Inorganic Chemistry
Article
1
2
1
H, CH ), 1.27 (t, J = 6, 6H, Is Me), 1.21−1.20 (br m, 6H, Is Me),
At −70 °C, from integration of the H NMR Me signals, the C :C
2
2
1
.17−1.16 (m, 6H, Is Me), 0.84 (d, J = 7, 6H, DuPhos i-Pr Me), 0.78
ratio was ca. 1.3:1.
+
(
d, J = 7, 6H, DuPhos i-Pr Me), 0.64 (d, J = 7, 6H, DuPhos i-Pr Me),
HRMS m/z calcd for C H P Cu (M ): 727.2942. Found: m/z
4
0
60 4
1
3
1
31
1
0
.57 (d, J = 7, 6H, DuPhos i-Pr Me). C{ H} NMR (CD Cl , 25
727.2941. P{ H} NMR (CD Cl , 25 °C): δ 22.8 (br, DuPhos),
2 2
1
2
2
°C): δ 152.5 (quat Is), 152.3 (quat Is), 152.1 (t, J = 9, quat Is), 142.0
(t, J = 24, quat DuPhos Ar), 135.6 (t, J = 3, DuPhos Ar CH), 131.4
(DuPhos Ar CH), 124.0 (m, ipso quat Is), 123.0 (t, J = 6, Is CH),
−29.5 (br, PhHP(CH ) PHPh), −145 (septet, J = 710, PF ). H
2
2
6
NMR (CD Cl , 25 °C): δ 7.70−7.65 (m, 3H), 7.56−7.45 (m, 11H),
2
2
5.53 (br d, J = 324, C ′ PH), 5.43 (br dm, J = 333, C PH), 5.34 (br
2
2
1
18.9 (br, quat NCMe), 53.0 (t, J = 9, DuPhos CH), 52.5 (t, J = 9,
ddm, J = 318, 24, C PH), 5.23 (d of apparent sextets, J = 304, 8, C
1
1
DuPhos CH), 35.1 (d, J = 2, CH), 33.9 (d, J = 12, CH), 32.8 (CH2),
3
2
Me), 21.2 (br, Me), 20.2 (t, J = 5, Me), 10.6 (d, J = 21, P-Me), 9.8 (d,
J = 20, P-Me), 2.1 (NCMe).
PH), 2.78−2.66 (m, 1H), 2.59−2.52 (septet, J = 6, 2H, DuPhos CH),
2.52−2.40 (m, 2H, CH ), 2.37−2.23 (m, 5H (2H CH , 1H i-Pr CH,
2.0 (t, J = 8, CH), 29.6 (CH ), 29.2 (CH), 25.42 (Me), 25.39 (Me),
2
2
2
5.23 (Me), 25.19 (Me), 24.9 (Me), 24.4 (t, J = 5, Me), 24.1 (m,
2H DuPhos CH )), 2.16−2.08 (m, 3H, i-Pr CH), 1.94−1.87 (m, 2H,
2
DuPhos CH ), 1.67−1.60 (qd, J = 13, 6, 2H, DuPhos CH ), 1.52−
2
2
1
.45 (qd, J = 6, 13, 2H, DuPhos CH ), 1.29−1.23 (m, 2H, DuPhos
2
[
Cu((R,R)-Me-FerroLANE)(PHMe(Is))][PF ] (7). To a slurry of
6
CH), 1.19 (d, J = 7, 6H, C Me), 1.06−1.02 (br), 1.03 (d, J = 7, 6H,
2
[
Cu(NCMe) ][PF ] (85 mg, 0.23 mmol) in 2 mL of THF was added
4 6
C i-Pr Me), 1.0−0.7 (very br), 0.38 (br), 0.25 (d, J = 7, 6H, C i-Pr
2
2
a solution of (R,R)-Me-FerroLANE (95 mg, 0.23 mmol) in 2 mL of
THF, and the resulting orange solution was stirred for 20 min. A
solution of PHMe(Is) (58 mg, 0.23 mmol) in 2 mL of THF was
added, and the resulting solution was stirred for 10 min, filtered
through Celite, and concentrated under vacuum to give an orange
powder (149 mg, 92%). This material was a mixture of diastereomers
