30 Organometallics, Vol. 27, No. 1, 2008
Partyka et al.
Chart 1. Designation of Compounds
mg, 1.25 mmol), and to this solution was added a 30 mL aqueous
solution of KBr (840 mg, 7.06 mmol). The biphasic mixture was
stirred 4 h, and the organic layer was collected. The aqueous layer
was washed once with dichloromethane (10 mL), and the organic
layers were combined, washed with water (2 × 10 mL), dried with
MgSO4, and filtered. The filtrate was stripped of solvent via rotary
evaporation, and pentane was added to the resultant white residue.
Repeated scraping of the residue with a spatula into the pentane
liberated a free-flowing solid, which was collected and dried. Yield:
1
749 mg (93%). H NMR (C6D6): δ 7.53 (td, J ) 7.6, 1.2 Hz, 1H,
2′-methylbiphenyl), 7.39 (d, J ) 7.6 Hz, 1H, 2′-methylbiphenyl),
7.22 (t, J ) 7.6 Hz, 1H, 2′-methylbiphenyl), 7.09–7.14 (m, 1H,
2′-methylbiphenyl), 6.98–7.04 (m, 3H, 2′-methylbiphenyl), 6.89–6.93
(m, 1H, 2′-methylbiphenyl), 1.98 (s, 3H, CH3), 0.69–1.98 (m, 22H,
C6H11). 31P{1H} NMR (C6D6): δ 40.6 ppm. 13C{1H} NMR (C6D6):
δ 149.56 (d, J ) 13.7 Hz), 141.17 (d, J ) 6.1 Hz), 135.59 (s),
132.93 (d, J ) 3.8 Hz), 132.64 (d, J ) 7.7 Hz), 132.20 (s), 130.87
(d, J ) 2.3 Hz), 130.00 (s), 129.43 (s), 127.29 (d, J ) 7.7 Hz),
126.21 (s), 125.96 (s), 125.71 (s), 37.52 (d, J ) 31.3 Hz), 35.42
(d, J ) 33.5 Hz) 30.78 (m), 29.69 (s), 29.00 (s), 26.97 (s), 26.83
(d, J ) 4.6 Hz), 26.65 (d, J ) 3.8 Hz), 26.51 (s), 26.37 (s), 25.79
(d, J ) 7.6 Hz), 21.12 (s) ppm. Anal. Calcd for C25H33AuBrP: C,
46.82; H, 5.19. Found: C, 46.82; H, 5.04.
[(PCy2(2′,4′,6′-triisopropylbiphenyl))AuCl] (5). In a glovebox,
PCy2(2′,4′,6′-triisopropylbiphenyl) (560 mg, 1.17 mmol) was dis-
solved in 20 mL of toluene, and to this solution was added
[(tht)AuCl] (364 mg, 1.14 mol). The [(tht)AuCl] remained sus-
pended initially, but the suspension shortly became a solution. After
stirring 20 h, the solvent was stripped via rotary evaporation, and
pentane was added to the remaining white residue. The residue was
scraped repeatedly into the pentane, and the white powder that
separated was collected and dried. Yield: 755 mg (91%). 1H NMR
(C6D6): δ 7.40 (s, 2H, 2′,4′,6′-triisopropylbiphenyl), 7.16–7.19 (m,
1H, 2′,4′,6′-triisopropylbiphenyl), 6.93–7.06 (m, 3H, 2′,4′,6′-
triisopropylbiphenyl), 3.17 (sep, J ) 6.8 Hz, 1H, CH(CH3)2), 2.43
(sep, J ) 6.8 Hz, 2H, CH(CH3)2), 1.59 (d, J ) 6.8 Hz, 6H,
CH(CH3)2), 1.51 (d, J ) 6.8 Hz, 6H, CH(CH3)2) 1.05 (d, J ) 6.4
Hz, 6H, CH(CH3)2), 0.78–1.81 (m, 22H, C6H11) ppm. 31P{1H}
NMR (C6D6): δ 36.0 ppm. 13C{1H} NMR (C6D6): δ 150.96 (s),
148.12 (d, J ) 14.5 Hz), 145.83 (s), 135.91 (d, J ) 6.1 Hz), 134.04
(d, J ) 8.4 Hz), 132.22 (d, J ) 3.1 Hz), 130.37 (d, J ) 2.3 Hz),
127.16 (d, J ) 6.9 Hz), 122.36 (s), 37.37 (d, J ) 33.6 Hz), 35.17
(s), 31.46 (d, J ) 2.3 Hz), 31.18 (s), 30.23 (s), 27.16 (d, J ) 13.8
Hz), 26.79 (d, J ) 13.0 Hz), 26.08 (s), 25.83 (s), 24.92 (s), 23.41
(s) ppm. Anal. Calcd for C33H49AuClP: C, 55.89; H, 6.96. Found:
C, 55.81; H, 6.80.
