Coordination studies of a new nonsymmetric ditertiary phosphane bearing a single phosphaadamantane cage

Article abstract of DOI:10.1002/ejic.200800059

The new nonsymmetric ditertiary phosphane, Ph₂P(CH ₂)₂-PAd (1), was prepared in one-step from Ph ₂PCH=CH₂ and H-PAd (H-PAd = 1,3,5,7-tetramethyl-2,4,8- trioxa-6-phosphaadamantane) by a hydrophosphination reaction using 2,2′-azo-bisisobutyronitrile (AIBN) as free radical initiator. The sterically encumbered phosphaadamantane cage in 1 was found to influence the coordination capabilities of this ligand. The reaction of 1 with [PdCl ₂(cod)] or [Pt(CH₃)₂(cod)] (cod = cycloocta-1,5-diene) gave the corresponding κ²-P,P′- chelate complexes cis-[PdCl₂(1)] (2) and cis-[Pt(CH₃) ₂(1)] (3), respectively. The dinuclear gold(I) complex [Ph ₂P(AuCl)-(CH₂)₂PAd(AuCl)] (4) was prepared from 1 and 2 equiv. of [AuCl(tht)] (tht = tetrahydrothiophene). In contrast, the cleavage of the chloro-bridged dimers {RuCl₂(η⁶-p- cymene)}₂ or {MCl₂(η⁵-Cp*)} ₂ (M = Rh, Ir) with 1 gave the κ¹-P-monodentate complexes [RuCl₂(η⁶-p-cymene)(1)] (5), [RhCl ₂(η⁵-Cp*)(1)] (6) and [IrCl₂(η ⁵-Cp*)(1)] (7), respectively, in which the -PAd group is non-coordinating. Chloride abstraction from 6 (or 7) can be accomplished upon addition of Na[SbF₆] to generate the cationic κ²-P, P′-chelate complexes 8b (and 9b). Alternatively 8a (or 9a) could be observed, as their chloride salts, by ³¹P{¹H} NMR spectroscopy upon addition of several drops of CH₃OH to CDCl ₃ solutions of 6 (or 7). The reaction of 5-7 with [AuCl(tht)] gave the dinuclear complexes [κ²-P,P′-μ-RuCl ₂(η⁶-p-cymene){Ph₂P(CH₂) ₂PAd(AuCl)}] (10), [κ²-P,P′-μ-RhCl ₂(η⁵-Cp*){Ph₂P(CH₂) ₂PAd(AuCl)}] (11) and [κ²-P,P′-μ-IrCl ₂(η⁵-Cp*){Ph₂P(CH₂) ₂PAd(AuCl)}] (12). Reaction of two equiv. of 5 with the labile precursors [PdCl₂-(CH₃CN)₂] or [PtCl ₂(PhCN)₂] gave instead the novel trinuclear Ru ₂Pd and Ru₂Pt complexes trans-[{κ²-P, P′-μ-RuCl₂(η⁶-p-cymene){Ph ₂P(CH₂)₂PAd}}₂PdCl₂] (13) and trans-[{κ²-P,P′-μ-RuCl₂(η ⁶-p-cymene){Ph₂P(CH₂)₂PAd}} ₂PtCl₂] (14), respectively. All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore the structures of 3·CHC_l3, 4, 5, 7·CHCl₃, 10·CH₂Cl₂·0.5C₂H₁₀O and 13·2CH₂Cl₂ have been elucidated by single-crystal X-ray crystallography. The X-ray structures of 10·CH ₂Cl₂· 0.5C₄H₁₀O and 13·2CH₂Cl₂ demonstrate how nonsymmetric ditertiary phosphane complexes bearing one pendant phosphaadamantane moiety can be used as metalloligands in the controlled syntheses of novel bi- and trimetallic complexes. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejic.200800059

FULL PAPER
DOI: 10.1002/ejic.200800059
Coordination Studies of a New Nonsymmetric Ditertiary Phosphane Bearing a
Single Phosphaadamantane Cage
Tom J. Cunningham,[a] Mark R. J. Elsegood,[a] Paul F. Kelly,[a] Martin B. Smith,*[a] and
Paul M. Staniland[a]
Keywords: Coordination modes / Heterometallics / Late-transition metals / P ligands
The new nonsymmetric ditertiary phosphane, Ph2P(CH2)2-
PAd (1), was prepared in one-step from Ph2PCH=CH2 and
eral drops of CH3OH to CDCl3 solutions of 6 (or 7). The reac-
tion of 5–7 with [AuCl(tht)] gave the dinuclear complexes [κ2-
P,PЈ-µ-RuCl2(η6-p-cymene){Ph2P(CH2)2PAd(AuCl)}] (10), [κ2-
P,PЈ-µ-RhCl2(η5-Cp*){Ph2P(CH2)2PAd(AuCl)}] (11) and [κ2-
P,PЈ-µ-IrCl2(η5-Cp*){Ph2P(CH2)2PAd(AuCl)}] (12). Reaction of
H-PAd (H-PAd
= 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phos-
phaadamantane) by a hydrophosphination reaction using
2,2Ј-azo-bisisobutyronitrile (AIBN) as free radical initiator.
