Monophosphine and diphosphine ligands for diplatinum polyynediyl complexes: Efficient syntheses of new functionality-containing systems and model compounds

Article abstract of DOI:10.1016/j.jorganchem.2006.12.023

Br(CH₂)₄Br and NaO(CH₂)₂CH{double bond, long}CH₂ react under suitable conditions to give Br(CH₂)₄O(CH₂)₂CH{double bond, long}CH₂ (55%), which is

Full text of DOI:10.1016/j.jorganchem.2006.12.023

Journal of Organometallic Chemistry 692 (2007) 1859–1870
www.elsevier.com/locate/jorganchem
Monophosphine and diphosphine ligands for diplatinum
polyynediyl complexes: Efficient syntheses of new
functionality-containing systems and model compounds
*
Laura de Quadras, Jurgen Stahl, Fedor Zhuravlev, John A. Gladysz
¨
Institut fu¨r Organische Chemie, Friedrich-Alexander Universita¨t Erlangen-Nu¨rnberg, Henkestraße 42, 91054 Erlangen, Germany
Received 8 November 2006; received in revised form 18 December 2006; accepted 18 December 2006
Available online 23 December 2006
Dedicated with affection to Prof. Dr. Gyula Palyi on the occasion of his 70th birthday.
Abstract
Br(CH2)4Br and NaO(CH2)2CH@CH2 react under suitable conditions to give Br(CH2)4O(CH2)2CH@CH2 (55%), which is treated with
KPPh2 to yield the ether-containing phosphine Ph2P(CH2)4O(CH2)2CH@CH2 (83%). The reaction of CH3CH2OC(O)CH@C(CH3)2 and
BrMg(CH2)3CH@CH2 in the presence of CuCl (cat.) and ClSiMe3 yields CH3CH2OC(O)CH2C(CH3)2(CH2)3CH@CH2 (67%), which is
reduced to an alcohol that is brominated, reacted with Grubbs’ catalyst, hydrogenated, and treated with KPPh2 to give the bis(geminally
dimethylated) diphosphine Ph2P(CH2)2C(CH3)2(CH2)8C(CH3)2(CH2)2PPh2 (47% overall). The photochemical reaction of I(CF2)8I and
H2C@CHCH2SnBu3 yields H2C@CHCH2(CF2)8CH2CH@CH2 (52%), which is converted with 9-BBN to a diol (92%) that is brominated
and treated with LiPR2 to give the fluorinated diphosphines R2P(CH2)3(CF2)8(CH2)3PR2 (R = a, p-tol, 67%; b, t-Bu, 69%; c, o-tol, 86%).
Reactions of Br(CH2)mBr and LiPR2 similarly yield R2P(CH2)mPR2 (m/R = 8/a, 95%; 14/a, 96%; 14/p-C6H4-t-Bu, 98%). Reactions of
0
0
0
KPPh2 with Br(CH2)m CH@CH2and Br(CH2)7CH3 give the corresponding monophosphines Ph2P(CH2)m CH@CH2 (m = 7, 82%; 10,
84%) and Ph2P(CH2)7CH3 (85%). When the former is combined with [Pt(l-Cl)(C6F5)(tht)]2 (tht = tetrahydrothiophene), trans-
0
(C6F5)(Ph2P(CH2)m CH@CH2)2PtCl (77–70%) is isolated. When the latter (excess) is combined with trans,trans-(C6F5)(p-tol3P)2-
Pt(C„C)4Pt(Pp-tol3)2(C6F5) (RT, 65 ꢀC), trans,trans-(C6F5)(Ph2P(CH2)7CH3)2Pt(C„ C)4Pt(Ph2P(CH2)7CH3)2(C6F5) (53%) is isolated.
ꢁ 2006 Elsevier B.V. All rights reserved.
Keywords: Functionalized phosphine; Fluorous; Platinum; Polyyne; Olefin metathesis
1. Introduction
inum endgroups of I are redox active, there are tantalizing
possibilities for ‘‘insulated molecular wires’’. Others have
also sought to sterically shield unsaturated ligands that
bridge two electroactive endgroups [2].
The synthesis and study of such complexes has
required a variety of monophosphines and a,x-diphos-
phines. Polyynediyl precursors with four monophosphine
Over the last five years, we have developed syntheses of
diplatinum polyynediyl complexes, LyPt(C„C)nPtLy, in
which the sp carbon chains are sterically shielded by two
flexible sp3 carbon chains that span the platinum termini
[1]. As shown in Scheme 1, such assemblies can adopt
two limiting conformations, Ia and Ib. In nearly all cases
where the sp3 chains are long enough, double helical con-
formations (Ia) are found in the solid state. Since the plat-
0
ligands that contain P(CH2)m CH@CH2 moieties (II,
Scheme 1) can be subjected to alkene metathesis/hydroge-
nation sequences [1a,1c,3]. Although the yields of I are
sometimes modest, this approach has broad generality.
Alternatively, in favorable cases precursors of the type
III and diphosphines react to give I. These can be viewed
*
Corresponding author. Tel.: +49 9131 8522540 fax: +49 9131 8526865.
E-mail address: gladysz@chemie.uni-erlangen.de (J.A. Gladysz).
0022-328X/$ - see front matter ꢁ 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2006.12.023

1860
L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
Scheme 1. Limiting structures for diplatinum polyynediyl complexes with termini-spanning diphosphines Ar2P(CH2)mPAr2 (Ia, Ib), and synthetic
pathways (m = 2m0 + 2).
as coordination-driven self assembly processes [1a,1b,3].
In our most recent efforts, we have sought to extend this
work to functionalized phosphines, for example with het-
eroatom or alkyl substituents [1c,3c].
Br
Br
+
NaO
O
Br
(excess)
1, 55%
In a previous full paper, an extensive series of diphos-
phines of the formula Ph2P(CH2)mPPh2 was described [4].
In this manuscript, syntheses of some related PAr2 species
are reported, as well as new oxygen-, fluorine-, methyl-,
and alkene-substituted monophosphines and diphosphines
that play key roles in upcoming full papers [3]. This avoids
the fragmentation of similar sequences, which in some
cases might be relegated to supporting information. Plati-
num complexes of selected ligands are also described, some
of which represent ‘‘missing links’’ with respect to series in
existing full papers [5] but have assumed importance
in subsequent efforts [3b]. Additional details can be found
in two dissertations [6].
KPPh2
Ph2P
O
2, 83%
Scheme 2. Synthesis of the oxygen-containing monophosphine 2.
Next, 1 and commercial KPPh2 were reacted. Workup
afforded the target polyfunctional monophosphine Ph2P-
(CH2)4O(CH2)2CH@CH2 (2) as an air-sensitive oil in 83%
yield. All new compounds were characterized by NMR
spectroscopy (1H, 13C, and (for phosphines) 31P), and often
by IR and mass spectrometry. Data are summarized in the
experimental section. In all cases, features were routine.
2. Results
2.1. Oxygen-containing monophosphines
Although 2 was P97% pure by H and 31P NMR, a satis-
1
One current goal involves the introduction of Lewis basic
functionality into the sp3 chains of I. Thus, expedient syn-
theses of polyether analogs were sought. One obvious route
would require alkene-containing monophosphines of the
factory microanalysis was not obtained.
2.2. Diphosphines with geminal dimethyl groups
00
000
formula Ph2P(CH2)m O(CH2)m CH@CH2. As shown in
Scheme 2, a Williamson ether synthesis involving the alkox-
ide of 3-buten-1-ol and the a,x-dibromide Br(CH2)4Br
(twofold excess) was attempted. After distillation to remove
the diether byproduct H2C@CH(CH2)2O (CH2)4O(CH2)2-
CH@CH2, the new a,x-bromoalkene Br(CH2)4O(CH2)2-
CH@CH2 (1) could be isolated in 55% yield based upon
the alkoxide.
Geminal dialkyl substituents can have a profound influ-
ence on conformational equilibria and product distributions
(e.g. intramolecular vs. intermolecular condensations) [7].
Accordingly, we sought to probe for effects on the equilib-
rium Ia/Ib, or the corresponding energy barrier. In view of
our many results with Ar2P(CH2)14PAr2-bridged systems
[1a,1b], symmetrically-substituted diphosphines with
bridges of fourteen sp3 carbon atoms were sought.

L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
1861
CuCl
(cat.)
2.3. Diphosphines with difluoromethylene segments
O
O
+
BrMg
O
O
ClSiMe3
0 ˚C
Perfluoroalkanes and other compounds with difluorom-
ethylene segments are known to adopt helical conforma-
tions [11]. It was thought that this might have an effect on
equilibria of the type Ia/Ib, and therefore appropriately fluo-
rinated diphosphines were sought. Although many phos-
phines with perfluoroalkyl groups are known [12],
diphosphines of the formula Ar2P(CF2)mPAr2 would be
too weakly nucleophilic and basic to give substitution reac-
tions as in Scheme 1 [13]. Hence, analogs with insulating
methylene groups were targeted. For reasons outlined above,
a system with fourteen sp3 carbon atoms was preferred.
Perfluoroalkyl iodides and allyl tin compounds readily
undergo free radical chain reactions to give allyl perflu-
oroalkyl species and tin iodides [14]. Thus, as shown in
Scheme 4, the commercial ‘‘fluorous’’ [15] a,x-diiodide
I(CF2)8I and H2C@CHCH2SnBu3 were irradiated. Twofold
allylation occurred to give the 14-carbon-atom a,x-bis-
(alkene) H2C@CHCH2(CF2)8CH2CH@CH2 (9), which
was isolated in 52% yield after distillation. A hydrobora-
tion/oxidation sequence afforded the a,x-diol HO-
(CH2)3(CF2)8(CH2)3OH (10, 92%), which was subsequently
brominated to give the a,x-dibromide Br(CH2)3(CF2)8-
(CH2)3Br (11, 87%).
