Alkene metatheses in transition metal coordination spheres: Dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands

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Alkene metatheses in transition metal coordination spheres:

dimacrocyclizations that join trans positions of square-planar

platinum complexes to give topologically novel diphosphine ligands

Takanori Shima, Eike B. Bauer, Frank Hampel and J. A. Gladysz*

Institut für Organische Chemie, Friedrich-Alexander-Universität Erlangen-Nürnberg,

Henkestrasse 42, 91054 Erlangen, Germany

Received 6th January 2004, Accepted 11th February 2004

First published as an Advance Article on the web 24th February 2004

The alkene-containing phosphines PPh((CH ) CH᎐CH ) ) (4) are prepared from PPhH , n-BuLi, and the

᎐

2

n

2

corresponding bromoalkenes (1 : 2 : 2), and combined with the platinum tetrahydrothiophene complex

[Pt(µ-Cl)(C F )(S(CH CH –) )] (12) to give the square-planar adducts trans-(Cl)(C F )Pt(PPh((CH ) CH᎐CH ) )

2 2 2

᎐

6

5

2

6

5

2

n

(11, 93–73%; n = a, 2; b, 3; c, 4; d, 5; e, 6; f, 8). Ring-closing metatheses with Grubbs’ catalyst (2) are studied. With

11e, two isomers of trans-(Cl)(C₆F₅)Pt(PPh(CH₂)₁₄P(CH₂)₁₄Ph) (15e) are isolated after hydrogenation. Both form via

dimacrocyclization between the trans-phosphine ligands, but diﬀer in the dispositions of the PPh rings (syn, 31%;

anti, 7%). The alternative intraligand metathesis product trans-(Cl)(C₆F₅)Pt(PPh(CH₂)₁₄)₂(16e) is independently

prepared by (i) protecting 4e as a borane adduct, H BؒPPh((CH ) CH᎐CH ) , (ii) cyclization with 2 and

᎐

3

2

6

2 2

hydrogenation to give H₃BؒPPh(CH₂)₁₄, (iii) deprotection and reaction with 12. The sample derived from 11e contains

≤2% 16e; mass spectra suggest that the other products are dimers or oligomers. The structures of syn-15e, anti-15e

and 16e are veriﬁed crystallographically, and the macrocycle conformations analyzed. As expected from the (CH₂)_n

segment length, 11a undergoes intraligand metathesis to give (Z,Z)-trans-(Cl)(C F )Pt(PPh(CH ) CH᎐CH(CH ) )

2 2 2

᎐

6

5

2

(86%), as conﬁrmed by a crystal structure of the hydrogenation product. Although 11b does not yield tractable

products, 11c gives syn-(E,E)-trans-(Cl)(C F )Pt(PPh(CH ) CH᎐CH(CH ) P(CH ) CH᎐CH(CH ) Ph) (21%). This

᎐

6

5

2

4

2

4

2

4

2 4

structure, and that of the hydrogenation product (syn-15c; 95%), are veriﬁed crystallographically. Analogous

sequences with 11d,f give syn-15d,f (5 and 14% overall).

with Grubbs’ catalyst (2) gave high yields of thirteen to twenty-

Introduction

three membered macrocycles featuring unusual trans-spanning

Alkene metathesis is seeing increasing use in syntheses of

metal-containing molecules.¹Among many applications, the

generation of topologically novel metallo- and metallamacro-

cycles has attracted particular interest. This rapidly growing

theme has its origins in Sauvage’s elegant syntheses of

catenanes,²and has been further developed by ourselves^3,4

and others.⁵In our previous full paper,^3dwe studied the series

of square-planar sixteen-valence-electron platinum complexes

diphosphine ligands.⁶Mixtures of E/Z C᎐C isomers were

᎐

obtained, but were easily hydrogenated to the saturated analogs

3, which were robust and readily crystallized.

We established the feasibility of analogous reaction

sequences with substituted polymethylene bridges^3dand related

square-planar rhodium complexes.^3cHowever, we wondered

whether this chemistry could be extended to topologically more

complicated substrates. In particular, what might occur with

similar complexes of phosphines containing two polymethylene

trans-(Cl)(C F )Pt(PPh (CH ) CH᎐CH ) (1) shown in Scheme

᎐

6

5

2

n

2 2

1. These feature monophosphine ligands with a polymethylene

bridge to a terminal alkenyl group. Ring-closing metatheses

bridges to terminal alkenyl groups – e.g., PPh((CH ) CH᎐CH )

᎐

2

n

2 2

(4)? As generalized in Scheme 2, two cyclization modes would

be possible: (a) reaction between the trans phosphine ligands

(interligand metathesis) to give an adduct of a macrocyclic

diphosphine, also a metalladimacrocycle (II), or (b) reaction

within the phosphine ligands (intraligand metathesis) to give a

bis(adduct) of a cyclic monophosphine (III).

Scheme 2 Possible ring-closing metathesis modes for trans donor

ligands with two alkene-containing substituents.

The feasibility of the second pathway had been explicitly

demonstrated for the rhenium complexes 5h,i shown in

Scheme 3, which feature one ligand of the type 4 (n = 6). The

Scheme 1 Monomacrocyclizations involving trans phosphine ligands

with one alkene-containing substituent.

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

T h i s j o u r n a l i s © T h e R o y a l S o c i e t y o f C h e m i s t r y 2 0 0 4

1012

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The phosphines 4a–f were combined with the platinum tetra-

hydrothiophene complex [Pt(µ-Cl)(C₆F₅)(S(CH₂CH₂–)₂)]₂(12)⁹

under conditions used to prepare the educts 1 in Scheme 1 earl-

ier.¹⁰As shown in Scheme 5, workups gave the bis(phosphine)

complexes 11a–f as colorless oils in 93–73% yields. The new

phosphines and platinum complexes were characterized by

NMR (¹H, ¹³C, ³¹P) and IR spectroscopy, mass spectrometry,

and microanalyses, as summarized in the experimental section.

The spectroscopic properties of 11a–f were similar to those of

the educts in Scheme 1 and related triarylphosphine complexes

reported previously.¹¹

Scheme 3 Monomacrocyclizations involving phosphine ligands with

two alkene-containing substituents.

metallomacrocycles 6h,i could be isolated in 94–81% yields.

The tungsten complex 7 in Scheme 4, which features three

such ligands, is also relevant. It gave a complicated and nearly

intractable mixture of all possible cyclization products (8, 9,

10), as established by mass spectrometric, HPLC, and crystallo-

graphic data. Although no attempt was made to vary the

lengths of the (CH₂)_nsegments, it was evident that a simpler

type of test substrate was needed. Accordingly, platinum

complexes of 4, trans-(Cl)(C F )Pt(PPh((CH ) CH᎐CH ) )

(11), were selected for intensive study.

᎐

6

5

2

n

2 2 2

Scheme 5 Synthesis of substrates for alkene metatheses.

In this paper, we describe the partitioning of 11 between the

cyclization modes in Scheme 2 as a function of the number

of methylene groups. Depending upon the chain length,

either can dominate. However, dimeric or oligomeric species

derived from intermolecular metathesis are generally the major

products. Nonetheless, signiﬁcant quantities of topologically

novel diphosphine complexes of the type II can be accessed

from several substrates. These would require lengthy syntheses

via conventional methodologies. The crystal structures of

four such compounds are determined, and their conformational

features analyzed in detail. A small portion of this work has

been communicated.^3b

2

Ring-closing metathesis of 11e

Alkene metatheses were conducted under conditions similar to

those used in Scheme 1. As shown in Scheme 6, 11e (ca. 0.0034

M) and 2 (10 mol%, added in two portions) were reacted in

reﬂuxing CH₂Cl₂. Although the catalyst loading might appear

somewhat high, it should be divided by two to normalize to

the number of ring closures. The mixture was ﬁltered through

alumina to separate the catalyst residue. The metathesis

products, for which 13e and 14e are the only possible

monomeric structures, were obtained in 97% yield. The sample

was characterized as described for 11a–f.

The ¹H NMR spectrum showed no terminal alkene residues,

indicating metathesis to be ≥98% complete. Accordingly, new

CH᎐CH signals were detected between 5.20 and 5.35 ppm,

Results

᎐

1

Starting phosphines and complexes

presumably due to both E and Z isomers. The ³¹P NMR

spectrum exhibited a multitude of peaks, the dominant one

of which represented 44% of the total area. The ¹³C NMR

spectrum exhibited an even more complex mixture of peaks.

These were not tabulated, but only signals in the aromatic/

alkene (132–126.5 ppm) and aliphatic (32.8–23.0 ppm) regions

were observed.

As shown in eqn. (1), commercial PPhH₂was successively

treated at 0 ЊC with n-BuLi (2.0–2.1 equiv.) and then an

α,ω-bromoalkene Br(CH ) CH᎐CH (n = a, 2; b, 3; c, 4; d, 5;

᎐

2

n

2

e, 6; f, 8; 2.0–2.1 equiv.). Workups gave the requisite tertiary

phosphines 4a–f as colorless oils in 98–89% yields. The bromo-

alkenes were either commercially available or prepared from

the corresponding alcohols as reported earlier.^3dOther syn-

theses of 4a,b have been published,^7,8and the preparation of 4e

by this procedure has been described previously.^3c

The microanalysis ﬁt the formulae of 13e, 14e, or related

species derived from intermolecular metathesis. The mass

spectrum showed a signiﬁcant ion with a mass corresponding

to [13e Ϫ Cl]^ϩor [14e Ϫ Cl]^ϩ(m/z 966, 45% relative intensity).

Another ion had the formal composition [2ؒ13e Ϫ Cl]^ϩor

[2ؒ14e Ϫ Cl]^ϩ(m/z 1969, 30%), indicating the presence of

dimeric or oligomeric byproducts. Analogous ions were

not observed for the macrocyclizations in Scheme 1. In order

to simplify further analysis and product isolation, a hydrogen-

ation was conducted.

(1)

The metathesis mixture was treated with H₂(1 atm) in the

presence of 10% Pd/C (Scheme 6). Filtration through alumina

Scheme 4 Polymacrocyclizations involving phosphine ligands with two alkene-containing substituents.

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1013

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Scheme 6 Ring-closing metathesis/hydrogenation sequence for 11e.

gave the crude saturated macrocycles (77%), for which 15e and

16e are the only possible monomeric structures. The H NMR

either to protected phosphines or alkene hydroboration. In

some cases, the latter event can be circumvented by introducing

the alkene moieties subsequent to phosphorus protection.^12a

Fortunately, the reaction of H₃BؒSMe₂and 4e at Ϫ20 ЊC gave

the target compound 17e in 65% yield. The ³¹P NMR spectrum

showed coupling to boron (¹J(³¹P,¹¹B) 75 Hz), and the ¹H NMR

spectrum exhibited a broad BH₃signal (1.0–0.2 ppm).

As illustrated in Scheme 7, ring-closing metathesis of 17e

with 2 gave the crude 15-membered cyclic phosphine derivative

18e in 62–91% yields. Unlike the monomacrocyclizations in

Scheme 1, the mass spectrum exhibited ions corresponding

both to intramolecular and intermolecular metathesis products

(18e^ϩ, m/z 315, 80%; formal composition [2ؒ18e]^ϩ, m/z 629,

20%). The ¹H NMR spectrum showed three closely spaced mul-

1

spectrum showed that all double bonds had been reduced,

but the ³¹P NMR spectrum still exhibited many signals. The

dominant peak represented 52% of the total area, and matched

the chemical shift of syn-15e (see below). The mass spectrum

showed signiﬁcant ions with masses corresponding to 15e^ϩ

or 16e^ϩ(m/z 1006, 40%) and [15e Ϫ Cl]^ϩor [16e Ϫ Cl]^ϩ

(m/z 970, 100%). Diplatinum ions of the formal composition

[2ؒ15e Ϫ Cl]^ϩor [2ؒ16e Ϫ Cl]^ϩ(m/z 1977, 20%) were also

evident.

The sample was chromatographed on alumina. The two least

polar products were isolated as white powders in 31 and 7%

yields, and characterized analogously to 11a–f. The mass

spectra indicated that both were monoplatinum species. The

ﬁrst product exhibited a single ³¹P NMR signal, and seven

methylene ¹³C NMR signals, whereas the second exhibited two

mutually coupled ³¹P NMR signals and several additional

methylene ¹³C NMR signals. Complexes of the type 15e can

exist as two stereoisomers, diﬀering in the relative orientations

of the phenyl groups (syn or anti). Accordingly, crystal

structures described below showed the products to be syn-15e

and anti-15e, respectively. The contrasting NMR properties are

further analyzed below.

tiplets in the CH᎐CH region (ca. 1 : 1 : 1), consistent with a

᎐

mixture of E/Z isomers and/or intra/intermolecular products.

When 18e was subjected to the hydrogenation conditions in

Schemes 1 and 6 (10% Pd/C, 1 atm H₂), as well as higher H₂

pressures (6 atm), no reaction occurred. Thus, 18e and H₂

(6 atm) were combined in the presence of Wilkinson’s catalyst.

Chromatography gave the saturated cyclic phosphine derivative

19e in 77–74% yields. The ³¹P NMR spectrum showed one

signal (¹J(³¹P,¹¹B) 70 Hz), and the ¹³C NMR spectrum was much

simpler than that of 19e. However, besides the seven expected

methylene signals, several minor peaks were evident (<10%).

The mass spectrum also showed, in addition to ions derived

from 19e, some diphosphorus species. Hence, the chromato-

graphy conditions did not completely remove the material

derived from intermolecular metathesis.

3

Independent synthesis of an intraligand metathesis product

We wanted to be certain that the workups in Scheme 6 did not

overlook products derived from intraligand metathesis (14e,

16e). Thus, an independent synthesis was sought. An initial

ring-closing metathesis of the free phosphine 4e was con-

sidered. However, Grubbs’ catalyst 2 is not normally eﬀective

with alkenes that contain phosphines,¹²and there are only

scattered successes with Schrock-type catalysts.^12b,13In contrast,

phosphines in which the lone pairs are protected with borane

are reliable substrates for alkene metatheses.¹²Hence, the

sequence summarized in Scheme 7 was investigated.

As shown in Scheme 7, 19e was deprotected by a standard

procedure using HNEt₂.¹⁴The crude cyclic phosphine

PPh(CH₂)₁₄(20e) was directly reacted with the tetrahydro-

thiophene complex 12. Chromatography gave the target

complex 16e in 24% overall yield from 19e. The mass spectrum

exhibited only monoplatinum ions. The most intense peaks

involved phosphine ligand loss, in contrast to syn-15e and

anti-15e where no such fragments were observed. NMR spectra

showed no traces of any byproducts. The ³¹P signal (7.2 ppm)

A potential problem was obvious at the outset. Reactions of

alkene-containing phosphines with borane sources can lead

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1014

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Scheme 7 Synthesis of an authentic sample of 16e.

Fig. 1 Molecular structure of syn-15e.

was considerably upﬁeld from those of syn-15e (11.8 ppm) and

anti-15e (15.8, 11.2 ppm).

in many crystallizations.¹⁶The average of the two centroid–

centroid distances in syn-15e is 4.05 Å. This is somewhat greater

than in 3e (3.60 Å), the related complex with only one

P(CH₂)₁₄P bridge. In contrast, anti-15e exhibits a single C₆H₅/

C₆F₅π interaction (Fig. 2). It is not as pronounced, with a

centroid–centroid distance of 4.26 Å.

The crystal structure of 16e was similarly determined. Views

that highlight the trans relationship of the macrocyclic mono-

phosphine ligands are given in Fig. 3. Selected metrical

parameters are listed in Table 3. Like anti-15e, 16e exhibits

a single, somewhat weak C₆H₅/C₆F₅π interaction, with a

centroid–centroid distance of 4.49 Å.

The ³¹P NMR spectrum of the crude hydrogenation product

in Scheme 6 was reinvestigated. A small peak with a chemical

shift close to that of 16e was apparent. Integration allowed an

upper limit of 2% to be placed upon the yield of 16e from 11e.