The sterically encumbered phosphaadamantane cage in 1
was found to influence the coordination capabilities of this
ligand. The reaction of 1 with [PdCl2(cod)] or [Pt(CH3)2(cod)]
(cod = cycloocta-1,5-diene) gave the corresponding κ2-P,PЈ-
chelate complexes cis-[PdCl2(1)] (2) and cis-[Pt(CH3)2(1)] (3),
respectively. The dinuclear gold(I) complex [Ph2P(AuCl)-
(CH2)2PAd(AuCl)] (4) was prepared from 1 and 2 equiv. of
[AuCl(tht)] (tht = tetrahydrothiophene). In contrast, the cleav-
age of the chloro-bridged dimers {RuCl2(η6-p-cymene)}2 or
two equiv. of
5
with the labile precursors [PdCl2-
(CH3CN)2] or [PtCl2(PhCN)2] gave instead the novel trinu-
clear Ru2Pd and Ru2Pt complexes trans-[{κ2-P,PЈ-µ-RuCl2(η6-
p-cymene){Ph2P(CH2)2PAd}}2PdCl2] (13) and trans-[{κ2-P,PЈ-
µ-RuCl2(η6-p-cymene){Ph2P(CH2)2PAd}}2PtCl2] (14), respec-
tively. All new compounds have been fully characterised by
spectroscopic and analytical methods. Furthermore the struc-
tures of 3·CHCl3, 4, 5, 7·CHCl3, 10·CH2Cl2·0.5C2H10O and
13·2CH2Cl2 have been elucidated by single-crystal X-ray
{MCl2(η5-Cp*)}2 (M = Rh, Ir) with 1 gave the κ1-P-mono- crystallography. The X-ray structures of 10·CH2Cl2·
dentate complexes [RuCl2(η6-p-cymene)(1)] (5), [RhCl2(η5-
0.5C4H10O and 13·2CH2Cl2 demonstrate how nonsymmetric
Cp*)(1)] (6) and [IrCl2(η5-Cp*)(1)] (7), respectively, in which ditertiary phosphane complexes bearing one pendant phos-
the -PAd group is non-coordinating. Chloride abstraction
from 6 (or 7) can be accomplished upon addition of Na[SbF6]
to generate the cationic κ2-P,PЈ-chelate complexes 8b (and
9b). Alternatively 8a (or 9a) could be observed, as their chlo-
phaadamantane moiety can be used as metalloligands in the
controlled syntheses of novel bi- and trimetallic complexes.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
ride salts, by 31P{1H} NMR spectroscopy upon addition of sev- Germany, 2008)
form complexes with Ru, Pd and Au metal centres[13,14] and
Introduction
in several cases, been investigated in a range of catalytic
metal-mediated transformations.[15–23] We recently reported
the synthesis and coordination studies of a new nonsym-
metric ditertiary phosphane containing a P–C–N(R)–C–P
skeletal backbone in which one of the P-based moieties was
a phosphaadamantane cage.[24] The presence of a bulky ad-
amantane cage imposed on this ligand the ability to adopt
a range of ligating modes including κ1-P-monodentate co-
ordination upon complexation to [RuCl2(η6-p-cymene)] or
[IrCl2(η5-Cp*)] metal fragments.[24] In an effort to promote
other coordinating capabilities employing the unique steric
properties of the phosphaadamantane group we report here
a simple one-step hydrophosphination procedure by which
a new saturated two-carbon spacer ditertiary phosphane
bearing non-equivalent groups (-PPh2 and -PAd) can be
prepared. Pringle and co-workers[25] recently reported the
synthesis of nonsymmetric diphosphanes based on a rigid
ethene backbone and furthermore, upon coordination, the
disposition of the phosphorus groups gave exclusive κ2-che-
As part of continuing studies[1–6] in our group we are
interested in developing new tertiary and symmetric diterti-
ary phosphane ligands using simple condensation reactions.
We, and others, have found that ditertiary phosphanes such
as those of general formula (R2PCH2)2N(R) have interest-
ing coordination properties[7,8] including their use in self-
assembly reactions through covalent bonds or H-bonding
contacts.[2–5,9] The tetraphenyl-substituted phosphane
(Ph2PCH2)2N(R), closely related to the three-carbon spacer
(Ph2PCH2)2CH2
[1,3-bis(diphenylphosphanyl)propane,
dppp], has been widely utilised in several metal-catalysed
reactions.[10–12]
Phosphaadamantane ligands containing one or more
trioxa- or carbon-only-based cages have been shown to
[a] Department of Chemistry, Loughborough University,
Loughborough, LE11 3TU Leics, UK,
Fax: +44-1509-223925
E-mail: m.b.smith@lboro.ac.uk
2326
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Coordination Chemistry of a Nonsymmetric Diphosphane
lation to square-planar metal centres. We demonstrate that phorus centres we observed, in the 31P{1H} NMR spectrum
our new, more flexible, ligand akin to the ubiquitous dppe of 1, two doublets at δ(P) –25.1 ppm and δ(P) –12.6 ppm
[1,2-bis(diphenylphosphanyl)ethane] exhibits diverse coor- (3JPP 35.6 Hz) assigned to the –PAd and –PPh2 groups,
dination behaviour towards a range of late transition-metals respectively. The 1H NMR spectrum of 1 was in accord
and can function in a κ1-P-monodentate manner in which with the chemical structure proposed and showed no indi-
the –PAd fragment remains non-coordinating. This has al- cation of a methine CH resonance that would be expected
lowed us to use these intermediates as metalloligands for if the branched regioisomer Ph2P(AdP)C(H)CH3 had been
the construction of heterobimetallic and, for the first time, formed instead via a Markovnikov addition. Exposing 1,
heterotrimetallic compounds as exemplified by our synthe- either as an oil or in solution, to air at ambient temperature
ses of complexes containing Ru/Au, Ir/Au, Ru2Pd and gave very little oxidation products demonstrating the air
Ru2Pt metal centre combinations. The single-crystal X-ray stable nature of this new diphosphane. Other characterising
structures of six compounds are reported here and dis- data for 1 are given in the Exp. Sect.
cussed.
Results and Discussion
Ligand Synthesis
(1)
Free radical, base or transition metal catalysed hydro-
phosphination reactions have previously been used to pre-
pare tertiary phosphane ligands.[26] The new ligand
Ph2P(CH2)2PAd (1) was prepared in a single-step, by a
Coordination Studies
AIBN free radical initiated hydrophosphination reaction of
Transition-metal complexes of trioxa- or carbon-only-
H-PAd (H-PAd = 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phos- based phosphaadamantanes have been relatively poorly
phaadamantane) with Ph2PCH=CH2 and could be ob- documented in the literature yet have started to show prom-
tained in high yield (ca. 80%) as a transparent colourless ise in various aspects relating to homogeneous cataly-
oil [Equation (1)]. Ligand 1 was of sufficient purity to be sis.[13–23] The goal of these studies was to probe the ligating
used directly in further complexation studies. Because the modes of this new ligand for the preparation of homobi-
nonsymmetric diphosphane contains two dissimilar phos- metallic and hetereometallic complexes. Diphosphanes with
Scheme 1.
Eur. J. Inorg. Chem. 2008, 2326–2335
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M. B. Smith et al.
