Mononuclear and heterodinuclear metal complexes of nonsymmetric ditertiary phosphanes derived from R2PCH2OH

Article abstract of DOI:10.1002/ejic.200601199

The new nonsymmetric ditertiary phosphanes, Ph₂PCH ₂N(R)CH₂PAd [3a: R = C₆H₅, 3b: R = C₆H₄(4-CH₃)] were prepared using a three-step sequence of condensation reactions. Hence treatment of AdP-H (AdP-H = 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantane) with (CH ₂O)_n at 110°C gave the adamantane-derived hydroxymethylphosphane 1, which upon condensation with C₆H ₅NH₂ or C₆H₄(4-CH ₃)NH₂ gave the secondary aminophosphanes HN(R)CH ₂PAd [2a: R = C₆H₅, 2b: R = C₆H ₄(4-CH₃)]. Further condensation of 2a or 2b with Ph ₂PCH₂OH gave 3a or 3b in high yields (ca. 85 %) containing the sterically encumbered adamantane cage. The coordination capabilities of 2a, 3a and 3b have been explored with various Pd^II, Pt^II, Ru^II, Ir^III and Au^I metal centres. Bridge cleavage of {Pd(κ²-C,N-C₁₆H₁₆N)Br} ₂ with 2 equiv. of 2a gave the neutral, mononuclear complex Pd(κ²-C,N-C₁₆H₁₆N)Br(2a) (4). Reaction of 3a/3b with MCl₂(cod) (M = Pt, Pd) gave the corresponding κ²-P,P′-chelate complexes cis-MCl₂(3) [5a: M = Pt, R = C₆H₅, 5b: Pt, R = C₆H ₄(4-CH₃), 5c: Pd, R = C₆H₅, 5d: Pd, R = C₆H₄(4-CH₃)]. In contrast, bridge cleavage of the dimers {RuCl₂(η⁶-p-cym)}₂ or {IrCl₂(η⁵-Cp*)}₂ with 3a gave the κ¹-P-monodentate complexes RuCl₂(η⁶- p-cym)(3a) (6) and IrCl₂(η⁵-Cp*)(3a) (7), respectively, in which the -PAd group is noncoordinating. Reaction of 6 or 7 with AuCl(tht) (tht = tetrahydrothiophene) gave the mixed-metal complexes κ²-P,P′-μ-RuCl₂(η⁶-p-cym) {Ph₂PCH₂N(Ph)CH₂PAd(AuCl)} (8) and κ²-P,P′-μ-IrCl₂(η⁵- Cp*){Ph₂PCH₂N(Ph)CH₂PAd(AuCl)} (9). All new compounds have been fully characterised by spectroscopic and analytical methods. Furthermore, the structures of 2a, 4, 5a, 5b and 6-9 have been elucidated by single-crystal X-ray crystallography. The X-ray structures of 5a, 5b and 6-9 represent the first examples of crystallographically characterised nonsymmetric ditertiary phosphane complexes bearing one adamantane moiety. Wiley-VCH Verlag GmbH & Cp. KGaA, 2007.

Full text of DOI:10.1002/ejic.200601199

FULL PAPER
DOI: 10.1002/ejic.200601199
Mononuclear and Heterodinuclear Metal Complexes of Nonsymmetric
Ditertiary Phosphanes Derived from R2PCH2OH
Gavin M. Brown,[a] Mark R. J. Elsegood,[a] Andrew J. Lake,[a]
Noelia M. Sanchez-Ballester,[a] Martin B. Smith,*[a] Thomas S. Varley,[a] and Kevin Blann*[b]
Keywords: Late-transition metals / P ligands / Heterobimetallics / Coordination modes
The new nonsymmetric ditertiary phosphanes, Ph2PCH2N-
CH3), 5c: Pd, R = C6H5, 5d: Pd, R = C6H4(4-CH3)]. In contrast,
(R)CH2PAd [3a: R = C6H5, 3b: R = C6H4(4-CH3)] were pre- bridge cleavage of the dimers {RuCl2(η6-p-cym)}2 or
pared using a three-step sequence of condensation reactions.
Hence treatment of AdP-H (AdP-H = 1,3,5,7-tetramethyl-
2,4,8-trioxa-6-phosphaadamantane) with (CH2O)n at 110 °C
gave the adamantane-derived hydroxymethylphosphane 1,
which upon condensation with C6H5NH2 or C6H4(4-CH3)-
NH2 gave the secondary aminophosphanes HN(R)CH2PAd
[2a: R = C6H5, 2b: R = C6H4(4-CH3)]. Further condensation
of 2a or 2b with Ph2PCH2OH gave 3a or 3b in high yields
(ca. 85%) containing the sterically encumbered adamantane
cage. The coordination capabilities of 2a, 3a and 3b have
been explored with various PdII, PtII, RuII, IrIII and AuI metal
centres. Bridge cleavage of {Pd(κ2-C,N-C16H16N)Br}2 with
2 equiv. of 2a gave the neutral, mononuclear complex Pd(κ2-
C,N-C16H16N)Br(2a) (4). Reaction of 3a/3b with MCl2(cod)
(M = Pt, Pd) gave the corresponding κ2-P,PЈ-chelate com-
plexes cis-MCl2(3) [5a: M = Pt, R = C6H5, 5b: Pt, R = C6H4(4-
{IrCl2(η5-Cp*)}2 with 3a gave the κ1-P-monodentate com-
plexes RuCl2(η6-p-cym)(3a) (6) and IrCl2(η5-Cp*)(3a) (7),
respectively, in which the –PAd group is noncoordinating.
