Combining ferrocenes and molecular squares: Self-assembly of heterobimetallic macrocyclic squares incorporating mixed transition metal systems and a main group element. Single-crystal X-ray structure of [Pt(dppf)(H2O)2][OTf]2

Article abstract of DOI:10.1021/om950781q

The preparation of the reactive diaqua complexes of (bis(diphenylphosphino)ferrocene)-palladium(II) and -platinum(II) bis(triflates) and the X-ray crystal structure of [Pt(dppf)-(H₂O)₂][OTf]₂ (dppf = 1,1′-bis(diphenylphosphino)ferrocene) are reported. Interaction of these complexes with 2,7-diazapyrene produced novel octanuclear square-shaped metallomacrocycles. Modular self-assembly of [Pd(dppf)H₂O)₂][OTf]₂ and [Pt(dppf)H₂O)₂][OTf]₂ with bis-[4-(4′-pyridyl)phenyl]iodonium triflate results in the facile formation of hexanuclear macrocyclic squares with alternating iodonium-late transition metals (Pd(II) or Pt(II)) at the corners and ferrocene complex as the chelating unit.

Full text of DOI:10.1021/om950781q

904
Organometallics 1996, 15, 904-908
Articles
Com bin in g F er r ocen es a n d Molecu la r Squ a r es:
Self-Assem bly of Heter obim eta llic Ma cr ocyclic Squ a r es
In cor p or a tin g Mixed Tr a n sition Meta l System s a n d a
Ma in Gr ou p Elem en t. Sin gle-Cr ysta l X-r a y Str u ctu r e of
[P t(d p p f)(H2O)2][OTf]2
Peter J . Stang,* Bogdan Olenyuk, J un Fan, and Atta M. Arif
Department of Chemistry, The University of Utah, Salt Lake City, Utah 84112
Received October 3, 1995X
The preparation of the reactive diaqua complexes of (bis(diphenylphosphino)ferrocene)-
palladium(II) and -platinum(II) bis(triflates) and the X-ray crystal structure of [Pt(dppf)-
(H2O)2][OTf]2 (dppf ) 1,1′-bis(diphenylphosphino)ferrocene) are reported. Interaction of these
complexes with 2,7-diazapyrene produced novel octanuclear square-shaped metallomacro-
cycles. Modular self-assembly of [Pd(dppf)(H2O)2][OTf]2 and [Pt(dppf)(H2O)2][OTf]2 with bis-
[4-(4′-pyridyl)phenyl]iodonium triflate results in the facile formation of hexanuclear
macrocyclic squares with alternating iodonium-late transition metals (Pd(II) or Pt(II)) at
the corners and ferrocene complex as the chelating unit.
In tr od u ction
for transition metal complexes with interesting proper-
ties and geometric features. It was extensively studied
and used as a ligand in the ruthenium-, rhodium-, and
palladium-catalyzed hydrogenation of olefins5 and
nickel- and palladium-catalyzed Grignard cross-coupling
reactions6 and as a ligand for catalytic olefin reduction.7
Our primary goal, therefore, was to establish its ap-
plicability in the preparation of the reactive Pd(II) and
Pt(II) complexes, suitable for the self-assembly of mac-
rocyclic squares. Also, since to date only bis(triflates)
of the transition metal bis(phosphines) and, sometimes,
their monoaqua complexes were used for self-assembly
in organic solvents, it was of particular interest to
ascertain the possible use of diaqua complexes of the
transition metal bis(triflates) in self-assembly, since
these diaqua complexes exhibit high air and thermal
stability, in contrast to some hygroscopic anhydrous bis-
(triflates).8
The design and study of various metal-containing
macrocycles is one of the most active and interesting
areas in modern supramolecular chemistry.1,2 Molec-
ular squares, a new family of conformationally rigid
metallomacrocycles with nearly 90° turns, have the
potential to become interesting targets for various
investigations of host-guest interactions and inclusion
phenomena as well as biomimetic studies. The prepa-
ration of most of these compounds requires reactive
transition metal complexes with nearly 90° bond angles,
as demanded by their rectangular geometry, and aza-
containing heterocycles which, upon coordination to the
transition metal centers, will form the sides of the
square. To date, there are two major types of squares,
incorporating transition metals: (1) all-metal systems3
and (2) hybrid species, with alternating hypervalent
iodine and transition metals at the corners.4
1,1′-Bis(diphenylphosphino)ferrocene, a member of a
family of ferrocenylphosphines, has been known for over
a decade and extensively employed as a chelating agent
(5) (a) Butler, I. R.; Cullen, W. R.; Kim, T.-J .; Rettig, S. J .; Trotter,
J . Organometallics 1985, 4, 972. (b) Cullen, W. R.; Appleton, T. D.;
Evans, S. V.; Kim, T. J .; Trotter, J . T. J . Organomet. Chem. 1985, 279,
5. (c) Cullen, W. R.; Einstein, F. W. B.; J ones, T.; Kim, T.-J .
