Complexes of 2,3-bis(diphenylphosphino)propene with PtII, PdII and RuII: Synthesis, characterisation and rearrangements to complexes of cis-1,2-bis(diphenylphosphino)propene

Article abstract of DOI:10.1039/a801351i

Treatment of [PdCl₂(PhCN)₂] with 1 equivalent of 2,3-bis(diphenylphosphino)propene (2,3-dpppn) in CH₂Cl₂ gave [PdCl₂(2,3-dpppn)] 1 together with some [PdCl₂(1,2-dpppn)] 2 [1,2-dpppn = cis-1,2-bis(diphenylphosphino)propene]. Treatment of 1 with an excess of benzylamine did not lead to addition to the double bond, but resulted in complete isomerisation to 2, as monitored by ³¹P-{¹H} and ¹H NMR spectroscopy. Metathesis of 2 with NaI in acetone gave [PdI₂(1,2-dpppn)] 3. Platinum(II) complexes [PtCl₂(2,3-dpppn)] 4 and [PtCl₂(1,2-dpppn)] 5 were prepared and characterised analogously. Treatment of 2 or 5 with an excess of MeLi gave [PdMe₂(1,2-dpppn)] 6 and [PtMe₂(1,2-dpppn)] 7 respectively, and treatment of 5 with hydrazine hydrate and an excess of HC≡CPh in ethanol gave [Pt(C≡CPh)₂(1,2-dpppn)] 8. Treatment of [PdCl₂(PhCN)₂] with 2 equivalents of AgBF₄ and 2 equivalents of 2,3-dpppn gave a mixture of at least four isomeric complexes, probably cis- and trans-[Pd(2,3-dpppn)₂][BF₄]₂ and cis- and trans-[Pd(1,2-dpppn)₂][BF₄]₂. On treatment with benzylamine, this mixture was converted into a ca. 1:1 mixture of two isomers, which NMR spectroscopic evidence suggested were cis- and trans-[Pd(1,2-dpppn)₂][BF₄]₂ 9. Similarly, treatment of [Pt(Cl₂(PhCN)₂] with AgBF₄-2,3-dpppn gave cis- and trans-[Pt(1,2-dpppn)₂][BF₄]₂ 10. A crystal structure determination was performed on the trans isomer, isolated on recrystallisation of the mixture from MeCN-Et₂O. Treatment of [RuCl₂(PPh₃)₃] with 2 equivalents of 2,3-dpppn gave a very insoluble complex, trans-[RuCl₂(dpppn)₂] 11. Treatment of [RuCl(η⁵-C₅H₅)(PPh₃) ₂] with 2,3-dpppn in refluxing benzene gave [RuCl(η⁵-C₅H₅)(1,2-dpppn)] 12. The formulation of 12 was confirmed by a single-crystal structure determination.

Full text of DOI:10.1039/a801351i

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Complexes of 2,3-bis(diphenylphosphino)propene with PtII, PdII and
RuII: synthesis, characterisation and rearrangements to complexes of
cis-1,2-bis(diphenylphosphino)propene
Jim Barkley, Simon J. Higgins* and Mark K. McCart
Department of Chemistry, University of Liverpool, Chemistry Buildings, Crown Street, Liverpool,
UK L69 7ZD
Treatment of [PdCl2(PhCN)2] with 1 equivalent of 2,3-bis(diphenylphosphino)propene (2,3-dpppn) in CH2Cl2
gave [PdCl2(2,3-dpppn)] 1 together with some [PdCl2(1,2-dpppn)] 2 [1,2-dpppn = cis-1,2-
bis(diphenylphosphino)propene]. Treatment of 1 with an excess of benzylamine did not lead to addition to the
double bond, but resulted in complete isomerisation to 2, as monitored by 31P-{1H} and 1H NMR spectroscopy.
Metathesis of 2 with NaI in acetone gave [PdI2(1,2-dpppn)] 3. Platinum() complexes [PtCl2(2,3-dpppn)] 4 and
[PtCl2(1,2-dpppn)] 5 were prepared and characterised analogously. Treatment of 2 or 5 with an excess of MeLi
gave [PdMe2(1,2-dpppn)] 6 and [PtMe2(1,2-dpppn)] 7 respectively, and treatment of 5 with hydrazine hydrate
᎐
᎐
and an excess of HC᎐CPh in ethanol gave [Pt(C᎐CPh) (1,2-dpppn)] 8. Treatment of [PdCl (PhCN) ] with 2
᎐
᎐
2
2
2
equivalents of AgBF4 and 2 equivalents of 2,3-dpppn gave a mixture of at least four isomeric complexes, probably
cis- and trans-[Pd(2,3-dpppn)2][BF4]2 and cis- and trans-[Pd(1,2-dpppn)2][BF4]2. On treatment with benzylamine,
this mixture was converted into a ca. 1:1 mixture of two isomers, which NMR spectroscopic evidence suggested
were cis- and trans-[Pd(1,2-dpppn)2][BF4]2 9. Similarly, treatment of [PtCl2(PhCN)2] with AgBF4–2,3-dpppn gave
cis- and trans-[Pt(1,2-dpppn)2][BF4]2 10. A crystal structure determination was performed on the trans isomer,
isolated on recrystallisation of the mixture from MeCN–Et2O. Treatment of [RuCl2(PPh3)3] with 2 equivalents of
2,3-dpppn gave a very insoluble complex, trans-[RuCl2(dpppn)2] 11. Treatment of [RuCl(η5-C5H5)(PPh3)2] with
2,3-dpppn in refluxing benzene gave [RuCl(η5-C5H5)(1,2-dpppn)] 12. The formulation of 12 was confirmed by a
single-crystal structure determination.
The chemistry of alkenyldiphosphines has been extensively
investigated. For example, the readily synthesized 1,1-bis-
(diphenylphosphino)ethene1 undergoes base-catalysed addition
of P᎐H bonds, and this has been used to synthesize new
multidentate phosphines such as 1,1,2-tris(diphenylphosphino)-
which the free diphosphine could be displaced by treatment
with an excess of CNϪ.15
The ligand 2,3-bis(diphenylphosphino)propene (2,3-dpppn)
has been described.16 Complexes [M(2,3-dpppn)(CO)4] (M =
Cr, Mo or W) were found to undergo rearrangement to
[M(1,2-dpppn)(CO)4] [1,2-dpppn = cis-1,2-bis(diphenylphos-
phino)propene] on treatment with catalytic amounts of KOBut
and HPPh2. Nucleophilic addition to co-ordinated 2,3-dpppn
would not be expected to be as favourable as addition to co-
ordinated 1,1-bis(diphenylphosphino)ethene, as the relief of
angle strain is unlikely to be an important consideration for the
five-membered chelate ring. Nevertheless, excess of HPPh2
was reported to undergo base-catalysed addition to [M(2,3-
dpppn)(CO)4] (M = Cr, Mo or W), to give η2-co-ordinated
1,2,3-tris(diphenylphosphino)propane, whereas this reaction
did not occur with free 2,3-dpppn.16
Previously, it was shown that the double bond of 1,1-bis-
(diphenylphosphino)ethene was activated to nucleophilic
addition much more by co-ordination to metals in a higher
oxidation state (e.g. PdII, PtII, PtIV) than by co-ordination to M0
(M = Cr, Mo or W).5,6 It was therefore of interest to investigate
the co-ordination chemistry of 2,3-dpppn with PdII, PtII and
RuII, and to investigate whether the co-ordinated ligand would
undergo nucleophilic addition. In this paper, we report the syn-
theses and characterisation of neutral and cationic 2,3-dpppn
complexes of these metals, and some chemistry of the co-
ordinated ligand.