Reaction of 6 or 7 with AuCl(tht) (tht = tetrahydrothiophene)
gave the mixed-metal complexes κ2-P,PЈ-µ-RuCl2(η6-p-
cym){Ph2PCH2N(Ph)CH2PAd(AuCl)} (8) and κ2-P,PЈ-µ-
IrCl2(η5-Cp*){Ph2PCH2N(Ph)CH2PAd(AuCl)} (9). All new
compounds have been fully characterised by spectroscopic
and analytical methods. Furthermore, the structures of 2a, 4,
5a, 5b and 6–9 have been elucidated by single-crystal X-ray
crystallography. The X-ray structures of 5a, 5b and 6–9 repre-
sent the first examples of crystallographically characterised
nonsymmetric ditertiary phosphane complexes bearing one
adamantane moiety.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2007)
electron-rich diphosphane (AdPCH2)2CH2 (bpap) recently
reported by Pringle and co-workers.[15,16] Both bpap and
related diphospha-adamantane ligands have been shown to
form complexes with Ru, Pd and Au metal centres.[15,16]
There has also been interest in these adamantane-based
phosphane ligands for their important uses in a range of
catalytic metal-mediated transformations such as amina-
tions, hydroformylation, hydrogenations, methoxycarbon-
ylation of internal alkenes and Suzuki and Sonogashira
couplings.[17–25]
Nonsymmetric ditertiary phosphanes have seldom been
studied in relation to their symmetric counterparts possibly
reflecting the necessity to perform multistep syntheses.[26–31]
When considering possible coordination modes for non-
symmetric diphosphanes of the type R2PCH2XCH2PRЈ2
various coordination modes are plausible some of which are
shown in Figure 1. Hence κ1-P-monodentate coordination
is possible at either –PR2 or –PRЈ2 centres (structures I and
II) and µ-PPЈ bridging between similar/disparate metal
centres (structures III–V; the presence of a metal–metal in-
teraction is illustrated by a dashed line). Alternatively such
mixed ligands may adopt a more classic κ2-PPЈ-chelating
mode to a single metal centre (structure VI). Finally, de-
pending on the nature of the X spacer group [e.g. N-
Introduction
As part of ongoing studies[1–5] in our group we have been
interested in developing new tertiary and symmetric diterti-
ary phosphanes using Mannich-based condensation reac-
tions. Compounds of the formula (R2PCH2)2N(R) and
{(R2PCH2)2N}2(R) are two such examples[6–10] which have
interesting coordination properties, catalytic applications
and, more recently, are important ligands for self-assembly
reactions using covalent bonds or H-bonding interac-
tions.[1,2,4,11] The tetraphenyl-substituted phosphane
(Ph2PCH2)2N(R), closely related to the three-carbon spacer
(Ph2PCH2)2CH2
[1,3-bis(diphenylphosphanyl)propane,
dppp], has been successfully utilised in several metal-cata-
lysed reactions.[12–14] Furthermore, a related C3 backbone
diphosphane structurally comparable to dppp, is the bulky
[a] Department of Chemistry, Loughborough University, Lough-
borough, Leics,
UK, LE11 3TU, UK
Fax: +44-1509-223925
E-mail: m.b.smith@lboro.ac.uk
[b] Sasol Technology (Pty) Ltd., R&D Division,
1 Klasie Havenga Road, Sasolburg, 1947, South Africa
Fax: +27-11-52-3190
E-mail: kevin.blann@sasol.com
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M. B. Smith et al.
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(CH2)4] separating the two phosphorus donor atoms, κ3- Ph2PCH2N(H)R] or symmetric ditertiary phosphanes [of
PNPЈ-tridentate coordination is possible utilising all three the type (Ph2PCH2)2N(R)] depending on the R group.[1–5]
group-15 donor atoms (structure VII).[8]
We have found that by using two consecutive Mannich
based condensation reactions, nonsymmetric ditertiary
phosphanes such as 3a and 3b can be realised. Accordingly,
insertion of paraformaldehyde into the P–H bond of AdP-
H (1:1 ratio) at 110 °C for 90 min affords the hy-
droxymethyl-functionalised phosphane 1. Mannich conden-
sation of 1 with H2NC6H5 (1:1 ratio) in CH3OH at room
temperature, under anaerobic conditions, gave the second-
ary aminophosphane 2a as a racemic mixture of enantio-
mers. Similarly, 2b could be prepared from H2NC6H4(4-
CH3) employing a similar method (Scheme 2). Further
treatment of 2a (or 2b) with Ph2PCH2OH in CH3OH at
room temperature gave the desired nonsymmetric ditertiary
phosphanes 3a (or 3b) in good yields (ca. 85%). The formu-
lation of these compounds were confirmed by a combina-
tion of spectroscopic and analytical methods.
Figure 1. Schematic representation of the possible coordination
modes for R2PCH2XCH2PRЈ2.
Herein we report a simple two-step condensation pro-
cedure (Scheme 1, pathway b/c) by which ditertiary phos-
phanes bearing non-equivalent groups (–PPh2 and –PAd)
can be obtained. In contrast, while pathway a generally af-
fords symmetric diphosphanes, pathway b gives initially a
secondary aminophosphane that can undergo further reac-
tion with a second different hydroxymethylphosphane pre-
cursor (pathway c) to yield the desired nonsymmetric di-
phosphane. We demonstrate that these ligands exhibit di-
verse coordination behaviour towards a range of late transi-
tion metals, and can function in a κ1-P-monodentate man-
ner in which the –PAd fragment remains non-coordinating
(structure I). This has allowed us to use these intermediates
as “metalloligands” for the construction of heterobimetallic
species as exemplified by our syntheses of complexes con-
taining Ru/Au and Ir/Au metal centre combinations. The
single-crystal X-ray structures of eight compounds are re-
ported.
Scheme 2.
The 31P{1H} NMR chemical shifts for 1, 2a and 2b are
all similar [δ(P) –31.2, –32.2 and –32.4 ppm, respectively],
but differ from the starting secondary phosphane AdP-H,
by ca. 20 ppm [δ(P) –49.7 ppm, CDCl3].[32] Furthermore,
the 31P{1H} NMR chemical shifts for 1, 2a and 2b differ
by ca. 10 ppm with respect to the phenyl-modified phospha-
adamantanes, AdP-Ph, previously reported.[19] Upon sec-
ond condensation the 31P resonance for the –PAd group is
shifted upfield by ca. 10 ppm to –41.5 ppm (for 3a) and
–42.0 ppm (for 3b). The –PPh2 resonance is observed at δ(P)
–27.4 ppm (for 3a) and –27.6 ppm (for 3b), which differs by
ca. 10 ppm with respect to dppp [δ(P) –17.3 ppm, CDCl3].
1
In the H NMR spectra of 2a and 2b the CH2 hydrogen
atoms are diastereotopic as two separate doublet of dou-
blets are observed at ca. 3.4 and 2.9 ppm. On the basis of
FT-IR spectroscopy (KBr pellets), characteristic νO–H and
νN–H stretches were observed at 3470 cm–1, 3367 cm–1 and
3319 cm–1 for 1, 2a and 2b, respectively, yet these fre-
quencies were absent in either 3a or 3b as would be ex-
pected. Other characterising data are given in Table 1 and
the Exp. Sect.