[(PCy2(2′,4′,6′-triisopropylbiphenyl))AuBr] (6). In 20 mL of
dichloromethane was dissolved [(PCy2(2′,4′,6′-triisopropylbiphe-
nyl))AuCl] (214 mg, 0.30 mmol), and to this solution was added a
15 mL aqueous solution of KBr (210 mg, 1.76 mmol). The biphasic
mixture was stirred 4 h, and the organic layer was collected. The
aqueous layer was washed twice with dichloromethane (5 mL), and
the organic layers were combined, washed with water (2 × 10 mL),
dried with MgSO4, and filtered. The filtrate was stripped of solvent
via rotary evaporation, and pentane was added to the resultant white
residue. Repeated scraping of the residue with a spatula into the
pentane liberated a free-flowing solid, which was collected and
dried. Yield: 173 mg (76%). 1H NMR (C6D6): δ 7.38 (s, 2H, 2′,4′,6′-
triisopropylbiphenyl), 7.12–7.17 (m, 1H, 2′,4′,6′-triisopropylbiphe-
nyl), 6.94–7.07 (m, 3H, 2′,4′,6′-triisopropylbiphenyl), 3.20 (sep, J
) 6.8 Hz, 1H, CH(CH3)2), 2.43 (sep, J ) 6.8 Hz, 2H, CH(CH3)2),
1.58 (d, J ) 6.8 Hz, 6H, CH(CH3)2), 1.51 (d, J ) 6.8 Hz, 6H,
CH(CH3)2) 1.05 (d, J ) 6.4 Hz, 6H, CH(CH3)2), 0.79–1.83 (m,
22H, C6H11) ppm. 31P{1H} NMR (C6D6): δ 37.9 ppm. 13C{1H}
NMR (C6D6): δ 150.82 (s), 148.00 (d, J ) 14.5 Hz), 145.79 (s),
136.02 (d, J ) 6.2 Hz), 134.03 (d, J ) 7.6 Hz), 132.37 (d, J ) 3.0
Hz), 130.44 (d, J ) 2.3 Hz), 127.28 (d, J ) 6.8 Hz), 122.45 (s),
PCy2(2′-methylbiphenyl),45,46 and PCy2(2′,4′,6′-triisopropylbiphe-
nyl)47 were purchased from Strem Chemicals, Inc.
[(PCy2(o-biphenyl))AuBr] (2). In 30 mL of dichloromethane
was dissolved [(PCy2(o-biphenyl))AuCl]48 (419 mg, 0.719 mmol),
and to this solution was added a 25 mL aqueous solution of KBr
(475 mg, 3.99 mmol). The biphasic mixture was stirred 4 h, and
the organic layer was collected. The aqueous layer was washed
once with dichloromethane (10 mL), and the organic layers were
combined, washed with water (2 × 10 mL), dried with MgSO4,
and filtered. The filtrate was stripped of solvent via rotary
evaporation, and pentane was added to the resultant white residue.
