Inorganic Chemistry
Article
Et
NaOH solution and drying over anhydrous Na SO afforded product 6
( phoscat)Pd(pdi). A mixture of (CH CN) PdCl (127 mg, 0.500
3 2 2
2
4
in pure form as a yellow oil (18 g, 64%). While 6 is a known
mmol) and N,N′-bis(mesityl)phenanthrene-9,10-diimine (222 mg,
compound, its 13C NMR data has not been reported. H NMR (500
38
1
0.500 mmol) was stirred in CH Cl (5 mL) at room temperature for
2
2
Et
MHz, CDCl ) δ 7.61 (dd, J = 8.2, 1.7 Hz, 1H), 7.38 (d, J = 1.7 Hz,
12 h. To the resulting dark red solution, ( phoscat)H (123 mg, 0.500
3
2
1
1
H), 6.73 (d, J = 8.2 Hz, 1H), 4.32 (q, J = 7.1 Hz, 2H), 1.69 (s, 6H),
mmol) was added followed by tert-butylamine (105 μL, 1.00 mmol).
After 12 h of stirring at the same temperature, the reaction mixture was
filtered to remove tert-butylamine hydrochloride, and the solvent was
removed under vacuum. The solid residue was recrystallized from a
minimum amount of dichloromethane and pentane (−35 °C) to give
.36 (t, J = 7.1 Hz, 3H); 13C NMR (125 MHz, CDCl ) δ 166.5 (q,
3
CO), 151.7 (aryl-C−O), 147.8 (aryl-C−O), 125.1 (aryl-C), 124.2
(
(
2
1
aryl-qC), 119.4 (C(CH ) ), 109.7 (aryl-C), 108.1 (aryl-C), 61.1
CH −O), 26.2 ((CH ) C), 14.7 (CH ); FTIR (neat) ν/cm 2991,
3 2
−1
2
3
2
3
31
937, 1714 st, 1622, 1607, 1495 st, 1445 st, 1371, 1281 st, 1213 st,
the product as a dark brown solid (260 mg, 66% yield). P NMR (162
1
096, 1020, 980, 839, 821; HRMS (ESI) m/z calcd for C H O (M +
MHz, CDCl ) δ 25.64; H NMR (500 MHz, CDCl ) δ 8.15 (d, J = 8.0
12
14
4
3
3
+
Na) 245.0790, found 245.0789.
2,2-Dimethylbenzo[1,3]dioxol-5-yl)methanol (7). Compound
was prepared from 2.77 g of 6 (12 mmol) and 1.97 g of LiAlH (52
Hz, 2H), 7.62 (appar t, J = 7.7 Hz, 2H), 7.37 (d, J = 8.3 Hz, 1H), 7.32
(d, J = 8.3 Hz, 1H), 7.12 (appar q, J = 7.3 Hz, 2H), 7.05 (s, 4H), 6.82−
6.74 (m, 2H), 6.38 (dd, J = 8.1 Hz, J = 5.0 Hz, 1H), 4.00−3.83 (m,
4H), 2.43 (s, 3H), 2.42 (s, 3H), 2.29 (s, 12H), 1.20 (t, J = 7.1 Hz,
(
7
4
3
9
mmol) in cold THF using a slightly modified literature procedure.
6H); 13C NMR (125 MHz, CDCl
) δ 169.5 (d, J = 3.2 Hz, aryl-C−O),
Standard aqueous workup afforded 2.0 g of 7 as a yellow oil (89%
yield). The H and C NMR spectra of 7 are in agreement with the
literature data.
