Reaction of an (Alkyl)(alkenyl)(alkynyl)Ir(III) Complex
Organometallics, Vol. 18, No. 23, 1999 4815
(CDCl3): δ 173.0 (t, J P-C ) 6.5 Hz, Ir-CO), 131.3 (s, Ir-CHd
CH), 129.6 (t, Ir-CHdCH, J P-C ) 7.8 Hz), 112.3 (s, Ir-CtC),
85.8 (t, J P-C ) 18.2 Hz, Ir-CtC), 53.5 (s, N(CH2CH3)3), 20.9
(s, p-C6H4CH3), 6.8 (s, N(CH2CH3)3), -28.7 (t, J P-C ) 5.7 Hz,
Ir-CH3). 31P NMR (CDCl3): δ -16.1 (s). IR (KBr, cm-1): ν-
(CtC) 2115.5 (s), ν(CO) 2018.5 (s), ν(ClO4-) 1080.0 (s, br, due
tetrahedral ClO4-). Anal. Calcd for IrP2C45H47NCl3O5: C,
51.84; H, 4.55; N, 1.34. Found: C, 51.59; H, 4.58; N, 1.41.
Data for 7 are as follows. 1H NMR (500 MHz, CDCl3): δ
7.12-7.22 (AB quartet with ∆ν/J ) 2.3, 4H, J H
) 8.0 Hz,
-H
A
B
p-C6H4CH3), 6.40 (dd, 1H, J H-H ) 11.4 Hz, 1.5 Hz, CH3CHd
CH), 5.74 (dq, 1H, J H-H ) 11.4, 7.2 Hz, CH3CHdCH), 2.36 (s,
3H, p-C6H4CH3), 1.89 (dd, 3H, J H-H ) 7.2, 1.5 Hz, CH3CHd
CH). 13C NMR (MHz, CDCl3): δ 14.6 (s, CH3CHdCH), 21.1
(s, p-C6H4CH3), 136.1, 134.8, 129.7, 128.8, 128.7, 126.0 (s,
olefinic carbons and p-C6H4CH3). Mass: M+ at m/z 132.
Reaction of 5 with HCl was carried out in the same manner
as described for the formation of 6 and 7 from the reaction of
3 with aqueous HCl using 5 (0.2 g, 0.17 mmol). The yield of 6
was 0.11 g (62%).
to noncoordinated tetrahedral ClO4-). Anal. Calcd for IrP2C55H57
-
NClO5: C, 59.96; H, 5.23; N, 1.27. Found: C, 59.51; H, 5.27;
N, 1.27.
P r ep a r a tion of cis,tr a n s-Ir (CH3)(CtC(p-C6H4CH3))2-
(CO)(P P h 3)2 (4). This compound was prepared by the same
manner as described for 3 using 2 (0.1 g, 0.1 mmol), HCtC(p-
C6H4CH3) (0.15 mmol), and NEt3 (0.11 mmol), except that the
reaction mixture was stirred at 0 °C for 30 min. The yield was
0.07 g (71%). 1H NMR (300 MHz, CDCl3): δ 6.59-6.92 (a
Rea ction s of [Ir (CH3)(CtC(p-C6H4CH3))(CH3CN)(CO)-
(P P h 3)2]ClO4 (2) a n d [Ir (CH3)(CtC(p-C6H4CH3))2(CO)-
(P P h 3)2]ClO4 (4) w ith HCl: F or m a tion of CH2dCdCH(p-
C6H4CH3) (9). HCl (2.0 mmol, 0.19 mL of H2O containing 32
wt % HCl) was added to a solution of 2 (0.2 g, 0.2 mmol) in
CHCl3 (5 mL) at 25 °C, and the reaction mixture was stirred
for 12 h, during which time white microcrystals precipitated.
Excess HCl was removed by washing with H2O using a
separatory funnel. Compound 10 (white microcrystals) was
collected by centrifugal separation, washed with n-hexane,
dried under vacuum, and identified by spectral data (see text).
The yield was 0.13 g (76% based on Ir(H)(Cl)2(CO)(PPh3)2). The
supernatant was distilled under vacuum to collect 9 in the cold
trap of a dry ice/isopropyl alcohol bath. The yield of 9 was ca.