FULL PAPER
Table 1. Selected spectroscopic data for compounds 1–14.[a]
δ(P) /-PPh2
δ(P) /-PAd 3J(PP)
J(PtPPh2) J(PtPAd)
J(RhPPh2)
J(RhPAd) 2J(PP)
νPdCl
νAuCl
1
2
3
4
5
6
7
8
–12.6
65.8
–25.1
60.9
38.2
31.1[b]
–26.5
–25.7
–24.8
55.9
47.7
28.5
19.2
22.3
31.0
31.6
10.0
9.6
35.6
8.1
8.9
285
49.5
1749
1688
29.9[b]
25.4
47
35.6
38
329
30.4
143
–1.7
40.5
63.0[c]
61.4
128
131
134
134
15.4
25.2
13
9
31.7[c]
30.7
3
10
11
12
13
30.7
28.5
46
48.1
48.6
322
330
324
147
–2.0
24.3[d]
23.9
296
14
24.0[d]
23.6
2.5
3.1
2590
2585
296[e]
[a] Chemical shifts in ppm, coupling constants in Hz. [b] The assignments are tentative due to the close appearance of both phosphorus
–
resonances. [c] Recorded as the SbF6 salt. The two sets of 31P resonances correspond to two diastereomers present in solution. For 8,
ca. 73:27 ratio respectively. For 9, ca. 74:26 ratio respectively. [d] For 13, ca. 50:50 ratio; 14, ca. 57:43 ratio respectively. [e] νPtCl vibration.
a two-carbon backbone are known to chelate metal proximately square planar. Clear differences are seen in the
centres[25] and are observed here for the synthesis of the P–Pt–C bond angles as a consequence of the different steric
dichloropalladium(II) and dimethylplatinum(II) complexes sizes between the –PAd [P(1)–Pt(1)–C(1) 97.25(18)°] and
cis-[PdCl2{κ2-P, P Ј-Ph2P(CH2)2PAd}] (2) and cis-[Pt(CH3)2-
{κ2-P, P Ј-Ph2P(CH2)2PAd}] (3), respectively. Both com-
pounds were prepared by displacement of cod from either
[PdCl2(cod)] or [Pt(CH3)2(cod)] as shown in Scheme 1. The
31P{1H} NMR spectra of 2 and 3 showed two doublet reso-
nances shifted considerably downfield as a consequence of
five-membered chelate ring formation (Table 1). In 3 the 31
P
resonance at δ(P) 49.5 ppm can be assigned the –PPh2
group by close analogy with the 31P chemical shift found
for [Pt(CH3)2(dppe)].[27] Furthermore, in the case of 3, the
observed 1J(PtP) coupling constants of 1688 Hz and
1749 Hz indicate similar stereoelectronic properties between
both –PAd and –PPh2 groups. These coupling constants are
in good agreement with those of other platinum(II) com-
plexes containing chelating diphosphanes trans to methyl
Figure 1. Molecular structure of 3. All hydrogen atoms and chloro-
form solvent molecule have been removed for clarity.
1
ligands.[27,28] The H NMR spectrum of 3 showed Pt-CH3
signals as two distinct phosphorus coupled multiplets with
195Pt satellites (2JPtH ca. 71 Hz for both Pt-CH3 groups). In
an attempt to explore the stability of the five-membered
chelate ring formed in 3 we repeated the reaction of
[Pt(CH3)2(cod)] with two equiv. of 1 instead and monitored
the reaction by 31P{1H} NMR spectroscopy. However, the
only species observed were 3 and unreacted 1 with no
31P{1H} NMR evidence for κ1-monodentate species of the
type cis-[Pt(CH3)2{κ1-P-Ph2P(CH2)2PAd}2]. Further char-
acterising details for 2 and 3 are given in Table 1 and the
Exp. Sect.
The X-ray structure of 3·CHCl3 has been determined
(Figure 1 and Table 2). Suitable crystals of 3·CHCl3 were
obtained by slow diffusion of petroleum ether (b.p. 60–
80 °C) into a CHCl3 solution. The X-ray structure confirms
that 1 adopts a κ2-P, P Ј-chelating coordination mode and
the environment about the platinum(II) metal centre is ap-
Table 2. Selected bond lengths [Å] and angles [°] for compound 3.
Pt(1)–P(1)
Pt(1)–P(2)
Pt(1)–C(1)
Pt(1)–C(2)
P(1)–C(3)
C(3)–C(4)
C(4)–P(2)
P(1)–Pt(1)–P(2)
P(1)–Pt(1)–C(1)
P(1)–Pt(1)–C(2)
P(2)–Pt(1)–C(1)
P(2)–Pt(1)–C(2)
C(1)–Pt(1)–C(2)
Pt(1)–P(1)–C(3)
P(1)–C(3)–C(4)
C(3)–C(4)–P(2)
C(4)–P(2)–Pt(1)
C(5)–P(1)–C(8)
2.2765(17)
2.2706(19)
2.136(6)
2.109(7)
1.845(7)
1.518(10)
1.845(7)
85.73(7)
97.25(18)
172.4(3)
176.42(18)
92.9(2)
83.9(3)
108.7(2)
110.9(5)
110.7(5)
109.1(2)
93.6(3)
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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Coordination Chemistry of a Nonsymmetric Diphosphane
–PPh2 groups [P(2)–Pt(1)–C(2) 92.9(2)°]. The Pt–P and Pt– Table 3. Selected bond lengths [Å] and angles [°] for compound 4.
C bond lengths and angles are comparable with those of
Au(1)–P(1)
Au(1)–Cl(1)
Au(2)–P(2)
Au(2)–Cl(2)
P(1)–C(1)
C(1)–C(2)
C(2)–P(2)
Cl(1)–Au(1)–P(1)
Cl(2)–Au(1)–P(2)
Au(1)–P(1)–C(1)
P(1)–C(1)–C(2)
C(1)–C(2)–P(2)
C(2)–P(2)–Au(2)
2.2328(16)
2.2919(16)
2.2357(16)
2.2996(17)
1.828(6)
1.550(9)
1.822(6)
175.55(7)
176.78(7)
115.2(2)
112.9(5)
115.0(5)
[Pt(CH3)2(Ph2PCH=CHPPh2)] and [Pt(CH3)2(Et2dppp)].[28]
Hence in the case of [Pt(CH3)2(Ph2PCH=CHPPh2)] the Pt–
P distances are 2.246(2) and 2.254(2) Å whereas the Pt–C
bond lengths are 2.108(7) and 2.112(6) Å. The Pt(1)–P(1)–
C(3)–C(4)–P(2) backbone in 3 is twisted as expected for a
saturated two carbon linker. The C(3) and C(4) deviations
of the ethyl backbone from the P(1)–Pt(1)–P(2) plane in 3
are 0.33 Å and 0.29 Å, respectively. The small P···P separa-
tion in 3 of 3.093 Å is as expected for a chelating ligand of
this general type.