13
1
Me), 0.15 (d, J = 7, 6H, C i-Pr Me). C{ H} NMR (CD Cl , 25
2
2
2
°
C): δ 142.0 (tt, J = 25, 4, quat DuPhos), 134.6 (br), 134.3 (t, J = 4,
Ar CH), 132.9 (d, J = 11, Ar CH), 132.1 (t, J = 6, Ar CH), 131.7 (d, J
11, Ar CH), 131.0−130.7 (m, quat Ar), 130.9 (Ar CH), 130.5 (Ar
=
CH), 130.4−130.3 (br, Ar CH), 130.3 (Ar CH), 130.1 (Ar CH),
1
5
29.6−129.5 (m, Ar CH), 129.3 (d, J = 8, Ar CH), 53.0−52.0 (br),
2.0−50.0 (br), 51.7 (t, J = 9, DuPhos CH), 49.8 (t, J = 9, DuPhos
3
1
1
1
A and B (∼2:1) from P{ H} and H NMR integration, but only one
1
13
set each of H and C NMR signals was observed at room
temperature, except for the PH resonances. The NMR spectra were
concentration-dependent, presumably due to faster intermolecular
exchange at higher concentrations.
CH), 32.8 (very br), 31.6 (DuPhos CH ), 31.4 (t, J = 8, i-Pr CH),
2
2
8.8 (DuPhos CH ), 28.4 (i-Pr CH), 23.8 (t, J = 4, Me), 23.6−23.3
2
(
m, CH , C isomer), 23.5 (br m, Me), 23.1 (tt, J = 19, 4, CH ),
2
1
2
2
1.8−21.5 (m, CH ,C isomer), 21.0−20.4 (br), 20.3 (t, J = 3, Me),
+
2
1
HRMS m/z calcd for C H P FeCu(M ): 727.2475. Found:
3
8
59 3
1
9.9 (br m, Me), 19.0 (very broad).
3
1
1
7
27.2474. P{ H} NMR (CDCl , 25 °C, 0.1 M): δ 10.6
31
1
3
P{ H} NMR (CD Cl , −70 °C): δ 23.3 (br, DuPhos), 19.4 (br,
2
2
(
FerroLANE), −90.5 (PHMe(Is)), −93.1 (PHMe(Is)), −142.8
septet, J
DuPhos), −28.5 to −33.2 (br, PhHP(CH ) PHPh), −144.8 (septet, J
31 1
2 2
(
= 713, PF ). P{ H} NMR (CDCl , 25 °C, 0.01 M):
1
P−F
6
3
=
713, PF ). H NMR (CD Cl , −70 °C, selected data): δ 5.48 (br d,
6
2
2
δ 11.0 (d, J = 113, FerroLANE), −90.3 (t, J = 113, PHMeIs), −92.9
J = 319, C ′ PH), 5.38 (br d, J = 340, C PH), 5.31 (br dd, J = 318, 25,
1
2
2
(
t, J = 107, PHMeIs), −142.8 (septet, J
= 713, PF ). H NMR
P−F 6
C PH), 5.06 (br dm, J = 312, C PH), 1.19 (d, J = 6, 6H, C Me),
1
1
2
(
CDCl , 25 °C, 0.1 M): δ 7.09 (2H, Is Ar), 5.86 (br dm, J = 321, 1H,
3
1
.02 (d, J = 6, 3H, C Me), 0.96 (d, J = 6, 6H, C Me), 0.92 (m, 6H, 2
1
2
P−H), 4.68 (2H, Cp), 4.43 (2H, Cp), 4.28 (2H, Cp), 4.24 (2H, Cp),
C Me), 0.64 (d, J = 6, 3H, C Me), 0.30 (d, J = 6, 3H, C Me), 0.19
1
1
1
3
.36 (2H, CH), 2.89−2.87 (m, 4H, CH), 2.34−2.31 (br m, 3H, CH
(
d, J = 6, 3H, C Me), 0.14 (d, J = 6, 6H, C Me), 0.082 (d, J = 6, 6H,
1
2
and CH ), 1.93 (3H, CH ), 1.49 (very broad, 7H, Me), 1.34−1.23
2
2
C Me), 0.038 (d, J = 6, 3H, C Me), −0.16 (d, J = 6, 3H, C Me).
