t, JCP = 7 Hz, CO trans to OTf). 19F{1H} NMR
A solution of [ReH(CO)5] (0.1 mL, 0.7 mmol) in THF
(10 mL) was added to a solution of [1,2-bis(dicyclohexyl-
(376 MHz, CDCl3): d ꢁ76.8 (s).