Dalton Transactions
Page 4 of 15
ARTICLE
DOI: 10.1039/C7DT00782E
it was stirred for 2 h at room temperature. The yellow solution (CB3), 120.6 (CC6). 31P NMR (202 MHz, acetoneꢀ
d
6) δ/ppm –
was filtered and the solvent was removed from the filtrate. The 13.4 (broad, FWHM = 200 Hz), –144.3 (septet, JPF = 710 Hz,
solid material was washed with hexane (2 × 30 ml) and dried [PF6]–). ESI MS: m/z 883.1 [MꢀPF6]+ (base peak, calc. 883.2).
under vacuum. [Cu(1ꢀNaphbpy)(xantphos)][PF6] (251 mg, 0.24 UVꢀVis (CH2Cl2, 2.5 × 10–5 mol dm–3):
λ
/nm (
ε
/dm3 mol–1 cm–
mmol, 94%) was isolated as a yellow solid. 1H NMR (500 1) 232 (67600), 288 (28800), 389 (2600). Found: C 64.94, H
MHz, acetoneꢀ
HB3), 8.83 (d,
HB4), 8.17 (d,
HN4), 8.14 (td,
d
J
J
6, 223 K) δ/ppm: 8.87 (dd, J = 8.1, 1.1 Hz, 1H, 4.61, N 2.92; C56H42CuF6N2OP3 requires C 65.34, H 4.11, N
= 8.2 Hz, 1H, HA3), 8.41 (t,
= 8.3 Hz, 1H, HN5), 8.30 (d,
J
J
= 7.9 Hz, 1H, 2.72%.
= 8.3 Hz, 1H, [Cu(2-Naphbpy)(xantphos)][PF6]. This compound was
J
= 7.9, 1.7 Hz, 1H, HA4), 7.84 (dt,
J
= 8.0, 1.6 prepared by the same procedure as for [Cu(1ꢀ
= 7.7, 1.0 Hz, 1H, HB5), 7.57ꢀ7.49 Naphbpy)(xantphos)][PF6] using 2ꢀNaphbpy (70.6 mg, 0.25
(overlapping m, 2H, HD4a+N6), 7.46 (td,
= 7.4, 1.3 Hz, 1H, mmol) instead of 1ꢀNaphbpy. [Cu(2ꢀNaphbpy)(xantphos)][PF6]
HD4b), 7.37ꢀ7.26 (overlapping m, 5H, HD3a+D3b+C4a), 7.25ꢀ7.13 was isolated as a yellow powder (256 mg, 0.24 mmol, 96%). 1H
(overlapping m, 4H, HC4b+N3+D4c+D4d), 7.08ꢀ7.03 (overlapping NMR (500 MHz, acetoneꢀd6
/ppm: 8.63 (dt, = 8.3, 1.0 Hz,
m, 2H, HA5+N8), 6.90ꢀ6.82 (overlapping m, 4H, HD3c+D3d), 6.69ꢀ 1H, HA3), 8.55 (dd, = 8.0, 1.0 Hz, 1H, HB3), 8.24 (t,
= 7.9
6.53 (overlapping m, 7H, HA6+D2a+D2b+C3a+N7), 6.46 (d, = 6.5 Hz, 1H, HB4), 8.12 (m 1H, HA4), 8.00 (m, 1H, HN5), 7.77ꢀ7.73
Hz, 1H, HN2), 6.30ꢀ6.20 (overlapping m, 3H, HC3b+D2c), 5.66 (overlapping m, 4H, HC5+B5+N1), 7.67 (ddd,
= 8.3, 6.8, 1.3 Hz,
(broad m, 2H, HD2d), 2.06 (s, HMe, overlaps with acetoneꢀ 6 and 1H, HN6), 7.53 (ddd, = 8.1, 6.7, 1.2 Hz, 1H, HN7), 7.50ꢀ7.42
assigned from 2D spectra), 1.32 (s, 3H, HMe'). 13C NMR (126 (overlapping m Hz, 4H, HN3+N8+D4a), 7.28 (t,
= 7.7 Hz, 4H,
MHz, acetoneꢀd6, 223 K)
/ppm: 160.2 (CB6), 155.0 (CC1a), HD3a), 7.28 (t, = 7.7 Hz, 2H, HC4), 7.17ꢀ7.11 (overlapping m,
