(qt, 3JCF = 5.3 Hz, 2JCP = 5.5 Hz, RuCH CHCF3), 134.0 (s, ipso-
PCHCH3/RuOOCC6H4CH CH), 24.9 (vt, JPC = 9.9 Hz,
=
=
≡
≡
=
C/OOCC6H4C CH), 132.3 (s, o-C/OOCC6H4C CH), 129.1 (s,
PCHCH3/RuCH CHC6H4COO), 20.2–19.8 (m, PCHCH3).
1
m-C/OOCC6H4C CH), 125.4 (s, p-C/OOCC6H4C CH), 122.6
31P{ H}-NMR (600 MHz, CD2Cl2)
d
(ppm): 39.1 (s,
≡
≡
1
4
=
=
=
(tq, JCF = 269.8 Hz, JCP = 1.5 Hz, RuCH CHCF3), 119.7
P/RuCH CHC6H4COO), 38.7 (s, P/RuOOCC6H4CH CH).
Anal. Calc. for C55H97ClO4P4Ru2 (1183.84): C, 55.80; H, 8.26.
Found: C, 55.32; H, 7.99.
2
3
=
(tq, JCF = 30.5 Hz, JCP = 2.7 Hz, RuCH CHCF3), 83.4 (s,
≡
≡
OOCC6H4C CH), 79.7 (s, OOCC6H4C CH), 25.1 (vt, JPC
=
1
9.7 Hz, PCHCH3), 19.8 (s(br), PCHCH3) ppm. 31P{ H}-NMR
5
1
(600 MHz, CD2Cl2) d (ppm): 38.9 (q, JFP = 2.7 Hz).19F{ H}-
NMR (600 MHz, CD2Cl2): d (ppm): -62.2 (t, 5JFP = 2.7 Hz). Anal.
Calc. for C31H51F3O3P2Ru (691.74): C, 53.82; H, 7.43. Found: C,
53.69; H, 7.53.
i
=
=
{(P Pr3)2(CO)(CH CHCF3)(Ru}(l-OOCC6H4CH CH)-
{RuCl(CO)(PiPr3)2} 3b
In analogy to the synthesis of 3a a solution of RuClH(CO)(PiPr3)2
(62.5 mg, 0.129 mmol) in CH2Cl2 (10 mL) was added to 2b (89 mg,
0.129 mmol) dissolved in CH2Cl2 (5 mL). After stirring for 30 min
the red solution was evaporated to dryness to give 3b as a red
solid (144 mg, 0.122 mmol, 95%). 1H-NMR (600 MHz, CD2Cl2)
≡
RuCl2(p-cymene)(NC5H4C CH), 2c
A suspension of [RuCl2(p-cymene)]2 (500 mg, 0.816 mmol, 1 eq)
in 12 mL THF was treated with a solution of 4-ethynylpyridine
(205 mg, 1.99 mmol, 2.4 eq) in 2 mL THF. The dark orange
suspension was stirred for 5 d whereupon the colour changed
to light brown. All volatiles were then removed and 2c was
obtained as a yellow brown, microcrystalline product after
d (ppm): 9.19 (d(br), 3JHH = 15.96 Hz, 1H, RuCH=CHCF3), 8.93
3
=
(d, JHH = 13.35 Hz, 1H, OOCC6H4CH CHRu), 7.73 (d, 2H,
3
3
=
JHH = 7.95 Hz, o-H/OOCC6H4CH CHRu), 7.00 (d, 2H, JHH
=
3
=
7.95 Hz, m-H/OOCC6H4CH CHRu), 6.07 (d, JHH = 13.35 Hz,
=
=
1H, OOCC6H4CH CHRu), 5.40 (m, 1H, RuCH CHCF3),
=
washing with ether and hexanes (614 mg, 1.50 mmol 92%).
