Inorganic Chemistry
ARTICLE
122.23 (s, aromatic C), 121.40 (s, aromatic C), 120.01 (s, aromatic C),
112.42 (s, aromatic C), 106.76 (s, aromatic C), 105.43 (s, aromatic C),
29.78 (s, CHMe2), 23.74 (s, CHMe2), 10.84 (d, 1JPC = 71.7 Hz, PCH3).
31P{1H} NMR (CD2Cl2): δ 38.00 (s). 19F NMR (CD2Cl2): δ À132.20
(br, 8F, m-C6F5). 11B{1H} NMR (CD2Cl2): δ À16.68 (br s). Anal.
Calcd for C55H33BF20NOP: C, 57.66; H, 2.90; N, 1.22. Found: C, 57.63;
H, 2.88; N, 1.24. X-ray quality crystals of 9 were grown from a solution of
the compound in CH2Cl2 and pentane.
(t, 3JHH = 7.2 Hz, 4H, p-Ph), 4.82 (br s, 1H, NH), 2.24 (s, 3H, p-Me),
1.99 (d, 2JHP = 12.9 Hz, 3H, PCH3), 1.95 (s, 6H, o-Me). 13C{1H} NMR
(CD2Cl2): δ 164.58 (q, 1:1:1:1, 1JBC = 49.1 Hz, ipso-BPh4À), 156.72 (s,
dbf), 156.57 (s, dbf), 139.26 (d, 3JCP = 2.3 Hz, dbf), 137.44 (d, 3JCP
=
3
(br, 8F, o-C6F5), À162.82 (t, JFF = 21.2 Hz, 4F, p-C6F5), À166.67
3.0 Hz, dbf), 136.49 (s, aromatic C), 136.16 (d, 3JCP = 3.0 Hz, aromatic
2
C), 132.33 (d, JCP = 12.1 Hz, aromatic C), 130.68 (m, aromatic C),
129.67 (s, aromatic C), 129.56 (d, 3JCP = 3.8 Hz, aromatic C), 129.09 (d,
3JCP = 2.7 Hz, aromatic C), 126.69 (d, 3JCP = 6.8 Hz, aromatic C), 126.20
2
(m, aromatic C), 125.07 (s, aromatic C), 124.82 (d, JCP = 11.3 Hz,
aromatic C), 122.63 (s, aromatic C), 122.32 (s, aromatic C), 122.06 (s,
aromatic C), 120.96 (s, aromatic C), 112.46 (s, aromatic C), 107.36 (s,
aromatic C), 106.03 (s, aromatic C), 21.05 (s, p-CH3), 19.78 (s, o-CH3),
[(dbf)MePhPdNHMes][B(C6F5)4] (10). The synthetic proce-
dure for compound 10 follows that given for 9. Compound 8 (0.282 g,
0.665 mmol) and [H(Et2O)2][B(C6F5)4] (0.551 g, 0.665 mmol) were
1
10.00 (d, JCP = 70.2 Hz, PCH3). 31P{1H} NMR (CD2Cl2): δ 37.27.
1
reacted to give compound 10 (0.690 g, 94%). H NMR (CD2Cl2): δ
11B{1H} NMR (CD2Cl2): δ À6.53 (s). Anal. Calcd for C52H47BNOP:
C, 83.98; H, 6.37; N, 1.88. Found: C, 83.70; H, 6.20; N, 1.87. Single
crystals of 12 suitable for X-ray analysis were obtained from a solution of
the compound in CH2Cl2 and pentane.
