Behavior of neutral phosphido derivatives of platinum and palladium toward silver centers

Article abstract of DOI:10.1021/ic201354s

The reaction of the neutral binuclear complexes [(R_F) ₂Pt(μ-PPh₂)₂M(phen)] (phen = 1,10-phenanthroline, R_F = C₆F₅; M = Pt, 1; M = Pd, 2) with AgClO₄ or [Ag(OClO_3<

Full text of DOI:10.1021/ic201354s

ARTICLE
pubs.acs.org/IC
Behavior of Neutral Phosphido Derivatives of Platinum and Palladium
toward Silver Centers
Juan Forniꢀes,* Consuelo Fortu~no,* Susana Ibꢀa~nez, and Antonio Martín
Departamento de Química Inorgꢀanica, Instituto de Síntesis Química y Catꢀalisis Homogꢀenea, Universidad de Zaragoza-C.S.I.C.,
E-50009 Zaragoza, Spain
Piero Mastrorilli and Vito Gallo
Dipartimento di Ingegneria delle Acque e di Chimica del Politecnico di Bari, via Orabona 4, I-70125 bari, Italy
S Supporting Information
b
ABSTRACT: The reaction of the neutral binuclear complexes
[(RF)2Pt(μ-PPh2)2M(phen)] (phen = 1,10-phenanthroline,
RF = C6F5; M = Pt, 1; M = Pd, 2) with AgClO4 or [Ag
(OClO3)(PPh3)] affords the trinuclear complexes [AgPt2(μ-
PPh2)2(RF)2(phen)(OClO3)] (7a) or [AgPtM(μ-PPh2)2-
(RF)2(phen)(PPh3)][ClO4] (M = Pt, 8; M = Pd, 9), which
display an “open-book” type structure and two (7a) or one
(8, 9) PtꢀAg bonds. The neutral diphosphine complexes [(RF)2
Pt(μ-PPh2)2M(PꢀP)] (PꢀP = 1,2-bis(diphenylphosphino)-
methane, dppm, M = Pt, 3; M = Pd, 4; PꢀP = 1,2-bis(diphenylphosphino)ethane, dppe, M = Pt, 5; M = Pd, 6) react with AgClO4 or
[Ag(OClO3)(PPh3)], and the nature of the resulting complexes is dependent on both M and the diphosphine. The dppm PtꢀPt
complex 3 reacts with [Ag(OClO3)(PPh3)], affording a silver adduct 10 in which the Ag atom interacts with the Pt atoms, while the
dppm PtꢀPd complex 4 reacts with [Ag(OClO3)(PPh3)], forming a 1:1 mixture of [AgPdPt(μ-PPh2)2(RF)2(OClO3)(dppm)]
(11), in which the silver atom is connected to the PtꢀPd moiety through Pdꢀ(μ-PPh2)ꢀAg and AgꢀP(k1-dppm) interactions, and
[AgPdPt(μ-PPh2)2(RF)2(OClO3)(PPh3)2][ClO4] (12). The reaction of complex 4 with AgClO4 gives the trinuclear derivative 11
as the only product. Complex 11 shows a dynamic process in solution in which the silver atom interacts alternatively with both
PdꢀμPPh2 bonds. When PꢀP is dppe, both complexes 5 and 6 react with AgClO4 or [Ag(OClO3)(PPh3)], forming the saturated
complexes [(PPh2C6F5)(RF)Pt(μ-PPh2)(μꢀOH)M(dppe)][ClO4] (M = Pt, 13; Pd, 14), which are the result of an oxidation
followed by a PPh2/C6F5 reductive coupling. Finally, the oxidation of trinuclear derivatives [(RF)2PtII(μ-PPh2)2PtII(μ-
PPh2)2PtIIL2] (L2 = phen, 15; L = PPh3, 16) by AgClO4 results in the formation of the unsaturated 46 VEC complexes
[(RF)2PtIII(μ-PPh2)2PtIII(μ-PPh2)2PtIIL2][ClO4]2 (17 and 18, respectively) which display Pt(III)ꢀPt(III) bonds.
’ INTRODUCTION
n = 1 and 2 L = acetylacetonate, acac, the formation of “open
book” type B complexes, with one or two MꢀAg bonds
(Scheme 1),17 was observed. Finally, when n = 0, M = Pt, and
L = PPh3, the silver ion inserts into the MꢀPPh3 bond of
the neutral starting material, giving rise to a type C cluster
(Scheme 1) with a planar core in which a Mꢀ(μ-P) bond of
a bridging phosphido group acts as a donor to the silver
center in a 3cꢀ2e bond.35 In Table 1 are reported the known
examples of types AꢀC complexes.
Heteropolynuclear complexes of palladium and platinum
containing Ag(I) centers are well-known today.1ꢀ10 In some
cases, the d8ꢀd10 derivatives show MꢀAg (M = Pt or Pd
throughout the paper) donorꢀacceptor bonds.11ꢀ25 These types
of complexes have been also proposed as unstable intermediates
both in halide abstraction processes, with elimination of AgX,
and in oxidation processes, with the formation of Ag0.26ꢀ33 In the
course of our current research on phosphido derivatives, we have
studied the behavior of the dinuclear complexes of platinum and
palladium(II) of the general formula [(RF)2Pt(μ-PPh2)2ML2]nꢀ
(RF = C6F5) toward silver derivatives obtaining either complexes
with M(II)ꢀAg(I) bond or M(III)ꢀM(III) binuclear com-
plexes. For n = 2, M = Pt, and L = RF, the electron transfer
process affords a Pt(III)ꢀPt(III) complex of the type A
(Scheme 1).34 Surprisingly, this type of complex displays
the Pt(III) centers in square planar environments with
PtꢀPt and Ptꢀligand bonds lying in the same plane. When
In this paper, we describe the reactions of other platinum
or palladium phosphido complexes toward silver derivatives
in an attempt to gain insights into the factors which address
the reactions toward the formation of A, B, or C type
complexes.
Received: June 23, 2011
Published: September 26, 2011
r
2011 American Chemical Society
10798
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|

Inorganic Chemistry
ARTICLE
Scheme 1
The heterodinuclear complexes 2, 4, and 6 were prepared from
cis-[Pt(RF)2(PPh2)2]2ꢀ and [PdCl2(phen)], [PdCl2(dppm)], or
[PdCl2(dppe)], respectively, in a way similar to that followed
for the synthesis of 3.36 Complex 5 was synthesized from
[(RF)2Pt(μ-PPh2)2Pt(NCCH3)2]37 and dppe (1:1 molar ratio).
The elimination of two acetonitrile ligands and coordination of
the dppe gave 5 in very good yield. These new neutral complexes
were characterized by elemental analysis and spectroscopic
methods. All data are given in the Experimental Section, and
they compare well with those found for related saturated di-
nuclear 32 VEC derivatives previously prepared by us.22,36,38
The reaction of 1 (Scheme 2) with AgClO4 even in excess affords
the type Btrinuclear complex [AgPt2(μ-PPh2)2(RF)2(OClO3)(phen)]
(7a), in which both Pt atoms of the starting material act as donors
toward the silver center, forming two PtꢀAg bonds (Scheme 2).
The structure of this type B trinuclear complex has been
established by an X-ray diffraction study. A noteworthy feature of
this structure is that two different trinuclear complexes are
copresent in the asymmetric part of the unit cell. Figure 1 shows
these structures, 7a and 7b, and Table 2 lists the most relevant
bond lengths and angles. Complexes 7a and 7b differ in the
coordination environment of the silver center. In fact, while in 7a
the silver atom completes its coordination sphere with an O atom
of the perchlorate counterion (Figure 1a), in 7b the oxygen atom
bonded to Ag belongs to a water molecule, presumably present in
the crystallization solvents (Figure 1b). Moreover, this water
moiety establishes a hydrogen bond with the “free” ClO4ꢀ anion.
The existence of these two different coordination modes of the
silver center in the same crystal isꢀprobably due to the weak
coordinating ability of the OClO3 ligand, which is partially
displaced from 7a by traces of water in the crystallization process.
Both complexes are trinuclear, with the Pt atoms in square planar
environments, and display “open book” structures, characteristic
of type B complexes. Thus, the two square planar environments
of the platinum atoms are not coplanar but form an angle of
40.1(1)° for 7a and 35.2(1)° for 7b. The silver atoms lie in the
“inner side of the book”, forming two PtꢀAg donorꢀacceptor
bonds and a PtꢀAg axis tending to perpendicularity with respect
to its corresponding Pt plane. As has been observed in previous
cases, the shorter PtꢀAg bonds correspond to the Pt centers
which are bonded to the pentafluorophenyl ligands [Pt(1)ꢀAg(1) =
2.7684(6) Å, Pt(3)ꢀAg(2) = 2.8184(6) Å], while the Pt atoms
bonded to the phenanthroline establish longer bond distances
[Pt(2)ꢀAg(1) = 2.8773(7) Å, Pt(4)ꢀAg(2) = 2.9051(6) Å]. It
can be noticed that the shorter distance is related to a stronger
bond formed with the Pt atoms bearing C6F5 groups and thus is
more basic in character.
Table 1. Reaction of Platinum or Palladium Phosphido
Derivatives Towards Silver Salts
entry
m
2 L
2RF
M
n
type
ref
1
1
1
1
1
1
1
1
1
1
2
2
2
2
Pt
Pt
Pd
Pt
Pd
Pt
Pd
Pt
Pd
Pt
Pt
Pt
Pt
2
1
1
0
0
0
0
0
0
2
1
0
0
A
B
B
C
C
B
B
B
C
A
A
A
A
34
17
17
35
35
2
acac
3
acac
4
2PPh3
2PPh3
phen
phen
dppm
dppm
2RF
5
6
this work
this work
this work
this work
39
7
8
9
10
11
12
13
acac
28
phen
2PPh3
this work
this work
’ RESULTS AND DISCUSSION
Behavior of Dinuclear Derivatives toward Ag(I). The results
of the study on dinuclear phosphido bridged derivatives toward
silver salts carried out so far (Table 1, entries 1ꢀ5) point out that
the platinum center of a monoanionic derivative is basic enough
to form stable donorꢀacceptor platinumꢀsilver bonds in the
complexes of type B (Table 1, entries 2 and 3).17 Nevertheless,
for a complex carrying two negative charges (Table 1, entry 1),
the putative PtꢀAg bond is a result of electron transfer from the
platinum center to the silver one, affording a Pt(III)ꢀPt(III)
complex of type A.34 Interestingly, for neutral phosphido bridged
PtꢀM derivatives (Table 1, entries 4 and 5), the (μ-P)ꢀM bond
competes with the metal centers as a basic site, and an unusual
3cꢀ2e bond between the (μ-P)ꢀM bond and the silver cation is
formed.35 In order to establish whether the neutral nature of the
starting material reduces the basic nature of the platinum or
palladium centers and warrants the formation of the aforemen-
tioned 3cꢀ2e bond, we have explored the reactivity of the neutral
complexes [(RF)2Pt(μ-PPh2)2ML2] (2 L = phen, M = Pt 1,36 Pd
2; 2 L = dppm, M = Pt 3,36 Pd 4; 2 L = dppe, M = Pt 5, Pd 6)
toward AgClO4 and [AgClO4(PPh3)].