Organomettallics, 1983, 2, 714. (d) Cullen, W. R.; Woolins, J . D. Can.
J . Chem. 1982, 60, 1793. (e) Hayashi, T.; Kumada, M. Acc. Chem. Res.
1982, 15, 395. (f) Cullen, W. R.; Woollings, J . D. Coord. Chem. Rev.
1982, 39, 1.
(6) (a) Brown, J . M.; Cooley, N. A. Organomettallics 1990, 9, 353.
(b) Hayashi, T.; Konishi, M.; Kobori, Y.; Kumada, M.; Higuchi, T.;
Hirotsu, K. J . Am. Chem. Soc. 1984, 106, 158. (c) Hayashi, T.; Konishi,
M.; Ito, H.; Kumada, M. J . Am. Chem. Soc. 1982, 104, 4962. (d)
Hayashi, T.; Konishi, M.; Fukushima, M.; Mise, T.; Kagotani, M.;
Tajika, M.; Kumada, M. J . Am. Chem. Soc. 1982, 104, 189. (e) Kumada,
M. Pure Appl. Chem. 1980, 52, 669.
X Abstract published in Advance ACS Abstracts, J anuary 1, 1996.
(1) (a) Lehn, J .-M. Supramolecular Chemistry; VCH Publishers:
New York, 1995. (b) Cram, D. J .; Cram, J . M Container Molecules and
Their Guests; The Royal Society of Chemistry: Cambridge, U.K., 1994.
(2) (a) Supramolecular Chemistry; Balzani, V., DeCola, L., Eds.;
Kluwer Academic Publishers: Dordrecht, The Netherlands, 1992. (b)
Frontiers in Supramolecular Chemistry; Schneider, H., Du¨rr, H., Eds.;
VCH Publishers: Weinheim, Germany, 1991. (c) Monographs in
Supramolecular Chemistry; Stoddart, J . F., Ed.; Royal Society of
Chemistry: Cambridge, U.K., 1989; Vol. 1.
(3) (a) Stang, P. J .; Cao, D. H.; Saito, S.; Arif, A. M. J . Am. Chem.
Soc. 1995, 117, 6273. (b) Drain, C. M.; Lehn, J .-M. J . Chem. Soc., Chem.
Commun. 1994, 2313. (c) Stang, P. J .; Whiteford, J . A. Organometallics
1994, 13, 3776. (d) Stang, P. J .; Cao, D. H. J . Am. Chem. Soc. 1994,
116, 4981. (e) Fujita, M.; Kwon, Y. J .; Washizu, S.; Ogura, K. J . Am.
Chem. Soc. 1994, 116, 1151. (f) Rauter, H.; Hillgeris, E. C.; Erxleben,
A.; Lippert, B. J . Am. Chem. Soc. 1994, 116, 616. (g) Fujita, M.; Nagao,
S.; Iida, M.; Ogura, K. J . Am. Chem. Soc. 1993, 115, 1574. (h) Fujita,
M.; Yazaki, J .; Ogura, K. J . Am. Chem. Soc. 1990, 112, 5645.
(4) (a) Stang, P. J .; Chen, K.; Arif, A. M. J . Am. Chem. Soc. 1995,
117, 8793. (b) Stang, P. J .; Chen, K. J . Am. Chem. Soc. 1995, 117,
1667.
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metallics 1985, 4, 316.
(8) The role of hydrogen bonding in the stabilization of the solid-
state structure of aqua-transition metal complexes has long been
recognized: (a) Rochon, F. D.; Melanson, R. Inorg. Chem. 1987, 26,
989. (b) Britten, J . F.; Lippert, B.; Lock, C. J .; Pilon, P. Inorg. Chem.
1982, 21, 1936. (c) Hollis, L. S.; Lippard, S. J . Inorg. Chem. 1983, 22,
2605. (d) Brown, I. D. Structure and Bonding in Crystals; Academic
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G. R. Organometallics 1994, 13, 3532.
