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lyst, piperidine (3 drops). After 3 h, the bright orange solution was
allowed to cool to room temperature and the yellow precipitate
which formed was collected (via filtration), washed with cold meth-
anol as well as petroleum ether. Yield = 95%, M.P. = 234–237 °C.
under reflux for 3 h. A maroon precipitate was filtered by gravity,
dissolved in dichloromethane and the resultant solution was lay-
ered with hexane. After several days of slow diffusion red, cubic
crystals, which were ideal for X-ray analysis, were attained.
IR (m
max/cmꢀ1):
m(C@O) 1678 (s),
m
(C@N) 1596 (s); 1H NMR
Yield = 73%, M.P. = 271–274 °C. IR (
m m(C@O) 1686 (s),
max/cmꢀ1):
(295 K/ppm, see Fig. S2): 9.70 (s, 2H, H4, H8), 8.33 (d, 2H, H5, H7),
7.78 (t, 1H, H6), 7.46 (br, s, 4H, N(1)H2, N(11)H2), 3.41 (s, 6H, C3H3,
C9H3), 3.19 (s, 6H, C2H3, C10H3). 13C NMR (295 K/ppm): 214.30,
206.92, 157.65, 157.11, 154.41, 150.89, 150.24, 150.13, 29.90,
m(C@N) 1618 (s),
m
(Ru-PPh3) 696 (m); 1H NMR (295 K/ppm): 8.59
(s, 1H, H7), 8.31 (s, 1H, H13), 7.85 (br, s, 2H, N3H2), 7.46–7.21 (m,
15H, PPh3), 7.17 (d, 1H, H9), 7.03 (d, 1H, H11), 6.83 (t, 1H, H10),
5.77 (s, 1H, N7H) 3.55 (s, 3H, C3H3), 3.03 (s, 6H, C1H3, C16H3),
2.79 (s, 3H, C18H3); 31P NMR (295 K/ppm): 36.89. 13C NMR
(295 K/ppm): 206.57, 137.63, 133.44, 132.40, 132.09, 132.06,
131.77, 131.67, 128.75, 128.63, 128.51, 128.27, 127.96, 127.71,
127.48, 125.01, 124.77, 124.53, 29.88, 29.83, 29.63, 29.44. UV–Vis
28.91. UV–Vis (DMF, (kmax
(e,
Mꢀ1 cmꢀ1))): 233 nm (7900),
278 nm (sh, 4900), 285 nm (5000), 368 nm (8800), 451 nm (600),
588 nm (600). Calc. for C19H21N9O4: C, 51.93; H, 4.82; N, 28.69.
Found: C, 51.45; H, 4.50; N, 28.27%
(DMF, (kmax (e
, Mꢀ1 cmꢀ1))): 267 nm (sh, 20500); 387 nm (7100);
419 nm (sh, 6800); 474 (sh, 4800); 556 nm (sh, 3800). Conductivity
(DMF, 10ꢀ3 M): 11.17 ohmꢀ1 cm2 molꢀ1. Calc. for C38H35Cl3N9O4-
PRu: C, 49.60; H, 3.83; N, 13.70. Found: C, 50.07; H, 4.63; N, 13.32%.
2.8. cis-[RuIICl2(bpap)(PPh3)] (4)
The title compound was formed from the 1:1 molar ratio reac-
tion of bpap (0.0527 g; 104
(0.100 g, 104
mol) in (20 cm3) toluene after 6 h of reflux. A dark
brown precipitate was filtered and recrystallized via the slow dif-
fusion of a dichloromethane and n-hexane [1:1 ( )] solution
which resulted in the formation of brown XRD quality parallelo-
grams. Yield = 63%, M.P. = 323–327 °C. IR ( (C@O)
max/cmꢀ1):
1667, 1655, 1638 (s), (C@N) 1591 (s),
(Ru-PPh3) 695 (vs); 1H
lmol) and trans-[RuCl2(PPh3)3]
l
II
.
2.5. trans-[Ru Cl(pap)(PPh3)2]BF4 (1)
v:v
Equimolar amounts of pap (0.0305 g, 104 lmol) and trans-
[RuCl2(PPh3)3] (0.100 g, 104
lmol) were refluxed for 12 h in anhy-
m
m
drous toluene (30 cm3). A dark-blue precipitate was collected by
filtration, washed with anhydrous di-ethyl ether and dried under
vacuum. This precipitate along with an excess of NH4BF4 was dis-
solved in a CH2Cl2:EtOH (2:1, v:v) solvent mixture and from the
slow evaporation of the resultant solution, dark blue cubic-shaped
crystals suitable for X-ray crystallographic analysis were obtained.