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Inorganic Chemistry
ARTICLE
Scheme 2
The geometries around the silver centers for 7a and 7b are
also different. While in complex 7a the Pt(1), Ag(1), and O(1)
display a nearly linear disposition [Pt(1)ꢀAg(1)ꢀO(1) angle =
162.32(11)°], and the Pt(2)ꢀAg(1)ꢀO(1) angle [117.60(12)°]
is significantly more acute, in 7b these values are inverted for the
analogous Pt atoms, being 132.26(9)° for the Pt(3)ꢀAg(2)ꢀO(5)
angle and 151.76(10)° for the Pt(4)ꢀAg(2)ꢀO(5) one. In all
likelihood, these differences are due to the copresence in 7b of
water and ClO4 in the Pt(4)Ag(2)O(5) region.
The strong tendency of water to replace the perchlorate in the
Ag coordination sphere of 7a was confirmed by 31P{1H} NMR
experiments. The 31P{1H} NMR spectrum of a CD2Cl2 solution
of 7a kept at 193 K showed only a signal at δ ꢀ140.6 broadened
by the couplings with 107/109Ag and flanked by two sets of 195Pt
satellites (1JP,Pt =1843 and 2342 Hz). Monitoring the solution at
intervals of 5 min revealed the progressive decreasing of the
signal at δ ꢀ140.6, with a contemporary appearance of a signal
at δ ꢀ108.1 (1JP,Pt =1452 and 2091 Hz), which became the
only signal after 30 min. On warming the solution up to 298 K,
the chemical shift of this species did not significantly change
(δ ꢀ106), but the signal became considerably broad (Δν1/2
=
250 Hz). We interpret these results admitting that the species at
δ ꢀ140.6 is the perchlorate adduct 7a, which reacts with the
water present in the CD2Cl2 to give the H2O adduct of silver 7b.
The 19F NMR spectrum of 7b (the stable form in commercial
CD2Cl2) at 193 K showed five broad signals (see Experimental
Section) of the same intensity, thus indicating that the two C6F5
groups are equivalent and the two halves of each C6F5 ring are
unequivalent. This pattern is in agreement with the presence
of the PtꢀAg bonds in solution and with a hindered rotation
about the PtꢀC bonds. Upon warming the solution up to room
temperature, the C6F5 rings can freely rotate, and the 19F
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Inorganic Chemistry
ARTICLE
Table 2. Selected Bond Lengths (Å) and Angles (deg) for
7 0.50H2O 1.25CH2Cl2
3
3
Pt(1)ꢀC(1)
Pt(1)ꢀC(7)
Pt(1)ꢀP(2)
Pt(1)ꢀP(1)
Pt(1)ꢀAg(1)
Pt(2)ꢀN(1)
Pt(2)ꢀN(2)
Pt(2)ꢀP(2)
Pt(2)ꢀP(1)
Pt(2)ꢀAg(1)
Ag(1)ꢀO(1)
2.072(5) Pt(3)ꢀC(55)
2.078(5) Pt(3)ꢀC(49)
2.3084(13) Pt(3)ꢀP(3)
2.3093(14) Pt(3)ꢀP(4)
2.7684(6) Pt(3)ꢀAg(2)
2.101(4) Pt(4)ꢀN(3)
2.112(4) Pt(4)ꢀN(4)
2.2871(13) Pt(4)ꢀP(4)
2.2930(13) Pt(4)ꢀP(3)
2.8773(7) Pt(4)ꢀAg(2)
2.285(4) Ag(2)ꢀO(5)
2.080(5)
2.082(5)
2.3044(14)
2.3053(12)
2.8184(6)
2.106(4)
2.121(4)
2.2970(14)
2.2987(12)
2.9051(6)
2.323(4)
C(1)ꢀPt(1)ꢀC(7)
91.84(19) C(55)ꢀPt(3)ꢀC(49) 90.44(19)
C(1)ꢀPt(1)ꢀP(2) 170.88(14) C(55)ꢀPt(3)ꢀP(3) 172.58(13)
C(7)ꢀPt(1)ꢀP(2)
C(1)ꢀPt(1)ꢀP(1)
95.12(14) C(49)ꢀPt(3)ꢀP(3)
97.80(15) C(55)ꢀPt(3)ꢀP(4)
95.19(15)
99.49(13)
C(7)ꢀPt(1)ꢀP(1) 169.27(14) C(49)ꢀPt(3)ꢀP(4) 169.74(15)
P(2)ꢀPt(1)ꢀP(1)
74.83(5)
P(3)ꢀPt(3)ꢀP(4)
74.70(5)
C(1)ꢀPt(1)ꢀAg(1) 97.55(14) C(55)ꢀPt(3)ꢀAg(2) 98.91(14)
C(7)ꢀPt(1)ꢀAg(1) 96.22(14) C(49)ꢀPt(3)ꢀAg(2) 99.09(14)
P(2)ꢀPt(1)ꢀAg(1) 75.87(3)
P(1)ꢀPt(1)ꢀAg(1) 77.91(3)
P(3)ꢀPt(3)ꢀAg(2)
P(4)ꢀPt(3)ꢀAg(2)
75.46(3)
76.96(3)
N(1)ꢀPt(2)ꢀN(2) 78.78(16) N(3)ꢀPt(4)ꢀN(4)
N(1)ꢀPt(2)ꢀP(2) 173.71(11) N(3)ꢀPt(4)ꢀP(4)
N(2)ꢀPt(2)ꢀP(2) 103.08(12) N(4)ꢀPt(4)ꢀP(4)
N(1)ꢀPt(2)ꢀP(1) 101.99(12) N(3)ꢀPt(4)ꢀP(3)
N(2)ꢀPt(2)ꢀP(1) 174.21(11) N(4)ꢀPt(4)ꢀP(3)
78.72(16)
177.90(11)
103.36(13)
102.94(11)
177.71(12)
74.97(5)
P(2)ꢀPt(2)ꢀP(1)
75.55(5)
P(4)ꢀPt(4)ꢀP(3)
N(1)ꢀPt(2)ꢀAg(1) 99.88(11) N(3)ꢀPt(4)ꢀAg(2) 104.07(10)
N(2)ꢀPt(2)ꢀAg(1) 98.32(11) N(4)ꢀPt(4)ꢀAg(2) 104.35(10)
P(2)ꢀPt(2)ꢀAg(1) 73.95(3)
P(1)ꢀPt(2)ꢀAg(1) 75.89(3)
P(4)ꢀPt(4)ꢀAg(2)
P(3)ꢀPt(4)ꢀAg(2)
75.29(3)
73.78(3)
O(1)ꢀAg(1)ꢀPt(1) 162.32(11) O(5)ꢀAg(2)ꢀPt(3) 132.26(9)
O(1)ꢀAg(1)ꢀPt(2) 117.60(12) O(5)ꢀAg(2)ꢀPt(4) 151.76(10)
Pt(1)ꢀAg(1)ꢀPt(2) 74.895(11) Pt(3)ꢀAg(2)ꢀPt(4) 74.446(11)
Figure 1. Drawings of the two complexes found in the crystal structure
of 7 (7a and 7b).
Pt(2)ꢀP(1)ꢀPt(1)
Pt(2)ꢀP(2)ꢀPt(1)
96.51(5)
96.70(5)
Pt(4)ꢀP(3)ꢀPt(3)
Pt(4)ꢀP(4)ꢀPt(3)
97.58(5)
97.60(5)
spectrum showed the expected three signals in 2:1:2 intensity
ratio for the o-, p-, and m-F atoms of both rings. This behavior is
analogous to that previously observed for the silver adduct of the
[(RF)2Pt(μ-PPh2)2M(acac)]ꢀ species.17
For cluster 8, the 31P{1H} NMR spectrum at 293 K showed a
broad signal at δ ꢀ129.2 (1JP,Pt =1792 and 2240 Hz) attributable
to the bridging phosphides and a couple of doublets centered at δ
8.8 attributable to the coordinated PPh3 (1JP,107Ag = 680 Hz;
1JP,109Ag = 760 Hz), while for cluster 9 the bridging phosphides
and the coordinated PPh3 gave signals at δ ꢀ111.0 (1JP,Pt =1441
Hz) and at δ 12.3, respectively.
As to the 195Pt NMR of 7b, we were able to find the signals
of Pt3 (δPt3 ꢀ3340) and Pt4 (δPt4 ꢀ3450) by recording the
1Hꢀ195Pt HMQC spectrum which showed the cross peaks
between a phenanthroline proton and Pt4 and between the ortho
phenyl protons and Pt3 (see Figure 1 for Pt atom numbering).
The treatment of CH2Cl2 solutions of 1 and 2 with
[Ag(OClO3)(PPh3)] (1:1 molar ratio) afforded yellow solids
which can be formulated as [AgMPt(μ-PPh2)2(RF)2(PPh3)-
(phen)][ClO4] (M = Pt, 8; M = Pd, 9; Scheme 2). Despite
several attempts, only low quality crystals could be obtained,
and thus no complete X-ray studies could be performed.
Nevertheless, the connectivity of the atoms could be established
unambiguously, indicating that the complexes formed are of type
B, but with only one of the metal centers (the platinum atom
bonded to the two C6F5 groups) establishing a bond with the Ag
center.
The 19F NMR spectra of 8 and 9 (CD2Cl2 solution) at room
temperature showed three signals in a 2:1:2 intensity ratio for
the o-, p-, and m-F atoms of both rings. In contrast to the case of
7b, at 193 K, only a signal broadening is observed, indicating that
for 8 and 9 the C6F5 rings can freely rotate even at low T.
The 195Pt signal of 9 was found at δ ꢀ3431 by means of a
19Fꢀ195Pt HMQC spectrum. Given that the projection of the 2D
spectrum on F1 appears as a pseudoquartet (Figure 2), it can be
affirmed that the direct 195Ptꢀ107/109Ag coupling constants are of
the same order of magnitude as the 1JPt,P (1440 Hz).