The NMR tube was doped with a small amount of the

independently synthesized 16e to conﬁrm that the chemical

shifts were identical. Finally, syn-15e, anti-15e, and 16e were

compared by alumina TLC (1 : 3 v/v CH₂Cl₂–hexanes). R_f

values of 0.56, 0.44, and 0.20 were found. Those of the various

byproducts from Scheme 6 were much lower.

The symmetry properties of syn-15e and anti-15e are relevant

to several observations. As illustrated in Fig. 4, syn-15e has

idealized C_2vsymmetry. The phosphorus atoms and phenyl

rings are homotopic; they can be exchanged by a rotation

around the Cl–Pt–C₆F₅axis. Each carbon atom of a given

macrocycle has a homotopic counterpart in the other macro-

cycle. In addition, the carbon atoms labeled C_ain Fig. 4 are

enantiotopic with the carbon atoms labeled C_b. However, the

geminal protons of each methylene group are diastereotopic.

In contrast, anti-15e has C₁symmetry. As illustrated in

Fig. 4, both phosphorus atoms and phenyl rings are

diastereotopic. The same holds for all carbon atoms of the

macrocycles, as well as the geminal protons of the methylene

groups. Hence, the NMR spectra of anti-15e should be more

complicated than those of syn-15e, in accord with observations

above and additional details provided in the experimental

section. For example, the ³¹P NMR spectrum of anti-15e shows

an AB spin system, with distinct ¹J_PtPvalues for each signal.

4

Structural and dynamic properties of syn-15e, anti-15e and 16e

The crystal structures of syn-15e and anti-15e were determined

as summarized in Table 1 and the experimental section.

Key bond lengths, bond angles, and torsion angles are listed in

Table 2.¹⁵The two macrocycles in each compound are given

primed and unprimed atom labels so that their features are

more easily compared. The molecular structure of syn-15e is

depicted in Fig. 1 and that of anti-15e in Fig. 2. The left views

in Figs. 1 and 2 highlight the contrasting orientations of

the phenyl rings with respect to the platinum square planes.

The isomers also exhibit markedly diﬀerent macrocycle

conformations.

A C₆H₅/C₆F₅/C₆H₅π stacking interaction is evident in

syn-15e (Fig. 1). This feature is also found in the crystal

structures of 3c,e–g, (Scheme 1).^3dIt is now well established that

C₆H₅/C₆F₅π interactions are attractive and a driving force

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1015

D

Table 1 General crystallographic data^a

Complex

syn-(E,E)-13c

syn-15c

syn-15e

anti-15e

16a

16e

Formula

Formula weight

Crystal system

Space group

a/Å

b/Å

c/Å

C₃₈H₄₆ClF₅P₂Pt

890.23

Monoclinic

P2₁/n

13.64790(10)

19.0165(3)

15.0138(2)

90

106.7190(10)

90

3731.89(8)

4

1.584

3.968

1776

C₃₈H₅₀ClF₅P₂Pt

894.26

Monoclinic

P2₁/c

23.5432(11)

15.7182(6)

21.5805(6)

90

112.273(2)

90

7390.2(5)

8

1.607

4.008

3584

C₄₆H₆₆ClF₅P₂Pt

1006.47

Monoclinic

P2₁/c

24.8121(3)

10.5438(2)

18.0730(4)

90

104.6070(10)

90

4575.32(14)

4

1.461

3.246

2048

C₄₆H₆₆ClF₅P₂Pt

1006.47

C₃₀H₃₄ClF₅P₂Pt

782.05

Orthorhombic

Pbcn

18.5572(3)

10.9033(2)

28.7856(5)

90

C₄₆H₆₆ClF₅P₂Pt

1006.47

Triclinic

¯

P1

11.69470(10)

13.29450(10)

14.9666(2)

88.3340(10)

81.1850(10)

76.1950(10)

2232.96(4)

2

10.57500(10)

12.2670(2)

18.1630(3)

72.9290(9)

84.6100(8)

82.4310(8)

2228.93(6)

2

α/Њ

β/Њ

90

γ/Њ

V/Å³

5824.33(17)

8

1.784

5.071

Z

D_c/Mg m^Ϫ3

µ/mm^Ϫ1

F(000)

1.495

3.325

1022

1.500

3.331

1024

3072

Crystal size/mm

θ Limit/Њ

Index ranges hkl

0.35 × 0.20 × 0.20

1.89–27.48

Ϫ17 to 17, Ϫ24 to 24,

Ϫ19 to 19

16508

8549

7851

8549/0/424

1.061

0.10 × 0.10 × 0.10

1.60–25.02

Ϫ27 to 28, Ϫ18 to 18,

Ϫ24 to 25

43886

13024

6875

13024/0/847

0.930

R1 = 0.0449, wR2 = 0.0958

R1 = 0.1156, wR2 = 0.1319

0.894 and Ϫ1.307

0.30 × 0.20 × 0.10

2.11–27.51

Ϫ31 to 32, Ϫ12 to 13,

Ϫ23 to 23

17699

10322

7022

10322/0/496

0.998

R1 = 0.0404, wR2 = 0.0695

R1 = 0.0860, wR2 = 0.0796

2.621 and Ϫ1.408

0.1 × 0.1 × 0.1

1.38–25.05

Ϫ13 to 13, Ϫ15 to 15,

Ϫ17 to 17

15379

7900

7011

7900/0/496

1.152

R1 = 0.0247, wR2 = 0.0601

R1 = 0.0324, wR2 = 0.0751

1.371 and Ϫ0.978

0.30 × 0.20 × 0.20

1.41–27.48

Ϫ24 to 24, Ϫ14 to 14,

Ϫ37 to 37

12286

6642

5538

6642/0/352

1.116

0.20 × 0.20 × 0.10

2.21–27.52

Ϫ13 to 13, Ϫ15 to 15,

Ϫ23 to 23

19533

10238

9428

10238/0/496

1.029

R1 = 0.0268, wR2 = 0.0621

R1 = 0.0305, wR2 = 0.0636

1.431 and Ϫ0.920

Reﬂections collected

Independent reﬂections

Reﬂections [I > 2σ(I )]

Data/restraints/parameters

Goodness-of-ﬁt on F ²

Final R indices [I >2σ(I )]

R Indices (all data)

R1 = 0.0199, wR2 = 0.0491

R1 = 0.0233, wR2 = 0.0505

0.997 and Ϫ0.966

R1 = 0.0240, wR2 = 0.0602

R1 = 0.0334, wR2 = 0.0751

0.893 and Ϫ0.996

Largest diﬀ. peak and

hole ∆ρ/e Å^Ϫ3

^aData common to all structures: diﬀractometer, Nonius Kappa CCD; wavelength, 0.71073 Å; temperature, 173(2) K.

Table 2 Key bond lengths, bond angles, and torsion angles for interligand metathesis products

syn-15c

Complex

syn-(E,E)-13c

First molecule^a

Second molecule^a

syn-15e

anti-15e

Bond lengths (Å)

Pt–P(1)/Pt–P(2)

Pt–Cl

2.3064(6)/2.2984(6)

2.3671(5)

2.313(2)/2.303(2)

2.377(2)

2.323(2)/2.318(3)

2.380(3)

2.3139(11)/2.3075(11)

2.3778(11)

2.2970(10)/2.2986(9)

2.3560(10)

Pt–C(30)

2.015(2)

1.989(10)

2.005(11)

2.002(4)

2.017(4)

C(1)–C(2)/C(1Ј)–C(2Ј)

C(2)–C(3)/C(2Ј)–C(3Ј)

C(3)–C(4)/C(3Ј)–C(4Ј)

C(4)–C(5)/C(4Ј)–C(5Ј)

C(5)–C(6)/C(5Ј)–C(6Ј)

C(6)–C(7)/C(6Ј)–C(7Ј)

C(7)–C(8)/C(7Ј)–C(8Ј)

C(8)–C(9)/C(8Ј)–C(9Ј)

C(9)–C(10)/C(9Ј)–C(10Ј)

C(10)–C(11)/C(10Ј)–C(11Ј)

C(11)–C(12)/C(11Ј)–C(12Ј)

C(12)–C(13)/C(12Ј)–C(13Ј)

C(13)–C(14)/C(13Ј)–C(14Ј)

1.531(3)/1.533(3)

1.523(3)/1.528(3)

1.530(3)/1.530(4)

1.493(4)/1.502(4)

1.316(4)/1.314(4)

1.492(4)/1.502(4)

1.526(4)/1.529(4)

1.525(3)/1.521(3)

1.524(3)/1.530(3)

–

1.526(14)/1.522(14)

1.532(14)/1.569(18)

1.508(15)/1.345(19)

1.505(14)/1.471(16)

1.523(13)/1.526(16)

1.502(13)/1.490(15)

1.525(15)/1.509(16)

1.504(14)/1.456(16)

1.533(14)/1.500(15)

–

1.529(13)/1.520(17)

1.517(13)/1.533(17)

1.491(14)/1.536(18)

1.558(15)/1.497(17)

1.430(17)/1.513(17)

1.565(15)/1.506(15)

1.470(16)/1.494(15)

1.549(14)/1.497(15)

1.515(15)/1.484(16)

–

1.515(6)/1.540(5)

1.518(6)/1.514(6)

1.518(6)/1.504(6)

1.520(6)/1.516(6)

1.518(7)/1.521(6)

1.509(7)/1.534(6)

1.515(7)/1.505(7)

1.547(6)/1.545(7)

1.515(6)/1.531(7)

1.520(6)/1.508(6)

1.518(6)/1.508(6)

1.513(6)/1.528(6)

1.526(6)/1.525(6)

1.522(6)/1.522(5)

1.533(7)/1.532(6)

1.503(8)/1.513(7)

1.508(7)/1.520(6)

1.519(8)/1.522(7)

1.489(8)/1.513(6)

1.530(8)/1.525(6)

1.548(7)/1.521(6)

1.524(7)/1.523(6)

1.509(7)/1.513(6)

1.511(7)/1.515(6)

1.521(6)/1.517(6)

1.527(6)/1.529(5)

–

Bond angles (Њ)

C(30)–Pt–P(1)

C(30)–Pt–P(2)

P(1)–Pt–P(2)

C(30)–Pt–Cl

P(1)–Pt–Cl

94.00(6)

91.50(6)

174.41(2)

178.06(6)

84.062(19)

90.44(2)

94.6(3)

91.3(3)

172.21(10)

178.3(3)

86.83(9)

87.37(9)

89.4(3)

93.1(3)

173.96(11)

179.3(3)

90.42(10)

86.94(9)

90.47(12)

91.51(12)

177.99(4)

178.89(13)

88.89(4)

93.31(10)

87.42(10)

173.33(3)

175.18(11)

86.71(3)

P(2)–Pt–Cl

89.14(4)

93.12(3)

Torsion angles (Њ)

P(2)–Pt–P(1)–C(1)/P(2)–Pt–P(1)–C(1Ј)

Pt–P(1)–C(1)–C(2)/Pt–P(1)–C(1Ј)–C(2Ј)

45.2(2)/–70.5(2)

35.56(19)/–50.42(19)

Ϫ176.85(17)/179.15(18)

172.4(2)/–75.0(3)

Ϫ64.2(3)/–67.6(3)

131.5(3)/129.7(3)

Ϫ175.2(2)/179.4(2)

118.4(3)/132.5(3)

Ϫ66.7(3)/–68.5(3)

179.6(2)/166.0(2)

–

19.8(9)/–95.2(8)

59.0(8)/–70.8(9)

176.6(7)/69.1(12)

60.8(12)/156.7(16)

53.5(13)/174.3(13)

52.8(14)/83.8(19)

170.5(9)/–157.9(13)

56.0(13)/97.0(14)

53.6(14)/–58.9(15)

Ϫ179.1(8)/176.0(11)

–

Ϫ22.4(11)/–139.9(10)

47.8(9)/51.5(11)

Ϫ157.9(8)/–94.5(13)

179.6(9)/172.6(11)

Ϫ67.6(14)/172.8(12)

107.7(13)/45.1(16)

177.0(10)/60.4(15)

59.4(15)/–169.9(11)

57.9(15)/–166.1(11)

Ϫ174.7(10)/–61.8(15)

–

Ϫ69.1(12)/49.8(12)

46.5(4)/56.5(3)

90.3(3)/–145.5(3)

Ϫ160.1(3)/–44.7(3)

172.5(3)/161.9(3)

Ϫ54.1(5)/Ϫ174.3(3)

Ϫ59.0(5)/60.7(5)

178.1(4)/56.0(5)

179.6(4)/169.1(4)

71.5(6)/–175.8(4)

75.9(6)/–179.1(4)

Ϫ167.7(4)/72.4(5)

Ϫ173.7(4)/72.9(5)

Ϫ167.2(4)/–177.4(3)

73.8(5)/62.0(5)

.

P(1)–C(1)–C(2)–C(3)/P(1)–C(1Ј)–C(2Ј)–C(3Ј)

C(1)–C(2)–C(3)–C(4)/C(1Ј)–C(2Ј)–C(3Ј)–C(4Ј)

C(2)–C(3)–C(4)–C(5)/C(2Ј)–C(3Ј)–C(4Ј)–C(5Ј)

C(3)–C(4)–C(5)–C(6)/C(3Ј)–C(4Ј)–C(5Ј)–C(6Ј)

C(4)–C(5)–C(6)–C(7)/C(4Ј)–C(5Ј)–C(6Ј)–C(7Ј)

C(5)–C(6)–C(7)–C(8)/C(5Ј)–C(6Ј)–C(7Ј)–C(8Ј)

C(6)–C(7)–C(8)–C(9)/C(6Ј)–C(7Ј)–C(8Ј)–C(9Ј)

C(7)–C(8)–C(9)–C(10)/C(7Ј)–C(8Ј)–C(9Ј)–C(10Ј)

C(8)–C(9)–C(10)–C(11)/C(8Ј)–C(9Ј)–C(10Ј)–C(11Ј)

C(9)–C(10)–C(11)–C(12)/C(9Ј)–C(10Ј)–C(11Ј)–C(12Ј)

C(10)–C(11)–C(12)–C(13)/C(10Ј)–C(11Ј)–C(12Ј)–C(13Ј)

C(11)–C(12)–C(13)–C(14)/C(11Ј)–C(12Ј)–C(13Ј)–C(14Ј)

C(n Ϫ 2)–C(n Ϫ 1)–C(n)–P(2)/C(nЈ Ϫ 2)–C(nЈ Ϫ 1)–C(nЈ)–P(2)^b

C(n Ϫ 1)–C(n)–P(2)–Pt/C(nЈ Ϫ 1)–C(nЈ)–P(2)–Pt^b

C(n)–P(2)–Pt–P(1)/C(nЈ)–P(2)–Pt–P(1)^b

Ϫ175.3(3)/–164.6(3)

178.8(4)/–180.0(4)

Ϫ176.7(4)/–177.4(4)

Ϫ170.2(4)/–176.5(4)

Ϫ51.7(6)/–60.6(7)

Ϫ62.1(6)/–67.0(7)

Ϫ179.6(4)/–176.7(4)

Ϫ61.9(6)/–60.5(7)

Ϫ59.7(6)/–50.4(7)

Ϫ178.6(4)/–171.3(4)

176.3(4)/–170.4(4)

Ϫ179.1(4)/–174.0(4)

Ϫ169.7(3)/–172.2(3)

56.0(4)/39.2(4)

–

75.0(5)/51.8(5)

175.99(19)/–163.28(17)

42.9(2)/53.70(18)

Ϫ74.4(2)/43.0(2)

154.6(7)/–168.0(9)

Ϫ44.2(8)/36.9(11)

Ϫ11.6(9)/102.2(8)

169.8(7)/–69.7(13)

Ϫ48.2(9)/82.7(9)

8.6(12)/121.2(10)

177.4(3)/–179.7(3)

53.6(3)/167.6(3)

Ϫ23.4(3)/96.9(3)

28.1(12)/Ϫ91.9(12)

^aIndependent molecules in the unit cell. ^bn = Number of carbons in macrocycle.

View Article Online

Fig. 2 Molecular structure of anti-15e.

Fig. 3 Molecular structure of 16e.

