Organometallics
Article
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7.24−7.18 (m, 2H, {Ar}Hmeta), 7.14−7.12 (m, 1H, {Ar}Hpara), 4.74
(br s, 2H, {Bn}CH2). 13C{1H} NMR (δ, CDCl3, 125 MHz, 298 K): 65
(s, 1C, {Bn}CH2), 118.54−114.46 (d, J = 10, 1C, {Ar}C3), 121.25−
121.15 (d, J = 12, 1C, {Ar}C5), 122.8 (br s, 1C, {Ar}C4, 127 (s, 1C,
{Bn}Cpara), 128 (br s, 2C, {Bn}Cortho), 128.7 (s, 2C, {Bn}Cmeta), 128.6
(br s, 4C, m-C in PPh2), 130 (s, 2C, p-C in PPh2), 130.8−130.6 (d, JCP
= 22 Hz, 4C, o-C in PPh2), 132−131.8 (d, JCP = 24 Hz, 2C, i-C in
PPh2), 138 (s, 1C, {Bn}Cipso), 139.3 (s, 1C, {Ar}C6), 140.98−140.75
m-C in PPh2) 130.74−130.57(d, JCP = 22.3 Hz, 4C, o-C in PPh2),
135.56−135.34 (dd, JCP = 19.25 Hz 2C, i-C in PPh2), 138.45 (s, 1C,
{Ar}Cpara), 140.95−140.82 (d, JCP = 17.5 Hz, 1C, {Ar}C1), 157.73−
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157.65 (m, 1C, {Ar}C6), 158.2 (br s, 1C, CHN). 31P{1H} NMR
(CDCl3, 202 MHz, 298 K): δ 110 (s, 1P). MS (ESI-HRMS, hexane)
(m/z): [M + H]+ (C25H27NOP) calcd 388.18248; found 388.18228;
diff 0.51 ppm.
κP,κC,κN-{2,6-(Ph2PO)(C6H3)(CHNBn)}NiBr (1). A solution of e
(0.30 g, 0.76 mmol) in 2 mL of toluene was slowly added to the
stirring suspension of NiBr2(CH3CN)x (0.34 g, 1.14 mmol) and NEt3
(0.16 mL, 1.14 mmol) in toluene (5 mL) at rt. The resulting dark
brown mixture was then heated for 2 h at 110 °C. Removal of the
solvent and purification of the solid residues by column chromatog-
raphy on SiO2 (eluents: 50:50 CH2Cl2:hexane) furnished 1 as an
(d, J = 17 Hz, 1C, {Ar}C1), 157.82−157.73 (d, J = 10 Hz, 1C,
{Ar}C2), 161.6 (br s, 1C, CHN). 31P{1H} NMR (CDCl3, 202 MHz,
298 K): δ 111 (s, 1P). MS (ESI-HRMS, hexane) (m/z): [M + H]+
(C26H23NOP) calcd 396.15118; found 396.15065; diff 1.33 ppm.
(3-((Diphenylphosphino)oxy)benzylidene)aniline (f). To a
solution of ClPPh2 (2.13 mL, 9.64 mmol) in THF (5 mL) was
added a solution of b (1.46 g, 7.42 mmol) and NEt3 (1.55 mL, 11.12
mmol) in THF (15 mL). The resulting mixture was stirred for 2 h.
Evaporation of the solvent and extraction of the residue with toluene
(4 × 10 mL) followed by filtration of the combined extracts and
evaporation gave the desired product f as a brown oil, (2.32 g, 82%).
