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2
3
4
5
6
7
8
9
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Preparation of [PdCl2(3)2] was briefly described as unpublished
results in Ref. 5, p. 880.
fcpp was prepared according to the methods described in Ref
3c.
Reactions were carried out under an N2 atmosphere. cis-
[PtCl2(NCPh)2] (266 mg, 0.564 mmol), fcpp (347 mg, 1.188
mmol), and CH2Cl2 (15 mL) were put in Schlenk tube, and the
solution was stirred for 30 min. After the volume of the solu-
tion was reduced to ca. 5 mL, hexane (20 mL) was added to
complete precipitation. The product was washed twice with
hexane (10 mL), and dried in vaccuo. cis-[PtCl2(fcpp)2] (4) was
obtained as a monosolvate of CH2Cl2. Yield: 388 mg (97%).
1H NMR (300 MHz, CDCl3) δ 4.18 (br, 2H, Fc), 4.37 (br, 4H,
Fc), 4.61 (br, 2H, Fc), 7.43 (m, 2H, Ph), 7.54 (m, 1H, Ph), 7.95,
(m, 2H, Ph). Anal. Found: C, 42.30; H, 2.76 %. Calcd for
C33H28Cl4Fe2P2Pt: C, 42.39; H, 3.02 %.
10 M. Roundhill, "Comprehensive Coordination Chemistry," ed.
by G. Wilkinson, Pergamon Press, Oxford, U. K. (1987), Vol. 5,
pp. 448–449.
11 4 (312 mg, 0.333 mmol), fcpp (107 mg, 0.366 mmol), and
CH2Cl2 (40 mL) were put in a Schlenk tube. To the solution
thus obtained was added excess AgBF4 (136 mg, 0.699 mmol).
The suspension was stirred for 30 min, and then the precipitate
was filtered off. The volume of the filtrate was reduced to ca. 10
mL, and then hexane (20 mL) was added slowly. The precipitate
was collected by filtration, washed twice with hexane (10 mL),
and dried in vaccuo. Yield: 398 mg (93%). 1H NMR (300 MHz,
CDCl3) δ 3.86 (br, 2H, Fc),4.08 (br, 2H, Fc), 4.12 (br, 2H, Fc),
4.18 (br, 2H, Fc), 4.45 (br, 2H, Fc), 4.51 (br, 2H, Fc), 4.70 (br,
6H, Fc),4.76 (br, 4H, Fc), 4.94 (br, 2H, Fc), 7.32 (m, 1H, Ph),
7.45 (m, 4H, Ph), 7.57, (m, 4H, Ph), 7.78 (m, 2H, Ph), 7.94, (m,
4H, Ph). Anal. Found: C, 46.95; H, 3.22 %. Calcd for a partial
solvate, C48H39BClF4Fe3P3Pt·(CH2Cl2)0.6: C, 46.90; H, 3.26 %.
12 Crystal data for 4: dark red crystals, monoclinic, space group
P21/n (No. 14), formula C33H28Cl4Fe2P2Pt, formula weight
935.13; a = 18.576(3), b = 17.409(3), c = 9.888(2) Å, β =
96.13(1)°, V = 3179.3(8) Å3; Z = 4, Dcalc = 1.954 g cm–3, R =
0.039, Rw = 0.046 for 4479 reflections with Fo > 3σ(Fo), 377
parameters, GOF = 1.07.
iron, as discussed previously.6 The interaction is considered to
be enhanced when the phosphorus atom coordinates to an elec-
tron-withdrawing metal fragment.
Recently, we found that two neutral complexes having one
fcpp unit, [MnCp(CO)2(fcpp)] and [W(CO)5(fcpp)], successful-
ly polymerize upon UV irradiation in THF or acetonitrile.15
Thus, a similar photolysis was carried out for the neutral 4.
Upon irradiation of 4 for 1 h, a brown precipitate was formed
and a 31P{1H} NMR spectrum of the supernatant solution
showed complete disappearance of the signal due to the starting
4. Unfortunately, owing to very low solubility of the precipi-
tate, detailed spectroscopic characterization is difficult at pres-
ent, but elemental analyses indicate that a formula of the prod-
uct is close to that of 4. We consider that the product is a poly-
4 having a cross-linked structure which is responsible for the
low solubility. Reactivity of 5 is now under investigation.
13 Crystal data for 5: dark red crystals, monoclinic, space group
P21/n (No. 14), formula C49H41BCl3F4Fe3P3Pt, formula weight
1278.58; a = 20.133(3), b = 14.540(2), c = 17.319(3) Å, β =
110.08(1)°, V = 4761(1) Å3; Z = 4, Dcalc = 1.783 g cm-3, R =
0.037, Rw = 0.047 for 5526 reflections with Fo > 3σ(Fo), 578
parameters, GOF = 1.14.
This work was supported by a Grant-in-Aid for Scientific
Research (Grant No. 11740372 and Grant No. 12640540) from
the Ministry of Education, Science, Sports, and Culture of Japan.
14 I. R. Butler, W. R. Cullen, F. W. B. Einstein, S. J. Rettig, and A.
J. Willis, Organometallics, 2, 128 (1983).
15 T. Mizuta, M. Onishi, and K. Miyoshi, submitted for publica-
tion.
References and Notes
1
Recent reviews on poly(ferrocenes): a) I. Manners, Adv.
Organomet. Chem., 37, 131 (1995). b) I. Manners, Polyhedron,