Repeated scraping of the residue with a spatula into the pentane
liberated a free-flowing solid, which was collected and dried. Yield:
1
416 mg (92%). H NMR (C6D6): δ 7.44 (t, J ) 7.2 Hz, 1H, 2′-
biphenyl), 7.29–7.37 (m, 3H, 2′-biphenyl), 7.09 (d, J ) 6.8 Hz,
2H, 2′-biphenyl), 6.94–7.02 (m, 3H, 2′-biphenyl), 0.77–1.29 (m,
22H, C6H11). 31P{1H} NMR (C6D6): δ 46.0 ppm. 13C{1H} NMR
(C6D6): δ 149.45 (d, J ) 11.4 Hz), 141.71 (d, J ) 5.4 Hz), 134.31
(d, J ) 7.7 Hz), 132.67 (d, J ) 7.7 Hz), 130.60 (d, J ) 2.2 Hz),
129.48 (s), 129.19 (s), 128.96 (s), 127.41 (d, J ) 8.4 Hz), 126.20
(s), 125.71 (s), 36.89 (d, J ) 32.1 Hz), 31.15 (d, J ) 4.5 Hz),
29.54 (s), 26.74 (s), 26.61 (s), 26.46 (s), 25.67 (s) ppm. Anal. Calcd
for C24H31AuBrP: C, 45.95; H, 4.98. Found: C, 45.66; H, 5.06.
(PCy2(2′-methylbiphenyl))AuCl (3). In a glovebox, (PCy2(2′-
methylbiphenyl) (488 mg, 1.34 mmol) was dissolved in 15 mL of
toluene, and to this solution was added [Au(tht)Cl] (tht )
tetrahydrothiophene) (424 mg, 1.32 mmol). The resultant solution
was stirred 24 h under argon, during which it became a white
suspension. The suspension was stripped of solvent in vacuo to
yield a white residue, to which pentane was added. Repeated
scraping of the residue with a spatula into the pentane liberated a
free-flowing solid, which was collected and dried. Yield: 765 mg
(97%). 1H NMR (C6D6): δ 7.53 (td, J ) 7.6, 1.6 Hz, 1H,
2′-methylbiphenyl), 7.41 (d, J ) 7.6 Hz, 1H, 2′-methylbiphenyl),
7.23 (t, J ) 7.6 Hz, 1H, 2′-methylbiphenyl), 6.88–7.14 (m, 5H,
2′-methylbiphenyl), 1.99 (s, 3H, CH3), 0.78–1.91 (m, 22H, C6H11).
31P{1H} NMR (C6D6): δ 38.6 ppm. 13C{1H} NMR (C6D6): δ
149.61 (d, J ) 13.0 Hz), 141.06 (d, J ) 6.1 Hz), 135.64 (s), 132.87
(d, J ) 4.5 Hz), 132.64 (d, J ) 7.6 Hz), 132.00 (s), 130.83 (d, J
) 2.3 Hz), 129.98 (s), 129.47 (s), 127.21 (d, J ) 7.6 Hz), 126.08
(s), 125.90 (s), 125.58 (s), 37.41 (d, J ) 32.1 Hz), 35.30 (d, J )
34.3 Hz), 30.84 (m), 29.71 (s) 29.00 (s), 26.95 (s), 26.82 (d, J )
4.6 Hz), 26.63 (d, J ) 3.8 Hz), 26.48 (s), 26.34 (s), 25.77 (d, J )
10.6 Hz), 21.13 (s) ppm. Anal. Calcd for C25H33AuClP: C, 50.30;
H, 5.57. Found: C, 50.09; H, 5.45.
[(PCy2(2′-methylbiphenyl))AuBr] (4). In 40 mL of dichlo-
romethane was dissolved [(PCy2(2′-methylbiphenyl))AuCl] (749
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