Alkynylbis(bidentate phosphine)ruthenium Dendrimers
Organometallics, Vol. 22, No. 7, 2003 1405
7
.41 (AA′BB′, 8H, C
6
H
6
4
), 7.57 (d, J HH ) 2 Hz, 2H, C
3
6
H
3
), 7.58
5.98 (AA′BB, 6H, CH), 6.80-7.70 (m, 129H, PPh + CH +
1
3
13
(t, J HH ) 2 Hz, 1H, C
H
). C NMR: δ -0.2 (Me), 88.7 and
C
6
H
3
2
). C NMR: δ 45.9 (m, CH ), 88.2 and 90.5 (CtC), 120.0,
8
1
9.4 (CtC), 96.0 (tC), 103.0 (SiCt), 121.6, 122.9, 123.6, 124.0,
31.7, 133.0, 134.1, 134.5.
126.6, 126.7 (Cd), 127.9, 129.1, 130.4, 131.2, 131.6, 133.7,
132.8 (d, J CP ) 63 Hz), 356.4 (dCRu). 31P NMR: δ -15.8
1
-Me
3
SiCtC-3,5-(4-IC
6
H
4
CtC)
2
C
6
H
3
(11). tert-Butyllith-
(PPh
,3,5-C
NaPF (0.20 g, 1.2 mmol) was added to a solution of 2 (0.090
g, 0.20 mmol) and cis-[RuCl (dppe) ] (1.00 g, 1.02 mmol) in
CH Cl (25 mL) and the mixture stirred for 12 h. NEt (1 mL)
2
).
ium (8.7 mL, 1.5 M solution in hexane, 13.1 mmol) was slowly
added to a cooled solution (-78 °C) of 10 (1.70 g, 3.19 mmol)
in Et
1
6 3 6 4 2 3
H {4-CtCC H CtC-tr a n s-[Ru Cl(d p p e) ]} (5).
6
2
O (100 mL) and the mixture stirred for 30 min. A solution
O (50 mL) was then added
2
2
of iodine (2.10 g, 8.27 mmol) in Et
2
2
2
3
slowly via a cannula. The mixture was stirred for 10 min and
allowed to warm to room temperature with stirring over 30
min. The mixture was washed with saturated aqueous sodium
thiosulfate solution, and the organic layer collected and dried
using magnesium sulfate. The mixture was filtered and the
was added and the mixture stirred for a further 5 min. The
solvent was removed in vacuo, and the residue purified on an
alumina column. Elution with acetone/Et
2
O (1:19) to remove
Cl to
trans-[RuCl (dppe) ] was followed by elution with CH
2
2
2
2
remove the product. Evaporation of the solvent from the eluent
afforded 5 as a yellow powder (440 mg, 68% based on 2). MS:
solvent removed from the filtrate. Precipitation from a CH
Cl /petrol solution by slow evaporation afforded 11 as a white
solid (1.65 g, 82%). HRMS (EI) C27 : calcd 625.9424,
found 625.9427. UV-vis: 31 800 [8.05], 33 800 [8.08], 37 100
2
-
2
3
C
249 ([M] , 20), 898 ([Ru(dppe)
: C, 71.01; H, 4.94. Found: C, 70.90; H, 5.20.
UV-vis: 24 200 [9.90], 33 300 [6.60], 40 000 [13.7]. IR:
+
] , 100). Anal. Calcd for
+
2
H
20SiI
2
192 3 3
H159Cl P12Ru
-
1
1
[
7
(
8
1
5.60]. IR: ν(CtC) 2154 cm . H NMR: δ 0.23 (s, 9H, Me),
.44 (AA′BB′, 8H, C ), 7.56 (d, J HH ) 1.5 Hz, 2H, C ), 7.58
t, J HH ) 1.5 Hz, 1H, C ). C NMR: δ -0.2 (Me), 89.0 and
9.6 (CtC), 94.6 (CI), 96.0 (tC), 103.0 (SiCt), 122.2, 123.6,
24.0, 133.1, 134.1, 134.5, 137.6.
-Me SiCtC-3,5-(4-HCtCC
-1 1
ν(CtC) 2204, 2065 cm . H NMR: δ 2.69 (m, 24H, CH
2
), 6.56
6
H
4
6 3
H
(
AA′BB′, 6H, CH), 6.93-7.46 (m, 126H, PPh + CH), 7.59 (s,
1
3
6
H
3
13
3
1
1
H, C
6
H
3
2
). C NMR: δ 30.6 (m, CH ), 88.3 and 91.5 (CtC),
16.2 (Ct), 127.0, 127.2, 128.9, 130.0, 130.9, 134.2, 134.4,
31
35.5, 136.3. P NMR: δ 49.9.