114.8(2)
To further explore the versatility of this ligand to accom-
modate different bonding modes we treated 1 with
two equiv. of [AuCl(tht)] and isolated the digold(I) com-
We next sought to explore whether some kind of steric
pound 4 in high yield (83%). A downfield δ(P) shift for control on the outcome of a complexation reaction using
both inequivalent phosphorus nuclei and the observation of ligand 1 could be imposed. This could be achieved through
a νAuCl vibration at 329 cm–1 in the FT-IR spectrum sup- appropriate choice of metal precursors with bulky ancillary
port linear, two-coordinate gold(I) metal centres. Suitable ligands present. In this manner it may be anticipated that
crystals of 4 were obtained by slow diffusion of CH3OH κ1-P-monodentate coordination could be favoured leaving
into a CH2Cl2 solution followed by slow evaporation. The a pendant phosphorus group available for further complex-
X-ray structure of 4 (Figure 2, Table 3) showed an essen- ation. Cleavage reactions of chloro-bridged RuII, RhIII and
tially linear arrangement about each gold(I) centre [P(1)– IrIII metal dimers are well known.[3,6] Recent work by inde-
Au(1)–Cl(1) 175.55(7)° and P(2)–Au(2)–Cl(2) 176.78(7)°] pendent groups have shown that half-sandwich complexes
with typical Au–Cl and Au–P bond lengths.[5] The P(1)– containing FeII or RuII centres bearing a single dppm
Au(1)···Au(2)–P(2) torsion angle in 4 is –65.98(6)°. A strong [dppm = 1,1-bis(diphenylphosphanyl)methane] ligand can
intramolecular aurophilic interaction is evident in 4 [Au(1)··· function in a κ1-P-monodentate fashion.[31,32] Reaction of
Au(2) 2.9811(4) Å] and contrasts that of (AuCl)2(µ-dppe) in [RuCl2(η6-p-cymene)]2 or [MCl2(η5-Cp*)]2 (M = Rh, Ir)
which only large intramolecular Au···Au separations (Ͼ 6 Å with 1 in dichloromethane gave the κ1-P-monodentate com-
for all polymorphic forms) are present.[29,30] There are no plexes 5–7 in high yields. The 31P{1H} NMR spectra
significant intermolecular Au···Au separations observed in (Table 1) are especially informative showing downfield
4, again different from the previously reported X-ray struc- shifts for the –PPh2 group whilst the “dangling” –PAd arm
tures for (AuCl)2(µ-dppe) which display short intermo- is observed at similar phosphorus chemical shifts to that of
lecular Au···Au contacts.[29,30] As would be expected for 1 free ligand 1. Additionally, for 6 and 7 the 31P resonances
adopting a bridging mode, the P···P separation in 4 of for the –PPh2 groups [δ(P) 30.4 ppm for 6; –1.7 ppm for
3.796 Å is enlarged with respect to that found in 3.
7] are similar to those observed previously for κ2-P, P Ј-µ-
{MCl2(η5-Cp*)}2(dppe) [M = Rh, δ(P) 29.5 ppm; M = Ir,
δ(P) –1.0 ppm][33] and [κ1-P-IrCl2(η5-Cp*)(Ph2PCH2-
NHC6H4PPh2)] [δ(P) 0.10 ppm].[34] The rhodium(III) and
iridium(III) complexes are solvent dependant and undergo
smooth isomerism to cationic κ2-P, P Ј-chelate complexes in
solution. Hence addition of several drops of CH3OH to
CDCl3 solutions of 6 (or 7) and monitoring by 31P{1H}
NMR spectroscopy showed the disappearance of signals at-
tributed to the κ1-P-monodentate complexes and new
downfield shifted signals (1JRhP couplings in the range 128–
134 Hz) assigned to the cationic P, P Ј-chelate half-sandwich
complexes
[RhCl(η5-Cp*){κ2-P, P Ј-Ph2P(CH2)2PAd}]Cl
(8a) and [IrCl(η5-Cp*){κ2-P, P Ј-Ph2P(CH2)2PAd}]Cl (9a).
In both cases the presence of two well-resolved sets of 31P
resonances infer two diastereomers are present [73:27 ratio
(for 8a) and 74:26 ratio (for 9a)] because the resulting cat-
ionic complexes are now chiral-at-metal.[35] The compounds
8b and 9b were isolated, albeit in low to moderate yields, as
the hexafluoroantimonate salts and have been characterised
(see Exp. Sect. for details).
The X-ray structures of the piano-stool complexes 5 and
7·CHCl3 have been established by X-ray crystallography
Figure 2. Molecular structure of 4. All hydrogen atoms have been
removed for clarity.
Eur. J. Inorg. Chem. 2008, 2326–2335
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M. B. Smith et al.
FULL PAPER
(Figure 3 and Figure 4, Table 4). Suitable crystals of 5 were
obtained by slow diffusion of hexanes into a CHCl3 solu-
tion followed by slow evaporation whilst crystals of
7·CHCl3 were obtained by allowing a CHCl3/Et2O/petro-
leum ether (b.p 60–80 °C) filtrate to stand for several days.
Within the coordination sphere of 5 the Ru–P, Ru–Cl and
Ru–Carene bond lengths are comparable to those of the half-
sandwich ruthenium(II) complex [RuCl2(η6-p-cymene){κ1-
P-Ph2PCH2N(Ph)CH2PAd}] recently described by us.[24]
Similarly the Ir–P, Ir–Cl and Ir–Ccentroid metric parameters
are comparable to those of other iridium(III) half-sandwich
compounds.[24,36] The P···P separations within 5 and
7·CHCl3 are 4.514 Å and 4.545 Å respectively and larger
than in 4. Presumably the strong aurophilic interaction seen
in 4 may account for this shorter P···P separation.
Figure 4. Molecular structure of 7. Hydrogen atoms and solvent
molecules are not shown for clarity.
Reaction of 5–7 with one equiv. of [AuCl(tht)] in CH2Cl2
gave the Ru/Au, Rh/Au and Ir/Au bimetallic complexes 10–
12 in good yields. For all three compounds significant
downfield shifts for the –PAd group were observed upon
gold(I) complexation [δ(P) 22.3–31.6 ppm] and further-
more, in the FT-IR spectra of 10–12, νAuCl vibrations in
the range 322–330 cm–1 were observed. Crystals of
10·CH2Cl2·0.5C4H10O suitable for X-ray diffraction were
grown from a CH2Cl2 solution layered with diethyl ether
and petroleum ether (b.p. 60–80 °C) with selected bond
lengths and angles given in Table 4. The RuII centre (Fig-
ure 5) remains coordinated to the –PPh2 group of 1 and the
other coordination sites are occupied by two chlorides and
Figure 3. Molecular structure of 5. Hydrogen atoms are not shown
for clarity.
Table 4. Selected bond lengths [Å] and angles [°] for compounds 5, 7·CHCl3, 10·CH2Cl2·0.5C4H10O and 13·2CH2Cl2.
