Gold(I) and Gold(III) Complexes
precipitated with hexane. Yield: 0.20 g (63%). Analytical data,
Found: C, 46.43; H, 3.81; N, 4.04. Calcd for C26H26N2SeAuP: C,
Synthesis of [Au2{SeC6H4(CH2NMe2)-2}2(µ-dppf)] (5). A solu-
tion of KB[CH(CH3)C2H5]3H (K-selectride) 1 M (0.47 mL, 0.47
mmol) in THF was added to a solution of [2-(Me2NCH2)C6H4]2Se2
(0.1 g, 0.23 mmol) in 20 mL of anhydrous THF, and the reaction
mixture was stirred for 4 h at room temperature, under argon. The
resulting yellow solution with white precipitate was treated (at -78
°C) with [Au2Cl2(µ-dppf)] (0.24 g, 0.23 mmol). After stirring for
an additional 1 h the solvent was removed in vacuum, and the
remaining solid was treated with methylene dichloride. The white
KCl was filtered off, and the yellow solution was concentrated under
reduced pressure, then precipitated with hexane. The yellow product
was recrystallized from methylene dichloride/n-hexane (1:5, v/v).
Yield: 0.25 g (80%). Analytical data, Found: C, 45.43; H, 3.81; N,
2.04. Calcd for C52H52Au2FeN2P2Se2: C, 45.58; H, 4.01; N, 2.03.
1H (CDCl3, 400 MHz): δ 2.29 (12H, s, N-CH3), 3.76 (4H, s,
-CH2-N), 4.18, 4.52 (8H, m, br, C5H4-ferocene), 6.89 (2H, ddd,
1
46.37; H, 3.89; N, 4.16. H (CDCl3, 400 MHz): δ 2.26 (6H, s,
N-CH3), 3.75 (2H, s, -CH2-N), 6.93 (1H, ddd, H5, 3JHH 7.5, 4JHH
1.5 Hz), 7.08 (1H, ddd, H4, 3JHH 7.5, 4JHH 1.3 Hz), 7.34 [2H, m, H3
+ H5′ (PPy)], 7.40 (4H, m, P-C6H5-meta), 7.48 (2H, m, P-C6H5-
para), 7.68 [5H, m, P-C6H5-ortho + H4′ (PPy)], 7.83 [1H, dd, H3′
3
3
3
4
(PPy), JPH 7.5, JHH 7.5 Hz], 7.99 (1H, dd, H6, JHH 7.7, JHH 1.2
Hz), 8.74 [1H, dm, H6′ (PPy), JPH 4.7 Hz]. 13C (CDCl3, 100.6
3
MHz): δ 45.77 (s, N-CH3), 65.16 (s, -CH2-N), 125.04 [d, C5′
4
(PPy), JPC 2.0 Hz], 125.17 (s, C4), 126.09 (s, C5), 129.02 (d,
3
1
P-C6H5-meta, JPC 11.5 Hz), 129.28 (d, P-C6H5-ipso, JPC 55.5
Hz), 129.42 (s, C3), 130.95 [d, C3′ (PPy), 2JPC 31.6 Hz], 131.68 (d,
4
P-C6H5-para, JPC 2.1 Hz), 132.71 (s, C1), 134.45 (d, P-C6H5-
2
3
ortho, JPC 13.8 Hz), 136.43 [d, C4′ (PPy), JPC 10.4 Hz], 137.90
(s, C6), 141.01 (s, C2), 151.19 [d, C6′ (PPy), 3JPC 15.2 Hz], 154.98
(d, C2′ (PPy), 1JPC 77.2 Hz). 31P (CDCl3, 161.9 MHz): δ 37.0. 77Se
(CDCl3, 76.4 MHz): δ 120.3.