0276-7333/96/2315-0904$12.00/0 © 1996 American Chemical Society

Ferrocenes and Molecular Squares
Organometallics, Vol. 15, No. 3, 1996 905
Sch em e 1
Resu lts a n d Discu ssion
Syn th esis of Dia qu a Com p lexes of Tr a n sition
Meta l Bis(tr ifla tes). The general protocol for the
preparation of various transition metal bis(triflates)
involves reaction of the transition metal dihalide with
silver triflate in an appropriate organic solvent. When
the bis(triflate) products are treated with exactly 2 equiv
of water or, in some cases, simply exposed to air, they
readily form stable diaqua complexes: (1,1′-bis(diphen-
ylphosphino)ferrocene)palladium(II) and -platinum(II)
complexes were prepared this way and spectroscopic
data confirmed the formation of the diaqua complexes
(Scheme 1). The low-field shift of the signal in the 31P
spectrum of 3, relative to that of 1 in the palladium
complex, and the high-field shift in the phosphine region
of 4, relatively to 2, as well as the presence of water
signals in the 1H spectrum clearly indicated water
coordination to the transition metals, which was con-
firmed by x-ray data.
F igu r e 1. ORTEP diagram and summary of important
geometric features of cationic part of complex 4.
X-r a y Cr ysta l Str u ctu r e of 4. Slow evaporation of
a dichloromethane solution of 4 provided x-ray quality
crystals, suitable for structure determination. The
ORTEP diagram of complex 4 is presented in Figure 1.
The centroids of the ferrocene unit are located es-
sentially in the Pt(II) coordination plane, with a P(1)-
Pt-P(2) angle of 97.3° (Table 1). The angle between
platinum and the two coordinated water molecules is
86°, thereby manifesting the suitability of this com-
pound for the preparation of molecular squares.
Self-Assem bly of Ma cr ocyclic, F er r ocen e-Con -
ta in in g Octa n u clea r Molecu la r Squ a r es. Interac-
tion of 2,7-diazapyrene3a with the diaqua complexes of
1,1′-bis(diphenylphosphino)ferrocene palladium(II) and
platinum(II) bis(triflates) 3 and 4 in nitromethane at
room temperature provided molecular squares 5 and 6
in high isolated yields (Scheme 2). These compounds
are air-stable, albeit hygroscopic, microcrystalline solids
with high decomposition points. They are readily
soluble in polar organic solvents, such as acetone,
methanol, or nitromethane, and essentially insoluble in
less polar solvents, such as ether. As demanded by their
geometry, both squares display a sharp singlet for the
equivalent phosphorous atoms in the 31P{1H} NMR
spectra, with appropriate Pt satellites for the Pt square
6. The 31P signals are shifted downfield relative to that
of the precursors 3 and 4. The presence of the ionic
triflate counterions is indicated by the single signal in
the 19F NMR between -74 and -78 ppm and the
characteristic infrared absorption spectra, as detailed
in the Experimental Section.
Ta ble 1. Im p or ta n t Bon d An gles (d eg) a n d Bon d
Dista n ces (Å) for [P t(d p p f)(H2O)2][OTf]2 (4)
anglea
dista
O(2)-Pt-O(1)
O(2)-Pt-P(1)
O(1)-Pt-P(1)
O(2)-Pt-P(2)
O(1)-Pt-P(2)
P(1)-Pt-P(2)
86.0(2)
Pt-P(1)
Pt-P(2)
Pt-O(1)
Pt-O(2)
Fe-C(1)
Fe-C(6)
2.243(2)
2.246(2)
2.122(4)
2.103(5)
1.996(7)
2.012(1)
90.25(14)
174.72(14)
172.17(14)
86.54(13)
97.37(7)
a
Numbers in parentheses are estimated standard deviations
in the least significant digits.
P r ep a r a tion of Ma cr ocyclic Hexa n u clea r Mo-
lecu la r Squ a r es. Reaction of complexes 3 and 4 with
bis[4-(4′-pyridyl)phenyl]iodonium triflate4 in acetone at
room temperature provided the predicted desired squares
7 and 8 in a matter of minutes, in excellent isolated
yields (Scheme 3). The 31P spectra of both products
exhibit high-field shifts, indicative of nitrogen coordina-
tion to the transition metal. Interestingly, this reaction
is also accompanied by a change of the absorbance
spectra of both compounds (Figure 2). When the
nitrogen of the heteroaryl replaces the weakly donating
water ligands, a series of red shifts is observed in the
UV-vis spectrum. This can also be followed visually,
due to the change of color of the solutions upon com-
plexation.