ethane
and
bis[2,2-bis(diphenylphosphino)ethyl]phenyl-
phosphine.2 In its chelate complexes the double bond of
1,1-bis(diphenylphosphino)ethene becomes greatly activated to
nucleophilic addition,3 probably because this reduces angle
strain in the four-membered chelate rings. This is a convenient
way of preparing complexes of functionalised diphosphine
ligands,4–6 and we have recently used such chemistry to syn-
thesize redox-active ruthenium() complexes for anchoring to
oxide surfaces7,8 or for incorporation into electrochemically
generated conjugated polymers.9 Recently, gold()–methanide
complexes have been synthesized by nucleophilic addition to
[Au(C F ) Cl{(Ph P) C᎐CH }];10 the latter chemistry is interest-
᎐
6
5
2
2
2
2
ing as methanide complexes may be intermediates in the form-
ation of co-ordinated (Ph2P)2CHCH2X (XH = nucleophile) in
the earlier papers.
Convenient syntheses of diphosphines capable of forming
five- or six-membered chelate rings, and bearing additional
functionality, would be of considerable interest, but relatively few
examples have been reported.11 Efforts have been made to use
co-ordinated alkenyldiphosphines and alkynylphosphines for
this purpose. Complexes of (Ph PCH ) C᎐CH with Cr0, Mo0
᎐
2
2
2
2
and W0 12,13 and with PtII 14 have been described. Deprotonation
of the complexed ligand gave resonance-stabilised co-ordinated
bis(diphenylphosphino)allyl anions, which on treatment with
electrophiles R᎐X gave complexes of the corresponding
Results and Discussion
Neutral complexes of PdII and PtII
coordinated Z-Ph PCH᎐CHMeCHRPPh . Some time ago the
᎐
2
2
addition of HPRЈ2 (RЈ = Ph or C2H4CN) or HP(Et)Ph to cis-
The ligand 2,3-dpppn was prepared by the literature route, reac-
tion between 2,3-dichloropropene and NaPPh2 in liquid
ammonia.16 Recrystallisation from CH2Cl2–EtOH is necessary
t
᎐
[MCl (Ph PC᎐CR) ] (M = Pd or Pt; R = Bu , Ph or CF ) was
᎐
2
2
2
3
reported to give complexes [MCl (cis-Ph PCH᎐CRPRЈ )], from
᎐
2
2
2
J. Chem. Soc., Dalton Trans., 1998, Pages 1787–1792
1787

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to free the ligand from traces of trans-1,2-bis(diphenylphos-
phino)propene in the crude product. The latter is formed by
base-catalysed allylic rearrangement of 2,3-dpppn, and has
been independently synthesized using this reaction.16
trans to Cl. The 1H NMR spectrum, recorded in CD2Cl2, shows
resonances characteristic of co-ordinated 2,3-dpppn (Experi-
mental section). In particular, there are two multiplets for the
two protons Hα and HαЈ at δ 6.03 and 5.27 respectively (the
latter partially obscured by the CHDCl2 resonance). Coupling to
195Pt was not resolved for these resonances. A multiplet with
195Pt satellites at δ 3.16 is assigned to the Hγ protons. The 31P-
{1H} NMR spectrum again showed the presence of a second
complex, this time 10% of the total signal intensity, with two
equally intense doublets at δ 53.1 and 35.3. The satellites due to
coupling to 195Pt were not resolved because of the poor signal-
to-noise ratio in this case. That this was the isomer [PtCl2(1,2-
dpppn)] 5 was again confirmed when treatment of 4 with ben-
zylamine in refluxing chlorobenzene resulted in a slow but total
conversion into 5, enabling 5 to be independently characterised.
The 31P-{1H} NMR spectrum of 5 is similar to those of
Hα
Hα′
Hγ
Ph2PX
1,2–dpppn
CHα
3
Hγ
Hγ
PAPh2
Ph2PX
PAPh2
2,3–dpppn
Treatment of [PdCl2(PhCN)2] with 1 equivalent of 2,3-dpppn
in CH2Cl2 gave yellow [PdCl2(2,3-dpppn)] 1. This complex was
insoluble in benzene, alcohols, acetone and thf, and only spar-
ingly soluble in CH2Cl2 and CHCl3. It was characterised by
correct microanalyses (C and H; Experimental section), FAB
mass spectrometry (Experimental section), which showed a
cluster of peaks at m/z 553 corresponding to [M Ϫ Cl]ϩ, and by
NMR spectroscopy (Experimental section; for convenience, we
adopt the labelling scheme originally used for these ligands,16
illustrated). The 31P-{1H} NMR spectrum showed two doublets
of equal intensity, at δ 56.9 and 42.0, with JPP 12 Hz. As
expected for a five-membered chelate ring diphosphine complex
of PdII, the resonances are shifted considerably downfield from
the free diphosphine values.17 The 31P-{1H} NMR spectrum also
revealed the presence of a second, minor species (4% total sig-
nal), giving two more doublets of equal intensity at δ 77.2 and
58.3 (JPP 15 Hz). These parameters are comparable with those
[PtCl (cis-Ph PCH᎐CRPPh )] (R = CF , Ph or But),15 except
᎐
2
2
2
3
that whereas the JPP for the latter complexes were reportedly
too small to be observed we found that JPP for 5 was 15 Hz. The
phosphine trans to Hγ is again assigned as having the more
downfield chemical shift (and therefore the larger value of
1JPtP), by analogy with 2, and with [PtCl (cis-Ph PCH᎐
᎐
2
2
CRPPh2)] (R = CF3, Ph or But).15 The presence of an amine was
essential; refluxing 4 in chlorobenzene alone (16 h) did not
result in isomerisation. On the other hand, prolonged treatment
of a CH2Cl2 solution of 4 with catalytic amounts of KOBut/18-
crown-6, or 1,8-bis(dimethylamino)naphthalene, did not result
in significant conversion into 5 either.