8.45 (m, 1H, dbf), 8.10 (d, 3JHH = 7.5 Hz, 1H, dbf), 7.85À7.75 (m, 3H,
dbf), 7.66À7.51 (m, 7H, dbf + Ph), 6.88 (s, 2H, m-Mes), 5.07 (br, 1H,
NH), 2.49 (d, 2JHP = 13.0 Hz, 3H, PMe), 2.22 (s, 3H, p-Me), 2.02 (s, 6H,
o-Me). 13C{1H} NMR (CD2Cl2): δ 156.90 (d, JCP = 2.0 Hz, dbf-
quaternary), 156.72 (s, dbf-quaternary), 150.32 (br, C6F5), 147.06 (br,
C6F5), 140.35 (br, C6F5), 139.37 (d, JCP = 2.0 Hz, aromatic C), 138.50
(br, C6F5), 137.22 (br ov d, 2JCP = 4.0, aromatic C + C6F5), 136.45 (d,
[{(dbf)MePhPdNDipp}ZnEt][B(C6F5)4] (13). In a J-Young
tube, compound 9 (0.83 g, 0.072 mmol) and an excess of diethylzinc
(0.1 mL) were dissolved in C6D5Br (0.5 mL). The tube was immersed in
liquid N2, evacuated (10À2 Torr), and heated to 100 °C. Monitoring the
reaction by 31P{1H} NMR spectroscopy indicated it had proceeded to
completion after 6 h. All volatiles were removed in vacuo, and the residue
was successively washed with benzene (0.5 Â 3 mL) and pentane (1 Â
3 mL), and then dried under vacuum. Complex 13 was isolated as an
analytically pure white solid (0.78 g, 87%). 1H NMR (CD2Cl2): δ 8.46
(d, 3JHH = 7.8 Hz, 1H, dbf), 8.16 (d, 3JHH = 6.6 Hz, 1H, dbf), 7.78 (s, 1H,
dbf), 7.71À7.50 (m, 9H, dbf + Ph), 7.24 (br, 2H, m-Dipp), 7.11 (br, 1H,
p-Dipp), 3.35 (sp, 3JHH = 6.6 Hz, 1H, CHMe2), 2.84 (sp, 3JHH = 6.6 Hz,
J
CP = 3.0 Hz, aromatic C), 135.21 (br, C6F5), 132.26 (d, 2JCP = 11.0 Hz,
aromatic C), 130.89 (m, aromatic C), 129.87 (m, aromatic C), 129.32 (d,
JCP = 3.0 Hz, aromatic C), 128.86 (s, aromatic C), 127.11 (d, JCP
=
7.5 Hz, aromatic C), 125.25 (s, aromatic C), 124.85 (d, 2JCP = 12.0 Hz,
aromatic C), 122.72 (s, aromatic C), 122.61 (s, aromatic C), 122.15
(s, aromatic C), 121.33 (s, aromatic C), 112.46 (s, aromatic C), 107.83
(s, aromatic C), 106.50 (s, aromatic C), 20.99 (s, p-Me), 19.74 (s, o-Me),
10.60 (d, 1JCP = 72 Hz, PCH3). 31P{1H} NMR (CD2Cl2): δ 35.92 (s).
3
19F NMR (CD2Cl2): δ À132.25 (br, 8F, o-C6F5), À162.81 (t, JFF
=
2
3
21.2 Hz, 4F, p-C6F5), À166.66 (br t, 3JFF = 21.2 Hz, 8F, m-C6F5). 11B{1H}
NMR (CD2Cl2): δ À16.65 (s). Anal. Calcd for C52H27BF20NOP: C,
56.60; H, 2.47; N, 1.27. Found: C, 56.92; H, 2.76; N, 1.24.
