5
468 Organometallics, Vol. 23, No. 23, 2004
Garc ´ı a-Yebra et al.
2 3 5
Complex 15. A mixture of [IrBr (η -C H )(COD)] (13; 204.0
mg, 0.42 mmol), 7a (156.0 mg, 0.42 mmol), and THF (2 mL)
was stirred for 1 h at room temperature, at which point a clear
orange-brown solution was obtained. After removal of the
3
MHz, 25 °C, CD
2
Cl
2
; for numbering of atoms see Scheme 4
3
and Table 3): δ -0.01 (d, 3 H, J(H,H) ) 6.8 Hz, CH(CH
3
)
2
),
), 2.16-2.40 (m, 1 H,
3 2
CH(CH ) ), 2.90 (d, 1 H, J(H,H) ) 9.7 Hz, 1A-Ha), 3.27 (d, 1
3
3 2
0.84 (d, 3 H, J(H,H) ) 7.0 Hz, CH(CH )
3
3
3
H, J(H,H) ) 6.15 Hz, 1A-Hs), 4.42 (dd, 1 H, J(H,H) ) 6.6,
solvent under vacuum, crystallization of the residue from CH
Cl /diethyl ether yielded yellow crystals of the title complex,
which were washed twice with diethyl ether and dried. Yield:
2
-
2
2
3
J(H,H) ) 9.2 Hz, 5-H), 3.79 (dd, 1 H, J(H,H) ) 9.2, J(H,H)
10.0 Hz, 5-H), 5.10-5.35 (m, 1 H, 2A-H), 5.74 (d, 1 H,
J(H,H) ) 10.9 Hz, 3A-H), 5.83-5.97 (m, 1 H, 4-H), 6.26 (dd,
2
)
3
1
182.0 mg (58%). H NMR (500 MHz, 25 °C, C
6 6
D ; numbering
3
1
H, J(H,P) ) 8.85, J(H,H) ) 10.9 Hz, Ar H), 6.75-6.90 (m, 2
of atoms see Scheme 4 and Table 3): δ 0.22 (d, 3 H, J(H,H)
3
H, Ar H), 6.91-7.06 (m, 4 H, Ar H), 7.07-7.28 (m, 6 H, Ar H),
) 7.4 Hz, CH(CH
(CH ), 2.45 (dqq, 1 H, J(H,H) ) 3.35, J(H,H) ) 7.0, J(H,H)
) 7.0 Hz, CH(CH
3 2
) ), 0.54 (d, 3 H, J(H,H) ) 7.35 Hz, CH-
3
3
3
7
.26-7.38 (m, 1 H, Ar H), 7.40-7.63 (m, 4 H, Ar H), 8.13-
3 2
)
3
1
1
3
8.22 (m, 1 H, 11-H). P { H} NMR (202.46 MHz, 25 °C, CD
2
-
):
3 2
) ), 3.24 (d, 1 H, J(H,H) ) 6.7 Hz, 1A-Hs),
1
3
1
3
2
Cl
2
): δ -16.0 (s). C{ H} NMR (125.77 MHz, 25 °C, CD
), 28.9 (s, CH(CH ), 34.4 (s,
C-1A), 66.6 (s, C-3A), 68.4 (s, C-5), 72.0 (s, C-4), 83.6 (s, C-2A),
2
Cl
2
3.54 (d, 1 H, J(H,H) ) 7.4 Hz, 1A-Hs), 3.58 (dd, 1 H, J(H,H)
3
3
δ 13.4, 19.5 (both s, CH(CH
3
)
2
3
)
2
) 8.7, J(H,H) ) 10.7 Hz, anti 5-H), 3.67 (d, 1 H, J(H,H) )
3
2
10.0 Hz, 1A-Ha), 3.74 (dd, 1 H, J(H,H) ) 6.7, J(H,H) ) 8.7
1
3
1
26.4 (d, J(C,P) ) 59.7 Hz, ipso-C
6
H
5
P), 126.9, 128.6, 128.8,
Hz, syn 5-H), 3.93 (m, 1 H, 2A-H), 4.20 (d, 1 H, J(H,H) )
3
3
(
all s, allyl-bound Ar CH), 129.0, 129.0, 129.1 (all s, Ar CH
10.7 Hz, allylic 1A-Ha), 6.23 (ddd, 1 H, J(H,H) ) 3.35, J(H,H)
1
3
3
