Organometallics
ARTICLE
(2 ꢁ s, 8 H, py and pz CH2), 6.11 (s, 1 H, pz H4), 7.05 (ddd, 4JHH
=
L6H.15 1H NMR (500.13 MHz, C6D6): δ 2.84 (s, broad, 6 H, CH3),
4.82 (s, broad, 4 H, CH2), 6.73 (dd, 3JHH = 4.1 Hz, 3JHH = 8.2 Hz, 2 H,
quin H3), 6.81 (d, broad, 3JHH = 7.2 Hz, 2 H, quin H7), 6.91ꢀ6.94 (m,
1.6 Hz, 3JHH = 4.8 Hz, 3JHH = 6.7 Hz, 2 H, py H5), 7.53ꢀ7.58 (m, 4 H, py
H
3,4), 8.39ꢀ8.40 (m, 2 H, py H6). 13C NMR (75.47 MHz, C6D6):
δ 26.3 (CH2, cy C3), 26.5 (CH2, cy C4), 29.4 (CH2, cy C2), 47.6
(broad), 56.3 (py and pz CH2), 60.0 (CH, cy C1), 103.2 (CH, pz C4),
121.6 (CH, py C5), 122.6 (CH, py C3), 136.0 (CH, py C4), 149.1 (CH,
py C6), 162.2 (C, py C2). The signal of pz C3,5 is too broad to be
detected. 13C NMR (125.77 MHz, THF-d8): δ 27.0 (CH2, cy C3), 27.3
(CH2, cy C4), 29.8 (CH2, cy C2), 47.8 (broad), 56.7 (py and pz CH2),
60.3 (CH, cy C1), 103.9 (CH, pz C4), 122.1 (CH, py C5), 123.0 (CH, py
C3), 136.6 (CH, py C4), ∼147 (br, C, pz C3,5), 149.4 (CH, py C6), 162.8
(C, py C2). MS (EI): m/z (relative intensity) 472 (1) [M]þ, 380 (100)
[M ꢀ (C6H6N)]þ, 284 (19) [M ꢀ (C6H6N)(C6H11N) þ H]þ, 283
(14) [Mꢀ (C6H6N)(C6H11N)]þ, 191 (32) [M ꢀ (C6H6N)(C6H11N) ꢀ
(C6H6N)]þ, 93 (21) [C6H7N]þ. HRMS (ESI(þ) in MeOH): m/z
calcd for C29H41N6 [M þ H]þ 473.339 27, found 473.339 07.
1 H, p-Ph), 6.96ꢀ7.00 (m, 2 H, m-Ph), 7.02 (dd, 4JHH = 1.2 Hz, 3JHH
=
8.1 Hz, 2 H, quin H5), 7.12ꢀ7.15 (m, overlaid by the benzene signal,
2 H, quin H6), 7.25ꢀ7.27 (m, 2 H, o-Ph), 7.52 (dd, 4JHH = 1.8 Hz, 3JHH
= 8.3 Hz, 2 H, quin H4), ∼8.41 (m, broad, 2 H, quin H2). 13C NMR
(125.77 MHz, C6D6): δ 40.1 (broad, CH3), 51.6 (CH2), 116.2 (CH,
quin C7), 120.0 (CH, quin C5), 120.7 (C, pz C4), 120.7 (CH, quin C3),
126.1 (CH, p-Ph), 126.9 (CH, quin C6), ∼128.0 (CH, overlaid by
benzene signal, m-Ph), 130.0 (C, quin C4a), 130.3 (CH, o-Ph), 133.9
(C, i-Ph), 136.3 (CH, quin C4), 143.1 (C, quin C8a), 147.3 (CH, quin
C2), 149.5 (C, quin C8). The signal of pz C3,5 is too broad to be
detected.