[Cu((R,R)-i-Pr-DuPhos)(PhHP(CH
slurry of [Cu(NCMe) ][PF ] (85 mg, 0.23 mmol) in 5 mL of
CH Cl was added a solution of (R,R)-i-Pr-DuPhos (117 mg, 0.28
2
1
1
(
overlapping signals, 30H, Is and phospholane Me, plus 2H CH ),
2
1
3
1
2
)
3
PHPh)][PF
6
] (9). To a
0
2
.88−0.86 (3H, Me). All signals were broad. C{ H} NMR (CDCl ,
3
4
6
5 °C, 0.1 M): δ 151.9 (quat Is), 151.4 (br m, quat Is), 151.3 (br m,
2
2
quat Is), 122.4−122.3 (br m, Is Ar CH), 76.1 (t, J = 11, Cp CH), 74.6
mmol, 1.2 equiv) in 2 mL of CH Cl , and the resulting solution was
2
2
(
Cp CH), 72.0 (Cp CH), 71.7 (Cp CH), 70.6 (br, quat Cp), 36.0 (t,
stirred for 20 min. A solution of PhHP(CH ) PHPh (82 mg, 0.32
mmol, 1.4 equiv) in 2 mL of CH Cl was added, and the resulting
2
3
J = 13, CH), 35.7 (CH ), 35.6 (CH ), 34.3−34.0 (br m, CH), 33.9
2
2
2
2
(
CH), 25.3 (Me), 24.8 (Me), 23.9 (Me), 23.8 (Me), 21.4 (t, J = 9,
1
solution was stirred for 10 min, filtered through Celite, and placed
under vacuum to give a white solid (224 mg, 110%). The solid was
washed with ether and pentane in an attempt to remove impurities,
but they were not soluble. The ether extract was stored at −20 °C,
and after 2 weeks, long, X-ray quality white needles had formed.
HRMS m/z calcd for C H P Cu (M ): 741.3098. Found: m/z
41.3094. P{ H} NMR (CD Cl , 25 °C): δ 20.0 (br m, i-Pr-
Me), 14.8 (Me). The P-Is quaternary aryl signal was not observed. H
NMR (THF-d , 25 °C, 0.01 M): δ 7.19 (br d, J = 3, 2H, Is Ar), 6.06−
8
6
.01 (overlapping br dq, 1H, J
= 329, 7; J
= 330, 6), 4.72 (2H,
P‑HA
P‑HB
Cp), 4.47 (2H, Cp), 4.46 (overlapping, 2H, Cp), 4.39 (2H, Cp),
3
.51−3.49 (br m, 2H, CH), 3.00 (br m, 3H, CH), 2.93−2.89 (m, 1H,
+
CH), 2.31 (br m, 3H, CH and CH ), 2.15 (br, 2H), 1.93 (br m, 3H,
41 62 4
2
3
1
1
7
CH ), 1.51 (8H), 1.38 (d, 9H, J = 7, Me and CH ), 1.34−1.32
2 2
2
2
DuPhos), −37.7 (br m, PhHP(CH ) PHPh), −145 (sp, J = 711,
(
7
overlapping d, 9H, Me and CH ), 1.26−1.24 (overlapping d, J = 7, 7,
2
3
P−F
2
1
PF ). H NMR (CDCl , 25 °C): δ 7.85−7.80 (m, 3H), 7.65−7.25 (br
H, Me), 0.89−0.87 (3H, Me).
