Gold and Silver Complexes with the Ferrocenyl Phosphine FcCH2PPh2 [Fc = (η5-,C5H5)Fe(η5-C5H4)]

Article abstract of DOI:10.1021/ic9905446

Linear gold(I) and silver(I) complexes with the ferrocenyl phosphine FcCH₂PPh₂ [Fc = (η⁵-C₅H₅)Fe(η⁵-C₅H₄)] of the types [AuR(PPh₂CH₂Fc)], [M(PPh<

Full text of DOI:10.1021/ic9905446

680
Inorg. Chem. 2000, 39, 680-687
Gold and Silver Complexes with the Ferrocenyl Phosphine FcCH2PPh2
[Fc ) (η5-C5H5)Fe(η5-C5H4)]
Eva M. Barranco, Olga Crespo, M. Concepcio´n Gimeno, and Antonio Laguna*
Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-CSIC, E-50009 Zaragoza, Spain
Peter G. Jones and Birte Ahrens
Institut fu¨r Anorganische und Analytische Chemie der Technischen Universita¨t, Postfach 3329,
D-38023 Braunschweig, Germany
ReceiVed May 17, 1999
Linear gold(I) and silver(I) complexes with the ferrocenyl phosphine FcCH2PPh2 [Fc ) (η5-C5H5)Fe(η5-C5H4)]
of the types [AuR(PPh2CH2Fc)], [M(PPh3)(PPh2CH2Fc)]OTf, and [M(PPh2CH2Fc)2]OTf (M ) Au, Ag) have
been obtained. Three-coordinate gold(I) and silver(I) derivatives of the types [AuCl(PPh2CH2Fc)2] and [M(PPh2-
CH2Fc)3]X (M ) Au, X ) ClO4; M ) Ag, X ) OTf) have been obtained from the corresponding gold and silver
precursors in the appropriate molar ratio, although some of them are involved in equilibria in solution. The crystal
structures of [AuR(PPh2CH2Fc)] (R ) Cl, C6F5), [AuL(PPh2CH2Fc)]OTf (L ) PPh3, FcCH2PPh2), [Au(C6F5)3(PPh2-
CH2Fc)], and [Ag(PPh2CH2Fc)3]OTf have been determined by X-ray diffraction studies.
Introduction
and silver complexes with the (ferrocenylmethyl)phosphine
FcCH2PPh2, whose coordination chemistry has not yet been
studied. Two- and three-coordinate gold and silver complexes
have been prepared. Cyclic voltammetry shows one-electron
reversible oxidation based on the ferrocene moiety.
Phosphine ligands containing ferrocene moieties currently
attract a great deal of interest, as is shown by the large number
of transition metal complexes described for the chelating ligand
1,1′-bis(diphenylphosphino)ferrocene (dppf).1 Much attention
has also been paid to chiral ferrocenyl phosphines in asymmetric
catalysis.2,3 In all of these ligands the phosphine moiety is linked
directly by a P-C bond to the cyclopentadienyl ring of the
ferrocene. However, examples of ferrocenyl phosphines contain-
ing a carbon spacer between the cyclopentadienyl ring and the
phosphorus atom are rare. Although the synthesis of the first
(ferrocenylmethyl)phosphine was reported as early as 1963,4,5
only recently has the 1,1′-bis(diphenylphosphinomethyl)-
ferrocene been synthesized6 or the reactivity of FcCH2P(CH2-
OH)2 (leading to various ferrocene-derived phosphines or metal
complexes) studied.7-10
Results and Discussion
Synthesis. The reaction of FcCH2PPh2 with 1 equiv of [AuX-
(tht)] (tht ) tetrahydrothiophene) in dichloromethane gives
orange solids of the neutral complexes [AuR(PPh2CH2Fc)] (R
) Cl, 1; C6F5, 2) (see Scheme 1). These are air- and moisture-
stable and are nonconducting in acetone solutions. Their IR
spectra show the vibration ν(Au-Cl) at 336 (m) cm-1 (1) and
the bands arising at the pentafluorophenyl group bonded to gold-
(I) at 1505 (vs), 954 (s), and 790 (m) cm-1 (2).
1
The H NMR spectra show two multiplets for the R and â
As part of our studies in ferrocene derivatives as ligands in
gold chemistry,11 we report here the synthesis of several gold
protons of the substituted cyclopentadienyl group, a singlet for
the protons of the unsubstituted Cp, and a doublet for the protons
of the methylene group, which are coupled with the phosphorus
atom. The 19F NMR spectrum of 2 presents three resonances
for the three different fluorines of the pentafluorophenyl group.
(1) Gan, K. S.; Hor, T. S. A. In Ferrocenes. Homogeneous Catalysis,
Organic Synthesis and Materials Science; Togni, A., Hayashi, T., Eds.;
VCH: Weinheim, 1995; Chapter 1 and references therein.
(2) Hayashi, T. Ferrocenes. In Homogeneous Catalysis, Organic Synthesis
and Materials Science; Togni, A., Hayashi, T., Eds.; VCH: Weinheim,
1995; Chapter 2 and referencess therein.
(3) Togni, A. In Metallocenes; Togni, A., Halterman, R. L., Eds.; VCH:
Weinheim, 1998; Vol. 2, Chapter 11.
(4) Pauson, P. L.; Watts, W. E. J. Chem. Soc. 1963, 2990.
(5) Marr, G.; White, T. M. J. Chem. Soc., Perkin Trans. 1 1973, 1955.
(6) Yamamoto, Y.; Tanese, T.; Mori, I.; Nakamura, Y. J. Chem. Soc.,
Dalton Trans. 1994, 3191.
(7) Goodwin, N. J.; Henderson, W.; Sarfo, J. K. Chem. Commun.
(Cambridge) 1996, 1551.
(8) Goodwin, N. J.; Henderson, W.; Nicholson, B. K.; Sarfo, J. K.;
Fawcett, J.; Russell, D. R. J. Chem. Soc., Dalton Trans. 1997, 4377.
(9) Goodwin, N. J.; Henderson, W.; Nicholson, B. K. Chem. Commun.
(Cambridge) 1997, 31.
(11) (a) Gimeno, M. C.; Laguna, A.; Sarroca, C.; Jones, P. G. Inorg. Chem.
1993, 32, 5926. (b) Gimeno, M. C.; Laguna, A.; Sarroca, C.; Jones,
P. G. J. Chem Soc., Dalton Trans. 1995, 1473. (c) Gimeno, M. C.;
Jones, P. G.; Laguna, A.; Sarroca, C. J. Chem Soc., Dalton Trans.
1995, 3563. (d) Canales, F.; Gimeno, M. C.; Laguna, A.; Jones, P. G.
J. Am. Chem. Soc. 1996, 118, 4839. (e) Canales, F.; Gimeno, M. C.;
Laguna, A.; Jones, P. G. Organometallics 1996, 15, 3412. (f) Gimeno,
M. C.; Jones, P. G.; Laguna, A.; Sarroca, C. J. Chem Soc., Dalton
Trans. 1998, 1277. (g) Crespo, O.; Gimeno, M. C.; Jones, P. G.;
Laguna, A.; Sarroca, C. Chem. Commun. (Cambridge) 1998, 1481.