The neutral dinuclear diphosphine complexes [(RF)2Pt
(μ-PPh2)2M(PꢀP)] [PꢀP = dppm, M = Pt (3) or Pd (4);
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PꢀP = dppe, M = Pt (5) or Pd (6)] displayed different behavior
when reacted with silver derivatives. While a mixture of uni-
dentified compounds was obtained from the reaction of 3 with
AgClO4, a single species formed by the reaction of 3 with an
equimolar amount of [Ag(OClO3)(PPh3)]. Such a species dis-
plays dynamic behavior in solution, and good quality crystals for
XRD analysis were not obtained. However, elemental analysis and
spectroscopic features indicate the formula [(RF)2Pt(μ-PPh2)2
Pt(dppm)Ag(PPh3)][ClO4] (10) and a structure of type B.
The 31P{1H}NMR in CDCl3 at 213 K of 10 showed, besides a
increasing the temperature the AgꢀPt2 bond is continuously
broken and reformed, as depicted in Scheme 3. Since the room
temperature 1H NMR spectrum showed the methylene protons
as a broad triplet, it can be assumed that dissociation-recoordina-
tion of the Ag(PPh3) moiety may also occur in solution at
room temperature, thus rendering equivalent the two methylene
protons.
The heterodinuclear complex 4, in which the dppm ligand is
bonded to the palladium center, reacts with silver derivatives to
afford type C species (Scheme 2). The reaction of 4 with AgClO4
produces [AgPdPt(μ-PPh2)2(RF)2(OClO3)(dppm)] (11). Two
different crystals of 11 have been studied by X-ray diffraction, but
in both cases their low quality prevented the measurement of
good sets of diffraction data and thus a complete characterization
of the crystal structure. Nevertheless, the connectivity of the
atoms in complex 11 could be unambiguously established as that
represented in Scheme 2. As can be observed, the “AgOClO3”
fragment is inserted into the PdꢀPPh2CH2PPh2 bond, and at the
same time, the (μ-P)ꢀPd bond of the phosphido group behaves
as a donor toward the silver center. The electronic requirements
of the palladium center are fulfilled by a PtꢀPd bond.
couple of doublets due to the Ag-bound PPh3 (δ 10.0; 1J107Ag,P
=
1
691 Hz; J109Ag,P = 795 Hz), two mutually coupled multiplets
arising from an AA0XX0 system due to the μ-PPh2 (δ ꢀ143.5)
0
and to the dppm P atoms (δ ꢀ24.1, JAX + JAX = 315 Hz). The
appearance of the μ-PPh2 signals at a high field indicate that the
bridging phosphides do not subtend a PtꢀM bond,34,35,39ꢀ41
thus excluding for 10 a structure of type A or C. The most
remarkable feature of the 1H NMR spectrum of 10 in CDCl3 at
213 K is that the methylene protons gave two separate reso-
nances at δ 5.0 and δ 4.5, indicating that the position of the
Ag(PPh3) moiety at low T renders inequivalent the two methy-
lene protons. All of these data, along with the 195Pt resonance of
Pt1, which was found at δ ꢀ3390 (19Fꢀ195Pt HMQC), a value
comparable to that obtained for the analogous Pt1 atoms of
complexes 7b (δPt3 ꢀ3340) or 9 (δ ꢀ3431), suggest for 10 at
low T an “open book” structure with two PtꢀAg bonds.
The addition of [Ag(OClO3)(PPh3)] to 4 (1:1 molar ratio)
afforded a solid made up of a 1:1 mixture of 11 and the previously
reported[AgPdPt(μ-PPh2)2(RF)2(PPh3)2][ClO4] (12;35 Table1,
entry 5) along with minor amounts of other unidentified
byproducts (NMR spectroscopy). The formation of the 11/12
mixture, together with the detection in solution of free dppm, can
be explained, according to Scheme 4, by admitting that complex 4
reacts with [Ag(OClO3)(PPh3)], giving 11 and free PPh3, which,
in turn, can attack the not yet reacted 4 to give an intermediate
in which the Pd atom is bonded to dppm (which behaves as
a monodentate ligand) and to PPh3. The reaction of fresh
[Ag(OClO3)(PPh3)] with the latter intermediate can afford,
upon a loss of dppm, the product 12.
The three 31P{1H} NMR signals of 10 are quite broad at room
temperature (the broadest one being that of the μ-PPh2) but
maintain the multiplicity observed at low T, indicating the
occurrence of a dynamic process that does not affect the mutual
position of the P atoms. A plausible dynamic process which
accounts for the experimental data is depicted in Scheme 3.
While at low T the Ag(PPh3) moiety bridges to both Pt atoms, on
The 31P{1H} NMR spectrum of 11 shows four signals (see
Scheme 2 for the atom numbering) and indicates that the
structure proposed in the solid state is maintained in solution.
The two signals due to the P atoms of the phosphido ligands
appear at low fields, in agreement with the presence of the
bridging phosphides subtending a PdꢀPt bond.35,41ꢀ44 The
presence of the PtꢀPd bond is also supported by the value of
the coupling between Pt and P3 atoms, 92 Hz.45ꢀ51 Moreover,
the chemical shift of the P2 atom (phosphido group bridging two
metal centers, μ2-PPh2) appears at δ 293.2, while the P1 atom
(phosphido group bridging three metal centers, μ3-PPh2) ap-
pears at δ 138.3. This decrease in the value of δ on going from a
μ2-PPh2 coordination mode to a μ3-PPh2 one has been observed
before,35,42,52ꢀ55 and in complex 11, this Δδ (155 ppm) is
greater than in the previously reported complexes [MM0Pt(μ-
PPh2)2(RF)2(PPh3)2][ClO4] (M = Pt, Pd; M0 = Ag, Au).35
Figure 2. 19Fꢀ195Pt HMQC spectrum of 9 (CD2Cl2, 213 K).
Scheme 3. Dynamic Behavior Observed for 10 in Solution at Room Temperature
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Scheme 4. Plausible Mechanism for the Reaction between 4 and [Ag(OClO3)PPh3]
Scheme 5. The Dynamic Process Occurring for 11 in
Solution
Figure 3. 31P{1H} EXSY spectrum of 11 (CDCl3, 255 K).
Different resultsare observed when the startingmaterials arethe
dppe-containing derivatives 5 and 6. Complexes 5 and 6 react with
AgClO4 or [Ag(OClO3)(PPh3)] (room temperature, 1:2 molar
ratio) producing a silver mirror and the cationic complexes
[(PPh2C6F5)(C6F5)Pt(μ-PPh2)(μ-OH)M(dppe)][ClO4] (M =
Pt, 13; Pd, 14). The formation of these 32-VEC Pt(II)/M(II)
saturated complexes 13 and 14 which contain PPh2C6F5 is a clear
indication that the treatment of 5 and 6 with silver salts results in
the oxidation of the dinuclear Pt(II)/Pd(II) derivatives (reduction
to Ag0 is observed) probably to the dicationic Pt/Pd(III) inter-
mediates [(RF)2PtIII(μ-PPh2)2MIII(dppe)2]2+ (although a mixed
valence M(II),M(IV) cannot be discounted), which were neither
isolated nor identified. Their very low stability could easily produce
the reductive PPh2/C6F5 coupling, favored by the presence of the
nucleophile OHꢀ in the process, probably due to the presence of
moisture inthe system, andforming13 and 14. Wehave previously
observed this type of process, and we have reported that poly-
nuclear Pt(III)/Pd(III) derivatives are not very stable. These
dinuclear derivatives evolve in the presence of nucleophiles
such as Iꢀ or Brꢀ, and the trinuclear ones evolve even without the
presence of nucleophiles, through a reductive PPh2/C6F5 or
PPh2/PPh2 coupling, with the formation of PꢀC (PPh2C6F5) or
PꢀP (PPh2-PPh2) bonds respectively and new platinum/
palladium(II) derivatives.28,29,38,47,56 In some cases, the M(III)
intermediates are isolated, but in others the proposed M(III)
intermediates are neither isolated nor identified.28,29,39,56
Assuming that this decrease of the chemical shift is related to the
2eꢀ3c bonding mode, it can be concluded that the interaction of
the (μ-P)ꢀPd bond with the silver center in 11 is strong. This
P1 Ag interaction is also supported by the coupling between
3 3 3
P1 and P4, 123 Hz, while the coupling of P1 with P3 is smaller, 81 Hz.
The 31P{1H} and 19F NMR features of 11 suggest the occur-
rence of dynamic processes in solution. In fact, while the 19F NMR
spectrum of 11 at 213 K showed the expected six signals with
a 2:2:1:1:2:2 intensity ratio (o,o0,p,p0,m,m0) due to two unequivalent
C6F5 groups, at room temperature only one (averaged) signal is
observed for the four o-F atoms, one signal for the four m-F
atoms and one signal for the two p-F atoms. This behavior is
analogous to that observed for the related cluster 1235 and indicates
that a dynamic behavior rendering the two C6F5 groups equivalent
at room temperature is operating.35
The broadness of the 31P{1H} NMR signals, especially those of P1
and P2, is also in accord with the fluxional behavior of 11. In order to
gain insight into the dynamic process occurring for 11, we recorded
a 31P{1H} EXSY spectrum at 255 K (Figure 3) which showed cross
peaks between the P1 (δ139) and P2 (δ293) signals but not between
P3 (δ 30) and P4 (δ 1.8). This evidence is compatible with the
mechanism shown in Scheme 5 in which the PdꢀAg and P1ꢀAg
bonds are continuously broken and reformed, while the Pd and
P3 atoms remain bonded to each other. The mechanism envisages
the breaking and reforming of the weakest bonds in the molecule,
and it parallels the mechanism validated for the dynamic process
occurring for 12 in solution,35 which is depicted in Scheme 6.