Scheme 1.
Results and Discussion
The X-ray structure of 2a has been determined (Figure 2,
Table 2) and confirms the presence of the phospha-ada-
Ligand Syntheses
Previous studies using Ph2PCH2OH have shown that mantane cage. While a few crystallographic examples of ste-
condensation with primary amines (RNH2) can be used to rically hindered phosphanes containing this cage have been
access either singly substituted products [of the type reported in the literature[15–19,21,25] this structure represents
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Complexes with Nonsymmetric Ditertiary Phosphanes
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Table 1. Selected spectroscopic data for compounds 1–10.[a]
δ(P) / –PPh2
δ(P) / –PAd
–31.2
–32.2
–32.4
–41.5
–42.0
18.7
4J(PP)
J(PtPPh2)
J(PtPAd)
2J(PP)
ν(OH)/ ν(NH)
ν(MCl)
1
3470
3367
3319
2a
2b
3a
3b
4
–27.4
–27.6
5
4
3297
5a
5b
5c
5d
6
–8.0
–8.0
9.6
–19.0
–18.9
–4.0
3233
3230
3489
3489
19
19
8
315, 293
315, 292
304, 291
304, 291
9.6
–3.9
10
23.6
–5.1
28.4
17.5
14
–39.0
–38.7
24.1
–3.2
10
n.r.
5
11
9
7
8
331
336
329
9
10[b]
n.r.
[a] Chemical shifts in ppm, coupling constants in Hz. [b] Recorded at –50 °C in CDCl3. n.r. = not resolved.
the first example of such a compound bearing a remote, similar to other documented tertiary phosphanes bearing
secondary amine functional group. The P(1)–C(11) phenyl substituents on phosphorus [P–C 1.8208(19),
[1.8591(19) Å] and C(11)–N(1) [1.456(2) Å] distances are 1.8515(18) Å; C–N 1.456(2), 1.454(2) Å] illustrating that the
adamantane cage has negligible electronic/steric effects on
these structural parameters.[1,33]
Coordination Studies
Given the paucity of palladium complexes with ada-
mantane-based phosphorus ligands documented in the lit-
erature[17,19,25] we prepared the palladium(II) complex 4 by
bridge cleavage of the known[34] dimeric compound {Pd(κ2-
C,N-C16H16N)Br}2 with 2a in refluxing acetone [Equation
(1)]. Compound 4 displayed a singlet at δ(P) 18.7 ppm in
the 31P{1H} NMR spectrum (Table 1) and furthermore was
characterised by single-crystal X-ray crystallography.
Figure 2. Molecular structure of 2a; all hydrogen atoms except on
N(1) have been removed for clarity.
Table 2. Selected bond lengths [Å] and angles [°] for compounds 2a
and 4.
2a
4
Pd(1)–Br(1)
Pd(1)–P(1)
Pd(1)–N(2)
Pd(1)–C(33)
2.5676(3)
2.2522(6)
2.1291(18)
2.050(2)
N(2)–C(24)
P(1)–C(11)
C(11)–N(1)
1.282(3)
1.872(2)
1.444(3)
1.8591(19)
1.456(2)
Br(1)–Pd(1)–P(1)
Br(1)–Pd(1)–C(33)
Br(1)–Pd(1)–N(2)
P(1)–Pd(1)–C(33)
P(1)–Pd(1)–N(2)
C(33)–Pd(1)–N(2)
Pd(1)–P(1)–C(11)
P(1)–C(11)–N(1)
94.067(16)
167.48(7)
89.01(5)
95.42(7)
173.14(5)
82.47(8)
(1)
The X-ray structure (Figure 3, Table 2) confirmed a near
square-planar arrangement about palladium with angles in
the range 82.47(8)–95.42(7) Å. The Pd(1)–P(1) distance in
4 [2.2522(6) Å] is as expected. As previously observed for
111.02(2)
117.08(16)
108.35(13)
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M. B. Smith et al.
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other cyclometallated complexes of palladium the phos- [83.07(5)°] bond angle is contracted by some 10° with re-
phane 2a is trans to the imine nitrogen N(2).[35] Within the spect to P(1)–Pt(1)–Cl(1) [93.87(6)°] clearly reflecting the
κ2-C,N-metallated ligand an E configuration is adopted by different steric effects of phenyl vs. adamantane groups. The
the two arene groups located about the C(24)=N(2) imine P(1)–Pt(1)–P(2) hinge angle is 96.33(5)° which compares
double bond. The six-membered PdC4N metallacycle favourably with the previously reported angle for the sym-
adopts a nonplanar conformation hinged about C(24)/ metric, bulky diphosphane palladium(II) complex
C(33). The Pd deviates from the P(1)/Br(1)/N(2)/C(33) PdCl2(bpap), previously reported by Pringle and co-
mean plane by 0.0242 Å. Within the bonded P ligand the workers.[15] The Pt–P [2.2362(16), 2.2373(14) Å] and Pt–Cl
intra-cage C–P–C angle is 94.05(10)° which is slightly en- [2.3545(14), 2.3499(14) Å] bond lengths are similar and il-
larged with respect to 2a [92.90(8)°] but similar in magni- lustrate the negligible effect the different substituents on P
tude to other coordinated phospha-adamantane li- have on these distances. The Pt is out of the mean plane
gands.[16,19] The amine group forms an intramolecular hy- [defined by the donor atoms P(1), P(2), Cl(1) and Cl(2)] by
drogen bond to the coordinated bromide ligand [N(1)··· 0.0139 Å (for 5a) and 0.0451 Å (for 5b). The six-membered
Br(1) 3.265(2) Å, H(1)···Br(1) 2.61(3) Å; N(1)–H(1)···Br(1) Pt–P–C–N–C–PЈ rings in 5a and 5b adopt a conformation
137(2)°].
in which the Pt(1), P(1), P(2), C(11) and C(18) atoms are
essentially flat (to within Ϯ0.07 Å for 5a; Ϯ0.19 Å for 5b)
and N(1) is out of this plane by 0.74 Å (for 5a) and 0.66 Å
(for 5b). Furthermore the N–arene torsion angles, defined
by the C(11)/N(1)/C(18) and C(12)ϾC(17) mean planes, are
37° and 76° for 5a and 5b respectively. Analysis of the pack-
ing in the two crystal structures shows the orientations of
the N–arene rings are determined by weak C–H(Me or
Ph)···π(N–arene) interactions to neighbouring molecules.