PHOX), 129.6 (d, J(C,P) ) 55.1 Hz ipso-C
6
H
5
P), 129.9 (d,
) 6.7, J(H,H) ) 10.7 Hz, 3-H), 6.48 (dd, 1 H, J(H,H) ) 8.7,
2
3
3
3
J(C,P) ) 9.8 Hz, Ar CH PHOX), 130.7 (d, J(C,P) ) 28.4 Hz,
J(H,P) ) 11.7 Hz, 8-H), 6.70 (dd, 2 H, J(H,H) ) 7.7, J(H,P)
1
4
3
C-6), 130.9 (d, J(C,P) ) 42.0 Hz, C-7), 131.7 (d, J(C,P) ) 7.8
6 5
) 9.7 Hz, o-C H ), 6.75 (tt, 1 H, J(H,P) ) 1.0, J(H,H) ) 7.7
4
3
3
Hz, Ar CH PHOX), 131.9 (d, J(C,P) ) 1.95 Hz, Ar CH PHOX),
Hz, 9-H), 6.80 (ddd, 2 H, J(H,P) ) 2.35, J(H,H) ) 7.7, J(H,H)
5
3
1
8
32.0 (d, J(C,P) ) 1.95 Hz, Ar CH PHOX), 133.0 (d, J(C,P) )
.8 Hz, Ar CH PHOX), 133.2 (d, J(C,P) ) 7.8 Hz, Ar CH
) 8.0 Hz, m-C
6
H
5
), 6.89 (tt, 1 H, J(H,P) ) 1.35, J(H,H) )
6.7 Hz, p-C
6
H
5
4
), 6.92-7.08 (m, 6 H, 4-H, o-, m-, and p-C ),
8.00 (dd, 1 H, J(H,P) ) 4.0, J(H,H) ) 8.0 Hz, 11-H). P{ H}
6 5
H
3
31
1
PHOX), 133.2 (d, J(C,P) ) 3.9 Hz, Ar CH PHOX), 140.0 (s,
allylic ipso-C
3
13
1
6
H
5
), 164.4 (d, J(C,P) ) 4.9 Hz, C-2). MS (FAB):
NMR (202.45 MHz, 25 °C, C
(125.77 MHz, 25 °C, C ): δ 12.6 (s, CH(CH
(CH ), 28.2 (s, CH(CH ), 40.0, 41.7 (both s, C-1A), 67.7 (s,
C-5), 73.3 (s, C-4), 84.6 (s, C-2A), 128.0 (d, J(C,P) ) 24.4 Hz,
6
D
6
): δ 5.37 (s). C{ H} NMR
+
+
m/z 753 (10) [M] , 718 (30) [M - Cl] , 600.1 (40) {M - Cl -
6
D
6
3 2
)
), 18.7 (s, CH-
+
[
5
CH
2
CHCH(C
6
H
5
)]} . Anal. Calcd for C33
H
33Cl
2
NOPIr: C,
3
)
2
3 2
)
1
2.58; H, 4.42; N, 1.86. Found: C, 52.73; H,4.70; N, 1.82.
1
1
6 5 6 5
ipso-C H P), 128.2 (d, J(C,P) ) 32.9 Hz, ipso-C H P), 129.1,
3
:4:2 Mixture of Isomers 14A-C. H NMR (500.13 MHz,
3
129.2 (both s, Ar CH), 130.4 (d, J(C,P) ) 9.4 Hz, Ar C), 130.5
-
8
40 °C, [D ]toluene): isomer 14A, δ -0.19 (d, 3 H, J(H,H) )
1
3
(d, J(C,P) ) 27.3 Hz, C-7), 131.1 (d, J(C,P) ) 2.9 Hz, Ar CH),
6
.6 Hz, CH(CH ),
3
)
2
), 0.58 (d, 3 H, J(H,H) ) 6.6 Hz, CH(CH
3
)
2
3
131.2 (d, J(C,P) ) 8.4 Hz, Ar CH), 131.3 (d, J(C,P) ) 1.9 Hz,
Ar CH), 131.7 (d, J(C,P) ) 2.8 Hz, Ar CH), 132.2 (d, J(C,P) )
9.4 Hz, Ar CH), 132.3 (d, J(C,P) ) 2.8 Hz, Ar CH), 132.5 (d,
2
.40-2.50 (m, 1 H, CH(CH ) ), 3.15 (d, J(H,H) ) 5.5 Hz, 1A-
3 2
3
Hs), 3.29 (d, 1 H, J(H,H) ) 8.8 Hz, 1A-Ha), 3.46 (dd, 1 H,
2
3
3
J(H,H) ) 8.5, J(H,H) ) 10.2 Hz, 5-H), 3.70 (dd, 1 H, J(H,H)
3
2
J(C,P) ) 8.5 Hz, Ar CH), 163.7 (d, J(C,P) ) 5.7 Hz, C-2). Anal.