Scheme 8 Ring-closing metathesis/hydrogenation sequence for 11a.

appeared. Application of the coalescence formula,¹⁷using the

∆ν and J values for the phosphorus atoms from the low tem-

perature limit (618.2 and 426.8 Hz, 25 ЊC), allowed a lower limit

of 16.4 kcal mol^Ϫ1(95 ЊC) to be placed on any process capable

of rendering the phosphorus atoms of anti-15e equivalent. One

such possibility, which should become accessible with longer

P(CH₂)_nP bridges, is analyzed in the discussion section.

5

Ring-closing metatheses of 11a,b,c,d,f

Complex 11a, which features short (CH₂)₂segments between

the phosphorus and terminal alkenyl moieties, would be a very

unlikely candidate for interligand metathesis, or cyclization

mode II in Scheme 2. The trans phosphorus atoms would be

bridged by only six carbon atoms, resulting in a highly strained

nine-membered ring. The shortest known saturated bridge

between trans phosphorus atoms in a square planar complex

consists of nine methylene groups, giving a twelve-membered

ring.^6,18

Fig. 4 Idealized structures and stereochemical relationships in 15.

A toluene-d₈solution of anti-15e was warmed to 95 ЊC while

³¹P NMR spectra were periodically recorded. No coalescence

or signiﬁcant broadening of the ³¹P NMR signals was noted,

and no new peaks derived from syn-15e or other species

As shown in Scheme 8, 11a (0.0093 M) and 2 were combined

under conditions analogous to those in Schemes 1 and 6.

Workup gave the expected intraligand metathesis product,

bis(monophosphine) complex (Z,Z)-14a, in 86% yield.

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1018

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Table 3 Key bond lengths, bond angles, and torsion angles for intraligand metathesis products

Complex

16a

16e

Bond lengths (Å)

Pt–P(1)/Pt–P(2)

Pt–Cl

2.3129(9)/2.3056(9)

2.3660(8)

2.2972(7)/2.3049(7)

2.3554(7)

Pt–C(30)

2.017(3)

C(1)–C(2)/C(1Ј)–C(2Ј)

C(2)–C(3)/C(2Ј)–C(3Ј)

C(3)–C(4)/C(3Ј)–C(4Ј)

C(4)–C(5)/C(4Ј)–C(5Ј)

C(5)–C(6)/C(5Ј)–C(6Ј)

C(6)–C(7)/C(6Ј)–C(7Ј)

C(7)–C(8)/C(7Ј)–C(8Ј)

C(8)–C(9)/C(8Ј)–C(9Ј)

C(9)–C(10)/C(9Ј)–C(10Ј)

C(10)–C(11)/C(10Ј)–C(11Ј)

C(11)–C(12)/C(11Ј)–C(12Ј)

C(12)–C(13)/C(12Ј)–C(13Ј)

C(13)–C(14)/C(13Ј)–C(14Ј)

1.527(6)/1.537(5)

1.510(7)/1.516(6)

1.513(7)/1.533(6)

1.523(5)/1.527(6)

1.540(5)/1.530(5)

1.535(4)/1.533(4)

1.520(4)/1.515(5)

1.530(5)/1.512(6)

1.519(5)/1.564(9)

1.524(5)/1.291(11)^b

1.522(5)/1.428(11)^b

1.517(6)/1.388(9)^b

1.562(6)/1.578(8)

1.504(5)/1.487(7)

1.513(6)/1.554(8)

1.503(5)/1.531(6)

1.528(5)/1.524(5)

1.541(4)/1.532(4)

–

Bond angles (Њ)

C(30)–Pt–P(1)/C(30)–Pt–P(2)

P(1)–Pt–P(2)

C(30)–Pt–Cl

91.23(9)/93.41(9)

174.84(3)

177.99(10)

93.69(7)/87.72(7)

175.54(3)

177.52(8)

P(1)–Pt–Cl/P(2)–Pt–Cl

86.85(3)/88.53(3)

86.39(3)/92.38(3)

Torsion angles (Њ)

P(2)–Pt–P(1)–C(1)/P(1)–Pt–P(2)–C(1Ј)

Pt–P(1)–C(1)–C(2)/Pt–P(2)–C(1Ј)–C(2Ј)

32.9(4)/–170.9(4)

Ϫ152.5(3)/–49.7(3)

63.4(5)/–33.1(4)

Ϫ94.9(5)/–49.2(5)

Ϫ104.1(3)/77.9(3)

Ϫ176.24(18)/–170.6(2)

Ϫ166.7(2)/–173.1(3)

Ϫ177.8(3)/–57.8(5)

Ϫ54.3(4)/–55.5(5)

Ϫ54.9(4)/–148.0(9)

178.3(3)/–162.0(2)

Ϫ169.2(3)/–60.6(14)

60.5(5)/77.8(11)

P(1)–C(1)–C(2)–C(3)/P(2)–C(1Ј)–C(2Ј)–C(3Ј)

C(1)–C(2)–C(3)–C(4)/C(1Ј)–C(2Ј)–C(3Ј)–C(4Ј)

C(2)–C(3)–C(4)–C(5)/C(2Ј)–C(3Ј)–C(4Ј)–C(5Ј)

C(3)–C(4)–C(5)–C(6)/C(3Ј)–C(4Ј)–C(5Ј)–C(6Ј)

C(4)–C(5)–C(6)–C(7)/C(4Ј)–C(5Ј)–C(6Ј)–C(7Ј)

C(5)–C(6)–C(7)–C(8)/C(5Ј)–C(6Ј)–C(7Ј)–C(8Ј)

C(6)–C(7)–C(8)–C(9)/C(6Ј)–C(7Ј)–C(8Ј)–C(9Ј)

C(7)–C(8)–C(9)–C(10)/C(7Ј)–C(8Ј)–C(9Ј)–C(10Ј)

C(8)–C(9)–C(10)–C(11)/C(8Ј)–C(9Ј)–C(10Ј)–C(11Ј)

C(9)–C(10)–C(11)–C(12)/C(9Ј)–C(10Ј)–C(11Ј)–C(12Ј)

C(10)–C(11)–C(12)–C(13)/C(10Ј)–C(11Ј)–C(12Ј)–C(13Ј)

C(11)–C(12)–C(13)–C(14)/C(11Ј)–C(12Ј)–C(13Ј)–C(14Ј)

C(n Ϫ 2)–C(n Ϫ 1)–C(n)–P(1)/C(n Ϫ 2Ј)–C(n Ϫ 1Ј)–C(nЈ)–P(2)^a

C(n Ϫ 1)–C(n)–P(1)–C(1)/C(n Ϫ 1Ј)–C(nЈ)–P(2)–C(1Ј)^a

C(n)–P(1)–C(1)–C(2)/C(nЈ)–P(2)–C(1Ј)–C(2Ј)^a

Pt–P(1)–C(n)–C(n Ϫ 1)/Pt–P(2)–C(nЈ)–C(n Ϫ 1Ј)^a

P(2)–Pt–P(1)–C(n)/P(1)–Pt–P(2)–C(nЈ)^a

39.1(5)/94.8(4)

50.0(5)/–72.3(4)

–

52.3(5)/56.7(9)

170.6(3)/171.8(5)

57.5(4)/61.9(5)

53.5(5)/58.1(5)

52.9(4)/–179.9(3)

161.3(2)/171.4(2)

50.3(2)/–46.1(3)

57.0(3)/–63.1(2)

Ϫ79.9(2)/63.0(2)

Ϫ133.0(3)/–42.3(4)

Ϫ92.7(4)/59.1(4)

54.1(3)/–70.6(3)

Ϫ30.9(4)/79.2(3)

174.5(2)/61.5(3)

Ϫ86.4(4)/65.5(4)

^an = Number of methylene groups in macrocycle. ^bThe thermal ellipsoids for C(5Ј) to C(8Ј) are very elongated.

Fig. 5 Molecular structure of 16a.

Hydrogenation as in Schemes 1 and 6 gave 16a in 64% yield

after workup. The crystal structure was determined as sum-

marized in Table 1 and the experimental section. Metrical

parameters are listed in Table 3. The molecular structure is

depicted in Fig. 5. There is a single C₆H₅/C₆F₅π interaction,

with a centroid–centroid distance of 3.58 Å.

Complex 11b, which could cyclize to an eleven-membered

interligand metathesis product or a nine-membered intraligand

metathesis product, was similarly combined with 2. However,

no tractable products could be isolated, even when reactions

were conducted at higher dilution (0.0033 M). Complex 11c

gave similar results in comparable concentration ranges. How-

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1019

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Scheme 9 Ring-closing metathesis/hydrogenation sequence for 11c.

Fig. 6 Molecular structure of syn-(E,E)-13c (top left and right) and syn-15c (bottom left, ﬁrst independent molecule; bottom right, second

independent molecule).

ever, when 0.00067 M solutions were used as shown in Scheme 9,

a monoplatinum product could be isolated in 21% yield. A

crystal structure established the formation of the intraligand

metathesis product syn-(E,E)-13c.¹⁹The molecular structure

is depicted in Fig. 6 (top), and metrical parameters are listed in

Table 2.

Hydrogenation of syn-(E,E)-13c gave the saturated analog

syn-15c in 95% yield. The crystal structure of this compound, a

lower homolog of syn-15e (Fig. 1), was similarly determined.

The unit cell contained two independent molecules. As

illustrated in Fig. 6 (bottom), they diﬀer in the macro-

cycle conformations. Both syn-(E,E)-13c and syn-15c

exhibit C₆H₅/C₆F₅/C₆H₅π stacking interactions, with average

centroid–centroid distances of 4.16 and 3.85–3.94 Å, respect-

ively. They also give a single ³¹P NMR signal, as expected for

syn isomers from the analysis in Fig. 4. The ring-closing

metathesis of 1c (Scheme 1), which yields a P(CH ) CH᎐

CH(CH₂)₄P bridge as in syn-(E,E)-13c, gives a 93 : 7 mixture of

Scheme 10 Ring-closing metathesis/hydrogenation sequences for

11d,f.

᎐

2

4

E/Z isomers.

Since 11d contains a longer methylene segment and inter-

ligand metathesis would generate a presumably less strained

ﬁfteen-membered ring, enhanced selectivity for cyclization

mode II was expected. However, only very small amounts

of non-oligomeric products could be isolated, even when

0.0019 M solutions of 11d were treated with 2. As shown in

Scheme 10, the crude reaction mixture was directly hydro-

genated. Chromatography gave syn-15d in 5% overall yield.¹⁹

The syn stereochemistry was assigned based upon NMR

properties as described above. Although a crystal structure

could not be solved, the data were of suﬃcient quality to

exclude the intraligand metathesis product 16d. Also, no ions

derived from loss of a monophosphine ligand were evident in

the mass spectrum.

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1020

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Fig. 7 Some representative conformations of 11 for interligand metathesis.

Given the yield trends in Scheme 1, it was thought that 11f

products dramatically increases with the size of the phosphorus

substituent.

and 11e might give comparable amounts of interligand

metathesis products. As shown in Scheme 10, the reaction

of 11f (0.0033 M) and 2 was followed by hydrogenation.

Chromatography gave syn-15f in 14% overall yield.¹⁹Other

fractions gave material with ³¹P NMR signal patterns suggestive

of anti-15f, but samples could not be puriﬁed. Since it has not

yet been possible to crystallographically characterize syn-15f, a

remote possibility remains that it might be the intraligand

metathesis product 16f. However, the complexes assigned as

syn-15c,d,e,f exhibit several monotonic trends (e.g., ³¹P NMR

16.2, 12.5, 11.8, 10.8 ppm; J_PPt2612, 2590, 2560, 2551 Hz), in

accord with a homologous series.

The PPh₂and PPhR units in our platinum complexes

promote gauche conformations in the solid state, as described

below. However, for the monomacrocyclizations of 1 in

Scheme 1, we see no obvious factor that should direct the

alkenyl moieties on the same sides of the platinum square

plane. Also, no axial bonding interactions involving pendant

22

᎐

or bridging C᎐C (or C᎐C) moieties have ever been observed

᎐

(e.g., syn-(E,E)-13c, Fig. 6). Nonetheless, the yields of intra-

molecular metathesis products are not much lower than with

21, which as noted above is geometrically predisposed to cycliz-

ation. The new data in this paper do not oﬀer additional insight

on this point, and pose several further questions, such as: (i)

why is intraligand metathesis (III, Scheme 2) disfavored in

Schemes 6, 9 and 10? (ii) why do the yields of monoplatinum

interligand metathesis products drop relative to Scheme 1,

despite comparable dilution levels? In analyzing these issues, we

presume that our product mixtures are under kinetic control.¹⁹

Appreciable quantities of intraligand metathesis products

are found only with 11a (Scheme 8), for which interligand

metathesis is impossible. Complex 11b, for which interligand

metathesis would also be unlikely, gives exclusively inter-

molecular metathesis. Perhaps intraligand metathesis, which

would give a nine-membered cyclic phosphine ligand, is

kinetically less favorable than with 11a, allowing bimolecular

condensations to compete. However, with 11c,d,e,f, all of which

give at least some intramolecular metathesis, we have no ration-

ale for the absence of intraligand cyclization. Note that high

yields of ﬁfteen-membered cyclic phosphine complexes are

obtained by intraligand metathesis in Scheme 3.

Discussion

1

Scope and eﬃciency of macrocyclizations

Schemes 6, 9 and 10 establish that complexes of doubly trans-

spanning diphosphine ligands are easily accessed by alkene

metatheses. Although the yields are modest, advanced gener-

ation metathesis catalysts may help in certain cases,¹⁹and other

routes would require many additional steps. Such complexes are

to our knowledge unknown. However, as shown in Scheme 11, a

conceptually related doubly trans-spanning bis(pyridine) com-

plex has also been accessed by alkene metathesis.²⁰In the educt

21, each pyridine nitrogen is ﬂanked by two ortho homoallyl

groups. These would be expected to extend above and below the

palladium square plane, preorganizing the alkenyl moieties

for interligand metathesis. Accordingly, 22 is isolated in 80%

yield. Hence, alkene metathesis may prove to be a general route

to metalladimacrocycles of the type II (Scheme 2), albeit in

variable yields.

Given that intraligand metathesis is not very rapid with

11c,d,e,f, why are the yields of interligand metathesis products

lower than in Scheme 1? Fig. 7 shows two representative

conformations of 11 (VI, VII) as viewed down the phosphorus–

carbon bond axes, the energies of which should be nearly equal.

The chlorine and C₆F₅ligands can be visualized as directly

behind and in front of the “Pt”. In both cases, gauche

Pt–PPhR–CH₂–CH₂conformations are used to direct two

(CH ) CH᎐CH moieties on the same side of the platinum

᎐

2

n

2

square plane, and in orientations that are favorable for

interligand metathesis. Many other conformations are possible

that are to varying degrees less favorable for macrocyclization,

as analyzed elsewhere.²³

Scheme 11 A doubly trans-spanning bis(pyridine) complex.

Importantly, VI can only lead to syn isomers of 13, whereas

VII can only lead to anti isomers. Hence, the syn/anti stereo-

chemistry is set by the ﬁrst metathesis. Furthermore, in the

macrocycle resulting from VII, the two remaining (CH₂)_n-

In earlier papers, we have argued that alkene metatheses in

metal coordination spheres are often aided by some analog of

the “geminal dialkyl eﬀect”.²¹A PPh₂, MPPh, or similar group

might play a role analogous to a CR₂group in making gauche

conformations of four-atom segments energetically more com-

petitive with anti conformations. When only anti linkages are

present, the termini of α,ω-difunctionalized systems cannot

approach one another. Shaw and co-workers have furthermore

studied reactions of diphosphines R₂P(CH₂)_nPR₂and square

planar complexes that lead to trans substitution products.¹⁸

They ﬁnd that the ratio of monometallic to di- and polymetallic

CH᎐CH moieties will be directed on opposite sides of the

᎐

2

platinum square plane, an orientation unfavorable for intra-

molecular metathesis. Thus, bimolecular condensations should

be more competitive, and more oligomeric products should

arise from this manifold. This would result in lower yields of

monoplatinum interligand metathesis products. Accordingly,

only in the case of 15e is an anti isomer isolated. Finally, we

note in passing that it might be easier to incorporate a C₆H₅/

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1021

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C₆F₅/C₆H₅π stacking interaction into the transition state

derived from VI.