1
3
6
H
4
CtC)
2
C
6
H
3
(12). Zinc(II)
1
,3,5-C
NaPF (48 mg, 0.28 mmol) was added to a solution of 2 (20
mg, 0.044 mmol) and cis-[RuCl (dppm) ] (300 mg, 0.22 mmol)
in CH Cl (20 mL) and the mixture stirred for 3 h. Deoxygen-
ated petrol (50 mL) was added and the mixture filtered. The
filtrate was dissolved in CH Cl (15 mL), NEt (5 mL) added,
and the mixture stirred for 1 h. The reaction mixture was
placed on a basic alumina column and eluted with CH Cl
petrol (1:1). The eluent was taken to dryness to give a pale
orange solid; recrystallization from CH Cl /MeOH at -20 °C
afforded orange crystals identified as 6 (100 mg, 75%). MS:
6 3 6 4 2 3
H {4-CtCC H CtC-tr a n s-[Ru Cl(d p p m ) ]} (6).
bromide (1.08 g, 4.8 mmol) was flame dried under vacuum in
a Schlenk tube and thf (10 mL) added. A solution of ethynyl-
magnesium bromide (10 mL, 0.5 M in thf, 5.0 mmol) was added
and the mixture stirred for 5 min. Compound 11 (1.0 g, 1.6
6
2
2
2
2
2 3 2
mmol) and PdCl (PPh ) (200 mg, 0.3 mmol) were added, and
2
2
3
the resultant mixture was stirred a further 2 h. The mixture
was washed with aqueous ammonium chloride, and the organic
layer was collected, dried with magnesium sulfate, and filtered.
The solvent was removed from the filtrate, and the resulting
residue purified by column chromatography on silica, eluting
2
2
/
2
2
with a CH
afforded 12 as a white powder (340 mg, 50%). HRMS (EI)
22Si: calcd 422.1491, found 422.1488. UV-vis: 31 100
8.55], 33 200 [8.62], 37 000 [4.60]. IR: ν(CtC) 2109, 2155,
2 2
Cl /petrol mixture (1:19). Removal of the solvent
+
+
2
] , 100). Anal. Calcd for
3
164 ([M] , 5), 869 ([Ru(dppm)
: C, 69.82; H, 4.68. Found: C, 69.05; H, 4.93.
C
186 3 3
H147Cl P12Ru
31
C H
-
1
1
UV-vis: 24 700 [5.60]. IR (KBr): ν(CtC) 2106 cm
. H
[
NMR: δ 4.90 (m, 12H, CH ), 5.97 (AA′BB′, 6H, CH), 6.80-
2
-
1 1
ν(HCt) 3296 cm . H NMR: δ 0.24 (s, 9H, Me), 3.17 (s, 2H,
tCH), 7.45 (m, 8H, C ), 7.57 (d, J HH ) 1.5 Hz, 2H, C ),
). C NMR: δ -0.2 (Me), 79.1,
1
3
7
8
(
.70 (m, 129H, PPh + CH + C
6
H
3
2
). C NMR: δ 50.2 (m, CH ),
6
H
4
6 3
H
7.9 and 91.6 (CtC), 124.4, 127.5, 129.2, 129.9, 130.3, 133.4
1
3
7
8
1
6 3
.60 (t, J HH ) 1.5 Hz, 1H, C H
d, J CP 64 Hz), 134.0, 134.8 (m), 135.6. 31P NMR: δ -5.8.
,3 ,5 -C {4 -C tC C C tC -t r a n s -[R u (C tC P h )-
d p p e) ]} (7). NaPF (50 mg, 0.30 mmol) and NEt (0.5 mL)
3.1 (CtC), 89.6 and 89.9 (CtC), 96.0, 103.0 (CtC), 122.2,
23.1, 123.6, 124.0, 131.6, 132.1, 134.2, 134.6.
1
6
H
3
6 4
H
(
2
3
6
3
Syn th eses of Vin ylid en e- a n d Alk yn ylr u th en iu m Com -
were added to a solution of 5 (155 mg, 0.048 mmol) and
phenylacetylene (0.05 mL, 0.46 mmol) in CH Cl (15 mL), and
plexes. [1,3,5-C
6
H
2
3
{4-CtCC
(3). NaPF
6
H
4
CHdC-tr a n s-Ru Cl(dppe)
(130 mg, 0.600 mmol) was added
(dppe)
(20 mL) and the mixture
stirred for 3 h. Deoxygenated petrol (50 mL) was added and
the mixture filtered; the precipitate was washed with Et O (2
10 mL) to afford 3 as a pale orange solid (220 mg, 70%).