1H NMR (CDCl3, 500 MHz, 298 K): δ 8.4 (br s, 1H, CHN),
7.7−7.26 (m, 13H, {Ph2P}Hortho, {PhN}Hpara, {Ph2P}Hpara, {Ph2P}
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orange solid (0.36 g, 88%). H NMR (CD3CN, 500 MHz, 298 K): δ
8.25−8.24 (d of ps-t, 4JHP = 3.8 Hz, 1H, CHN), 7.97−7.93 (m, 4H,
{Ph2P}Hortho), 7.64−7.60 (m, 2H, {Ph2P}Hpara), 7.56−7.52 (m, 4H
{Ph2P}Hmeta), 7.46−7.44 (m, 2H, {Bn}Hortho), 7.39−7.36 (m, 2H,
{Bn}Hmeta), 7.32−7.29 (m, 1H, {Bn}Hpara), 7.12−7.06 (m, 2H,
{Ar}Hmeta), 6.84−6.82 (dd, JHH = 1.4 Hz, 1H, {Ar}Hpara), 4.94 (br s,
2H, {Bn}CH2). 13C{1H} NMR (δ, (CD3)2CO, 125 MHz, 298 K): 60
(s, 1C, {Bn}CH2), 114.89−114.77 (d, J = 14, 1C, {Ar}C3), 122.8 (br s,
1C, {Ar}C5), 128.3 (br s, 2C, {Ar}C4 and {Bn}Cpara), 128.4 (br s, 2C,
H
meta, {PhN}Hortho), 7.25−7.21 (m, 2H, {PhN}Hmeta), 7.20−7.17 (m,
3H, {Ar}Hmeta and {Ar}Hpara). 13C{1H} NMR (δ, CDCl3, 125 MHz,
{Bn}Cortho), 130 (s, 2C, {Bn}Cmeta), 129.68−129.48 (t, JCP = 13 Hz,
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298 K): 118.84−118.76 (d, JCP = 11 Hz, 1C, {Ar}C5), 126 (s, 1C,
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{Ar}C3), 128 (br s, 2C, {Ar}Cpara and {PhN}Cpara), 129 (br s, 2C,
{PhN}Cortho), 130 (s, 2C, {PhN}Cmeta), 130.8−130.6 (d, JCP = 23 Hz,
4C, o-C in PPh2), 132.8−131.4 (m, 6C, m-C in PPh2 and p-C in
PPh2), 135.6−135.4 (m, 1C, {Ar}C2), 138 (s, 1C, { PhN }Cipso),
140.81−140.67 (d, JCP = 18 Hz, 2C, i-C in PPh2), 152 (s, 1C,{Ar}C1),
4C, m-C in PPh2), 133.07−132.76 (m, 6C, o-C in PPh2 and p-C in
PPh2), 133.64−133.33 (d, JCP = 39 Hz, 2C, i-C in PPh2), 139.11 (s,
1C, {Bn}Cipso), 149.2 (s, 1C, {Ar}C6), 153.54−153.24 (d, 2J = 37 Hz,
1C, {Ar}C1), 164.39−164.28 (d, 2J = 13 Hz, 1C, {Ar}C2), 175.7 (br s,
1C, CHN). 31P{1H} NMR ((CD3)2CO, 202 MHz, 298 K): δ 150
(s, 1P). Anal. Calcd for [C26H21NBrNiOP]: C, 58.59; H, 3.97; N, 2.63.
Found: C, 59.55; H, 3.98; N, 2.52.
157.95−157.87 (d, J = 10 Hz, 1C, {Ar}C6), 160 (br s, 1C, CHN).
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31P{1H} NMR (CDCl3, 202 MHz, 298 K): δ 112 (s, 1P). MS (ESI-
HRMS, hexane) (m/z): [M + H]+ (C25H21NOP) calcd 382.13553;
found 382.13516; diff 0.96 ppm.