Having established these nonsymmetric ligands success-
fully P,PЈ-chelate to platinum(II) and palladium(II) metal
centres we next sought to establish whether the sterically
demanding adamantane group could impose a P-mono-
dentate mode of binding through the sterically less encum-
bered –PPh2 group. This sort of P-monodentate behaviour,
whilst known for flexible small bite angle diphosphanes
such as dppm,[36] dppa [bis(phenylphosphanyl)amine][37]
and others,[28] is less prevalent with dppp bearing an ex-
tended C3 spacer. Gratifyingly when we reacted 3a with
{RuCl2(η6-p-cym)}2 or {IrCl2(η5-Cp*)}2 in dichlorometh-
ane we obtained the κ1-P-monodentate complexes 6 and 7
in high yields. Presumably under these experimental condi-
tions the –PAd group is too bulky to coordinate to the
Figure 3. Molecular structure of 4. All hydrogen atoms except on
N(1) have been removed for clarity.
Reaction of 3a (and 3b) with MCl2(cod) (M = Pt, Pd) RuCl2(η6-p-cym) or IrCl2(η5-Cp*) fragments [vide infra for
gave the dichloro κ2-P,PЈ-chelate compounds MCl2(3a) [M reactions with AuCl(tht)]. The 31P{1H} NMR spectra
= Pt 5a; Pd 5c] and MCl2(3b) [M = Pt 5b; Pd 5d] in high (Table 1) are particularly informative showing new down-
yields (Scheme 3). By virtue of the different substituents on field δ(P) resonances for the coordinated –PPh2 group at
each phosphorus the 31P{1H} NMR spectra of the chelate δ(P) 23.6 ppm (for 6) and –5.1 ppm (for 7) whilst the pen-
complexes 5a–5d are particularly diagnostic showing a clas- dant –PAd group is observed at δ(P) ca. –39 ppm (cf. –41.5
sical AX pattern (Table 1). The 31P chemical shifts between ppm for 3a).
the two phosphorus nuclei differ by ca. 10 ppm whilst the
The X-ray structures of the piano-stool complexes 6 and
J(PtP) couplings differ by ca. 250 Hz with the J(PtP) coup- 7 have both been established by X-ray crystallography (see
ling to the –PAd group being the larger of the two. These Figures 6 and 7, Table 3). Within the coordination sphere
variations can presumably be ascribed to the difference in of 6 the Ru–P, Ru–Cl or Ru–Carene bond lengths are com-
stereoelectronic properties between the two phosphorus parable to other half-sandwich compounds e. g. RuCl2(p-
centres.
cym)PTA (PTA = 1,3,5-triaza-7-phosphatricyclo[3.3.1.1]-
The X-ray structures of the nonsymmetric diphosphane decane), RuCl2(p-cym)Ph2P(2-C5H4N) and RuCl2(p-cym)
platinum(II) complexes 5a and 5b have been determined Ph2PCH2Y [Y = –NHC6H4(2-CO2H), –NHC6H4(2-OH), –
(Figure 4, Figure 5 and Table 3). Suitable crystals of 5a and NHC6H4(2-CH2OH)].[1,38] As a consequence of κ1-P-
5b were obtained by slow diffusion of diethyl ether into a monodentate coordination the C(11)–N(1)–C(18) bond an-
CDCl3 solution. The X-ray structures show that both 5a gle has marginally increased by ca. 3° for 6 (and 4° for 7)
and 5b adopt a chelating coordination mode and further- with respect to that observed in the κ2-P,PЈ-chelate com-
more, the coordination environment around platinum is os- plexes 5a and 5b. The P···P separations within 6 and 7 are
tensibly square-planar. In 5a the P(2)–Pt(1)–Cl(2) 4.868 Å and 5.319 Å, respectively.
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Complexes with Nonsymmetric Ditertiary Phosphanes
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Scheme 3.
Figure 4. Molecular structure of 5a. All hydrogen atoms and sol-
vent have been removed for clarity.
Figure 5. Molecular structure of 5b. All hydrogen atoms and sol-
vent have been removed for clarity.
In order to pursue the possibility of introducing a second
metal centre we elected to react both 6 and 7 with 1 equiv.
of AuCl(tht) in dichloromethane at room temperature. Af-
Upon complexation the gold(I) chloride fragment is ap-
ter work up the red/orange solids κ2-P,PЈ-µ-RuCl2(η6-p- proximately linear with respect to the coordinated –PAd
cym){Ph2PCH2N(Ph)CH2PAd(AuCl)} 8 and κ2-P,PЈ-µ- moiety (see Figures 8 and 9, Table 4). The Au–Cl and Au–
IrCl2(η5-Cp*){Ph2PCH2N(Ph)CH2PAd(AuCl)} 9 were iso- P bond lengths are normal and in the region previously
lated in 93% and 77% yields respectively. The 31P{1H} observed for phosphane gold(I) complexes.[4,39–41] No sig-
NMR spectra were particularly informative showing a nificant changes are observed for the M–Cl and M–P (M =
downfield shift for –PAd to δ(P) 24.1 ppm (for 8) and δ(P) Ru or Ir) distances/bond angles upon gold complexation.
–3.2 ppm (for 9) with respect to the noncomplexed –PAd In addition the Cl(1)–Au(1)–P(1) angles [177.18(4)° for 8;
group in 6 and 7 (Table 1). Further indication for gold(I) 174.42(8)° for 9] suggest very minimal steric congestion be-
coordination was evident from the IR spectra which clearly tween the adamantane cage or neighbouring N–Ph group.
showed νAuCl vibrations at 331 cm–1 and 336 cm–1 for 8 and Furthermore, the C(11)–N(1)–C(18) angles for 8 and 9 are
9, respectively.
115.9(2)° and 115.5(6)°, respectively, whilst the N–arene
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Table 3. Selected bond lengths [Å] and angles [°] for compounds 5a
and 5b.