3, 67%
LiAlH4
O
Br
Br
Br Br
PPh3
Br
HO
5, 88%
4, 88%
Grubbs'
catalyst
Br
Br
6, 90%
(Ph3P)3RhCl (cat.), H2
Br
Br
7, 81%
KPPh2
As shown in Scheme 4, 11 was treated with aromatic
and aliphatic LiPR2 reagents that had been generated by
PPh2
Ph2P
8, 83%
Scheme 3. Synthesis of the bis(geminally dimethylated) diphosphine 8.
F F F F F F
F F F F F F
F F
F F
SnBu3
(excess)
I
+
I
F F F F F F
F F F F F F
F
F
F
F
As shown in Scheme 3, ethyl 3-methylcrotonoate and
the Grignard reagent derived from Br(CH2)3CH@CH2
were combined in the presence of copper(I). In accord with
a report of Brunel and Rousseau [8], conjugate addition
occurred, giving the a,x-carboethoxyalkene CH3CH2O-
C(O)CH2C(CH3)2(CH2)3CH@CH2 (3) in 67% yield after
workup. This compound, which features a geminal
dimethyl group b to the carbonyl group, has only been
partially characterized [8,9]. Routine reduction and bro-
mination [10] steps gave the a,x-hydroxyalkene HOCH2-
CH2C(CH3)2(CH2)3CH@CH2 (4) [9] and a,x-bromoalkene
BrCH2CH2C(CH3)2(CH2)3CH@CH2 (5) [9] in 88% and
88% yields. We have previously synthesized the latter com-
pound, but by a less efficient pathway [5a].
9, 52%
1. 9-BBN
2. H2O2/NaOH
F F F F F F
F F
OH
HO
F F F F F F
10, 92%
O
F
F
Br
Br
PPh3
Br Br
F F
Reaction of 5 with Grubbs’ catalyst gave the crude
metathesis product 6 (Scheme 3) as a mixture of Z/E
isomers in 90% yield. Subsequent hydrogenation afforded
the saturated a,x-dibromide Br(CH2)2C(CH3)2(CH2)8-
C(CH3)2(CH2)2Br (7) in 81% yield. Treatment with
2.0 equiv. of KPPh2 afforded the target diphosphine
Ph2P(CH2)2C(CH3)2(CH2)8C(CH3)2(CH2)2PPh2 (8), with
a 14-carbon bridge and a geminal dimethyl group c to each
phosphorus, as a spectroscopically pure white solid in 83%
yield. Solutions of 8 were quite air sensitive, but solid sam-
F F F F F F
Br
Br
F F F F F F
F
F
11, 87%
LiPR2
F F F F F F
F F
PR2
R2P
F F F F F F
F
F
12
R = a,
b,
p
-tol, 67%
-Bu, 69%
o-tol, 86%
1
ples survived brief exposures. The H and 13C NMR spec-
t
c,
tra of this entire series of compounds showed the expected
singlets for the dimethyl groups.
Scheme 4. Syntheses of the fluorinated diphosphines 12.

1862
L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
F
deprotonations of secondary phosphines. Workups gave
the target diphosphines R2P(CH2)3(CF2)8(CH2)3PR2 (12;
R = a, p-tol; b, t-Bu; c, o-tol) in 67–86% yields. In contrast
to the other diphosphines in this paper, 12a–c were stable
for extended periods in air, presumably due to the residual
electron-withdrawing effects of the perfluoroalkyl segments
F
F
S
F
Cl
Cl
F
F
+
Pt
Pt
Ph2P
F
F
F
m'-6
S
F
15, 16
1
at phosphorus [13]. The H and 13C NMR signals associ-
ated with the PCH2CH2CH2 moieties were similar to those
of closely related fluorous trialkylphosphines [14].
F
F
F
F
Interestingly, all of the fluorinated compounds except 9
were white solids, and correct microanalyses were obtained
in each case. Free radical additions of secondary phos-
phines to terminal alkenes – including RfCH@CH2 and
RfCH2CH@CH2 systems – are often efficient preparative
reactions [14,16]. However, extensive efforts to access 12
via additions of HPAr2 species to 9 were unsuccessful.
F
Ph2P
Pt
PPh2
18, m' = 7, 77%
19, m' = 10, 70%
Cl
m'-6
m'-6
2.4. Additional diphosphines and monophosphines
F
F
F
F
F
F
F
F
p
-tol3P
P
p-tol3
+
Non-fluorinated diphosphines with substituted aryl
groups that would give easily monitored NMR signals were
sought. Thus, as shown in Scheme 5 (top), the commercial
a,x-dibromide Br(CH2)8Br was treated with LiPp-tol2.
Workup gave the diphosphine p-tol2P(CH2)8Pp-tol2 (13a)
as a white solid in 95% yield. Similarly, the longer-chain
dibromide Br(CH2)14Br was treated with LiPp-tol2 and
LiP(p-C6H4-t-Bu)2. Workups gave p-tol2P(CH2)14Pp-tol2
(14a) and (p-t-BuC6H4)2P(CH2)14P(p-C6H4-t-Bu)2 (14d) as
analytically pure white solids in 96% and 98% yields. As
F
Pt C C C C C C C C Pt
F
Ph2P
Pp
-tol3
p
-tol3P
20
17
Ph
P
F
F
2 F
F
F
P
p
-tol3
F
F
Pt
C
C C C C C C C Pt
P
P
F
F
Ph2 F
Ph2
1
expected, the H and 13C NMR spectra of all three com-
22
65 ˚C
pounds exhibited sharp singlets for the p-methyl and p-t-
Ph2
P
Ph
2 F
P
F
F
F
F
F
F
LiPp-tol2
Br
Pp-tol2
Br
Br
p-tol2P
F
F
Pt
C
C C C C C C C Pt
P
P
Ph2 F
Ph2
13a, 95%
21, 53%
LiPAr2
Scheme 6. Syntheses of new platinum complexes.
Br
butyl groups. Their air sensitivities were similar to that of
8.
PA r2
Ar2P
In order to better define the generality of the synthesis of
I from II as a function of sp and sp3 carbon chain lengths, a
wider variety of alkene-containing monophosphines
Ph2PðCH2Þm0 CH@CH2 were required. As shown in Scheme
5 (bottom), two examples were synthesized by reactions of
KPPh2 and the corresponding a,x-bromoalkenes. Work-
ups gave Ph2P(CH2)7CH@CH2 (15) and Ph2P(CH2)10-
CH@CH2 (16) as moderately air sensitive oils in 82% and
84% yields. The spectroscopic properties were similar to
those of previously reported analogs (m0 = 4, 5, 6, 8, 9)
[5]. In order to provide a non-cyclized reference compound
for I, the phosphine Ph2P(CH2)7CH3 (17) was similarly
prepared from KPPh2 and Br(CH2)7CH3 (Scheme 5, bot-
tom). Although this compound has been reported twice
14
-tol, 67%
-C6H4-
Ar = a,
d,
p
p
t
-Bu, 69%
KPPh2
Br
Ph2P
m'-6
m'-6
15, m' = 7, 82%
16, m' = 10, 84%
KPPh2
Br
Ph2P
17, 85%
Scheme 5. Other new syntheses of monophosphines and diphosphines.

L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
1863
previously [17], one synthesis is longer; for the other (from
PPh2
Ph2P
the corresponding alkyl chloride), only a 31P NMR spec-
trum was given.
m-7
m
= 8, 10, 11, 12, 14, 18, 19, 20, 22, 24, 28, 32
2.5. Selected platinum complexes
The three preceding monophosphines were applied in
syntheses. Complexes of the formula trans-(C6F5)(L)2PtCl
are easily prepared from the substitution-labile platinum
tetrahydrothiophene complex [Pt(l-Cl)(C6F5)(tht)]2 [18].
As shown in Scheme 6 (top), reactions with 15 and 16 gave
Ph2P
Ph2P
m'-6
23
m' = 4, 5, 6, 7 (15, this work),
8, 9, 10 (16, this work)
Fig. 1. Related phosphine ligands reported previously.
0
the new adducts trans-(C6F5)(Ph2P(CH2)m CH@CH2)2PtCl
(m0 = 7, 18; 10, 19) in 77–70% yields. The spectroscopic
properties were similar to those of previously reported ana-
logs [5].
cases, platinum complexes analogous to 18 and 19 have
been prepared. In connection with other objectives, related
dialkyl and trialkyl phosphines of the formulae
PhP((CH2)m CH@CH2)2 and P((CH2)m CH@CH2)3 have
also been synthesized [22–24]. The diphosphines 13a and
14a,d (Scheme 5) complement the extensive series of phe-
nyl-substituted analogs Ph2P(CH2)mPPh2 reported in our
previous full paper (Fig. 1) [4].
As will be detailed in future full papers [3], nearly all of
the above types of functionalized monophosphines and
diphosphines can be elaborated into analogs of I. For
these, complex 21 in Scheme 6 – derived from an unfunc-
tionalized monophosphine – provides an important refer-
ence compound. Other types of functional phosphines
that may serve as precursors to derivatives of I are under
active investigation and will be reported in due course [25].
A reference compound that would electronically resem-
ble the alkyl(diaryl)phosphine complexes I but lack the ter-
mini-spanning sp3 chains was sought. As shown in Scheme 6
(bottom), the diplatinum octatetraynediyl complex trans,-
0
0
trans-(C6F5)(p-tol3P)2Pt(C„C)4Pt(Pp-tol3)2(C6F5)
(20)
[19] was treated with an excess of the n-octyl phosphine
17 at room temperature. Substitution occurred to give the
target molecule trans,trans-(C6F5)(Ph2P(CH2)7CH3)2Pt-
(C„C)4Pt(Ph2P(CH2)7CH3)2(C6F5) (21). However, an
appreciable amount of the corresponding trisubstitution
product 22 (Scheme 6) was also present, as evidenced by
three 31P NMR signals. Two were of lesser intensity, and
strongly coupled to each other (2JPP = 409 Hz; Pp-tol3
and 17 with trans relationship). Reaction of the mixture
with a second charge of 17 at 65 ꢀC gave analytically pure
21 in 53% yield after chromatography. The 13C NMR spec-
trum of 21 exhibited PtC„CC„C signals that were very
similar to those of the precursor 20 (100.0, 94.2, 63.7,
57.9 ppm vs. 100.6, 96.7, 64.1, 58.1 ppm) [19], and the
UV–vis spectra were essentially identical.
