E. Sola, L. A. Oro et al.
J
C
G
1H; CH), 7.36 (d, J
G
N
293 K): d=À152.5 (s); IR (KBr): n˜ =3412 (O-H), 2179 (IrH), 1755 cmÀ1
(Ir-HI-r); MS (FAB+): m/z (%): 882 (45) [M +ÀOH2]; elemental analy-
sis calcd (%) for C26H56N5BF4Ir2OP2: C 31.61, H 5.71, N 7.09; found: C
32.01, H 5.57, N 6.97. The crystals used in the X-ray diffraction experi-
ment were obtained by slow diffusion of hexane into a saturated solution
of 7 in CH2Cl2 at 253 K.
s; PCHCH3), 23.21 (d, J
30.9 Hz; PCHCH3), 103.87 (d, J
2.7 Hz; CH), 117.40 (s; NCCH3), 134.47 (d, J
(d, J(C,P)=4.1 Hz; CH), 141.09 (d, J(C,P)=5.1 Hz; CH), 141.63 (d,
(C,P)=3.2 Hz; CH); IR (KBr): n˜ =2206 (Ir-H), 1761 cmÀ1 (Ir-H-Ir); MS
E
ACHTREUNG
G
ACHTREUNG
AHCTREUNG
G
ACHTREUNG
J
ACHTREUNG
A
(FAB+): m/z (%): 918 (22) [M +]; elemental analysis calcd (%) for
C26H54N5ClIr2P2: C 34.00, H 5.93, N 7.62; found: C 34.21, H 5.99, N 7.60.
The crystals used in the X-ray diffraction experiment were obtained by
slow diffusion of hexane into a saturated solution of 9 in CH2Cl2 at
253 K.
resulting suspension was taken to dryness and the residue was extracted
with toluene (5 mL) and filtered through Celite. The resulting colorless
solution was dried and the residue treated with hexane to give a white
solid, which was separated by decantation, washed with hexane, and
dried in vacuo (75.0 mg, 73%).
A
G
(m-Pz)2H2
G
G
A
was prepared as detailed for 5, using 4 (128.8 mg, 0.11 mmol) and benzal-
dehyde (34.0 mL, 0.33 mmol): yield 104.0 mg (87%). 1H NMR (CDCl3,
Method 2: A solution of 1 (210.7 mg, 0.24 mmol) in toluene (5 mL) was
treated with MeOSO2CF3 (27.0 mL, 0.24 mmol) and stirred for 1 h at
273 K. The resulting solution was filtered through Celite and taken to
dryness. The residue was treated with hexane to give a white solid, which
was separated by decantation, washed with hexane, and dried in vacuo
(218.7 mg, 89%). Compound 8 was also found by NMR to be quantita-
tively formed in the reaction of 1 with one equivalent of [PhNH=
CHPh]SO3CF3 in CD2Cl2 at 233 K. 1H NMR ([D8]toluene, 293 K): d=
293 K): d=À21.81 (dd, J
(dddd, J(H,P)=12.9, 3.6, J
(H,P)=19.8, J(H,H)=3.6 Hz, 1H; IrH), 0.87, 1.07, 1.16 (all dd, J
13.8, (H,H)=6.9 Hz, 9H each; PCHCH3), 1.25 (dd, (H,P)=13.5,
(H,H)=7.2 Hz, 9H; PCHCH3), 2.11, 2.22 (2m, 3H each; PCHCH3),
2.60 (s, 3H; NCCH3), 5.70 (dt, J(H,P)=J(H,H)=1.8 Hz, 1H; CH), 6.00
(dt, J(H,P)=J(H,H)=1.6 Hz, 1H; CH), 6.70 (m, 1H; CH), 7.19 (m, 2H;
CH), 7.49 (d, J(H,H)=1.6 Hz, 1H; CH), 7.51 (dd, J(H,H)=8.1, 6.9 Hz,