(h) Gimeno, M. C.; Jones, P. G.; Laguna, A.; Sarroca, C. Polyhedron
1998, 17, 3681. (i) Gimeno, M. C.; Jones, P. G.; Laguna, A.; Sarroca,
C.; Calhorda, M. J.; Veiros, L. F. Chem.sEur. J. 1998, 4, 2308. (j)
Barranco, E. M.; Gimeno, M. C.; Laguna, A.; Villacampa, M. D.;
Jones, P. G. Inorg. Chem. 1999, 38, 702.
(10) Goodwin, N. J.; Henderson, W. Polyhedron 1998, 17, 4071.
10.1021/ic9905446 CCC: $19.00 © 2000 American Chemical Society
Published on Web 01/29/2000

Gold and Silver Complexes with FcCH2PPh2
Inorganic Chemistry, Vol. 39, No. 4, 2000 681
Scheme 1a
a (i) [AuCl(tht)] or [Au(C6F5)(tht)], (ii) 1/2[Au(tht)2]ClO4 or Ag(OTf), (iii) 1/3[Au(tht)2]ClO4 or Ag(OTf), (iv) 1/2[AuCl(tht)], (v) [Au(C6F5)3(tht)],
(vi) [Au(OTf)(PPh3)] or [Ag(OTf)(PPh3)].
In the positive liquid secondary-ion mass spectra (LSIMS) the
molecular peaks appear at m/z ) 616 (1, 100%) and 748 (2,
100%). Other fragmentation peaks [M - X]+ or association
peaks [M + Au]+ and [2M - X]+ are present in both spectra.
We have also prepared homoleptic cationic gold(I) or silver-
(I) complexes of the type [M(PPh2CH2Fc)2]X (M ) Au, X )
ClO4, 5; M ) Ag, X ) OTf, 6) starting from [Au(tht)2]ClO4 or
AgOTf in dichloromethane or diethyl ether, respectively. They
are air- and moisture-stable yellow solids that behave as 1:1
electrolytes in acetone solutions. Their IR spectra show the
bands of the ferrocenyl phosphine ligand and of the anion OTf
or ClO4 [1100 (vs, br) and 620 (s) cm-1]. The 1H NMR spectra
show the typical pattern of a monosubstituted ferrocene and
two multiplets for the methylene and phenyl protons. The 31P-
{1H} NMR spectra consist of a singlet for the gold complex
and a broad signal for the silver derivative; the latter splits into
two doublets by coupling with the two silver nuclei 107Ag and
109Ag. In the positive secondary-ion mass spectra the molecular
peaks appear at m/z ) 1064 (5, 3%) and 1026 (6, 3%), although
with low intensity; in both cases the most intense peaks are the
cationic molecular peaks that appear at m/z ) 965 and 875,
respectively.
The treatment of FcCH2PPh2 with [M(OTf)PPh3] in dichlo-
romethane and in equal molar ratio leads to the cationic
complexes [M(PPh3)(PPh2CH2Fc)]OTf (M ) Au, 3; Ag, 4) in
high yield. Complexes 3 and 4 are air- and moisture-stable
yellow solids that behave as 1:1 electrolytes in acetone solutions.
Their IR spectra show, apart from the bands arising from the
phosphine ligands, those of the trifluoromethanesulfonate at
1265 (vs, br) [νas(SO3)], 1223 (s) [νs(CF3)], 1150 (s) [νas(CF3)],
and 1023 (s) [νs(SO3)] cm-1
.
1
The H NMR spectrum of complex 3 shows, apart from the
multiplet from the phenyl protons, the signals of the ferrocenyl
unit as one multiplet for the unsubstituted Cp ring, two multiplets
for the R and â protons of the substituted cyclopentadienyl ring,
and one multiplet for the protons of the methylene group.
Variable-temperature NMR spectra (CD2Cl2) show no variation
of the appearance of the signals with the temperature up to -80
°C. The 31P{1H} NMR spectrum shows two resonances at 44.0
and 44.8 ppm for the two different phosphorus environments.
Variable-temperature studies also show no variation of the
signals. Usually in this type of complex an AB system appears,
which in this case is not observed owing to fast ligand exchange
in solution even at -80 °C. Complex 4 shows five multiplets
with a 25:5:2:2:2 ratio for the phenyl protons and ferrocene
moiety. The 31P{1H} NMR spectrum at room temperature
consists of a broad signal that sharpens into an AB system
coupled to both silver nuclei 107Ag and 109Ag. The simulated
spectrum agrees with the experimental.
The gold(III) derivative, [Au(C6F5)3(PPh2CH2Fc)] (7), has
been prepared by reaction of the phosphine with [Au(C6F5)3-
(OEt2)] in a 1:1 molar ratio. Complex 7 is an air- and moisture-
stable solid that behaves as nonconductor in acetone solutions.
Its IR spectrum shows the typical pattern for an “Au(C6F5)3”
unit, with bands at 970 (s), 803 (s), and 795 (m) cm-1, and the
bands from the ferrocenyl phosphine.
1
The H NMR spectrum shows a doublet for the methylene
protons coupled to the phosphorus atom, two multiplets for the
R and â protons of the C5H4 ring, and a singlet for the C5H5
ring. The 31P{1H} NMR spectrum consists of a multiplet as a
result of the coupling of the phosphorus atoms with the fluorine
nuclei. The 19F NMR spectrum shows six resonances corre-
sponding to two types of pentafluorophenyl groups in a 2:1 ratio,
corresponding to the ortho, meta, and para fluorines of each
C6F5 unit.
In the positive liquid secondary-ion mass spectra (LSIMS),
the cationic molecular peaks appear at m/z ) 843 (3, 100%)
and 753 (4, 46%), respectively.

682 Inorganic Chemistry, Vol. 39, No. 4, 2000
Barranco et al.
Scheme 2
1
1
/
/
Low-temperature 31P{1H} NMR spectral studies have been
carried out for both complexes. For complex 9 the initial
resonance at 41.7 splits into three with different intensities at
43.8, 38.3, and 28.2 ppm. We also propose an equilibrium
between the different species, [Au(PPh2CH2Fc)2]+, [Au(PPh2-
CH2Fc)3]+, and [Au(PPh2CH2Fc)4]+, respectively, in a manner
similar to that reported for other tertiary phosphines (eq 1).12
Complex 10 shows two doublets in the 31P spectrum because
of the coupling of the equivalent phosphorus with both silver
nuclei.
The LSIMS mass spectrum shows the molecular peak at m/z
) 1082 (100%) and other fragmentation peaks at m/z ) 748
([Au(C6F5)(PPh2CH2Fc)]+), 581 ([Au(PPh2CH2Fc)]+), and 384
(PPh2CH2Fc+).