5a
5b
Pt(1)–Cl(1)
Pt(1)–Cl(2)
Pt(1)–P(1)
Pt(1)–P(2)
2.3545(14)
2.3499(14)
2.2362(16)
2.2373(14)
1.852(6)
2.3544(15)
2.3553(14)
2.2436(14)
2.2330(14)
1.833(5)
P(1)–C(11)
C(11)–N(1)
N(1)–C(18)
1.456(8)
1.462(7)
1.468(7)
1.469(7)
C(18)–P(2)
1.834(6)
93.87(6)
169.29(5)
87.05(5)
83.07(5)
174.86(5)
96.33(5)
116.9(2)
110.7(4)
112.4(5)
1.830(5)
94.67(5)
171.83(5)
85.97(5)
85.91(5)
176.54(5)
93.38(5)
118.12(18)
113.4(3)
112.0(4)
110.3(3)
Cl(1)–Pt(1)–P(1)
Cl(1)–Pt(1)–P(2)
Cl(1)–Pt(1)–Cl(2)
Cl(2)–Pt(1)–P(2)
Cl(2)–Pt(1)–P(1)
P(1)–Pt(1)–P(2)
Pt(1)–P(1)–C(11)
P(1)–C(11)–N(1)
C(11)–N(1)–C(18)
N(1)–C(18)–P(2)
C(18)–P(2)–Pt(1)
Figure 7. Molecular structure of 7; all hydrogen atoms and solvent
have been removed for clarity.
111.6(4)
117.53(19)
117.22(19)
Figure 8. Molecular structure of 8; all hydrogen atoms and solvent
have been removed for clarity.
Figure 6. Molecular structure of 6; all hydrogen atoms and solvent
have been removed for clarity.
torsion angles for 6–9, defined by the C(11)/N(1)/C(18) and
C(12)ϾC(17) mean planes, are all in the range 7.6–17.3°.
The P···P distances in both heterobimetallic complexes are
5.238 Å and 5.283 Å for 8 and 9, which also dictate large
Ru···Au [8.304 Å] and Ir···Au [8.481 Å] separations. The
shortest intermolecular Au···Au separations are 7.628 Å
and 5.987 Å, respectively, indicating the absence of any sig-
nificant aurophilic interactions between neighbouring P–
Au–Cl units.[42]
We next sought to demonstrate whether 3a could bridge
two identical metal centres and accordingly prepared the
digold(I) compound 10 from 2 AuCl(tht) and 1 equiv. of 3a
in CH2Cl2. The ambient temperature 31P{1H} NMR spec-
trum of 10 in CDCl3 revealed two broad resonances around
Figure 9. Molecular structure of 9; all hydrogen atoms have been
removed for clarity.
δ(P) 15 ppm which sharpened upon cooling to –50 °C (Fig- downfield resonance at δ(P) 14 ppm is tentatively assigned
ure 10). The close similarity of both phosphorus signals to the –PPh2(AuCl) bonded metal centre by analogy with
makes assignment of these somewhat speculative. The PhN(CH2PPh2AuCl)2 which has recently been reported.[4]
1410
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 1405–1414

Complexes with Nonsymmetric Ditertiary Phosphanes
FULL PAPER
Table 4. Selected bond lengths [Å] and angles [°] for compounds 6– with that of others who have shown that dppp can readily
9.
act as a bridging ligand affording symmetric dinuclear com-
plexes based on e. g. Mo,[43] Ru,[44] Ir,[45] Ni,[46] Pd[47] and
6
7
8
9
Au[48] metal fragments. However, crystallographic examples
where dppp bridges two different metal sites are extremely
scarce.[45b] Dinuclear Rh/Au complexes[49] have recently
been reported using κ3-PN2-bridged pyridylphosphanes
whilst {Ph2PCH2}2PPh has been used to generate, amongst
others, cationic Ru/Rh and Ru/Ag heteronuclear com-
plexes.[50,51] Further studies are in progress and will be re-
ported in due course.
M = Ru
M = Ir
M = Ru
M = Ir
M(1)–Cl(2)
M(1)–Cl(3)
M(1)–P(2)
M(1)–Ccentroid
P(2)–C(18)
C(18)–N(1)
N(1)–C(11)
C(11)–P(1)
P(1)–Au(1)
Au(1)–Cl(1)
2.4039(17) 2.408(2)
2.4063(17) 2.398(2)
2.3391(18) 2.3091(19) 2.3420(8)
2.4160(8)
2.4090(3)
2.4010(19)
2.424(2)
2.3047(19)
1.805
1.698
1.814
1.709
1.894(6)
1.435(8)
1.459(8)
1.885(7)
1.900(7)
1.451(9)
1.474(10)
1.869(8)
1.888(3)
1.454(4)
1.449(4)
1.851(3)
2.2227(8)
2.2804(9)
87.45(3)
85.55(3)
84.49(3)
113.49(10)
116.9(2)
115.9(2)
113.2(2)
118.16(10)
177.18(4)
1.881(8)
1.452(9)
1.444(9)
1.869(8)
2.223(2)
2.280(2)
89.02(7)
85.05(7)
88.29(7)
112.0(2)
116.4(5)
115.5(6)
115.1(5)
115.6(3)
174.42(8)
Cl(2)–M(1)–Cl(3) 88.63(6)
89.24(8)
88.64(7)
85.18(7)
112.4(2)
114.4(5)
115.9(6)
113.4(5)
Experimental Section
Cl(2)–M(1)–P(2)
Cl(3)–M(1)–P(2)
83.64(6)
84.40(6)
M(1)–P(2)–C(18) 113.3(2)
P(2)–C(18)–N(1) 118.4(4)
C(18)–N(1)–C(11) 115.0(5)
Materials: Standard Schlenk techniques were used for the synthesis
of 1, 2a, 2b, 3a and 3b whilst all other reactions were carried out
in air using previously distilled solvents unless otherwise stated.
(Diphenylphosphanyl)methanol[52] and the metal complexes
AuCl(tht) (tht = tetrahydrothiophene),[53] {RuCl2(η6-p-cym)}2,[54]
N(1)–C(11)–P(1)
C(11)–P(1)–Au(1)
P(1)–Au(1)–Cl(1)
112.5(4)
{IrCl2(η5-Cp*)}2 (Cp*
=
1,2,3,4,5-pentamethylcyclopentadi-
enyl),[55] MCl2(cod) (M = Pd, Pt)[56] and {Pd(κ2-C,N-C16H16N)-
[34]
Br}2
were prepared according to known procedures. All other
chemicals were obtained from commercial suppliers and used di-
rectly without further purification.