1H-NMR (300 MHz, CDCl3) d (ppm): 9.02 (d, 2H, JHH
2.75 (m, 6H, PCHCH3/RuCH CHC6H4COO), 2.34 (m,
3
=
=
6H, PCHCH/RuOOCC6H4CH CH), 1.34–1.20 (m, 72 H,
3
1
6.70 Hz, o-H/NC5H4C CH), 7.44 (d, 2H, JHH = 6.70 Hz, m-
PCHCH3). 13C{ H}-NMR (600 MHz, CD2Cl2)
d (ppm):
≡
3
2
≡
=
H/NC5H4C CH), 5.45 (d, 2H, JHH = 6.03 Hz, o-H/p-cymene),
208.7 (t, JCP
=
=
13.94 Hz, CO/RuCH CHC6H4COO),
3
2
=
5.22 (d, 2H, JHH = 6.03 Hz, m-H/p-cymene), 3.45 (s, 1H,
203.1 (t, JCP
12.84 Hz, CO/RuOOCC6H4CH CH),
3
≡
=
=
NC5H4C CH)), 3.00 (sept, 1H, JHH = 6.93 Hz, CH(CH3)2/p-
178.1 (s, OOCC6H4CH CHRu), 173.2 (m, RuCH CHCF3),
2
cymene), 2.11 (s, 3H, CH3/p-cymene), 1.31 (d, 6H, 3JHH = 6.93 Hz,
CH(CH3)2/p-cymene). Anal. Calc. for C17H19Cl2NRu (409.31): C,
49.88; H, 4.68; N, 3.42. Found: C, 49.43; H, 4.95; N, 3.10%.
157.0 (t, JCP
= 10.64 Hz, OOCC6H4CH=CHRu), 141.9
=
=
(s, p-C/OOCC6H4CH CHRu), 134.3 (s, OOCC6H4CH
=
CHRu),
129.4
(s,
o-C/OOCC6H4CH CHRu),
129.3
=
(s, ipso-C/OOCC6H4CH CHRu), 123.6 (s, m-C/OO-
1
=
=
CC6H4CH CHRu), 122.7 (q, JCF = 269.2, RuCH CHCF3),
i
=
=
{(CO)(P Pr3)2(CO)(PhCH CH)Ru}(l-OOCC6H4CH CH)-
2
=
119.5 (q, JCF = 30.1, RuCH CHCF3), 25.1 (vt, JPC
=
=
{RuCl(CO)(PiPr3)2}, 3a
=
9.5 Hz, PCHCH3/RuOOCC6H4CH CH), 24.9 (vt, JPC
=
To a solution of 2a (78 mg, 0.112 mmol) in CH2Cl2 (6 mL) was
added a solution of RuClH(CO)(PiPr3)2 (55 mg, 0.112 mmol)
in CH2Cl2 (7 mL). The mixture rapidly turned from yellow
to deep red. After stirring for 30 min the solvent was
removed in vacuo to give 3a as a deep red solid (127 mg,
9.9 Hz, PCHCH3/RuCH CHC6H4COO), 20.2–19.7 (m,
1
PCHCH3). 31P{ H}-NMR (600 MHz, CD2Cl2)
d (ppm):
5
=
39.4 (q, JFP = 2.80 Hz, P/RuOOCC6H4CH CH), 39.1 (s,
P/RuCH CHC6H4COO). 19F-NMR (600 MHz, CD2Cl2):
=
5
d
(ppm): -61.6 (t, JFP
C50H92ClF3O4P4Ru2 (1175.74): C, 51.08; H, 7.89. Found: C,
=
2.80 Hz). Anal. Calc. for
0.107 mmol, 96%). 1H-NMR (600 MHz, CD2Cl2) d (ppm):
3
=
8.91 (d, JHH = 13.38 Hz, 1H, OOCC6H4CH CHRu), 8.83
49.85; H, 7.95.