The three-coordinate gold complex [AuCl(PPh2CH2Fc)2] (8)
has been obtained by reaction of [AuCl(tht)] and 2 equiv of
PPh2CH2Fc.
The 1H NMR spectrum of complex 8 at room temperature in
dichloromethane shows three multiplets in a 2:2:5 ratio for the
ferrocene protons and a doublet for the methylene protons. In
the 31P{1H} NMR spectrum, a broad singlet at 33.8 appears
because of the equivalence of the phosphorus atoms. The
variable-temperature 1H NMR spectra show broadening of the
signals in the range -20 to -40 °C, and below -60 °C five
signals appear in the ferrocene region. The 31P{1H} NMR
spectrum also shows broadening of the signal; at -20 °C two
broad signals appear, from -40 to -60 °C two singlets are
present at 32.4 and 42.3 ppm, and at -80 °C two more small
resonances appear at 38.5 and 28.2 ppm. The two main
resonances possess chemical shifts close to those in the
complexes [Au(PPh2CH2Fc)2]ClO4 and [AuCl(PPh2CH2Fc)].
According to these data we propose that there is an equilibrium
between three- and two-coordinate species such that at room
temperature the three-coordinate complex is present and at low
temperature a reorganization process takes place (Scheme 2).
If this process takes place, the presence of free phosphine should
be observed, but we do not see this in the NMR time scale;
therefore, we propose that the free phosphine would react
immediately with the [AuP2]+ complex to give the three-
coordinate species. The latter, as we propose below, is in
equilibrium with the linear and four-coordinate species. This
explain the four resonances present that are only seen at -80
°C. To corroborate this we have also carried out variable-
temperature studies of a sample prepared “in situ” from 1 equiv
of [AuCl(tht)] and 2 equiv of the phosphine. The spectra at
different temperatures are similar, but now below -60 °C the
four signals can be observed and those at 28.2 (AuP4+) and
38.3 (AuP3+) ppm with more intensity.
2[Au(PPh2CH2Fc)3]ClO4 h
[Au(PPh2CH2Fc)2]ClO4 + [Au(PPh2CH2Fc)4]ClO4 (1)
Crystal Structure Determinations. Crystal Structures of
[AuR(PPh2CH2Fc)] (R ) Cl (1), C6F5 (2)). The crystal
structures of the neutral complexes [AuR(PPh2CH2Fc)] (R )
Cl (1), C6F5 (2)) have been determined by X-ray diffraction
studies. Figures 1a and 2 show their molecular structures, and
a selection of bond lengths and angles are presented in Tables
1 and 2. In these complexes the gold atoms exhibit a very regular
linear geometry, with P-Au-Cl and P-Au-C angles of
176.01(7)° and 174.3(2)°, respectively. For complex 1 the Au-
Cl distance, 2.3014(18) Å, is similar to those found in complexes
with ferrocenyl phosphines such as [Au2Cl2(µ-dppf)] (dppf )
1,1′-bis(diphenylphosphino)ferrocene) (two independent deter-
minations: 2.2815(13), 2.273-2.300 Å)13,14 or [AuCl(PFc2Ph)]
(2.289(2) Å).15 The shortest gold-gold distance in the lattice
is 5.388 Å, which excludes the possibility of any bonding
interaction between gold atoms. However, there are unusually
short H‚‚‚Au contacts: H11‚‚‚Au (1 - x, -y, 1 - z) 2.73,
H33‚‚‚Au (x, 0.5 - y, -0.5 + z) 2.76 Å, and also three weak
intermolecular C-H‚‚‚Cl contacts (H‚‚‚Cl 2.88-2.91 Å) of
acceptable linearity that may correspond to weak hydrogen
bonds. The secondary contacts are shown in Figure 1b.
The Au-C(11) distance in 2, 2.070(5) Å, compares well with
those obtained for other gold(I) complexes, such as [Au(C6F5)-
(PPh3)] (2.07(2) Å)16 or the ferrocene derivative [Au2(µ-dppf)-
(C16H9)2] (2.061(8) Å).17 Again the complex does not display
aurophilic interactions (the shortest gold-gold distance is 5.560
Å); but in the lattice there are contacts F2‚‚‚F2 of 2.858 Å and
F‚‚‚H34 of 2.55 and 2.60 Å.
The LSIMS mass spectrum shows the molecular peak at m/z
) 1001, although with very low intensity (3%). The most intense
peak appears at m/z ) 965 and corresponds to the loss of the
chlorine ligand.
We have also carried out the reactions of 3 equiv of the
phosphine PPh2CH2Fc with [Au(tht)2]ClO4 or AgOTf, leading
to the three-coordinate compounds [Au(PPh2CH2Fc)3]ClO4 (9)
and [Ag(PPh2CH2Fc)3]OTf (10). The 1H NMR spectra of both
complexes show multiplets for the methylene, substituted and
unsubstituted Cp, and phenyl protons, whereas the 31P{1H}
spectra show broad signals at chemical shifts different from
those observed for complexes 5 or 6. In the LSIMS mass spectra
the molecular peak appears only for complex 10 at m/z ) 1349
(2%).
(12) Gimeno, M. C.; Laguna, A. Chem. ReV. 1997, 97, 511 and references
therein.
(13) Hill, D. T.; Girard, G. R.; McCabe, F. L.; Johnson, R. K.; Stupik, P.
D.; Zhang, J. H.; Reiff, W. M.; Eggleston, D. S. Inorg. Chem. 1989,
28, 3529.
(14) Canales, F.; Gimeno, M. C.; Jones, P. G.; Laguna, A.; Sarroca, C.
Inorg. Chem. 1997, 36, 5206.
(15) Jones, P. G.; Freire Erdbru¨gger, C.; Hohbein, R.; Schwarzmann, E.
Acta Crystallogr. 1988, C44, 1302.
(16) Baker, R. W.; Pauling, J. P. J. Chem. Soc. Dalton Trans. 1972, 2264.
(17) Yam, V. W. W.; Choi, S. W. K.; Cheung, K. K. J. Chem Soc., Dalton
Trans. 1996, 3411.

Gold and Silver Complexes with FcCH2PPh2
Inorganic Chemistry, Vol. 39, No. 4, 2000 683
Table 2. Selected Bond Lengths (Å) and Angles (deg) for
Complex 2
Au-C(11)
P-C(21)
P-C(1)
2.070(5)
1.818(6)
1.828(5)
Au-P
P-C(31)
C(1)-C(41)
2.284(2)
1.819(5)
1.498(7)
C(11)-Au-P
C(21)-P-C(1)
C(21)-P-Au
C(1)-P-Au
174.3(2)
107.3(3)
112.1(2)
110.6(2)
C(21)-P-C(31)
C(31)-P-C(1)
C(31)-P-Au
105.3(2)
104.0(2)
116.8(2)
111.4(3)
C(41)-C(1)-P
Figure 2. Molecular structure of complex 2 in the crystal. H atoms
are omitted for clarity.