The structure of 14 has been established in an X-ray diffraction
study. Figure 4 shows the structure of the complex cation, and
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Scheme 6. The Dissociative Mechanism Occurring for 12 in Solution35
Table 3. Selected Bond Lengths (Å) and Angles (deg) for
14 2CH2Cl2
3
PtꢀC(1)
2.065(7)
2.116(5)
2.199(2)
2.3225(19)
89.5(2)
PdꢀO(1)
2.158(5)
2.221(2)
2.335(2)
2.348(2)
171.15(14)
77.26(15)
101.03(7)
99.71(15)
83.20(8)
171.29(7)
41.61(13)
141.70(6)
46.94(5)
125.94(5)
95.8(2)
PtꢀO(1)
PdꢀP(3)
PtꢀP(1)
PtꢀP(2)
PdꢀP(2)
PdꢀP(4)
C(1)ꢀPtꢀO(1)
C(1)ꢀPtꢀP(1)
O(1)ꢀPtꢀP(1)
C(1)ꢀPtꢀP(2)
O(1)ꢀPtꢀP(2)
P(1)ꢀPtꢀP(2)
C(1)ꢀPtꢀPd
O(1)ꢀPtꢀPd
P(1)ꢀPtꢀPd
P(2)ꢀPtꢀPd
PtꢀP(2)ꢀPd
O(1)ꢀPdꢀP(3)
O(1)ꢀPdꢀP(2)
P(3)ꢀPdꢀP(2)
O(1)ꢀPdꢀP(4)
P(3)ꢀPdꢀP(4)
P(2)ꢀPdꢀP(4)
O(1)ꢀPdꢀPt
P(3)ꢀPdꢀPt
P(2)ꢀPdꢀPt
P(4)ꢀPdꢀPt
PtꢀO(1)ꢀPd
91.3(2)
178.09(14)
167.8(2)
78.33(15)
100.92(7)
123.0(2)
42.62(13)
135.73(5)
47.26(5)
85.80(7)
Figure 4. Drawing of the crystal structure of the complex cation of 14.
type B, but oxidation of Pt(III)ꢀPt(III) derivatives occurs. The
oxidized complexes are very unstable, and 13 and 14 result from
the reductive coupling of PPh2/C6F5. For L2 = dppm, two
different situations are produced. When M = Pd, the higher
lability of the PdꢀP bonds and the low stability of the four-
membered ring formed results in the opening of the Pd(dppm)
ring and formation of the compound type C. Finally, for M = Pt,
the higher stability of the PtꢀP bonds precludes opening of
the ring and formation of compound type C, and complex 10
(type B) is formed instead.
Behavior of Trinuclear Derivatives toward Ag(I). As far as
the trinuclear derivatives are concerned, we have found that the
anionic trinuclear platinum(II) complexes [(RF)2Pt(μ-PPh2)2Pt-
(μ-PPh2)2Pt(RF)2]2ꢀ and [(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt-
(acac)]ꢀ are oxidized by AgClO4, affording the correspond-
ing Pt(III)/Pt(III)/Pt(II) derivatives with a structure of type A
(Table 1, entries 10 and 12).39,40 We have completed this study
by exploring the reactivity of the neutral trinuclear complexes of
formula [(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2PtL2] (L2 = phen, 15;
L2 = 2 PPh3, 16) bearing nitrogen or phosphorus donor ligands
toward Ag derivatives.
The trinuclear complexes 15 and 16 were prepared by
treating the hexanuclear species [NBu4]2[{(RF)2Pt(μ-PPh2)2Pt-
(μ-PPh2)2Pt(μ-Cl)}2] with an excess of the ligand L2, which
replaced the bridging chloro ligands. Complex 15 is slightly
soluble in acetone, but 16 is sparingly soluble in all common
organic solvents. Both precipitate from the reaction mixtures.
The reaction of suspensions of complexes 15 and 16 in
CH2Cl2 with AgClO4 results in the formation of Ag0 and
the cationic complexes [(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2PtL2]-
[ClO4]2, L2 = phen, 17; 2 PPh3, 18 (46-VEC) endowed with a
Table 3 lists the most relevant bond lengths and angles. The
cation of 14 is a dinuclear species in which both the platinum and
palladium atoms have conventional square planar environments.
They are not coplanar but form a dihedral angle of 46.4(1)°. The
intermetallic distance is 3.170(1) Å. The formation of the
PPh2C6F5 ligand confirms the coupling of a terminal pentafluo-
phenyl group and a bridging diphenylphosphido ligand. The
vacancy produced by the transformation of the PPh2 group is
occupied by a bridging hydroxo group. It is noteworthy that the
new PPh2C6F5 and OH ligands are coordinated mutually trans,
which implies an isomerization process after the coupling of the
PPh2 and C6F5 groups, initially located mutually cis.
The 19F NMR spectra of 13 and 14 at room temperature show
six signals in a 2:2:1:1:2:2 intensity ratio (see the Experimental
Section), in agreement with the presence of two kinds of
pentafluorophenyl groups and the equivalence in solution of
the two o-F atoms, as well as the m-F atoms, within each ring. The
different chemical shifts of the F atoms of C6F5 groups bonded to
the platinum or to the phosphorus atoms allow the assignment of
these signals unequivocally.28,38,40,54,56
The 31P{1H} NMR spectra of the analogous complexes 13
and 14 are in full agreement with the presence of a “Pt(μ-
PPh2)(μ-X)M” fragment without a metalꢀmetal bond46,47,57ꢀ59
and with the solid-state structure of 14, and all data are collected
in the Experimental Section.
These results point out that the binuclear neutral [(RF)2Pt(μ-
PPh2)2ML2]nꢀ complexes react with Ag+ or Ag(PPh3)+, produ-
cing three different types of complexes. For L2 = phen, adducts
with one or two PtꢀAg bonds (complexes type B) are formed.
For L2 = dppe, Ag(PPh3)+ is not able to form stable adducts of
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PtꢀPt bond between the central Pt atom and the Pt bonded to
the C6F5 groups. Several batches of crystals of complex 18 with
perchlorate or triflate as a counterion were grown, but again their
poor quality prevented a satisfactory X-ray diffraction study.
Nevertheless, it was possible to establish the connectivity of the
atoms of the complex cation of 18, which confirmed a structure of
type A. The IR absorption in the 950 cmꢀ1 region due to the
C6F5 groups in 15 and 16 appears at 964 cmꢀ1 in the oxidized
complexes 17 and 18. The blue-shift of this absorption is largely
related to the increase in the formal oxidation state of the metal
bonded to the C6F5 groups.34,39,44,60
for 15 min, and then [PdCl2(phen)] (0.198 g, 0.554 mmol) was added
and allowed to react at room temperature for 16 h. The resulting yellow
suspension was evaporated to dryness. CH2Cl2 (40 mL) was added to
the residue. The mixture was filtered through Celite, and the resulting
solution was evaporated to ca. 1 mL. The addition of methanol (10 mL)
causes the crystallization of 2 as a yellow solid, which was filtered off and
washed with methanol (2 ꢁ 0.5 mL). Yield: 0.466 g, 71%. Anal. Found
(calcd for C48F10H28N2P2PdPt): C, 48.36 (48.60); H, 2.35 (2.38); N,
2.37 (2.36). IR (cmꢀ1): 841 (phen); 782 and 774 (X-sensitive C6F5).
19F NMR (CD2Cl2, 293 K, 282.4 MHz): δ ꢀ115.7 (4 o-F, 3J(Pt,F) = 334
Hz), ꢀ165.3 (2 p-F), ꢀ165.5 (4 m-F). 31P{1H} NMR (CD2Cl2, 293 K,
121.5 MHz): δ ꢀ109.6 ppm, 1J(Pt,P) = 1710 Hz.
The 19F NMR spectra of 15 or 17 and 18 (the poor solubility
of 16 in all common organic solvents precluded an NMR study)
in a solution of (CD3)CO, CD2Cl2, and CH3Cl, respectively,
showed three signals due to the ortho, meta, and para F atoms
(2:2:1 intensity ratio, respectively), as a result of the symmetry of
these molecules. The 31P{1H} NMR spectrum of 17 (18)
showed a very low field signal at δ 272.9 (δ 268.8), in agreement
with the presence of two bridging phosphides subtending a
metalꢀmetal bond.39,40 The high field signal due to the P atoms
of the μ-PPh2 not subtending a PtꢀPt bond fell at δ ꢀ135.1
(δ ꢀ151.4).39,40 In addition, a signal at δ 17.1 is observed in the
spectrum of 18 for the P atoms of the PPh3 ligands.
Synthesis of [(RF)2Pt(μ-PPh2)2Pd(dppm)] (4). LiBu (0.44 mL
of a hexane solution, 1.1 mmol) was added under an argon atmosphere
to a colorless solution of cis-[Pt(C6F5)2(PPh2H)2] (0.500 g, 0.554
mmol) in THF (10 mL) at ca. ꢀ78 °C. The yellow solution was stirred
for 15 min, and then [PdCl2(dppm)] (0.311 g, 0.554 mmol) was added
and allowed to react at room temperature for 16 h. The resulting orange
suspension was evaporated to dryness. CH2Cl2 (40 mL) was added to
the residue. The mixture was filtered through Celite, and the resulting
solution was evaporated to ca. 1 mL. The addition of CHCl3 (10 mL)
causes the crystallization of 4 as an orange solid, which was filtered off
and washed with CHCl3 (2 ꢁ 0.5 mL). Yield: 0.498 g, 65%. Anal. Found
(calcd for C61F10H42P4PdPt): C, 52.51 (52.65); H, 2.91 (3.04). IR
(cmꢀ1): 782 and 773 (X-sensitive C6F5). 19F NMR (acetone-d6, 293 K,
3
282.4 MHz): δ ꢀ113.7 (4 o-F, J(Pt,F) = 313 Hz), ꢀ166.0 (4 m-F),
’ CONCLUDING REMARKS
ꢀ166.2 (2 p-F). 31P{1H} NMR (acetone-d6, 293 K, 121.5 MHz):
δ ꢀ22.0 (dppm), ꢀ124.9 (PPh2, 1J(PtꢀP) = 1714 Hz) ppm. N = JAX
The dinuclear phosphido complexes [(RF)2Pt(μ-PPh2)2
PtL2]nꢀ react with Ag+ or Ag(PPh3)+, producing complexes
of the type A, B, or C, the formation of which is essentially
dependent on ligand L2 (L2 = 2 C6F5, acac, 2PPh3, phen, dppm,
dppe). For C type complexes, dynamic behavior consisting of the
detachment and rebinding of the silver atom onto the Mꢀμ-P
bonds was invariably found.
On the other hand, anionic and neutral trinuclear phosphido
derivatives of the general formula [(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2-
PtL2]nꢀ react with silver(I), giving in all cases complexes of
the type A (Table 1, entries 10ꢀ13). In no case were the putative
intermediates of type B or C observed. In addition, the
Pt(III)ꢀPt(III) bond present in the 46 VEC derivatives is
formed by the terminal Pt center bonded to the C6F5 groups
and the central Pt atom, and in no case is the fragment bonded to
the ligands L involved in the PtꢀPt bond.
0
+ JAX = 330 Hz.