Con clu sion . A new class of ferrocene-containing
macrocyclic molecular squares is prepared, via self-
assembly of the reactive diaqua complexes of the mixed
transition metal bis(triflates) and a coordinating ligand,

906 Organometallics, Vol. 15, No. 3, 1996
Stang et al.
Sch em e 2
Sch em e 3
F igu r e 2. Absorbance spectra of compounds 3 and 4 and
molecular squares 7 and 8.
the products may be handled in air. NMR spectra were
recorded on a Varian XL-300 or Unity-300 spectrometer. 1H
spectra were recorded at 300 MHz, and all chemical shifts (δ)
are reported in ppm relative to tetramethylsilane (Me4Si) as
an internal standard (0.0 ppm) or the proton resonance
resulting from incomplete deuteration of the NMR solvent:
CD2Cl2 (5.32 ppm), acetone-d6 (2.05 ppm), or CD3NO2 (4.33
ppm). 13C spectra were recorded at 75 MHz, and all chemical
shifts (δ) are reported in ppm relative to the carbon resonance
of the deuterated NMR solvent: CD2Cl2 (53.8 ppm), acetone-
d6 (28.0 ppm), or CD3NO2 (62.8 ppm). 31P spectra were
recorded at 121 MHz, and all chemical shifts (δ) are reported
in ppm relative to external 85% H3PO4 at 0.00 ppm. 19F
spectra were recorded at 282 MHz, and all chemical shifts are
reported relative to external CFCl3 at 0.00 ppm. Coupling
constants J are in Hz. IR spectra were recorded on a Mattson
Polaris FT-IR spectrophotometer. Absorbance spectra were
measured on a Hewlett-Packard UV-vis spectrophotometer.
Microanalyses were performed by Atlantic Microlab Inc.,
Norcross, GA. Melting points were obtained with a Mel-Temp
capillary melting point apparatus and were uncorrected. The
water signals in the 1H spectrum were omitted. Abbrevia-
tions: br, broad; Ho, ortho-proton; Hm; meta-proton; Hp, para-
proton; Ci, ipso-carbons; Co, ortho-carbons; Cm meta-carbons;
Cp, para-carbons.
such as 2,7-diazapyrene or a heteroaryl iodonium moi-
ety. This establishes the suitability of the transition
metal diaqua complexes for self-assembly of macrocyclic
molecular squares, as well as the usefulness of the
ferrocenylphosphine complexes as auxiliary systems for
such self-assembly. This combination of several ferro-
cene-late transition metal systems suggests that it may
be fruitful to look at the redox chemistry of these
species. Moreover, these molecules provide an impor-
tant link between the chemistry of ferrocenes, the
quintessential transition metal species, and molecular
squares, the latest member of the family of supra-
molecular assemblies.
Ma ter ia ls. Solvents were purified as follows: CH2Cl2 was
purified according to the literature procedure9 and distilled
over CaH2; Et2O was purified by the literature procedure9 and
distilled over Na/benzophenone; CD2Cl2 was vacuum trans-
ferred from CaH2.
All commercial reagents were ACS reagent grade. 1,1′-Bis-
(diphenylphosphino)ferrocene and silver triflate were obtained
from Aldrich and were used as received. The precursor, [Pd-
(dppf)Cl2], was prepared according to the literature method.10
(9) Perrin, D. D.; Armarego, W. L. F. Purification of Laboratory
Chemicals; Pergamon Press: Oxford, U.K., 1988.
(10) Reaction of Pd(cod)Cl2 with 1,1′-bis(diphenylphosphino)-
ferrocene provided [Pd(dppf)Cl2] in 90% yield. See also ref 6a for
another method of preparation of this complex.
Exp er im en ta l Section
Gen er a l Meth od s. All reactions were conducted under a
dry nitrogen atmosphere using Schlenk techniques; however,

Ferrocenes and Molecular Squares
Organometallics, Vol. 15, No. 3, 1996 907
1252, 1163, 1102, 1029 (OTf). Anal. Calcd for C200H144
P8N8Fe4Pd4O24S8F24‚4H2O: C, 50.84; H, 3.24; N, 2.37; S, 5.43.
Found: C, 51.06; H, 3.20; N, 2.45; S, 5.33.