Figure 1. (a) Structure of complex 1 in the crystal with the atom-
numbering scheme. The H atoms are omitted for clarity. (b) Environ-
ment of the molecule of 1. The parent molecule is drawn with thick
bonds, and secondary contacts (see text) are drawn as broken bonds.
Only H atoms involved in secondary contacts are shown. Ferrocene
moieties of peripheral molecules are omitted for clarity.
Table 1. Selected Bond Lengths (Å) and Angles (deg) for
Complex 1
Au-P
Au-Cl
P-C(31)
2.2366(18)
2.3014(18)
1.807(7)
P-C(21)
1.821(7)
1.843(6)
1.508(9)
Figure 3. Structure of the cation of complex 3 in the crystal. H atoms
are omitted for clarity.
P-C(11)
C(1)-C(11)
of the cations of 3 and 5, and Tables 3 and 4 show a selection
of bond lengths and angles. The gold atom in complex 3 exhibits
a distorted linear geometry with an angle P-Au-P of 168.74-
(4)°, whereas in 5, with imposed symmetry, the gold center
displays an ideal linear geometry. Deviation from ideal linearity,
sometimes by more than 10°, seems to be common for these
bis(phosphine) complexes; some examples are [Au(PFc2Ph)2]X
(X ) ClO4 or PF6) (169.41(6)°)18,19 and [Au{Fc(CH2P(CH2-
OH)2}]Cl (176.51(6)°).10 The Au-P distances are 2.3210(13)
and 2.3259(13) Å in 3, with different phosphine ligands, and
2.309(2) Å in 5. The latter value is similar to those found in
P-Au-Cl
176.01(7)
108.5(3)
100.4(3)
106.6(3)
116.2(2)
110.3(2)
114.2(2)
C(9)-C(10)-Fe
C(1)-C(11)-P
C(26)-C(21)-P
C(22)-C(21)-P
C(36)-C(31)-P
C(32)-C(31)-P
70.4(4)
111.9(4)
118.2(5)
122.8(5)
119.7(5)
118.6(5)
C(31)-P-C(21)
C(31)-P-C(11)
C(21)-P-C(11)
C(31)-P-Au
C(21)-P-Au
C(11)-P-Au
The Au-P distances are 2.2366(18) Å in 1 and 2.284(2) Å
in 2; the difference may be attributable to the higher trans
influence of the pentafluorophenyl group compared with the
chloro ligand. They are of the same order as found in other
similar complexes such as [AuCl(PFc2Ph)] (2.234(2) Å)15 for
1 and [Au(C6F5)(PPh3)] (2.265(2) Å)16 or [Au2(µ-dppf)(C16H9)2]
(2.295(2) Å)17 for 2.
(18) Gimeno, M. C.; Jones, P. G.; Laguna, A.; Sarroca, C. J. Organomet.
Chem. 1999, 579, 206.
(19) Mu¨ller, T. E.; Green, J. C.; Mingos, D. M. P.; MacPartlin, C. M.;
Whittingham, C.; Williams, D. J.; Woodroffe, T. M. J. Organomet.
Chem. 1998, 551, 313.
Crystal Structures of [AuL(PPh2CH2Fc)]OTf (L ) PPh3
(3), FcCH2PPh2 (5)). Figures 3 and 4 show the crystal structures

684 Inorganic Chemistry, Vol. 39, No. 4, 2000
Barranco et al.
Figure 4. Perspective view of the cation of complex 5 in the crystal.
H atoms are omitted for clarity.
Table 3. Selected Bond Lengths (Å) and Angles (deg) for 3
Figure 5. Molecular structure of complex 7 in the crystal. H atoms
are omitted for clarity.
Au-P(2)
2.3210(13)
1.823(4)
1.829(4)
1.831(4)
1.511(6)
Au-P(1)
2.3259(13)
1.824(4)
1.827(4)
1.842(4)
P(1)-C(21)
P(1)-C(31)
P(2)-C(41)
C(1)-C(60)
P(1)-C(11)
P(2)-C(51)
P(2)-C(60)
Table 5. Selected Bond Lengths (Å) and Angles (deg) for 7
Au-C(21)
Au-C(31)
P-C(41)
P-C(1)
2.067(3)
2.080(4)
1.804(4)
1.835(4)
Au-C(11)
Au-P
P-C(51)
C(1)-C(61)
2.068(4)
2.3503(9)
1.809(4)
1.496(5)
P(2)-Au-P(1)
168.74(4)
C(21)-P(1)-C(11) 104.5(2)
C(11)-P(1)-C(31) 106.3(2)
C(21)-P(1)-C(31) 106.2(2)
C(21)-P(1)-Au
119.66(14) C(11)-P(1)-Au
108.75(14) C(51)-P(2)-C(41) 106.0(2)
110.64(14)
C(31)-P(1)-Au
C(21)-Au-C(11)
86.91(13) C(21)-Au-C(31)
88.59(13)
179.43(11)
91.23(9)
107.1(2)
109.89(12)
112.99(11)
C(51)-P(2)-C(60) 105.4(2)
C(41)-P(2)-C(60) 107.1(2)
C(11)-Au-C(31) 174.80(13) C(21)-Au-P
C(51)-P(2)-Au
C(60)-P(2)-Au
116.42(14) C(41)-P(2)-Au 113.2(2)
108.2(2)
C(11)-Au-P
C(41)-P-C(51)
C(51)-P-C(1)
C(51)-P-Au
C(61)-C(1)-P
93.30(9)
108.9(2)
105.1(2)
C(31)-Au-P
C(41)-P-C(1)
C(41)-P-Au
C(12)-C(11)-P(1) 118.9(3)
C(22)-C(21)-P(1) 121.3(3)
C(36)-C(31)-P(1) 121.7(3)
C(42)-C(41)-P(2) 120.5(3)
C(52)-C(51)-P(2) 122.1(3)
C(16)-C(11)-P(1) 121.3(3)
C(26)-C(21)-P(1) 119.7(3)
C(32)-C(31)-P(1) 118.4(3)
C(46)-C(41)-P(2) 120.7(3)
C(56)-C(51)-P(2) 118.6(3)
112.69(12) C(1)-P-Au
114.9(3)
C(1)-C(60)-P(2)
111.3(3)
CH2PPh2}2Au]23 (2.367(2) Å) and [AuMe3(PPh3)]24 (2.350(6)
Å and 2.347(6) Å, two independent molecules), but longer than
in [AuCl3(PPh3)]25 (2.335(4) Å) or [Au(C6F5)(S2C6H4)(PPh3)]26
(2.340(1) Å), consistent with the higher trans influence of the
pentafluorophenyl groups.