C₆F₅group must also be able to pass under the methylene

chain.

The distance from the platinum to the para ﬂuorine atom in

anti-15e is 6.18 Å. This is nearly as great as the distance from

platinum to the most remote macrocyclic carbons (7.19/6.85 Å).

When the van der Waals radius of ﬂuorine (1.47 Å) is added to

the former value, and the van der Waals radius of carbon (1.70

Å) is subtracted from the latter values,²⁴it is obvious that the

“vehicle height” is much greater than the “bridge height”

(7.65 Å vs. 5.49/5.15 Å). Accordingly, two ³¹P NMR signals are

observed. However, with still longer methylene bridges, rotation

of the Cl–Pt–C₆F₅moiety should become possible, leading to

dynamic NMR phenomena.

2

Macrocycle structures

Various crystallographic features are relevant to phenomena

analyzed above. First, the interligand metathesis products

in Table 2 have bond lengths and angles about platinum similar

to those of the intraligand metathesis products in Table 3.

The P–Pt–P bond angles (177.99(4)–172.21(10)Њ vs. 175.54(3)–

174.84(3)Њ) might have contracted if the ring strain associated

with the trans-spanning ligands were signiﬁcant.

Consider the torsion angle patterns of the complexes in Table

2 next. With syn-15e, the macrocycles are homologous. All

four Pt–PPh–CH₂–CH₂segments (Pt–P(1)–C(1)–C(2), C(13)–

C(14)–P(2)–Pt, and primed analogs) exhibit gauche conform-

ations with torsion angles of 46.5/56.5Њ and 56.0/39.2Њ. This

is in accord with an analog of a “germinal dialkyl eﬀect” as

discussed in the previous section, and as exploited in the cycliz-

ation-favorable conformations in Fig. 7. All of the macrocycles

in Scheme 1 (3c,e,f,g) crystallize similarly. The four PPh–CH₂–

CH₂–CH₂segments in syn-15e exhibit anti conformations, with

torsion angles of Ϫ175.3/Ϫ164.6Њ and Ϫ169.7/Ϫ172.2Њ. The

three subsequent four-carbon sequences in each ring also show

anti conformations. However, of the ﬁve remaining four-carbon

sequences, four exhibit gauche conformations, with torsion

angles of Ϫ51.7/Ϫ60.6Њ, Ϫ62.1/Ϫ67.0Њ, Ϫ61.9/Ϫ60.5Њ, and

Ϫ59.7/Ϫ50.4Њ.

The torsion angle patterns of the macrocycles in anti-15e are

not homologous, and diﬀer signiﬁcantly from those of syn-15e.

One of the two Pt–PPh–CH₂–CH₂segments in each ring now

exhibits a gauche conformation (C(13)–C(14)–P(2)–Pt Ϫ53.6Њ;

Pt–P(1)–C(1Ј)–C(2Ј) Ϫ44.7Њ), while the other remains anti

(Ϫ160.1Њ, 167.6Њ). All PPh–CH₂–CH₂–CH₂sequences again

show anti conformations. However, now there are six four-

carbon gauche segments in each ring, for a total of seven gauche

moieties – one more than in each ring of syn-15e. Although an

ensemble of accessible conformations would be expected in

solution, this suggests (in the absence of non-bonded inter-

actions) that anti-15e is more highly strained. As summarized

in Table 3, each ﬁfteen-membered ring in the constitutional

isomer 16e exhibits seven four-carbon gauche segments.

Furthermore, all C(13)–C(14)–P–C(1) and C(14)–P–C(1)–C(2)

sequences have gauche conformations (50.3/Ϫ46.1Њ, 57.0/

Ϫ63.1Њ), consistent with a PPhPt-based “geminal dialkyl

eﬀect”.

Complex syn-15c, with two thirteen-membered rings, crystal-

lizes with two independent molecules in the unit cell. Although

none of the torsion angle patterns are homologous, all eight

Pt–PPh–CH₂–CH₂segments exhibit gauche conformations,

with torsion angles of 36.9Њ to 82.7Њ. Two of the four

rings exhibit three additional gauche PPh–CH₂–CH₂–CH₂or

four-carbon segments, and the other rings exhibit four and

ﬁve. The unsaturated analog syn-(E,E)-13c also crystallizes

with gauche Pt–PPh–CH₂–CH₂segments. One ring features

only two additional gauche segments, and the other three (four-

3

Summary and prospective

Architecturally novel doubly trans-spanning diphosphine

complexes are easily accessed by interligand alkene metatheses

of the bis(phosphine) complexes 11c,d,e,f (Schemes 6, 9 and

10). Although the yields are lower than those of the singly

trans-spanning diphosphine complexes obtained from 1c,e,f,g

(Scheme 1), advanced-generation metatheses catalysts may

oﬀer improvements.¹⁹In any event, conventional syntheses

would require many additional steps. Curiously, intraligand

metathesis products are observed only when the carbon bridges

would be too short to span trans positions (Scheme 8). One

attempt to extend these reactions to still more complex educts

that can lead to higher polycycles was disappointing (Scheme

4). However, as will be described in future papers, others

have been spectacularly successful.²⁵Taken together, these

investigations – as well as clever ﬁndings by others^2,5– are

signiﬁcantly advancing the utility of alkene metatheses in

syntheses of topologically unusual inorganic and organo-

metallic systems.

Experimental

General data

All reactions were conducted under N₂(or H₂) atmospheres.

Chemicals were treated as follows: THF, ether, benzene, and

toluene, distilled from Na/benzophenone; CH₂Cl₂, distilled

from CaH₂(for reactions) or simple distillation (chromato-

graphy); hexanes and ethanol, simple distillation; HNEt₂,

distilled from NaOH; CDCl₃, ClCH₂CH₂Cl (99%, Fluka),

Ru(᎐CHPh)(PCy ) (Cl) (2, Strem), H BؒSMe (Fluka, 99%),

᎐

3

2

3

2

Rh(PPh₃)₃(Cl) (Strem), 10% Pd/C (Lancaster or Acros), PPhH₂

(99%, Strem), n-BuLi (Acros, 2.5 M in hexanes), Br(CH ) CH᎐

᎐

2

n

CH₂(n = 2, 98%, Fluka; 3, 95%, Aldrich; 4, 90%, Fluka; 5, 97%,

Aldrich), used as received.

NMR spectra were obtained on Bruker or Jeol 400 MHz

spectrometers. IR and mass spectra were recorded on ASI

React-IR 1000 and Micromass Zabspec instruments, respect-

ively. DSC and TGA data were obtained with a Mettler-Toledo

DSC-821 instrument.²⁶Microanalyses were conducted with a

Carlo Erba EA1110 instrument (in-house).

carbon in each case). The Z C᎐C moiety enforces one anti

linkage.

᎐

PPh((CH ) CH᎐CH ) (4a)⁷

᎐

2

2 2

A ﬁnal structural issue involves the size relationship between

the macrocycle and the other ligands on platinum. Consider

ﬁrst 3e (Scheme 1), which has a single trans-spanning P(CH₂)₁₄P

bridge. A 180Њ rotation of the Cl–Pt–C₆F₅moiety, with the

smaller chlorine ligand passing under the bridge, is rapid on

the NMR time scale and renders diastereotopic groups equiv-

alent.^3dIn 3c, which has a shorter P(CH₂)₁₀P bridge, the

rotational barrier becomes much higher and separate NMR

signals for diastereotopic groups are observed. As can be

visualized from V in Fig. 4, analogous 180Њ rotations would also

exchange the diastereotopic phosphorus atoms of anti-15e.

However, since there are now two P(CH₂)₁₄P bridges, the larger

A Schlenk ﬂask was charged with PPhH₂(0.514 g, 4.67 mmol)

and THF (20 mL) and cooled to 0 ЊC. Then n-BuLi (2.5 M in

hexanes, 3.75 mL, 9.4 mmol) was added dropwise with stirring

over 10 min. The colorless solution turned yellow–orange. After

5 min, Br(CH ) CH᎐CH (0.95 mL, 9.4 mmol) was added. The

᎐

2

solution became colorless. The cold bath was removed. After

3.5 h, solvent was removed by oil-pump vacuum. The residue

was ﬁltered through a silica plug (5 cm) with hexanes–toluene

(1 : 1 v/v). The ﬁltrate was taken to dryness by oil-pump

vacuum to give 4a (0.916 g, 4.20 mmol, 90%) as a colorless

oil. Calc. for C₁₄H₁₉P: C, 77.06; H, 8.72. Found: C, 77.54; H,

9.51%.

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1022

View Article Online

NMR:^{27 1}H 7.56–7.52 (m, 2 H of Ph), 7.37 (m, 3 H of Ph),

5.92–5.82 (m, 2 H, 2CH᎐), 5.05–4.96 (m, 4 H, 2 ᎐CH ), 2.17–

CH₂), 29.3 (s, CH₂), 28.7 (d, J_CP= 10.9, CH₂), 26.3 (d, J_CP=

13.4, CH₂); ³¹P{¹H} Ϫ23.2 (s).

MS:²⁹387 (4f^ϩ, 100%).

᎐

2

2.10 (m, 4 H, 2CH₂), 1.85–1.79 (m, 4 H, 2CH₂); ¹³C{¹H}²⁸139.3

(d, J_CP= 11.9, CH᎐), 138.4 (d, ¹J_CP= 14.7, i-Ph), 132.9 (d, ²J_CP

=

᎐

18.8, o-Ph), 129.3 (s, p-Ph), 128.8 (d, ³J_CP= 7.0, m-Ph), 114.8 (s,

trans-(Cl)(C F )Pt(PPh((CH ) CH᎐CH ) ) (11a)

᎐

6

5

2

2 2 2

᎐CH ), 30.4 (d, J = 14.8, CH₂), 27.8 (d, J_CP= 11.9, CH₂);

᎐

2

CP

³¹P{¹H} Ϫ23.0 (s).

A Schlenk ﬂask was charged with [Pt(µ-Cl)(C₆F₅)(S(CH₂-

CH₂)₂)]₂(12; 0.460 g, 0.474 mmol),⁹4a (0.424 g, 1.945 mmol)

and CH₂Cl₂(30 mL). The pale green mixture was stirred (14 h)

and became colorless. Solvent was removed by oil-pump

vacuum. The residue was ﬁltered through neutral alumina

(3.0 × 2.5 cm column) using 1 : 1 v/v CH₂Cl₂–hexanes. Solvent

was removed from the product fraction by oil-pump vacuum to

yield 11a as a colorless oil (0.627 g, 0.752 mmol, 79%). Calc. for

C₃₄H₃₈ClF₅P₂Pt: C, 48.95; H, 4.56. Found: C, 49.33; H, 4.80%.

NMR:^{27 1}H 7.44 (m, 4 H of 2Ph), 7.35 (m, 6 H of 2Ph), 5.84–

5.75 (m, 4 H, 4CH᎐), 5.03–4.97 (m, 8 H, 4 ᎐CH ), 2.37–2.27 (m,

PPh((CH ) CH᎐CH ) (4b)⁸

᎐

2

3

2 2

PPhH₂(0.685 g, 6.23 mmol), THF (20 mL), n-BuLi (2.5 M in

hexanes, 5.0 mL, 12.5 mmol) and Br(CH ) CH᎐CH (1.48 mL,

᎐

2

3

2

12.5 mmol) were combined in a procedure analogous to that for

4a. An identical workup gave 4b (1.41 g, 5.73 mmol, 92%) as a

colorless oil.

NMR:^{27 1}H 7.55–7.51 (m, 2 H of Ph), 7.38–7.35 (m, 3 H of

Ph), 5.81–5.73 (m, 2 H, 2CH᎐), 5.04–4.96 (m, 4 H, 2 ᎐CH ),

᎐

2

᎐

2

8 H, 4CH₂), 2.19–2.09 (m, 8 H, 4CH₂); ¹³C{¹H}^31a,32,33137.8

2.17–2.12 (m, 4 H, 2CH₂), 1.76–1.70 (m, 4 H, 2CH₂), 1.54–1.48

34

(m, 4 H, 2CH₂); ¹³C{¹H}²⁸138.8 (d, ¹J_CP= 15.0, i-Ph), 138.4 (s,

(virtual t,

130.6 (s, p-Ph), 130.0 (virtual t,

t,³⁴J_CP= 4.8, m-Ph), 115.6 (s, ᎐CH ), 28.4 (s, PCH CH ), 22.6

J

= 7.5, CH᎐), 131.6 (virtual t,

J

= 5.3, o-Ph),

᎐

CP

34

CH᎐), 132.6 (d, ²J_CP= 18.3, o-Ph), 128.9 (s, p-Ph), 128.5 (d, ³J_CP

J

= 26.0, i-Ph), 128.7 (virtual

CP

᎐

= 7.0, m-Ph), 115.0 (s, ᎐CH ), 35.4 (d, J_CP= 11.8, CH₂), 27.8 (d,

᎐

2

᎐

2

34

(virtual t,

J

= 16.4, PCH₂); ³¹P{¹H} 10.7 (s, J_PPt= 2564).³⁵

J_CP= 10.8, CH₂), 25.4 (d, J_CP= 14.3, CH₂); ³¹P{¹H} Ϫ23.5 (s).

CP

IR (cm^Ϫ1, oil ﬁlm) 3080 (w), 2980 (w), 2934 (w), 2864 (w),

1640 (m), 1502 (s), 1459 (s), 1436 (s), 1108 (m), 1058 (m), 953

(s), 911 (s), 803 (s), 722 (s), 687 (s). MS:²⁹798 ([11a Ϫ Cl]^ϩ,

100%), 579 ([11a Ϫ Cl Ϫ 4a]^ϩ, 40%), 411 ([11a Ϫ Cl Ϫ C₆F₅Ϫ

PPh((CH ) CH᎐CH ) (4c)

᎐

2

4

2 2

PPhH₂(0.572 g, 5.20 mmol), THF (20 mL), n-BuLi (2.5 M in

hexanes, 4.2 mL, 10.5 mmol) and Br(CH ) CH᎐CH (1.4 mL,

2

4

2

4a]^ϩ, 80%), 219 (4a^ϩ, 80%), 164 ([4a Ϫ (CH ) CH᎐CH ]^ϩ, 70%).

᎐

2

4

2

10.4 mmol) were combined in a procedure analogous to that for

4a. An identical workup gave 4c (1.27 g, 4.63 mmol, 89%) as a

colorless oil. Calc. for C₁₈H₂₇P: C, 78.83; H, 9.85. Found C,

79.11; H, 10.04%.

trans-(Cl)(C F )Pt(PPh((CH ) CH᎐CH ) ) (11b)

᎐

6

5

2

3

2 2 2

Complex 12 (0.430 g, 0.443 mmol), 4b (0.440 g, 1.79 mmol) and

CH₂Cl₂(25 mL) were combined in a procedure analogous to

that for 11a (17 h stirring). An identical workup gave 11b as a

colorless oil (0.675 g, 0.759 mmol, 86%). Calc. for C₃₈H₄₆-

ClF₅P₂Pt: C, 51.27; H, 5.17. Found: C, 50.48; H, 5.12%.

NMR:^{27 1}H 7.44 (m, 2 H of Ph), 7.26 (m, 3 H of Ph), 5.67 (m,

2 H, 2CH᎐), 4.86 (m, 4 H, 2 ᎐CH ), 1.98–1.91 (m, 4 H, 2CH ),

᎐

2

1.64–1.59 (m, 4 H, 2CH₂), 1.42–1.29 (m, 8 H, 4CH₂); ¹³C{¹H}²⁸

139.1 (s, CH᎐), 138.6 (d, ¹J_CP= 16.0, i-Ph), 132.7 (d, ²J_CP= 19.0,

o-Ph), 129.1 (s, p-Ph), 128.7 (d, J_CP= 7.0, m-Ph), 114.8

᎐

NMR:^{27 1}H 7.47–7.43 (m, 4 H of 2Ph), 7.35–7.30 (m, 6 H of

3

2Ph), 5.76–5.66 (m, 4 H, 4CH᎐), 5.02–4.98 (m, 8 H, 4 ᎐CH ),

᎐

(s, ᎐CH ), 33.8 (s, CH ), 30.8 (d, J_CP= 11.0, CH₂), 28.4 (d, J_CP

=

2

᎐

2

11.0, CH₂), 25.8 (d, J_CP= 13.0, CH₂); ³¹P{¹H} Ϫ23.0 (s).