[P t(d p p f)Cl2] (2). A 50-mL Schlenk flask was charged with
0.183 g (0.330 mmol) of 1,1′-bis(diphenylphosphino)ferrocene,
0.112 g (0.300 mmol) of Pt(cod)Cl2 (cod ) cyclooctadiene), and
20 mL of CH2Cl2. The yellow solution was stirred at room
temperature for 10 min, transferred into a 25-mL flask, and
reduced in volume to 2 mL. Diethyl ether was then added,
resulting in the formation of a yellow precipitate, which was
collected and dried in vacuo, to yield 0.211 g (82%). Mp )
340-342 °C dec. 1H NMR (CD2Cl2): 7.90-7.83 (m, 8H, Ho-
PhP), 7.54-7.40 (m, 12H, Hp,Hm-PhP), 4.40 (s, 4H, HR-ferr),
4.22 (s, 4H, Hâ-ferr). 13C NMR (CD2Cl2): 135.3 (t, J ) 5.5,
Co-PhP), 131.7 (s, Cp-PhP), 131.4 (t, J ) 34, Ci-PhP), 128.4 (t,
J ) 5.7, Cm-PhP), 76.3 (t, J ) 5.2, CR-ferr), 74.5 (t, J ) 3.2,
Câ-ferr), 73.2 (t, J ) 35.3, Ci-ferr). 31P NMR (CD2Cl2): 15.5
(s, 195Pt satellites, J ) 3766). IR (neat, cm-1): 3044, 1480,
1435 (Ar). Anal. Calcd for C34H28P2FePtCl2‚2H2O: C, 47.68;
H, 3.77. Found: C, 47.78; H, 3.51.
[P d (d p p f)(H2O)2][OTf]2 (3). To a dark-red solution of
0.452 mg (0.588 mmol) of [Pd(dppf)Cl2] in 40 mL of CH2Cl2
was added 0.428 g (1.67 mmol) of AgOTf, and the mixture was
stirred for 18 h at room temperature. The white precipitate
was filtered off, and the solution was allowed to stir in air for
10 min. The solution was transferred into a 100-mL flask and
reduced in volume to 2 mL. Diethyl ether was then added,
and the green precipitate was collected, washed with diethyl
ether, and dried in vacuo. Yield: 0.552 g (94%). Mp ) 198-
200 °C dec. 1H NMR (CD2Cl2): 7.95-7.74 (m, 8H, dppf Ph
Ho), 7.74-7.62 (m, 8H, dppf Ph Hp), 7.60-7.46 (m, 8H, dppf
Ph Hm), 4.67 (s, 4H, HR-ferr), 4.63 (s, 4H, Hâ-ferr). 13C NMR
(CD2Cl2): 134.7 (t, J ) 6.2, Co-PhP), 133.8 (s, Cp-PhP), 129.9
(t, J ) 6.2, Cm-PhP), 128.0 (t, Ci-PhP), 122.2 (q, J ) 319, OTf),
78.6 (t, J ) 5.9, CR-ferr), 76.4 (t, J ) 4.4, Câ-ferr), 69.8 (t, J )
37.8, Ci-ferr). 31P NMR (CD2Cl2): 51.1 (s). 19F NMR
(CD2Cl2): -79.2 (s, OTf). IR (neat, cm-1): 1437 (Ar), 1300,
-
[P t(d p p f)(2,7-d ia za p yr en e)]4[OTf]8 (6). To a solution of
2.70 mg (0.0132 mmol) of 2,7-diazapyrene in 1 mL of dry
nitromethane was added 13.4 mg (0.0128 mmol) of [Pt(dppf)-
(H2O)2][OTf]2 (4), and the resulting orange solution was stirred
at room temperature for 20 min. Diethyl ether was then
added, resulting in the formation of an orange precipitate,
which was filtered off, washed with diethyl ether, and dried
in vacuo to yield 11.8 mg of 6 (74%). Mp ) 310-314 °C dec.