5
7·CHCl3
M = Ir
10·CH2Cl2·0.5C4H10O
M = Ru
13·2CH2Cl2
M = Ru
M = Ru
M(1)–P(2)
M(1)–Cl(1)
M(1)–Cl(2)
M(1)–Ccentroid
P(1)–C(1)
C(1)–C(2)
C(2)–P(2)
2.3347(6)
2.4110(6)
2.4085(6)
1.7014(10)
1.856(3)
1.523(4)
1.839(3)
2.303(2)
2.407(3)
2.412(2)
1.817(4)
1.853(8)
1.525(11)
1.847(8)
2.3545(17)
2.4068(18)
2.4059(19)
1.707(3)
1.814(7)
1.515(10)
1.829(7)
2.3570(14)
2.4162(16)
2.4147(16)
1.709(2)
1.833(5)
1.524(7)
1.852(5)
Au(1)–P(1)
Au(1)–Cl(3)
2.2316(19)
2.280(2)
Pd(1)–P(1)
Pd(1)–Cl(3)
Pd(1)–Cl(4)
2.3406(15)
2.282(2)
2.304(2)
89.61(6)
88.92(5)
82.46(5)
119.85(19)
116.7(4)
111.1(4)
94.2(3)
Cl(1)–M(1)–Cl(2)
Cl(1)–M(1)–P(2)
Cl(2)–M(1)–P(2)
M(1)–P(2)–C(2)
P(2)–C(2)–C(1)
C(2)–C(1)–P(1)
C(3)–P(1)–C(6)
Cl(3)–Au(1)–P(1)
C(1)–P(1)–Au(1)
Cl(3)–Pd(1)–Cl(4)
Cl(3)–Pd(1)–P(1)
Cl(4)–Pd(1)–P(1)
P(1)–Pd(1)–P(1Ј)
C(1)–P(1)–Pd(1)
85.54(2)
86.42(2)
85.48(2)
116.18(8)
114.70(19)
113.6(2)
92.23(14)
87.46(9)
87.55(8)
91.13(8)
117.8(3)
114.9(6)
113.8(6)
93.0(5)
86.15(6)
87.86(6)
86.84(6)
118.1(2)
114.0(5)
115.6(5)
95.2(3)
177.11(10)
112.9(2)
180.0
93.91(4)
86.09(4)
172.18(7)
112.3(2)
2330
www.eurjic.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 2326–2335

Coordination Chemistry of a Nonsymmetric Diphosphane
(2)
an η6-p-cymene arene ligand. The Ru–P, Ru–Cl, Au–Cl and
Au–P lengths are all similar and as anticipated. The AuI
metal centre is essentially linear in geometry [Cl(1)–Au(1)–
P(1) 177.11(10)°]. The P···P separation in 10 is 4.487 Å
whilst the Ru···Au separation is 7.162 Å. Both are smaller
than those previously documented[24] and is a consequence
of the longer P–C–N–C–P backbone between the two dif-
ferent phosphorus centres than observed here with 1 (P–
C–C–P). The intermolecular Au···Au separation [5.594 Å]
infers no significant aurophilic interactions between neigh-
bouring P–Au–Cl units.
Figure 6. 31P{1H} NMR spectrum of 13 recorded in CDCl3 at
298 K.
In the case of 13 suitable crystals were obtained for X-
ray crystallography and the structure is shown in Figure 7
(Table 4 for selected metric parameters). Crystals of
13·2CH2Cl2 suitable for X-ray diffraction were grown by
Figure 5. Molecular structure of 10. Hydrogen atoms and solvent
molecules are not shown for clarity.
Reaction of two equiv. of 5 with either [PdCl2(CH3CN)2]
or [PtCl2(PhCN)2] in CH2Cl2 gave the trinuclear complexes
trans-[{κ2-P, P Ј-µ-RuCl2(η6-p-cymene){Ph2P(CH2)2PAd}}2-
PdCl2] (13) and trans-[{κ2-P, P Ј-µ-RuCl2(η6-p-cymene)-
{Ph2P(CH2)2PAd}}2PtCl2] (14), as orange solids, in 83%
and 74% yield respectively [Equation (2)]. The 31P{1H}
NMR spectra (Table 1, Figure 6 for 13) were informative
and confirmed, in both cases, coordination of the –PAd
group by the new downfield phosphorus signals with re-
spect to 5. Furthermore, the 31P{1H} NMR spectra of 13
and 14 showed pairs of closely spaced “triplets” for the
–PAd and –PPh2 groups consistent with the presence of two
diastereomers (in approx. equal ratios). Compound 14
showed additional 195Pt coupling to –PAd (1JPtP ca.
2500 Hz) in accord with a trans disposition of phosphane
ligands about the platinum(II) centre.[17b]
Figure 7. Molecular structure of 13. Hydrogen atoms and solvent
molecules are not shown for clarity. Only the ipso carbon atoms of
the phenyl rings bound to P(2) are shown.
Eur. J. Inorg. Chem. 2008, 2326–2335
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
2331

M. B. Smith et al.
FULL PAPER
the Loughborough University Analytical Service within the De-
partment of Chemistry.
diffusion of diethyl ether into a CH2Cl2 solution. The coor-
dination sphere of the palladium(II) metal centre comprises
two trans disposed metalloligands 5 and two chlorides.[17b]
The geometry of the two trans phosphane ligands is slightly
distorted from 180° [P(2A)–Pd(1)–P(2) 172.18(7)°]. The
RuII centre is pseudotetrahedral in geometry with typical
Ru–Cl and Ru–P bond lengths.[37] The P···P separation in
13·2CH2Cl2 is 4.516 Å and similar to that found in
10·CH2Cl2·0.5C4H10O. Balakrishna and co-workers re-
cently reported the synthesis of heterotrinuclear Pd/Au2, Pt/
Au2 and Cu/Au2 complexes using a cyclodiphosphazane li-
gand.[38]
Preparation of Ph2P(CH2)2PAd (1): Vinyldiphenylphosphane
(0.515 g, 2.42 mmol) was heated to 110 °C and 1,3,5,7-tetramethyl-
2,4,8-trioxa-6-phosphaadamantane (0.521 g, 2.42 mmol) added in
several portions with stirring. 2,2Ј-azobis(isobutyronitrile) (0.02 g)
was added and the reaction mixture stirred for 6 h. The tempera-
ture was reduced to 80 °C and the system placed under vacuum to
remove any volatile components giving the product as a colourless
oil which was used directly in all coordination studies. Yield
1
0.769 g, 74%. Selected spectroscopic data: H NMR (CDCl3): δ =
7.45–7.30 (m, arom. H), 2.21 (m, CH2), 1.95–1.21 (m, CH2, Ad
cage) ppm. ES-MS: m/z = 428 [M+]. C24H30O3P2 (428.47): calcd.