Treatment of complex 2 in dry diethyl ether with an excess of
MeLi gave [PdMe2(1,2-dpppn)] 6 in good yield, and treatment
of 5 with MeLi gave [PtMe2(1,2-dpppn)] 7; characterising data
of the known complexes [PtCl (cis-Ph PCH᎐CRPPh )]
᎐
2
2
2
(R = CF3, Ph or But),15 suggesting that partial isomerisation
had occurred to give [PdCl2(1,2-dpppn)].†
1
are in the Experimental section. In the H NMR spectra of 6
We wished to examine whether amines would add to the
double bond of co-ordinated 2,3-dpppn, in a similar fashion to
the addition of HPPh2 to complexes [M(2,3-dpppn)(CO)4]
(M = Cr, Mo or W),16 or whether this would result in base-
catalysed isomerisation to co-ordinated cis-1,2-bis(diphenyl-
phosphino)propene. Accordingly, we treated 1 with a large
excess of benzylamine in chlorobenzene, and monitored the
progress of the reaction by 31P-{1H} NMR spectroscopy. The
only changes noted were that the proportion of the minor com-
ponent in the spectrum increased. When the solution was
refluxed overnight and re-examined the signals due to complex
1 had disappeared, and only the two doublets assigned to 2 were
observed. The identity of 2 was confirmed by the isolation and
characterisation of the complex. In particular, the micro-
analyses and FAB mass spectrum were consistent with it being
and 7 the alkenyl proton resonances are once again well
resolved and clear of the aromatic resonances. The two methyl
ligand resonances appear as deceptively simple triplets18 (in
the case of 7, with satellites due to JPtH) and occur at signifi-
cantly different chemical shifts; we do not know which is which.
Treatment of 5 with hydrazine hydrate and an excess of
᎐
᎐
HC᎐CPh in ethanol gave [Pt(C᎐CPh) (1,2-dpppn)] 8 in moder-
᎐
᎐
2
ate yield. Although the alkenyl resonance is obscured by the
1
phenyl resonances in the H NMR spectrum of this complex
the characteristic resonance for the methyl group is evident.
Complexes 6–8 were significantly soluble in thf and toluene,
facilitating spectroscopic characterisation.
Cationic complexes of PdII and PtII
1
an isomer of 1. The H NMR spectrum showed a doublet of
Treatment of [PdCl2(PhCN)2] with 2 equivalents of AgBF4 and
2 equivalents of 2,3-dpppn in MeCN–CH2Cl2 gave a white solid
on work-up. This had correct microanalyses (C and H) for a
complex [Pd(dpppn)2][BF4]2 and showed clusters of peaks at
m/z 1013 ([M Ϫ BF4]ϩ) and 926 ([M Ϫ HBF4 Ϫ BF4]ϩ) in the
FAB mass spectrum. The complex was sparingly soluble in
MeCN and the 31P-{1H} NMR spectrum, though noisy, was
consistent with the presence of at least four isomeric complexes,
probably cis- and trans-[Pd(2,3-dpppn)2][BF4]2 and cis- and
trans-[Pd(1,2-dpppn)2][BF4]2 (cis- and trans-9, Scheme 1). The
presence in the mixture of small amounts of additional isomers
of the type [Pd(1,2-dpppn)(2,3-dpppn)]2ϩ cannot be ruled out;
their 31P-{1H} spectra, which one would expect to be very com-
plex, may be lost in the noise. Prolonged treatment of this mix-
ture with an excess of benzylamine resulted in conversion into a
ca. 1:1 mixture of cis- and trans-9, as revealed by the 31P-{1H}
spectrum (Fig. 1). Both isomers show AAЈXXЈ spectra as
expected. The resonances of the trans isomer are ‘virtual’ trip-
lets owing to the strong P-trans-P coupling, typical of pal-
ladium() complexes.17 Although line shape analysis was not
possible, an empirical simulation of peak positions and inten-
sities was carried out using the program gNMR. The coupling
constants used (Experimental section) are consistent with
doublets for the single alkenyl proton Hγ at δ 6.85, due to coup-
ling to both phosphorus atoms (Experimental section), with a
further small coupling to the protons of the methyl group,
in turn seen at δ 2.11. This contrasts with the spectra of
[PdCl (cis-Ph PCH᎐CRPPh )] (R = CF , Ph or But) which were
᎐
2
2
2
3
reported, somewhat surprisingly, to show only doublet reson-
ances for the alkenyl protons where these were not obscured by
the phenyl resonances.15 The assignment of the more downfield
31P-{1H} resonance to PA (Experimental section), as for the
complexes [M(CO)4(1,2-dpppn)],16 was confirmed by recording
the 31P NMR spectrum; the resonance at δ 58.3 was simply
broadened compared with the 31P-{1H} spectrum, but the res-
onance at δ 77.2 was a broad doublet (JPH ca. 60 Hz), clearly
due to the large coupling to the trans proton Hγ. Metathesis of 2
with LiI in hot acetone afforded yellow [PdI2(1,2-dpppn)] 3,
characterised similarly (Experimental section).
Treatment of [PtCl2(PhCN)2] in refluxing benzene with 2,3-
1
dpppn gave [PtCl2(2,3-dpppn)] 4. The values of JPtP for both
doublets in the 31P-{1H} NMR spectrum of 4 are typical of P
† Throughout this paper, the abbreviation 1,2-dpppn refers to the cis
isomer of 1,2-bis(diphenylphosphino)propene as shown.