m
m
NMR (295 K/ppm): 8.21–8.02 (m, 4H, H12, H14, H15, H16, H18),
7.60–6.62 (m, 25H, PPh3, H2, H3, H4, H5, H6, H25, H26, H27, H28,
H29), 3.21 (s, 6H, C7H3, C9H3), 2.92 (s, 6H, C21H3, C22H3); 31P
NMR (295 K/ppm): 31.22. 13C NMR (295 K/ppm): 206.58, 137.63,
128.74, 128.51, 128.27, 127.95, 127.71, 125.04, 124.78, 124.51,
Yield = 65%, M.P. = 250–255 °C. IR (
m
max/cmꢀ1):
m(C@O) 1902 (vs),
124.09, 29.87, 29.57. UV–Vis (DMF, (kmax (e
, Mꢀ1 cmꢀ1))): 244 nm
m
(C@N) 1621 (s); 1H NMR (295 K/ppm): 8.49 (d, 1H, H1), 8.11 (s,
(sh, 26400); 279 nm (16400); 418 nm (5000); 498 nm (sh,
2800); 599 nm (sh, 1400). Conductivity (DMF, 10ꢀ3 M):
15.39 ohmꢀ1 cm2 molꢀ1. Calc. for C49H44Cl8N7O2PRu: C, 49.93; H,
3.76; N, 8.32. Found: C, 49.47; H, 3.39; N, 8.72%.
1H, H5), 7.59 (t, 1H, H3), 7.24–7.16 (m, 34H, H2, H4, 2 x PPh3),
7.07–7.02 (m, 3H, H6, H8, H10); 6.88 (t, 2H, H7, H9); 2.98 (s, 3H,
N-CH3), 2.16 (s, 3H, CH3); 31P NMR (295 K/ppm): 34.23. 13C NMR
(295 K/ppm): 206.42, 137.31, 133.36, 129.99, 129.81, 128.86,
128.16, 127.84, 125.27, 124.47, 124.12, 30.64, 20.89. UV–Vis
(DMF, (kmax
(e
,
Mꢀ1 cmꢀ1))): 281 nm (sh, 145200); 357 nm
2.9. X-ray diffraction
(11200); 359 nm (sh, 9400); 598 (4200). Conductivity (DCM,
10ꢀ3 M): 127.09 ohmꢀ1 cm2 molꢀ1. Calc. for C49H40Cl2N4P2BF4Ru:
C, 58.52; H, 4.01; N, 5.57. Found: C, 58.48; H, 4.22; N, 5.32%.
The X-ray data for all the metal complexes were recorded on a
Bruker Apex Duo equipped with an Oxford Instruments Cryojet
operating at 100(2) K and an Incoatec microsource operating at
30 W power. For 1, a low resolution structure could only be
attained, see Fig. S4. Crystal and structure refinement data for
the metal complexes 2, 3 and 4 are given in Table 1. Selected bond
lengths and angles are given in Tables 2–4. In all three cases the
data were collected with Mo Ka (k = 0.71073 Å) radiation at a crys-
tal-to-detector distance of 50 mm. The following conditions were
used for the data collection: omega and phi scans with exposures
2.6. trans-P, cis-Cl-[RuIII(pch)Cl2(PPh3)2] (2)
A 1:1 molar reaction mixture of pch (0.0261 g; 104
lmol) and
trans-[RuCl2(PPh3)3] (0.100 g, 104 mol) was heated at refluxed in
l
ethanol (30 cm3) for 3 h. A blue precipitate was collected by filtra-
tion and washed with anhydrous di-ethyl ether. This precipitate
was dissolved in chloroform and layered with hexane and after
several days, XRD quality blue parallelograms were attained
using the slow diffusion method. Yield = 74%, M.P. = 247–253 °C.
taken at 30 W X-ray power and 0.50° frame widths using APEX
2
[19]. The data were reduced with the programme SAINT [20] using
outlier rejection, scan speed scaling, as well as standard Lorentz
and polarization correction factors. A SADABS semi-empirical multi-
scan absorption correction was applied to the data [21]. Direct
methods, SHELXS-97 [22] and WinGX [23] were used to solve all
three structures. All non-hydrogen atoms were located in the dif-
ference density map and refined anisotropically with SHELXL-97
[22]. All hydrogen atoms were included as idealized contributors
in the least squares process. Their positions were calculated using
a standard riding model with C–Haromatic distances of 0.93 Å and
Uiso = 1.2 Ueq. The amido N–H bond of 2 was located in the differ-
ence density map and refined isotropically.
IR (
1508 (s),
271 nm (9900); 322 nm (4900); 386 nm (3800); 478 nm (sh, 800);
636 (300). Conductivity (DCM, 10ꢀ3 M): 78.74 ohmꢀ1 cm2 molꢀ1
m
max/cmꢀ1):
[Ru-(PPh3)2] 693 (s). UV–Vis (DMF, (kmax
m
(C@O) 1639 (m),
m
(C@N) 1613 (m),
m(C–O–C)
m
(e
, Mꢀ1 cmꢀ1))):
.
Calc. for C53H41Cl8N2O2P2Ru: C, 53.74; H, 3.49; N, 2.36. Found: C,
53.93; H, 3.22; N, 2.01%.
2.7. [RuII(H3ucp)Cl(PPh3)] (3)
A mixture of H4ucp (0.0458 g; 0.104 mmol) and trans-[RuCl2
(PPh3)3] (0.100 g; 0.104 mmol) in methanol (20 cm3) was heated