1H NMR (CD3NO2): 9.29 (d, J ) 0.3, 16H, HR-diazp), 7.90 (m,
32H, dppf Ho), 7.76 (s, 16H, Hγ-diazp), 7.52 (m, 16H, dppf Ph
Hp), 7.41 (m, 32H, dppf Ph Hm), 4.91 (s, 16H, HR-ferr), 4.75 (s,
16H, Hâ-ferr). 13C NMR (CD3NO2): 146.9 (s, CR-diazp), 135.6
(t, dppp Ph Co), 134.5 (s, dppp Ph Cp), 131.0 (s, dppp Ph Cm),
129.1 (s, Cγ-diazp), 129.0 (s, Ci-diazp), 127.6 (t, J ) 58, dppp
Ph Ci), 125.3 (s, Câ-diazp), 121.3 (q, J ) 319, OTf), 77.8 (t,
CR-ferr), 77.5 (t, Câ-ferr), 67.9 (t, J ) 64, Ci-ferr). 31P NMR
(CD3NO2): 8.36 (s, 195Pt satellites, J Pt-P ) 3432). 19F NMR
(CD3NO2): -74.6 (s, OTf). IR (neat, cm-1): 1437 (Ar), 1278,
1255, 1157, 1097, 1029 (OTf). Anal. Calcd for C200H144P8-
N8Fe4Pt4O24S8F24‚4H2O: C, 47.29; H, 3.01; N, 2.21; S, 5.05.
Found : C, 47.22; H, 2.99; N, 2.14; S, 4.97.
{[P d (d p p f)(NC5H4C6H4)2I][OTf]3}2 (7). A 25-mL Schlenk
flask was charged with 21.3 mg (0.0365 mmol) of bis(4-
phenylpyridine)iodonium triflate and 5 mL of acetone. To this
heterogeneous mixture was added, 35.0 mg (0.0352 mmol) of
[Pd(dppf)(H2O)2][OTf]2 (3), and the resulting deep purple
solution was stirred at room temperature for 20 min and then
reduced in volume to 1 mL. Diethyl ether was added, and the
resulting purple solid was collected and dried in vacuo.
Yield: 52.5 mg (93%). Mp ) 224-226 °C dec. 1H NMR
(acetone-d6): 8.92 (br d, J ) 3.3, 8H, HR-Py), 8.44 (d, J ) 8.5,
8H, HR-PhI), 8.06-7.98 (m, 16H, dppf Ph Ho), 7.81 (d, J )
8.5, 8H, Hâ-PhI), 7.78-7.62 (m, 24H, dppf Ph Hm + Hp), 7.49
(d, J ) 5.4, 8H, Hâ-Py), 4.93 (s, 8H, HR-ferr), 4.84 (s, 8H, Hâ-
ferr). 13C NMR (acetone-d6): 151.8 (s, CR-Py), 149.5 (s, Cγ-
Py), 140.0 (s, Cγ-PhI), 137.3 (s, CR-PhI), 135.1 (t, J ) 6.6, Co-
PhP), 133.8 (s, Cp-PhP), 131.7 (s, Câ-PhI), 130.7 (t, J ) 11.8,
Cm-PhP), 128.5 (t, J ) 28, Ci-PhP), 125.2 (s, Câ-Py), 122.2 (q,
J ) 319, OTf), 117.2 (s, C-I), 78.1 (t, J ) 6, CR-ferr), 76.7 (t,
J ) 4.6, Câ-ferr), 68.6 (t, J ) 39.8, Ci-ferr). 31P NMR (acetone-
d6): 38.7 (s). 19F NMR (acetone-d6): -77.6 (s, OTf). IR (neat,
cm-1): 1611, 1435 (Ar), 1279, 1251, 1157, 1027 (OTf). Anal.
Calcd for C118H88P4N4Fe2Pd2O18S6F18‚6H2O: C, 44.36; H, 3.15,
N, 1.75; S, 6.62. Found: C, 43.92; H, 2.95; N, 1.93; S, 6.05.
{[P t(d p p f)(NC5H4C6H4)2I][OTf]3}2 (8). To a heteroge-
neous mixture of 10.0 mg (0.0171 mmol) of bis(4-phenyl-
pyridine)iodonium triflate and 2 mL of acetone was added 17.9
mg (0.0165 mmol) of [Pt(dppf)(H2O)2][OTf]2 (3), and the yellow
solution was stirred at room temperature for 20 min. Diethyl
ether was added, and the resulting yellow precipitate was
collected and dried in vacuo. Yield: 24.5 mg (88%). Mp )
235-236 °C dec. 1H NMR (acetone-d6): 8.89 (br d, J ) 4.9,
8H, HR-Py), 8.38 (d, J ) 8.7, 8H, HR-PhI), 7.93 (m, 16H, dppf
Ho), 7.76 (d, J ) 8.7, 8H, Hâ-PhI), 7.69-7.53 (m, 24H, dppf Ph
Hm and Hp), 7.46 (d, J ) 5.0, 8H, Hâ-Py), 4.86 (s, 8H, HR-ferr),
4.75 (s, 8H, Hâ-ferr). 13C NMR (acetone-d6): 151.8 (s, CR-Py),
150.1 (s, Cγ-Py), 139.7 (s, Cγ-PhI), 137.5 (s, CR-PhI), 135.3 (t,
J ) 5.5, Co-PhP), 133.8 (s, Cp-PhP), 131.8 (s, Câ-PhI), 130.6 (t,
J ) 5.6, Cm-PhP), 127.8 (t, J ) 32, Ci-PhP), 125.7 (s, Câ-Py),
122.2 (q, J ) 319, OTf), 117.5 (s, C-I), 77.2 (t, J ) 6.0, CR-
ferr), 76.7 (t, J ) 4.6, Câ-ferr), 68.6 (t, J ) 39, Ci-ferr). 31P
NMR (acetone-d6): 7.7 (s, 195Pt satellites, J Pt-P ) 3402 Hz).