2H; CH), 7.67, 7.70 (2d, J(H,H)=1.8 Hz, 1H each; CH), 7.21 (t,
N
G
U
ACHTREUNG
J
N
N
ACHTREUNG
J
A
J
ACHTREUNG
J
ACHTREUNG
G
ACHTREUNG
A
ACHTREUNG
U
ACHTREUNG
À23.71 (dd, J
(H,P)=13.4, 6.3, J
20.2, J(H,H)=3.4 Hz, 1H; IrH), 1.22 (dd, J
9H; PCHCH3), 1.29 (dd, J(H,P)=14.5, J(H,H)=7.3 Hz, 9H; PCHCH3),
1.34 (dd, (H,P)=13.7, (H,H)=7.3 Hz, 9H; PCHCH3), 1.35 (dd,
(H,P)=13.2, J(H,H)=6.9 Hz, 9H; PCHCH3), 1.48 (s, 3H; NCCH3),
2.17, 2.36 (2m, 3H each; PCHCH3), 5.84 (td, J(H,H)=2.1, J(H,P)=
1.4 Hz, 1H; CH), 6.17 (td, J(H,H)=2.1, J(H,P)=1.5 Hz, 1H; CH), 7.00
(m, 1H; CH), 7.37 (d, J(H,H)=2.1 Hz, 1H; CH), 7.65 (m, 1H; CH), 8.17
(d, J
(H,H)=2.1 Hz, 1H; CH); 31P{1H} NMR ([D8]toluene, 293 K) d
11.12, 18.26 (2s); 13C{1H} NMR ([D8]toluene, 293 K): d=1.29 (s;
NCCH3), 18.65, 18.85, 19.22, 19.44 (all s; PCHCH3), 23.86 (d, J(C,P)=
29.2 Hz; PCHCH3), 26.51 (d, J(C,P)=31.0 Hz; PCHCH3), 104.15 (d,
(C,P)=3.0 Hz; CH), 104.69 (d, J(C,P)=2.9 Hz; CH), 117.06 (q, J(C,F)=
319.8 Hz; OSO2CF3), 117.71 (s; NCCH3), 134.70 (d, J(C,P)=3.8 Hz; CH),
136.21 (d, J(C,P)=2.9 Hz; CH), 142.45 (d, J(C,P)=2.8 Hz; CH), 143.75
(d, J
AHCTREUNG
J
J
(H,H)=8.1 Hz, 1H; CH), 10.25 (s, 1H; OCH); 31P{1H} NMR (CDCl3,
E
293 K): d=11.85, 17.23 (2s); 13C{1H} NMR (CDCl3, 293 K): d=3.11 (s;
NCCH3), 18.12, 18.25, 18.88, 18.95 (all s; PCHCH3), 23.37, 26.46 (2d,
J
J
C
G
J
CH), 131.21 (d, J
A
ACHTREUNG
G
ACHTREUNG
AHCTREUNG
ysis calcd (%) for C33H60N5BF4Ir2OP2: C 36.83, H 5.62, N 6.50. Found: C
36.55, H 5.52, N 6.54.
J
A
G
(m-Pz)2H2
G
G
N
was prepared as detailed for 5, using 4 (182.8 mg, 0.16 mmol) and aniline
(43.2 mL, 0.48 mmol): yield 143.2 mg (85%). 1H NMR (CDCl3, 293 K):
d=À23.77 (dd, J
(H,P)=12.3, 3.6, J
20.1, J(H,H)=1.8 Hz, 1H; IrH), 1.01 (dd, J
9H; PCHCH3), 1.19 (dd, J(H,P)=14.1, J(H,H)=7.2 Hz, 9H; PCHCH3),
1.30, 1.32 (2dd, J(H,P)=13.5, J(H,H)=6.9 Hz, 9H each; PCHCH3),
2.01, 2.37 (2m, 3H each; PCHCH3), 2.56 (s, 3H; NCCH3), 5.19, 5.48
(2d, J(H,H)=12.6 Hz, 1H each; NH), 5.73 (td, J(H,H)=2.1, J(H,P)=
1.5 Hz, 1H; CH), 5.95 (td, J(H,H)=2.1, J(H,P)=1.4 Hz, 1H; CH), 6.85
(H,H)=2.1 Hz, 1H; CH), 7.12 (m, 1H; CH), 7.22 (m, 2H; CH), 7.24
(H,H)=2.1 Hz, 1H; CH), 7.31 (m, 2H; CH), 7.35 (m, 1H; CH), 7.54
(H,H)=2.1 Hz, 1H; CH); 31P{1H} NMR (CDCl3, 293 K): d=9.20,
R
ACHTREUNG
CF3SO3); IR (KBr): n˜ =2175 (IrH), 1771 cmÀ1 (Ir-H-Ir); MS (FAB+):
m/z (%): 882 (24) [M +ÀOSO2CF3]; elemental analysis calcd (%) for
C27H54N5SF3Ir2O3P2: C 31.42, H 5.27, N 6.78, S 3.11; found: C 31.46, H
5.28, N 6.66, S 2.95.