1788
J. Chem. Soc., Dalton Trans., 1998, Pages 1787–1792

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2+
PA PA′
M
PA PA′
M
Table 1 Significant bond lengths (Å) and angles (Њ) for trans-[Pt(1,2-
dpppn)2][BF4]2 10
2 2,3–dpppn
2 AgBF4
PX PX′
PX PX′
[MCl2(PhCN)2]
Pt᎐P(1)
2.326(3)
2.329(4)
1.81(1)
1.82(2)
1.79(1)
P(2)᎐C(19)
P(2)᎐C(13)
P(2)᎐C(27)
C(25)᎐C(26)
C(25)᎐C(27)
1.82(1)
1.82(1)
1.83(1)
1.41(3)
1.32(2)
cis
cis
MeCN
Pt᎐P(2)
PA PX′
M
PA PX′
M
P(1)᎐C(1)
P(1)᎐C(25)
P(1)᎐C(7)
PX PA′
PX PA′
trans
trans
P(1)᎐Pt᎐P(1)
P(1)᎐Pt᎐P(2)
P(1)᎐Pt᎐P(2*)
Pt᎐P(1)᎐C(25)
P(1)᎐C(25)᎐C(27) 120(1)
P(2)᎐C(27)᎐C(25) 116(1)
Pt᎐P(2)᎐C(27)
Pt᎐P(1)᎐C(7)
Pt᎐P(1)᎐C(1)
180.00
82.5(1)
97.5(1)
107.3(5)
C(1)᎐P(1)᎐C(7)
C(7)᎐P(1)᎐C(25)
Pt᎐P(2)᎐C(13)
Pt᎐P(2)᎐C(19)
C(13)᎐P(2)᎐C(19) 107.5(6)
C(19)᎐P(2)᎐C(27) 104.4(6)
C(13)᎐P(2)᎐C(27) 104.2(6)
P(1)᎐C(25)᎐C(26) 123(1)
105.7(6)
104.7(7)
118.9(4)
112.9(4)
9
10
M = Pd M = Pt
M = Pd only
Scheme 1 Synthesis of isomers of cationic [Pd(dpppn)2]2ϩ complexes,
and structures of cis- and trans-9 and 10, showing the labelling scheme
for the 31P nuclei used in the discussion of the NMR data and the
assignments PA and PX in the Experimental section
107.7(5)
117.3(5)
115.0(4)
C(1)᎐P(1)᎐C(25)
105.7(7)
Fig. 1 The 31P-{1H} NMR spectrum (101 MHz, CD3CN) of complex
10, showing the mixture of the two isomers referred to in the text. The
two ‘virtual’ triplets are due to the trans isomer
Fig. 2 Molecular structure of the dication trans-10. Ellipsoids are
drawn at the 50% probability level
1
published values for related complexes.15 The H NMR spec-
high, as is the residual electron density, which is localised
around the BF4 ions. Attempts to improve the weighting
Ϫ
trum (CD3CN) showed two rather broad, overlapping multi-
plets at δ 2.15 and 2.09, assigned to the methyl groups of the
different isomers; we do not know which is which. The reson-
ances of the alkenyl protons could not be discerned, and are
presumably obscured by the rather broad aromatic resonances.
Treatment of [PtCl2(PhCN)2] with 2 equivalents of AgBF4
and 2 equivalents of 2,3-dpppn in MeCN–CH2Cl2 likewise gave
a white solid on work-up, the microanalyses and FAB mass
spectrum of which were consistent with the formulation
[Pt(dpppn)2][BF4]2. The 31P-{1H} NMR spectrum was consist-
scheme, or model the residual electron density in terms of frac-
tional amounts of solvent, or disordered BF4Ϫ, were unsuccess-
ful. The structure is illustrated in Fig. 2, and significant bond
lengths and angles are given in Table 1. The structure is similar
to that of [Pt(cis-Ph PCH᎐CHPPh ) ][BPh ] .20 The centro-
᎐
2
2
2
4 2
symmetric space group means that trans-10 has a crystal-
lographically imposed centre of symmetry, as does [Pt(cis-
Ph PCH᎐CHPPh ) ][BPh ] . The Pt᎐P bond lengths [mean
᎐
2
2
2
4 2
2.328(3) Å] are similar to those in [Pt(cis-Ph PCH᎐
᎐
2
1
ent with the presence of only two isomers in this case. The H
CHPPh2)2][BPh4]2 [mean 2.336(1) Å]. The complexes [PtCl2(cis-
NMR spectrum, though of poor quality owing to the limited
solubility of the complex, suggested that these were cis- and
trans-[Pt(1,2-dpppn)2][BF4]2 (cis- and trans-10); a broad multi-
plet at δ 2.16 is assigned to the ligand methyl protons. Further-
more, no alkenyl proton resonances were observed. Whereas
the single 1,2-dpppn alkenyl resonance is sometimes obscured
by the phenyl resonances, this is most unlikely to be the case
for the two more upfield alkenyl resonances characteristic of
2,3-dpppn. The 31P-{1H} NMR spectrum of a solution of the
isomer mixture in MeCN–CD3CN was recorded at regular
intervals for 2 weeks; no change was observed. We do not know
why PtII causes complete isomerisation to 1,2-dpppn whereas
PdII gives a mixture of 1,2-dpppn and 2,3-dpppn complexes in
these reactions.
Ph PCH᎐CHPPh )] and [Pt(cis-Ph PCH᎐CHPPh ) ][BPh ]
᎐ ᎐
2 2 2 2 2 4 2
have rigidly planar Pt᎐P᎐CH᎐CH᎐P units (within the e.s.d.s)
᎐
and short C᎐C bonds [1.28(2), 1.315(5) Å respectively], and this
᎐
was attributed to significant conjugation between the ligand
backbone and the PtP2 system.20 However, although complex
10 has a C᎐C bond length [1.31(2) Å] comparable with that of
᎐
[Pt(cis-Ph PCH᎐CHPPh ) ][BPh ] , it also has a torsion angle
᎐
2
2
2
4 2
Pt᎐P(1)᎐C(25)᎐C(27) of Ϫ13(1)Њ, so the PtP2C2 chelate atoms
are not coplanar in 10; this is also clear by inspection of Fig. 2.
Thus, crystal packing forces are at least as significant as any
additional π interactions due to the P᎐CH᎐CH᎐P chelate sys-
᎐
tem in these complexes.21
It is apparent that co-ordination of 2,3-dpppn to PdII and PtII
in complexes [M(2,3-dpppn)2]2ϩ activates it towards base-
catalysed rearrangement to co-ordinated cis-1,2-dpppn more
effectively than co-ordination to neutral [M(CO)4] (M = Cr,
Mo or W)16 or MCl2 (M = Pd or Pt). This suggests that depro-
tonation of complexes 9 and 10, followed by treatment with
Crystals of complex 10 were grown from MeCN–Et2O by
diffusion. That chosen for X-ray crystallographic analysis
proved to be trans-10. In spite of the low-temperature
(Ϫ120 ЊC) data collection, the final R and RЈ values are rather
J. Chem. Soc., Dalton Trans., 1998, Pages 1787–1792
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Table 2 Significant bond lengths (Å) and angles (Њ) for [RuCl(η5-
C5H5)(1,2-dpppn)] 12
Ru᎐Cl
2.436(1)
2.258(1)
2.269(1)
2.236(5)
2.223(5)
2.166(5)
Ru᎐C(7)
Ru᎐C(8)
P(1)᎐C(2)
P(2)᎐C(1)
C(1)᎐C(2)
C(1)᎐C(3)
2.167(4)
2.211(4)
1.825(4)
1.846(4)
1.334(5)
1.505(7)
Ru᎐P(1)
Ru᎐P(2)
Ru᎐C(4)
Ru᎐C(5)
Ru᎐C(6)
Cl᎐Ru᎐P(1)
Cl᎐Ru᎐P(2)
P(1)᎐Ru᎐P(2)
Ru᎐P(1)C(2)
P(1)᎐C(2)᎐C(1)
86.69(4)
89.47(5)
82.37(4)
109.8(1)
117.2(3)
P(2)᎐C(1)᎐C(2)
Ru᎐P(2)᎐C(1)
P(2)᎐C(1)᎐C(3)
C(2)᎐C(1)᎐C(3)
116.1(3)
109.2(1)
121.5(3)
112.4(4)
which it is in all key respects similar; significant bond lengths
and angles are in Table 2. The alkenyl double bond in 12
[1.334(5) Å] is slightly longer than that in 10.