Synthesis of [(RF)2Pt(μ-PPh2)2Pt(dppe)] (5). To a colorless
solution of [(C6F5)2Pt(μPPh2)2Pt(NCMe)2] (0.350 g, 0.298 mmol) in
acetone (10 mL) was added dppe (0.119 g, 0.298 mmol). The resulting
yellow solution was stirred at room temperature for 4 h and then
evaporated to 2 mL. Complex 5 crystallized as a yellow solid, which was
filtered and washed with cold acetone (2 ꢁ 0.5 mL). Yield: 0.187 g, 42%.
Anal. Found (calcd for C62F10H44P4Pt2): C, 49.66 (49.85); H, 2.93
(2.97). IR (cmꢀ1): 782 and 773 (X-sensitive C6F5). 19F NMR (CD2Cl2,
3
293 K, 282.4 MHz): δ ꢀ116.2 (4 o-F, J(Pt,F) = 320 Hz), ꢀ166.3
(4 m-F), ꢀ166.5 (2 p-F). 31P{1H} NMR (CD2Cl2, 293 K, 121.5 MHz):
δ 45.6 (dppe, 1J(PtꢀP) = 1988 Hz), ꢀ141.1 (PPh2, the platinum satellites
1
appears overlapped and the two values of J(PtꢀP) are ca. 1740 Hz)
0
ppm. N = JAX + JAX = 259 Hz.
Synthesis of [(RF)2Pt(μ-PPh2)2Pd(dppe)] (6). Complex 6 was
prepared similarly to 4 (from LiBu (1.1 mmol), cis-[Pt(C6F5)2-
(PPh2H)2] (0.500 g, 0.554 mmol) and [PdCl2(dppm)] (0.319 g,
0.554 mmol)) as an orange solid. Yield: 0.478 g, 62%. Anal. Found
(calcd for C62F10H44P4PdPt): C, 52.96 (52.99); H, 3.13 (3.16). IR
(cmꢀ1): 782 and 773 (X-sensitive C6F5). 19F NMR (acetone-d6, 293 K,
’ EXPERIMENTAL SECTION
General Procedures and Materials. C, H, and N analyses were
performed with a Perkin-Elmer 240B microanalyzer. IR spectra were
recorded on a Perkin-Elmer Spectrum One spectrophotometer (Nujol
mulls between polyethylene plates in the range 4000ꢀ350 cmꢀ1). NMR
spectra were recorded on Varian Unity 300, Bruker 300, and Bruker 400
spectrometers with SiMe4, CFCl3, 85% H3PO4, and H2PtCl6 as external
references for 1H, 19F, 31P, and195Pt, respectively. Literaturemethodswere
used to prepare the starting materials cis-[Pt(RF)2(PPh2H)2],36 [PdCl2-
(L-L)] (L-L = phen, dppm, dppe),61 [(RF)2Pt(μ-PPh2)2Pt(NCCH3)2],37
[NBu4]2[{(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(μ-Cl)}2],40 [(RF)2Pt(μ-PPh2)2-
Pt(phen)],36 and [(RF)2Pt(μ-PPh2)2Pt(dppm)].36
Caution! Perchlorate salts of metal complexes with organic ligands are
potentially explosive. Only small amounts of materials should be prepared,
and these should be handled with great caution.
Synthesis of [(RF)2Pt(μ-PPh2)2Pd(phen)] (2). LiBu (0.44 mL
of a hexane solution, 1.1 mmol) was added under an argon atmosphere
to a colorless solution of cis-[Pt(C6F5)2(PPh2H)2] (0.500 g, 0.554
mmol) in THF (10 mL) at ca. ꢀ78 °C. The yellow solution was stirred
3
282.4 MHz): δ ꢀ114.2 (4 o-F, J(Pt,F) = 308 Hz), ꢀ166.1 (4 m-F),
ꢀ166.7 (2 p-F). 31P{1H} NMR (acetone-d6, 293 K, 121.5 MHz): δ 43.9
1
0
(dppe), ꢀ134.9 (PPh2, J(PtꢀP) = 1677 Hz) ppm. N = JAX + JAX
=
282 Hz.
Reaction of [(RF)2Pt(μ-PPh2)2Pt(phen)] with AgClO4. Ag-
ClO4 (0.055 g, 0.265 mmol) was added to a yellow solution of
[(C6F5)2Pt(μ-PPh2)2Pt(phen)] (1; 0.150 g, 0.117 mmol) in CH2Cl2
(15 mL). The mixture was stirred at room temperature for 2 h with
the exclusion of light and filtered through Celite. The yellow solution
was evaporated to ca. 1 mL, and [(C6F5)2Pt(μ-PPh2)2Pt(phen)Ag-
(OClO3)] (7a+7b) crystallized as a yellow solid, which was filtered and
washed with cold CH2Cl2 (2 ꢁ 0.5 mL). Yield: 0.082 g, 47%. Anal.
Found (calcd for AgC48ClF10H28N2O4P2Pt2): C, 38.83 (38.89); H, 1.93
(1.90); N 1.86 (1.89). IR of 7a (cmꢀ1): 1092, 623 (broad) (ClO4);
844 (phen); 784 and 779 (X-sensitive C6F5). 7b. 19F NMR (CD2Cl2,
3
293 K, 282.4 MHz): δ ꢀ116.9 (4 o-F, J(Pt,F) = 389 Hz), ꢀ163.3
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(2 p-F), ꢀ163.8 (4 m-F) ppm. 19F NMR (CD2Cl2, 193 K, 282.4 MHz):
δ ꢀ115.7 (2 o-F), ꢀ117.8 (2 o-F), ꢀ162.4 (2 p-F), ꢀ162.8 (2 m-F),
ꢀ163.4 (2 m-F) ppm. 31P{1H} NMR (CD2Cl2, 193 K, 121.5 MHz):
δ ꢀ108.1 (1J(Pt,P) =1452and2091Hz) ppm.195Pt NMR (CD2Cl2, 273K,
86 MHz): δ ꢀ3340, Pt3; ꢀ3450 Pt4.
ppm. 19F NMR (CDCl3, 213 K, 282.4 MHz): δ ꢀ118.9 (2 o-F, 3J(Pt,F)
= 300 Hz), ꢀ119.6 (2 o-F, 3J(Pt,F) = 304 Hz), ꢀ159.1 (1 p-F), ꢀ160.9
(1 p-F), ꢀ162.4 (2 m-F), ꢀ163.0 (2 m-F) ppm. 31P{1H} NMR (CDCl3,
213 K, 121.5 MHz): δ 293.2 (m, P2, 1J(Pt,P2) = 1659 Hz), 138.3 (very
broad m, P1, platinum satellites are very broad and 1J(Pt,P1) can not be
measured), 28.9 (ddd, P3, 2J(P3,P2) = 22 Hz, 2J(P3,P1) = 81 Hz, 2J(P3,
P4) = 148 Hz, 2J(Pt,P3) = 92 Hz), 1.7 (two ddd, P4, 1J(109Ag,P4) = 422
Hz, 1J(107Ag,P4) = 365 Hz, 2J(P3,P4) = 148 Hz, 2J(P1,P4) = 123
Hz) ppm.
Reaction of [(RF)2Pt(μ-PPh2)2M(phen)] with [Ag(OClO3)
PPh3]. M = Pt. [Ag(OClO3)PPh3] (0.055 g, 0.117 mmol) was added
to a yellow solution of [(C6F5)2Pt(μ-PPh2)2Pt(phen)] (1; 0.150 g,
0.117 mmol) in CH2Cl2 (15 mL). The solution was stirred at room
temperature for 30 min with the exclusion of light. The yellow solution
was evaporated to ca. 1 mL. Hexane (2 mL) was added, and
[(C6F5)2Pt(μ-PPh2)2Pt(phen)Ag(PPh3)][ClO4)] (8) crystallized as a
yellow solid, which was filtered and washed with hexane (2 ꢁ 0.5 mL).
Yield: 0.157 g, 89%. Anal. Found (calcd for AgC66ClF10H43N2O4P3Pt2):
C, 45.22 (45.44); H, 2.82 (2.48); N 1.60 (1.60). IR (cmꢀ1): 1092, 623
(ClO4); 784 and 776 (X-sensitive C6F5). 19F NMR (CD2Cl2, 293 K,
282.4 MHz): δ ꢀ116.0 (4 o-F, 3J(Pt,F) = 333 Hz), ꢀ165.8 (2 p-F + 4 m-F).
31P{1H} NMR (CD2Cl2, 293 K, 121.5 MHz): δ 8.8 (PPh3, two d,
1J(109,107Ag,P) ≈760 and 680 Hz), ꢀ129.2 (PPh2, 1J(Pt,P) = 1792 and
2240 Hz) ppm.
Reaction of [(RF)2Pt(μ-PPh2)2M(dppe)] with AgClO4. M =
Pt. AgClO4 (0.049 g, 0.235 mmol) was added to a yellow solution of
[(C6F5)2Pt(μ-PPh2)2Pt(dppe)] (5; 0.150 g, 0.100 mmol) in CH2Cl2
(15 mL). The mixture was stirred at room temperature for 4 h with the
exclusion of light and filtered through Celite. The yellow solution
was evaporated to ca. 1 mL, and Et2O (2 mL) was added. [(PPh2
C6F5)(C6F5)Pt(μ-PPh2)(μ-OH)Pt(dppe)][ClO4], 13, crystallized as a
yellow solid, which was filtered and washed with Et2O (2 ꢁ 0.5 mL).
Yield: 0.129 g, 75%. Anal. Found (calcd for C62ClF10H45O5P4Pt2): C,
46.18 (46.26); H, 2.80 (2.82.). IR (cmꢀ1): 3603 (OH); 1094, 623
(ClO4); 1520, 981 (PPh2C6F5); 786 (X-sensitive C6F5). 1H NMR
(CD2Cl2, 293 K, 300 MHz): δ from 7.7 to 6.8 (m, 40 H, C6H5), 2.4
M = Pd. A similar procedure was used: [(C6F5)2Pt(μ-PPh2)2Pd-
(phen)] (2; 0.150 g, 0.126 mmol) and [Ag(OClO3)(PPh3)] (0.059 g,
0.126 mmol) give [(C6F5)2Pt(μ-PPh2)2Pd(phen)Ag(PPh3)][ClO4)]
(9) as a yellow solid. Yield: 0.186 g, 89%. Anal. Found (calcd for
AgC66ClF10H43N2O4P3PdPt): C, 48.10 (47.87); H, 2.91 (2.62); N 1.77
(1.69). IR (cmꢀ1): 1092, 623 (ClO4); 784 and 776 (X-sensitive C6F5).