Crystal Structure of [Ag(PPh2CH2Fc)3]OTf (10). The
structure of the cation of complex 10 is shown in Figure 6,
with a selection of bond lengths and angles in Table 6. The
silver atom presents a slightly distorted trigonal geometry, lying
0.046 Å out of the plane of the three phosphorus atoms. The
Ag-P distances (2.440(4)-2.483(4) Å) are similar to those
obtained for three-coordinate silver complexes such as [AgX-
(L-L)]27 (L-L ) 2,11-bis(diphenylphosphino)methylbenzo[c]-
phenanthrene, X ) Cl, SnCl3, ClO4, or NO3) (2.40(3)-2.455(1)
Å), [Ag(dppf)(PPh3)]ClO4 (2.4386(13)-2.4870(12) Å)11b or to
the highest values for [Ag(7.8-(PPh2)2-7.8-C2B9H10)(PPh3)]
(2.3974(10)-2.4942(10) Å)28 which correspond to the Ag-
P(diphosphine) bonds.
Table 4. Selected Bond Lengths (Å) and Angles (deg) for
Complex 5
Au-P#1a
P-C(21)
P-C(31)
2.309(2)
1.819(8)
1.820(8)
P-C(11)
C(1)-C(11)
1.825(8)
1.484(10)
P#1-Au-P
180.00(5)
C(21)-P-Au
C(31)-P-Au
C(11)-P-Au
111.6(2)
111.3(2)
111.7(3)
C(21)-P-C(31)
C(21)-P-C(11)
C(31)-P-C(11)
105.6(3)
107.9(3)
108.5(3)
a Symmetry transformations used to generate equivalent atoms: (#1)
-x, -y + 1, -z.
the complex [Au(PFc2Ph)2]ClO4 (2.293(2) and 2.301(2) Å),
whereas the former are more similar to those in alkyl or aryl
phosphine complexes such as [Au(PR3)2]+ (PR3 ) PPh2Me,
2.316(4) Å; PCy3, 2.321(2) Å).20,21
Crystal Structure of [Au(C6F5)3(PPh2CH2Fc)] (7). The
molecular structure of complex 7 is shown in Figure 5, with
selected bond lengths and angles in Table 5. The gold center
exhibits the expected square planar coordination, lying 0.015-
(1) Å out of the ligand plane. The Au-C distances are in the
range 2.067(3)-2.080(4) Å and are similar to those found in
other tris(pentafluorophenyl)gold(III) derivatives.22 The Au-P
distance (2.3503(9) Å) compares well with the longest found
in phosphinogold(III) complexes such as NBu4[{Au(C6F5)3PPh2-
Electrochemistry. The electrochemical behavior of these
complexes has been studied by cyclic voltammetry at a platinum
(23) Fernandez, E. J.; Gimeno, M. C.; Jones, P. G.; Laguna, A.; Lopez-
de-Luzuriaga, J. M. Organometallics 1995, 14, 2918.
(24) Stein, J.; Fackler, J. P., Jr.; Paparizos, C.; Chen, H. W. J. Am. Chem.
Soc. 1981, 103, 2192.
(25) Bandali, G.; Clemente, D. A.; Marangoni, G.; Cattalini, L. J. J. Chem.
Soc., Dalton Trans. 1973, 886.
(26) Cerrada, E.; Fernandez, E. J.; Gimeno, M. C.; Laguna, A.; Laguna,
M.; Terroba, R.; Villacampa, M. D. J. Organomet. Chem. 1995, 492,
105.
(27) Barrow, M.; Bu¨rgi, H. B.; Camalli, M.; Caruso, F.; Fisher, E.; Venanzi,
L. M.; Zambonelli, L. Inorg. Chem. 1983, 22, 2356.
(28) Crespo, O.; Gimeno, M. C.; Jones, P. G.; Laguna, A. J. Chem Soc.,
Dalton Trans. 1996, 4583.
(20) Guy, J. J.; Jones, P. G.; Sheldrick, G. M. Acta Crystallogr. 1976, B32,
1937.
(21) Muir, J. A.; Muir, M. M.; Pulgar, L. B.; Jones, L. B.; Sheldrick, G.
M. Acta Crystallogr. 1985, C41, 1174.
(22) Uso´n, R.; Laguna, A.; Laguna, M.; Castilla, M. L.; Jones, P. G.;
Fittschen, C. J. Chem Soc., Dalton Trans. 1987, 3017.

Gold and Silver Complexes with FcCH2PPh2
Inorganic Chemistry, Vol. 39, No. 4, 2000 685
Table 7. Electrochemical Data for Complexes 1-10
compound E1 (V)
1 [AuCl(PPh2CH2Fc)] 0.51
E2 (V)
2 [Au(C6F5)(PPh2CH2Fc)]
3 [Au(PPh3)(PPh2CH2Fc)]OTf
4 [Ag(PPh3)(PPh2CH2Fc)]OTf
5 [Au(PPh2CH2Fc)2]ClO4
6 [Ag(PPh2CH2Fc)2]OTf
7 [Au(C6F5)3(PPh2CH2Fc)]
8 [AuCl(PPh2CH2Fc)2]
0.48
0.51
0.45
0.53
0.48
0.56
0.54
0.53
0.49
1.18
1.16
9 [Au(PPh2CH2Fc)3]ClO4
10 [Ag(PPh2CH2Fc)3]OTf
1.1
processes take place in the three-coordinate gold(I) derivatives
to give a mixture of the linear, three-coordinate, and four-
coordinate species. Several complexes have been characterized
by X-ray diffraction; one shows interesting C-H‚‚‚Cl and
H‚‚‚Au intermolecular contacts that can be considered as weak
hydrogen bonds. The electrochemical behavior consists of one
reversible electron oxidation process for the gold compounds
at slightly higher potential than the ferrocene itself; the silver
complexes also show one irreversible wave corresponding to
Figure 6. Structure of the cation of complex 10 in the crystal. H atoms
are omitted for clarity.
the oxidation to Ag2+
.
Table 6. Selected Bond Lengths (Å) and Angles (deg) for
Complex 10
Experimental Section
Instrumentation. Infrared spectra were recorded in the range 4000-
200 cm-1 on a Perkin-Elmer 883 spectrophotometer using Nujol mulls
between polyethylene sheets. Conductivities were measured in ca. 5
× 10-4 mol dm-3 solutions with a Philips 9509 conductimeter. C, H,
and S analyses were carried out with a Perkin-Elmer 2400 microana-
lyzer. Mass spectra were recorded on a VG Autospec, with the liquid
secondary-ion mass spectra (LSIMS) technique, using nitrobenzyl
alcohol as matrix. NMR spectra were recorded on a Varian Unity 300
spectrometer and a Bruker ARX 300 spectrometer in CDCl3 (otherwise
stated). Chemical shifts are cited relative to SiMe4 (1H, external) and
85% H3PO4 (31P, external). Cyclic voltammetric experiments were
performed by employing an EG&G PARC model 273 potentiostat. A
three-electrode system was used, which consists of a platinum disk
working electrode, a platinum wire auxiliary electrode, and a saturated
calomel reference electrode. The measurements were carried out in CH2-
Cl2 solutions with 0.1 M Bu4NPF6 as a supporting electrolyte. Under
the present experimental conditions, the ferrocenium/ferrocene couple
was located at 0.47 V vs SCE.
