2512 Organometallics, Vol. 29, No. 11, 2010
Drinkel et al.
over 10 min to a vigorously stirred blood red solution of [Rh((S,
microcrystals (0.75 g, 33%). Anal. Found: C, 64.87; H, 4.53; N,
S)-2)2]BF4 2/5Et2O (11, 289.0 mg, 0.2341 mmol) in CH2Cl2 (5 g)
4.86. Calcd for CuIN4O2P2C62H54 1/2H2O: C, 64.84; H, 4.83;
3
3
to afford an orange solution that was stirred for 2 h and then
evaporated to dryness. This left a microcrystalline, free-flowing
orange-red powder that was washed with Et2O (12 mL). Separa-
tion by filtration and drying in vacuo afforded 290 mg (92%) of
an orange powder. Anal. Found: C, 68.99; H, 3.95; N, 3.06.
Calcd for RhBF4C77H51P2O4N3: C, 69.33; H, 3.85; N, 3.15. 1H
NMR (400 MHz, CDCl3): δ 4.30-4.40 (m, 1H), 4.55-4.65 (m,
2H), 4.65-4.75 (m, 1H), 5.25-5.30 (m, 1H), 5.55-5.65 (m, 1H),
5.95-6.10 (m, 2H), 6.35-6.45 (m, 1H), 6.45-6.65 (m, 3H),
6.65-6.75 (m, 2H), 6.80-6.90 (m, 3H), 6.95-7.15 (m, 8H),
7.20-7.90 (m, 16H), 8.05-8.25 (m, 5H), 8.30-8.40 (m, 2H),
8.50-8.60 (m, 1H), 8.85-8.95 (m, 1H), 9.35-9.45 (m, 1H). 31P-
{1H} NMR (162 MHz, CD2Cl2): δ 115.7 (dd, JRhP = 299 Hz,
N, 4.88. 1H NMR (400 MHz, C6D6): δ 0.90-1.05 (m, 2H),
1.20-1.45 (m, 6H), 2.85-2.95 (m, 2H), 3.45-3.55 (m, 2H),
3.55-3.75 (br, 2H), 6.55-6.70 (m, 6H), 6.80-7.40 (m, 28H),
7.40-7.55 (m, 6H). 31P{1H} NMR (162 MHz): δ 116 (br, C6D6);
114 (br, CD2Cl2). Quantitative 13C NMR (101 MHz, CD2Cl2): δ
27.1 (s, 2C), 29.1 (s, 2C), 46.0 (s, 2C), 68.7 (s, 2C), 94.3 (s, 2C),
126.0-129.0 (m, 34C), 129.4 (s, 2C), 130.0 (s, 4C), 132.3 (s, 2C),
137.0 (s, 2C), 137.8 (s, 2C), 140.4 (s, 2C), 142.2 (s, 2C), 144.0 (s,
2C), 145.6 (s, 2C).
[CuI((R,R)-5)2] (17). Benzene (3 g) was added to CuI (93.5 mg,
0.491 mmol) and (R,R)-5 (376 mg, 0.982 mmol), and the
resulting mixture was stirred, forming a clear pale yellow solu-
tion within 5 min. The solution was stirred overnight, and then
the volatiles were evaporated, affording a white solid which was
slurried in pentane (8 mL) for 12 h and then separated by
filtration. HV drying afforded 378 mg (80%) of a fine white
solid. Anal. Found: C, 51.80; H, 4.50; N, 2.84. Calcd for
JPP = 59 Hz), 182.1 (dd, JRhP = 246 Hz, JPP =59Hz). 13CNMR
(101 MHz, CDCl3): δ 88.9 (m), 96.9, 118.7, 120.6, 121.2,
122.0-123.0 (m), 125.0-132.5 (m), 136.3, 137.7, 138.1 (m), 139.0
(m), 139.3, 140.5-141.0 (m), 147.0-148.5 (m), 150.7, 156.0.
0
0
0
[Rh((S,S)-2)2(imidazole)2]BF4 3/5Et2O (14). A solution of
CuIN2O8P2C42H44 H2O: C, 51.73; H, 4.75; N, 2.87. 1H NMR
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3
imidazole (35.4 mg, 0.520 mmol) in CH2Cl2 (5 g) was added
dropwise at ca. 270 K over 10 min to a vigorously stirred, blood
(400 MHz, C6D6): δ 1.21 (s, 6H), 1.33 (s, 6H), 3.50-3.65 (m,
2H), 3.75-3.85 (m, 2H), 3.90-4.10 (m, 6H), 6.60-6.70 (m, 4H),
6.85-7.05 (m, 8H), 7.05-7.20 (m, 4H), 7.60-7.70 (m, 4H).