Hz, 2H, HC5a+C5b), 7.61 (dd,
J
J
)
δ
J
J
J
J
J
d
J
J
δ
J
154.4 (CC1b), 153.5 (CA2), 153.0 (CB2), 147.5 (CA6), 139.7 3H, HA5+D4b), 6.82 (m Hz, 4H, HD2a), 6.80ꢀ6.73 (overlapping m,
(CA4+B4), 139.0 (CN1), 134.6 (CN4a), 134.5 (CC6a+C6b), 134.4 5H, HA6+D3b), 6.67ꢀ6.59 (overlapping m, 6H, HC3+D2b), 1.91
(CD2a), 134.0 (CD2c), 133.3 (CD2b), 132.4 (CD2d), 131.3 (CC3b), (broad s, 3H, HMe), 1.46 (s, 3H, HMe'). 13C NMR (126 MHz,
131.2 (CD4a), 131.1 (CN8a), 130.9 (CC3a), 130.7 (CD4b), 130.1 acetoneꢀd6 /ppm: 161.7 (CB6), 155.5 (t, = 6.3 Hz, CC1),
) δ J
(CD4c), 130.1 (CN4), 129.7 (CD4d), 129.6 (CD1a), 129.5 154.3 (CA2), 154.0 (CB2), 148.9 (CA6), 140.3 (CB4), 140.1 (CA4),
(CD3a+D3b), 129.4 (CB5), 129.3 (CN5), 128.9 (CD1c+D1d), 128.7 139.2 (CN2), 135.6 (CD1a), 134.9 (CC6), 134.5 (CN4a), 134.1
(CD3c+D3d), 128.0 (CC5a+C5b), 127.5 (CN7), 127.4 (CN2), 127.3 (CN8a), 133.9 (t,
J
= 7.7 Hz, CD2a+D2b), 131.5 (CC3), 131.1 (CD4a),
= 4.5 Hz, CD3a), 129.5
= 4.7 Hz, CD3a), 128.9 (CN5), 128.7 (CN1),
6, 223 128.3 (CC5), 128.2 (CN6), 127.9 (CB5), 126.4 (CA5), 126.2 (t,
= 110 2.2 Hz, CC4), 126.0 (CN3), 124.5 (CA3), 123.3 (CB3), 121.9
PF = 710 Hz, [PF6]–). ESI MS: m/z 923.1 (CN7), 121.1 (t, = 13.1 Hz, CC2), 36.8 (Cq), 30.8 (CMe'), 25.3
[MꢀPF6]+ (base peak, calc. 923.2). UVꢀVis (CH2Cl2, 2.5 × 10–5 (CMe). 31P NMR (202 MHz, acetoneꢀ
6) δ/ppm –12.8 (broad,
mol dm–3): /dm3 mol–1 cm–1) 230 (60800), 289 (29900), FWHM = 210 Hz), –144.3 (septet, JPF = 710 Hz, [PF6]–). ESI
/nm (
328sh (7800), 392 (2500). Found: C 66.29, H 4.78, N 2.86; MS: m/z 923.2 [M–PF6]+ (base peak, calc. 923.2). UVꢀVis
C59H46CuF6N2OP3 requires C 66.26, H 4.34, N 2.62%. /nm (
(CH2Cl2, 2.5 × 10–5 mol dm–3): /dm3 mol–1 cm–1) 230
[Cu(2-Naphbpy)(POP)][PF6]. [Cu(2ꢀNaphbpy)(POP)][PF6] (67000), 284 (32800), 388 (2500). Found: C 66.18, H 4.79, N
(CN6), 126.8 (CN3), 126.1 (CC4b), 125.9 (CC4a), 125.8 (CN8+A5), 130.8 (CD1b), 130.6 (CD4b), 129.8 (t,
124.5 (CA3), 123.3 (CB3), 121.5 (CC2a), 120.2 (CC2b), 36.7 (Cq), (CN8), 129.1 (t,
32.0 (CMe), 23.0 (CMe'). 31P NMR (202 MHz, acetoneꢀ
K) δ/ppm –10.9 (broad d, = 110 Hz), –13.4 (broad d,
Hz), –144.5 (septet,
J
J
d
J =
J
J
J
J
d
λ
ε
λ
ε
was prepared according to the procedure for [Cu(1ꢀ 2.90; C59H46CuF6N2OP3 requires C 66.26, H 4.34, N 2.62%.