C 67.28, H 7.06; found C 66.74, H 7.12.
Preparation of cis-[PdCl2{Ph2P(CH2)2PAd}] (2): Compound
1
Conclusions
(0.060 g, 0.14 mmol) was dissolved in CH2Cl2 (10 mL) and added
dropwise to a solution of [PdCl2(PhCN)2] (0.055 g, 0.14 mmol) dis-
solved separately in CH2Cl2 (10 mL). After stirring for 3 h, the vol-
ume of the solution was reduced to ca. 2–3 mL and Et2O (60 mL)
added. The resulting yellow precipitate was filtered and dried in
A simple procedure to a new nonsymmetric diphos-
phane, akin to dppe, has been developed and its coordina-
tion chemistry investigated. Whilst κ2-P, P Ј-chelation is ob-
served upon complexation to square planar metal centres
such as PdII and PtII we have found that 1 can efficiently
function as a κ1-P-monodentate tertiary phosphane. Facile
coordination to one or two additional metal precursors af-
ford new examples of late transition metal hetero-bimetallic
and trimetallic compounds bridged by phosphane 1. Our
work has shown that, not only can the phosphadamantane
cage impart good solubility and crystallisation properties
on its resulting compounds but furthermore, the steric size
of the cage can be utilised in controlling the ligating modes
of this ligand. Our work should be contrasted, for example,
with that of Keim and co-workers[33] who showed that RuII,
RhIII and IrIII complexes of dppe readily bridge two metal
fragments affording symmetric dinuclear compounds. The
use of bidentate and polyphosphane ligands in the con-
struction of heterometallic species remains an interesting
area of coordination chemistry.[39,40] Further studies are on-
going and will be reported later.
1
vacuo. Yield 0.112 g, 76%. H NMR (CDCl3): δ = 7.99 (dd, arom.
H), 7.57–7.35 (m, arom. H), 3.63 (dd, CH2), 2.81–2.17 (m, CH2),
1.83–1.19 (m, Ad cage) ppm. FAB-MS: m/z = 570 [M – Cl]+.
C24H30Cl2O3P2Pd (605.79): calcd. C 47.59, H 4.99; found C 47.78,
H 4.94.
Preparation of cis-[Pt(CH3)2{Ph2P(CH2)2PAd}] (3): Compound 1
(0.095 g, 0.234 mmol) was dissolved in CH2Cl2 (5 mL) and added
dropwise to a separate solution of [Pt(CH3)2(cod)] (0.078 g,
0.234 mmol) in CH2Cl2 (10 mL) with stirring. The colourless solu-
tion was stirred for 3 h after which the volume of solution was
reduced to ca. 2–3 mL. Addition of petroleum ether (60–80 °C,
40 mL) gave a white solid which was filtered and dried in vacuo.
Yield 0.051 g, 32%. 1H NMR (CDCl3): δ = 7.69–7.26 (m, arom.
2
H), 2.54 (dd, CH2), 2.23–1.11 (m, CH2, Ad cage), 0.83 (tt, JPtH =
3
2
3
71, JPH = 14 Hz, Pt-CH3), 0.51 (tt, JPtH = 71, JPH = 15 Hz, Pt-
CH3) ppm. FAB-MS: m/z
=
653 [M+]. C26H36O3P2Pt·Et2O
(727.76): calcd. C 49.52, H 6.37; found C 49.55, H 5.69.
Preparation of [(AuCl)2{µ-Ph2P(CH2)2PAd}] (4): To a CH2Cl2
(10 mL) solution of AuCl(tht) (0.154 g, 0.480 mmol) was added 1
(0.112 g, 0.261 mmol) in CH2Cl2 (5 mL) dropwise. The colourless
solution was stirred for 30 min and the volume concentrated under
reduced pressure to ca. 1–2 mL. Addition of diethyl ether (15 mL)
and hexanes (15 mL) gave solid 1 which was collected and dried in
vacuo. Yield 0.178 g, 83%. 1H NMR (CDCl3): δ = 7.76–7.53 (m,
arom. H), 2.80 (br, CH2), 2.35–1.26 (m, CH2, Ad cage) ppm. FAB-
MS: m/z = 857 [M – Cl]+. C24H30Au2Cl2O3P2·0.25Et2O (911.84):
calcd. C 32.93, H 3.60; found C 33.55, H 3.46.
Experimental Section
Materials: Standard Schlenk techniques were used for the synthesis
of 1 whilst all other reactions were carried out in air using pre-
viously distilled solvents unless otherwise stated. The metal com-
plexes [AuCl(tht)] (tht = tetrahydrothiophene),[41] [RuCl2(η6-p-cy-
mene)]2,[42] [MCl2(η5-Cp*)]2 (M = Rh, Ir; Cp* = 1,2,3,4,5-penta-
methylcyclopentadienyl)[43] and [Pt(CH3)2(cod)][44] were prepared
according to known procedures. All other chemicals were obtained
from commercial suppliers and used directly without further purifi-
cation.
Preparation
of
[RuCl2(η6-p-cymene){Ph2P(CH2)2PAd}]
(5):
[RuCl(µ-Cl)(η6-p-cymene)]2 (0.131 g, 0.021 mmol) was dissolved in
CH2Cl2 (10 mL). Separately, 1 (0.184 g, 0.043 mmol) was dissolved
in CH2Cl2 (15 mL) and added dropwise to the stirred solution of
[RuCl(µ-Cl)(η6-p-cymene)]2. The mixture was stirred for ca. 3 h af-
ter which the solution was concentrated to 2–3 mL and Et2O
Instrumentation: Infrared spectra were recorded as KBr pellets in
the range 4000–200 cm–1 with a Perkin–Elmer System 2000 Fou- (50 mL) added to afford a bright orange solid which was filtered
rier-transform spectrometer, 1H NMR spectra (400 MHz) with a
Bruker DPX-400 FT spectrometer with chemical shifts (δ) in ppm
to high frequency of SiMe4 and coupling constants (J) in Hz,
31P{1H} NMR spectra (162 MHz) were recorded with a Bruker
DPX-400 FT spectrometer with chemical shifts (δ) in ppm to high
frequency of 85% H3PO4. All NMR spectra were measured in
and dried in vacuo. Yield 0.104 g, 66%. 1H NMR (CDCl3): δ =
7.86–7.39 (m, arom. H), 5.20–4.89 (m, p-cymene arom. H), 2.77
(m, CH2), 2.52 (m, CH2), 2.47 (sept, p-cymene CH), 1.83 (s, p-
cymene CH3), 1.75–0.74 (m, Ad cage, p-cymene C(CH3)2) ppm.