4. Experimental
4.1. General
Instrumentation and general methods were identical to
those in previous papers [5a]. Chemicals were used as fol-
lows: THF and Et2O, distilled from Na/benzophenone;
CH2Cl2, distilled from CaH2; hexanes, simple distillation;
HO(CH2)2CH@CH2 (Aldrich), distilled from Na; toluene
and Br(CH2)4Br (Acros), distilled; n-BuLi (Acros, 1.6 M
in hexane) and t-BuLi (Aldrich, 1.52 M in pentane), stan-
dardized [26]; CuCl (Aldrich, 99.99%), ClSiMe3 (Acros,
98%), Br(CH2)3CH@CH2, Br(CH2)8Br (2 · Acros), CH3-
CH2OC(O)CH@C(CH3)2, 9-BBN, 2,4,4,6-tetrabromo-2,5-
cyclohexadienone, Br(CH2)7CH3 (4 · Aldrich), LiAlH4
(Fluka), Grubbs’ catalyst (Strem), KPPh2 (Fluka, 0.5 M in
THF), Ph3P, I(CF2)8I, CF3C6F11 (3 · ABCR), H2C@
CHCH2SnBu3 (Lancaster), (Ph3P)3RhCl, HPp-tol2, HP-
(t-Bu)2 (3 · Strem), and other materials, used as received.
3. Discussion
This study has provided efficient syntheses of a variety
of functionalized monophosphines and diphosphines. To
our knowledge, the oxygenated and fluorinated systems 2
and 12a–c (Schemes 2 and 4) have no previous counterpart.
However, there is a substantial literature involving oxygen-
ated diphosphines that can give crown-ether-like metal
complexes [20]. Also, Gray has reported the synthesis of
the tetraether Ph2PCH2(CH2OCH2)4CH2PPh2, in which
the phosphorus atoms are linked by 14 sp3 hybridized
atoms [21]. The diphosphines 12a–c and their precursors
(Scheme 4) may have independent applications in fluorous
chemistry [15].
No close analogs of the bis(geminally dimethylated)
diphosphine 18 (Scheme 3) are known. However, the dime-
thylated monophosphine 23, depicted in Fig. 1, has been
prepared from the a,x-bromoalkene 5 (Scheme 3) and
KPPh2 [5a]. As noted above, a number of alkene contain-
ing phosphines that complement 15 and 16 have been
reported [5]; these are also summarized in Fig. 1. In all
4.2. Br(CH2)4O(CH2)2CH@CH2 (1)
A Schlenk flask was fitted with a condenser and charged
with sodium (0.831 g, 36.1 mmol), and HO(CH2)2CH@
CH2 (12.0 mL, 139 mmol) was slowly added with stirring.
The mixture was heated at 80 ꢀC until the sodium dissolved
(ca. 2 h). Then Br(CH2)4Br was added (8.3 mL, 73 mmol),

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L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
and the mixture was refluxed. After 3 h, excess alcohol was
recovered by distillation (110 ꢀC). The residue was cooled
and poured into water (30 mL). The organic layer was sep-
arated. The aqueous layer was washed with ether (2 ·
10 mL). The combined organic phases were washed with
water (2 · 5 mL) and dried (CaCl2). The solvent was
removed by rotary evaporation. The residue was chro-
matographed on a silica gel column (20 · 2.5 cm, 70:30 v/
v hexanes/CH2Cl2). The first fraction contained the excess
Br(CH2)4Br. The solvent was removed from the second
fraction by rotary evaporation and oil pump vacuum to
give 1 as a colorless oil (4.284 g, 19.92 mmol, 55%).
(5.00 mL, 39.2 mmol), and cooled to 0 ꢀC. The Grignard
solution was transferred via cannula to the second flask
with stirring [8]. The cold bath was removed. After 1.5 h,
saturated aqueous NH4Cl (60 mL) was added. The aque-
ous phase was washed with Et2O (2 · 60 mL). The com-
bined organic phases were dried (MgSO4). The solvent
was removed by rotary evaporation. The residue was dis-
tilled (Kugelrohr) to give 3 as a colorless liquid (4.32 g,
21.8 mmol, 67%) [8,9].
NMR (d, CDCl3), 1H 5.79 (ddt, 1H, 3JHHtrans = 17.0 Hz,
3
3JHHcis = 10.5, JHH = 6.5 Hz, CH@), 4.97 (dm, 1H,
3
3JHHtrans = 17.0 Hz, @CHEHZ), 4.90 (dm, 1H, JHHcis
=
3
NMR (d, CDCl3), 1H 5.79 (ddt, 1H, 3JHHtrans = 17.1 Hz,
10.5 Hz, @CHEHZ), 4.07 (q, 2H, JHH = 7.1 Hz, CH2O),
2.15 (s, 2H, C(O)CH2), 1.99 (apparent quartet, 2H,
3JHH = 6.9 Hz, CH2CH@), 1.40–1.24 (m, 4H, CH2), 1.21
3
3JHHcis = 10.3 Hz, JHH = 6.8 Hz, CH@), 5.05 (br d, 1H,
3JHHtrans = 17.2 Hz, @CHEHZ), 5.00 (br d, 1H,
3JHHcis = 10.2 Hz, @CHEHZ), 3.45–3.39 (m, 6H,
BrCH2CH2CH2CH2OCH2), 2.32–2.27 (m, 2H, CH2CH@),
1.93–1.88 and 1.70–1.67 (2 m, 4H, BrCH2CH2CH2);
13C{1H} 135.2 (s, CH@), 116.3 (s, @CH2), 70.1, 69.7 (2 s,
CH2OCH2), 34.2, 33.8 (2 s, CH2CH@ and BrCH2), 29.7,
28.2 (2 s, BrCH2CH2CH2).
3
(t, 3H, JHH 7.1 = Hz, CH3CH2), 0.95 (s, 6H, C(CH3)2);
13C{1H} 172.3 (s, C@O), 138.9 (s, CH@), 114.3 (s,
@CH2), 59.8 (s, CH2O), 46.0 (s, C(O)CH2), 41.7 (s,
C(CH3)2CH2), 34.4 (s, CH2CH@), 33.2 (s, C(CH3)2), 27.3
(s, C(CH3)2), 23.4 (s, CH2CH2CH@), 14.3 (s, CH3CH2).
IR (cmꢀ1, liquid film), 3080 (w), 2961 (m), 2937 (m),
1733 (vs), 1644 (w), 1467 (w), 1455 (w), 1370 (m), 1227
(s), 1146 (s), 1127 (m), 1034 (m), 996 (w), 911 (m), 849 (w).
4.3. Ph2P(CH2)4O(CH2)2CH@CH2 (2)
A Schlenk flask was charged with Br(CH2)4O(CH2)2-
CH@CH2 (0.929 g, 4.49 mmol) and THF (20 mL), and
cooled to 0 ꢀC. Then KPPh2 (9.0 mL, 0.5 M in THF,
4.5 mmol) was added dropwise with stirring until a red
color persisted. A white precipitate formed. The mixture
was stirred at 0 ꢀC for 0.5 h, and the cold bath was
removed. After 1 h, the solvent was removed by oil pump
vacuum. The residue was extracted with CH2Cl2. The
extract was filtered through a short silica gel column
(5 · 2.5 cm, CH2Cl2 rinses). The solvent was removed from
the filtrate by oil pump vacuum to give 2 as an air sensitive,
spectroscopically pure white oil (1.16 g, 3.73 mmol, 83%).
4.5. HOCH2CH2C(CH3)2(CH2)3CH@CH2 (4)
A Schlenk flask was charged with LiAlH4 (0.436 g,
11.5 mmol) and Et2O (30 mL), and fitted with a condenser.
A solution of 3 (4.100 g, 20.67 mmol) in Et2O (20 mL) was
added with stirring. The mixture was refluxed (2 h) and
cooled to room temperature. Then ice water (3 mL) and
H2SO4 (10 mL, 10% in H2O) were added with stirring.
The aqueous phase was separated and extracted with
Et2O (3 · 20 mL). The combined organic phases were
washed with saturated brine and dried (MgSO4). The sol-
vent was removed by rotary evaporation to give 4 as a col-
orless liquid (2.857 g, 18.28 mmol, 88%) [9].
1
NMR (d, CDCl3), H 7.45–7.37 (m, 4H of 2 Ph), 7.33–
7.29 (m, 6H of 2 Ph), 5.81–5.74 (m, 1H, CH@), 5.07–4.98
(m, 2H, @CH2), 3.43–3.38 (m, 4H, CH2OCH2), 2.34–2.26
(m, 2H, CH2CH@), 2.07–2.00 (m, 2H, PCH2), 1.70–1.67
(m, 2H, PCH2CH2), 1.54–1.47 (m, 2H, OCH2CH2);
NMR (d, CDCl3), 1H 5.77 (ddt, 1H, 3JHHtrans = 17.0 Hz,
3
3JHHcis = 10.5, JHH = 6.5 Hz, CH@), 4.98 (dm, 1H,
3JHHtrans = 17.0 Hz, @CHEHZ), 4.90 (dm, 1H, JHHcis
=
3
10.5 Hz, @CHEHZ), 3.63 (m, 2H, HOCH2), 1.98 (apparent
1
3
13C{1H} [27] 138.8 (d, JCP = 13.0 Hz, i to P), 135.3 (s,
quartet, 2H, JHH = 7.1 Hz, CH2CH@), 1.57 (br s, 1H,
2
CH@), 132.6 (d, JCP = 18.4 Hz, o to P), 128.4 (s, p to
HO), 1.48 (m, 2H, HOCH2CH2), 1.35–1.28 (m, 2H,
CH2), 1.19–1.13 (m, 2H, CH2), 0.85 (s, 6H, CH3). IR
(cmꢀ1, liquid film), mOH 3339 (m); 3080 (w), 2957 (m),
2937 (s), 2868 (w), 1640 (w), 1471 (m), 1444 (w), 1417
(w), 1386 (m), 1366 (m), 1104 (m), 1046 (s), 1031 (s), 996
(m), 911 (vs).