3
1
13
164.7 (d, J = 20.8 Hz, aryl-C−O), 163.1 (CN), 162.9 (CN),
144.4 (mesityl-C−N), 144.3 (mesityl-C−N), 138.0 (mesityl-qC),
137.9 (mesityl-qC), 134.11 (pdi qC), 134.10 (pdi qC), 133.7 (pdi aryl-
C), 133.6 (pdi ary-C), 130.2 (mesityl-C), 129.69 (pdi aryl-C), 129.67
(pdi aryl-C), 129.1 (meistyl-qC), 129.0 (mesityl-qC), 128.63 (pdi aryl-
C), 128.56 (pdi aryl-C), 126.6 (pdi qC), 126.5 (pdi qC), 125.12 (pdi
aryl-C), 125.10 (pdi aryl-C), 122.2 (d, J = 11.1 Hz, cat aryl-C), 119.6
(d, J = 12.5 Hz, cat aryl-C), 116.4 (d, J = 19.4 Hz, cat aryl-C), 113.3
(d, J = 190.0 Hz cat aryl-qC), 61.6 (d, J = 4.6 Hz, C−O), 21.65
5
-(Bromomethyl)-2,2-dimethylbenzo[1,3]dioxole (8). To a
cold (0 °C) solution of dioxole 7 (2.0 g, 11.1 mmol) and pyridine
0.95 mL, 11.6 mmol) in anhydrous Et O (21 mL) was added
(
2
dropwise a solution of PBr (0.41 mL, 4.3 mmol) in Et O (20 mL).
3
2
The mixture was stirred for 2 h at room temperature and then
quenched with ice−water (40 mL). The organic layer was separated,
washed with ice-cold 1 N HCl solution (5 mL) and dried with
anhydrous Na SO . The removal of solvent by rotary evaporation
yielded benzyl bromide 8 as a colorless oil (2.2 g, 81%), which was
sufficiently pure to be used directly in the next step. H NMR (400
MHz, CDCl ) δ 6.81 (d, J = 7.9 Hz, 1H), 6.78 (s, 1H), 6.65 (d, J = 7.9
Hz, 2H), 4.46 (s, 2H), 1.67 (s, 6H); C NMR (125 MHz, CDCl ) δ
1
1
(mesityl-CH
(mesityl-CH
), 21.64 (mesityl-CH
), 16.7 (d, J = 6.9 Hz, CH
), 19.1 (mesityl-CH
), 19.0
2
4
3
3
3
−
1
); FTIR (KBr) ν/cm
3
3
1
3543, 3478, 3417, 3247, 2972, 2906, 2862, 1637, 1615, 1497, 1470,
1352, 1308 st, 1050, 1023; UV−vis−NIR (CH Cl
) λmax/nm (ε/M−
1
3
2 2
13
−1
cm ) 984 (8210); HRMS (ESI) m/z calcd for C42
H
43
N
O
2
PPd (M +
3
5
+
48.1 (aryl-C−O), 148.0 (aryl-C−O), 131.1 (aryl-C), 122.5 (aryl-qC),
Na) 815.1858, found 815.1871.
Et
18.8 (aryl-qC), 109.6 (aryl-C), 108.4 (aryl-C), 35.0 (CH −Br), 26.2
( Bnphoscat)Pd(pdi). This complex was prepared in a manner
2
−1
−1
Et
Et
(
(CH ) C); FTIR (neat) ν/cm FTIR (KBr) ν/cm 2989, 2935,
similar to that described for ( phoscat)Pd(pdi) using ( Bnphoscat)H
2
3
2
1
600, 1494 st, 1448, 1257 st, 1209 st, 979, 835; HRMS (CI, positive)
(135 mg, 0.500 mmol). Recrystallization from THF and pentane (−35
+
31
m/z calcd for C H BrO (M) 241.9942, found 241.9953