Ag-P(1)
2.440(4)
2.443(4)
2.483(4)
1.822(8)
1.821(8)
1.832(13)
P(2)-C(38)
P(2)-C(31)
P(2)-C(50)
P(3)-C(67)
P(3)-C(61)
P(3)-C(80)
1.775(12)
1.811(9)
1.851(15)
1.813(9)
1.825(8)
1.842(14)
Ag-P(3)
Ag-P(2)
P(1)-C(1)
P(1)-C(7)
P(1)-C(20)
P(1)-Ag-P(3)
P(1)-Ag-P(2)
P(3)-Ag-P(2)
C(1)-P(1)-C(7)
C(1)-P(1)-C(20)
C(7)-P(1)-C(20)
C(1)-P(1)-Ag
C(7)-P(1)-Ag
C(20)-P(1)-Ag
135.11(14) C(67)-P(3)-C(80) 106.8(6)
112.87(14) C(61)-P(3)-C(80) 101.6(6)
111.32(14) C(67)-P(3)-Ag
112.9(4)
122.5(3)
108.5(5)
117.0(6)
123.0(6)
118.5(5)
121.3(5)
102.8(5)
104.8(6)
102.3(6)
120.0(4)
119.2(3)
105.6(5)
C(61)-P(3)-Ag
C(80)-P(3)-Ag
C(2)-C(1)-P(1)
C(6)-C(1)-P(1)
C(8)-C(7)-P(1)
C(12)-C(7)-P(1)
C(38)-P(2)-C(31) 105.3(6)
C(38)-P(2)-C(50) 105.9(7)
C(31)-P(2)-C(50) 103.8(6)
C(21)-C(20)-P(1) 110.6(8)
C(39)-C(38)-P(2) 121.2(9)
C(51)-C(50)-P(2) 115.2(10)
C(66)-C(61)-P(3) 118.6(5)
C(68)-C(67)-P(3) 119.3(7)
C(72)-C(67)-P(3) 120.6(7)
C(81)-C(80)-P(3) 110.7(9)
Materials. The starting materials FcCH2PPh2,5 [AuCl(tht)],29 [Au-
(C6F5)(tht)],30 and [Au(C6F5)3(OEt2)]31 were prepared by published
procedures. [Au(OTf)(PPh3)] was prepared from [AuCl(PPh3)]32 by
reaction with AgOTf in dichloromethane and [Ag(OTf)(PPh3)] by
reaction of AgOTf and PPh3 in diethyl ether.
C(38)-P(2)-Ag
C(31)-P(2)-Ag
C(50)-P(2)-Ag
104.3(5)
117.2(4)
119.0(5)
C(67)-P(3)-C(61) 103.1(5)
electrode in CH2Cl2. The redox pattern of the free phosphine
ligand is complicated and resembles that of the 1,1′-bis-
(diphenylphosphino)ferrocene ligand. Thus the phosphine un-
dergoes a quasi-reversible one-electron oxidation process, based
on the ferrocene unit, followed by a chemical reaction involving
the phosphorus substituent. The cyclic voltammograms, at a scan
rate of 100 mV s-1, of the gold derivatives show an essentially
reversible wave arising from the oxidation-reduction of the
ferrocene moiety at slightly higher potentials than the phos-
phine-ferrocene ligand. The silver(I) compounds show, in
addition to the wave due to the ferrocene oxidation, a more
anodic irreversible wave that can be assigned to the one-electron
oxidation of Ag+ to Ag2+. Table 7 summarizes the electro-
chemical data for these compounds.
Safety Note. CAUTION! Perchlorate salts of metal complexes with
organic ligands are potentially explosive. Only small amounts of
material should be prepared, and these should be handled with great
caution.
Syntheses. [AuR(PPh2CH2Fc)] [R ) Cl (1), C6F5 (2)]. To a solution
of [AuCl(tht)] (0.032 g, 0.1 mmol) or [Au(C6F5)(tht)] (0.045 g, 0.1
mmol) in 20 mL of dichloromethane was added PPh2CH2Fc (0.038 g,
0.1 mmol), and the mixture was stirred for 1 h. Concentration of the
solution to ca. 5 mL and addition of hexane (10 mL) gave complexes
1 or 2 as orange solids. Complex 1: yield 79%. ΛM ) 0.4 Ω-1 cm2
mol-1. Elemental anal. Found: C, 44.87; H, 3.11. Calcd for C23H21-
1
AuClFeP: C, 44.80; H, 3.43. H NMR, δ: 3.56 (d, 2H, CH2, J(PH)
10.16 Hz), 4.01 (m, 2H, C5H4), 4.04 (m, 2H, C5H4), 4.10 (m, 5H, C5H5),
7.2-7.6 (m, 10H, Ph). 31P{1H} NMR, δ: 30.9 (s). Complex 2: yield
(29) Uso´n, R.; Laguna, A. Organomet. Synth. 1989, 3, 322.
(30) Uso´n, R.; Laguna, A.; de la Orden, M. U.; Arrese, M. L. Synth. React.
Inorg. Met.-Org. Chem. 1984, 14, 369.
(31) Uso´n, R.; Laguna, A.; Laguna, M.; Jime´nez, J.; Durana, E. Inorg.
Chim. Acta 1990, 168, 89.
Conclusions
We have reported on a series of new gold and silver
complexes with ferrocenylmethylphosphine in different coor-
dination numbers. Interesting equilibria or reorganization
(32) Uso´n, R.; Laguna, A. Inorg. Synth. 1982, 21, 71.

686 Inorganic Chemistry, Vol. 39, No. 4, 2000
Barranco et al.
Table 8. Details of Data Collection and Structure Refinement for the Complexes 1-3
1
2
3
chem formula
cryst habit
cryst size/mm
λ
cryst syst
space group
a/Å
C23H21AuClFeP
yellow block
0.20 × 0.20 × 0.15
0.710 73
monoclinic
P21/c
9.886(3)
17.539(4)
11.867(3)
C29H21AuF5FeP
yellow tablet
0.38 × 0.21 × 0.17
0.710 73
triclinic
P1h
10.960(2)
11.049(2)
12.562(2)
115.374(14)
109.135(12)
94.918(14)
1252.1(4)
2
C42H36AuF3FeO3P2S
orange tablet
0.68 × 0.48 × 0.16
0.710 73
triclinic
P1h
10.859(3)
11.463(4)
16.517(5)
74.69(2)
80.33(2)
79.98(2)
1919.1(10)
2
b/Å
c/Å
R/deg
â/deg
99.35(2)
γ/deg
V/Å3
2030.3(9)
4
2.017
616.63
1184
Z
Dc/g cm-3
M
1.985
748.24
720
1.718
992.52
980
F(000)
T/°C
-100
-100
-100
2θmax/deg
µ(Mo KR)/cm-1
transmission
no. of reflns meas
no. of unique reflns
Rint
50
50
48
81.48
0.595-0.801
5922
65.50
0.705-0.922
4199
4158
0.0145
0.03
0.052
4158
355
93
0.888
43.87
0.610-0.958
6993
5931
0.014
0.029
0.072
5927
478
365
0.996
3564
0.0393
0.0328
0.0723
3564
244
213
Ra (F > 4σ(F))
Rwb (F2, all reflns)
no. of reflns used
no. of params
no. of restraints
Sc
0.898
1.271
max ∆F/e Å-3
0.908
2.72
a R(F) ) ∑||Fo| - |Fc||/∑|Fo|. b Rw(F2) ) [∑{w(Fo2 - Fc2)2}/∑{w(Fo )2}]0.5; w-1 ) σ2(Fo ) + (aP)2 + bP, where P ) [Fo2 + 2Fc2]/3 and a and
2
2
b are constants adjusted by the program. c S ) [∑{w(Fo - Fc2)2}/(n - p)]0.5, where n is the number of data and p the number of parameters.
