1
52
J Chem Crystallogr (2014) 44:151–160
concentrated and treated with hexane to give the product as
1
red crystals. Yield 0.011 g (63 %). H NMR (CDCl3,
Preparation of [Ir(8OQd)(H)(SiPh
)(cod)] (4)
3
3
00 K) d 8.33 (dd (J 8.0, 1.4), 1H, quin 4-H), 8.11 (dd
J 5.0, 1.4), 1H, quin 2-H), 7.50 (t (J 8.0), 1H, quin 6-H),
A solution of [Ir (OMe) (cod) ] (0.010 g 0.030 mmol) in
2
2
2
(
diethyl ether (*0.5 ml) at room temperature was treated
firstly with a solution of 8-hydroxyquinaldine (0.050 g,
0.031 mmol) in diethyl ether (*0.5 ml), with an imme-
diate colour change from yellow to red, followed, within
1–2 min, by a solution of triphenylsilane (0.045 g,
0.17 mmol) in diethyl ether, with an immediate colour
change from red to yellow. The yellow solution was con-
centrated, treated with hexane and allowed to stand at
7
.43 (dd (J 8.3, 5.0), 1H, quin 3-H), 7.16 (dd (J 7.9, 1.0),
H, quin 7-H), 7.02 (dd (J 8.0, 1.0), 1H, quin 5-H), 4.62
1
(
mult, 2H, alkene), 3.81 (mult, 2H, alkene), 2.35 (mult, 4H,
1
3
CH ), 1.86 (mult, 2H, CH ), 1.74 (mult, 2H, CH );
2
C
2
2
NMR (CDCl , 300 K) d 169.68 (quin 8-C), 146.25 (quin
3
8
a-C), 145.03 (quin 2-C), 139.46 (quin 4-C), 131.07 (quin
-C), 130.63 (quin 4a-C), 120.55 (quin 3-C), 115.72 (quin
-C), 113.38 (quin 5-C), 69.94 (alkene), 53.19 (alkene),
6
7
-20 °C for 3 days to give the product as red-brown crys-
1
5
1
talline lumps. Yield 0.012 g (56 %). H NMR (C
3
1.30 (CH ), 31.15 (CH ); N NMR (CDCl , 300 K) d
6
D
6
,
2
2
3
-
148.24. Anal. Calc. for C H IrNO: C, 45.93; H, 4.08;
7 18
300 K, solution containing 10 equivalents of Ph
(25 mg, *0.20 M) in order to stabilise the complex) d
.80, 7.58, 7.15, 7.05 (mults, Ph SiH), 7.39 (dd (J 7.9, 1.0),
3
SiH
1
N, 3.15. Found: C, 45.56; H, 4.13; N, 3.06.
7
3
Preparation of [Ir(8OQd)(cod)] (2)
1H, OQd 7-H), 7.23 (t (J 7.9), 1H, OQd 6-H), 7.08 (mult,
H, OQd 4-H), 6.38 (d (J 7.7), 1H, OQd 5-H), 6.34 (d
1
Solutions of [Ir (OMe) (cod) ] (0.020 g, 0.060 mmol based
2
(J 8.4), 1H, OQd 3-H), 4.82 (mult, 1H, alkene), 4.39 (mult,
2
2
on Ir) in diethylether (*1 ml) and 8-hydroxyquinaldine (2-
methyl-8-hydroxyquinoline; 0.0096 g, 0.061 mmol) in die-
thyl ether (*0.5 ml) at room temperature were mixed
together with an immediate change of colour to red. After a
1H, alkene), 4.29 (mult, 1H, alkene), 3.90 (mult, 1H,
alkene), 2.56 (mult, 1H, CH
(s, 3H, CH ), 2.41 (mult, 1H, CH
1.84 (mult, 1H, CH ), 1.59 (mult, 1H, CH
1H, CH ), 1.49 (mult, 1H, CH
NMR (C
Ph SiH) d 145–125 (signals from Ph
), 2.53 (mult, 1H, CH
), 2.36 (mult, 1H, CH
2
), 2.49
),
), 1.56 (mult,
2
2
3
2
2
2
1
3
few seconds red crystals began to form. Yield 0.016 g
1
2
2
), -14.88 (s, 1H, HIr);
C
(
58 %). H NMR (CDCl , 300 K) d 8.14 (d (J 8.4), 1H, quin
6
D
6
, 300 K, solution containing 10 equivalents of
Si), 170.77 (OQd
3
4-H), 7.39 (t (J 7.9), 1H, quin 6-H), 7.23 (d (J 8.4), 1H, quin