Instrumentation: Infrared spectra were recorded as KBr pellets in
the range 4000–200 cm–1 with a Perkin–Elmer System 2000 Fou-
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
CDCl3 unless otherwise stated. Elemental analyses (Perkin–Elmer
2400 CHN or Exeter Analytical, Inc. CE-440 Elemental Analyzers)
were performed by the Loughborough University Analytical Ser-
vice within the Department of Chemistry.
Preparation of 1: 1,3,5,7-Tetramethyl-2,4,8-trioxa-6-phosphaadaman-
tane (0.649 g, 2.91 mmol) and (CH2O)n (0.096 g, 3.20 mmol) were
heated at 110 °C for 90 min affording a yellow oil which was used
directly in subsequent condensation reactions. Compound 1 slowly
crystallises upon standing in a freezer. Routinely the purity of 1 was
shown, by 31P{1H} NMR, to be ca. 85%. 1H NMR (CDCl3): δ =
4.06 (m, CH2), 2.45 (s, OH), 1.97–1.35 (m, Ad cage) ppm.
Figure 10. Variable temperature 31P{1H} NMR spectra for 10 re-
corded in the range 20 to –50 °C.
Preparation of 2a: A solution of C6H5NH2 (5.561 g, 59.7 mmol) in
methanol (HPLC grade, 35 mL) was added to a methanol (HPLC
grade, 35 mL) solution of 1 (2.714 g, 9.37 mmol) by cannula. The
resulting mixture was stirred for 17 h and then concentrated under
reduced pressure to ca. 10 mL. The solid was collected by suction
filtration and dried in vacuo. Yield: 2.455 g, 84%. 1H NMR
(CDCl3): δ = 7.16–6.58 (m, arom. H), 3.85 (NH), 3.43 (dd, J =
12 Hz, 1.6 Hz, CH2), 2.91 (dd, J = 13 Hz, 3.2 Hz, CH2), 1.92–1.30
(m, Ad cage) ppm. C17H24NO3P (321.37): calcd. C 63.54, H 7.53,
N 4.36; found C 63.05, H 7.52, N 4.30. This procedure was also
used for the preparation of 2b albeit in lower yield (53%). For 2b:
1H NMR (CDCl3): δ = 7.01 (d, J = 8 Hz, arom. H), 6.60 (d, J =
8.4 Hz, arom. H), 3.90 (NH), 3.48 (dd, J = 13 Hz, 1.4 Hz, CH2),
2.96 (dd, J = 13.2 Hz, 3.2 Hz, CH2), 2.25 (CH3), 1.98–1.33 (m, Ad
cage) ppm. C18H26NO3P (335.4): calcd. C 64.46, H 7.81, N 4.18;
found C 64.37, H 7.79, N 4.26.
Conclusions
In summary, we have developed a facile method for the
synthesis of two nonsymmetric ditertiary phosphanes bear-
ing one bulky substituent on phosphorus. This procedure
is potentially a valuable synthetic route to highly modular
nonsymmetric diphosphanes with tuneable stereoelectronic
properties. Whilst κ2-P,PЈ-chelation is observed upon com-
plexation to square-planar metal centres we have shown the
ability of one of these ligands to function as a κ1-P-mono-
dentate tertiary phosphane. Coordination to a second, dif-
ferent metal, affords new examples of late transition metal
heterobimetallic compounds bridged by the phosphane 3a.
This clearly illustrates the importance of steric effects on
phosphorus and how this can be implemented in directing
Preparation of 3a:
A
solution of Ph2PCH2OH (0.245 g,
variable ligating modes. Our work should be contrasted 0.906 mmol) in methanol (HPLC grade, 5 mL) was added to a
Eur. J. Inorg. Chem. 2007, 1405–1414
© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
1411

M. B. Smith et al.
FULL PAPER
methanol (HPLC grade, 5 mL) suspension of
0.906 mmol) by cannula. The mixture was stirred for 24 h and the
2
(0.327 g,
2 mL under reduced pressure. Addition of diethyl ether (25 mL)
and hexane (25 mL) afforded a red/orange solid which was col-
lected by suction filtration and dried in vacuo. Yield: 0.049 g, 93%.
solid 3a collected by suction filtration and dried in vacuo. Yield:
1
0.412 g, 87%. For 3a, H NMR (CDCl3): δ = 7.38–6.72 (m, arom. For 8, C40H49AuCl3NO3P2Ru (1058.22): calcd. C 45.40, H 4.67, N
H), 4.33–4.11 (m, CH2), 3.56 (d, J = 14.4 Hz, CH2), 3.10 (dd, J = 1.32; found C 46.26, H 4.48, N 1.06. A similar procedure was also
14.4 Hz, 5.2 Hz, CH2), 1.88–1.08 (m, Ad cage) ppm. This pro-
cedure was also used for the preparation of 3b (85%). The purity
of 3a (and 3b) were shown, by 31P{1H} NMR, to be ca. 75–80%.
used for the preparation of the iridium(III) complex 9 (77%). For
9, 1H NMR (CDCl3): δ = 7.89–6.45 (m, arom. H), 5.26 (d, J =
16.8 Hz, CH2) and 4.95 (d, J = 16 Hz, CH2), 3.56 (d, J = 16 Hz,
CH2) and 3.30 (dd, J = 15.8 Hz, 4.2 Hz, CH2), 2.19–1.10 (m, Ad
1
For 3b, H NMR (CDCl3): δ = 7.44–7.24 (m, arom. H), 6.97 (d, J
= 8.4 Hz, arom. H), 6.76 (d, J = 8.8 Hz, arom. H), 4.26–4.13 (m,
CH2), 3.53 (d, J = 14.4 Hz, CH2), 3.10 (dd, J = 14.6 Hz, 5 Hz,
CH2), 2.19 (CH3), 1.83–1.02 (m, Ad cage) ppm. All efforts to ob-
tain analytical samples of 3a (and 3b) have so far been unsuccessful.
cage), 1.28 (d, J = 2 Hz, Cp*) ppm. C40H50AuCl3IrNO3P2
(1150.36): calcd. C 41.77, H 4.38, N 1.22; found C 41.69, H 4.17,
N 1.20.