31P{1H} NMR (162 MHz, C6D6): δ 116 (s, br). 13C NMR (101
MHz, C6D6): δ 26.8 (d, 28 Hz), 65.0 (d, 11 Hz), 78.9, 79.6, 110.9,
126.6 (d, 5 Hz), 128.8, 129.1, 129.3, 129.4, 131.0, 131.6, 136.3 (d,
7 Hz), 142.1, 142.6 (d, 11 Hz).
red solution of [Rh((S,S)-2)2]BF4 2/5Et2O (12; 301.5 mg, 0.2478
3
mmol) in CH2Cl2 (5 g) to afford a bright yellow solution that
was stirred for 2 h and then evaporated to dryness. This left a
microcrystalline, free-flowing lemon yellow solid that was
washed with Et2O (2 ꢀ 7 mL). Separation by filtration and
drying in vacuo afforded 325 mg (95%) of a fine yellow powder.
Anal. Found: C, 65.24; H, 4.28; N, 6.00. Calcd for RhBF4C74-
H52P2O4N6 3/5Et2O H2O: C, 65.39; H, 4.31; N, 5.99. 1H NMR
Cu((S)-2)2(BF4) (18). A solution of AgBF4 (156.2 mg, 0.8023
mmol) in THF (10 g) was added dropwise over 10 min to a
vigorously stirred clear, colorless solution of 15 (1011 mg,
0.7985 mmol) in THF (12 g) to afford a greenish white pre-
cipitate with a colorless supernatant. The mixture was stirred for
24 h, the precipitate separated by centrifugation (4000 rpm, 60
min), and the clear supernatant solution was evaporated to
dryness and the white solid dried in HV (915 mg, 98%). Anal.
Found: C, 67.28; H, 3.78; N, 2.15. Calcd for C68H44CuP2-
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3
(400 MHz, CD2Cl2): δ 5.18 (br, 2H), 5.43 (br, 2H), 5.60 (br, 2H),
6.14 (br, 1H), 6.16 (br, 1H), 6.25-6.40 (m, 4H), 6.55-6.70
(m, 4H), 6.70-6.80 (m, 2H), 6.95-7.15 (m, 7H), 7.15-7.30
(m, 6H), 7.30-7.40 (m, 2H), 7.40-7.50 (m, 2H), 7.60-7.85
(m, 13H), 7.90-7.95 (m, 2H), 11.63 (br, 2H). The spectrum
indicates the presence of ca. 0.6 equiv of Et2O. 31P{1H} NMR
(162 MHz, CDCl3): δ 147.8 (d, JRhP = 273 Hz). 13C NMR (101
MHz, CDCl3): δ 120.6, 121.5, 122.1, 124.8, 125.0, 125.2, 125.8,
126.0, 126.2, 126.5-131.5 (m), 131.7, 132.2, 132.9, 134.9, 135.9,
138.3 (m), 141.3, 142.2 (m), 147.7, 149.1. The spectrum indicates
the presence of Et2O.
1
N2O4BF4 2.5H2O: C, 67.48; H, 4.08; N, 2.31. H NMR (400
3
MHz, CD2Cl2): δ 5.10-5.25 (m br, 2H), 6.20-6.30 (m, 2H),
6.35-6.55 (m, 4H), 6.60-6.80 (m, 4H), 6.85-7.05 (m, 8H),
7.05-7.45 (m, 12H), 7.50-7.60 (m, 4H), 7.75-7.85 (m, 2H),
7.90-8.00 (m, 2H), 8.05-8.15 (m, 2H), 8.20-8.30 (m, 2H).
31P{1H} NMR (162 MHz, CD2Cl2): δ 114 (s, br). 13C NMR (101
MHz, CD2Cl2): δ 120.4, 120.7, 122.4, 122.8, 125.3, 125.6, 126.2,
126.4 (m, br), 126.5, 126.8, 127.0 (br), 128.2, 128.5, 128.6, 129.0,
129.2, 129.3, 129.6, 129.7, 130.8, 131.2, 131.4, 131.8, 132.3,
132.8, 135.0, 136.1, 139.7, 140.4 (m) 147.2, 147.6 (m). Large
single crystals grew from a filtered (cotton plug plus Celite)
warm solution of the compound (120 mg) in toluene (4.5 g).