2 3
} ]-
2
2
[
P F ‚0.5CH Cl
6
]
3
2
6
the mixture stirred for 5 h. The solvent was removed in vacuo
and the residue chromatographed on an alumina column.
to a solution of 2 (48 mg, 0.124 mmol) and cis-[RuCl
600 mg, 0.620 mmol) in CH Cl
2
2
]
(
2
2
Elution with a mixture of CH
phenylacetylene was followed by elution with a mixture of CH
Cl /petrol (3:2) to remove the product. Evaporation of the
solvent from the eluent afforded 7 as a yellow powder (105
2 2
Cl /petrol (1:19) to remove excess
2
-
2
2
×
+
+
2
] , 100). Anal.
MS: 3540 ([M - PF
6
] , 0.25), 933 ([RuCl(dppe)
+
+
2
] , 100). Anal.
mg, 64%). MS: 3445 ([M] , 0.4), 898 ([Ru(dppe)
Calcd for C216 : C, 75.32; H, 5.09. Found: C, 74.98;
H, 5.60. UV-vis: 24 300 [11.6], 31 740 [9.81]. IR: ν(CtC)
Calcd for C192.5
H163Cl F P15Ru : C, 62.04; H, 4.41. Found: C,
4 18 3
H
174 3
P12Ru
6
1.83; H, 5.29. UV-vis: 24 200 [2.40]. IR: ν(CtC) 2065, ν-
-
1 1
(
3
C)C) 1636, ν(PF) 847 cm . H NMR: δ 2.89 (m, 24H, CH
.75 (m, 3H, dCH), 5.28 (s, 1H, CH Cl ), 5.60 (AA′BB′, 6H,
CH), 6.60-7.40 (m, 126H, PPh + CH), 7.52 (s, 3H, C
NMR: δ 28.6 (m, CH ), 88.0 and 90.5 (CtC), 123.8, 126.4,
26.8 (Cd), 127.4, 128.8, 130.6, 131.1, 131.3, 134.3, 133.5 (d,
2
),
-1 1
2
203, 2057 cm . H NMR: δ 2.63 (m, 24H, CH
2
), 6.65 (AA′BB′,
2
2
1
3
6H, CH), 6.81 (AA′BB′, 6H, CH), 6.92-7.61 (m, 138H, PPh +
6
H
3
).
C
1
3
CPh + C
6
H
3
). C NMR: δ 31.4 (m, CH
2
), 88.3 and 91.6
2
(
CtC), 116.2 (Ct), 117.2 (tC), 127.0, 127.4, 128.6, 128.7,
129.9, 130.5, 130.9, 134.1, 134.3, 136.9 (m). P NMR: δ 54.5.
1
3
1
3
1
J
CP ) 64 Hz), 353.9 (dCRu). P NMR: δ 37.7 (PPh
1,3,5-C {4-CtCC CH dC-tr a n s-R u Cl(d p p m )
P F (4). NaPF (100 mg, 0.60 mmol) was added to a solution
of 2 (50 mg, 0.101 mmol) and cis-[RuCl (dppm) ] (500 mg, 0.40
mmol) in CH Cl (20 mL) and the mixture stirred for 3 h.
Deoxygenated petrol (50 mL) was added and the mixture
filtered. The precipitate was washed with Et
O (2 × 10 mL)
to afford a pale orange solid identified as 4 (450 mg, 76%).
2
).
[
6
H
3
6
H
4
2 3
} ]-
Alter n a tive P r ep a r a tion of 7. A mixture of trans-[Ru(4-
[
6
]
3
6
CtCC
triiodobenzene (50 mg, 0.11 mmol), PdCl
mmol), and CuI (15 mg, 0.08 mmol) in thf (30 mL) and NEt
3
6
H
4
CtCH)(CtCPh)(dppe)
2
] (400 mg, 0.356 mmol), 1,3,5-
2
(PPh (15 mg, 0.02
3 2
)
2
2
2
2
(1 mL) was stirred at room temperature overnight. The solvent
was removed in vacuo and the residue subjected to column
chromatography on alumina, eluting with 3:7 dichloromethane/
petrol. A broad yellow band was slowly eluted, the faster-
2
+
+
MS: 3457 ([M - PF ] , 0.6), 905 ([RuCl(dppm) ] , 100). Slow
compound decomposition over a period of days precluded a
6
2
moving portion of which was identified as trans-[(dppe)
CtC)Ru (4,4′-CtCC CtCCtCC CtC)Ru (CtCP h )-
], with the rest of the band identified as a mixture of
2
(Ph-
microanalysis. UV-vis: 24 100 [0.90]. IR: ν(CtC) 2068,
6
H
4
6 4
H
ν(CdC) 1640, ν(PF) 846 cm 1. 1H NMR: δ 4.96 (m, 12H, CH
-
),
(dppe)
2
62
2