19F NMR (CD2Cl2, 293 K, 282.4 MHz): δ ꢀ116.0 (4 o-F, 3J(Pt,F) = 339
Hz), ꢀ162.2 (2 p-F), ꢀ163.8 (4 m-F). 31P{1H} NMR (CD2Cl2, 183 K,
121.5 MHz): δ 9.4 (PPh3, broad d), ꢀ120.2 (PPh2, 1J(Pt,P) = 1302 Hz)
ppm. 195Pt NMR (CD2Cl2, 213 K, 86 MHz): δ ꢀ3431.
(broad m, 2H, CH2), 2.3 (broad m, 2H, CH2), 0.3 (s, 1H, OH) ppm. 19
F
NMR (CD2Cl2, 293 K, 282.4 MHz): δ ꢀ118.9 (2 o-F, 3J(Pt,F) = 244
Hz), ꢀ122.7 (2 o-F, PPh2C6F5), ꢀ146.7 (1 p-F, PPh2C6F5), ꢀ159.5
(1 p-F), ꢀ159.7 (2 m-F, PPh2C6F5), ꢀ162.9 (2 m-F) ppm. 31P{1H} NMR
(CD2Cl2, 293 K, 121.5 MHz): δ 50.3 (d, P4, 2J(P2,P4) = 282 Hz, 1J(Pt2,
P4) = 2206 Hz), 28.9 (d, P3, 2J(P3,P2) = 14 Hz, 1J(Pt2,P3) = 3810 Hz),
ꢀ13.4 (d, P1, 2J(P1,P2) = 13 Hz, 1J(Pt1,P1) = 4352 Hz), ꢀ29.3 (broad d,
1
P2, 2J(P2,P4) = 282 Hz, 1J(Pt1,P2) ≈ J(Pt2,P2) ≈ 1820 Hz) ppm.
M = Pd. AgClO4 (0.049 g, 0.235 mmol) was added to a yellow
solution of [(C6F5)2Pt(μ-PPh2)2Pd(dppe)] (6; 0.150 g, 0.107 mmol) in
CH2Cl2 (15 mL). The mixture was stirred at room temperature for 7 h
with the exclusion of light and filtered through Celite. The yellow
solution was evaporated to ca. 1 mL, and a mixture of MeOH/iPrOH (3/
3 mL) was added. [(PPh2C6F5)(C6F5)Pt(μ-PPh2)(μ-OH)Pd(dppe)]-
[ClO4], 14, crystallized as a yellow solid, which was filtered and washed
with iPrOH (2 ꢁ 0.5 mL). Yield: 0.109 g, 67%. Anal. Found (calcd for
C62ClF10H45O5P4PdPt): C, 48.55 (48.94); H, 3.01 (2.98). IR (cmꢀ1):
3578 (OH); 1094, 623 (ClO4); 1520, 981 (PPh2C6F5); 787 (X-sensitive
Reaction of [(C6F5)2Pt(μ-PPh2)2Pt(dppm)] with [Ag(OClO3)
(PPh3)]. [Ag(OClO3)PPh3] (0.038 g, 0.081 mmol) was added to a yellow
solution of [(C6F5)2Pt(μ-PPh2)2Pt(dppm)] (3; 0.120 g, 0.081 mmol) in
CH2Cl2 (15 mL). The solution was stirred at room temperature for 30 min
with the exclusion of light. The yellow solution was evaporated to ca. 1 mL.
n-Hexane (5 mL) was added, and [(C6F5)2Pt(μ-PPh2)2Pt(dppm)Ag-
(PPh3)][ClO4)] (10) crystallized as a yellow solid, which was filtered
and washed with hexane (2 ꢁ 0.5 mL). Yield: 0.136 g, 86%. Anal. Found
(calcd for AgC79ClF10H57O4P5Pt2): C, 48.54 (48.69); H, 2.62 (2.95). IR
1
(cmꢀ1): 1096, 622 (ClO4); 782 and 773 (X-sensitive C6F5). H NMR
1
C6F5). H NMR (CDCl3, 293 K, 300 MHz): δ 7.6ꢀ6.9 (m, 40 H,
C6H5), 2.7 (dm, 2H, CH2, 2J(P,H) = 33 Hz), 2.5 (dm, 2H, CH2, 2J(P,H)
= 30 Hz),), ꢀ0.6 (m, 1H, OH) ppm. 19F NMR (CDCl3, 293 K, 282.4
MHz): δ ꢀ118.5 (2 o-F, 3J(Pt,F) = 275 Hz), ꢀ122.2 (2 o-F, PPh2C6F5),
ꢀ145.9 (1 p-F, PPh2C6F5), ꢀ158.6 (1 p-F), ꢀ159.0 (2 m-F, PPh2C6F5),
ꢀ161.9 (2 m-F) ppm. 31P{1H} NMR (CDCl3, 293 K, 121.5 MHz): δ
55.9 (d, P3, 2J(P3,P4) = 20 Hz), 52.3 (d, P4, 2J(P2,P4) = 300 Hz), ꢀ11.5
(s, P1, 1J(Pt,P1) = 4208 Hz), ꢀ19.9 (d, P2, 2J(P2,P4) = 300 Hz,
1J(Pt,P2) = 1810 Hz) ppm.
(CDCl3, 293 K, 300 MHz): δ 7.5ꢀ6.8 (m, 55 H, C6H5), 4.8 (t, 2 H, CH2,
2J(PꢀH) = 10.5 Hz) ppm. 1HNMR(CDCl3, 213 K, 300 MHz): δ7.6ꢀ6.8
(m, 55H, C6H5), 5.0 (very broad signal, 1 H, CH2), 4.5 (very broad signal, 1
H, CH2) ppm. 19F NMR (CDCl3, 293 K, 282.4 MHz): δ ꢀ115.4 (4 o-F,
3J(Pt,F) = 350 Hz), ꢀ162.9 (2 p-F), ꢀ164.3 (4 m-F) ppm. 19F NMR
(CDCl3, 213 K, 282.4 MHz): δ ꢀ114.9 (2 o-F, very broad signal) ꢀ116.5
(2 o-F, 3J(Pt,F) = 484 Hz), ꢀ161.8 (2 p-F), ꢀ163.2 (4 m-F) ppm. 31P{1H}
NMR (CDCl3, 213 K, 121.5 MHz): δ 10.0 (broad doublet, PPh3, 1J(109Ag,P)
= 795 Hz, 1J(107Ag,P) = 691 Hz) ꢀ24.1 (1J(195PtꢀP) = 1860 Hz), ꢀ143.5
(platinum satellites appear overlapped and the two values 1J(195PtꢀP) can
Synthesis of [(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(phen)] (15).
To a yellow solution of [NBu4]2[{(C6F5)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt-
(μ-Cl)}2] (0.500 g, 0.129 mmol) in acetone (20 mL) was added 1,10-
not be measured) ppm. N = JAX +JAX =315Hz. 195Pt NMR (CDCl3, 275 K,
0
86 MHz),: ꢀ3390, Pt1.
phen H20 (0.058 g, 0.290 mmol). The solution was stirred for 7 h at
3
Reaction of [(RF)2Pt(μ-PPh2)2Pd(dppm)] with AgClO4. Ag-
ClO4 (0.048 g, 0.231 mmol) was added to an orange solution of
[(C6F5)2Pt(μ-PPh2)2Pd(dppm)] (4; 0.150 g, 0.107 mmol) in CH2Cl2
(15 mL). The mixture was stirred at room temperature for 5 h with the
exclusion of light and filtered through Celite. The resulting red solu-
tion was evaporated to ca. 1 mL, and n-hexane (3 mL) was added.
[AgPdPt(μ-PPh2)2(RF)2(OClO3)(dppm)], 11, crystallized as a red
solid, which was filtered and washed with hexane (2 ꢁ 0.5 mL). Yield:
0.132 g, 77%. Anal. Found (calcd for AgC61ClF10H42O4P4PdPt): C,
45.61 (45.78); H, 2.56 (2.63). IR (cmꢀ1): 1098, 623 (broad) (ClO4);
791 and 780 (X-sensitive C6F5). 19F NMR (CDCl3, 293 K, 282.4 MHz):
δ ꢀ118.7 (4 o-F, 3J(Pt,F) = 294 Hz), ꢀ160.6 (2 p-F), ꢀ163.2 (4 m-F)
room temperature and evaporated to ca. 2 mL. CHCl3 (6 mL) was
added, and [(C6F5)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(phen)] (15) crystal-
lized as a yellow solid, which was filtered and washed with CHCl3
(2 ꢁ 0.5 mL). Yield: 0.285 g, 60%. Anal. Found (calcd for C72F10H48
N2P4Pt3): C, 46.60 (46.99); H, 2.42 (2.63.); N 1.40 (1.52). IR (cmꢀ1):
843 (phen); 778 and 769 (X-sensitive C6F5). 19F NMR (acetone-d6,
293 K, 282.4 MHz): δ ꢀ114.2 (4 o-F, 3J(Pt,F) = 344 Hz), ꢀ167.6 (4 m-F),
ꢀ168.6 (2 p-F) ppm. 31P{1H} NMR (acetone-d6, 293 K, 121.5 MHz):
δ ꢀ115.7 (PA, PPh2 groups in trans position to the C6F5 groups,
1J(Pt,P) = 1775 and 1687 Hz), ꢀ130.3 (PX, 1J(Pt,P) = 2268 Hz, 1J(Pt,P)
= 1649 Hz) ppm; N = JAX + JAX = 309 Hz.