3
P), 128.3 (d, JCP = 6.5 Hz, m to P), 116.2 (s, @CH2),
70.3 and 70.0 (2 s, CH2OCH2), 34.2 (s, CH2CH@), 31.1
(d, JCP = 13.0 Hz, PCH2CH2CH2), 27.9 (d, JCP =
1
1
1
11.2 Hz, PCH2), 22.7 (d, JCP = 16.7 Hz, PCH2CH2);
31P{1H} ꢀ15.8 (s).
4.4. CH3CH2OC(O)CH2C(CH3)2(CH2)3CH@CH2 (3)
4.6. BrCH2CH2C(CH3)2(CH2)3CH@CH2 (5)
A Schlenk flask was charged with Mg (0.920 g,
37.8 mmol), THF (40 mL), and Br(CH2)3CH@CH2
(5.14 g, 34.6 mmol). The mixture was stirred for 1.5 h at
A Schlenk flask was charged with Ph3P (5.54 g,
21.1 mmol) and CH2Cl2 (50 mL), and cooled to 0 ꢀC. Then
2,4,4,6-tetrabromocyclohexa-2,5-dienone (8.65 g, 21.1
mmol) was added with stirring. After 1.5 h, 4 (1.500 g,
9.600 mmol) was added [10]. The cold bath was removed.
The mixture was stirred for 16 h. The solvent was removed
50 ꢀC.
A second Schlenk flask was charged with
CH3CH2OC(O)CH@C(CH3)2 (4.18 g, 32.6 mmol), THF
(50 mL), CuCl (0.098 g, 1.00 mmol), and ClSiMe3

L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
1865
1
by rotary evaporation. The yellow residue was extracted
with hexanes (5 · 20 mL). The extract was filtered through
silica gel (10 cm, hexanes rinses). The solvent was removed
from the filtrate by rotary evaporation to give 5 as a color-
less liquid (1.854 g, 8.460 mmol, 88%) [5a,9].
NMR (d, CDCl3), H 3.38–3.31 (m, 4H, CH2Br), 1.85–
1.77 (m, 4H, CH2CH2Br), 1.31–1.11 (m, 16H, remaining
CH2), 0.85 (s, 12H, CH3); 13C{1H} 45.6 (s, CH2), 41.9 (s,
CH2), 34.3 (s, C(CH3)2), 30.5 (s, CH2), 29.7 (s, CH2),
29.6 (s, CH2), 26.9 (s, CH3), 23.9 (s, CH2). IR (cmꢀ1, liquid
film), 2957 (s), 2930 (vs), 2856 (s), 1471 (s), 1390 (w), 1366
(m), 1336 (w), 1239 (m), 749 (w), 722 (w); MS [28], 303 ([7–
CH2CH2Br]+, 23%), and additional ions from the loss of
CH2.
NMR (d, CDCl3), 1H 5.78 (ddt, 1H, 3JHHtrans = 17.1 Hz,
3
3JHHcis = 10.4, JHH = 6.7 Hz, CH@), 4.97 (dm, 1H,
3
3JHHtrans = 17.1 Hz, @CHEHZ), 4.93 (dm, 1H, JHHcis
=
10.4 Hz, @CHEHZ), 3.35 (m, 2H, BrCH2), 2.00 (apparent
3
quartet, 2H, JHH = 7.2 Hz, @CHCH2), 1.85–1.78 (m,
2H, BrCH2CH2), 1.36–1.27 (m, 2H, CH2), 1.20–1.14 (m,
2H, CH2), 0.86 (s, 6H, CH3); 13C{1H} 138.8 (s, CH2CH@),
114.5 (s, @CH2), 45.5 (s, CH2), 41.3 (s, CH2), 34.4 (s,
C(CH3)2), 34.3 (s, CH2), 29.6 (s, CH2), 26.9 (s, CH3),
23.3 (s, CH2). The IR spectrum [6a] agreed with those
reported earlier [5a,9]. MS [28], 218 (11+, 1%), 190 ([11–
4.9. Ph2P(CH2)2C(CH3)2(CH2)8C(CH3)2(CH2)2PPh2
(8)
A Schlenk flask was charged with 7 (0.600 g, 1.46 mmol)
and THF (15 mL). Then KPPh2 (5.84 mL, 0.5 M in THF,
2.92 mmol) was added dropwise with stirring until a light
yellow color persisted. After 1 h, the solvent was removed
by oil pump vacuum. The residue was extracted with
CH2Cl2 (3 · 10 mL). The extracts were filtered through a
silica gel pad (4 cm, CH2Cl2 rinses). The solvent was
removed from the filtrate by oil pump vacuum to give a
colorless oil. The oil was distilled (Kugelrohr, 200 ꢀC, oil
pump vacuum) to give 8 as a spectroscopically pure white
solid (0.753 g, 1.21 mmol, 83%).
2CH2]+, 6%), 176 ([11–3CH2]+, 42%), 149 (BrC5Hþ ,
10
50%), 111 (C8Hþ15, 61%), 69 (C5Hþ9 , 100%).
4.7. BrCH2CH2C(CH3)2CH2CH2CH2CH@CHCH2CH2-
CH2C(CH3)2CH2CH2Br (6)
A Schlenk flask was charged with Grubbs’ catalyst
(0.124 g, 0.150 mmol), CH2Cl2 (50 mL), and 5 (0.548 g,
2.50 mmol). The mixture was stirred for 4 h. A second
charge of Grubbs’ catalyst (0.041 g, 0.050 mmol) was
added. After 16 h, the solvent was removed by rotary evap-
oration. The brown residue was extracted with hexanes
(2 · 5 mL). The extracts were filtered through a silica gel
pad (15 cm, hexanes rinses). The solvent was removed from
the filtrate by oil pump vacuum to give 6 as a colorless
liquid (0.464 g, 1.13 mmol, 90%, mixture of Z/E isomers
with minor impurities).
1
NMR (d, CDCl3), H 7.44–7.38 (m, 8H of 4Ph), 7.34–
7.26 (m, 12H of 4Ph), 1.98–1.91 (m, 4H, PCH2), 1.33–
1.23 (m, 4H, PCH2CH2), 1.23–1.03 (m, 16H, remaining
CH2), 0.82 (s, 12H, CH3); 13C{1H} [27] 138.7 (d,
2
1JCP = 12.6 Hz, i to P), 132.7 (d, JCP = 18.1 Hz, o to P),
3
128.5 (s, p to P), 128.4 (d, JCP = 6.6 Hz, m to P), 41.1 (s,
2
CH2), 37.6 (d, JCP = 16.5 Hz, PCH2CH2C) [34], 33.4 (d,
3JCP = 13.2 Hz, PCH2CH2C) [29], 30.6 (s, CH2), 29.8 (s,
1
CH2), 27.0 (s, CH3), 23.9 (s, CH2), 22.4 (d, JCP = 9.9 Hz,
1
NMR (d, CDCl3, major isomer only), H 5.39–5.35 (m,
PCH2) [29]; 31P{1H} ꢀ13.6 (s). IR (cmꢀ1, powder film),
2922 (s), 2856 (m), 1471 (m), 1432 (m), 1386 (w), 1363
(w), 1096 (w), 1069 (w), 1031 (w), 1000 (w), 737 (s), 718
(m), 691 (vs). MS [28], 622 (8+, 20%), 325 (C22H30P+,
60%), and additional ions from the loss of CH2.
2H, @CH), 3.37–3.32 (m, 4H, CH2Br), 2.01–1.90 (m, 4H,
@CHCH2), 1.84–1.78 (m, 4H, CH2CH2Br), 1.33–1.22 (m,
4H, CH2), 1.20–1.12 (m, 4H, CH2), 0.86 (s, 12H, CH3);
13C{1H} 130.4 (s, @CH), 45.5 (s, CH2), 41.3 (s, CH2),
34.3 (s, C(CH3)2), 33.2 (s, CH2), 29.6 (s, CH2), 26.9 (s,
C(CH3)2), 24.0 (s, CH2). IR (cmꢀ1, liquid film), 2957 (vs),
2934 (vs), 2868 (m), 1471 (s), 1390 (w), 1366 (m), 1336
(w), 1235 (s), 969 (s), 745 (w), 695 (w). MS [28], 410 (6+,
1%), 301 ([6–CH2CH2Br]+, 2%), 259 (C13H24Br+, 3%),
219 (C10H20Br+, 50%), 191 (C8H16Br+, 62%), 149
(BrC5Hþ10, 76%), 111 (C8H1þ5, 87%).
4.10. H2C@CHCH2(CF2)8CH2CH@CH2 (9)
A Schlenk flask was charged with I(CF2)8I (3.190 g,
4.880 mmol), H2C@CHCH2SnBu3 (6.460 g, 19.50 mmol),
and carefully degassed CH2Cl2 (three freeze/pump/thaw
cycles; total volume 50 mL). The solution was cooled to
0 ꢀC and photolyzed (high pressure mercury lamp; through
Pyrex) with stirring. After 5 h, the solvent was removed by
rotary evaporation. The residue was distilled (Kugelrohr).
The distillate (which contained traces of ISnBu3) was fil-
tered through a short alumina column with CF3C6F11.
The solvent was removed from the filtrate by rotary evap-
oration to give 9 as a clear liquid (1.220 g, 2.53 mmol,
52%). Calcd. for C14H10F16: C, 34.87; H 2.09. Found: C,
34.30; H, 2.28%.