Fig. 3 Molecular structure of complex 12. Ellipsoids are drawn at the
50% probability level
Clearly, under these experimental conditions (prolonged
reflux; complexation to RuII), isomerisation of the double bond
has occurred without added base as a catalyst, in contrast to the
behaviour of the platinum() complex 4. It is possible that the
displaced PPh3 acts as a catalyst in the case of the ruthenium()
complex. Whereas several reports of metal-promoted isomeri-
sation of double bonds within alkenylmonophosphines
exist,26,27 these ligands chelate via both phosphorus and alkene,
and the reaction probably occurs via allyl-metal formation; this
is most unlikely with 2,3-dpppn.
electrophiles, might afford functionalised five-membered che-
late ring diphosphine complexes, and we are currently investi-
gating this.
Complexes with RuII
Treatment of [RuCl2(PPh3)3] with 2 equivalents of 2,3-dpppn in
CH2Cl2 gave a yellow precipitate. The microanalytical data were
consistent with the formulation [RuCl2(dpppn)2]ؒCH2Cl2 11.
The FAB mass spectrum of 11 showed a molecular ion at m/z
992 together with peaks due to loss of ClϪ and (ClϪ ϩ HCl), as
observed for similar [RuCl2(diphosphine)2] complexes.8 It
proved difficult to characterise 11 further because of its limited
solubility; after overnight accumulation in CDCl3 the 31P-{1H}
NMR spectrum (10 Hz line broadening) showed two broad
peaks at δ 45.96 and 28.65. Although it has not so far been
possible to determine whether 11 is a 1,2-dpppn or 2,3-dpppn
complex, this spectrum does show that chemically different
phosphorus atoms must be mutually cis, since P-trans-P coup-
ling constants for ruthenium() complexes are typically 400
Hz.22,23 Treatment of [RuCl2(PPh3)3] with 2 equivalents of other
five-membered ring chelate diphosphines under similarly mild
conditions usually gives trans-[RuCl2(diphosphine)2].24 It might
be expected that 11 would also adopt this geometry, and that
therefore it is either all-trans-[RuCl2(1,2-dpppn)2] or all-trans-
[RuCl2(2,3-dpppn)2]. Recently, ruthenium() complexes of the
Experimental
General methods were as described in previous papers from
this laboratory.6,8 Some fast atom bombardment mass spectra
were run at the EPSRC National Mass Spectrometry Service
(Swansea, UK). All reactions were performed under a nitrogen
atmosphere. Light petroleum was of boiling range 40–60 ЊC.
The ligand 2,3-dpppn was prepared from 2,3-dichloropropene
(Aldrich Chemical Co.; used as supplied) and NaPPh2 in liquid
ammonia by the published route,16 and was recrystallised from
CH2Cl2–EtOH (1:3).
Preparations
[PdCl2(2,3-dpppn)] 1. To a solution of [PdCl2(PhCN)2] (0.21
g, 0.55 mmol) in CH2Cl2 (20 cm3) was added the diphosphine
(0.23 g, 0.55 mmol). The mixture was refluxed with stirring
for 30 min. A yellow solid precipitated. The mixture was
cooled to room temperature and filtered. The solid was washed
with MeOH (3 × 3 cm3) and Et2O (3 × 3 cm3) and dried in
vacuo. Yield 0.19 g, 59% (Found: C, 55.26; H, 4.10.
C27H24Cl2P2Pd requires C, 55.18; H, 4.12%) Mass spectrum
(FAB, Xeϩ): m/z 553 ([M Ϫ Cl]ϩ). 31P-{1H} NMR (CDCl3, 101
related ligand cis-Ph PCH᎐CHPPh have been described.25
᎐
2
2
Treatment of [RuCl2(PPh3)3] with
2 equivalents of cis-
Ph PCH᎐CHPPh in refluxing ethanol gave a mixture of cis-
᎐
2
2
and trans-[RuCl (Ph PCH᎐CHPPh ) ]; the trans isomer was
᎐
2
2
2 2
characterised crystallographically.
Treatment of [RuCl(η5-C5H5)(PPh3)2] in refluxing benzene
with 2,3-dpppn for 20 min gave a red solution. The 31P-{1H}
NMR spectrum of this showed {in addition to free 2,3-dpppn,
PPh3 and unchanged [Ru(η5-C5H5)Cl(PPh3)2]} two pairs of
doublets, a more intense pair at δ 62.90 and 76.50 (JPP 34 Hz)
due to [RuCl(η5-C5H5)(2,3-dpppn)], and a less intense pair
at δ 87.08 and 73.3 (JPP 35 Hz) due to [RuCl(η5-C5H5)(1,2-
dpppn)]. After prolonged reflux and work-up a single product
was isolated, identified as [RuCl(η5-C5H5)(1,2-dpppn)] 12 from
the microanalytical and FAB mass spectral data (Experimental
section), the 31P-{1H} NMR spectrum and, in particular, the 1H
NMR spectrum, which showed a singlet due to the cyclopenta-
dienyl protons at δ 4.45 and a doublet of triplets at δ 2.22,
clearly due to the methyl group. The alkenyl proton resonance
was obscured by the aromatic resonances. However, crystals
formed when the CD2Cl2 solution was set aside at room tem-
perature, and the subsequent crystal structure determination
(Fig. 3) confirms the identity of the complex. The structure
of 12 has no remarkable features, and can be compared with
that of (S)-[RuCl(η5-C5H5){(R)-Ph2PCH2CH(Me)PPh2}], with
1
MHz): δ 42.0 (d, PX, JAX 12 Hz) and 56.9 (d, PA). Selected H
NMR (CDCl3, 200 MHz): δ 3.20 [2 H, ddd, Hγ, 3J(PAHγ) 25.5,
4
3
2J(PXHγ) 12.9, J(HαHγ) 1.5], 5.19 [1 H, dd, br, HαЈ, J(PAHαЈ)
15.4, 4J(PXHαЈ) 5.5, 2J(HαHαЈ) 0] and 5.95 [1 H, ddt, Hα,
3J(PAHα) 32.0, 4J(PXHα) 5.2 Hz].