)
6
6.6, J(H,H) ) 8.5 Hz, 5-H), 4.95-5.08 (m, 1 H, 2A-H), 6.10-
3
3
27 29 2
Calcd for C H Br NOPIr: C, 42.35; H, 3.82; N, 1.83. Found:
.24 (m, 1 H, 4-H), 6.28 (dd, 1 H, J(H,H) ) 7.7, J(H,P) )
1.3 Hz, 8-H), 6.25-6.38 (m, 1 H, Ar H PHOX), 6.50 (d, 1 H,
+
C, 42.72; H, 3.89; N, 1.87. HR-MS (FAB): calcd for [M]
1
79
81
191
3
4
3
27 29
(C H ON[ Br][ Br]P[ Ir]) 764.9939, found 764.9946; calcd
for [M] (C H [ Br] NOP[ Ir]) 766.9919, found 766.9918;
27 29 2
calcd for [M - Br] (C H [ Br]NOP[ Ir]) 686.0756, found
27 29
J(H,H) ) 11.0 Hz, 3A-H), 8.00 (dd, 1 H, J(H,P) ) 4.0, J(H,H)
+
81
191
3
)
7.7 Hz, 11-H); isomer 14B, 0.12 (d, 3 H, J(H,H) ) 6.9 Hz,
+
81
191
3
CH(CH
3 2
)
), 0.75 (d, 3 H, J(H,H) ) 6.6 Hz, CH(CH
3
)
2
), 2.68-
6
86.0761.
2
.79 (m, 1 H, CH(CH
3 2
)
), 3.26-3.34 (m, 1 H, 5-H), 3.55-3.65
3
(
m, 1 H, 5-H), 3.76 (d, 1 H, J(H,H) ) 7.0 Hz, 1A-Hs), 3.84 (d,
2 3 2
Complex 16. A 0.5 M solution of NaCH(CO CH ) (0.08
3
1
H, J(H,H) ) 11.4 Hz, 1A-Ha), 4.02-4.10 (m, 1 H, 4-H), 5.69
mmol) in THF (0.16 mL) was added to a solution of the complex
exo-14 (30.2 mg, 40.00 mmol) in THF (1 mL) at -30 °C. The
reaction mixture was stirred and allowed to reach room
temperature within 4 h and then left to stand overnight at
-5 °C. The mixture was filtered and the filtrate concentrated
in vacuo. The residue crystallized upon treatment with diethyl
ether/pentane as a yellow powder (9:1 mixture of two isomers).
Yield: 23.5 mg (62%). For the numbering of the atoms of the
3
3
(
(
(
5
(
dd, 1 H, J(H,P) ) 8.8, J(H,H) ) 13.1 Hz, 3A-H), 6.12-6.23
m, 1 H, 2A-H), 7.90-7.97 (m, 1 H, 11-H); isomer 14C, δ 0.17
d, 3 H, J(H,H) ) 6.9 Hz, CH(CH
.9 Hz, CH(CH ), 2.31-2.40 (m, 1 H, CH(CH
overlapped signals, 2 H, 1A-Hs and 5-H), 4.16 (d, 1 H, J(H,H)
3
3
3 2
)
), 0.34 (d, 3 H, J(H,H) )
)
3 2
3 2
)
), 3.55-3.67
3
2
3
)
10.6 Hz, 1A-Ha), 4.21 (dd, 1 H, J(H,H) ) 9.2, J(H,H) )
3
9
9
8
6
.5 Hz, 5-H), 4.40-4.48 (m, 1H, 4-H), 5.09 (dd, 1 H, J(H,P) )
3
1
.5, J(H,H) ) 12.7 Hz, 3A-H), 6.12-6.23 (m, 1 H, 2A-H), 8.03-
PHOX ligand, see Scheme 6. Major isomer: H NMR (500.13
3
.08 (m, 1 H, 11-H); aromatic protons for all isomers, 6.62-
MHz, 25 °C, C
6
D
6
) δ 0.11 (d, 3 H, J(H,H) ) 6.7 Hz, CH(CH
3
)
2
),
), 1.73 (dd, 1 H,
), 1.92 (ddd, 1 H,
J(H,P) ) 4.0, J(H,H) ) 7.0, J(H,H) ) 7.0 Hz, IrCH ), 2.25-
), 2.85 (s, 3 H, CH[CH(CO CH ]), 2.88
]), 3.31 (s, 3 H, CH[CH(CO CH ]),