κP,κC,κN-{2,6-(Ph2PO)(C6H3)(CHNPh)}NiBr (2). A solution of f
(2.32 g, 6.08 mmol) in 5 mL of toluene was slowly added to the
stirring suspension of NiBr2(CH3CN)x (2.74 g, 9.12 mmol) and NEt3
(1.27 mL, 9.12 mmol) in toluene (5 mL) at rt. The resulting dark
brown mixture was then heated for 3 h at 110 °C. Removal of the
solvent and purification of the solid residues by column chromatog-
raphy on SiO2 (eluents: 30:70 CH2Cl2:hexane) furnished complex 2 as
(3-((Diphenylphosphino)oxy)benzylidene)-tert-butyl (g). To
a solution of c (0.9 g, 5.09 mmol) and NEt3 (1.06 mL, 7.63 mmol) in
THF (15 mL) was added ClPPh2 (1.13 mL, 6.1 mmol). The resulting
mixture was stirred at 60 °C for 3 h and evaporated under pressure to
give an oily heterogeneous mixture. The desired product was extracted
from the salt with toluene (5 × 10 mL). Evaporation of the combined
extracts furnished g as a yellowish oil (m = 1.72 g, 94%). 31P{1H}
NMR (CD2Cl2, 202 MHz, 298 K): δ 112 (s, 1P).
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a brick-red powder (2.40 g, 76%). H NMR ((CD3)2CO, 500 MHz,
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298 K): δ 8.48−8.47 (d, JHP = 4 Hz, 1H, CHN), 8.09−8.05 (m,
4H, {Ph2P}Hortho), 7.92−7.89 (m, 1H, {PhN}Hpara), 7.66−7.62 (m,
2H, {Ph2P}Hpara), 7.58−7.55 (m, 4H {Ph2P}Hmeta), 7.51−7.37 (m,
2H, {PhN}Hortho), 7.30−7.27 (m, 2H, {PhN}Hmeta), 7.20−7.10 (m,
1H NMR (CDCl3, 500 MHz, 298 K): δ 8.01 (br s, 1H, CHN),
7.81−7.5 (m, 8H, {Ph2P}Hortho and {Ph2P}Hmeta), 7.4−7.3 (m, 2H,
{Ph2P}Hpara), 7.17−7.12 (m, 2H, {Ar}Hmeta) 7.03 (m, 1H,{Ar}Hpara),
1.16 (s, 9H, (CH3)3−CN). 13C{1H} NMR (δ, CDCl3, 125 MHz,
298 K): 29.8 (s, 3C, (CH3)3−CN), 57 (s, 1C, (CH3)3−CN), 118
and 120 (m, 2C, {Ar}Cmeta), 122 (br s, 1C, {Ar}C2), 128.66−128.60
(d, JCP = 7 Hz, 4C, m-C in PPh2) 129.9−129.7 (m, 2C, p-C in PPh2),
2H, {Ar}Hmeta), 6.96−6.94 (dd, JHP = 7.5 Hz, 1H, {Ar}Hpara).
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13C{1H} NMR (δ, (CD3)2CO, 125 MHz, 298 K): 115.42−115.31 (d,
3JCP = 14 Hz, 1C, {Ar}C5), 121.9 (s, 1C, {Ar}C3), 124 (br s, 2C, {Ar}
Cpara and {PhN}Cpara), 125.1 (br s, 2C, {PhN}Cortho), 130 (s, 2C,
{PhN}Cmeta), 128.49−127.91 (d, JCP = 72 Hz, 4C, o-C in PPh2),
129.8−129.5 (m, 6C, m-C in PPh2 and p-C in PPh2), 133.11−133.09
130.7−130.6 (d, 3JCP = 23 Hz, 4C, o-C in PPh2), 132−131.9 (d, JCP
=
=
(d, JCP = 2 Hz, 1C, {Ar}C2), 133.32−133.28 (d, JCP = 12 Hz, 1C, {
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10.5 Hz 2C, i-C in PPh2), 139 (s, 1C, {Ar}Cpara), 141−140.8 (d, 2JCP
PhN }Cipso), 149.86−149.29 (d, JCP = 72 Hz, 2C, i-C in PPh2),
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18 Hz, 1C, {Ar}C1), 157.73−157.65 (d, J = 10 Hz, 1C, {Ar}C6),
154.8 (s, 1C, CHN). 31P{1H} NMR (CDCl3, 202 MHz, 298 K): δ
110 (s, 1P). MS (ESI-HRMS, hexane) (m/z): [M + H]+
(C23H25NOP) calcd 362.16683; found 362.16689; diff −0.17 ppm.