[PdCl2(1,2-dpppn)] 2. To a solution of complex 1 (0.22 g,
0.374 mmol) in chlorobenzene (30 cm3) was added benzylamine
(2.0 cm3). The mixture was refluxed for 24 h. An off-white solid
was observed, and further solid precipitated on cooling to 4 ЊC.
This was filtered off, washed with MeOH (3 × 3 cm3) and Et2O
(3 × 3 cm3) and dried in vacuo. Yield 0.21 g, 97% (Found: C,
55.16; H, 4.12. C27H24Cl2P2Pd requires C, 55.18; H, 4.12%).
Mass spectrum (FAB, Xeϩ): m/z 553 ([M Ϫ Cl]ϩ) 31P-{1H}
NMR (CDCl3, 101 MHz): δ 58.3 (d, PX, JAX 15 Hz) and 77.2 (d,
1
PA). Selected H NMR (CDCl3, 200 MHz): δ 2.11 [3 H, dt,
4
4
3J(PAHα) 6.9, J(PXHα) 1.4, J(HαHγ) 1.4] and 6.85 [1 H, ddq,
3J(PAHγ) 64.6, 2J(PXHγ) 14.2 Hz].
1790
J. Chem. Soc., Dalton Trans., 1998, Pages 1787–1792

View Article Online
1
[PdI2(1,2-dpppn)] 3. To a solution of complex 2 (0.50 g, 0.852
mmol) in acetone (30 cm3) was added sodium iodide (1.27 g,
8.52 mmol). The mixture was stirred for 1 h. The volume was
reduced to ca. 3 cm3 at the pump, and Et2O (5 cm3) was added.
The yellow solid that precipitated was filtered off, washed with
water (3 cm3), EtOH (3 × 3 cm3) and Et2O (3 × 3 cm3) and dried
in vacuo. Yield 0.41 g, 63% (Found: C, 42.84; H, 3.36.
C27H24I2P2Pd requires C, 42.89; H, 3.34%). Mass spectrometry
(FAB, Xeϩ): m/z 770 (Mϩ) and 643 ([M Ϫ I]ϩ) 31P-{1H} NMR
(CDCl3, 101 MHz): δ 55.3 (d, PX, JAX 15) and 75.9 (d, PA).
Selected 1H NMR (CDCl3, 200 MHz): δ 2.08 [3 H, ddd,
NMR (CDCl3, 101 MHz): δ 42.35 (d, PX, JAX 14.6, JPtP 1772)
and 61.2 (d, PA, 1JPtP 1772 Hz). Selected 1H NMR (CDCl3, 200
3
MHz): δ 0.60 (3 H, Pt᎐CH3, |JAH ϩ JXH| 7.4, JPtH 73.7), 0.75
(Pt᎐CH3), |JAH ϩ JXH| 7.4, 3JPtH 71.4), 2.18 [3 H, d, br, 3J(PAHα)
6.1] and 7.11 [1 H, dd, br, 3J(PAHγ) ca. 50, 2J(PXHγ) 8 Hz].
᎐
[Pt(C᎐CPh) (1.2-dpppn)] 8. To a suspension of finely ground
᎐
2
5 (0.202 g, 0.298 mmol) in EtOH (5 cm3) was added
H2NNH2ؒH2O (57.8 µl, 1.18 mmol). The mixture was refluxed,
and after 10 min PhC᎐CH (249 µl, 2.36 mmol) was added.
᎐
᎐
A further 15 min reflux resulted in the formation of a yellow
solution. This was cooled to 0 ЊC and set aside for 1 h. The
white crystalline solid that precipitated was filtered off, washed
with a little cold EtOH and dried in vacuo. Yield 0.14 g, 59%
(Found: C, 63.94; H, 4.24. C43H34P2Pt requires C, 63.95; H,
4.24%). Mass spectrometry (FAB, Xeϩ): m/z 808 (Mϩ), 706
4
4
3J(PAHα) 7.8, J(PXHα) 1.9, J(HαHγ) 1.4] and 6.71 [1 H, ddq,
3J(PAH) 65.6, 2J(PXHγ) 12.1 Hz].
[PtCl2(2,3-dpppn)] 4. To a solution of [PtCl2(PhCN)2] (0.60 g,
1.27 mmol) in benzene (30 cm3) was added the diphosphine
(0.52 g, 1.27 mmol). The mixture was refluxed for 1 h. A white
solid precipitated. The mixture was cooled to room temperature
and filtered. The solid was washed with a little cold benzene and
Et2O (3 × 3 cm3), and dried in vacuo. Yield 0.63 g, 73% (Found:
C, 48.30; H, 3.39. C27H24Cl2P2Pt requires C, 47.96; H, 3.58%).
Mass spectrometry (FAB, Xeϩ): m/z 676 (Mϩ) and 641
([M Ϫ Cl]ϩ) 31P-{1H} NMR (CDCl3, 101 MHz) δ 21.2 (d, PX,
([M Ϫ C᎐CPh] ) and 605 ([M Ϫ C᎐CPh᎐HC᎐CPh] ). 31P-{1H}
ϩ
ϩ
᎐
᎐
᎐
᎐
᎐
᎐
1
NMR (CDCl3, 101 MHz): δ 37.7 (d, PX, JAX 14.8, JPtP 2242)
1
1
and 60.0 (d, PA, JPtP 2244). Selected H NMR (CDCl3, 200
MHz): δ 2.28 [3 H, d, br, 3J(PAHα) 7.6 Hz].
cis- and trans-[Pd(1,2-dpppn)2][BF4]2 9. To a solution of
[PdCl2(PhCN)2] (0.51 g, 1.30 mmol) in MeCN (35 cm3) and
CH2Cl2 (25 cm3) was added AgBF4 (0.52 g, 2.7 mmol) and 2,3-
dpppn (1.10 g, 2.7 mmol). The mixture was stirred for 30 min
in the dark. The AgCl was filtered off using a Kieselguhr pad
(3 cm depth) on a glass sinter, and solvent was removed in
vacuo. The yellow solid was taken up in MeCN (2 cm3) and
Et2O was added, precipitating a pale yellow solid. This was
filtered off, washed with Et2O and dried. Yield 1.08 g, 82%.
This was shown to be a mixture of at least four complexes
(Results and Discussion). The mixture was then refluxed over-
night in chlorobenzene in the presence of benzylamine (2 cm3).
The solution was cooled to 4 ЊC, and the off-white solid was
filtered off and dried in vacuo. Yield 1.05 g, 80% (Found: C,
48.63; H, 4.37. C54H48B2F8P4Pd requires C, 58.93; H, 4.39%).