ꢁ
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dx.doi.org/10.1021/ic201354s |Inorg. Chem. 2011, 50, 10798–10809

Inorganic Chemistry
ARTICLE
Table 4. Crystal Data and Structure Refinement for 7 0.50H2O 1.25CH2Cl2 and 14 2CH2Cl2
3
3
3
7 0.50H2O 1.25CH2Cl2
14 2CH2Cl2
3
3
3
empirical formula
C48H29ClF10P2O4Pt2Ag
0.50H2O 1.25CH2Cl2
C62H108ClF10N2O5P4PdPt
2CH2Cl2
3
3
3
fw
3194.66
1690.65
unit cell dimensions
a (Å)
12.109(2)
18.910(3)
23.260(4)
68.679(3)
88.867(3)
88.136(3)
13.3787(16)
19.201(2)
24.777(3)
90
b (Å)
c (Å)
α (deg)
β (deg)
γ (deg)
V (Å3), Z
94.573(2
90
4958.5(15), 4
2.140
6344.7(13), 4
1.770
calc dens (g cmꢀ1
wavelength (Å)
temp (K)
)
0.71073
100(1)
0.71073
100(1)
radiation
graphite monochromated Mo Kα
cryst syst
triclinic
monoclinic
space group
P1
P21/c
cryst dimens (mm)
color/habit
0.41 ꢁ 0.22 ꢁ 0.19
yellow/prismatic
6.360
0.26 ꢁ 0.34 ꢁ 0.37
yellow/prismatic
2.877
abs coeff (mmꢀ1
)
abs cor
SADABS63
3.36ꢀ50.06
27205
SADABS63
2θ range for data collect. (deg)
no. rflns collected
3.06ꢀ50.08
34463
no. indep rflns
17275 [R(int) = 0.0296]
11190 [R(int) = 0.0589]
refinement method
full-matrix least-squares on F2
goodness-of-fit on F2a
final R indices (I > 2σ(I))b
1.011
1.006
R1 = 0.0326
wR2 = 0.0821
R1 = 0.0367
wR2 = 0.0849
R1 = 0.0508
wR2 = 0.1220
R1 = 0.0727
wR2 = 0.1328
R indices (all data)
a Goodness-of-fit = [∑ w(Fo ꢀ Fc2)2/(nobs ꢀ nparam)]1/2. b R1 = ∑(|Fo| ꢀ |Fc|)/∑ |Fo|. wR2 = [∑w (Fo ꢀ Fc2)2/∑w(Fo ) ]1/2
.
2
2
2 2
Synthesis of [(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(PPh3)2] 16. To
a yellow solution of [NBu4]2[{(C6F5)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(μ-
Cl)}2] (0.500 g, 0.129 mmol) in a mixture of CH2Cl2/MeOH (80/
20 mL) was added PPh3 (0.203 g, 0.774 mmol). The mixture was
stirred for 24 h at room temperature, while [(C6F5)2Pt(μ-PPh2)2Pt(μ-
PPh2)2Pt(PPh3)2] (16) precipitates as a yellow solid, which was filtered
and washed with MeOH (2 ꢁ 1 mL). Yield: 0.442 g, 78%. Anal.
Found (calcd for C96F10H70P6Pt3): C, 52.49 (52.77); H, 3.17 (3.23). IR
(cmꢀ1): 778 and 771 (X-sensitive C6F5).
Reaction of [(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(PPh3)2] (16)
with AgClO4. To a yellow suspension of 16 (0.500 g, 0.229 mmol)
in acetone (20 mL) was added AgClO4 (0.005 g, 0.458 mmol). The
mixture was stirred at room temperature for 1 h with the exclusion of
light and filtered through Celite. The orange solution was evaporated to
ca. 2 mL, and the complex [(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(PPh3)2]-
[ClO4]2 (18) crystallized as an orange solid, which was filtered and
washed with a mixture (1:1) of acetone/hexane (2 ꢁ 1 mL). Yield:
0.306 g, 56%. Anal. Found (calcd for C96Cl2F10H70O8P6Pt3): C, 48.65
(48.35); H, 2.94 (2.94.). IR (cmꢀ1): 1091, 624 (ClO4); 793 and 780
(X-sensitive C6F5). 19F NMR (CDCl3, 293 K, 282.4 MHz): δ ꢀ120.8
Reaction of [(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(phen)] (15)
with AgClO4. To a yellow suspension of 15 (0.250 g, 0.136 mmol)
in CH2Cl2 (20 mL) was added AgClO4 (0.058 g, 0.280 mmol). The
mixture was stirred at room temperature for 2 h with the exclusion of
light and filtered through Celite. The orange solution was evaporated to
ca. 2 mL and kept in the freezer at 253 K for 14 h. The complex
[(RF)2Pt(μ-PPh2)2Pt(μ-PPh2)2Pt(phen)][ClO4]2 (17) crystallized as
an orange solid, which was filtered and washed with cold CH2Cl2
(2 ꢁ 0.5 mL). Yield: 0.145 g, 52%. Anal. Found (calcd for
C72Cl2F10H48N2O8P4Pt3): C, 42.18 (42.38); H, 2.27 (2.35.); 1.30
(1.37). IR (cmꢀ1): 1093, 624 (ClO4); 851 (phen); 793 and 783 (X-
sensitive C6F5). 19F NMR (CD2Cl2, 293 K, 282.4 MHz): δ ꢀ119.3 (4 o-
F, 3J(Pt,F) = 286 Hz), ꢀ156.8 (2 p-F,), ꢀ161.4 (4 m-F) ppm. 31P{1H}
NMR (CD2Cl2, 293 K, 121.5 MHz): δ 272.9 (PA, PPh2 groups in trans
position to the C6F5 groups, 1J(Pt,P) = 1290 and 1174 Hz), ꢀ135.1 (PX,
3
(4 o-F, J(Pt,F) = 285 Hz), ꢀ157.0 (2 p-F,), ꢀ161.9 (4 m-F) ppm.
31P{1H} NMR (CDCl3, 293 K, 121.5 MHz): δ 268.8 (PPh2 groups in
trans position to the C6F5 groups, 1J(Pt,P) ≈ 1300 Hz for both values),
1
17.1 (PPh3, J(Pt,P) = 2258 Hz), ꢀ151.4 (1J(Pt,P) ≈ 1800 Hz, 195Pt
satellites appear overlapped) ppm.
X-Ray Structure Determination. Crystal data and other details
of the structure analysis are presented in Table 4. Suitable crystals of
7 0.50H2O 1.25CH2Cl2 and 14 2CH2Cl2 were obtained by slow
3
3
3
diffusion of n-hexane into CH2Cl2 solutions of the complexes. Crystals
were mounted at the end of quartz fibers. Data collections were
performed at 100 K temperature on a Bruker Smart CCD diffractometer
using graphite monochromated Mo Kα radiation (λ = 0.71073 Å) with
a nominal crystal to detector distance of 6.0 cm. Unit cell dimensions
were initially determined from the positions of 346 reflections for
1J(Pt,P) = 2688 and 1906 Hz) ppm; N = JAX + JAX = 148 Hz.
ꢁ
10807
dx.doi.org/10.1021/ic201354s |Inorg. Chem. 2011, 50, 10798–10809

Inorganic Chemistry
ARTICLE
7 0.50H2O 1.25CH2Cl2 and 47 reflections for 14 2CH2Cl2 in 60
(3) Forniꢀes, J.; Martín, A.; Sicilia, V.; Martín, L. F. Chem.—Eur. J.
2003, 9, 3427–3435.
(4) Lang, H.; Villar, A. d. J. Organomet. Chem. 2003, 670, 45–55.
(5) Che, Y. D.; Qin, Y. H.; Zhang, L. Y.; Shi, L. X.; Chen, Z. N. Inorg.
Chem. 2004, 43, 1197–1205.
(6) Yoon, I.; Seo, J.; Lee, J. E.; Park, K. M.; Kim, J. S.; Lah, M. S.; Lee,
S. S. Inorg. Chem. 2006, 45, 3487–3489.
(7) Ara, I.; Forniꢀes, J.; Lasheras, R.; Martín, A.; Sicilia, V. Eur. J. Inorg.
Chem. 2006, 948–957.
(8) Forniꢀes, J.; Fuertes, S.; Martín, A.; Sicilia, V.; Lalinde, E.;
Moreno, M. T. Chem.—Eur. J. 2006, 12, 8253–8266.
(9) Robertson, S. D.; Slawin, A. M. Z.; Woollins, J. D. Eur. J. Inorg.
Chem. 2007, 247–253.
3
3
3
intensity frames measured at 0.3° intervals in ω and subsequently
refined on the basis of positions of 1004 reflections for 7 0.50H2O
3
3
1.25CH2Cl2 and 1024 reflections for 14 2CH2Cl2 from the main data
3
set. The diffraction frames were integrated using the SAINT package62
and corrected for absorption with SADABS.63 Lorentz and polarization
corrections were applied.
The structures were solved by Patterson and Fourier methods. All
refinements were carried out using the program SHELXL-97.64 All non-
hydrogen atoms were assigned anisotropic displacement parameters
and refined without positional constraints, except as noted below. All
hydrogen atoms were constrained to idealized geometries and assigned
isotropic displacement parameters 1.2 times the Uiso value of their
attached carbon atoms (1.5 times for methyl hydrogen atoms). For
7 0.50H2O 1.25CH2Cl2, the position of one of the hydrogen atoms of
(10) Shen, W. Z.; Costisella, B.; Lippert, B. Dalton Trans. 2007, 851–858.
(11) Moret, M. E.; Chen, P. J. Am. Chem. Soc. 2009, 131, 5675–5690.
(12) Forniꢀes, J.; Martín, A. In Metal Clusters in Chemistry; Braunstein,
P., Oro, L. A., Raithby, P. R., Eds.; Wiley-VCH: Weinheim, Germany,
1999; Vol. 1, pp 417ꢀ443.
3
3
the water ligand (H(5)) was found from the density maps and refined
with the OꢀH constrained to a sensible value. The other hydrogen atom
of the water was not found in the density map nor geometrically added to
the model. The CꢀCl distance for the half present CH2Cl2 molecule
(13) Archambault, C.; Bender, R.; Braunstein, P.; Dusausoy, Y.
J. Chem. Soc., Dalton Trans. 2002, 4084–4090.
(14) Janzen, D. E.; Mehne, L. F.; VanDerveer, D. G.; Grant, G. J.
Inorg. Chem. 2005, 44, 8182–8184.
(15) Oberbeckmann-Winter, N.; Morise, X.; Braunstein, P.; Welter,
R. Inorg. Chem. 2005, 44, 1391–1403.
(16) Song, H.-B.; Zhang, Z.-Z.; Hui, Z.; Che, C.-M.; Mak, T. C. W.
Inorg. Chem. 2002, 41, 3146–3154.
(17) Alonso, E.; Forniꢀes, J.; Fortu~no, C.; Martín, A.; Orpen, A. G.
Organometallics 2003, 22, 5011–5019.
was constrained to a sensible value. For 14 2CH2Cl2, one very diffuse
3
solvent molecule of CH2Cl2 was found during the last stages of the
refinement. It was modeled as two disordered moieties (occupancy
0.6/0.4) sharing the same C atom. Geometrical constraints were used in
this solvent molecule, and all of the anisotropic thermal parameters of
the Cl atoms were constrained to be the same. No hydrogen atoms were
included in this molecule. Also, no H atom was added to the bridging
OH group either. Full-matrix least-squares refinement of these model
against F2 converged to final residual indices given in Table 4.
(18) Braunstein, P.; Frison, U.; Oberbeckmann-Winter, N.; Morise,
X.; Messaoudi, A.; Bꢀenard, M.; Rohmer, M.-M.; Welter, R. Angew. Chem.,
Int. Ed. Engl. 2004, 43, 6120–6125.