(3-((Diphenylphosphino)oxy)benzylidene)cyclohexylamine
(h). To a solution of d (0.9 g, 4.33 mmol) and NEt3 (1.06 mL, 7.63
mmol) in THF (15 mL) was added ClPPh2 (0.96 mL, 5.2 mmol). The
resulting mixture was stirred at 60 °C for 4 h and evaporated under
pressure to give an oily heterogeneous mixture. The desired product
was extracted from the salt with toluene (4 × 10 mL). Evaporation of
the combined extracts furnished h as brown gel (m = 1.38 g, 82%).
1H NMR (CDCl3, 500 MHz, 298 K): δ 8.13 (br s, 1H, CHN),
7.49−7.46 (m, 4H, {Ph2P}Hortho), 7.41−7.7.39 (m, 2H, {Ph2P}Hpara),
7.37−7.32 (m, 4H {Ph2P}Hmeta), 7.17 and 7.1 (m, 3H, {Ar}Hmeta and
{Ar}Hpara), 7.05 and 7.03 (m, 1H, {Ar}H2) 1.7, 1.57, and 1.44 (m,
11H, {Cy}H). 13C{1H} NMR (δ, CDCl3, 125 MHz, 298 K): 24.9 (s,
2C, {Cy}Cmeta), 25.8 (s, 1C, {Cy}Cpara), 34.4 (s, 2C, {Cy}Cortho), 70
(s, 1C, {Cy}Cipso), 118.43−118.36 (d, JCP = 10 Hz, 1C, {Ar}C5),
120.66−120.56 (d, JCP = 12 Hz, 1C, {Ar}C2), 122.5 (s, 2C, p-C in
PPh2), 124.3 (s, 1C, 1C, {Ar}C3), 128.66−128.60 (d, JCP = 7 Hz, 4C,
154.44−154.13 (d, JCP = 38 Hz, 1C,{Ar}C1), 164.6−164.49 (d, J =
13 Hz, 1C, {Ar}C6), 175.7 (br d, JCP = 3 Hz, 1C, CHN). 31P{1H}
NMR ((CD3)2CO, 202 MHz, 298 K): δ 149 (s, 1P). Anal. Calcd for
[C25H19BrNNiOP]: C, 57.86; H, 3.69; N, 2.70. Found: C, 59.55; H,
4.03; N, 2.45.
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κP,κC,κN-{2,6-(Ph2PO)(C6H3)(CHNtBu)}NiBr (3). A solution of g
(1.72 g, 4.77 mmol) in 5 mL of toluene was slowly added to the
stirring suspension of NiBr2(CH3CN)x (1.37 g, 6.20 mmol) and NEt3
(1 mL, 7.16 mmol) in toluene (5 mL) at rt. The resulting red mixture
was then heated for 3 h at 110 °C. Removal of the solvent and
purification of the solid residues by column chromatography on SiO2
(eluents: 30:70 CH2Cl2:hexane) furnished 3 as an orange powder
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(1.71 g, 71.84%). H NMR ((CD3)2CO, 500 MHz, 298 K): δ 8.34−
8.33 (d, 4JHP = 4 Hz, 1H, CHN), 8.06−8.02 (m, 4H, {Ph2P}Hortho),
7.65−7.62 (m, 2H, {Ph2P}Hpara), 7.58−7.54 (m, 4H {Ph2P}Hmeta),
7.10 and 6.78 (m, 3H, {Ar}Hmeta and {Ar}Hpara), 1.56 (s, 9H, (CH3)3−
CN). 13C{1H} NMR (δ, (CD3)2CO, 125 MHz, 298 K): 30 (s, 3C,
(CH3)3−CN), 63 (s, 1C, (CH3)3−CN), 114 and 123 (m, 2C,
{Ar}Cmeta), 129.5−129.4 (d, JCP = 17 Hz, 1C, 1C, {Ar}C2), 133 (d, JCP
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dx.doi.org/10.1021/om500529e | Organometallics XXXX, XXX, XXX−XXX