Preparation of 10: 3a (75% purity, 0.117 g, 0.164 mmol) was added
as a solid to a CH2Cl2 (10 mL) solution of AuCl(tht) (0.105 g,
0.328 mmol). The solution was stirred for 45 min in the dark and
then concentrated to ca. 1–2 mL under reduced pressure. Addition
of diethyl ether (25 mL) and hexane (25 mL) afforded solid 10
which was collected by suction filtration and dried in vacuo. Yield:
0.135 g, 84%. C30H35Au2Cl2NO3P2·0.75C6H14 (1049.08): calcd. C
39.50, H 4.37, N 1.34; found C 39.25, H 3.76, N 1.55.
Preparation of 4: A mixture of 2a (0.071 g, 0.221 mmol) and {Pd(κ2-
C,N-C16H16N)Br}2 (0.090 g, 0.110 mmol) in HPLC grade acetone
(10 mL) were refluxed for 75 min. After cooling the solution was con-
centrated under reduced pressure to ca. 2–3 mL and diethyl ether
(10 mL)/hexanes (10 mL) added. The solid was collected by suction
filtration and dried in vacuo. Yield: 0.113 g, 70%. 1H NMR (CDCl3):
δ = 8.22 (d, J = 12.4 Hz, CH=N), 7.67–6.43 (arom. H), 4.70 (NH),
4.23 (d, J = 12.8 Hz, CH2), 3.77–3.63 (m, CH2), 2.43 and 2.24 (CH3),
2.41–1.46 (m, Ad cage) ppm. C33H37BrN2O3PPd (726.99): calcd. C
54.52, H 5.13, N 3.85; found C 54.09, H 5.47, N 3.77.
X-ray Crystallography: Vapour diffusion of diethyl ether into an
acetone solution (for 4) or CDCl3 solutions (for 5a or 5b) over
several days afforded suitable X-ray quality crystals. Compound 9
was obtained by slow diffusion of petroleum ether (b.p. 60–80 °C)
into a CDCl3 solution whereas slow diffusion of hexane into a
CH2Cl2 solution gave suitable crystals of compound 6. Compound
2a was obtained upon allowing a CH3OH filtrate to stand for sev-
eral days. Compounds 7 and 8 were obtained by slow evaporation
to dryness of a CH2Cl2/petroleum ether (b.p. 60–80 °C) or CHCl3/
hexane solution respectively. Details for the crystal data of 2a and
4–9 and a summary of data collection parameters are given in
Table 5 and Table 6.
Preparation of 5a: 3a (0.119 g, 0.192 mmol) was added as a solid
to a CH2Cl2 (10 mL) solution of PtCl2(cod) (0.072 g, 0.192 mmol).
The solution was stirred for 2.5 h and then concentrated to ca. 1–
2 mL under reduced pressure. Addition of diethyl ether (20 mL)
afforded a solid which was collected by suction filtration and dried
in vacuo. Yield: 0.129 g, 85%. C30H35Cl2NO3P2Pt·0.5CH2Cl2
(828.04): calcd. C 44.24, H 4.38, N 1.69; found C 43.94, H 3.89, N
2.04. A similar procedure was also used for the preparation of 5b
1
(92%). H NMR (CDCl3): δ = 8.02–7.31 (m, arom. H), 7.04 (d, J
= 8.4 Hz, arom. H), 6.80 (d, J = 8.8 Hz, arom. H), 4.27–4.09 (m,
CH2), 3.47–3.23 (m, CH2), 2.23 (CH3), 1.76–1.19 (m, Ad cage)
ppm. C31H37Cl2NO3P2Pt·CH2Cl2 (884.53): calcd. C 43.44, H 4.44,
N 1.58; found C 42.94, H 4.03, N 1.49. The dichloropalladium(II)
complexes 5c (from 3a) and 5d (from 3b) were prepared in 98%
and 92% yields respectively. For 5c: C30H35Cl2NO3P2Pd·
0.75CH2Cl2 (760.61): calcd. C 48.56, H 4.84, N 1.84; found C
48.84, H 4.48, N 1.57. For 5d, 1H NMR (CDCl3): δ = 7.97–7.33
(m, arom. H), 7.04 (d, J = 8 Hz, arom. H), 6.76 (d, J = 8 Hz, arom.
H), 4.11–4.03 and 3.52–3.22 (m, CH2), 2.23 (CH3), 1.81–1.27 (m,
Ad cage) ppm. C31H37Cl2NO3P2Pd·2.5CH2Cl2 (923.27): calcd. C
43.58, H 4.59, N 1.52; found C 43.09, H 4.24, N 1.71.
Measurements were made with either a Bruker AXS SMART 1000
CCD area-detector diffractometer[57] for 2a, 4, 5a, 5b and 8 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[58,59] equipped with a rotating anode generator for
6, 7 and 9. Cell parameters were refined from the observed ω angles
of all strong reflections in each data set. Intensities were corrected
semiempirically for absorption, on the basis of symmetry-equiva-
lent and repeated reflections. The structures were solved by direct
methods (Patterson synthesis for 5a, 5b, 8 and 9), and refined on
F2 values for all unique data by full-matrix least-squares.[60]
Tables 5 and 6 give further details. All non-hydrogen atoms were
refined anisotropically. For 5b a molecule of Et2O is badly disor-
dered over an inversion centre while in 7 there is a disordered mole-
cule of CH2Cl2 in a general position; these were modelled by the
Platon Squeeze procedure.[61] In 6 a molecule of CH2Cl2 is disor-
dered over an inversion centre. In 8 a molecule of CHCl3 was disor-
dered with the three Cl atoms split over two sets of positions, the
major sites occupied 72.1(3)%. The disorder in 6 and 8 was mod-
elled with restraints applied to assist geometry and anisotropic dis-
placement parameters.
Preparation of 6: 3a (0.098 g, 0.151 mmol) was added as a solid to
a
CH2Cl2 (10 mL) solution of {RuCl2(η6-p-cym)}2 (0.046 g,
0.075 mmol). The solution was stirred for 45 min and then concen-
trated to ca. 1–2 mL under reduced pressure. Addition of diethyl
ether (25 mL) and hexane (25 mL) afforded a red/orange solid
which was collected by suction filtration and dried in vacuo. Yield:
0.078 g, 63%. C40H49Cl2NO3P2Ru·0.25CH2Cl2 (847.03): calcd. C
57.07, H 5.89, N 1.65; found C 56.97, H 6.27, N 1.66. A similar
procedure was also used for the preparation of the iridium(III)
complex 7 (96%). For 7, 1H NMR (CDCl3): δ = 7.86–6.36 (m,
arom. H), 5.26 (d, J = 4 Hz, CH2) and 5.08 (d, J = 16 Hz, CH2),
2.98 (dd, J = 15.2 Hz, 4.4 Hz, CH2) and 2.71 (d, J = 15.2 Hz, CH2),
CCDC-629342 to -629349 (for compounds 2a, 4 and 5a–9) contain
the the complete set of X-ray crystallographic structural data.