°C) afforded the product as a brown solid (313 mg, 77%). P NMR
10
11
2
1
Diethyl ((2,2-Dimethylbenzo[1,3]dioxol-5-yl)methyl)-
phosphonate (9). A solution of benzyl bromide 8 (11 g, 45
mmol) in neat triethyl phosphite (7.8 mL, 45 mmol) was refluxed for
(162 MHz, CDCl
3
) δ 29.5; H NMR (500 MHz, CDCl
3
) δ 8.16 (d, J
= 8.3 Hz, 2H), 7.59 (appar t, J = 7.3 Hz, 2H), 7.33 (d, J = 8.4 Hz, 1H),
7.30 (d, J = 8.4 Hz, 1H), 7.09 (appar td, J = 8.3 Hz, 3.3 Hz, 2H), 7.04
(s, 4H), 6.35 (s, 1H), 6.34 (d, J = 8.0 Hz, 1H), 6.26 (d, J = 8.0 Hz,
1H), 3.94 (m, 4H), 2.96 (d, J = 20.8 Hz, 2H), 2.42 (s, 3H), 2.41 (s,
1
2 h. Upon the completion of the reaction, the obtained crude material
was purified by silica gel column chromatography (EtOAc/hexanes,
4
CDCl , major) δ 28.0; H NMR (500 MHz, CDCl ) δ 6.66−6.59 (m,
31
13
2:58) to afford 9 as a yellow oil (11 g, 81%). P NMR (162 MHz,
3H), 2.29 (s, 12H), 1.19 (t, J = 7.2 Hz, 6H); C NMR (125 MHz,
1
CDCl ) δ 165.6 (aryl-C−O), 164.9 (aryl-C−O), 161.77 (CN),
3
3
3
3
6
1
1
H), 3.98 (appar q, J = 7.3 Hz, 4H), 3.02 (d, J = 11.0 Hz, 2H), 1.61 (s,
161.70 (CN), 144.73 (mesityl-C−N), 144.68 (mesityl-C−N),
137.49 (mesityl-qC), 137.46 (mesityl-qC), 133.61 (pdi qC), 133.59
(pdi qC), 132.7 (pdi aryl-C), 130.00 (pdi aryl-C), 129.97 (pdi-aryl-C),
129.5 (mesityl-qC), 129.34 (pdi aryl-C), 129.31 (pdi-arylC), 128.0
(pdi-arylC), 126.8 (pdi-qC), 124.9 (pdi-arylC), 120.0 (d, J = 9.3 Hz,
cat qC), 119.3 (d, J = 6.0 Hz, cat aryl-C), 118.1 (d, J = 6.5 Hz, cat aryl-
C), 116.2 (d, J = 2.3 Hz, cat aryl-C), 62.3 (d, J = 6.9 Hz, C−O), 33.7
H), 1.21 (appar t, J = 7.3 Hz, 6H); 13C NMR (125 MHz, CDCl ) δ
3
47.8 (d, J = 3.2 Hz, aryl-C−O), 146.7 (d, J = 3.2 Hz, aryl-C−O),
24.4 (d, J = 9.7 Hz, aryl-qC), 122.5 (d, J = 7.9 Hz, aryl-C), 118.1
(
C(CH ) ), 110.4 (d, J = 6.0 Hz, aryl-C), 108.3 (d, J = 3.2 Hz, aryl-C),
3 2
6
2.3 (d, J = 6.9 Hz, CH −O), 34.1 (d, J = 139.2 Hz, CH −P), 26.0
−1
2
2
(
CH ), 16.6 (d, J = 6.0 Hz, CH ); FTIR (neat) ν/cm 2988, 2911,
3
3
1
650, 1609, 1498 st, 1380, 1231 st, 1048 st, 957 st 825 st; HRMS
(d, J = 137.3 Hz, CH
19.07 (mesityl-CH ), 16.7 (d, J = 6.5 Hz, CH
3570, 3541, 3470, 3405, 2958, 2900, 1635, 1597, 1436, 1357, 1310,
2
−P), 21.6 (mesityl-CH
3
), 19.08 (mesityl-CH ),
); FTIR (KBr) ν/cm
3
3
+
−1
(
ESI) m/z calcd for C H O P (M + Na) 323.1024, found 323.1028.