3,45 (dd, 1 H, J(H,H) ) 9.2, J(H,H) ) 9.7 Hz, 5-H), 3.63 (dd,
.73, 6.74-7.18, 7.42-7.50, 7.67-7.75 (all m, 18 H). 31P{ H}
1
0.35 (d, 3 H, J(H,H) ) 7.0 Hz, CH(CH
J(H,H) ) 7.0, J(H,H) ) 8.4 Hz, IrCH
2
3
)
3
2
2
3
3
NMR (202.46 MHz, -40 °C, [D
s); isomer 14B, δ -3.04 (s). isomer 14C, δ -4.01 (s). C{ H}
NMR (125.77 MHz, -40 °C, [D ]toluene): isomer 14A, δ 12.3,
8.5 (both s, CH(CH ), 27.9 (s, CH(CH ), 33.8 (s, C-1A), 65.2
s, C-3A), 67.2 (s, C-5), 70.9 (s, C-4), 82.5 (s, C-2A), 139.1 (s,
8
]toluene): isomer 14A, δ -15.9
1
3
1
2
3
(
2
8
2.32 (m, 1 H, CH(CH
3
)
2
2
3 2
)
2
1
(
)
3 2
)
3 2
(s, 3 H, Ir[CH(CO CH
2
3
)
2
3 2
)
2
3
3
3
2
allylic ipso-C
δ 14.0, 17.5 (both s, CH(CH
6
H
5
), 161.6 (d, J(C,P) ) 4.7 Hz, C-2); isomer 14B,
), 27.5 (s, CH(CH ), 30.2 (s,
1 H, J(H,H) ) 5.3, J(H,H) ) 9.2 Hz, 5-H), 3.65 (s, 3 H, Ir-
3
3
)
2
3
)
2
[CH(CO
CH ]), 3.92-4.01 (m, 2 H, CH[CH(CO
4.29 (ddd, 1 H, J(H,H) ) 3.35, J(H,H) ) 5.35, J(H,H) ) 9.7
2
CH
3
)
2
]), 3.76 (d, 1 H, J(H,H) ) 8.7 Hz, CH[CH(CO
2
-
2
C-1A), 67.7 (s, C-5), 73.8 (s, C-4), 83.5 (d, J(C,P) ) 36.7 Hz,
3
)
2
2
CH ] and IrCH(C )),
3
)
2
6 5
H
3
3
3
3
C-3A), 113.3 (broad s, C-2A), 142.7 (d, J(C,P) ) 4.7 Hz, allyl-
3
3
bound ipso-C
6 5
H
), 162.2 (d, J(C,P) ) 2.8 Hz, C-2); isomer 14C,
Hz, 4-H), 5.06 (s, 1 H, Ir[CH(CO
2
CH
3 2
) ]), 6.51 (dd, 1 H, J(H,H)
3
3
3 2 3 2
δ 13.7, 18.0 (both s, CH(CH ) ), 27.0 (s, CH(CH ) ), 30.5 (s,
) 8.0, J(H,P) ) 10.0 Hz, 8-H), 6.58 (dd, 1 H, J(H,H) ) 7.7,
2
3
4
3
C-1A), 67.4 (s, C-5), 74.9 (s, C-4), 83.6 (d, J(C,P) ) 38.6 Hz
J(H,H) ) 8.0 Hz, 9-H), 6.63 (ddd, 2 H, J(H,P) ) 2.3, J(H,H)
3
3
C-3A), 112.0 (broad s, C-2A), 142.5 (d, J(C,P) ) 5.4 Hz, allyl-
) 7.65, J(H,H) ) 7.65 Hz, m-C
H, o- or m-C of IrCH(C )), 6.76 (t, 1 H, J(H,H) ) 7.0
Hz, p-C of IrCH(C )), 6.78 (ddd, 1 H, J(H,P) ) 1.0,
J(H,H) ) 8.0, J(H,H) ) 8.0 Hz, 10-H), 6.85-7.05 (m, 2 H, o-
6 5
H PHOX), 6.65-6.73 (m, 2
3
3
bound ipso-C
6
H
5
), 163.0 (d, J(C,P) ) 3.7 Hz, C-2); aromatic
6
H
5
6 5
H
5
carbons for all isomers, 124.6, 127.5, 128.2, 128.3, 128.4, 129.1,
6
H
5
6 5
H
3
3
1
1
30.4, 130.7, 130.9, 131.2, 132.3, 134.7 (d, J(C,P) ) 9.4 Hz),
34.8, 134.9(d, J(C,P) ) 9.5 Hz); other signals overlapped with
5
3
or m-C H
6 5
of IrCH(C
6 5
H )), 6.86 (td, 1 H, J(H,P) ) 1.3, J(H,H)
PHOX), 7.05-7.12 (m, 3 H, signals over-
those of the solvent.
) 7.4 Hz, p-C H
6 5