3
4
3
4
H5, JHH 7.5, JHH 1.4 Hz), 7.06 (2H, ddd, H4, JHH 7.4, JHH 1.2
Hz), 7.34 (2H, dd, H3, 3JHH 7.5, 4JHH 0.9 Hz), 7.39 (8H, m, P-C6H5-
meta), 7.48 (12H, m, P-C6H5-ortho+para), 7.98 (2H, dd, H6, 3JHH
Synthesis of [Au2{SeC6H4(CH2NMe2)-2}2(µ-dppm)] (3). A
solution of KB[CH(CH3)C2H5]3H (K-selectride) 1 M (0.56 mL, 0.56
mmol) in THF was added to a solution of [2-(Me2NCH2)C6H4]2Se2
(0.12 g, 0.28 mmol) in 20 mL of anhydrous THF, and the reaction
mixture was stirred for 3 h at room temperature, under argon. The
resulting yellow solution with white precipitate was treated dropwise
(at -78 °C) with a solution of [Au2Cl2(µ-dppm)] (0.24 g, 0.28
mmol) in 20 mL of THF. After stirring for an additional 1 h the
solvent was removed in vacuum, and the remaining solid was treated
with acetone. The white KCl deposited and was filtered off. The
yellow solution was concentrated under reduced pressure and precipi-
tated with hexane. The yellow product was recrystallized from
methylene dichloride/n-hexane (1:5, v/v). Yield: 0.25 g (75%).
Analytical data, Found: C, 41.89; H, 2.06; N, 3.34. Calcd for
C43H46N2Se2Au2P2: C, 42.87; H, 2.32; N, 3.84. 1H (CDCl3, 400 MHz):
δ 2.30 (12H, s, N-CH3), 3.56 (2H, m, P-CH2-P), 3.80 (4H, s,
-CH2-N), 7.49 (28H, m, -C6H4- + P-C6H5). 31P (CDCl3, 161,9
MHz): δ 29.4 (s, 2P). 77Se (CDCl3, 76.4 MHz): δ 161.3 (s, 2Se).
Synthesis of [Au2{SeC6H4(CH2NMe2)-2}2(µ-dppe)] (4). El-
emental selenium (0.04 g, 0.50 mmol) was added to a solution of
[2-(Me2NCH2)C6H4]Li (0.07 g, 0.50 mmol) in 50 mL of anhydrous
THF, and the reaction mixture was stirred for 2 h at room
temperature, under argon. The resulting yellow solution was treated
with [Au2Cl2(µ-dppe)] (0.21 g, 0.25 mmol). After stirring for an
additional 2 h the solvent was removed in vacuum, and the
remaining solid was treated with methylene dichloride. The white
LiCl deposited and was filtered off. The yellow-orange solution
was concentrated under reduced pressure until a solid deposited.
The yellow-orange product was recrystallized from methylene
dichloride/n-hexane (1:5, v/v). Yield: 0.17 g (56%), mp 150 °C.
Analytical data, Found: C, 43.20; H, 4.09; N, 2.26. Calcd for
4
7.7, JHH 1.0 Hz). 13C (CDCl3, 100.6 MHz): δ 45.80 (s, N-CH3),
65.10 (s, -CH2-N), 74.72 (m, C5H4-ferocene), 125.09 (s, C4),
125.90 (s, C5), 128.91 (d, P-C6H5-meta, 3JPC 11.4 Hz), 129.24 (s,
1
C3), 131.41 (d, P-C6H5-ipso, JPC 15.9 Hz), 131.43 (s, P-C6H5-
2
para), 132.91 (s, C1), 133.47 (d, P-C6H5-ortho, JPC 14.1 Hz),
137.98 (s, C6), 141.31 (s, C2). 31P (CDCl3, 161.9 MHz): δ 32.8 (s,
2P). 77Se (CDCl3, 76.4 MHz): δ 424.2 (s, 2Se).
Synthesis of Bu4N[Au(C6F5)3{SeC6H4(CH2NMe2)-2}] (6). A
solution of KB[CH(CH3)C2H5]3H (K-selectride) 1 M (0.28 mL, 0.28
mmol) in THF was added to a solution of [2-(Me2NCH2)C6H4]2Se2
(0.06 g, 0.14 mmol) in 20 mL of anhydrous THF, and the reaction
mixture was stirred for 4 h at room temperature, under argon. The
resulting yellow solution with white precipitate was treated (at -78
°C) with Bu4N[AuBr(C6F5)3] (0.28 g, 0.28 mmol). After stirring
for an additional 2 h the solvent was removed in vacuum, and the
remaining solid was treated with methylene dichloride. The white
KBr deposited and was filtered off. The pale yellow solution was
concentrated under reduced pressure and precipitated with hexane.