6
3
m, 11H), 5.44 (br d, J = 303, 2H, C ′ PH), 5.37 (br dm, J = 318, 5,
[
Cu((R,R)-i-Pr-DuPhos)(PhHP(CH ) PHPh)][PF ] (8). To a
2
2
2
6
2
H, C PH), 5.29−5.19 (br dm, J ∼ 305, 2H, C PH), 2.48−2.41 (br
slurry of [Cu(NCMe) ][PF ] (85 mg, 0.23 mmol) in 5 mL of
2
1
4
6
m, 4H), 2.35−2.30 (br m, 6H), 2.10−2.02 (br m, 6H), 1.65−1.61 (br
ether was added a solution of (R,R)-i-Pr-DuPhos (117 mg, 0.28
mmol, 1.2 equiv) in 2 mL of ether, and the resulting slurry was stirred
for 20 min. A solution of PhHP(CH ) PHPh (80 mg, 0.32 mmol, 1.4
equiv) in 2 mL of ether was added, and the resulting slurry was stirred
for 10 min. The ether was decanted, and the white solid was washed
m, 4H), 1.52 (br, 2H), 1.24 (d, J = 7, 6H, Me), 1.07−1.01 (br m),
0
.94−0.84 (br m), 0.87 (d, J = 7, 6H, Me), 0.72−0.68 (br m), 0.42−
2
2
0
.38 (br m), 0.26 (d, J = 7, 6H, Me), −0.01 (d, J = 7, 6H, Me).
1
3
1
C{ H} NMR (CDCl
, 25 °C): δ 142.0 (tt, J = 25, 4, quat DuPhos),
3
(
3 × 2 mL) with fresh ether before being dried under vacuum to yield
135.0−134.6 (br m), 134.5 (Ar CH), 134.4 (Ar CH), 134.3 (t, J = 4,
Ar CH), 133.2 (br), 133.0 (t, J = 5, Ar CH), 132.6 (d, J = 10, Ar CH),
131.7 (m, Ar CH), 131.5 (Ar CH), 131.4 (m, Ar CH), 130.9 (Ar
CH), 130.6 (d, J = 20, Ar CH), 130.5 (d, J = 21, Ar CH), 129.7 (m,
Ar CH), 129.4 (d, J = 8, Ar CH), 53.5−52.7 (br), 52.3 (t, J = 9,
DuPhos CH), 50.6−50.4 (br m), 50.2 (t, J = 9, DuPhos CH), 33.0−
a white solid (169 mg, 84%). The fluxional behavior of the C isomer
1
at room temperature made spectral assignments difficult, with several
broad 1H NMR signals. From the PH region of the H NMR
spectrum, there appeared to be three isomers, two C and one C , in a
1
2
1
ratio of approximately 1(C ′):3.3(C ):5(C ). However, most of the
2
2
1
1
other well-resolved H NMR signals at room temperature could be
32.0 (very br), 32.0 (DuPhos CH ), 31.8 (t, J = 8, i-Pr CH), 29.0
2
assigned to the major C isomer. Similarly, most of the well-resolved
C{ H} NMR signals at room temperature could be assigned to the
(DuPhos CH ), 28.8 (i-Pr CH), 25.5 (br m, CH ), 25.0−24.9 (br m,
2
2
2
13
1
minor CH ), 24.6 (t, J = 4, Me), 24.5−24.2 (br), 23.1, 20.9 (CH ),
2
2
major C isomer, but several broad peaks and a few sharp ones,
20.8 (t, J = 3, Me), 20.7 (t, J = 3, Me), 19.4 (br, Me). Note: in
contrast to 8, peak overlap in the PH region precluded determination
2
especially in the aryl region, are presumably due to the other isomers.
H
Inorg. Chem. XXXX, XXX, XXX−XXX