19F NMR (acetone-d6): -77.7 (s, OTf). IR (neat, cm-1): 1613,
1437 (Ar), 1271, 1253, 1160, 1028 (OTf). Anal. Calcd for
1228, 1168, 1028 (OTf). Anal. Calcd for
PdO8S2F6: C, 43.46; H, 3.24; S, 6.44. Found: C, 43.57; H, 3.27,
S, 6.45.
C36H32P2Fe-
[P t(d p p f)(H2O)2][OTf]2 (4). A 50-mL Schlenk flask was
charged with 0.380 g (0.444 mmol) of [Pt(dppf)Cl2] and 40 mL
of CH2Cl2 to give an orange solution. To this was added 0.834
g (3.24 mmol) of AgOTf, and the mixture was stirred at room
temperature for 3 days. The precipitate was filtered off, and
the filtrate was stirred in air for 10 min and then reduced in
volume to 2 mL. After addition of diethyl ether, the orange
precipitate was filtered off, washed with ether, and dried in
vacuo. Yield: 0.434 g (90%). Mp ) 192-193 °C dec. 1H NMR
(CD2Cl2): 7.79-7.63 (m, 12H, dppf Ph Ho and Hp), 7.56-7.48
(m, 8H, dppf Ph Hm), 4.65 (s, 4H, HR-ferr), 4.48 (s, 4H, Hâ-
ferr). 13C NMR (CD2Cl2): 134.4 (t, J ) 5.6, Co-PhP), 133.6 (s,
Cp-PhP), 129.8 (t, J ) 6.0, Cm-PhP), 127.4-126.4 (t, Ci-PhP),
122.6 (q, J ) 319, OTf), 77.3 (t, J ) 5.9, CR-ferr), 76.2 (t, J )
4.7, Câ-ferr), 68.0 (t, J ) 42.0, Ci-ferr). 31P NMR (CD2Cl2): 11.1
(s, 195Pt satellites, J ) 4195 Hz). 19F NMR (CD2Cl2): -79.1
(s, OTf). IR (neat, cm-1): 1436 (Ar), 1265, 1174, 1028 (OTf).
Anal. Calcd for C36H32P2FePtO8S2F6: C, 39.90; H, 2.60; S,
5.92. Found: C, 39.95; H, 3.00, S, 6.00.
[P d (d p p f)(2,7-d ia za p yr en e)]4[OTf]8 (5). The solution of
3.60 mg (0.0176 mmol) of 2,7-diazapyrene in 1.2 mL of dry
nitromethane was allowed to react with 16.1 mg (0.0168 mmol)
of [Pd(dppf)(H2O)2][OTf]2 (3) for 20 min at room temperature.
Addition of the diethyl ether resulted in a pink solid, which
was washed with ether and dried in vacuo. Yield of 5: 16.6
mg (84%). Mp ) 290-292 °C. 1H NMR (CD3NO2): 9.26 (d, J
) 2, 16H, HR-diazp), 7.91 (m, 32H, dppf Ho), 7.71 (s, 16H, Hγ-
diazp), 7.56 (m, 16H, dppf Ph Hp), 7.43 (m, 32H, dppf Ph Hm),
4.92 (s, 16H, HR-ferr), 4.79 (s, 16H, Hâ-ferr). 13C NMR
(CD3NO2): 146.7 (s, CR-diazp), 135.6 (t, dppp Ph Co), 134.6 (s,
dppp Ph Cp), 131.0 (s, dppp Ph Cm), 129.8 (s, Cγ-diazp), 128.6
(s, Ci-diazp), 128.0 (t, J ) 53, dppp Ph Ci), 125.3 (s, Câ-diazp),
121.3 (q, J ) 319, OTf), 78.8 (t, CR-ferr), 77.6 (t, Câ-ferr), 68.4
(t, J ) 54, Ci-ferr). 31P NMR (CD3NO2): 38.51 (s). 19F NMR
(CD3NO2): -74.6 (s, OTf). IR (neat, cm-1): 1437 (Ar), 1283,
C
118H88P4N4Fe2Pt2O18S6F18: C, 43.42; H, 2.72; N, 1.72; S, 5.89.