4.8. Br(CH2)2C(CH3)2(CH2)8C(CH3)2(CH2)2Br (7)
A Fisher-Porter bottle was charged with 6 (0.142 g,
0.346 mmol), toluene (35 mL), and (Ph3P)3RhCl (0.032 g,
0.035 mmol). Then H2 (4 bar) was introduced, and the mix-
ture was stirred. After 16 h, the solvent was removed by oil
pump vacuum. The residue was extracted with hexanes
(2 · 5 mL). The extracts were filtered through a silica gel
pad (4 cm, hexanes rinses). The solvent was removed from
the filtrate by oil pump vacuum to give 7 as a colorless
liquid (0.115 g, 0.279 mmol, 81%).
1
NMR (d, CDCl3), H 5.87–5.70 (m, 2H, CH@), 5.36–
3
5.26 (m, 4H, @CH2), 2.86 (pseudo td, 4H, JHH = 7 Hz,
3JHF = 18 Hz, CF2CH2); 13C{1H} 126.1, 123.3 (2 s,

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L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
2
1
CH@CH2), 36.7 (t, JCF = 45 Hz, CF2CH2) [19]; F{1H}
ꢀ113.7 to ꢀ114.0 (m, 4F), ꢀ122.1 to ꢀ122.7 (m, 8F),
ꢀ123.6 to ꢀ123.9 (m, 4F). IR (cmꢀ1, powder film), 1208,
1150.
NMR (d, C6D6), H 7.37 and 6.96 (2 d, 8H and 8H,
3JHH = 7 Hz, C6H4), 2.06 (s, 12H, CH3), 1.92–1.58 (m,
12H, CH2CH2CH2); 13C{1H} [27b] 138.7 (s, p to P),
1
2
135.7 (d, JCP = 13 Hz, i to P), 133.1 (d, JCP = 19 Hz, o
to P), 129.6 (d, JCP = 7 Hz, m to P), 30.6 (m, CF2CH2),
3
2
4.11. HO(CH2)3(CF2)8(CH2)3OH (10)
27.9 (d, JCP = 13 Hz, CH2CH2CH2), 21.1 (s, CH3), 17.3
(br d, JCP = 20 Hz,CH2P); 31P{1H} ꢀ18.9 (s); 19F{1H}
1
A flask was charged with 9 (1.481 g, 3.071 mmol), 9-
BBN (0.900 g 7.37 mmol), and toluene (5 mL) in a glove
box. The mixture was stirred overnight, and the solvent
was removed by rotary evaporation. Then NaOH
(25 mL, 5 M) and 30% H2O2 (25 mL; exotherm!) were
slowly added with stirring. After 2 h, the white solid was fil-
tered, washed with water, and dried by oil pump vacuum to
give 10 as a white solid (1.457 g, 2.811 mmol, 92%), m.p.
109–112 ꢀC. Calcd. for C14H14F16O2: C, 32.45; H 2.72.
Found: C, 32.62; H, 2.99%.
ꢀ114.1 to ꢀ114.6 (m, 4F), ꢀ121.6 to ꢀ122.0 (m, 8F),
ꢀ123.5 to ꢀ123.9 (m, 4F). IR (cmꢀ1, powder film), 2952,
1208, 1102, 1065, 800, 733.
4.14. t-Bu2P(CH2)3(CF2)8(CH2)3Pt-Bu2 (12b)
A Schlenk flask was charged with HPt-Bu2 (0.455 g,
3.19 mmol) and THF (30 mL), and cooled to 0 ꢀC. Then
t-BuLi (2.44 mL, 1.52 M in pentane, 3.71 mmol) was added
with stirring. After 5 min, 11 (0.742 g, 1.01 mmol) in THF
(15 mL) was added to the yellow solution. After 1 h, the
flask was connected via a frit to another Schlenk flask.
The solvent was removed by oil pump vacuum and the res-
idue extracted with hexane. In a glove box, the extract was
filtered through a short plug of silica gel (toluene rinses).
The solvent was removed from the filtrate by oil pump vac-
uum to give 12b as a waxy white solid (0.543 g, 0.70 mmol,
69%), m.p. 52–54 ꢀC. Calcd. for C30H48F16P2: C, 46.52; H,
6.25. Found: C, 46.39; H, 6.08%.
NMR (d, CD3OD), 1H 3.53 (t, 4H, JHH = 6 Hz,
3
CH2OH), 2.24–2.06 (m, 4H, CF2CH2), 1.75–1.66 (m, 4H,
CH2CH2OH); 13C{1H} 60.9 (s, CH2OH), 28.2 (t,
2JCF = 22 Hz, CF2CH2), 23.9 (s, CH2CH2OH); 19F{1H}
ꢀ115.8 to ꢀ115.9 (m, 4F), ꢀ123.2 to ꢀ123.4 (m, 8F),
ꢀ124.9 to ꢀ125.1 (m, 4F). IR (cmꢀ1, powder film), mOH
3250; 1206, 1142.
4.12. Br(CH2)3(CF2)8(CH2)3Br (11)
NMR (d, C6D6), 1H 2.10–1.93, 1.82–1.68, and 1.44–1.39
(3 m, 4H, 4H, and 4H, CH2CH2CH2), 1.01 (d, 36H,
3JCP = 11 Hz, CH3); 13C{1H} 32.0 (m, CF2CH2), 31.1 (d,
A flask was charged with PPh3 (4.050 g, 15.44 mmol),
2,4,4,6-tetrabromo-2,5-cyclohexadienone (6.330 g, 15.44
mmol) and CH2Cl2 (15 mL). The mixture was cooled to
0 ꢀC and stirred. After 15 min, 10 (2.00 g, 3.86 mmol) was
added. After 12 h, the solvent was removed by rotary evap-
oration. Chromatography of the residue (silica gel column,
hexane) gave 11 as a white solid, which was dried by oil
pump vacuum (2.157 g, 3.349 mmol, 87%), m.p. 109–
112 ꢀC. Calcd. for C14H12Br2F16: C, 26.11; H, 1.88. Found:
C, 26.83; H, 2.18%.
1JCP = 22 Hz, C(CH3)3), 29.6 (d, JCP = 14 Hz, CH3),
2
2
1
21.1 (d, JCP = 25 Hz, CH2CH2CH2), 20.8 (d, JCP
=
23 Hz, CH2P); 31P{1H} 25.5 (s); 19F{1H} ꢀ113.7 to
ꢀ114.6 (m, 4F), ꢀ121.6 to ꢀ122.3 (m, 8F), ꢀ123.4 to
ꢀ123.9 (m, 4F).
4.15. o-tol2P(CH2)3(CF2)8(CH2)3Po-tol2 (12c)
NMR (d, CDCl3), 1H 3.46 (t, 4H, 3JHH = 6 Hz, CH2Br),
2.38–2.10 (m, 8H, CF2CH2CH2); 13C{1H} 32.0 (s, CH2Br),
A procedure analogous to that for 12a but using HPo-
tol2 (0.429 g, 2.00 mmol) [30] and 11 (0.645 g, 1.01 mmol)
gave 12c as a white solid (0.786 g, 0.863 mmol, 86%),
m.p. 94–96 ꢀC. Calcd. for C42H40F16P2: C, 55.39; H, 4.43.
Found: C, 55.34; H, 4.87%.
2
30.0 (t, JCF = 22 Hz, CF2CH2), 23.9 (s, CH2CH2Br);
19F{1H} ꢀ114.2 to ꢀ114.6 (m, 4F), ꢀ121.9 to ꢀ122.6 (m,
8F), ꢀ123.7 to ꢀ124.2 (m, 4F). IR (cmꢀ1, powder film),
1208, 1191, 1144, 735.
1
NMR (d, C6D6): H 7.21–6.24 (m, 16H, C6H4), 2.39 (s,
12H, CH3), 1.91–1.76 and 1.72–1.55 (2 m, 4H and 8H,
CH2CH2CH2); 13C{1H} 142.6 (d, JCP = 26 Hz, Csp2),
137.0 (d, JCP = 14 Hz, Csp2), 131.3 (s, Csp2), 130.5 (d,
JCP = 4 Hz, Csp2), 128.9 (s, Csp2), 126.5 (s, Csp2) 31.9 (m,
4.13. p-tol2P(CH2)3(CF2)8(CH2)3Pp-tol2 (12a)
A Schlenk flask was charged with HPp-tol2 (0.514 g,
2.40 mmol) and THF (35 mL, via vacuum transfer), and
n-BuLi (1.62 mL, 1.49 M in hexane, 2.41 mmol) was slowly
added with stirring. After 15 min, 11 (0.773 g, 1.20 mmol)
in THF (15 mL) was added to the red solution. After 1 h,
the solvent was removed by rotary evaporation. Chroma-
tography of the residue (silica gel column, 2:1 v/v hex-
ane/toluene) gave 12a as an oil, which was dried by oil
pump vacuum and gave a white solid upon standing
(0.732 g, 0.800 mmol, 67%), m.p. 60–63 ꢀC. Calcd. for
C42H40F16P2: C, 55.39; H, 4.43. Found: C, 55.38; H, 4.50%.
2
CF2CH2), 26.8 (d, JCP = 13 Hz, CH2CH2CH2), 21.2 (d,
1
3JCP = 22 Hz, CH3), 17.2 (d, JCP = 20 Hz, CH2P);
31P{1H} ꢀ39.3 (s); 19F ꢀ114.1 to ꢀ114.7 (m, 4F), ꢀ121.6
to ꢀ122.3 (m, 8F), ꢀ123.3 to ꢀ124.0 (m, 4F). IR (cmꢀ1
,
powder film), 2952, 1208, 1102, 1065, 800, 733.