2.19–2.07 (m, 12 H, 6CH₂), 2.00–1.96 (m, 4 H, 2CH₂), 1.81–

1.70 (m, 4 H, 2CH₂), 1.50–1.42 (m, 4 H, 2CH₂); ¹³C{¹H}^31,32,33

MS:²⁹275 (4c^ϩ, 100%), 192 ([4c Ϫ (CH ) CH᎐CH ]^ϩ, 92%).

᎐

2

4

2

137.6 (s, CH᎐), 131.5 (virtual t,³⁴J_CP= 5.3, o-Ph), 130.2 (s,

᎐

34

p-Ph), 128.4 (virtual t,

J

= 4.8, m-Ph), 115.8 (s, ᎐CH ), 35.1

᎐

CP 2

PPh((CH ) CH᎐CH ) (4d)

᎐

2

5

2 2

(virtual t,³⁴J_CP= 7.1, PCH₂CH₂CH₂), 23.3 (s, PCH₂CH₂),

22.5 (virtual t,³⁴J_CP= 16.8, PCH₂); ³¹P{¹H} 10.2 (s, J_PPt

=

PPhH₂(0.606 g, 5.51 mmol), THF (20 mL), n-BuLi (2.5 M in

2551).³⁵

hexanes, 4.5 mL, 11.3 mmol) and Br(CH ) CH᎐CH (1.73 mL,

᎐

2

5

2

IR (cm^Ϫ1, oil ﬁlm) 3080 (w), 2980 (w), 2934 (w), 2864 (w),

1640 (m), 1502 (s), 1459 (s), 1436 (s), 1108 (m), 1058 (m), 953

(s), 911 (s), 803 (s), 722 (s), 687 (s). MS:²⁹854 ([11b Ϫ Cl]^ϩ,

80%), 606 ([11b Ϫ Cl Ϫ 4b]^ϩ, 40%), 440 ([11b Ϫ Cl Ϫ C₆F₅Ϫ

11.4 mmol) were combined in a procedure analogous to that

for 4a. An identical workup gave 4d (1.55 g, 5.12 mmol, 93%) as

a colorless oil. Calc. for C₂₀H₃₁P: C, 79.47; H, 10.26. Found C,

78.89; H, 10.61%.

NMR:^{27 1}H 7.54–7.53 (m, 2 H of Ph), 7.38–7.36 (m, 3 H of

Ph), 5.82–5.80 (m, 2 H, 2CH᎐), 5.02–4.94 (m, 4 H, 2 ᎐CH ),

4b]^ϩ, 100%), 245 (4b^ϩ, 80%), 178 ([4b Ϫ (CH ) CH᎐CH ]^ϩ,

᎐

2

3

2

100%).

᎐

2

2.05–2.00 (m, 4 H, 2CH₂), 1.73–1.70 (m, 4 H, 2CH₂), 1.45–1.36

1

(m, 12 H, 6CH₂); ¹³C{¹H}²⁸139.4 (d, J_CP= 18.3, i-Ph), 139.3

trans-(Cl)(C F )Pt(PPh((CH ) CH᎐CH ) ) (11c)

᎐

6

5

2

4

2 2 2

(s, CH᎐), 132.7 (d, ²J_CP= 18.4, o-Ph), 129.0 (s, p-Ph), 128.6 (d,

᎐

³J_CP= 6.7, m-Ph), 114.7 (s, ᎐CH ), 34.0 (s, CH ), 31.1 (d, J

=

Complex 12 (0.522 g, 0.537 mmol), 4c (0.495 g, 1.81 mmol) and

CH₂Cl₂(30 mL) were combined in a procedure analogous to

that for 11a (18 h stirring). An identical workup gave 11c as a

colorless oil (0.738 g, 0.780 mmol, 73%). Calc. for C₄₂H₅₄-

ClF₅P₂Pt: C, 53.31; H, 5.71. Found: C, 53.45; H, 5.85%.

᎐

2

CP

11.5, CH₂), 29.0 (s, CH₂), 28.6 (d, J_CP= 11.0, CH₂), 26.2 (d, J_CP

= 13.6, CH₂); ³¹P{¹H} Ϫ23.3 (s).

MS:²⁹303 (4d^ϩ, 100%), 206 ([4d Ϫ (CH ) CH᎐CH ]^ϩ, 62%).

᎐

2

5

2

NMR:^{27 1}H 7.39 (m, 4 H of 2Ph), 7.29 (m, 6 H of 2Ph),

PPh((CH ) CH᎐CH ) (4f)

᎐

2

8

2 2

5.71–5.60 (m, 4 H, 4CH᎐), 4.94–4.84 (m, 8 H, 4 ᎐CH ), 2.20–

᎐

2

PPhH₂(0.152 g, 1.38 mmol), THF (10 mL), n-BuLi (2.5 M in

2.10 (m, 4 H, 2CH₂), 2.03–1.96 (m, 12 H, 6CH₂), 1.62–1.51 (m,

hexanes, 1.1 mL, 2.8 mmol) and Br(CH ) CH᎐CH (0.55 mL,

4 H, 2CH₂), 1.44–1.32 (m, 12 H, 6CH₂); ¹³C{¹H}^31a,32,33138.6 (s,

᎐

2

8

2

34

2.75 mmol)^3dwere combined in a procedure analogous to that

for 4a. An identical workup gave 4f (0.521 g, 1.35 mmol, 98%)

as a colorless oil.³⁰

CH᎐), 131.6 (virtual t,

J

CP

= 5.1, o-Ph), 130.6 (virtual t,

J

CP

=

᎐

25.9, i-Ph), 130.3 (s, p-Ph), 128.5 (virtual t,³⁴J_CP= 4.7, m-Ph),

115.2 (s, ᎐CH ), 33.6 (s, CH ), 30.7 (virtual t,³⁴J_CP= 6.9,

᎐

2

NMR:^{27 1}H 7.52 (m, 2 H of Ph), 7.36 (m, 3 H of Ph), 5.80 (m,

2 H, 2CH᎐), 5.03–4.92 (m, 4 H, 2 ᎐CH ), 2.08–2.00 (m, 4 H,

PCH₂CH₂CH₂), 23.6 (s, CH₂), 22.9 (virtual t,³⁴J_CP= 16.6,

PCH₂); ³¹P{¹H} 10.1 (s, J_PPt= 2543).³⁵

᎐

2

2CH₂), 1.37–1.27 (m, 28 H, 14CH₂); ¹³C{¹H}²⁸139.6 (s, CH᎐),

IR (cm^Ϫ1, oil ﬁlm) 3080 (w), 2930 (m), 2860 (w), 1640 (w),

1502 (s), 1459 (s), 1440 (s), 1108 (m), 1061 (s), 957 (s), 911 (s),

799 (s), 741 (s), 695 (s). MS:²⁹910 ([11c Ϫ Cl]^ϩ, 40%), 741 ([11c

Ϫ Cl Ϫ C₆F₅]^ϩ, 20%), 467 ([11c Ϫ Cl Ϫ C₆F₅Ϫ 4c]^ϩ, 50%), 385

᎐

139.5 (d, ¹J_CP= 19.9, i-Ph), 132.7 (d, ²J_CP= 18.3, o-Ph), 128.9 (s,

p-Ph), 128.6 (d, ³J_CP= 9.1, m-Ph), 114.5 (s, ᎐CH ), 34.2 (s, CH ),

᎐

2

31.6 (d, J_CP= 11.5, CH₂), 29.7 (s, CH₂), 29.6 (s, CH₂), 29.5 (s,

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1023

View Article Online

([11c Ϫ Cl Ϫ C F Ϫ 4c Ϫ (CH ) CH᎐CH ]^ϩ, 45%), 275 (4c^ϩ,

Metathesis of 11a; (Z,Z )-trans-(Cl)(C₆F₅)Pt-

(PPh(CH ) CH᎐CH(CH ) ) ((Z,Z )-14a)

᎐

6

5

2

4

2

70%), 192 ([4c Ϫ (CH ) CH᎐CH ]^ϩ, 100%).

᎐

2

4

2

᎐

2

2 2 2

A two-necked ﬂask was charged with 11a (0.465 g, 0.558

mmol), Grubbs’ catalyst 2 (ca. half of 0.036 g, 0.0390 mmol, 14

mol%) and CH₂Cl₂(60 mL; the resulting solution is 0.0093 M in

11a), and ﬁtted with a condenser. The solution was reﬂuxed.

After 2 h, the remaining 2 was added. After 2 h, solvent was

removed by oil-pump vacuum. The residue was ﬁltered through

neutral alumina (2.5 × 2.5 cm column) using CH₂Cl₂. Solvent

was removed from the ﬁltrate by oil-pump vacuum to give

(Z,Z)-14a as a pale pink solid (0.371 g, 0.477 mmol, 86%), mp

218–220 ЊC (decomp.) (capillary). Calc. for C₃₀H₃₀ClF₅P₂Pt: C,

46.31; H, 3.86. Found: C, 46.81; H, 4.28%.

trans-(Cl)(C F )Pt(PPh((CH ) CH᎐CH ) ) (11d)

᎐

6

5

2

5

2 2 2

Complex 12 (0.260 g, 0.268 mmol), 4d (0.340 g, 1.13 mmol) and

CH₂Cl₂(20 mL) were combined in a procedure analogous to

that for 11a. An identical workup gave 11d as a colorless oil

(0.497 g, 0.496 mmol, 93%). Calc. for C₄₆H₆₂ClF₅P₂Pt: C, 55.12;

H, 6.19. Found: C, 54.75; H, 6.50.

NMR:^{27 1}H 7.43–7.41 (m, 4 H of 2Ph), 7.34–7.28 (m, 6 H of

2Ph), 5.82–5.75 (m, 4 H, 4CH᎐), 5.01–4.93 (m, 8 H, 4 ᎐CH ),

᎐

2

2.20–2.12 (m, 4 H, 2CH₂), 2.01–1.95 (m, 12 H, 6CH₂),

1.70–1.55 (m, 4 H, 2CH₂), 1.45–1.30 (m, 20 H, 10CH₂);

¹³C{¹H}^31a,32,33139.1 (s, CH᎐), 131.6 (virtual t,³⁴J_CP= 5.1,

NMR:^{27 1}H 7.45–7.39 (m, 4 H of 2Ph), 7.35–7.28 (m, 6 H of

2Ph), 5.79–5.75 (m, 4 H, 2CH᎐CH), 2.55–2.43 (m, 8 H, 4CH ),

᎐

34

o-Ph), 130.7 (virtual t,

J

= 26.1, i-Ph), 130.3 (s, p-Ph), 128.5

CP

᎐

2

34

2.32–2.20 (m, 8 H, 4CH₂); ¹³C{¹H}^31a,32131.8 (s, CH᎐CH),

(virtual t,

J

= 4.6, m-Ph), 114.9 (s, ᎐CH ), 33.9 (s, CH ), 31.0

᎐

CP 2 2

᎐

(virtual t,³⁴J_CP= 7.0, PCH₂CH₂CH₂), 28.7 (s, CH₂), 24.1 (s,

34

131.3 (virtual t,

J

= 4.8, o-Ph), 130.4 (virtual t,

J

= 25.9,

= 4.8, m-Ph), 22.4 (s,

CP

34

CH₂), 23.1 (virtual t,

2543).³⁵

J

= 16.7, PCH₂); ³¹P{¹H} 10.2 (s, J_PPt

=

CP

34

i-Ph), 130.3 (s, p-Ph), 128.8 (virtual t,

J

CP

34

CH₂), 21.5 (virtual t,

2511).³⁵

J

= 16.1, CH₂); ³¹P{¹H} 15.8 (s, J_PPt

=

CP

IR (cm^Ϫ1, oil ﬁlm) 3080 (w), 2930 (m), 2856 (m), 1640 (m),

1502 (s), 1459 (s), 1440 (s), 1061 (s), 957 (s), 907 (s), 799 (s),

741 (s), 694 (s). MS:²⁹966 ([11d Ϫ Cl]^ϩ, 20%), 797 ([11d Ϫ Cl

Ϫ C₆F₅]^ϩ, 20%), 495 ([11d Ϫ Cl Ϫ C₆F₅Ϫ 4d]^ϩ, 60%), 397 ([11d

IR (cm^Ϫ1, powder ﬁlm) 3030 (w), 2930 (w), 2856 (w), 1502 (s),

1459 (s), 1058 (m), 953 (s), 718 (s), 695 (s). MS:²⁹742 ([14a Ϫ

Cl]^ϩ, 100%), 552 ([14a Ϫ Cl Ϫ PhP((CH )CH᎐CH(CH ))]^ϩ,

᎐

2

Ϫ Cl Ϫ C F Ϫ 4d Ϫ (CH ) CH᎐CH ]^ϩ, 50%), 303 (4d^ϩ, 100%),

30%).

᎐

6

5

2

5

2

192 ([4d Ϫ (CH ) CH᎐CH ]^ϩ, 70%).

᎐

2

5

2

trans-(Cl)(C₆F₅)Pt(PPh((CH₂)₆)₂(16a)

trans-(Cl)(C F )Pt(PPh((CH ) CH᎐CH ) ) (11e)

᎐

6

5

2

6

2 2 2

A two-necked ﬂask was charged with 14a (0.371 g, 0.477

mmol), 10% Pd/C (0.064 g, 0.0601 mmol Pd), ClCH₂CH₂Cl (20

mL) and ethanol (20 mL), ﬂushed with H₂, and ﬁtted with a

balloon of H₂. The mixture was stirred for 69 h. Solvent was

removed by oil-pump vacuum. The residue was ﬁltered through

neutral alumina (2.5 × 2.5 cm column) using 3 : 1 v/v hexanes–

CH₂Cl₂. Solvent was removed from the ﬁltrate by oil-pump

vacuum to give 16a as a white powder (0.240 g, 0.307 mmol,

64%), mp 145 ЊC (capillary), 147 ЊC (DSC; T _i/T _e/T _p/T _c/T _f

120.7/145.3/147.0/149.0/179.8 ЊC). TGA: onset of mass loss,

285 ЊC (T _e). Calc. for C₃₀H₃₄ClF₅P₂Pt: C, 46.07; H, 4.35.

Found: C, 45.98; H, 4.43%.

Complex 12 (0.416 g, 0.430 mmol), 4e (0.568 g, 1.719 mmol)^3c

and CH₂Cl₂(30 mL) were combined in a procedure analogous

to that for 11a (16 h stirring). A similar workup (2.5 × 2.5 cm

column, 3 : 1 v/v CH₂Cl₂–hexanes) gave 11e as a colorless oil

(0.824 g, 0.779 mmol, 91%). Calc. for C₅₀H₇₀ClF₅P₂Pt: C, 56.73;

H, 6.66. Found: C, 56.12; H, 6.58%.

