5
424 Organometallics, Vol. 17, No. 24, 1998
Steenwinkel et al.
filtration and subsequently recrystallized by cooling a hot
saturated solution in MeCN. The colorless crystals of 5b that
formed were collected by filtration, washed with cold MeCN
Syn th esis of [2,3,5,6-Tetr akis{(dim eth ylam in o)m eth yl}-
p h en ylen e-1-(a cet on it r ilep la t in u m (II))-4-(a cet on it r ile-
palladiu m (II))] Bis(tr iflu or om eth an esu lfon ate) (9). Prepa-
ration was as described for 5a , using the neutral Pt/Pd complex
(
0
7
2
10 mL) and Et O (50 mL), and then dried in vacuo. Yield:
1
.89 g (92%), mp > 200 °C. H NMR (CD
.32-7.24 (m, 16 H, Ar), 7.05-6.95 (m, 16 H, Ar), 6.90-6.80
), 2.79 (s, 24 H, NMe ). Anal.
]: C, 67.92; H, 6.35; N, 6.79. Found:
3
CN, 200 MHz): δ
8 (48 mg, 74 µmol) as starting material. Yield: 68 mg (92%),
1
white solid (mp 141-144 °C). H NMR (CD
3
CN + 10% D
), 3.86 (s, 4
) 39.0 Hz, NMe ), 2.80 (s, 12
2
O,
3
(
m, 8 H, Ar), 3.83 (s, 8 H, NCH
2
2
200 MHz): δ 4.08 (s, 4 H, J Pt-H ) 46.5 Hz, NCH
2
3
Calcd for [C70
H
78
B
2
N
6
Pd
2
2 Pt-H
H, NCH ), 2.96 (s, 12 H, J
2
1
3
C, 67.72; H, 6.30; N, 6.85.
H, NMe ). C NMR (CD CN + 10% D O, 50 MHz): δ 152.7,
141.2, 138.9 ( J Pt-C ) 82 Hz), 138.8 ( J Pt-C ) 43 Hz), 75.7
2
3
2
2
3
Syn th esis of [2,3,5,6-Tetr akis{(dim eth ylam in o)m eth yl}-
p h en ylen e-1,4-b is(p yr id in ep a lla d iu m (II))] Bis(t r iflu o-
r om eth a n esu lfon a te) (6). A stirred colorless solution of the
bisacetonitrile complex 5a (55 mg, 61 µmol) in MeCN (2 mL)
was treated with pyridine (0.2 mL, excess) at room tempera-
ture. The color of the reaction mixture turned to pale yellow
instantaniously. The reaction mixture was stirred at room
temperature for 5 min, after which time Et O (3 mL) was
2
slowly added by vapor diffusion. This resulted in the formation
of pale yellow crystals of 6, which were filtered off, washed
2
4
(NCH
(NMe
2
,
J
Pt-C ) 64 Hz), 72.8 (NCH
2
, J Pt-C ) 11 Hz), 55.1
2
2
, J Pt-C ) 16 Hz), 53.4.
Syn th esis of [2,3,5,6-Tetr akis{(dim eth ylam in o)m eth yl}-
p h en ylen e-1-(a cet on it r ilep la t in u m (II))-4-(a cet on it r ile-
p a lla d iu m (II))] Bis(tetr a p h en ylbor a te) (10). Preparation
as described for 5b, using the Pt/Pd bistriflate complex 9 (40
mg, 41 µmol) as starting material. Yield: 48 mg (89%),
colorless crystals, mp 167-169 °C (dec). Anal. Calcd for
[
C
70
H
78
B
2
N
6
3
PdPt + 2CH CN]: C, 63.10; H, 6.01; N, 7.95.
with Et
2
O (2 × 5 mL), and dried in vacuo. Yield: 39 mg (73%),
Found: C, 63.14; H, 5.90; N, 7.78.