1. A solution of L3H (199 mg, 0.42 mmol) in THF (10 mL) was
treated dropwise with a 2 M solution of Na(N(SiMe3)2) in THF
(0.21 mL, 0.42 mmol). After it was stirred for 5 min, this solution was
added to a suspension of [Cu(CH3CN)4]BF4 (264 mg, 0.84 mmol) in
THF (20 mL). After this mixture was stirred for 22 h, a 1 M solution of
PMe3 in THF (0.84 mL, 0.84 mmol) was added. The suspension was
stirred for 6 days, then filtered over Kieselgur, and the resulting clear
yellow to orange solution was concentrated in vacuo to 5 mL. Slow
diffusion of diethyl ether (15 mL) into the solution at 4 °C over the
course of 11 days afforded small pale yellow crystals. The orange
solution was decanted, and the crystalline solid was washed with cold
diethyl ether and then dried in vacuo for 18 h. Yield: 150 mg (0.18 mmol,
43%). Anal. Calcd for C35H57N6P2Cu2BF4: C, 50.18; H, 6.86; N, 10.03.
L4H. This compound was prepared according to the method
described for L1H by the use of Na2CO3 (5.315 g, 50.15 mmol), 3,5-
bis(chloromethyl)-1-(tetrahydropyran-2-yl)-4-phenylpyrazole (1.608 g,
4.94 mmol), and N-(2-picolyl)cyclohexylamine (1.885 g, 9.91 mmol),
which were heated in solution to reflux for 90 h. Recrystallization from
diethyl ether and drying in vacuo for 15 h gave a beige powder. Yield:
1.010 g (1.84 mmol, 37%). Mp: 127 °C. Anal. Calcd for C35H44N6: C,
76.60; H, 8.08; N, 15.31. Found: C, 75.93; H, 8.13; N, 15.00. 1H NMR
(500.13 MHz, C6D6): δ 0.81ꢀ0.88 (m, 2 H, cy H4a), 0.92ꢀ1.12 (m,
8 H, cy H3a,2a), 1.39 (d, JHH = 12.3 Hz, 2 H, cy H4e), 1.54 (d, JHH
=
12.3 Hz, 2 H, cy H3e), ∼1.71ꢀ1.72 (m, broad, 4 H, cy H2e),
∼2.50ꢀ2.55 (m, broad, 2 H, cy H1), 3.92 (broad), 3.94 (2 ꢁ s, 8 H,
py and pz CH2), 6.56 (dd, 3JHH = 4.9 Hz, 3JHH = 8.2 Hz, 2H, py H5), 7.04
(t, 3JHH = 6.4 Hz, 2 H, py H4), ∼7.15 (m, broad, overlaid by the benzene
signal, 2 H, py H3), 7.15ꢀ7.19 (m, overlaid by the benzene signal, 1 H,
p-Ph), 7.29ꢀ7.33 (m, 2 H, m-Ph), 7.61ꢀ7.63 (m, 2 H, o-Ph), 8.36ꢀ8.37
(m, 2 H, py H6). 13C NMR (125.77 MHz, C6D6): δ 26.4 (CH2, cy C3),
26.5 (CH2, cy C4), 29.2 (CH2, cy C2), 46.8 (broad), 56.2 (py and pz
CH2), 60.5 (CH, cy C1), 118.7 (C, pz C4), 121.5 (CH, py C5), 122.7
(CH, py C3), 126.3 (CH, p-Ph), 128.5 (CH, m-Ph), 130.3 (CH, o-Ph),
135.2 (C, i-Ph), 135.9 (CH, py C4), 149.1 (CH, py C6), 162.1 (C, py C2).
The signal of pz C3,5 is too broad to be detected. MS (EI): m/z (relative
intensity) 548 (1) [M]þ, 456 (100) [M ꢀ (C6H6N)]þ, 360 (24) [M ꢀ
(C6H6N)(C6H11N) þ H]þ, 359 (17) [M ꢀ (C6H6N)(C6H11N)]þ, 267
(12) [Mꢀ (C6H6N)(C6H11N) ꢀ (C6H6N)]þ, 266 (51) [M ꢀ (C6H6N)
(C6H11N) ꢀ (C6H6N) ꢀ H]þ, 191 (25) [M ꢀ (C6H6N)(C6H11N) ꢀ
(C6H6N) ꢀ (C6H5) þ H]þ, 93 (31) [C6H7N]þ. HRMS (ESI(þ) in
MeOH): m/zcalcd for C35H45N6 [Mþ H]þ 549.370 57, found 549.370 13.