3-H), 7.07 (dd (J 7.9, 1.2) 1H, quin 7-H), 6.92 (dd (J 7.9, 1.2),
1H, quin 5-H), 4.56 (mult, 2H alkene), 4.24 (mult, 2H,
3
3
8-C), 154.28 (OQd 2-C), 145.56 (OQd 8a-C), 137.27 (OQd
4-C), 130.14 (OQd 4a-C), 129.16 (OQd 6-C), 122.35 (OQd
3-C), 118.18 (OQd 7-C), 110.24 (OQd 5-C), 109.06
(alkene), 102.21 (alkene), 70.74 (alkene), 66.30 (alkene),
alkene), 2.64 (s, 3H, CH ), 2.38 (mult, 2H, CH ), 2.26 (mult,
3
2
3
2
H, CH ) 1.75 (mult, 2H, CH ), 1.59 (mult, 2H, CH ); C
2 2 2
NMR (CDCl , 300 K) d 169.50 (quin 8-C), 161.70 (quin
38.47 (CH
2
), 31.97 (CH
3
), 30.82 (CH
), 29.57 (CH ), 25.71
2 2
3
1
5
2
6
7
3
3
4
-C), 146.00 (quin 8a-C), 139.99 (quin 4-C), 129.38 (quin
-C), 128.80 (quin 4a-C), 124.08 (quin 3-C), 115.81 (quin
-C), 113.49 (quin 5-C), 67.24 (alkene), 55.37 (alkene),
(CH
equivalents of Ph
solution containing 10 equivalents of Ph
Anal. Calc. for C36 36IrNOSi: C, 60.14; H, 5.05; N, 1.95.
2
); N NMR (C
6
D
6
, 300 K, solution containing 10
2
9
SiH) d -153.2; Si NMR (C
D , 300 K,
6 6
3
SiH) -11.71.
3
1
5
3.80 (CH ), 29.60 (CH ), 23.82 (CH ); N NMR (CDCl3,
2
H
2
3
00 K) d -145.60. Anal. Calc. for C H IrNO: C, 47.14; H,
Found: C, 60.08; H, 5.15; N, 1.84.
1
8 20
.40; N, 3.05. Found: C, 47.44; H, 4.64; N, 3.05.
Preparation of [Ir(8OQd)(H)(SnPh )(cod)] (5)
3
7
Preparation of [Ir (7AI) (cod) ] (3)
2
2
2
A solution of [Ir(8OQd)(cod)] (1) (0.008 g, 0.017 mmol) in
dichloromethane (*1 ml) at room temperature was treated
with triphenyltin hydride (0.007 g, 0.020 mmol). An
immediate colour change from red to yellow was observed
on mixing. The solution was concentrated and hexane was
Solutions of [Ir (OMe) (cod) ] (0.010 g, 0.030 mmol
2
2
2
based on Ir) in diethyl ether (*1 ml) and 7-azaindole
0.005 g, 0.042 mmol) in diethyl ether (*1 ml) at room
(
temperature were mixed together, with an immediate
change in colour to red. The solution was concentrated and
treated with hexane to give the product as fibrous red
crystals. Yield 0.0067 g (53 %). Anal. Calc. for
C H IrN : C, 43.15; H, 4.10; N, 6.71. Found: C, 42.80;
added to give the product as yellow crystals. Yield
1
0.0105 g (76 %). H NMR (CDCl
, 300 K) d 7.54 (d
3
(J 8.4), 1H, quin 4-H), 7.29 (mult, 6H), PhSn ortho), 7.23 (t
(J 7.9), 1H, quin 6-H), 7.10 (mult, 3H, PhSn para), 7.06
(mult, 6H, PhSn meta), 7.03 (dd (J 8.0, 1.2), 1H, quin 7-H),
6.82 (d (J 8.4), 1H, quin 3-H), 6.52 (dd (J 7.8, 1.1), 1H,
quin 5-H), 4.87 (mult, 1H, alkene), 4.80 (mult, 1H, alkene),
4.72 (mult, 1H, alkene), 3.70 (mult, 1H, alkene), 2.82–2.71
1
5
17
2
H, 3.93; N, 6.82. Spectral data are reported in [6]. Crystals
containing co-crystallised benzene suitable for X-ray
crystallography were grown by slow evaporation (6 weeks)
of a solution of 3 (prepared using benzene as solvent) in
chloroform.
(mults, 2H, CH ), 2.77 (s, 3H, CH ), 2.61–.45 (mults, 2H,
2 3
1
23