1
mp 152 °C (dec). H NMR (CD
3
CN, 200 MHz): δ 8.77 (d, 4 H,
Syn th esis of [2,3,5,6-Tetr akis{(dim eth ylam in o)m eth yl}-
p h en ylen e-1,4-bis(ch lor op la tin u m (II))] (13). A solution of
n-BuLi (7.5 mL, 1.6 M solution in hexanes, 12 mmol) was
added to a stirred suspension of the aryl dibromide 11 (2.32
3
3
J
HH ) 4.4 Hz, py-H), 7.93 (t, 2 H, J HH ) 7.6 Hz, py-H), 7.54
m, 4 H, py-H), 3.94 (s, 8 H, NCH ), 2.69 (s, 24 H, NMe ). Anal.
Calcd for [C30 Pd ]: C, 37.32; H, 3.55; N, 8.70.
(
2
2
H
34
F
6
N
6
O
6
2 2
S
Found: C, 37.25; H, 3.68; N, 8.62.
g, 5 mmol) in Et O (100 mL) at -78 °C. The resulting reaction
2
Syn th esis of [2,3,5,6-Tetr akis{(dim eth ylam in o)m eth yl}-
p h en ylen e-1-tr im eth ylsilyl-4-(ch lor op la tin u m (II))] (7). A
solution of n-BuLi (1.1 mL, 1.6 M solution in hexanes, 1.76
mmol) was added dropwise over 5 min to a solution of the
monosilylated aryltetramine 3 (0.62 g, 1.64 mmol) in hexane
mixture was stirred for 15 min at -78 °C, then allowed to
warm to room temperature and subsequently stirred for an
additional 30 min at this temperature. The precipitated
organodilithium compound 12 was collected by centrifugation,
washed with Et
To this white stirred suspension was added a solution of [PtCl
SEt ] (4.91 g, 11 mmol) in THF (100 mL) at room temper-
2
O (50 mL), and suspended in THF (50 mL).
(30 mL) at room temperature, and the resulting reaction
2
-
mixture was stirred for 18 h at this temperature. After this
time, the volatiles were removed in vacuo, and the residue was
(
2 2
)
ature. The reaction mixture was stirred for 30 min, and the
product that had precipitated during this time was collected
by filtration. The product was washed with MeOH (3 × 50
then dissolved in Et
stirred suspension of [PtCl
2
O (15 mL) and added in one portion to a
(SEt ] in Et O (15 mL) at room
2
2
)
2
2
temperature. The resulting reaction mixture was stirred at
room temperature for 2 h, after which the solvent was
evaporated. The crude oily product was purified by column
mL) and Et
2
O (2 × 50 mL) and dried in vacuo to afford the
bisplatinum(II) complex 13 (3.58 g, 94% based on the dibro-
mide 11) as a white solid (mp > 200 °C). H NMR (CDCl ,
3
1
chromatography (neutral alumina) using the mixture CH
2 2
Cl /
3
2
2
00 MHz): δ 3.88 (s, 8H, NCH
2
, J Pt-H not observed), 2.27 (s,
, J Pt-H not observed due to very poor S/N ratio).
Rea ction of 13 w ith SO . A 300 mg portion of the bis-
chloroplatinum) complex 13 was suspended in CH Cl (75 mL)
in a 200 mL Schlenk tube, and SO was bubbled through this
EtOAc/Et N ) 35:60:5 as eluent. The fractions that contained
3
3
4H, NMe
2
the desired product (identified by TLC) were collected together
and concentrated in vacuo. The solid residue was subse-
quently recrystallized from warm hexane. This resulted in
the formation of white crystals of the Pt/Si complex 7, which
2
(
2
2
2
stirred suspension at room temperature. The color of the
reaction mixture immediately turned to deep orange, and when
were collected by filtration and dried in vacuo. Yield: 0.35 g
1
(
(
1
35%), mp 78-81 °C (dec). H NMR (CDCl
3
, 300 MHz): δ 4.11
), 3.37 (s, 4 H, NCH ), 3.04 (s,
), 2.01 (s, 12 H, NMe ), 0.31 (s,
). C NMR (CDCl , 75 MHz): δ 147.0 (Cipso-Pt,
3
the solution was saturated with SO
A saturated solution of SO in Et O (75 mL) in a Schlenk tube
was then connected through a knee tube to the one containing
the metal complex. Slow vapor diffusion of Et O into the CH
Cl solution then afforded dark orange crystals of the Pt/Pt
bis(SO ) adduct 16, which were suitable for an X-ray analysis
2
, all solids had dissolved.