[CuI((S)-2)2] (15). Benzene (16 g) was rapidly added to CuI
(616.2 mg, 3.235 mmol) and (S)-2 (3322 mg, 6.472 mmol), and
the resulting mixture was stirred for 24 h, affording a white
precipitate and a yellow supernatant solution. The solid was
separated by filtration (GF/B) and dried in vacuo to yield 3.76 g
(93%) of a white powder. Anal. Found: C, 68.50; H, 3.63; N,
2.25. Calcd for N2O4P2CuC68H44I 1/2C6H6: C, 68.52; H, 3.81;
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1
Cu(BF4)((R,R)-4)2 THF (19). A solution of AgBF4 (87.1 mg,
N, 2.25. H NMR (400 MHz, C6D6): δ 5.74 (br, 1H), 6.17 (m,
3
0.447 mmol) in THF (6 g) was added dropwise over 10 min to a
vigorously stirred clear, colorless solution of 16 (508.5 mg,
0.4462 mmol) in THF (6 g) to afford a greenish white precipitate
with a colorless supernatant. The mixture was stirred for 8 h.
The solid was separated by filtration, dried in vacuo, and then
extracted with CH2Cl2 (16 g) by filtration (GF/B glass fiber).
The clear mother liquor was evaporated to an off-white solid
that was slurried in THF (5 mL) for 30 min, separated by
filtration, and finally dried in HV to afford 382 mg (73%) of
a snow white powder. This material is usually 95% isomeri-
cally pure (the impurity is characterized by a pair of doublets
in the 31P{1H} NMR spectrum; see below). The impurity was
removed by successive washings in benzene. Anal. Found: C,
2H), 6.30 (br, 1H), 6.42 (m, 2H), 6.55-6.75 (m, 8H), 6.90-7.00
(m, 4H), 7.00-7.20 (m, 10H), 7.30-7.45 (m, 8H), 7.60 (m, 2H),
7.69 (m, 2H), 7.80 (m, 2H), 8.43 (br, 2H). The spectrum
indicated the presence of ca. 0.5 equiv of cocrystallized benzene.
31P{1H} NMR (162 MHz, C6D6): δ 120 (br). Single crystals
suitable for an X-ray diffraction analysis were obtained by
dissolving the complex (78 mg) in boiling benzene (1.2 g) and
slowly cooling the solution to room temperature.
[CuI((S,S)-4)2] (16). Benzene (20 mL) was rapidly added to a
mixture of CuI (382.8 mg, 2.010 mmol) and (S,S)-4 (1.908 g,
4.021 mmol) with vigorous stirring, and the resulting clear pale
yellow solution was stirred for 8 h. Evaporation of the volatiles
afforded an off-white solid which was pure enough for most
applications. The product was recrystallized by dissolving it in
hot toluene (20 mL), followed by filtration over glass fiber (GF/
B) and cooling to 250 K for 2 days. The resulting white crystals
were separated from the mother liquor by decanting and were
dried in vacuo (1.16 g, 51%). This batch afforded single crystals
suitable for an X-ray diffraction analysis. The mother liquor was
concentrated to ca. 10 mL, Et2O (15 mL) was added, and the
mixture kept at 250 K for 2 days to afford another crop of white
65.72; H, 5.03, N, 4.68. Calcd for CuBF4N4O2P2C62H54
C4H8O 1/2CH2Cl2: C, 65.79; H, 5.23; N, 4.62. 31P{1H} NMR
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(162 MHz, C6D6): δ 106 (s, br), isomeric impurity (5-8%): 116
1
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0
(d, JPP = 53 Hz), 121 (d, JPP = 53 Hz). H NMR (400 MHz,
C6D6): δ 1.10-1.25 (m, 2H), 1.50-1.60 (m, 2H), 1.60-1.80
(m, 6H), 1.85-1.95 (m, 2H), 2.85-3.00 (m, 4H), 3.00-3.10 (m,
2H), 3.35-3.50 (m, 4H), 6.45-6.50 (m, 2H), 6.65-6.75
(m, 2H), 6.85-6.95 (m, 2H), 6.95-7.05 (m, 2H), 7.05-7.45