L5H. This compound was prepared according to the method des-
cribed for L1H by the use of Na2CO3 (4.410 g, 41.61 mmol), 3,5-
bis(chloromethyl)-1-(tetrahydropyran-2-yl)-4-phenylpyrazole (1.350 g,
4.15 mmol), and N-bis(2-picolyl)amine (1.650 g, 8.28 mmol), which
were heated in solution to reflux for 48 h. The resulting oily residue was
dried in vacuo (5 ꢁ 10ꢀ4 mbar, 100 °C). A beige to brownish resin was
1
Found: C, 49.74; H, 6.98; N, 9.78. H NMR (500.13 MHz, C6D6):
δ 0.77ꢀ1.02 (m, 10 H, cy H2aꢀ4a), 1.27 (d, 2JHP = 5.9 Hz, 18 H, PMe3),
1.38ꢀ1.42 (m, 2 H, cy H4e), 1.48ꢀ1.50 (m, 4 H, cy H3e), 1.72ꢀ1.75 (m,
4 H, cy H2e), 2.41ꢀ2.45 (m, 2 H, cy H1), 3.37, 3.65 (2 ꢁ s, broad, 8 H, py
and pz CH2), 6.00 (s, 1 H, pz H4), 6.43 (d, 3JHH = 7.8 Hz, 2 H, py H3),
7.12ꢀ7.15 (m, overlaid by the benzene signal, 2 H, py H4), 7.49ꢀ7.51 (m,
2 H, py H5), 9.14 (d, 3JHH = 4.8 Hz, 2 H, py H6). 1H NMR (after 8 weeks,
500.13 MHz, C6D6): δ 0.80ꢀ1.07 (m, 10 H, cy H2aꢀ4a), 1.26 (d, 2JHP
=
5.8 Hz, 18 H, PMe3), 1.37ꢀ1.42 (m, 2 H, cy H4e), 1.50ꢀ1.52 (m, 4 H, cy
H3e), 1.76ꢀ1.78 (m, 4 H, cy H2e), 2.43ꢀ2.48 (m, 2 H, cy H1), 3.43, 3.65
(2 ꢁ s, broad, 8 H, py and pz CH2), 5.98 (s, 1 H, pz H4), 6.60 (d, 3JHH
=
7.7 Hz, 2 H, py H3), 7.27 (t, 3JHH = 7.4 Hz, 2 H, pyH4), 7.49ꢀ7.52 (m, 2 H,
py H5), 9.00ꢀ9.01 (m, 2 H, py H6). 1H NMR (500.13 MHz, THF-d8):
δ 1.05ꢀ1.41 (m, 10 H, cy H2aꢀ4a), 1.28 (d, 2JHP = 5.8 Hz, 18 H, PMe3),
1.57ꢀ1.60 (m, 2 H, cy H4e), 1.73ꢀ1.76 (m, overlaid by the THF signal,
4 H, cy H3e), 2.00ꢀ2.03 (m, 4 H, cy H2e), 2.67ꢀ2.72 (m, 2 H, cy H1), 3.77,
3.83 (2 ꢁ s, broad, 8 H, py and pz CH2), 5.71 (s, 1 H, pz H4), 7.29 (d, 3JHH
= 7.5 Hz, 2 H, py H3), 7.38ꢀ7.41 (m, 2 H, py H5), 7.72 (t, 3JHH = 7.4 Hz, 2
H, py H4), 8.66ꢀ8.67 (m, 2 H, py H6). 13C NMR (125.77 MHz, C6D6): δ
16.5 (d, 1JCP = 20.9 Hz, CH3, PMe3), 26.0 (CH2, cyC3), 26.2 (CH2, cyC4),
29.9 (broad, CH2, cy C2), 52.5, 55.2 (py and pz CH2), 64.4 (CH, cy C1),
98.3 (CH, pz C4), 121.7 (CH, py C3), 124.6 (CH, py C5), 137.2 (CH, py