(19) Liu, Y.; Lee, K. H.; Vittal, J. J.; Hor, T. S. A. J. Chem. Soc., Dalton
Trans. 2002, 2747–2751.
’ ASSOCIATED CONTENT
(20) Kickman, J. E.; Loeb, J. J. Organometallics 1995, 14, 3584–3587.
(21) Xia, B.-H.; Zhang, H.-X.; Che, C.-M.; Leung, K.-H.; Phillips,
D. L.; Zhu, N.; Zhou, Z.-Y. J. Am. Chem. Soc. 2003, 125, 10362–10374.
(22) Falvello, L. R.; Forniꢀes, J.; Fortu~no, C.; Durꢀan, F.; Martín, A.
Organometallics 2002, 21, 2226–2234.
(23) Falvello, L. R.; Forniꢀes, J.; Lalinde, E.; Menjꢀon, B.; García-Monforte,
M. A.; Moreno, M. T.; Tomꢀas, M. Chem. Commun. 2007, 3838–3840.
(24) Forniꢀes, J.; Ibꢀa~nez, S.; Martín, A.; Sanz, M.; Berenguer, J. R.;
Lalinde, E.; Torroba, J. Inorg. Chem. 2006, 25, 4331–4340.
(25) Liu, F. H.; Chen, W. Z.; Wang, D. Q. Dalton Trans. 2006,
3015–3024.
S
Supporting Information. Further details of the structure
b
determinations of 7 0.50H2O 1.25CH2Cl2 and 14 2CH2Cl2
3
3
3
including atomic coordinates, bond distances and angles, and
thermal parameters. This material is available free of charge via
the Internet at http://pubs.acs.org
’ AUTHOR INFORMATION
Corresponding Author
*E-mail: juan.fornies@unizar.es.
(26) Karshtedt, D.; Bell, A. T.; Tilley, T. D. Organometallics 2004,
23, 4169–4171.
Notes
§Polynuclear Homo- or Heterometallic Palladium(II)ꢀPlatinum
(II) Pentafluorophenyl Complexes Containing Bridging Diphe-
nylphosphido Ligands. 28. For part 27, see ref 65.
(27) van Leeuven, P. W. N. M.; Zuideveld, M. A.; Swennenhuis,
B. H. G.; Freixa, Z.; Kamer, P. C. J.; Goubitz, K.; Fraanje, J.; Lutz, M.;
Spek, A. L. J. Am. Chem. Soc. 2003, 125, 5523–5539.
(28) Forniꢀes, J.; Fortu~no, C.; Ibꢀa~nez, S.; Martín, A. Inorg. Chem.
2008, 47, 5978–5987.
(29) Forniꢀes, J.; Fortu~no, C.; Ibꢀa~nez, S.; Martín, A.; Tsipis, A. C.;
Tsipis, C. A. Angew. Chem., Int. Ed. 2005, 44, 2407–2410.
(30) Connelly, N. G.; Geiger, W. E. Chem. Rev. 1996, 96, 877–910.
(31) Ebihara, M.; Iiba, M.; Matsuoka, H.; Okuda, C.; Kawamura, T.
J. Organomet. Chem. 2004, 689, 146–153.
(32) Song, L.; Trogler, W. Angew. Chem., Int. Ed. 1992, 31, 770–772.
(33) Rendina, L. M.; Hambley, T. W. In Comprehensive Coordination
Chemistry II; McCleverty, J. A., Meyer, T. J., Eds.; Elsevier Inc.: San
Diego, 2004; Vol. 6.
(34) Alonso, E.; Casas, J. M.; Cotton, F. A.; Feng, X. J.; Forniꢀes, J.;
Fortu~no, C.; Tomꢀas, M. Inorg. Chem. 1999, 38, 5034–5040.
(35) Alonso, E.; Forniꢀes, J.; Fortu~no, C.; Lledꢀos, A.; Martín, A.;
Nova, A. Inorg. Chem. 2009, 48, 7679–7690.
(36) Forniꢀes, J.; Fortu~no, C.; Navarro, R.; Martínez, F.; Welch, A. J.
J. Organomet. Chem. 1990, 394, 643–658.
’ ACKNOWLEDGMENT
This work was supported by the Spanish MICINN (DGI)/
FEDER (Project CTQ2008-06669-C02-01/BQU and the
Gobierno de Aragꢀon (Grupo de Excelencia: Química Inorgꢀanica
y de los Compuestos Organometꢀalicos). COST Phosphorus Science
Network (PhoSciNet, project CM0802) is also gratefully acknowl-
edged for financial support. S. I. acknowledges the Ministerio de
Educaciꢀon y Ciencia for a grant.
’ REFERENCES
(1) Fernꢀandez-Anca, D.; García-Seijo, M. I.; Casti~neiras, A.; García-
Fernꢀandez, M. E. Inorg. Chem. 2008, 47, 5685–5695.
(37) Ara, I.; Chaouche, N.; Forniꢀes, J.; Fortu~no, C.; Kribii, A.;
Martín, A. Eur. J. Inorg. Chem. 2005, 3894–3901.
(2) Li, Q. S.; Xu, F. B.; Cui, D. J.; Yu, K.; Zeng, X. S.; Leng, X. B.;
Song, H. B.; Zhang, Z. Z. Dalton Trans. 2003, 1551–1557.
10808
dx.doi.org/10.1021/ic201354s |Inorg. Chem. 2011, 50, 10798–10809

Inorganic Chemistry
ARTICLE
(38) Ara, I.; Chaouche, N.; Forniꢀes, J.; Fortu~no, C.; Kribii, A.; Tsipis,
A. C. Organometallics 2006, 25, 1084–1091.
(39) Alonso, E.; Casas, J. M.; Forniꢀes, J.; Fortu~no, C.; Martín, A.; Orpen,
A. G.; Tsipis, C. A.; Tsipis, A. C. Organometallics 2001, 20, 5571–5582.
(40) Ara, I.; Forniꢀes, J.; Fortu~no, C.; Ibꢀa~nez, S.; Martín, A.; Mastrorilli,
P.; Gallo, V. Inorg. Chem. 2008, 47, 9069–9080.
(41) Mastrorilli, P. Eur. J. Inorg. Chem. 2008, 4835–4850.
(42) Alonso, E.; Forniꢀes, J.; Fortu~no, C.; Martín, A.; Orpen, A. G.
Organometallics 2000, 19, 2690–2697.
(43) Chaouche, N.; Forniꢀes, J.; Fortu~no, C.; Kribii, A.; Martín, A.
J. Organomet. Chem. 2007, 692, 1168–1172.
(44) Alonso, E.; Forniꢀes, J.; Fortu~no, C.; Martín, A.; Orpen, A. G.
Organometallics 2001, 20, 850–859.
(45) Falvello, L. R.; Forniꢀes, J.; Fortu~no, C.; Martínez, F. Inorg.
Chem. 1994, 33, 6242–6246.
(46) Forniꢀes, J.; Fortu~no, C.; Gil, R.; Martín, A. Inorg. Chem. 2005,
44, 9534–9541.
(47) Forniꢀes, J.; Fortu~no, C.; Ibꢀa~nez, S.; Martín, A. Inorg. Chem.
2006, 45, 4850–4858.
(48) Latronico, M.; Mastrorilli, P.; Gallo, V.; Dell’Anna, M. M.;
Creati, F.; Re, N.; Englert, U. Inorg. Chem. 2011, 50, 3539–3558.
(49) Mastrorilli, P.; Latronico, M.; Gallo, V.; Polini, F.; Re, N.;
Marrone, A.; Gobetto, R.; Ellena, S. J. Am. Chem. Soc. 2010, 132,
4752–4765.
(50) Latronico, M.; Polini, F.; Gallo, V.; Mastrorilli, P.; Calmushi-
Cula, B.; Englert, U.; Re, N.; Repo, T.; Raisanen, M. Inorg. Chem. 2008,
47, 9779–9796.
(51) Mastrorilli, P. Dalton Trans. 2008, 4555–4557.
(52) Alonso, E.; Forniꢀes, J.; Fortu~no, C.; Martín, A.; Orpen, A. G.
Organometallics 2003, 22, 2723–2728.
(53) Alonso, E.; Forniꢀes, J.; Fortu~no, C.; Martín, A.; Orpen, A. G.
Chem. Commun. 1996, 231–232.
(54) Falvello, L. R.; Forniꢀes, J.; Fortu~no, C.; Martín, A.; Martínez-
Sari~nena, A. P. Organometallics 1997, 16, 5849–5856.
(55) Leoni, P.; Marchetti, F.; Marchetti, L.; Passarelli, V. Chem.
Commun. 2004, 2346–2347.
(56) Chaouche, N.; Forniꢀes, J.; Fortu~no, C.; Kribii, A.; Martín, A.;
Karipidis, P.; Tsipis, A. C.; Tsipis, C. A. Organometallics 2004, 23,
1797–1810.
(57) Alonso, E.; Forniꢀes, J.; Fortu~no, C.; Tomꢀas, M. J. Chem. Soc.,
Dalton Trans. 1995, 3777–3784.
(58) Alonso, E.; Forniꢀes, J.; Fortu~no, C.; Martín, A.; Rosair, G. M.;
Welch, A. J. Inorg. Chem. 1997, 36, 4426–4431.
(59) Ara, I.; Chaouche, N.; Forniꢀes, J.; Fortu~no, C.; Kribii, A.; Tsipis,
A. C.; Tsipis, C. A. Inorg. Chim. Acta 2005, 358, 1377–1385.
(60) Forniꢀes, J.; Fortu~no, C.; Goꢀmez, M. A.; Menjꢀon, B.; Herdtweck,
H. Organometallics 1993, 12, 4368–4375.
(61) Steffen, W. L.; Palenik, G. J. Inorg. Chem. 1976, 15, 2432–2439.
(62) SAINT, version 5.0; Bruker Analytical X-raySystems: Madison,
WI.
(63) Sheldrick, G. M. SADABS; University of Gottingen: Gottingen,
Germany, 1996.
(64) Sheldrick, G. M. SHELXL-97; University of Gottingen:
Gottingen, Germany, 1997.
(65) Forniꢀes, J.; Fortu~no, C.; Ibꢀa~nez, S.; Martín, A.; Romero, P.;
Mastrorilli, P.; Gallo, V. Inorg. Chem. 2011, 50, 285–298.
10809
dx.doi.org/10.1021/ic201354s |Inorg. Chem. 2011, 50, 10798–10809