3
14
21
5
4
-(Diethoxyphosphorylmethyl)benzene-1,2-diol,
(EtBnphoscat)H . To a solution of 9 (2.5 g, 8.0 mmol) in dry CH Cl
−1
−1
2
2
2
1025 st, 954; UV−vis−NIR (CH Cl ) λmax/nm (ε/M cm ) 1298
2
2
+
(
200 mL) was added BCl (20 mL, 1 M in hexanes) at −78 °C under a
(9360); HRMS (ESI) m/z calcd for C H N O PPd (M + Na)
3
43 45 2 5
nitrogen atmosphere. The mixture was stirred at the same temperature
for 12 h and then allowed to warm slowly to room temperature and
quenched with MeOH (4 mL). The solvent was removed in vacuo to
give an oily residue, which was purified by silica gel column
829.2015, found 829.2024.
t
(cat Bu )Pd(pdi). This complex was prepared in a manner similar
2
Et
to that described for ( phoscat)Pd(pdi) using 3,5-di-tert-butylcatechol
(111 mg, 0.500 mmol). Recrystallization from dichloromethane and
chromatography (gradient MeOH/CHCl , 7:93) to afford product
pentane (−35 °C) afforded the product as a dark brown solid (360
3
Et
31
1
(
Bnphoscat)H as a white solid (1.5 g, 71%). P NMR (162 MHz,
mg, 73%). H NMR (500 MHz, CDCl ) δ 8.20 (appar t, J = 7.5 Hz,
2
3
1
CDCl ) δ 29.5; H NMR (500 MHz, CDCl ) δ 8.18 (s, 1H), 7.01 (s,
2H), 7.57−7.50 (m, 2H and m,1H), 7.30 (d, J = 8.3 Hz, 1H), 7.11−
7.05 (appar quint, J = 8.0 Hz 2H), 7.04 (s, 2H), 7.00 (s, 2H), 6.42, (br
s, 1H), 6.39 (s, 1H), 2.44 (s, 3H), 2.42 (d, 3H), 2.31 (s, 6H), 2.30 (s,
3
3
1
4
H), 6.91 (s, 1H), 6.66 (d, J = 8.6, 1H), 6.55 (d, J = 8.6, 1H), 4.02 (m,
H), 3.06 (d, J = 20.5 Hz, 2H), 1.26 (t, J = 7.2 Hz, 6H); 13C NMR
6H), 1.17 (s, 9H), 1.02 (s, 9 H); 13C NMR (125 MHz, CDCl ) δ
(
125 MHz, CDCl ) δ 145.1 (d, J = 3.2 Hz, aryl-C−O), 140.0 (d, J =
3
3
3
.6 Hz, aryl-C−O), 122.0 (d, J = 9.3 Hz, aryl-qC), 121.8 (d, J = 6.94
Hz, aryl-C), 116.8 (d, J = 6.0 Hz, aryl-C), 115.6 (d, J = 3.2 Hz, aryl-C),
3.2 (d, J = 7.4 Hz, CH −O), 33.6 (d, J = 140.6 Hz, CH −P), 16.7 (d,
167.5 (aryl-C−O), 164.0 (aryl-C−O), 159.3 (CN), 158.6 (CN),
145.50 (mesityl-C−N), 145.48 (mesityl-C−N), 142.8 (cat aryl-qC),
138.0 (cat aryl-qC), 136.9, (mesityl-qC) 136.8 (mesityl-qC), 132.7
(pdi qC), 132.5 (pdi qC), 131.0 (pdi aryl-C), 130.9 (pdi aryl-C), 130.3
(mesityl-qC), 129.9 (mesityl-qC), 129.8 (mesityl-C), 129.7 (mesityl-
C), 128.8 (pdi aryl-C), 128.7 (pdi aryl-C), 127.24 (pdi qC), 127.20
6
2
2
−1
J = 6.0 Hz, CH ); FTIR (KBr) ν/cm 3395 br, 3170 br, 2988, 1612,
3
1
536, 1448, 1365, 1274, 1160, 1010, 860; HRMS (ESI) m/z calcd for
+
C H O P (M + Na) 283.0711, found 283.0704.
1
1
17
5
C
Inorg. Chem. XXXX, XXX, XXX−XXX