2
Table 9. Details of Data Collection and Structure Refinement for the Complexes 5, 7, and 10
5
7
10
chem formula
cryst habit
cryst size/mm
cryst system
space group
a/Å
C47H44AuCl3Fe2O4P2
orange plate
0.20 × 0.20 × 0.05
triclinic
P1h
9.0828(18)
9.5568(16)
13.501(2)
86.587(12)
89.573(14)
77.154(14)
1140.6(4)
1
1.674
1149.18
570
-100
50
41.24
0.789-0.991
4031
C41H21AuF15FeP
orange prism
0.50 × 0.40 × 0.20
monoclinic
P21/n
13.6515(14)
17.101(2)
C71H65AgCl2F3Fe3O3P3S
dull orange tablet
0.35 × 0.30 × 0.15
monoclinic
P21/c
12.692(3)
b/Å
c/Å
18.467(4)
28.693(6)
16.274(2)
R/deg
â/deg
91.566(7)
93.08(2)
γ/deg
V/Å3
3797.7(6)
4
1.893
1082.36
2088
-100
50
43.88
0.608-0.966
6694
6716(3)
4
1.478
1494.52
3048
-100
46
Z
Dc/g cm-3
M
F(000)
T/°C
2θmax/deg
µ(Mo KR)/cm-1
transmission
no. of reflns meas
no. of unique reflns
Rint
11.59
9408
8750
0.058
0.095
0.278
8750
258
19
0.878
1.252
4003
0.038
0.049
0.1254
4003
290
281
0.973
6676
0.016
0.025
0.044
6676
532
507
Ra (F > 4σ(F))
Rwb (F2, all reflns)
no. of reflns used
no. of params
no. of restraints
Sc
0.886
0.368
max ∆F/e Å-3
1.723
2
2
a R(F) ) ∑||Fo| - |Fc||/∑|Fo|. b Rw(F2) ) [∑{w(Fo2 - Fc2)2}/∑{w(Fo )2}]0.5; w-1 ) σ2(Fo ) + (aP)2 + bP, where P ) [Fo2 + 2Fc2]/3 and a and
b are constants adjusted by the program. c S ) [∑{w(Fo - Fc2)2}/(n - p)]0.5, where n is the number of data and p the number of parameters.
2
85%. ΛM ) 1.7 Ω-1 cm2 mol-1. Elemental anal. Found: C, 46.73; H,
3.22. Calcd for C29H21AuF5FeP: C, 46.55; H, 2.83. 1H NMR, δ: 3.58
(d, 2H, CH2, J(PH) 9.43 Hz), 4.05 (m, 2H, C5H4), 4.08 (m, 2H, C5H4),
4.10 (m, 5H, C5H5), 7.2-7.7 (m, 10H, Ph). 31P{1H} NMR, δ: 30.1 (m).

Gold and Silver Complexes with FcCH2PPh2
Inorganic Chemistry, Vol. 39, No. 4, 2000 687
19F NMR, δ: -116.3 (m, 2F, o-F), -158.8 (t, 1F, p-F, J(FF) 20.0 Hz),
-162.7 (m, 2F, m-F).
orange solid. Complex 8: yield 50%. ΛM ) 14 Ω-1 cm2 mol-1
.
Elemental anal. Found: C, 55.73; H, 3.71. Calcd for C46H42-
1
[M(PPh2CH2Fc)(PPh3)]OTf [M ) Au (3), Ag (4)]. To a solution
of [Au(OTf)(PPh3)] (0.061 g, 0.1 mmol) or [Ag(OTf)(PPh3)] (0.052 g,
0.1 mmol) in 20 mL of dichloromethane was added PPh2CH2Fc (0.038
g, 0.1 mmol), and the mixture was stirred for 1 h. Concentration of the
solution to ca. 5 mL and addition of hexane (10 mL) gave 3 or 4 as
AuClFe2P2: C, 55.31; H, 4.03. H NMR, CD2Cl2, room temperature,
δ: 3.69 (d, 2H, CH2, J(PH) 9.6 Hz), 4.04 (m, 2H, C5H4), 4.05 (m, 2H,
C5H4), 4.14 (m, 5H, C5H5), 7.4-7.7 (m, 20H, Ph). 31P{1H} NMR, δ:
33.8 (s, br); -80 °C, 3.60 (d, 2H, CH2, J(PH) 10.5 Hz), 3.79 (m, C5H4),
3.95 (m, C5H4), 3.99 (m, C5H4), 4.01 (m, C5H4), 4.08 (m, C5H5), 7.4-
7.7 (m, Ph). 31P{1H} NMR, δ: 28.2 (s), 32.4 (s), 38.5(s), 42.3 (s).
[M(PPh2CH2Fc)3]X [M ) Au, X ) ClO4 (9); M ) Ag, X ) OTf
(10)]. To a solution of [Au(tht)2]ClO4 (0.047 g, 0.1 mmol) or AgOTf
(0.021 g, 0.1 mmol) in 20 mL of dichloromethane was added PPh2-
CH2Fc (0.114 g, 0.3 mmol), and the mixture was stirred for 1 h.
Concentration of the solution to ca. 5 mL and addition of hexane (10
yellow solids. Complex 3: yield 95%. ΛM ) 105 Ω-1 cm2 mol-1
.