The pale yellow product was recrystallized from methylene
dichloride/n-hexane (1:5, v/v). Yield: 0.13 g (80%). Analytical data,
Found: C, 45.03; H, 3.91; N, 2.34. Calcd for C43H48N2SeAuF15: C,
1
44.76; H, 4.19; N, 2.43. H (CDCl3, 400 MHz): δ 0.99 (12H, t,
CH3CH2CH2CH2-, 3JHH 7.3 Hz), 1.43 (8H, tq, CH3CH2CH2CH2-,
3JHH 7.4 Hz), 1.64 (8H, m, CH3CH2CH2CH2-), 2.27s (6H, N-
CH3), 3.16 (8H, m, CH3CH2CH2CH2-), 3.70 (2H, s, -CH2-N),
3
4
6.67 (1H, ddd, H5, JHH 7.4, JHH 1.3 Hz), 6.98 (1H, ddd, H4,
3JHH 7.4, JHH 1.2 Hz), 7.12 (1H, dd, H3, JHH 7.6, JHH 1.0
Hz), 7.31 (1H, d, H6, JHH 7.6 Hz). 13C (CDCl3, 100.6 MHz):
4
3
4
3
δ 13.37 (s, CH3CH2CH2CH2-), 19.55 (s, CH3CH2CH2CH2-),
23.76 (s, CH3CH2CH2CH2-), 45.48 (s, N-CH3), 58.79 (s,
CH3CH2CH2CH2-), 64.42 (s, -CH2-N), 115.60, 119.86 (m, C6F5),
125.13 (s, C5), 126.29 (s, C4), 128.12 (s, C3), 131.19 (s, C1), 135.70,
136.90, 138.18 (m, C6F5), 138.78 (s, C6), 139.25 (m, C6F5), 142.75
(s, C2), 143.80, 146.10 (m, C6F5).19F (CDCl3, 376.48 MHz): δ
-163.3 (4F, m, C6F5-meta), -162.9 (2F, m, C6F5-meta), -161.1
1
C44H48N2P2Se2Au2: C, 43.37; H, 3.97; N, 2.30. H (CDCl3, 400
MHz): δ 2.27 (12H, s, N-CH3), 2.64 (4H, s, br, -CH2-CH2-),
3.74 (4H, s, -CH2-N), 6.86 (2H, ddd, H5, 3JHH 7.5, 4JHH 1.2 Hz),
7.07 (2H, ddd, H4, 3JHH 7.4, 4JHH 0.9 Hz), 7.34 (2H, d, H3, 3JHH 7.5
3
Hz), 7.42 (8H, dd, P-C6H5-meta, JHH 7.3 Hz), 7.50 (4H, t,
P-C6H5-para, 3JHH 7.2 Hz), 7.61 (8H, dd, P-C6H5-ortho, 3JHP 12.8,
3JHH 6.9 Hz), 7.94 (2H, dd, H6, 3JHH 7.7, 4JHH 0.8 Hz). 13C (CDCl3,
(2F, t, C6F5-para, JFF 19.9 Hz), -160.0 (1F, t, C6F5-para, JFF
20.1 Hz), -121.2 (2F, m, C6F5-ortho), -119.2 (4F, m, C6F5-ortho).
77Se (CDCl3, 76.4 MHz): δ 205.9.
3
3
1
2
100.6 MHz): δ 24.18 (dd, P-CH2-CH2-P, JPC 18.3, JPC 18.3
Hz], 45.78 (s, N-CH3), 65.20 (s, -CH2-N), 125.12 (s, C4), 126.00
(s, C5), 129.47 (s, C3), 128.93 (m, P-C6H5-ipso), 129.50 (m,
P-C6H5-meta, 3JPC 11.2 Hz), 132.07 (s, P-C6H5-para), 132.82 (s,
C1), 133.20 (m, P-C6H5-ortho, 2JPC 13.8 Hz), 137.80 (s, C6), 141.24
(s, C2). 31P (CDCl3, 161.9 MHz): δ 36.2 (s, 2P). 77Se (CDCl3, 76.4
MHz): δ 125.2 (s, 2Se).
Crystal Structure Determinations. Table 4 lists details for
crystal and refinement data.
A block crystal of 4 was attached with epoxy glue on
cryoloops, and data were collected at room temperature on a
Bruker SMART APEX diffractometer, while for 5 a crystal was
mounted in inert oil on glass fiber and transferred to the cold
Inorganic Chemistry, Vol. 48, No. 9, 2009 4141