C4), 149.2 (C, pz C3,5), 151.2 (CH, py C6), 158.5 (C, py C2). 13C NMR
(after 8 weeks, 125.77 MHz, C6D6):δ16.5 (d, 1JCP = 20.7 Hz, CH3, PMe3),
26.1 (CH2, cy C3), 26.2 (CH2, cy C4), 29.7 (broad, CH2, cy C2), 52.3, 55.4
(py and pz CH2), 64.4 (CH, cy C1), 98.3 (CH, pz C4), 122.2 (CH, py C3),
124.6 (CH, py C5), 137.5 (CH, py C4), 149.3 (C, pz C3,5), 150.8 (CH, py
1
obtained. Yield: 1.354 g (2.39 mmol, 58%). H NMR (500.13 MHz,
C6D6): δ 3.91 (s, broad, 12 H, CH2), 6.55 (ddd, 4JHH = 0.9 Hz, 3JHH
=
4.9 Hz, 3JHH = 7.4 Hz, 4 H, py H5), 7.02 (dt, 4JHH = 1.5 Hz, 3JHH = 7.6
Hz, 4 H, py H4), 7.11ꢀ7.14 (m, 1 H, p-Ph), 7.18ꢀ7.21 (m and overlaid
broad band, 6 H, py H3, m-Ph), 7.45ꢀ7.48 (m, 2 H, o-Ph), 8.35 (d,
3JHH = 4.3 Hz, 4 H, py H6). 13C NMR (125.77 MHz, C6D6): δ 49.7
(broad), 59.8 (CH2), 120.0 (C, pz C4), 121.7 (CH, py C5), 123.4 (CH,
py C3), 126.2 (CH, p-Ph), 128.5 (CH, m-Ph), 130.3 (CH, o-Ph), 134.6
(C, i-Ph), 135.9 (CH, py C4), 149.2 (CH, py C6), 159.8 (C, py C2). The
signal of pz C3,5 is too broad to be detected. MS (EI): m/z (relative
intensity) 566.3 (1) [M]þ, 474.2 (37) [M ꢀ (C6H6N)]þ, 369.1 (12)
[M ꢀ (C12H12N3) þ H]þ, 275.0 (12) [M ꢀ (C12H12N3) ꢀ (C6H6N) ꢀ
H]þ, 92.9 (100) [C6H7N]þ. HRMS (ESI(þ) in MeOH): m/z calcd for
C35H35N8 [M þ H]þ 567.298 47, found 567.298 08.
C6), 158.7 (C, py C2). 13C NMR (125.77 MHz, THF-d8): δ 16.7 (d, 1JCP
=
20.4 Hz, CH3, PMe3), 26.8 (CH2, cy C3), 26.9 (CH2, cy C4), 30.5 (broad,
CH2, cy C2), 52.6, 56.1 (py and pz CH2), 65.2 (CH, cy C1), 98.4 (CH, pz
C4), 123.3 (CH, py C3), 124.5 (CH, py C5), 138.3 (CH, py C4), 149.8 (C,
pz C3,5), 150.7 (CH, py C6), 160.3 (C, py C2). 31P NMR (202.46 MHz,
C6D6): δ ꢀ51.1 (s). 31P NMR (202.46 MHz, THF-d8): δ ꢀ50.9 (s). MS
(ESI(þ) in CH3CN): m/z (relative intensity) 837.4 (3) [M þ H]þ, 749.3
(10) [L3Cu2(PMe3)2]þ, 673.2 (55) [L3Cu2(PMe3)]þ, 611.3 (71)
[L3Cu(PMe3) þ H]þ, 597.2 (89) [L3Cu2]þ, 535.5 (100) [L3Cu þ
H]þ, 215.1 (93) [Cu(PMe3)2]þ.
3720
dx.doi.org/10.1021/om100836j |Organometallics 2011, 30, 3708–3725