3
3
=
(d, 1H, JHH = 15.50 Hz, RuCH CHPh), 7.76 (d, 2H, JHH
=
=
8.20 Hz, o-H/OOCC6H4CH CHRu), 7.21–7.20 (m, 4H, o-
i
=
{(p-cymene)Cl2Ru}(l-NC5H4CH CH){RuCl(CO)(P Pr3)2}, 3c
3
=
H and m-H/RuCH CHPh), 7.01 (d, 2H, JHH = 8.20 Hz,
3
=
m-H/OOCC6H4CH CHRu), 6.92 (t, 1H, JHH = 7.14 Hz, p-
A suspension of RuCl2(p-cymene)(4-NC5H4CCH) 2c (77.7 mg,
0.190 mmol) in 15 mL of CH2Cl2 was treated with a solution of
RuClH(CO)(PiPr3)2 (92 mg, 0.190 mmol) in 8 mL of CH2Cl2.
The red solution was stirred for 30 min. After removal of
all volatiles in vacuo the product was obtained as a red solid
3
=
=
H/RuCH CHPh), 6.26 (d, JHH = 15.50 Hz, 1H, RuCH CHPh),
3
=
6.08 (d, JHH
=
13.38 Hz, 1H, OOCC6H4CH CHRu),
=
2.76 (m, 6H, PCHCH3/RuCH CHC6H4COO), 2.35 (m,
=
6H, PCHCH3/RuOOCC6H4CH CH), 1.34–1.23 (m, 72
1
H, PCHCH3). 13C{ H}-NMR (600 MHz, CD2Cl2)
d
(160 mg, 0.179 mmol, 94%). 1H-NMR (400 MHz, CDCl3) d
3
=
=
(ppm): 209.4 (s, CO/RuCH CHC6H4COO), 203.1 (s,
(ppm): 9.73 (d, 1H, JHH = 13.64 Hz, NC5H4CH CHRu), 8.56
3
=
=
=
CO/RuOOCC6H4CH CH), 177.5 (s, OOCC6H4CH CHRu),
(d, 2H, JHH = 6.80 Hz, o-H/NC5H4CH CHRu), 6.78 (d,
2
3
=
=
=
161.5 (t, JCP
2JCP
11.1 Hz, OOCC6H4CH CHRu), 141.56 (s, p-
C/OOCC6H4CH CHRu), 141.32 (s, ipso-C/RuCH CHPh),
11.2 Hz, RuCH CHPh), 156.5 (t,
2H, JHH = 6.80 Hz, m-H/NC5H4CH CHRu), 6.05 (d, 1H,
3
3
=
=
=
JHH = 13.64 Hz, NC5H4CH CHRu), 5.36 (d, 2H, JHH
=
3
=
=
6.00 Hz, m-H/p-cymene), 5.18 (d, 2H, JHH = 6.00 Hz, o-
3
=
=
134.4 (s, OOCC6H4CH CHRu), 133.6 (s, RuCH CHPh),
129.7 (s, ipso-C/OOCC6H4CH CHRu), 129.4 (s, o-
C/OOCC6H4CH CHRu), 128.6 (s, m-C/RuCH CHPh), 124.1
(s, o-C/RuCH CHPh), 123.6 (s, m-C/OOCC6H4CH CHRu),
H/p-cymene), 3.00 (sept, 1H, JHH = 6.90 Hz, CH(CH3)2/p-
=
cymene), 2.78-2.66 (m, 6H, PCHCH3), 2.11(s, CH3/p-cymene),
1
1.30–1.19 (m, 42H, CH(CH3)2/p-cymene, PCHCH3). 13C{ H}-
=
=
=
=
NMR (400 MHz, CDCl3) d (ppm): 202.0 (s, CO), 170.3 (s,
=
=
=
123.4 (s, p-C/RuCH CHPh), 25.2 (vt, JPC
=
9.3 Hz,
NC5H4CH CHRu), 153.8 (s, o-C/NC5H4CH CHRu), 144.6 (s,
8010 | Dalton Trans., 2010, 39, 8000–8011
This journal is The Royal Society of Chemistry 2010
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