30%, measured by 1H NMR in CDCl3. The reaction of 4 (0.2 g,
0.2 mmol) with HCl was carried out in the same manner as
described for the reaction of 2. Spectral data for 9 are as
follows. 1H NMR (500 MHz, CDCl3): δ 7.09-7.21 (AB quartet
couple of an AB quartet with ∆ν/J ) 7.3 and 7.5, 8H, J H
-H
A
B
) 8.2 and 8.0 Hz, (p-C6H4CH3)2), 2.26, 2.25 (both singlet, total
6H, (p-C6H4CH3)2), -0.33 (t, 3H, J P-H ) 5.0 Hz, Ir-CH3). 13C
NMR (CDCl3): δ 171.3 (t, J P-C ) 6.6 Hz, Ir-CO), 110.9, 108.3
(s, (Ir-CtC)2), 87.1, 81.3, (t, J P-C ) 18.2, 13.1 Hz, (Ir-Ct
C)2), 21.2, 21.1 (s, (p-C6H4CH3)2), -21.5 (t, J P-C ) 4.5 Hz, Ir-
CH3). 31P NMR (CDCl3): δ -10.9 (s). IR (KBr, cm-1): ν(CtC)
2104.0 (s), ν(CO) 2024.0 (s). Anal. Calcd for IrP2C56H47O: C,
67.92; H, 4.79. Found: C, 68.56; H, 4.75.
P r ep a r a tion of [Ir (C(CH3)dCH(p-C6H4CH3))(CHdCH-
NEt3)(Cl)(CO)(P P h 3)2]ClO4 (5). HCl (0.25 mmol, 0.024 mL
of H2O containing 32 wt % HCl) was added to a solution of 3
(0.22 g, 0.2 mmol) in CHCl3 (15 mL) at 25 °C, and the reaction
mixture was stirred for 1 h until it turned brown. Excess HCl
was removed from the reaction mixture by washing with H2O
(10 mL) using a separatory funnel. Addition of n-hexane (25
mL) to the CHCl3 solution resulted in orange microcrystals of
5, which were collected by filtration, washed with cold hexane
(3 × 10 mL), and dried under vacuum. The yield of 5 was 0.11
with ∆ν/J ) 1.5, 4H, J H
) 8.1 Hz, CH(p-C6H4CH3)), 6.14
-H
A
B
(t, 1H, J H-H ) 6.6 Hz, CH(p-C6H4CH3)), 5.12 (d, 2H, J H-H
)
g (47%). 1H NMR (300 MHz, CDCl3): δ 7.10 (d, 1H, J H-H
)
6.6 Hz, CH2dC), 2.32 (s, 3H, CH(p-C6H4CH3)). 13C NMR
(CDCl3): δ 93.7, 78.6, 77.4 (s, CdCdC), 21.1 (s, p-C6H4CH3).
IR (KBr, cm-1): ν(CdC) 1731.3 (s). Mass: M+ at m/z 130.
15.6 Hz, Ir-CHdCH), 7.04 (br, 2H, p-C6H4CH3 (meta protons)),
6.62 (br, 2H, p-C6H4CH3 (ortho protons)), 6.41 (br, 1H, Ir-
C(CH3)dCH), 4.87 (d, 1H, J H-H ) 15.6 Hz, Ir-CHdCH), 2.70
(q, 6H, J H-H ) 6.9 Hz, N(CH2CH3)3), 2.31 (s, 3H, p-C6H4CH3),
1.92 (s, 3H, Ir-C(CH3)dCH), 0.96 (t, 9H, J H-H ) 6.9 Hz,
N(CH2CH3)3). 13C NMR (CDCl3): δ 173.6 (br, Ir-CO), 138.2
(s, Ir-C(CH3)dCH2), 129.5 (s, Ir-CHdCH), 128.5 (br, Ir-CHd
CH), 121.1 (br, Ir-C(CH3)dCH), 54.4 (s, N(CH2CH3)3), 26.3
(br, Ir-C(CH3)dCH), 21.0 (s, p-C6H4CH3), 8.0 (s, N(CH2CH3)3).
31P NMR (CDCl3): δ -17.7 (s). IR (KBr, cm-1): ν(CO) 2044.7
(s), ν(ClO4-) 1093.1 (s, br, due to noncoordinated tetrahedral
ClO4-). Anal. Calcd for IrP2C55H58NCl2O5: C, 58.03; H, 5.15;
N, 1.23. Found: C, 57.62; H, 5.20; N, 1.25.