4.16. p-tol2P(CH2)8Pp-tol2 (13a)
A Schlenk flask was charged with Br(CH2)8Br (0.544 g,
2.00 mmol) and THF (8 mL). Then LiPp-tol2 (10.0 mL,

L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
1867
0.40 M in THF/hexane, 4.00 mmol), freshly prepared from
n-BuLi and HPp-tol2 (1:1) [31], was added via syringe with
stirring until a light yellow color persisted. After 1 h, the
solvent was removed by oil pump vacuum. The residue
was extracted with CH2Cl2 (2 · 10 mL). The extracts were
filtered through a silica gel pad (3 cm, CH2Cl2 rinses). The
solvent was removed from the filtrate at ꢀ40 ꢀC by oil
pump vacuum to give 13a as a white solid (1.025 g,
1.90 mmol, 95%), m.p. 66–69 ꢀC (capillary).
workup gave 14d as a white solid (1.550 g, 1.96 mmol,
98%), m.p. 82–85 ꢀC. Calcd for C54H80P2: C, 81.98; H,
10.19. Found: C, 81.60; H, 10.19%.
NMR (d, CDCl3), 1H 7.39–7.32 (m, 16H, C6H4), 2.03 (t,
3JHH = 7.5 Hz, 4H, PCH2), 1.46–1.36 (m, 8H, PCH2-
CH2CH2), 1.29 (s, 36H, CH3), 1.27–1.18 (m, 16H, remain-
ing CH2); 13C{1H} [27] 151.8 (s, p to P), 135.2 (d,
2
1JCP = 9.8 Hz, i to P), 132.5 (d, JCP = 18.0 Hz, o to P),
3
125.4 (d, JCP = 6.9 Hz, m to P), 34.6 (s, C(CH3)3), 31.2
1
3
NMR (d, CDCl3), H 7.36–7.31 (m, 8H, o to P), 7.17–
(s, CH3), 31.1 (d, JCP = 12.6 Hz, PCH2CH2CH2), 29.7
7.13 (m, 8H, m to P), 2.35 (s, 12H, CH3), 2.01 (t,
3JHH = 7.6 Hz, 4H, PCH2), 1.41 (m, 8H, PCH2CH2CH2),
1.26 (m, 4H, PCH2CH2CH2CH2); 13C{1H} [27] 138.2 (s,
(br s, CH2), 29.6 (s, CH2), 29.5 (s, CH2), 29.2 (s, CH2),
1
2
28.2 (d, JCP = 9.9 Hz, PCH2), 25.9 (d, JCP = 16.0 Hz,
PCH2CH2); 31P{1H} –17.7 (s). IR (cmꢀ1, powder film),
3073 (w), 3022 (w), 2964 (m), 2926 (s), 2853 (m), 1598
(w), 1494 (w), 1467 (m), 1390 (m), 1363 (w), 1266 (m),
1085 (s), 1019 (m), 822 (vs), 753 (m), 741 (m), 730 (m).
MS [28], 791 (14d+, 15%), 493 ([14d–P(C6H4Bu)2]+, 26%),
and additional ions from the loss of CH2, 297
([P(C6H4Bu)2]+, 100%), 164 ([PC6H4Bu]+, 61%).
1
p to P), 135.6 (d, JCP = 11.5 Hz, i to P), 132.6 (d,
3
2JCP = 18.7 Hz, o to P), 129.1 (d, JCP = 7.1 Hz, m to P),
3
31.8 (d, JCP = 13.2 Hz, PCH2CH2CH2), 29.0 (s, CH2),
1
2
28.1 (d, JCP = 10.4 Hz, PCH2), 25.9 (d, JCP = 15.9 Hz,
PCH2CH2), 21.2 (s, CH3); 31P{1H} ꢀ17.7 (s). IR (cmꢀ1
,
powder film), 3069 (w), 3034 (w), 3015 (w), 2926 (m),
2853 (m), 1598 (w), 1498 (m), 1463 (m), 1413 (w), 1309
(w), 1189 (w), 1092 (m), 1023 (m), 965 (w), 803 (vs), 722
(s). MS [28], 539 (13a+, 94%), 447 ([13a–tol]+, 20%), 325
([13a–Ptol2]+, 100%), and additional ions from loss of
CH2, 213 ([Ptol2]+, 59%).
4.19. Ph2P(CH2)7CH@CH2 (15)
A Schlenk flask was charged with Br(CH2)7CH@CH2
(2.216 g, 10.82 mmol) [6b,33] and THF (50 mL), and
cooled to 0 ꢀC. Then KPPh2 (21.6 mL, 0.5 M in THF,
10.8 mmol) was added dropwise with stirring until a red
color persisted. A white precipitate formed. The mixture
was stirred for 0.5 h at 0 ꢀC, and the cold bath was
removed. After 1 h, the solvent was removed by oil pump
vacuum. The residue was extracted with CH2Cl2. The
extract was filtered through a short silica gel column
(5 · 2.5 cm), which was rinsed with CH2Cl2 until UV mon-
itoring showed no absorbing material (ca. 200 mL). The
solvent was removed from the filtrate by oil pump vacuum
to give 15 as a viscous cloudy oil (2.728 g, 8.872 mmol,
82%).
4.17. p-tol2P(CH2)14Pp-tol2 (14a)
THF (10 mL), Br(CH2)14Br (0.712 g, 2.00 mmol) [32],
and LiPp-tol2 (10.0 mL, 0.40 M in THF/hexanes,
4.00 mmol) were combined in a procedure analogous to
that for 13a. An identical workup gave 14a as a white solid
(1.196 g, 1.92 mmol, 96%), m.p. 69–73 ꢀC. Calcd. for
C42H56P2: C, 80.99; H, 9.06. Found: C, 81.05; H, 8.91%.
1
NMR (d, CDCl3), H, 7.32–7.28 (m, 8H, o to P), 7.14–
7.11 (m, 8H, m to P), 2.32 (s, 12H, CH3), 1.99 (t,
3JHH = 7.6 Hz, 4H, PCH2), 1.42–1.37 (m, 8H,
PCH2CH2CH2), 1.24–1.17 (br m, 16H, remaining CH2);
1
NMR (d, CDCl3), H 7.41–7.38 (m, 4H of 2 Ph), 7.31–
1
3
13C{1H} [27] 138.2 (s, p to P), 135.6 (d, JCP = 11.4 Hz, i
7.29 (m, 6H of 2 Ph), 5.78 (ddt, 1H, JHHtrans = 17.0 Hz,
2
3
to P), 132.6 (d, JCP = 18.7 Hz, o to P), 129.1 (d,
3JHHcis = 10.3 Hz, JHH = 6.6 Hz, CH@), 4.95 (br d, 1H,
3
3JCP = 6.9 Hz, m to P), 31.2 (d, JCP = 12.6 Hz, PCH2-
3JHHtrans = 17.1 Hz, @CHEHZ), 4.91 (br d, 1H,
3JHHcis = 10.2 Hz, @CHEHZ), 2.04–1.98 (m, 4H, PCH2,
CH2CH@), 1.41–1.25 (m, 2H, CH2), 1.42–1.28 (m, 8H,
remaining CH2); 13C{1H} [27] 139.5 (s, CH@), 139.4 (d,
CH2CH2), 29.6 (br s, CH2), 29.6 (s, CH2), 29.5 (s, CH2),
1
2
28.2 (d, JCP = 10.7 Hz, PCH2), 25.9 (d, JCP = 16.0 Hz,
PCH2CH2), 21.2 (s, CH3); 31P{1H} ꢀ17.7 (s). IR (cmꢀ1
,
2
powder film), 3073 (w), 3038 (w), 3019 (w), 2918 (s), 2849
(m), 1602 (w), 1498 (m), 1467 (m), 1397 (w), 1309 (w),
1189 (w), 1092 (w), 1023 (w), 807 (vs), 776 (w), 737 (m),
722 (s). MS [28], 622 (14a+, 54%), 531 ([14a–tol]+, 10%),
409 ([14a–Ptol2]+, 100%), and additional ions from the loss
of CH2, 213 ([Ptol2]+, 53%), 122 ([Ptol]+, 42%).
1JCP = 13.0 Hz, i to P), 133.1 (d, JCP = 18.3 Hz, o to P),
3
128.8 (d, JCP = 3.0 Hz, m to P), 128.7 (s, p to P), 114.1
3
(s, @CH2), 34.2 (s, CH2CH@), 31.5 (d, JCP = 12.9 Hz,
PCH2CH2CH2), 29.6 (s, CH2), 29.38 (s, CH2), 29.35 (s,
1
CH2), 29.2 (s, CH2), 28.5 (d, JCP = 11.1 Hz, PCH2), 26.3
2
(d, JCP = 15.9 Hz, PCH2CH2); 31P{1H} ꢀ15.6 (s).
4.18. (p-t-BuC6H4)2P(CH2)14P(p-C6H4-t-Bu)2 (14d)
4.20. Ph2P(CH2)10CH@CH2 (16)
THF (10 mL), Br(CH2)14Br (0.712 g, 2.00 mmol) and
LiP(p-C6H4-t-Bu)2 (11.4 mL, 0.35 M in THF/hexanes,
4.00 mmol) that had been freshly prepared from HP(p-
C6H4-t-Bu)2 and n-BuLi (1.0 equiv.) [31] were combined
in a procedure analogous to that for 13a. An identical
Br(CH2)10CH@CH2 (3.600 g, 14.58 mmol) [6b,33], THF
(50 mL), and KPPh2 (29.5 mL, 0.5 M in THF, 14.6 mmol)
were combined in a procedure analogous to that for 15. An
identical workup gave 16 as a viscous cloudy oil (4.290 g,
12.25 mmol, 84%).