NMR:^{27 1}H 7.40–7.37 (m, 4 H of 2Ph), 7.30–7.26 (m, 6 H of

2Ph), 5.81–5.68 (m, 4 H, 4CH᎐), 4.98–4.89 (m, 8 H, 4᎐CH ),

᎐

2

2.10–2.09 (m, 4 H, 4PCHHЈ), 2.01–1.89 (m, 12 H, 4PCHHЈ,

4CH CH᎐), 1.60–1.56 (m, 4 H, 4PCH CHHЈ), 1.34–1.24

᎐

2

(m, 28 H, 4PCH₂CHHЈ, 12CH₂); ¹³C{¹H}^31a,32,33138.9 (s, CH᎐),

᎐

34

131.2 (virtual t,

i-Ph), 129.9 (s, p-Ph), 128.0 (virtual t,³⁴J_CP= 4.4, m-Ph),

114.3 (=CH ), 33.7 (s, CH CH᎐), 31.0 (virtual t,³⁴J_CP

J

= 5.1, o-Ph), 130.4 (virtual t,

J

= 25.8,

CP

NMR:^{27 1}H 7.44 (m, 4 H of 2Ph), 7.28 (m, 6 H of 2Ph),

2.52–2.58 (m, 4 H, 2CH₂), 2.28–2.24 (m, 4 H, 2CH₂), 1.91–1.88

(m, 4 H, 2CH₂), 1.70–1.65 (m, 8 H, 4CH₂), 1.55–1.53 (m, 4 H,

2CH₂); ¹³C{¹H}^31a,32132.1 (virtual t,³⁴J_CP= 25.4, i-Ph), 131.2

(virtual t,³⁴J_CP= 4.8, o-Ph), 130.0 (s, p-Ph), 128.5 (virtual t,³⁴

J_CP= 4.7, m-Ph), 29.3 (s, CH₂), 24.9 (virtual t,³⁴J_CP= 15.9,

CH₂), 23.4 (s, CH₂); ³¹P{¹H} 11.2 (s, J_PPt= 2488).³⁵

=

᎐

2

6.5, PCH₂CH₂CH₂), 28.7 (s, CH₂), 28.6 (s, CH₂), 23.7 (s, CH₂),

1

22.7 (virtual t,³⁴J_CP= 16.5, PCH₂); ³¹P{¹H} 9.3 (s, J_PPt

=

2540).³⁵

IR (cm^Ϫ1, powder ﬁlm) 3080 (w), 2930 (m), 2856 (w), 1502 (s),

1463 (s), 1436 (s), 1104 (m), 1061 (m), 1000 (m), 953 (s), 911 (s),

803 (m), 741 (s), 690 (s). MS:²⁹1059 (11e^ϩ, 2%), 1022

([11e Ϫ Cl]^ϩ, 40%), 853 ([11e Ϫ Cl Ϫ C₆F₅]^ϩ, 22%), 489 ([11e Ϫ

Cl Ϫ C₆F₅Ϫ 4e]^ϩ, 70%), 331 (4e^ϩ, 100%).

IR (cm^Ϫ1, powder ﬁlm) 2926 (m), 2860 (w), 1502 (s), 1459 (s),

1058 (s), 953 (s), 803 (s), 730 (s), 691 (s). MS:²⁹782 (16a^ϩ, 40%),

746 ([16a Ϫ Cl]^ϩ, 50%), 577 ([16a Ϫ Cl Ϫ C₆F₅]^ϩ, 100%).

Metathesis of 11b

trans-(Cl)(C F )Pt(PPh((CH ) CH᎐CH ) ) (11f)

᎐

6

5

2

8

2 2 2

Complex 11b (0.176 g, 0.198 mmol), 2 (0.039 g, 0.0474 mmol,

24 mol%), and CH₂Cl₂(60 mL; resulting solution 0.0033 M in

11b) were combined in a procedure analogous to that with 11a

(1.5 h, second catalyst charge, then 1.5 h). A similar workup

(2.5 × 3 cm column) gave a white powder comprised of poly-

meric and/or oligomeric products (0.140 g, 0.168 mmol, 85%).

Complex 12 (0.504 g, 0.519 mmol), 4f (0.839 g, 2.17 mmol) and

CH₂Cl₂(30 mL) were combined in a procedure analogous to

that for 11a (15 h stirring). An identical workup gave 11f as a

colorless oil (0.898 g, 0.768 mmol, 74%). Calc. for C₅₈H₈₆-

ClF₅P₂Pt: C, 59.80; H, 7.72. Found: C, 59.52; H, 7.35%.

NMR:^{27 1}H 7.43 (m, 4 H of 2Ph), 7.29 (m, 6 H of 2Ph), 5.82

NMR:^{27 1}H 7.32 (m, 10 H, 2Ph), 5.30 (m, 4 H, 2CH᎐CH),

᎐

(m, 4 H, 4CH᎐), 4.98 (m, 8 H, 4 ᎐CH ), 2.14–1.94 (m, 16 H,

᎐

2

2.02–1.25 (m, 24 H, 12CH₂); ³¹P{¹H} 10.0 (br s, J_PPt= 2561).³⁵

MS:²⁹1632 ([2ؒPt Ϫ Cl]^ϩ, 30%),³⁶1463 ([2ؒPt Ϫ Cl Ϫ C₆F₅]^ϩ,

8CH₂), 1.58 (m, 4 H, 2CH₂), 1.37–1.25 (m, 44 H, 22CH₂);

¹³C{¹H}^31a,32,33139.4 (s, CH᎐), 131.4 (virtual t,³⁴J_CP= 5.1,

᎐

34

20%),³⁶630 (Pt(PPh((CH ) CH᎐) ) ^ϩ, 100%).

᎐

2 2

2

3

o-Ph), 130.7 (virtual t,

J

= 25.6, i-Ph), 130.0 (s, p-Ph), 128.2

CP

34

(virtual t,

J

= 4.7, m-Ph), 114.3 (s, ᎐CH ), 34.0 (s, CH ), 31.4

᎐

CP 2 2

(virtual t,³⁴J_CP= 6.9, PCH₂CH₂CH₂), 29.7 (s, CH₂), 29.3 (s,

CH₂), 29.3 (s, CH₂), 29.0 (s, CH₂), 24.0 (s, CH₂), 22.9 (virtual t,³⁴

J_CP= 16.5, PCH₂); ³¹P{¹H} 10.1 (s, J_PPt= 2540).³⁵

Metathesis of 11c; syn-(E,E )-trans-(Cl)(C₆F₅)-

Pt(PPh(CH ) CH᎐CH(CH ) P(CH ) CH᎐CH(CH ) Ph)

᎐

2

4

2

4

2

4

2 4

(syn-(E,E )-13c)

IR (cm^Ϫ1, oil ﬁlm) 3080 (w), 2926 (s), 2856 (s), 1640 (w), 1502

(s), 1459 (s), 1061 (m), 957 (s), 907 (s), 799 (m), 741 (s), 695 (s).

MS:²⁹1134 ([11f Ϫ Cl]^ϩ, 100%), 965 ([11f Ϫ Cl Ϫ C₆F₅]^ϩ, 70%).

Complex 11c (0.191 g, 0.202 mmol), 2 (0.020 g, 0.0242 mmol,

12 mol%), and CH₂Cl₂(300 mL; resulting solution is 0.00067 M

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1024

View Article Online

in 11c) were combined in a procedure analogous to that with

11a (3 h, second catalyst charge, then 3 h; ³¹P{¹H} NMR of

residue (δ, CDCl₃): 18.7 (28%), 12.6 (11%), 12.0 (19%), 11.6

(23%), 11.1 (19%)) A similar workup (2.5 × 5 cm column using

2 : 1 v/v hexanes–CH₂Cl₂; solvent removal from ﬁrst fractions)

gave syn-(E,E)-13c as a white solid (0.0379 g, 0.0426 mmol,

21%), mp 265–268 ЊC (decomp.) (capillary). Calc. for

C₃₈H₄₆ClF₅P₂Pt: C, 51.26; H, 5.17. Found: C, 51.12; H, 5.25%.

NMR:^{27 1}H 7.21 (m, 2 H of 2Ph), 7.13–7.10 (m, 8 H of 2Ph),

32 H, 16CH₂); ¹³C{¹H}^31,32130.9 (virtual t,³⁴J_CP= 4.5, o-Ph),

34

130.0 (s, p-Ph), 127.9 (virtual t,

J

= 3.7, m-Ph), 30.2 (virtual

CP

34

t,

J

= 7.4, CH₂), 27.8 (s, CH₂), 27.3 (s, CH₂), 26.8 (virtual t,³⁴

CP

J_CP= 17.2, CH₂), 26.5 (s, CH₂), 24.9 (s, CH₂); ³¹P{¹H} 12.5

(s, J_PPt= 2590).³⁵

MS:²⁹949 (15d^ϩ, 30%), 913 ([15d Ϫ Cl]^ϩ, 100%), 743

([15d Ϫ Cl Ϫ C₆F₅]^ϩ, 70%).

Metathesis of 11e; trans-(Cl)(C₆F₅)-

5.50 (t, J_HH= 3.6, 4 H, 2CH᎐CH), 2.53–2.45 (m, 8 H, 4CH ),

᎐

2

Pt(PPh(CH ) CH᎐CH(CH ) P(CH ) CH᎐CH(CH ) Ph) (13e)

᎐

2

6

2

6

2

6

2 6

2.29–2.25 (m, 4 H, 2CH₂), 2.09–2.07 (m, 4 H, 2CH₂), 1.97–1.93

(m, 4 H, 2CH₂), 1.82–1.79 (m, 4 H, 2CH₂), 1.67–1.55 (m, 8 H,

Complex 11e (0.250 g, 0.236 mmol), 2 (0.0019 g, 0.0231 mmol,

10 mol%), and CH₂Cl₂(70 mL; resulting solution 0.0034 M in

11e) were combined in a procedure analogous to that with 11a

(2.5 h, second catalyst charge, 2.5 h). An identical workup gave

13e and other metathesis products as a pale pink powder (0.230

g, 0.230 mmol, 97%). Calc. for C₄₆H₆₂ClP₂F₅Pt: C, 55.12; H,

6.23. Found: C, 54.91; H, 6.00%.

4CH₂); ¹³C{¹H}^31,32131.5 (s, CH᎐CH), 130.7 (virtual t,³⁴J_CP

=

᎐

4.7, o-Ph), 130.0 (s, p-Ph), 128.0 (virtual t,³⁴J_CP= 4.6, m-Ph),

34

32.2 (s, CH₂), 31.1 (virtual t,

J

= 8.3, CH₂), 27.4 (virtual t,³⁴

CP

J_CP= 17.2, CH₂), 25.8 (s, CH₂); ³¹P{¹H} 18.7 (s, J_PPt= 2623).³⁵

IR (cm^Ϫ1, powder ﬁlm) 2930 (m), 2849 (w), 1498 (s), 1455 (s),

1436 (s), 1058 (s), 953 (s), 768 (s), 718 (s). MS:²⁹890 (13c^ϩ,

10%), 854 ([13c Ϫ Cl]^ϩ, 100%), 686 ([13c Ϫ Cl Ϫ C₆F₅]^ϩ, 60%).

The column was subsequently rinsed with CH₂Cl₂. Similar

concentration of the fractions gave a white solid (0.0754 g,

0.0848 mmol, 42%) comprised of polymeric and/or oligomeric

products.

NMR:^{27 1}H 7.41–7.05 (m, 10 H, 2Ph), 5.35–5.20 (m, 4 H,

2CH᎐), 2.40–2.33 (m, 2 H of 4PCH ), 2.02–1.76 (m, 18 H; 6 H

᎐

2

of 4PCH , 4 H of 4PCH CH , 4CH CH᎐), 1.48–1.23 (m, 28 H;

᎐

2

4 H of 4PCH₂CH₂, 12CH₂); ³¹P{¹H} (partial) 15.2 (s, 4%), 14.8

(s, 5%), 13.5 (s, J_PtP= 2579,³⁵44%), 12.3 (s, 9%), 10.9 (s, 8%),

1

³¹P{¹H} 12.6 (s, J_PPt= 2583,³⁵19%), 12.0 (s, J_PPt= 2552,³⁵

14%), 11.6 (s, J_PPt= 2573,³⁵45%), 11.1 (s, J_PPt= 2498,³⁵22%).

MS:²⁹1742 ([2ؒPt Ϫ Cl]^ϩ, 10%),³⁶1576 ([2ؒPt Ϫ Cl Ϫ C₆F₅]^ϩ,

5%),³⁶549 ([13c Ϫ Cl Ϫ C₆F₅Ϫ (CH₂)₁₀]^ϩ, 100%).

9.3 (s, 12%), 8.7 (s, 18%).

IR (cm^Ϫ1, powder ﬁlm) 3057 (w), 2926 (w), 2853 (m), 1502

(m), 1459 (m), 1436 (m), 1104 (m), 1058 (m), 957 (s), 803 (m),

737 (s), 690 (s). MS:²⁹1969 ([2ؒPt Ϫ Cl]^ϩ, 30%),36 1798

([2ؒPt Ϫ Cl Ϫ C₆F₅]^ϩ, 20%),³⁶966 ([13e Ϫ Cl]^ϩ, 45%), 797 ([13e

Ϫ Cl Ϫ C₆F₅]^ϩ, 100%).

syn-trans-(Cl)(C₆F₅)Pt(PPh(CH₂)₁₀P(CH₂)₁₀Ph) (syn-15c)

Complex 13c (0.0379 g, 0.0426 mmol), 10% Pd/C (0.019 g,

0.018 mmol Pd), ClCH₂CH₂Cl (10 mL), ethanol (10 mL), and

H₂were combined in a procedure analogous to that for 16a.

After 132 h, a similar workup (column rinsed with 2 : 1 v/v hex-

anes–CH₂Cl₂) gave syn-15c as a white powder (0.036 g, 0.0405

mmol, 95%), mp 256–258 ЊC (decomp.) (capillary), 255 ЊC

(DSC; T _i/T _e/T _p/T _c/T _f210.1/242.2/254.6/260.6/271.4 ЊC).

TGA: onset of mass loss, 328 ЊC (T _e). Calc. for C₃₈H₅₀ClF₅-

P₂Pt: C, 51.04; H, 5.60. Found: C, 51.00; H, 5.61%.

trans-(Cl)(C₆F₅)Pt(PPh(CH₂)₁₄P(CH₂)₁₄Ph) (15e)

Complex 13e and other metathesis products (0.154 g, 0.153

mmol), 10% Pd/C (0.016 g, 0.015 mmol Pd), ClCH₂CH₂Cl (6.5

mL), ethanol (6.5 mL), and H₂were combined in a procedure

analogous to that for 16a. After 48 h, a similar workup (3 ×

2.5 cm column rinsed with CH₂Cl₂) gave crude 15e as a white

powder (0.119 g, 0.118 mmol, 77%).

NMR:^{27 1}H 7.45–7.12 (m, 10 H, 2Ph), 2.40–2.36 (m, 4 H,

2PCH₂), 2.15–2.14 (m, 4 H, 2PCH₂), 1.88–1.87 (m, 4 H,

2PCH₂CH₂), 1.77–1.75 (m, 4H, 2PCH₂CH₂), 1.46–1.23 (m, 40

H, 20CH₂); ³¹P{¹H} (partial) 11.8 (s, ¹J_PtP= 2579,³⁵15e, 52%).

MS:²⁹1977 ([2ؒPt Ϫ Cl]^ϩ, 20%),³⁶1809 ([2ؒPt Ϫ Cl Ϫ C₆F₅]^ϩ,

10%),³⁶1006 (15e^ϩ, 40%), 970 ([15e Ϫ Cl]^ϩ, 100%), 801 ([15e Ϫ

Cl Ϫ C₆F₅]^ϩ, 90%).

NMR:^{27 1}H 7.18 (m, 2 H of 2Ph), 7.11 (m, 8 H of 2Ph), 2.56–

2.53 (m, 4 H, 2CH₂), 2.42–2.35 (m, 4 H, 2CH₂), 1.97–1.84 (m, 8

H, 4CH₂), 1.70–1.63 (m, 10 H, 5CH₂), 1.57–1.50 (m, 10 H,

5CH₂), 1.48–1.40 (m, 4 H, 2CH₂); ¹³C{¹H}^31a,32130.9 (virtual

34

t,

p-Ph), 127.9 (virtual t,

7.3, CH₂), 27.4 (s, CH₂), 26.6 (virtual t,

J

= 24.1, i-Ph), 130.7 (virtual t,

J

= 5.2, o-Ph), 130.0 (s,

CP

34

CP

34

J

CP

= 4.6, m-Ph), 29.5 (virtual t,

J

CP

=

34

J

CP

= 17.1, CH₂), 25.7

The sample was chromatographed on neutral alumina (10 ×

2.5 cm column) using 1 : 3 v/v CH₂Cl₂–hexanes. The two least

polar fractions were collected to give syn-15e (0.048 g, 0.0477

mmol, 31%) as a white powder, mp 155–157 ЊC, and anti-15e

(0.011g, 0.0100 mmol, 7%) as a white powder.