Found: C, 43.77; H, 2.93; N, 1.66; S, 5.65.
X-r a y Cr ysta llogr a p h ic An a lysis of 4. An X-ray quality
crystal was grown by the slow evaporation of a dichloro-
methane solution of 4. An orange prism, 0.36 × 0.36 × 0.29

908 Organometallics, Vol. 15, No. 3, 1996
Stang et al.
Ta ble 2. Cr ysta l Da ta a n d Str u ctu r e Refin em en t
for [P t(d p p f)(H2O)2][OTf]2 (4)
technique, with variable scanning rate, using monochromatic
Mo 0.710 73 Å radiation. Standard reflections showed no
decay for the crystal during data collection. Lorentz and
polarization corrections, and an empirical absorption correction
based upon a series of ψ scans, were applied to the data.
Intensities of equivalent reflections were averaged.
empirical formula
fw
C36H32F6FeO8P2PtS2
1083.62
temp
291(2) K
wavelength
cryst system
space group
unit cell dimens
0.710 73 Å
monoclinic
P21/n
a ) 12.292(2) Å, R ) 90°
b ) 17.988(4) Å, â ) 97.76(2)°
c ) 18.098(3) Å, γ) 90°
3965.2(13) Å3
The structure was solved by the standard heavy-atom
technique with the MolEN/VAX package. Non-hydrogen
atoms were refined with anisotropic thermal parameters.
Data were weighted using a non-Poisson scheme. All hydrogen
atoms were calculated and added to the structure factor
calculations. Scattering factors, and ∆f ′ and ∆f ′′ values, were
taken from the literature.11 All least-squares refinements were
done using SHELXL-93. There is a disorder in the crystal
exhibited by one of the triflate anions.
cell vol
Z
4
D(calcd)
abs coeff
1.815 Mg/m3
4.154 mm-1
F(000)
2128
cryst size
θ range for data collection
index ranges
0.36 × 0.36 × 0.29 mm
2.02-24.96°
0 e h e )14, 0 e k e 21,
-21 e l e )21
7306
Ack n ow led gm en t. We thank the National Science
Foundation for financial support and J ohnson-Matthey
for the generous loan of PtCl2.
reflcns collcd
indepdt reflcns
abs corr
6960 [R(int) ) 0.0161]
semiempirical from ψ-scans
99.88 and 78.80
full-matrix least-squares on F2
6960/236/517
max and min transm
refinement method
data/restraints/params
goodness-of-fit on F2
final R indices [I > 2σ(I)]
R indices (all data)
largest diff peak and hole
Su p p or tin g In for m a tion Ava ila ble: Crystal structure
data for 4 including tables of calculated positional parameters
and U values for the hydrogen atoms, non-hydrogen positional
and thermal parameters, complete bond lengths and bond
angles, and general displacement parameter expressions (10
pages). This material is contained in many libraries on
microfiche, immediately follows this article in the microfilm
version of the journal, can be ordered from ACS, and can be
downloaded from the Internet; see any current masthead page
for ordering information and Internet access instructions.
1.019
R1 ) 0.0306, wR2 ) 0.0713
R1 ) 0.0613, wR2 ) 0.0795
1.085 and -1.169 e‚Å-3
mm, was glued to a glass fiber and mounted for data collection
on Enraf-Nonius CAD4 diffractometer. Cell constants and
data collection parameters are presented in Table 2. The unit
cell parameters were obtained by a least-squares refinement
of 25 centered reflections in the range of 21 < 2θ < 28°. The
space group was determined from systematic absences (h01,
h + l ) 2n; 0k0, k ) 2n) and subsequent least-squares
refinement. The data were collected by the θ-2θ scan
OM950781Q
(11) Cromer, D. T.; Waber, J . T. In International Tables for X-ray
Crystallography; Ibers, J . A., Hamilton, W. C., Eds.; Kynoch Press:
Birmingham, U.K., 1974.