1868
L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
1
NMR (d, CDCl3), H 7.45–7.43 (m, 4H of 2 Ph), 7.34–
1JCF = 219 Hz, o to Pt), 139.0 (s, CH@), 136.2 (dm,
3
2
7.32 (m, 6H of 4 Ph), 5.79 (ddt, 1H, JHHtrans = 17.0 Hz,
1JCF = 247 Hz, m/p to Pt), 133.0 (virtual t, JCP = 5.7 Hz,
3JHHcis = 10.2 Hz, JHH = 6.7 Hz, CH@), 5.00 (br d, 1H,
o to P), 130.8 (virtual t, JCP = 27.2 Hz, i to P), 130.2 (s,
3
1
3JHHtrans = 17.1 Hz, @CHEHZ), 4.94 (br d, 1H,
3JHHcis = 10.2 Hz, @CHEHZ), 2.07–2.02 (m, 4H, PCH2,
and CH2CH@), 1.44–1.20 (m, 16H, 8CH2); 13C{1H} [27]
p to P), 127.9 (virtual t, JCP = 5.0 Hz, m to P), 114.2 (s,
3
3
@CH2), 33.7 (s, CH2CH@), 31.3 (virtual t, JCP = 7.6 Hz,
PCH2CH2CH2), 29.0 (s, CH2), 28.9 (s, CH2), 28.8 (s,
1
1
139.1 (s, CH@), 139.0 (d, JCP = 13.1 Hz, i to P), 132.6
(d, JCP = 18.3 Hz, o to P), 128.3 (d, JCP = 2.7 Hz, m to
CH2), 25.9 (virtual t, JCP = 17.3 Hz, PCH2), 25.5 (s,
2
3
1
PCH2CH2); 31P{1H} 16.4 (s, JPPt = 2658 Hz) [35]. IR
P), 128.2 (s, p to P), 114.1 (s, @CH2), 33.8 (s, CH2CH@),
31.1 (d, JCP = 12.9 Hz, PCH2CH2CH2), 29.5 (s, CH2),
(cmꢀ1, oil film), 3076 (vw), 2930 (m), 2856 (m), 1640 (s),
1502 (s), 1459 (s), 1436 (m), 1104 (m), 1058 (m), 996 (w),
953 (vs), 911 (w), 803 (m), 741 (s), 695 (vs). MS [28],
1017 (18+, 10%), 982 ([18–Cl]+, 100%), 813 ([18–Cl–
C6F5]+, 30%).
3
29.4 (s, double intensity, 2CH2), 29.2 (s, CH2), 29.1 (s,
1
CH2), 28.9 (s, CH2), 28.0 (d, JCP = 11.2 Hz, PCH2), 25.9
2
(d, JCP = 15.9 Hz, PCH2CH2); 31P{1H} ꢀ15.6 (s).
4.21. Ph2P(CH2)7CH3 (17)
4.23. trans-(C6F5)(Ph2P(CH2)10CH@CH2)2PtCl (19)
A Schlenk flask was charged with Br(CH2)7CH3
(1.39 mL, 8.00 mmol) and THF (20 mL). Then KPPh2
(16.0 mL, 0.5 M in THF, 8.0 mmol) was added with stir-
ring until a light yellow color persisted. After 1 h, the sol-
vent was removed by oil pump vacuum. The residue was
extracted with CH2Cl2 (2 · 10 mL). The extracts were fil-
tered through a silica gel pad (3 cm, CH2Cl2 rinses). The
solvent was removed from the filtrate by oil pump vacuum
to give 17 as a colorless oil (2.036 g, 6.823 mmol, 85%) [17].
[Pt(l-Cl)(C6F5)(tht)]2 (2.103 g, 2.165 mmol), 16 (3.298 g,
9.356 mmol), and CH2Cl2 (150 mL) were combined in a
procedure analogous to that for 18. A similar workup
(20 · 2.5 cm silica gel column, 80:20 v/v hexanes/CH2Cl2)
gave 19 as a colorless oil (3.341 g, 3.032 mmol, 70%).
Calcd. for C54H66ClF5P2Pt: C, 58.83; H, 6.03. Found: C,
59.63; H, 6.67%.
1
NMR (d, CDCl3), H 7.51–7.46 (m, 8H of 4 Ph), 7.34–
7.32 (m, 4H of 4 Ph), 7.29–7.23 (m, 8H of 4 Ph), 5.81
1
3
3
3
NMR (d, CDCl3), H 7.43–7.37 (m, 4H of 2 Ph), 7.32–
(ddt, 2H, JHHtrans = 17.0 Hz, JHHcis = 10.2 Hz, JHH =
3
3
7.28 (m, 6H of 2 Ph), 2.02 (t, JHH = 7.7 Hz, 2H, PCH2),
6.7 Hz, CH@), 4.99 (br d, 2H, JHHtrans = 17.1 Hz,
@CHEHZ), 4.92 (br d, 2H, JHHcis = 10.2 Hz, @CHEHZ),
3
1.40 (m, 4H, PCH2CH2CH2), 1.28–1.20 (m, 8H, remaining
CH2), 0.85 (t, 3JHH = 6.9 Hz, 3H, CH3); 13C{1H} [27] 138.9
2.62–2.58 (m, 4H, PCH2), 2.06–2.01 (m, 4H, CH2CH@),
1.80–1.77 (m, 4H, PCH2CH2), 1.40–1.37 (m, 28H, remain-
ing CH2); 13C{1H} [34] 139.2 (s, CH@), 133.0 (virtual t,
1
2
(d, JCP = 12.2 Hz, i to P), 132.7 (d, JCP = 18.3 Hz, o to
3
P), 128.4 (s, p to P), 128.3 (d, JCP = 6.6 Hz, m to P),
31.8 (s, CH2), 31.2 (d, JCP = 12.4 Hz, PCH2CH2CH2),
29.2 (s, CH2), 29.1 (s, CH2), 28.0 (d, JCP = 11.0 Hz,
3
1
2JCP = 5.8 Hz, o to P), 131.4 (virtual t, JCP = 27.9 Hz, i
1
3
to P), 130.2 (s, p to P), 127.9 (virtual t, JCP = 5.1 Hz, m
2
PCH2), 25.9 (d, JCP = 15.4 Hz, PCH2CH2), 22.6 (s,
to P), 114.1 (s, @CH2), 33.8 (s, CH2CH@), 31.3 (virtual
CH2CH3), 14.1 (s, CH3); 31P{1H} ꢀ15.5 (s). IR (cmꢀ1
,
t, JCP = 7.5 Hz, PCH2CH2CH2), 29.6 (s, CH2), 29.47 (s,
3
liquid film), 3073 (w), 2957 (w), 2926 (m), 2856 (w), 1586
(w), 1482 (w), 1463 (w), 1436 (m), 1200 (w), 1123 (w),
1096 (w), 1027 (w), 737 (s), 695 (vs).
CH2), 29.46 (s, CH2), 29.2 (s, CH2), 29.1 (s, CH2), 28.9
1
(s, CH2), 28.2 (virtual t, JCP = 17.8 Hz, PCH2), 25.5 (s,
1
PCH2CH2); 31P{1H} 16.1 (s, JPPt = 2665 Hz) [35]. IR
(cmꢀ1, oil film), 3078 (vw), 2925 (m), 2854 (m), 1640 (m),
1501 (s), 1461 (s), 1436 (m), 1104 (m), 1061 (m), 957 (vs),
908 (w), 804 (m), 741 (s), 695 (vs). MS [28], 1102 (19+,
10%), 1067 ([19–Cl]+, 100%), 898 ([19–Cl–C6F5]+, 60%).
4.22. trans-(C6F5)(Ph2P(CH2)7CH@CH2)2PtCl (18)
A Schlenk flask was charged with [Pt(l-Cl)(C6F5)(tht)]2
(1.010 g, 1.039 mmol; tht = tetrahydrothiophene) [18], 15
(1.668 g, 5.373 mmol), and CH2Cl2 (60 mL) with stirring.
After 20 h, the solvent was removed by rotary evaporation.
The residue was chromatographed (15 · 1.5 cm silica gel
column, 70:30 v/v hexanes/CH2Cl2). The solvent was
removed from the product-containing fractions by oil
pump vacuum to give 18 as a colorless oil (1.571 g,
1.542 mmol, 77%), which gave a white wax upon storage.
Calcd. for C48H54ClF5P2Pt: C, 56.61; H, 5.34. Found: C,
57.44; H, 5.78%.
4.24. trans,trans-(C6F5)(Ph2P(CH2)7CH3)2Pt(C„C)4Pt-
(Ph2P(CH2)7CH3)2(C6F5) (21)
A
Schlenk flask was charged with 17 (1.730 g,
5.800 mmol) and trans,trans-(C6F5)(p-tol3P)2Pt(C„C)4Pt-
(Pp-tol3)2(C6F5) (20 [19]; 0.408 g, 0.200 mmol) with stir-
ring. After 0.5 h, CH2Cl2 (2 mL) was added. After 16 h,
the solvent was removed by oil pump vacuum. The residue
was chromatographed (25 cm silica gel column, 80:20 v/v
hexanes/CH2Cl2) to give a yellow oil (0.235 g), that con-
tained 21 and an intermediate (22, Scheme 6; 31P{1H}
1
NMR (d, CDCl3), H 7.51–7.45 (m, 8H of 4 Ph), 7.34–
7.21 (m, 12H of 4 Ph), 5.84–5.75 (m, 2H, CH@) 4.99–
4.90 (m, 4H, @CH2), 2.58–2.54 (m, 4H, PCH2), 2.03–2.01
(m, 4H, CH2CH@), 1.88–1.86 (m, 4H, PCH2CH2), 1.40–
1.25 (m, 16H, remaining CH2); 13C{1H} [34] 145.1 (dm,
2
1
NMR (d, CDCl3) 17.9 (d, JPP = 409 Hz, JPPt = 2624 Hz
1
0
[35], PA), 14.2 (s, JPPt = 2566 Hz [35], PCC Þ, 14.1 (d,
2JPP = 409 Hz, JPPt = 2588 Hz [35], PB)). A Schlenk flask
1

L. de Quadras et al. / Journal of Organometallic Chemistry 692 (2007) 1859–1870
1869
(b) J. Terao, A. Tang, J.J. Michels, A. Krivokapic, H.L. Anderson,
Chem. Commun. (2004) 56;
(c) P.H. Kwan, T.M. Swager, Chem. Commun. (2005) 5211;
(d) C. Li, M. Numata, A.-H. Bae, K. Sakurai, S. Shinkai, J. Am.