(s, CH₂), 24.8 (s, CH₂); ³¹P{¹H} 16.2 (s, J_PPt= 2612).³⁵

IR (cm^Ϫ1, oil ﬁlm) 2926 (w), 2856 (w), 1502 (m), 1459 (m),

1231 (s), 1119 (s), 980 (s), 953 (s), 803 (m), 741 (m), 695 (m).

MS:²⁹894 (15c^ϩ, 35%), 858 ([15c Ϫ Cl]^ϩ, 100%), 689 ([15c Ϫ Cl

Ϫ C₆F₅]^ϩ, 50%).

syn-15e: Calc. for C₄₆H₆₆ClP₂F₅Pt: C, 54.89; H, 6.61. Found:

C, 54.93; H, 6.75.

NMR:^{27 1}H^33b7.17–7.08 (m, 10 H, 2Ph), 2.35–2.28 (m, 4 H,

4PCHHЈ), 2.15–2.04 (m, 4 H, 4PCHHЈ), 1.82–1.80 (m, 4 H,

4PCH₂CHHЈ), 1.73 (m, 4 H, 4PCH₂CHHЈ), 1.47–1.11 (m, 40

Metathesis of 11d; syn-trans-(Cl)(C₆F₅)Pt(PPh(CH₂)₁₂P(CH₂)₁₂-

Ph) (syn-15d)

Complex 11d (0.103 g, 0.103 mmol), 2 (0.018 g, 0.0218 mmol,

21 mol%), and CH₂Cl₂(55 mL; resulting solution 0.0019 M in

11d) were combined in a procedure analogous to that with 11a

(2 h, second catalyst charge, 2 h). The residue (³¹P{¹H} NMR

(δ, CDCl₃): 10.6 (s, 12%), 10.1 (br s, J_PPt= 2532.1, 88%))³⁵was

charged with 10% Pd/C (0.030 g, 0.028 mmol Pd), ClCH₂CH₂Cl

(10 mL) and ethanol (10 mL), ﬂushed with H₂, and ﬁtted with a

balloon of H₂. The mixture was stirred for 144 h. Solvent was

removed by oil-pump vacuum. The residue was ﬁltered through

neutral alumina (2.5 × 2.5 cm column) using 3 : 1 v/v hexanes–

CH₂Cl₂. Solvent was removed from the ﬁltrate to give syn-15d

as a white powder (0.005 g, 0.0053 mmol, 5%). Calc. for

C₄₂H₅₈ClF₅P₂Pt: C, 53.08; H, 6.11. Found: C, 53.34; H, 6.12%.

NMR:^{27 1}H 7.21–7.12 (m, 10 H, 2Ph), 2.53 (m, 4 H, 2CH₂),

2.17 (m, 4 H, 2CH₂), 1.95–1.80 (m, 8 H, 4CH₂), 1.56–1.41 (m,

H, 20CH₂); ¹³C{¹H}^31a,32,33130.3 (virtual t,³⁴J_CP= 4.6, o-Ph),

34

130.2 (virtual t,

J

= 26.0, i-Ph), 129.5 (s, p-Ph), 127.6 (virtual

CP

34

t,

J

CP

= 4.4, m-Ph), 30.4 (virtual t,

J

CP

= 6.4, PCH₂CH₂CH₂),

27.9 (s, CH₂), 27.3 (s, CH₂), 27.0 (s, CH₂), 26.9 (s, CH₂), 24.2 (s

and overlapping virtual t,³⁴J_CP= 17.5, PCH₂CH₂and PCH₂);

³¹P{¹H} 11.8 (s, ¹J_PtP= 2560).³⁵

IR (cm^Ϫ1, powder ﬁlm) 2926 (m), 2856 (m), 1502 (s), 1463

(m), 1058 (m), 957 (s). MS:²⁹1006 (15e^ϩ, 40%), 970 ([15e Ϫ

Cl]^ϩ, 100%), 801 ([15e Ϫ Cl Ϫ C₆F₅]^ϩ, 60%).

anti-15e: Calc. for C₄₆H₆₆ClP₂F₅Pt: C, 54.89; H, 6.61. Found:

C, 54.87; H, 6.91.

NMR:^{27 1}H 7.82–7.78 (m, 2H of 2Ph), 7.41–7.39 (4H of 2Ph),

7.30–7.10 (m, 4H of 2Ph), 2.30–2.26 (m, 2 H of 4PCHHЈ),³⁷

2.14–2.05 (m, 2 H of 4PCHHЈ),³⁷1.87–1.82 (m, 4 H of

4PCHHЈ),³⁷1.62–1.10 (m, 48 H, 24CH₂); ¹³C{¹H} (partial,

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1025

View Article Online

some assignments tentative)^31a,37133.7 (s, m-Ph), 133.6 (s,

m-PhЈ), 130.4 (br s, 2 p-Ph), 129.60 (s, i-Ph), 129.58 (s, i-PhЈ),

IR (cm^Ϫ1, oil ﬁlm) 2930, 2856, 2374, 2339, 1640, 1463, 1436,

1116, 1061, 996, 907, 799, 745, 695. MS:²⁹341 ([17e Ϫ 3H]^ϩ,³⁸

40%), 331 ([17e Ϫ H₃B]^ϩ, 100%).

34

127.8 (virtual t,

J

= 8.5, o-Ph), 127.99 (virtual t,

J

= 8.5,

CP

34

CP

34

o-PpЈ), 30.06 (virtual t,

J

= 11.5, CH₂), 30.04 (virtual t, J

CP

= 11.5, CH₂), 28.2 (s, CH₂), 28.0 (s, CH₂), 27.7 (br s, CH₂), 27.4

(br s, CH₂), 27.1 (br s, CH₂), 26.9 (br s, CH₂), 24.2 (br s, CH₂),

23.7 (br s, CH₂); ³¹P{¹H} 15.8 (²J_PPЈ= 426.8, ¹J_PPt= 2610),³⁵11.2

(²J_PЈP= 426.8, ¹J_PЈPt= 2556).³⁵

H BؒPPh(CH ) CH᎐CH(CH ) (18e)

᎐

3

2

6

2 6

A two-necked ﬂask was charged with 17e (0.141 g, 0.409 mmol),

2 (ca. half of 0.017 g, 0.0205 mmol, 5 mol%), and CH₂Cl₂(180

mL, the resulting solution is 0.0023 M in 17e), and ﬁtted with

a condenser. The solution was reﬂuxed. After 2.5 h, the

remaining 2 was added. After 2.5 h, solvent was removed by

rotary evaporation and oil-pump vacuum. The residue was

ﬁltered through neutral alumina (5 × 2.5 cm column) using

CH₂Cl₂. Solvent was removed from the ﬁltrate by rotary evap-

oration and oil-pump vacuum to give 18e as a pale pink oil

(0.080 g, 0.253 mmol, 62%). Calc. for C₂₀H₃₄BP: C, 75.95; H,

10.83. Found: C, 75.20; H, 11.25%.

IR (cm^Ϫ1, powder ﬁlm) 2926 (s), 2856 (s), 2362 (w), 2335 (w),

1502 (s), 1459 (m), 1440 (s), 1061 (s), 957 (s). MS:²⁹1006 (15e^ϩ,

20%), 971 ([15e Ϫ Cl]^ϩ, 90%), 799 ([15e Ϫ Cl Ϫ C₆F₅]^ϩ, 100%).

Metathesis of 11f: trans-(Cl)(C₆F₅)-

Pt(PPh(CH ) CH᎐CH(CH ) P(CH ) CH᎐CH(CH ) Ph) (13f)

᎐

2

8

2

8

2

8

2 8

Complex 11f (0.273 g, 0.233 mmol), 2 (ca. half of 0.050 g,

0.0608 mmol, 26 mol%), and CH₂Cl₂(70 mL; resulting solution

0.0033 M in 11f ) were combined in a procedure analogous to

that with 11a (2 h, second catalyst charge, 3.5 h). A similar

workup (2.5 × 3 cm column) gave 13f and other metathesis

products as a pale pink solid (0.238 g, 0.214 mmol, 92%). Calc.

for C₅₄H₇₈ClF₅P₂Pt: C, 58.20; H, 6.88. Found: C, 57.84; H,

7.30%.

NMR:^{27 1}H 7.72–7.70 (m, 2 H of Ph), 7.49–7.46 (m, 3 H of

Ph), 5.47–5.43/5.42–5.39/5.38–5.33 (3m, 2 H, 2CH᎐), 2.13–1.82

᎐

(m, 8 H, 2CH CH᎐, 2PCH ), 1.57–1.27 (m, 16 H, 8CH ),

᎐

2

1.0–0.3 (br, 3H, BH₃); ³¹P{¹H} 15.2 (m).

IR (cm^Ϫ1, oil ﬁlm) 2926, 2853, 2370, 2339, 1436, 1112, 1061,

969, 741, 695. MS:²⁹629 ([2ؒP]^ϩ, 20%),³⁶617 ([2ؒP Ϫ H₃B]^ϩ,

25%),³⁶605 ([2ؒP Ϫ 2H₃B]^ϩ, 30%),³⁶315 (18e^ϩ, 80%), 303 ([18e

Ϫ H₃B]^ϩ, 100%).

NMR:^{27 1}H 7.44–7.14 (m, 10 H, 2Ph), 5.36 (m, 4 H, 2CH᎐

᎐

CH), 2.27–1.86 (m, 16 H, 8CH₂), 1.46–1.11 (m, 48 H, 24CH₂);

³¹P{¹H} 13.5 (s, 7%), 13.1 (s, J_PPt= 2566,³⁵34%), 12.6 (11%),

10.7 (s, J_PPt= 2522,³⁵23%), 10.5 (s, J_PPt= 2522, 25%).³⁵

MS:²⁹1079 ([13f Ϫ Cl]^ϩ, 100%), 909 ([13f Ϫ Cl Ϫ C₆F₅]^ϩ,

80%).

H₃BؒPPh(CH₂)₁₄(19e)

A Fischer–Porter bottle was charged with 18e (0.072 g, 0.228

mmol), Rh(PPh₃)₃(Cl) (0.021 g, 0.0028 mmol, 10 mol%), and

benzene (25 mL), and ﬂushed with H₂. The mixture was stirred

under H₂(6 atm) for 20 h. Solvent was removed by oil-pump

vacuum. The residue was chromatographed on neutral alumina

(10 × 2.5 cm column) using 1 : 1 v/v CH₂Cl₂–hexanes. Solvent

was removed from the product fraction by oil-pump vacuum to

give 19e as a colorless oil (0.056 g, 0.176 mmol, 77%). Calc. for

C₂₀H₃₆BP: C, 75.74; H, 11.40. Found: C, 75.28; H, 11.54%.

NMR:^{27 1}H 7.73–7.70 (m, 2 H of Ph), 7.49–7.46 (m, 3 H of

Ph), 2.00–1.84 (m, 4 H, 2PCH₂), 1.57–1.21 (m, 24 H, 12CH₂),

1.1–0.3 (br, 3H, BH₃); ¹³C{¹H}²⁸131.3 (d, J_CP= 8.2, o-Ph),

syn-trans-(Cl)(C₆F₅)Pt(PPh(CH₂)₁₈P(CH₂)₁₈Ph) (syn-15f)

Complex 13f and other metathesis products (0.171 g, 0.154

mmol), 10% Pd/C (0.027 g, 0.0262 mmol Pd), ClCH₂CH₂Cl

(10 mL), ethanol (10 mL), and H₂were combined in a pro-

cedure analogous to that for 16a. After 71 h, a similar workup

(³¹P{¹H} NMR of residue (δ, CDCl₃): 11.9 (8%), 10.8 (39%),

10.3 (27%), 10.1 (21%), 8.7 (5%); 2.5 × 5 cm column) gave

syn-15f as a colorless oil (0.026 g, 0.023 mmol, 15%).³⁰

NMR:^{27 1}H 7.50–7.10 (m, 10 H, 2Ph), 2.15 (m, 10 H, 5CH₂),

1

130.9 (d, J_CP= 2.3, p-Ph) 130.2 (d, J_CP= 53.1, i-Ph), 128.7 (d,

34

1.35 (m, 62 H, 31CH₂); ¹³C{¹H}^31a,32131.4 (virtual t,

J

= 4.9,

CP

J_CP= 9.5, m-Ph), 28.9 (d, J_CP= 11.5, CH₂), 26.8 (s, CH₂), 26.57

(s, CH₂), 26.54 (s, CH₂), 26.3 (s, CH₂), 23.8 (d, J_CP= 34.5, CH₂),

21.5 (d, J_CP= 2.4, CH₂); ³¹P{¹H} 15.4 (apparent d, ¹J(¹¹B,³¹P) =

69.6).

34

o-Ph), 130.8 (virtual t,

J

= 26.0, i-Ph), 130.1 (s, p-Ph), 128.3

CP

(virtual t,³⁴J_CP= 4.8, m-Ph), 31.0 (virtual t,³⁴J_CP= 6.8, CH₂),

28.9, 28.8, 28.7, 28.6, 28.5, 28.4, 24.1 (s, CH₂), 23.6 (virtual t,³⁴

J_CP= 17.2, CH₂); ³¹P{¹H} 10.8 (s, J_PPt= 2551).³⁵

MS:²⁹1081 ([15f Ϫ Cl]^ϩ, 100%), 913 ([15f Ϫ Cl Ϫ C₆F₅]^ϩ,

90%).

IR (cm^Ϫ1, oil ﬁlm) 2926, 2853, 2374, 2343, 1459, 1435, 1112,

1065, 1000, 737, 691. MS:²⁹609 ([2ؒP Ϫ 2H₃B]^ϩ, 30%),³⁶315

([19e Ϫ 3H]^ϩ, 100%),³⁸305 ([19e Ϫ H₃B]^ϩ, 60%).

H BؒPPh((CH ) CH᎐CH ) (17e)

᎐

3

2

6

2 2

trans-(Cl)(C₆F₅)Pt(PPh(CH₂)₁₄)₂(16e)

A Schlenk ﬂask was charged with 4e (0.304g, 0.920 mmol)^3c

and THF (2 mL), cooled to Ϫ20 ЊC (N₂, acetone), and H₃Bؒ

SMe₂(0.0698g, 0.920 mmol) was added. The solution was

stirred for 1 h at Ϫ20 ЊC and 30 min at room temperature.

Solvent was removed by rotary evaporation and oil-pump

vacuum. The residue was ﬁltered through neutral alumina (6 ×

2.5 cm column) using 1 : 1 v/v CH₂Cl₂–hexanes. Solvent was

removed from the product fraction by oil-pump vacuum to give

17e as a colorless oil (0.205 g, 0.595 mmol, 65%). Calc. for

C₂₂H₃₈BP: C, 76.74; H, 11.12. Found: C, 76.46; H, 11.39%.

NMR:^{27 1}H 7.73–7.70 (m, 2 H of Ph), 7.60–7.47 (m, 3 H of

A Schlenk ﬂask was charged with 19e (0.112 g, 0.352 mmol)

and HNEt₂(2 mL). The mixture was heated to 50 ЊC and stirred

for 45 min. The HNEt₂was removed by oil-pump vacuum, and

the residue vacuum dried at 50 ЊC for an additional 20 min.

This operation was repeated twice (ﬁnal cycle: 2 h, 50 ЊC) to

give crude PPh(CH₂)₁₄(20e). The ﬂask was charged with 12

(0.085 g, 0.088 mmol)⁹and CH₂Cl₂(6 mL), and the mixture

was stirred (16 h). Solvent was removed by oil-pump vacuum.

The residue was chromatographed on neutral alumina (9 × 2.5

cm column) using 1 : 1 v/v CH₂Cl₂–hexanes. Solvent was

removed from the product fraction by oil-pump vacuum to

yield 16e as a colorless oil, which solidiﬁed over the course of

several days (0.042 g, 0.0417 mmol, 24% based on 19e). Calc.

for C₄₆H₆₆ClF₅P₂Pt: C, 54.89; H, 6.61. Found: C, 54.71; H,

6.55%.