s, 4 H, J Pt-H ) 45.3 Hz, NCH
2 H, J Pt-H ) 35.9 Hz, NMe
2
2
3
2
2
2
2
1
3
9
H, SiMe
3
3
1
3
2
2
-
J
Pt-C ) 1000 Hz), 141.7 (Cmeta, J Pt-C ) 75 Hz), 139.1 (Cortho
Pt-C ) 44 Hz), 133.5, 77.7 (NCH
,
2
2
2
J
2
,
J
Pt-C ) 60 Hz), 62.6
), 4.2 (SiMe ).
PtSi]: C, 41.47; H, 6.79; N, 9.21.
2
(NCH
2
), 54.4 (NMe
2
, J Pt-C ) 13 Hz), 44.6 (NMe
41ClN
2
3
2
2
when kept in an SO atmosphere. These crystals slowly
Anal. Calcd for [C21
H
4
decolorize in contact with air. 1H NMR (SO
-saturated CDCl
,
Found: C, 41.36; H, 6.75; N, 9.16.
Syn th esis of [2,3,5,6-Tetr akis{(dim eth ylam in o)m eth yl}-
p h en ylen e-1-(ch lor op la t in u m (II))-4-(ch lor op a lla d iu m -
2
3
3
2
00 MHz): δ 3.99 (s, 8 H, J Pt-H ) 46.4 Hz, NCH
2
), 2.99 (24
3
13
H, J Pt-H ) 38.8 Hz, NMe
5
2
). C NMR (SO
2
-saturated CDCl
3
,
1
0 MHz, 298 K): δ 145.2 (Cipso
,
J
Pt-C not observed), 135.3
(
(
II))] (8). A solution of [Pd(OAc)
5 mL) was added in one portion to a stirred solution of the
Cl (5 mL) at room
2
] (19 mg, 85 µmol) in MeOH
2
2
(C
ortho, J Pt-C not observed), 74.5 (NCH
2
, J Pt-C not observed),
Cl ): λmax [nm] (ꢀ
2
5
4.1 (NMe
2
, J Pt-C ) 26 Hz). UV/vis (CH
2
2
platinum complex 7 (50 mg, 82 µmol) in CH
2
2
10 M cm-1]) ) 434 (0.54), 348 (2.05).
4
-1
[
temperature. The reaction mixture was stirred for 1 h and
then filtered through Celite. The filtrate was added to a
stirred solution of LiCl (10 mg, 235 µmol) in MeOH, and the
resulting reaction mixture was stirred for 15 min. The
precipitated product was collected by centrifugation, washed
Syn th esis of [2,3,5,6-Tetr akis{(dim eth ylam in o)m eth yl}-
p h en ylen e-1,4-bis(a ceton itr ilep la tin u m (II))] Bis(tr iflu o-
r om eth a n esu lfon a te) (14a ). A stirred suspension of the
neutral bisplatinum complex 13 (3.58 g, 4.68 mmol) in a
mixture of MeCN and water (100 mL, 19:1) was titrated with
a solution of AgOTf (2.47 g, 9.6 mmol) in MeCN (25 mL) at
room temperature. During this procedure, AgCl precipitated
as a white solid. After removal of the AgCl by centrifugation,
the supernatant solution was filtered through Celite. The
resulting filtrate was then concentrated to ∼25 mL and layered
with MeOH (3 × 15 mL) and Et O (2 × 15 mL), and dried in
2
vacuo. Yield: 48 mg (90%), white solid (mp > 200 °C). This
product has very poor solubility properties, and conventional
1
13
H and C NMR spectroscopic characterization was not
successful. It was used without further purification for the
preparation of the more soluble and easily characterizable ionic
heterobimetallic species 9 and 10.
2
with Et O (50 mL). The precipitated product was collected