Elemental anal. Found: C, 50.39; H, 3.31; S, 3.31. Calcd for C42H36-
1
AuF3FeO3P2S: C, 50.82; H, 3.65; S, 3.23. H NMR, δ: 3.82 (m, 1H,
CH2), 3.90 (m, 1H, CH2), 3.93 (m, 2H, C5H4), 3.95 (m, 2H, C5H4),
4.12 (m, 5H, C5H5), 4.14 (s, 5H, C5H5), 7.2-7.7 (m, 25H, Ph). 31P-
{1H} NMR, δ: 44.4 (s), 45.3 (s). Complex 4: yield 65%. ΛM ) 104.2
Ω-1 cm2 mol-1. Elemental anal. Found: C, 55.95; H, 3.79; S, 3.33.
mL) gave 9 or 10 as yellow solids. Complex 9: yield 80%. ΛM
)
1
90.5 Ω-1 cm2 mol-1. Elemental anal. Found: C, 57.42; H, 3.92. Calcd
for C69H63AuClFe3O4P3: C, 57.19; H, 4.38. 1H NMR, room temperature,
δ: 3.77 (m, 6H, CH2), 3.94 (m, 12H, C5H4), 4.15 (m, 15H, C5H5),
7.2-7.8 (m, 30H, Ph). 31P{1H} NMR, δ: 41.7 (s, br); -60 °C, 3.77
(m), 3.84 (m), 3.97 (m), 4.10 (m), 7-7.8 (m, Ph). 31P{1H} NMR, δ:
28.2 (s), 38.3 (s), 43.8 (s). Complex 10: yield 85%. ΛM ) 107 Ω-1
cm2 mol-1. Elemental anal. Found: C, 59.7; H, 3.91; S, 2.82. Calcd
for C70H63AgF3Fe3O3P3S: C, 59.38; H, 4.40; S, 2.29. 1H NMR, δ: 3.37
(m, 2H, CH2), 3.81 (m, 2H, C5H4), 3.83 (m, 2H, C5H4), 4.05 (m, 5H,
C5H5), 7.3-7.5 (m, 30H, Ph). 31P{1H} NMR, -60 °C, δ: 14.8 ppm
(2d,
Calcd for C42H36AgF3FeO3P2S: C, 55.78; H, 4.01; S, 3.54. H NMR,
-80 °C, (CD3)2CO, δ: 3.55 (m, 2H, CH2), 3.80 (m, 2H, C5H4), 3.94
(m, 2H, C5H4), 4.06 (m, 5H, C5H5), 7.2-7.7 (m, 25H, Ph). 31P{1H}
109
NMR, δ: PA 12.4, PB 15.8, J(PAPB) 45 Hz, J(PA107Ag) 375 Hz, J(PA
-
Ag) 427.5 Hz, J(PB107Ag) 500 Hz, J(PB109Ag) 570 Hz.
[M(PPh2CH2Fc)2]X [M ) Au, X ) ClO4 (5); Ag, X ) OTf (6)].
To a solution of [Au(tht)2]ClO4 (0.047 g, 0.1 mmol) or AgOTf (0.021
g, 0.1 mmol) in 20 mL of dichloromethane was added PPh2CH2Fc
(0.076 g, 0.2 mmol), and the mixture was stirred for 1 h. Concentration
of the solution to ca. 5 mL and addition of hexane (10 mL) gave 5 or
6 as yellow solids. Complex 5: yield 93%. ΛM ) 100 Ω-1 cm2 mol-1
.
J(P107Ag) 509 Hz, J(P109Ag) 586.3 Hz).
Elemental anal. Found: C, 51.61; H, 3.73. Calcd for C46H42-
1
AuClFe2O4P2: C, 51.88; H, 3.97. H NMR, δ: 3.86 (m, 2H, CH2),
Crystallography. The crystals were mounted in inert oil on a glass
fiber and transferred to the cold gas stream of a Siemens P4
diffractometer equipped with an LT-2 or Oxford low-temperature
attachment. Data were collected using monochromated Mo KR radiation
(λ ) 0.710 73 Å). Scan type: ω or θ-2θ (3). Cell constants were
refined from setting angles of ca. 60 reflections in the range 2θ 7-25°.
Psi scans were applied for all of the complexes with the exception of
compound 10, for which no absorption correction was applied. The
structures were solved by direct methods for 3 and 10, otherwise by
the heavy-atom method, and refined on F2 using the programs
SHELXL-93 or SHELXL-97.33 All non-hydrogen atoms were refined
anisotropically (except for complex 10). Hydrogen atoms were included
using a riding model. Special refinement details: A system of restraints
to light-atom displacement-factor components and local ring symmetry
was used. Compounds 3 and 10 contain badly disordered solvent
(dichloromethane). Further details of the data collection are given in
Tables 8 and 9.
3.94 (m, 2H, C5H4), 3.98 (m, 2H, C5H4), 4.17 (m, 5H, C5H5), 7.4-7.8
(m, 20H, Ph). 31P{1H} NMR, δ: 44.2 (s). Complex 6: yield 65%. ΛM
) 115 Ω-1 cm2 mol-1. Elemental anal. Found: C, 55.62; H, 4.39; S,
1
2.74. Calcd for C47H42AgF3Fe2O3P2S: C, 55.05; H, 4.13; S, 3.12. H
NMR, δ: 3.26 (m, 2H, CH2), 3.72 (m, 2H, C5H4), 3.84 (m, 2H, C5H4),
4.03 (m, 5H, C5H5), 7.1-7.5 (m, 20H, Ph). 31P{1H} NMR, -60 °C
CDCl3, δ: 8.6 ppm (2d, J(P107Ag) 320 Hz, J(P109Ag) 367.8 Hz).
[Au(C6F5)3(PPh2CH2Fc)] (7). To a solution of [Au(C6F5)3(OEt2)]
(0.077 g, 0.1 mmol) in 20 mL of dichloromethane was added PPh2-
CH2Fc (0.038 g, 0.1 mmol), and the mixture was stirred for 1 h.
Concentration of the solution to ca. 5 mL and addition of hexane (10
mL) gave complex 7 as an orange solid. Yield: 91%. ΛM ) 0.4 Ω-1
cm2 mol-1. Elemental anal. Found: C, 45.68; H, 1.72. Calcd for C41H21-
1
AuF15FeP: C, 45.49; H, 1.95. H NMR, δ: 3.47 (d, 2H, CH2, J(PH)
7.87 Hz), 3.74 (m, 2H, C5H4), 3.99 (m, 2H, C5H4), 4.04 (m, 5H, C5H5),
7.2-7.7 (m, 10H, Ph). 31P{1H} NMR, δ: 13.9 (m). 19F NMR, δ: -120.1
(m, 4F, o-F), -121.8 (m, 2F, o-F), -156.9 (t, 2F, p-F, J(FF) 19.75
Hz), -157.4 (t, 1F, p-F, J(FF) 19.88 Hz), -160.7 (m, 4F, m-F), -161.4
(m, 2F, m-F).
[AuCl(PPh2CH2Fc)2] (8). To a solution of [AuCl(tht)] (0.032 g,
0.1 mmol) in 20 mL of dichloromethane was added PPh2CH2Fc (0.076
g, 0.2 mmol), and the mixture was stirred for 1 h. Concentration of the
solution to ca. 5 mL and addition of hexane (10 mL) gave 8 as an
Acknowledgment. We thank the Direccio´n General de
Investigacio´n Cient´ıfica y Te´cnica (No. PB97-1010-C02-01),
the Caja de Ahorros de la Inmaculada (No. CB4/98), and the
Fonds der Chemischen Industrie for financial support.
Supporting Information Available: Six X-ray crystallographic
files, in CIF format. This material is available free of charge via the
Internet at http://pubs.acs.org.
(33) Sheldrick, G. M. SHELXL-93 and SHELXL-97, Program for Crystal
Structure Refinement; University of Go¨ttingen: Go¨ttingen, Germany,
1993/1997.
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