Ph), 5.82–5.76 (m, 2 H, 2CH᎐), 5.01–4.92 (m, 4 H, 2 ᎐CH ),

᎐

2

2.02–1.99 (m, 4 H, 2CH CH᎐), 1.87–1.81 (m, 4 H, 2PCH ), 1.57

᎐

2

(m, 2 H, CH₂), 1.37–1.26 (m, 14 H, 7CH₂), 1.0–0.2 (br, 3 H,

BH₃); ¹³C{¹H}²⁸138.6 (s, CH᎐), 131.8 (d, J_CP= 7.6, o-Ph), 131.1

᎐

1

(d, J_CP= 2.2, p-Ph) 128.7 (d, J_CP= 9.5, m-Ph), 128.6 (d, J_CP

=

51.3, i-Ph), 114.5 (s, ᎐CH ), 33.6 (s, CH CH᎐), 30.9 (d, J

NMR:^{27 1}H 7.50–7.45 (m, 4 H of 2Ph), 7.36–7.28 (m, 6 H of

2Ph), 2.16–2.12 (m, 4 H of 4PCHHЈ),³⁷1.95–1.92 (m, 4 H of

4PCHHЈ),³⁷1.65–1.63 (m, 4 H of 4PCH₂CHHЈ),³⁷1.56–1.30

(m, 44 H; 4 H of 4PCH₂CHHЈ, 20CH₂);^{37 13}C{¹H}^31a,32,33131.2

᎐

2

CP

13.0, CH₂), 28.6 (s, CH₂), 28.5 (s, CH₂), 25.6 (d, J_CP= 36.0,

CH₂), 22.7 (s, CH₂); ³¹P{¹H} 15.3 (apparent d, J(¹¹B,³¹P) =

1

75.1).

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1026

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34

2002, 114, 1951; J. Stahl, J. C. Bohling, E. B. Bauer, T. B. Peters,

(virtual t,

J

CP

= 5.2, o-Ph), 130.9 (virtual t,

J

= 25.8, i-Ph),

CP

34

W. Mohr, J. M. Martín-Alvarez, F. Hampel and J. A. Gladysz,

Angew. Chem., Int. Ed., 2002, 41, 1872; (b) C. R. Horn,

J. M. Martín-Alvarez and J. A. Gladysz, Organometallics, 2002, 21,

5386.

129.8 (s, p-Ph), 128.1 (virtual t,

J

CP

= 4.7, m-Ph), 28.9 (virtual

t,³⁴J_CP= 6.6, PCH₂CH₂CH₂), 26.8 (s, CH₂), 26.63 (s, CH₂),

34

26.59 (s, CH₂), 26.3 (s, CH₂), 21.8 (s, CH₂), 21.2 (virtual t,

J

CP

= 16.6, PCH₂); ³¹P{¹H} 7.2 (s, ¹J_PPt= 2520).³⁵

5 (a) A. V. Chuchuryukin, H. P. Dijkstra, B. M. J. M. Suijkerbuijk,

R. J. M. Klein Gebbink, G. P. M. van Klink, A. M. Mills, A. L. Spek

and G. van Koten, Angew. Chem., 2003, 115, 238; A. V.

Chuchuryukin, H. P. Dijkstra, B. M. J. M. Suijkerbuijk, R. J. M.

Klein Gebbink, G. P. M. van Klink, A. M. Mills, A. L. Spek and

G. van Koten, Angew. Chem., Int. Ed., 2003, 42, 228; (b) V. Martinez,

J.-C. Blais and D. Astruc, Angew. Chem., 2003, 115, 4502;

V. Martinez, J.-C. Blais and D. Astruc, Angew. Chem., Int. Ed., 2003,

42, 4366; (c) T. Inomata and K. Konishi, Chem. Commun., 2003,

1282.

6 C. A. Bessel, P. Aggarwal, A. C. Marschilok and K. J. Takeuchi,

Chem. Rev., 2001, 101, 1031.

7 (a) P. E. Garrou and G. E. Hartwell, J. Organomet. Chem., 1974, 71,

443; (b) P. W. Clark, P. Hanisch and A. J. Jones, Inorg. Chem., 1979,

18, 2067.

IR (cm^Ϫ1, powder ﬁlm) 2926, 2856, 2374, 1502, 1455, 1112,

1061, 957, 803, 745, 695. MS:²⁹1006 (16e^ϩ, 15%), 970 ([16e Ϫ

Cl]^ϩ, 40%), 801 ([16e Ϫ Cl Ϫ C₆F₅]^ϩ, 60%)]^ϩ, 495 ([16e Ϫ Cl Ϫ

C₆F₅Ϫ 20e]^ϩ, 90%), 305 (20e^ϩ, 100%).

Crystallography.¹⁵

Toluene solutions of syn-15e, anti-15e and 16e were layered

with ethanol. The samples were stored at Ϫ20 ЊC. After three to

thirty days, colorless prisms had formed. Complexes 16a, syn-

(E,E)-13c, and syn-15c were suspended in methanol and

warmed. THF was added until the samples were homogeneous.

The mixtures were kept at room temperature. After one day,

colorless prisms had formed.

8 M. A. Bennett, H. W. Kouwenhoven, J. Lewis and R. S. Nyholm,

J. Chem. Soc., 1964, 4570.

Data were collected as outlined in Table 1. Cell parameters

were obtained from 10 frames using a 10Њ scan and reﬁned with

≥6873 reﬂections (syn-15e, 10003; anti-15e, 7885; 16e, 9914;

16a, 6873; syn-(E,E)-13c, 8701; syn-15c, 23439). Lorentz,

polarization, and absorption corrections were applied.³⁹The

space groups were determined from systematic absences and

subsequent least-squares reﬁnement. The structures were

solved by direct methods. The parameters were reﬁned with all

data by full-matrix-least-squares on F ²using SHELXL-97.⁴⁰

Non-hydrogen atoms were reﬁned with anisotropic thermal

parameters. The hydrogen atoms were ﬁxed in idealized

positions using a riding model. Scattering factors were taken

from literature.⁴¹The quality of the crystal of syn-15c, which

contained two independent molecules in the unit cell, was lower

than the others.

9 R. Usón, J. Forniés, P. Espinet and G. Alfranca, Synth. React. Inorg.

Met.-Org., Chem., 1980, 10, 579.

10 R. Usón, J. Forniés, P. Espinet, R. Navarro and C. Fortuño, J. Chem.

Soc., Dalton Trans., 1987, 2077.

11 W. Mohr, J. Stahl, F. Hampel and J. A. Gladysz, Chem. Eur. J., 2003,

9, 3324.

12 (a) M. Schuman, M. Trevitt, A. Redd and V. Gouverneur, Angew.

Chem., 2000, 112, 2604; M. Schuman, M. Trevitt, A. Redd

and V. Gouverneur, Angew. Chem., Int. Ed., 2000, 39, 2491; (b)

C. A. Slinn, A. J. Redgrave, S. L. Hind, C. Edlin, S. P. Nolan and

V. Gouverneur, Org. Biomol. Chem., 2003, 1, 3820.

13 M. Leconte, I. Jourdan, S. Pagano, F. Lefebvre and J.-M. Basset,

J. Chem. Soc., Chem. Commun., 1995, 857.

14 T. Imamoto, T. Kusumoto, N. Suzuki and K. Sato, J. Am. Chem.

Soc., 1985, 107, 5301.

15 The atom numbering in Tables 2 and 3, and Figs. 1–3, 5, and 6, has

been altered from those in the CIF ﬁles to facilitate comparisons

between molecules.

16 (a) J. C. Collings, K. P. Roscoe, E. G. Robins, A. S. Batsanov,

L. M. Stimson, J. A. K. Howard, S. J. Clark and T. B. Marder,

New J. Chem., 2002, 26, 1740, and references therein.; (b) F. Ponzini,

R. Zagha, K. Hardcastle and J. S. Siegel, Angew. Chem., 2000, 112,

2413; F. Ponzini, R. Zagha, K. Hardcastle and J. S. Siegel, Angew.

Chem., Int. Ed., 2000, 39, 2323; (c) G. W. Coates, A. R. Dunn,

L. M. Henling, J. W. Ziller, E. B. Lobkovsky and R. H. Grubbs,

J. Am. Chem. Soc., 1998, 120, 3641; (d ) M. L. Renak,

G. P. Bartholomew, S. Wang, P. J. Ricatto, R. J. Lachicotte and G. C.

Bazan, J. Am. Chem. Soc., 1999, 121, 7787.

17 J. Sandström, Dynamic NMR Spectroscopy, Academic Press,

New York, 1982; calculations utilized eqn. 7.4c.

18 (a) B. L. Shaw, J. Am. Chem. Soc., 1975, 97, 3856; (b) A. Pryde,

B. L. Shaw and B. Weeks, J. Chem. Soc., Dalton. Trans., 1976, 322.

19 While this paper was being reviewed, we found that syn-(E,E)-13c

could be isolated in up to 58% yield using Grubbs’ “second

CCDC reference numbers: syn-15e, 159809; anti-15e, 227266;

16e, 227267; 16a, 227269; syn-(E,E)-13c, 227270; syn-15c,

227268.

See http://ww w .rsc.org/suppdata/dt/b4/b400156g/ for crystal-

lographic data in CIF or other electronic format.

Acknowledgements

We thank the Deutsche Forschungsgemeinschaft (DFG,

GL 300/1–3), Alexander von Humboldt Foundation (Fellow-

ship to T. S.), and Johnson Matthey PMC (platinum and

ruthenium loans) for support.

References

generation” catalyst Ru(᎐CHPh)(H₂IMes)(PCy₃)(Cl)₂(20 mol%)

᎐

1 E. B. Bauer and J. A. Gladysz, in Handbook of Metathesis, ed.

R. H. Grubbs, Wiley-VCH, Weinheim, Germany, 2003, vol. 2,

pp 395–423.

and extended reaction times that partially transform the byproducts.

Analogous enhancements were not observed with 11d,f, nor with the

metatheses in Scheme 1.^3dThese results will described, together with

data for other advanced-generation catalysts, at a later date.

20 P. L. Ng and J. N. Lambert, Synlett, 1999, 1749.

21 (a) P. G. Sammes and D. J. Weller, Synthesis, 1995, 1205; (b) M. D. E.

Forbes, J. T. Patton, T. L. Myers, H. D. Maynard, D. W. Smith, Jr.,

G. R. Schulz and K. B. Wagener, J. Am. Chem. Soc., 1992, 114,

10978.

22 E. B. Bauer, S. Szafert, F. Hampel and J. A. Gladysz,

Organometallics, 2003, 22, 2184.

23 E. B. Bauer, Doctoral Dissertation, Universität Erlangen-Nürnberg,

2003.

2 (a) M. Weck, B. Mohr, J.-P. Sauvage and R. H. Grubbs, J. Org.

Chem., 1999, 64, 5463; (b) C. Dietrich-Buchecker, G. Rapenne and

J.-P. Sauvage, Chem. Commun., 1997, 2053; (c) C. Dietrich-

Buchecker and J.-P. Sauvage, Chem. Commun., 1999, 615; (d )

G. Rapenne, C. Dietrich-Buchecker and J.-P. Sauvage, J. Am. Chem.

Soc., 1999, 121, 994; (e) N. Belfrekh, C. Dietrich-Buchecker and

J.-P. Sauvage, Inorg. Chem., 2000, 39, 5169; ( f ) P. Mobian,

J.-M. Kern and J.-P. Sauvage, J. Am. Chem. Soc., 2003, 125, 2016;

(g) P. Mobian, J.-M. Kern and J.-P. Sauvage, Helv. Chim. Acta.,

2003, 86, 4195; (h) P. Mobian, J.-M. Kern and J.-P. Sauvage, Inorg.

Chem., 2003, 42, 8633.

24 A. Bondi, J. Phys. Chem., 1964, 68, 441.

3 (a) J. M. Martín-Alvarez, F. A. Hampel, A. M. Arif and

J. A. Gladysz, Organometallics, 1999, 18, 955; (b) E. B. Bauer,

J. Ruwwe, J. M. Martín-Alvarez, T. B. Peters, J. C. Bohling,

F. A. Hampel, S. Szafert, T. Lis and J. A. Gladysz, Chem. Commun.,

2000, 2261; (c) J. Ruwwe, J. M. Martín-Alvarez, C. R. Horn,

E. B. Bauer, S. Szafert, T. Lis, F. Hampel, P. C. Cagle and

J. A. Gladysz, Chem. Eur. J., 2001, 7, 3931; (d ) E. B. Bauer,

F. Hampel and J. A. Gladysz, Organometallics, 2003, 22, 5567.

4 (a) J. Stahl, J. C. Bohling, E. B. Bauer, T. B. Peters, W. Mohr,

J. M. Martín-Alvarez, F. Hampel and J. A. Gladysz, Angew. Chem.,

25 T. Shima, F. Hampel, J. A. Gladysz, manuscript in preparation.

26 H. K. Cammenga and M. Epple, Angew. Chem., 1995, 107, 1284;

H. K. Cammenga and M. Epple, Angew. Chem., Int. Ed., 1995, 34,

1171.

27 δ, CDCl₃; all J values are in Hz.

28 The PC₆H₅¹³C NMR signals were assigned as described by

B. E. Mann, J. Chem. Soc., Perkin Trans. 2, 1972, 30; that with the

chemical shift closest to benzene was attributed to the meta carbon,

and the least intense phosphorus-coupled signal was attributed to

the ipso, carbon.

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1027

View Article Online

29 FAB, 3-NBA, m/z, (relative intensity, %); the most intense peak of

isotope envelope is given.

35 This coupling represents a satellite (d; ¹⁹⁵Pt = 33.8%), and is not

reﬂected in the peak multiplicity given.

36 The abbreviations 2ؒPt and 2ؒP indicate ions with twice the mass of

the expected monoplatinum or monophosphorus products.

37 The PCH₂CH₂¹H and C₆H₅¹³C NMR signals were assigned by

analogy to syn-15e.

38 The isotope envelope calculated for this ion agreed with that

observed. For phosphine boranes that give analogous ions, see ref.

12a.

39 (a) “Collect” data collection software, Nonius B.V., Delft, 1998; (b)

“Scalepack” data processing software Z. Otwinowski and W. Minor,

Methods Enzymol. A, 1997, 276, 307.

40 G. M. Sheldrick, SHELX-97, Program for reﬁnement of crystal

structures, University of Göttingen, 1997.

41 D. T. Cromer and J. T. Waber, in International Tables for X-ray

Crystallography, ed. J. A. Ibers and W. C. Hamilton, Kynoch Press,

Birmingham, England, 1974.

30 A satisfactory microanalysis was not obtained.

31 (a) The C₆F₅¹³C NMR signals were not observed. These require

larger numbers of transients due to the ﬂuorine and platinum

couplings; (b) The ipso PC₆H₅¹³C NMR signals were not

observed.

32 The PtPC₆H₅¹³C NMR assignments have abundant precedent. See,

for example: P. W. Jolly and R. Mynott, Adv. Organomet. Chem.,

1981, 19, 257.

33 (a) For syn-15e, the PtPCH₂CH₂CH₂¹³C assignments were

1

conﬁrmed by a H,¹³C COSY spectrum. The corresponding signals

in 11b–f and 16e, and the PtPCH₂CH₂CH᎐ signals of 11a, were

᎐

assigned by analogy; (b) The ¹H assignments for syn-15e were in turn

veriﬁed by a ¹H,¹H COSY experiment.

34 P. S. Pregosin and L. M. Venanzi, Chem. Br., 1978, 276; the apparent,

coupling between adjacent peaks of the triplet is given.

D a l t o n T r a n s . , 2 0 0 4 , 1 0 1 2 – 1 0 2 8

1028

Article Doi

Alkene metatheses in transition metal coordination spheres: Dimacrocyclizations that join trans positions of square-planar platinum complexes to give topologically novel diphosphine ligands

DOI: 10.1039/b400156g

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