Mass spectrometry (FAB, Xeϩ): m/z 1013 ([M Ϫ BF4]ϩ) and 926
([M Ϫ HBF4 Ϫ BF4]ϩ). 31P-{1H} NMR (CD3CN, 101 MHz): δ
57.1, 74.9 (PX, PA respectively; cis-9, AAЈXXЈ, JAXЈ, 380, JAX
Ϫ24, JAAЈ Ϫ16, from simulation; see Results and Discussion),
57.7, 74.1 (PX, PA respectively; trans-9, AAЈXXЈ, JAAЈ 380, JAX
Ϫ18, JAXЈ Ϫ20 Hz, from simulation; see Results and Discus-
1
JAX 13, 1JPtP 3566) and 34.7 (d, PA, 1JPtP 3583 Hz). Selected H
NMR (CDCl3, 200 MHz): δ 3.16 [2 H, ddd, Hγ, 3J(PAHγ) 21.4,
4
3
2J(PXHγ) 12.6, J(HαHγ) 1.4, J(PtHγ) 37.7], 5.27 [1 H, dd, br,
3
4
2
HαЈ, J(PAHαЈ) 15.4, J(PXHαЈ) 3.8, J(HαHαЈ) 0] and 6.03 [1 H,
ddt, Hα, 3J(PAHα) 33.5, 4J(PXHα) 4.9 Hz].
[PtCl2(1,2-dpppn)] 5. To a suspension of complex 4 (0.52 g,
0.77 mmol) in chlorobenzene (40 cm3) was added benzylamine
(2.0 cm3). The mixture was refluxed for 24 h. A white solid was
observed, and further solid precipitated on cooling to 4 ЊC. This
was filtered off, washed with MeOH (3 × 3 cm3) and Et2O
(3 × 3 cm3) and dried in vacuo. Yield 0.47 g, 91% (Found: C,
47.73; H, 3.60. C27H24Cl2P2Pt requires C, 47.96; H, 3.58%). Mass
spectrometry (FAB, Xeϩ): m/z 641 ([M Ϫ Cl]ϩ). 31P-{1H} NMR
(CDCl3, 101 MHz): δ 35.3 (d, PX, JAx 14.5, 1JPtP 3582) and 53.1
1
1
(d, PA, JPtP 3635 Hz). Selected H NMR (CDCl3, 200 MHz):
3
4
4
δ 2.15 [3 H, dt, J(PAHα) 8.8, J(PXHα) 1.7, J(HαHγ) 1.7] and
6.87 [1 H, ddq, 3J(PAHγ) 53.9, 2J(PXHγ) 14.8 Hz].
1
[PdMe2(1,2-dpppn)] 6. To a suspension of complex 2 (0.256 g,
0.44 mmol) in Et2O (20 cm3) was added MeLi (0.80 cm3, 1.4 
in Et2O; 1.12 mmol). The mixture was stirred for 16 h. Some
white solid was observed suspended in an orange solution. The
mixture was hydrolysed with MeOH (0.5 cm3) whereupon the
mixture faded to colourless. The solid was filtered off, washed
with a little cold MeOH and dried in vacuo. More product was
obtained from the mother-liquor by precipitation with MeOH.
Yield 0.158 g, 66% (Found: C, 63.42; H, 5.39. C29H30P2Pd
requires C, 63.72; H, 5.51%). Mass spectrometry (FAB, Xeϩ):
m/z 531 ([M Ϫ Me]ϩ) and 516 ([M Ϫ CH4 Ϫ Me]ϩ) 31P-{1H}
NMR (CDCl3, 101 MHz): δ 37.0 (d, PX, JAX 15) and 56.2 (d,
PA). Selected 1H NMR (CDCl3, 200 MHz): δ 0.30 [3 H,
Pd᎐CH3, |JAH ϩ JXH| 7.6), 0.42 (Pd᎐CH3, |JAH ϩ JXH| 7.6), 2.13
sion). Selected H NMR (CD3CN, 200 MHz): δ 2.09, 2.15 (br,
m, Hα for different isomers).
cis- and trans-[Pt(1,2-dpppn)2][BF4]2 10. To a solution of
[PtCl2(PhCN)2] (0.52 g, 1.10 mmol) in MeCN (35 cm3) and
CH2Cl2 (25 cm3) was added AgBF4 (0.43 g, 2.2 mmol) and 2,3-
dpppn (0.91 g, 2.2 mmol). The mixture was stirred for 30 min in
the dark. The AgCl was filtered off using a Kieselguhr pad (3
cm depth) on a glass sinter, and solvent was removed in vacuo.
The off-white solid was taken up in MeCN (10 cm3), the solu-
tion was filtered and the volume was reduced to ca. 2 cm3 in
vacuo. On the addition of Et2O a white solid precipitated. This
was filtered off, washed with Et2O and dried. Yield 0.75 g, 57%
(Found: C, 54.51; H, 4.09. C54H48B2F8P4Pt requires C, 54.56; H,
4.07%). Mass spectrometry (FAB, Xeϩ): m/z 1102 ([M Ϫ BF4]ϩ)
and 1015 ([M Ϫ HBF4 Ϫ BF4]ϩ). 31P-{1H} NMR (CD3CN, 101
MHz): δ 48.9, 66.8 [PX, PA respectively; cis-10, AAЈXXЈ, JAXЈ
300 Hz, 1J(PtPA) 2358, 1J(PtPX) 2295], 50.3, 65.4 [PX, PA
respectively; trans-10, AAЈXXЈ, JAAЈ 300, JAX Ϫ10, JAXЈ Ϫ8
3
4
4
[3 H, dt, J(PAHα) 5.5, J(PXHα) 1.4, J(HαHγ) 1.4] and 7.04 [1
H, ddq, 3J(PAHγ) 51.4, 2J(PXHγ) 4.4 Hz].
[PtMe2(1,2-dpppn)] 7. To a suspension of complex 5 (0.205 g,
0.303 mmol) in Et2O (20 cm3) was added MeLi (0.76 cm3, 1  in
Et2O; 0.76 mmol). The mixture was stirred for 16 h. Some white
solid was observed suspended in a pink solution. The mixture
was hydrolysed with MeOH (0.5 cm3) whereupon the mixture
faded to colourless. The solid was filtered off, washed with a
little cold MeOH and dried in vacuo. More product was
obtained from the mother-liquor by precipitation with MeOH.
Yield 0.142 g, 74% (Found: C, 54.78; H, 4.74. C29H30P2Pt
requires C, 54.82; H, 4.76%). Mass spectrometry (FAB, Xeϩ):
m/z 620 ([M Ϫ Me]ϩ) and 604 ([M Ϫ CH4 Ϫ Me]ϩ). 31P-{1H}
1
(from simulation; see Results and Discussion), J(PtPA) 2354,
1J(PtPX) 2303 Hz]. Selected 1H NMR (CD3CN, 200 MHz);
δ 2.16 (br, m, Hα for different isomers).