Chem. Soc. 127 (2005) 4548.
was charged with this mixture, a fresh charge of
Ph2P(CH2)7CH3 (0.750 g, 2.51 mmol), and CH2Cl2
(2 mL) with stirring. After 16 h, the solution was concen-
trated. The flask was immersed in a 65 ꢀC oil bath, and
the sample stirred for 0.5 h. Chromatography as above
gave a yellow fraction. The solvent was removed by oil
pump vacuum to give 21 as a yellow oil that solidified after
several days (0.215 g, 0.107 mmol, 53%), m.p. 97–100 ꢀC,
dec. pt. 230 ꢀC (onset). Calcd. for C100H108F10P4Pt2: C,
59.64; H, 5.41. Found: C, 59.40; H, 5.33%. DSC [36]: melt-
ing endotherm with Ti, 90.3 ꢀC; Te, 97.4 ꢀC; Tp, 102.4 ꢀC;
Tc, 107.3 ꢀC; Tf, 112.2 ꢀC; exotherm with Ti, 243 ꢀC.
TGA [36]: onset of mass loss (Ti), 260 ꢀC.
[3] (a) J. Stahl, W. Mohr, L. de Quadras, T.B. Peters, J.C. Bohling, J.M.
´
Martın-Alvarez, G.R. Owen, F. Hampel, J.A Gladysz (in prepara-
tion);
(b) L. de Quadras, E.B. Bauer, W. Mohr, J.C. Bohling, T.B. Peters,
´
J.M. Martın-Alvarez, F. Hampel, J.A. Gladysz (in preparation);
(c) L. de Quadras, E.B. Bauer, J. Stahl, F. Zhuravlev, F. Hampel, J.A.
Gladysz (in preparation).
[4] W. Mohr, C.R. Horn, J. Stahl, J.A. Gladysz, Synthesis (2003) 1279.
[5] (a) E.B. Bauer, F. Hampel, J.A. Gladysz, Organometallics 22 (2003)
5567;
(b) N. Lewanzik, T. Oeser, J. Blumel, J.A. Gladysz, J. Mol. Catal. A
¨
254 (2006) 20.
1
NMR (d, CDCl3), H 7.48–7.42 (m, 16H of 8Ph), 7.34–
7.30 (m, 8H of 8Ph), 7.27–7.22 (m, 16H of 8Ph), 2.54 (m,
8H, PCH2), 1.75 (m, 8H, PCH2CH2), 1.37 (m, 8H,
PCH2CH2CH2), 1.30–1.20 (m, 32H, remaining CH2), 0.87
[6] (a) J. Stahl, Doctoral Dissertation, Universita¨t Erlangen-Nurnberg,
¨
2004;
(b) L. de Quadras, Doctoral Dissertation, Universita¨t Erlangen-
Nurnberg, 2006.
¨
1
(t, JHH = 6.8 Hz, 12H, CH3); 13C{1H} [34] 145.9 (dd,
[7] M.E. Jung, G. Piizzi, Chem. Rev. 105 (2005) 1735.
[8] (a) Y. Brunel, G. Rousseau, J. Org. Chem. 61 (1996) 5793, Only 1H
NMR data for 3 are reported;
(b) See also G. Cahiez, M. Alami, Tetrahedron Lett. 31 (1990) 7425.
[9] For alternative syntheses of 3–5, see J.R. Dias, Y. Sheikh, C.
Djerassi, J. Am. Chem. Soc. 94 (1972) 473, This paper reports IR and
mass spectrometric data for 3 and 5 and 1H NMR data for 3, but no
data for 4 and no reaction conditions.
[10] A. Tanaka, T. Oritani, Tetrahedron Lett. 38 (1997) 1955.
[11] (a) B. Albinsson, J. Michl, J. Phys. Chem. 100 (1996) 3418;
(b) J.D. Dunitz, A. Gavezzotti, W.B. Schweizer, Helv. Chim. Acta 86
(2003) 4073;
2
1JCF = 222 Hz, JCF 22 Hz,
o to Pt), 136.5 (dm,
1JCF = 240 Hz, m/p to Pt), 133.0 (virtual t, JCP = 6.0 Hz,
o to P), 131.3 (virtual t, JCP = 27.7 Hz, i to P), 130.2 (s,
2
1
3
p to P), 127.9 (virtual t, JCP = 5.2 Hz, m to P), 124.0 (t,
2JCF = 50.5 Hz, i to Pt), 100.0 (s, JCPt = 998 Hz, PtC„),
1
94.2 (s, 2JCPt = 271 Hz [35], PtC„C), 63.7 (s,
3JCPt = 32 Hz [35], PtC„CC), 57.9 (s, PtC„CC„C),
3
31.8 (s, CH2CH2CH3), 31.3 (virtual t, JCP = 7.4 Hz,
PCH2CH2CH2), 29.1 (s, 2CH2), 28.2 (virtual t,
1JCP = 17.8 Hz, PCH2), 25.5 (s, PCH2CH2), 22.6 (s,
CH2CH3), 14.1 (s, CH3); 31P{1H} 14.2 (s, 1JPPt = 2566 Hz)
(c) S.S. Jang, M. Blanco, W.A. Goddard III, G. Caldwell, R.B.
Ross, Macromolecules 36 (2003) 5331;
(d) A. Casnati, R. Liantonio, P. Metrangolo, G. Resnati, R. Ungaro,
F. Ugozzoli, Angew. Chem., Int. Ed. 45 (2006) 1915;
Angew. Chem. 118 (2006) 1949.
3
[35]; 19F{1H} ꢀ116.6 (m, JFPt = 289 Hz [35], 4F, o to Pt),
3
ꢀ163.3 (t, JFF = 19.6 Hz, 2F, p to Pt), ꢀ164.0 (m,
4JFPt = 106 Hz [35], 4F, m to Pt). IR (cmꢀ1, powder film),
mC„C 2146 (s), 2007 (m). UV–vis (nm (e, Mꢀ1 cmꢀ1),
1.25 · 10ꢀ5 M in CH2Cl2), 263 (89800), 292 (107000),
320 (132000), 353 (6400), 380 (5400), 412 (2900). MS
[28], 2013 ([21–H]+, 30%), 1353 ([(C6F5)Pt(Ph2P(CH2)7-
CH3)3C8]+, 30%), 958 ([(C6F5)Pt(Ph2P(CH2)7CH3)2]+,
100%), 789 ([Pt(Ph2P(CH2)7CH3)2–2H]+, 76%), 565
([Pt(Ph2P)2]+, 80%).
[12] M.B. Murphy-Jolly, L.C. Lewis, A.J.M. Caffyn, Chem. Commun.
(2005) 4479, and references therein.
´
[13] H. Jiao, S. Le Stang, T. Soos, R. Meier, K. Kowski, P. Rademacher,
L. Jafarpour, J.-B. Hamard, S.P. Nolan, J.A. Gladysz, J. Am. Chem.
Soc. 124 (2002) 1516.
[14] (a) L.J. Alvey, D. Rutherford, J.J.J. Juliette, J.A. Gladysz, J. Org.
Chem. 63 (1998) 6302;
(b) M. Wende, F. Seidel, J.A. Gladysz, J. Fluorine Chem. (2003) 45.
´
[15] J.A. Gladysz, D.P. Curran, I.T. Horvath (Eds.), Handbook of
Fluorous Chemistry, Wiley/VCH, Weinheim, 2004, pp. 1–4.
[16] D.G. Gilheany, C.M. Mitchell, in: F.R. Hartley (Ed.), The Chemistry
of Organophosphorus Compounds, vol. 1, Wiley & Sons, New York,
1990, p. 173.
[17] (a) A. Langer, K. Pu¨ntener, R. Stru¨mer, P. Knochel, Tetrahedron:
Asymmetry 8 (1997) 715;
Acknowledgments
We thank the Deutsche Forschungsgemeinschaft (SFB
583) and Johnson Matthey PMC (platinum loan) for support.
(b) E. Valls, J. Suades, R. Mathieu, Organometallics 18 (1999) 5475.
´
´
[18] R. Uson, J. Fornies, P. Espinet, G. Alfranca, Synth. React. Inorg.
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¨
and P(p-C6H4-t-Bu)3 with lithium, followed by the addition of
deoxygenated aqueous NHþ4 Clꢀ [30].
[32] Prepared from the commercial a,x-diol as described by G.C.H.
Stone, J. Am. Chem. Soc. 62 (1940) 571, This compound is also
sometimes commercially available.
[26] S.C. Watson, J.F. Eastham, J. Organomet. Chem. 9 (1967) 165.
[27] (a) Phosphines with Ph2PCH2CH2CH2 linkages exhibit a character-
istic pattern of 13C NMR signals that have been assigned by 2D NMR
experiments; see footnote 33 of Ref. [4];
(b) For Ar2P assignments, see footnote 36 of Ref. [5a].
[28] EI (phosphines and organic compounds) or FAB (platinum com-
plexes; 3-nitrobenzyl alcohol matrix); m/z for the most intense peak of
the isotope envelope.
[33] M.-C. Roux, R. Paugam, G. Rousseau, J. Org. Chem. 66 (2001)
4304, see page 4307, column 2, line 18.
[34] (a) In most 13C NMR spectra, the C6F5 signals were not observed;
(b) For virtual triplets W.H. Hersh, J. Chem. Educ. 74 (1997)
[29] Tentative assignment based upon coupling constants; the normal
chemical shift pattern27 was not observed.
[30] S. Grim, A.W. Yankowsky, J. Org. Chem. 42 (1977) 1236.
[31] (a) G. Reinhard, R. Soltek, G. Huttner, A. Barth, O. Walter, L.
Zsolnai, Chem. Ber. 129 (1996) 97;
1485, the
adjacent peaks.
J values represent the apparent couplings between
[35] This coupling represents a satellite (d; 195Pt = 33.8%), and is not
reflected in the peak multiplicity given.
[36] These data were treated as recommended by H.K. Cammenga, M.
Epple, Angew. Chem., Int. Ed. Engl. 34 (1995) 1171;
Angew Chem. 107 (1995) 1284.
(b) For these syntheses, the known secondary phosphines HPp-tol2
and HP(p-C6H4-t-Bu)2 were in turn prepared by reactions of Pp-tol3