Red u ctive Elim in a tion of [H(p-C6H4CH3)CdC(CH3)-
CHdCHNEt3]ClO4 (8) fr om [Ir (C(CH3)dCH(p-C6H4CH3))-
(CHdCHNEt3)(Cl)(CO)(P P h 3)2]ClO4 (5). Compound 5 (0.23
g, 0.2 mmol) was dissolved in CHCl3 (10 mL), and the solution
was refluxed for 2 h. Reducing the solution by distillation
under vacuum to 1 mL resulted in precipitation of the white
microcrystals of 8, which were collected by filtration, washed
with cold CHCl3 (3 mL), and dried under vacuum. The yield
was 0.04 g (56%). The electronic absorption spectrum of the
filtrate (CHCl3 solution) showed three distinctive absorption
bands at 338, 388, and 440 nm of Vaska’s compound, IrCl-
(CO)(PPh3)2.11 Spectral data for 8 are as follows. 1H NMR (500
MHz, CDCl3): δ 7.20-7.29 (AB quartet with ∆ν/J ) 2.2, 4H,
Rea ction s of [Ir (CH3)(CHdCHNEt3)(CtC(p-C6H4CH3))-
(CO)(P P h 3)2)]ClO4 (3) a n d [Ir (C(CH3)dCH(p-C6H4CH3))-
(CHdCHNEt3)(Cl)(CO)(P P h 3)2]ClO4 (5) w ith HCl: F or -
m a tion of [Ir (CHdCHNEt3)(Cl)2(CO)(P P h 3)2]ClO4 (6) a n d
cis-CH3CHdCH(p-C6H4CH3) (7). HCl (0.25 mmol, 0.024 mL
of H2O containing 32 wt % HCl) was added to a solution of 3
(0.22 g, 0.2 mmol) in CHCl3 (15 mL) at 25 °C; the reaction
mixture was stirred for 6 h. Excess HCl was removed by
washing with H2O. Addition of n-hexane (10 mL) to the CHCl3
solution resulted in beige microcrystals of 6, which were
collected by filtration, washed with CHCl3 (3 mL), and dried
under vacuum. The yield of 6 was 0.09 g (45%). The filtrate
was distilled under vacuum to collect 7 in the cold trap of a
dry ice/isopropyl alcohol bath. The yield of 7 was ca. 40%,
J H
) 8.2 Hz, CH(p-C6H4CH3)), 6.82 (s, 1H, HR), 6.73 (d,
-H
A
B
1H, J H-H ) 14.8 Hz, Hγ), 5.95 (d, 1H, J H-H ) 14.8 Hz, Hδ),
3.56 (q, 6H, J H-H ) 7.1 Hz, N(CH2CH3)3), 2.38 (s, 3H, CH(p-
C6H4CH3)), 2.08 (d, 3H, J H-H ) 0.9 Hz, (CH3)CdC), 1.36 (t,
9H, J H-H ) 7.1 Hz, N(CH2CH3)3). 13C NMR (CDCl3): δ 139.2,
138.9, 137.2, 134.0, 130.7, 130.1, 129.9, 123.0 (s, olefinic
carbons and p-C6H4CH3), 56.3 (s, N(CH2CH3)3), 21.7 (s, CH-
(p-C6H4CH3)), 14.5 (s, (CH3)CdC), 8.5 (s, N(CH2CH3)3). IR
(KBr, cm-1): ν(ClO4-) 1094.5 (s, br). Mp: 196 °C. Electronic
absorption: λmax 228, 292 nm. Mass: m/z 229 (M+ - C2H5-
ClO4).
1
measured by H NMR in CDCl3.
Rea ction s of [Ir (CH3)(CtC(p-C6H4CH3))(NCCH3)(CO)-
(P P h 3)2]ClO4 (2) w ith DCl: F or m a tion of CH 2dCdCD(p-
C6H4CH3) (9-d 1). This reaction was carried out using aqueous
DCl (37 wt % in D2O) in the same manner as described for
the reaction of 2 with HCl. The isotopomer 9-d 1 was identified
Data for 6 are as follows. 1H NMR (300 MHz, CDCl3): δ
7.90 (d, 1H, J H-H ) 15.3 Hz, Ir-CHdCH), 5.56 (d, 1H, J H-H
)
15.3 Hz, Ir-CHdCH), 2.96 (q, 6H, J H-H ) 7.2 Hz, N(CH2-
CH3)3), 0.88 (t, 9H, J H-H ) 7.2 Hz, N(CH2CH3)3). 13C NMR
(CDCl3): δ 160.1 (t, J P-C ) 6.5 Hz, Ir-CO), 133.1 (s, Ir-CHd
CH), 123.3 (br, Ir-CHdCH), 56.0 (s, N(CH2CH3)3), 8.5 (s,
N(CH2CH3)3). 31P NMR (CDCl3): δ -16.7 (s). IR (KBr, cm-1):
ν(CO) 2060.4 (s), ν(ClO4-) 1093.1 (s, br, due to noncoordinated
1
1
by H NMR and mass spectral measurements. H NMR (500
MHz, CDCl3): δ 7.09-7.21 (AB quartet with ∆ν/J ) 1.5, 4H,
J H
) 8.1 Hz, CH(p-C6H4CH3)), 5.12 (s, 2H, CH2dCdCD-
-H
A
B
(p-C6H4CH3), 2.32 (s, 3H, p-C6H4CH3). Mass: M+ at m/z 131.