J
N
N
ACHTREUNG
E
N
N
ACHTREUNG
R
ACHTREUNG
A
E
U
ACHTREUNG
(110.0 mg, 0.10 mmol) in methanol (5 mL) was treated with an excess of
NaCl (ca. 200 mg) and stirred for 2 h at room temperature. The resulting
suspension was taken to dryness and the residue was extracted with
CH2Cl2 (5 mL) and filtered through Celite. The resulting colorless solu-
tion was dried and the residue treated with hexane to give a white solid,
which was separated by decantation, washed with hexane, and dried in
vacuo (71.1 mg, 77%).
G
ACHTREUNG
(d, J
(d, J
ACHTREUNG
AHCTREUNG
(d, J
17.65 (2s); 13C{1H} NMR (CDCl3, 293 K): d=3.16 (s; NCCH3), 17.94,
18.65, 18.86, 19.27 (all s; PCHCH3), 23.79 (d, (C,P)=30.0 Hz;
PCHCH3), 26.87 (d, J(C,P)=30.9 Hz; PCHCH3), 104.92, 105.16 (2d,
(C,P)=3.2 Hz; CH), 118.19 (s; NCCH3), 122.88, 126.15, 128.66 (all s;
CH), 134.69 (d, J(C,P)=4.6 Hz; CH), 138.30 (d, J(C,P)=2.8 Hz; CH),
141.01 (d, J(C,P)=3.7 Hz; CH), 142.75 (d, J(C,P)=3.6 Hz; CH), 144.50
ACHTREUNG
J
ACHTREUNG
AHCTREUNG
Method 2: A solution of 1 (110.9 mg, 0.13 mmol) in CH2Cl2 (4 mL) was
treated with 1-(1-phenylethylidene)pyrrolidinium tetrafluoroborate
(31.0 mg, 0.13 mmol) and stirred for 15 min at room temperature. The re-
sulting orange solution was taken to dryness, and the residue was extract-
ed with diethyl ether (20 mL) and filtered through Celite. The solution
was dried and the residue treated with hexane to give a white solid. The
solid was separated by decantation, washed with hexane, and dried in
vacuo (76.8 mg, 67%). 1H NMR (CD2Cl2, 293 K): d=À26.62 (dd,
J
ACHTREUNG
E
ACHTREUNG
N
ACHTREUNG
(s; C); 19F NMR (CDCl3, 293 K): d=À154.6 (s); IR (KBr): n˜ =3288 (N-
H), 2183 (Ir-H), 1742 cmÀ1 (Ir-H-Ir); MS (FAB+): m/z (%): 975 (10)
[M +]; elemental analysis calcd (%) for C32H61N6BF4Ir2P2: C 36.15, H
5.78, N 7.90; found: C 36.22, H 5.42, N 7.87.
A
G
U
G
G
G
J
A
ACHTREUNG
G
A
ACHTREUNG
treated with MeOSO2CF3 (11.2 mL, 0.10 mmol) and stirred for 2 h at
273 K. The resulting solution was filtered through Celite and taken to
dryness. The residue was treated with hexane at 213 K to give a white
solid, which was separated by decantation, washed with hexane and dried
in vacuo (83.8 mg, 83%). 1H NMR ([D8]toluene, 293 K): d=À22.55 (dd,
J
G
J
ACHTREUNG
U
ACHTREUNG
U
ACHTREUNG
AHCTREUNG
G
E
ACHTREUNG
1H; CH), 6.94 (d, J
N
G
J
U
J
(H,H)=2.2 Hz, 1H; IrH), À16.81 (dd,
J(H,P)=16.8,
N
4066
ꢀ 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2006, 12, 4057 – 4068