[RuCl2(dpppn)2]ؒCH2Cl2 11. To [RuCl2(PPh3)3] (0.50 g,
0.52 mmol) in CH2Cl2 (20 cm3) was added 2,3-dpppn (0.43 g,
1.04 mmol) in CH2Cl2 (5 cm3). The mixture was set aside over-
night, yielding a yellow precipitate. This was filtered off, washed
with Et2O and dried in vacuo. Yield 0.44 g, 78% (Found: C,
J. Chem. Soc., Dalton Trans., 1998, Pages 1787–1792
1791

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60.98; H, 4.65. C54H48Cl2P4RuؒCH2Cl2 requires C, 61.29; H,
4.68%). Mass spectrometry (FAB, Xeϩ): m/z 992 (Mϩ), 957
([M Ϫ Cl]ϩ) and 921 ([M Ϫ HCl Ϫ Cl]ϩ). 31P-{1H} NMR
(CDCl3, 101 MHz); δ 28.6, 46.0 (m, br).
References
1 I. J. Colquhoun and W. McFarlane, J. Chem. Soc., Dalton Trans.,
1982, 1915.
2 J. L. Bookham, W. McFarlane and I. J. Colquhoun, J. Chem. Soc.,
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3 G. R. Cooper, D. M. McEwan and B. L. Shaw, Inorg. Chim. Acta,
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4 F. S. M. Hasssan, B. L. Shaw and M. Thornton-Pett, J. Chem. Soc.,
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5 F. S. M. Hassan, S. J. Higgins, G. B. Jacobsen, B. L. Shaw and M.
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[RuCl(ç-C5H5)(1,2-dpppn)] 12. To [RuCl(η-C5H5)(PPh3)2]
(0.22 g, 0.302 mmol) in benzene (50 cm3) was added 2,3-dpppn
(0.124 g, 0.300 mmol). The mixture was refluxed for 5 h, the
volume was then reduced to ca. 3 cm3 in vacuo, and hexane (50
cm3) was added. The mixture was set aside for 24 h at Ϫ20 ЊC,
yielding an orange precipitate. This was filtered off, washed
with hexane and dried in vacuo. Yield 0.11 g, 59% (Found: C,
62.66; H, 4.75. C32H29ClP2Ru requires C, 62.80; H, 4.78%).
Mass spectrometry (FAB, Xeϩ): m/z 612 (Mϩ) and 577
([M Ϫ Cl]ϩ). 31P-{1H} NMR (CDCl3, 101 MHz): δ 73.3 (d, PX,
1
9 S. J. Higgins, H. L. Jones, M. K. McCart and T. J. Pounds, Chem.
Commun., 1997, 1907.
10 E. J. Fernández, M. C. Gimeno, P. G. Jones, A. Laguna and E.
Olmos, Organometallics, 1997, 16, 1130.
JAX 35.2 Hz) and 87.1 (d, PA). Selected H NMR (CDCl3, 200
3
4
4
MHz) δ 2.22 [3H, ddd, J(PAHα) 6.6, J(PXHα) 1.5, J(HαHγ)
1.4 Hz] and 4.45 (5 H, s, C5H5).
11 O. Stéphan, N. Riegel and S. Jugé, J. Electroanal. Chem. Interfacial
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12 B. L. Shaw and J. D. Vessey, J. Chem. Soc., Dalton Trans., 1991,
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13 J. L. Bookham and W. McFarlane, Polyhedron, 1991, 10, 2381.
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15 A. J. Carty, D. K. Johnson and S. E. Jacobsen, J. Am. Chem. Soc.,
1979, 101, 5612.
Crystallography
trans-[Pt(1,2-dpppn)2][BF4]2 10. C54H48B2F8P4Pt, M = 1189.6,
monoclinic, space group P21/n, a = 11.205(5), b = 16.314(5),
c = 13.524(4) Å, β = 96.44(3)Њ, U = 2457(1) Å3, T = 153 K,
Z = 2, µ(Mo-Kα) 3.08 mmϪ1, 4718 reflections recorded, 4482
unique (Rint = 0.045), 2825 with I > 3σ(I) used in refinement.
The final wR(F2) was 0.076, R1 = 0.055.
16 J. L. Bookham and W. McFarlane, J. Chem. Soc., Dalton Trans.,
1990, 489.
17 P. S. Pregosin and R. W. Kuntz, 31P and 13C NMR of Transition
Metal–Phosphine Complexes, Springer, Berlin, 1979.
18 R. K. Harris, Can. J. Chem., 1964, 42, 2275.
19 gNMR, version 3.6.5, Chemical Scientific, Oxford, UK.
20 W. Oberhauser, C. Bachmann and P. Brüggeller, Inorg. Chim. Acta,
1995, 238, 35.
[RuCl(ç5-C5H5)(1,2-dpppn)] 12. C32H29ClP2Ru, M = 612.1,
monoclinic, space group P21/n, a = 14.866(8), b = 11.297(6),
c = 17.389(7) Å, β = 110.58(3)Њ, U = 2734(2) Å3, T = 296 K,
Z = 4, µ(Mo-Kα) 0.79 mmϪ1, 5297 reflections measured, 5092
unique (Rint = 0.030), 3770 with I > 3σ(I) used in refinement.
The final wR(F2) was 0.038, R1 = 0.030.
CCDC reference number 186/951.
See http://www.rsc.org/suppdata/dt/1998/1787/ for crystallo-
graphic files in .cif format.
21 A. Martin and A. G. Orpen, J. Am. Chem. Soc., 1996, 118, 1464.
22 L. L. Whinnery, H. J. Yue and J. A. Marsella, Inorg. Chem., 1986,
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23 B. Chaudret, G. Commenges and R. Poilblanc, J. Chem. Soc.,
Dalton Trans., 1984, 1635.
24 C. W. Jung, P. E. Garrou, P. R. Hoffman and K. G. Caulton, Inorg.
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25 A. A. Batista, L. A. C. Cordeiro, G. Oliva and O. R. Nascimento,
Inorg. Chim. Acta, 1997, 258, 131.
26 D. J. Irvine, C. Glidewell, D. J. Cole-Hamilton, J. C. Barnes and A.
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Acknowledgements
We thank the EPSRC (studentship, M. K. M.) and the Royal
Society for funding, the EPSRC mass spectrometry service at
Swansea for FAB mass spectra and Johnson-Matthey for a loan
of precious metal salts.
Received 17th February 1998; Paper 8/01351I
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J. Chem. Soc., Dalton Trans., 1998, Pages 1787–1792