FAB-MS: m/z = 735 [M+]. C34H44Cl2O3P2Ru (734.68): calcd. C
55.59, H 6.05; found C 55.25, H 6.02. A similar procedure was
CDCl3. Elemental analyses (Perkin–Elmer 2400 CHN or Exeter also used for the preparation of the rhodium(III) and iridium(III)
1
Analytical, Inc. CE-440 Elemental Analyzers) were performed by
complexes 6 (97%) and 7 (73%). 6: H NMR (CDCl3): δ = 7.86–
2332
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 2326–2335

Coordination Chemistry of a Nonsymmetric Diphosphane
7.42 (m, arom. H), 3.00 (m, CH2), 2.68 (m, CH2), 1.76–0.97 (m,
tively. For 11: 1H NMR (CDCl3): δ = 7.81–7.45 (m, arom. H), 3.13
(m, CH2), 2.64 (m, CH2), 2.37 (m, CH2), 2.18–1.04 (m, Ad cage),
4
Ad cage), 1.28 (d, JPH = 2 Hz, Cp*) ppm. FAB-MS: m/z = 702
[M – Cl]+. C34H45Cl2O3P2Rh·CH2Cl2 (822.45): calcd. C 51.11, H
1.29 (d, JPH = 1.5 Hz, Cp*) ppm. FAB-MS: m/z = 970 [M+].
4
1
5.77; found C 51.20, H 5.83. 7: H NMR (CDCl3): δ = 7.76–7.37 C34H45AuCl3O3P2Rh·CH2Cl2 (1054.87): calcd. C 39.85, H 4.50;
1
(m, arom. H), 3.08 (m, CH2), 2.78 (m, CH2), 1.74–0.81 (m, Ad found C 40.10, H 4.56. For 12: H NMR (CDCl3): δ = 7.73–7.37
4
cage), 1.28 (d, JPH = 2 Hz, Cp*) ppm. FAB-MS: m/z = 791 [M –
Cl]+. C34H45Cl2IrO3P2·CHCl3 (946.19): calcd. C 44.43, H 4.90;
found C 45.04, H 5.13.
(m, arom. H), 3.26 (m, CH2), 2.82 (m, CH2), 2.40 (m, CH2), 2.19–
1.02 (m, Ad cage), 1.28 (d, 4JPH = 1.6 Hz, Cp*) ppm. FAB-MS: m/z
1059 [M+]. C34H45AuCl3IrO3P2·CH2Cl2 (1144.16): calcd. C 36.74,
H 4.15; found C 37.05, H 4.18.
Preparation of [RhCl(η5-Cp*){Ph2P(CH2)2PAd}]SbF6 (8b): A sus-
pension of complex 6 (0.041 g, 0.056 mmol) and Na[SbF6] (0.016 g,
0.062 mmol) in CH2Cl2 (10 mL) was stirred at ambient temperature
for 5 d. The mixture was passed through a small Celite plug and
the solvent evaporated to dryness. The residue was taken up in the
minimum volume of CH2Cl2 (0.5 mL) and diethyl ether (15 mL)
added to give an orange solid. The solid was collected by suction
filtration and dried. Yield 0.018 g, 34%. 1H NMR (CDCl3): δ =
7.58–7.30 (m, arom. H), 3.21 (m, CH2), 2.51 (m, CH2), 2.20 (m,
CH2), 1.99–0.56 (m, Ad cage, Cp*) ppm. FAB-MS: m/z = 701 [M –
SbF6]+. C34H45ClF6O3P2RhSb (931.77): calcd. C 43.82, H 4.88;
Preparation of trans-[{RuCl2(η6-p-cymene){Ph2P(CH2)2PAd}}2-
PdCl2] (13): To a CH2Cl2 (5 mL) solution of [PdCl2(CH3CN)2]
(0.011 g, 0.042 mmol) was added 5 (0.060 g, 0.082 mmol) in
CH2Cl2 (5 mL). The orange solution was stirred for 18 h and con-
centrated to ca. 1–2 mL under reduced pressure. Addition of di-
ethyl ether (40 mL) afforded solid 13 which was collected by suction
filtration and dried in vacuo. Yield 0.058 g, 83%. 1H NMR
(CDCl3): δ = 7.92–7.41 (m, arom. H), 5.31–4.90 (m, p-cymene
arom. H), 3.24 (m, CH2), 3.00 (m, CH2), 2.70 (m, CH2), 2.50 (sept,
p-cymene CH), 2.03 (m, CH2), 1.90 (s, CH3), 1.89 (s, CH3),
1.65–1.19 (m, Ad cage), 0.98 [dd, p-cymene C(CH3)2], 0.87
[dd, p-cymene C(CH3)2] ppm. FAB-MS: m/z 1645 [M+].
C68H88Cl6O6P4PdRu2·CH2Cl2 (1646.54): calcd. C 47.86, H 5.25;
found C 47.85, H 5.17.
found
C 43.38, H
4.85. The iridium complex [IrCl(η5-
Cp*){Ph2P(CH2)2PAd}]SbF6 (9b) was isolated as a yellow solid
(50%). 1H NMR (CDCl3): δ = 7.64–7.34 (m, arom. H), 3.18 (m,
CH2), 2.51 (m, CH2), 2.38 (m, CH2), 2.17 (m, CH2), 2.05–0.63 (m,
Ad cage, Cp*) ppm. C34H45ClF6IrO3P2Sb (1021.07): calcd. C
39.99, H 4.45; found C 39.87, H 4.36.
Preparation of [RuCl2(η6-p-cymene){Ph2P(CH2)2PAd(AuCl)}] (10):
[AuCl(tht)] (0.035 g, 0.11 mmol) was dissolved in CH2Cl2 (5 mL)
Preparation of trans-[{RuCl2(η6-p-cymene){Ph2P(CH2)2PAd}}2-
PtCl2] (14): To a CH2Cl2 (5 mL) solution of [PtCl2(PhCN)2]
(0.019 g, 0.040 mmol) was added 5 (0.060 g, 0.082 mmol) in
and a separate solution of 5 (0.081 g, 0.11 mmol) in CH2Cl2 CH2Cl2 (5 mL). The orange solution was stirred for 22 h and con-
(10 mL) added dropwise. After stirring for 3 h the volume of the
solution was reduced to ca. 3 mL and Et2O (50 mL) added. The
resulting orange solid was filtered and dried in vacuo. Yield 0.053 g,
centrated to ca. 1–2 mL under reduced pressure. Addition of di-
ethyl ether (40 mL) afforded solid 14 which was collected by suction
filtration and dried in vacuo. Yield 0.052 g, 74%. 1H NMR
50%. 1H NMR (CDCl3): δ = 7.82–7.43 (m, arom. H), 5.29–4.69 (CDCl3): δ = 7.87–7.37 (m, arom. H), 5.25–4.77 (m, p-cymene
(m, p-cymene arom. H), 3.10 (m, CH2), 2.48 (sept, p-cymene CH),
2.34 (m, CH2), 1.87 (s, CH3), 1.82–1.04 (m, Ad cage), 1.01 [d, p-
cymene C(CH3)2], 0.85 [d, p-cymene C(CH3)2] ppm. C34H44Au-
Cl3O3P2Ru (967.09): calcd. C 42.20, H 4.59; found C 41.66, H 4.41.