1H, CHMe2), 2.28 (d, JHP = 12.6 Hz, 3H, PCH3), 1.22 (d, JHH
=
=
3
3
6.6 Hz, 3H, CH3), 1.09 (d, JHH = 6.6 Hz, 3H, CH3), 1.00 (t, JHH
7.8 Hz, 3H, CH2CH3), 0.86 (ov m, 5H, CH3 and CH2CH3), 0.73 (d,
3JHH = 6.6 Hz, 3H, CH3). 13C{1H} NMR (CD2Cl2): δ 156.43 (s, dbf),
156.23 (s, dbf), 150.26 (br, C6F5), 146.95 (br ov m, C6F5 + aromatic C),
140.40 (br, C6F5), 138.46 (br, C6F5), 137.14 (br, C6F5), 135.94 (s,
aromatic C), 135.26 (br, C6F5), 131.78 (d, 3JCP = 9.0 Hz, aromatic C),
131.16 (d, 2JCP = 12.8 Hz, aromatic C), 130.14 (m, aromatic C), 128.76
[(dbf)MePhPdNHDipp][B(C6H5)4] (11). Compound 7 (0.180 g,
0.387 mmol) was dissolved in methanol (2 mL), to which HCl(aq) (1 N,
0.4 mL) was added. With stirring, NaBPh4 (0.135 g, 0.387 mmol) in
methanol (1 mL) was added and a white precipitate formed immedi-
ately. The solid was isolated by filtration, washed with methanol and
dried in vacuo to yield 11 (0.277 g, 91%). 1H NMR (CD2Cl2): δ 8.39
(d, 3JHH = 7.8 Hz, 1H, dbf), 8.10 (d, 3JHH = 7.2 Hz, 1H, dbf), 7.81 (t,
3JHH = 7.5 Hz, 1H, dbf), 7.62À7.49 (m, 8H, dbf + Ph), 7.36À7.24 (ov m,
10H, Ph), 7.15 (d, 3JHH = 7.8 Hz, 2H, m-Dipp), 6.97 (t, 3JHH = 6.0 Hz,
8H, m-Ph), 6.80 (t, 3JHH = 7.2 Hz, 4H, p-Ph), 3.40 (s, 1H, NH), 2.86 (sp,
3JHH = 6.6 Hz, 2H, CHMe2), 1.95 (d, 2JHP = 12.9 Hz, 3H, PCH3), 0.98 (d,
3
(s, aromatic C), 128.42 (s, aromatic C), 127.06 (d, JCP = 6.8 Hz,
aromatic C), 126.42 (s, aromatic C), 126.02 (s, aromatic C), 125.90 (s, aro-
matic C), 125.75 (s, aromatic C), 125.50 (s, aromatic C), 125.04 (s,
aromatic C), 122.67 (s, aromatic C), 122.49 (s, aromatic C), 112.18 (s,
aromatic C), 111.36 (s, aromatic C), 110.04 (s, aromatic C), 29.63
(s, CHMe2), 29.35 (s, CHMe2), 26.10 (s, CHMe2), 25.82 (s, CHMe2),
22.30 (d, 1JCP = 28.7 Hz, PCH3), 10.79 (s, CH2CH3), 4.49 (s, CH2CH3).
31P{1H} NMR (CD2Cl2): δ 32.66. 19F NMR (CD2Cl2): δ À133.05 (br,
3
3JHH = 6.6 Hz, 6H, CHMe2), 0.90 (d, JHH = 6.6 Hz, 6H, CHMe2).
1
13C{1H} NMR (CD2Cl2): δ 164.63 (q, 1:1:1:1, JBC = 49.1, ipso-
8F, o-C6F5), À163.67 (t, 3JFF = 19.8 Hz, 4F, p-C6F5), À167.52 (t, 3JFF
=
BPh4À), 156.78 (s, dbf), 156.62 (s, dbf), 148.30 (d, 3JCP = 3.0 Hz, dbf),
136.47 (s, dbf), 136.34 (d, 3JCP = 3.0 Hz, dbf), 132.40 (d, 3JCP = 11.3 Hz,
aromatic C), 130.90 (s, aromatic C), 130.72 (m, aromatic C), 130.24 (s,
aromatic C), 129.79 (s, aromatic C), 129.18 (s, dbf), 128.52 (d, 3JCP = 5.3
Hz, aromatic C), 126.80 (d, 3JCP = 7.5 Hz, aromatic C), 126.21 (m, Ph),
125.15 (m, aromatic C), 124.86 (d, 3JCP = 3.8 Hz, aromatic C), 122.50 (s,
aromatic C), 122.27 (s, Ph), 122.13 (s, dbf), 121.59 (s, aromatic C), 29.59
(s, CHMe2), 23.85 (d, JCP = 3.0 Hz, CHMe2), 10.06 (d, 1JCP = 70.9 Hz,
PCH3). 31P{1H} NMR (CD2Cl2): δ 37.95 (s). 11B{1H} NMR (CD2Cl2):
δ À6.53 (br s). Anal. Calcd for C55H53BNOP: C, 84.07; H, 6.80; N, 1.78.