Naphbpy)(POP)][PF6] using 2ꢀNaphbpy (70.6 mg, 0.25 mmol) [Cu(1-Pyrbpy)(POP)][PF6]. [Cu(MeCN)4][PF6] (93.2 mg,
in place of 1ꢀNaphbpy. [Cu(2ꢀNaphbpy)(POP)][PF6] was 0.25 mmol) and POP (148 mg, 0.27 mmol) were dissolved in
1
isolated as a yellow powder (251 mg, 0.24 mmol, 98%). H CH2Cl2 (30 ml) and the mixture was stirred for 2 h at room
NMR (500 MHz, acetoneꢀd6
2H, HA3+B3), 8.30 (t, = 7.9 Hz, 1H, HB4), 8.12 (d,
1H, HA6), 8.09 (td, = 7.9, 1.7 Hz, 1H, HA4), 7.91 (m, 1H, HN5), and the solvent was removed from the filtrate. The solid
7.76 (dd,
)
δ
/ppm: 8.67ꢀ8.62 (overlapping m, temperature. 1ꢀPyrbpy (89.6 mg, 0.25 mmol) was added and
J
J
= 5.1 Hz, stirring was continued for 2 h. The yellow solution was filtered
J
J
= 7.7, 1.0 Hz, 1H, HB5), 7.65ꢀ7.61 (overlapping m, material was washed with hexane (2 × 30 ml), dried under
2H, HN6+N8), 7.57ꢀ7.52 (overlapping m, 2H, HN1+N7), 7.44ꢀ7.33 vacuum and redissolved in a small amount of acetone. The
(overlapping m, 6H, HN3+C5+D4a+N4), 7.31 (m, 2H, HD4b), 7.25 solution was layered with Et2O and left to crystallize for 2 days.
(m, 4H, HD3a), 7.16 (m, 2H, HC6), 7.13 (ddd,
Hz, 1H, HA5), 7.05ꢀ6.95 (overlapping m, 6H, HC4+D3b), 6.83 (m, dried under vacuum to give [Cu(1ꢀPyrbpy)(POP)][PF6] (105
4H, HD2a), 6.64ꢀ6.54 (overlapping m, 6H, HC3+D2b). 13C NMR mg, 0.10 mmol, 38%) as a yellow powder. 1H NMR (600 MHz,
(126 MHz, acetoneꢀd6
CC1), 154.4 (CB2), 153.8 (CA2), 149.7 (CA6), 140.3 (CB4), 139.7 8.78 (d,
(CA4), 139.0 (CN2), 135.3 (CC3), 134.6 (CD2b), 134.4 (CN4a), 8.45 (t,
133.5 (CN8a+D2a), 133.1 (CC5), 131.0 (CD4a), 130.8 (CD4b), 130.1 (d, = 5.1 Hz, 1H, HA6), 8.23 (d,
(CN4), 129.7 (CD3a), 129.5 (CN8), 129.3 (CD3b), 128.8 (CN1+N5), = 8.9 Hz, 1H, HP4), 8.14 (t, = 7.6 Hz, 1H, HP7), 8.13 (t,
128.1 (CN6), 128.0 (CB5), 127.9 (CN7), 126.4 (CA5+N3), 125.9 (t, 8.3 Hz, 1H, HA4), 7.80 (dd, = 7.6, 1.0 Hz, 1H, HB5), 7.70 (d,
= 2.1 Hz, CC4), 124.6 (t, = 14.2 Hz, CC2), 124.0 (CA3), 123.0 = 7.2 Hz, 1H, HP2), 7.69 (d, = 9.4 Hz, 1H, HP9), 7.62 (t,
J = 7.6, 5.2, 1.1 The resulting yellow crystals were ground to a powder and
)
δ
/ppm: 161.8 (CB6), 158.2 (t,
J
= 5.9 Hz, acetoneꢀ
d
J
6, 238 K)
= 8.3 Hz, 1H, HA3), 8.47 (d,
= 7.8 Hz, 1H, HB4), 8.42 (d, = 8.9 Hz, 1H, HP5), 8.32
= 7.6 Hz, 1H, HP8), 8.19 (d,
δ
/ppm: 8.89 (dd,
J
= 8.2, 1.0 Hz, 1H, HB3),
= 7.6 Hz, 1H, HP6),
J
J
J
J
J
J
J
J
=
J
J
J
J
J
J
=
4 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 2012