A similar procedure was also used for the preparation of the rhodi-
um(III) and iridium(III) complexes 11 (78%) and 12 (35%) respec-
arom. H), 3.16 (m, CH2), 2.91 (m, CH2), 2.53 (dt, CH2), 2.44 (sept,
p-cymene CH), 2.00 (m, CH2), 1.85 (s, CH3), 1.82 (s, CH3),
1.66–1.11 (m, Ad cage), 0.94 [t, p-cymene C(CH3)2], 0.76
[dd, p-cymene C(CH3)2] ppm. FAB-MS: m/z 1735 [M+].
C68H88Cl6O6P4PtRu2·0.25CH2Cl2 (1756.4): calcd. C 46.67, H 5.09;
found C 46.46, H 5.03.
Table 5. Crystallographic data for 3·CHCl3, 4 and 5.
Compound
3·CHCl3
4
5
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C27H37Cl3O3P2Pt
772.95
monoclinic
P21/c
11.5096(7)
11.4565(7)
23.1932(14)
C24H30Au2Cl2O3P2
893.25
monoclinic
P21/c
12.2059(4)
12.5859(3)
17.7503(5)
C34H44Cl2O3P2Ru
734.60
monoclinic
P21/c
7.4877(2)
13.4870(4)
33.2358(9)
α [°]
β [°]
98.545(2)
103.9388(12)
92.3280(4)
γ [°]
Volume [Å3]
Z
3024.3(3)
4
2646.54(13)
4
3353.60(16)
4
T [K]
150(2)
1.698
5.037
block, colourless
0.26ϫ0.21ϫ0.10
1.78–29.07
25066
120(2)
2.242
11.421
plate, colourless
0.14ϫ0.08ϫ0.02
3.03–27.48
27475
150(2)
1.455
0.755
block, dark red
0.49ϫ0.32ϫ0.23
1.63–30.55
38615
Density (calcd.) [Mg /m3]
Absorption coeff. [mm–1]
Crystal
Crystal size [mm3]
θ Range [°]
Reflections collected
Independent reflections
7322
6041
10239
[Rint = 0.058]
0.047, 0.113
[Rint = 0.041]
0.036, 0.076
[Rint = 0.041]
0.043, 0.100
Final R, Rw
Eur. J. Inorg. Chem. 2008, 2326–2335
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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2333

M. B. Smith et al.
FULL PAPER
Table 6. Crystallographic data for 7·CHCl3, 10·CH2Cl2·0.5C4H10O and 13·2CH2Cl2.
Compound
7·CHCl3
10·CH2Cl2·0.5C4H10O
13·2CH2Cl2
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C35H46Cl5IrO3P2
946.11
monoclinic
P21/c
14.437(3)
12.105(2)
22.147(4)
C37H51AuCl5O3P2Ru
1081.00
triclinic
C70H92Cl10O6P4PdRu2
1816.36
monoclinic
C2/c
29.148(2)
11.8624(9)
22.5109(16)
P-1
12.2147(12)
12.2872(12)
14.1978(14)
84.6310(16)
80.5268(17)
88.1919(16)
2092.3(4)
2
α [°]
β [°]
98.023(3)
98.431(2)
γ [°]
Volume [Å3]
Z
3832.6(11)
4
7699.4(10)
4
T [K]
150(2)
1.640
3.949
plate, yellow
0.34ϫ0.22ϫ0.05
1.86–25.00
27462
150(2)
1.729
4.292
plate, orange
0.34ϫ0.25ϫ0.02
1.66–25.00
15122
150(2)
1.567
1.097
needle, orange
0.49ϫ0.08ϫ0.06
1.83–29.02
33403
Density (calcd.) [Mg/m3]
Absorption coeff. [mm–1]
Crystal
Crystal size [mm3]
θ Range [°]
Reflections collected
Independent reflections
6755
7338
9320
[Rint = 0.038]
0.049, 0.144
[Rint = 0.038]
0.048, 0.121
[Rint = 0.072]
0.052, 0.137
[a]
Final R, Rw
2
2 2
[a] R = Σ||Fo| – |Fc||/Σ|Fo| for “observed” reflections having F2 Ͼ 2σ (F2). Rw = [Σw(Fo – Fc ) /Σw(Fo2)2]1/2 for all data.
X-ray Crystallography: Measurements were made with either a
Bruker AXS SMART 1000 CCD area-detector diffractometer[45]
for 3·CHCl3, 4, 5, 7·CHCl3, 10·CH2Cl2·0.5C4H10O and 13·2CH2Cl2
using sealed-tube graphite-monochromated Mo-Kα radiation and
narrow frame exposures (0.3°) in ω or a Bruker-Nonius 95 mm
CCD kappa diffractometer[46,47] equipped with a rotating anode
generator for 4. Cell parameters were refined from the observed
(ω) angles of all strong reflections in each data set. Intensities were
corrected semiempirically for absorption, based on symmetry-
equivalent and repeated reflections. All structures were solved by
direct methods and refined on F2 values for all unique data by full-
matrix least-squares.[48] Table 5 and Table 6 give further details. All
non-hydrogen atoms were refined anisotropically. For
10·CH2Cl2·0.5C4H10O a molecule of CH2Cl2 and an Et2O on an
inversion centre, both disordered, were modelled by the Platon
Squeeze procedure.[49] In 13·2CH2Cl2 the dichloromethane mole-
cule was modelled with one chlorine atom split over two sets of
positions. This disorder was modelled with restraints on anisotropic
displacement parameters.
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Acknowledgments
We thank the Engineering and Physical Sciences Research Council
(EPSRC) for half funding of this studentship (PMS). We are grate-
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cage phosphane used in this work and to Johnson-Matthey for
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Received: January 18, 2008
Published Online: April 2, 2008
Eur. J. Inorg. Chem. 2008, 2326–2335
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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