Found: C, 84.34; H, 7.13; N, 1.81. Single crystals of 11 suitable for X-ray
analysis were obtained from a concentrated solution of the compound in
CH2Cl2 and pentane.
19.8 Hz, 8F, m-C6F5). 11B{1H} NMR (CD2Cl2): δ À16.67 (br s). Anal.
Calcd for C57H37BF20NOPZn: C, 55.25; H, 3.01; N, 1.13. Found: C,
55.61; H, 3.14; N, 1.30.
[{(dbf)MePhPdNMes}ZnEt][B(C6F5)4] (14). Complex 14 was
prepared by a procedure similar to that described for complex 13. Using
10 (0.13 g, 1.176 mmol) and excess diethylzinc, 14 was obtained as a
white solid (0.10 g, 73%). 1H NMR (C6D5Br): δ 7.95 (d, 3JHH = 7.8 Hz,
1H, dbf), 7.72 (d, 3JHH = 7.5 Hz, 1H, dbf), 7.43À7.04 (m, 10H, dbf +
Ph), 6.72 (s, 1H, m-Mes), 6.55 (s, 1H, m-Mes), 2.15 (s, 3H, o-Me), 2.04
(d, 3JHH = 2.0 Hz, 3H, o-Me), 1.63 (d, 2JHP = 12.3 Hz, 3H, PCH3), 1.47
(s, 3H, p-Me), 0.81 (t, 3JHH = 7.8 Hz, 3H, CH2CH3), 0.23 (q, 3JHH = 7.8
Hz, 2H, CH2CH3). 13C{1H} NMR (C6D5Br): δ 156.02 (s, dbf), 155.48
(s, dbf), 150.23 (br, C6F5), 147.05 (br, C6F5), 140.10 (br, C6F5), 138.28
[(dbf)MePhPdNHMes][B(C6H5)4] (12). Compound 12 was pre-
pared by a procedure analogous to that used for 11. Reaction of 9 (0.656 g,
1.55 mol) with NaBPh4 (0.530 g, 1.55 mmol) yielded 12 1.08 g (90%).
3
(br, C6F5), 137.65 (d, JCP = 7.5 Hz, aromatic C), 136.85 (br, C6F5),
135.50 (d, 3JCP = 4.0 Hz, aromatic C), 135.06 (br ov m, C6F5), 134.63
(ov s, aromatic C), 131.85 (ov s, aromatic C), 130.32 (d, 3JCP = 9.8 Hz,
aromatic C), 127.34 (d, 3JCP = 5.0 Hz, aromatic C), 125.22 (s, aromatic
C), 124.70 (d, 2JCP = 11.0 Hz, aromatic C), 122.75 (ov s, aromatic C),
1H NMR (CD2Cl2): δ 8.39 (d, 3JHH = 7.8 Hz, 1H, dbf), 8.10 (d, 3JHH
=
7.5 Hz, 1H, dbf), 7.80 (s, 1H, dbf), 7.61À7.45 (m, 8H, dbf + Ph), 7.33
(s, 9H, Ph), 6.96 (t, 3JHH = 7.5 Hz, 8H, m-Ph), 6.87 (s, 2H, m-Mes), 6.81
8066
dx.doi.org/10.1021/ic201139b |Inorg. Chem. 2011, 50, 8063–8072