These data can be obtained free of charge from The Cambridge
Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_requ-
est/cif. at the Cambridge Crystallographic Data Centre, 12 Union
Road, Cambridge, CB2 1EZ, UK (Fax: +44-1223-336-033; E-mail:
deposit@ccdc.ac.uk) on request, quoting the deposition numbers.
1.79–1.11 (m, Ad cage), 1.28 (d,
J = 2 Hz, Cp*) ppm.
C40H50Cl2IrNO3P2·4.5CH2Cl2 (1300.26): calcd. C 41.11, H 4.57, N
1.08; found C 40.78, H 4.41, N 1.02.
Preparation of 8: AuCl(tht) (0.016 g, 0.050 mmol) was added as a
solid to a CH2Cl2 (10 mL) solution of 6 (0.055 g, 0.050 mmol). The
solution was stirred for 45 min and then concentrated to ca. 1–
1412
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© 2007 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2007, 1405–1414

Complexes with Nonsymmetric Ditertiary Phosphanes
FULL PAPER
Table 5. Crystallographic data for 2a, 4, 5a and 5b.
Compound
2a
4
5a·CHCl3
5b·CHCl3·1/2OEt2
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C17H24NO3P
321.34
monoclinic
C2/c
21.6340(12)
8.0270(4)
21.0236(12)
C33H40BrN2O3PPd
729.95
C31H36Cl5NO3P2Pt
904.89
monoclinic
P21/c
14.8165(10)
16.6937(11)
14.3993(10)
C34H43Cl5NO3.5P2Pt
955.97
monoclinic
P21/n
15.6828(7)
12.8162(6)
18.2303(8)
triclinic
¯
P1
10.0874(5)
12.1965(7)
14.4382(8)
70.580(2)
80.716(2)
75.021(2)
1612.81(15)
2
α [°]
β [°]
γ [°]
116.317(2)
90.655(2)
93.261(2)
Volume [Å3]
Z
3272.5(3)
8
3561.3(4)
4
3658.2(3)
4
T [K]
150(2)
200(2)
1.503
1.899
150(2)
1.688
4.437
150(2)
1.736
4.326
Density (calcd.) [Mg/m3] 1.304
Absorption coeff. [mm–1] 0.180
Crystal habit
colourless tablet
0.25ϫ0.19ϫ0.07
2.10–29.00
14145
3988 [Rint = 0.030]
0.041, 0.100
colourless block
0.60ϫ0.30ϫ0.25
1.81–28.88
14148
7379 [Rint = 0.019]
0.027, 0.069
colourless plate
0.31ϫ0.22ϫ0.05
1.84–29.03
31031
8608 [Rint = 0.048]
0.040, 0.101
colourless needle
0.36ϫ0.04ϫ0.02
1.67–29.09
31911
8854 [Rint = 0.039]
0.040, 0.117
Crystal size [mm3]
θ range [°]
Reflections collected
Independent reflections
Final R, Rw
Table 6. Crystallographic data for 6–9.
Compound
6·1/2CH2Cl2
7·CH2Cl2
8·CHCl3
9
Empirical formula
Formula weight
Crystal system
Space group
a [Å]
b [Å]
c [Å]
C40.50H50Cl3NO3P2Ru
868.17
C41H52Cl4IrNO3P2
1002.78
monoclinic
C2/c
27.2637(13)
11.6769(6)
27.5628(14)
C41H50AuCl6NO3P2Ru
1177.50
C40H50AuCl3IrNO3P2
1150.27
monoclinic
C2/c
27.5062(17)
11.7458(6)
27.3935(17)
triclinic
triclinic
¯
¯
P1
P1
12.7297(12)
13.6693(12)
13.9918(14)
65.609(5)
68.646(4)
66.295(6)
1972.2(3)
2
12.5894(6)
14.1427(6)
15.2006(7)
64.547(2)
80.820(2)
68.287(2)
2270.36(18)
2
α [°]
β [°]
γ [°]
112.943(2)
111.376(2)
Volume [Å3]
Z
8080.6(7)
8
8241.5(8)
8
T [K]
120(2)
120(2)
1.649
3.688
150(2)
1.722
4.021
120(2)
1.854
7.092
Density (calcd.) [Mg/m3] 1.462
Absorption coeff. [mm–1] 0.721
Crystal habit
orange plate
0.17ϫ0.14ϫ0.04
2.97–25.00
32530
6917 [Rint = 0.105]
0.075, 0.156
yellow plate
0.34ϫ0.30ϫ0.02
1.60–27.59
29404
8118 [Rint = 0.069]
0.057, 0.177
red block
0.37ϫ0.24ϫ0.16
1.69–28.99
20226
10522 [Rint = 0.020]
0.028, 0.060
orange lath
0.22ϫ0.06ϫ0.02
2.91–27.60
37377
9397 [Rint = 0.057]
0.051, 0.103
Crystal size [mm3]
θ range [°]
Reflections collected
Independent reflections
Final R, Rw
[2]
[3]
M. R. J. Elsegood, M. B. Smith, P. M. Staniland, Inorg. Chem.
2006, 45, 6761–6770.
J. H. Downing, M. B. Smith, Phosphorus Ligands in Compre-
hensive Coordination Chemistry II, vol. 1, Elsevier, Oxford,
2004, 253–296.
M. B. Smith, S. H. Dale, S. J. Coles, T. Gelbrich, M. B. Hurst-
house, M. E. Light, CrystEngComm 2006, 8, 140–149.
S. E. Durran, M. B. Smith, S. H. Dale, S. J. Coles, M. B. Hurst-
house, M. E. Light, Inorg. Chim. Acta 2006, 359, 2980–2988.
Acknowledgments
We thank the EPSRC, Sasol Technology (Pty) Ltd. and Loughbor-
ough University for studentships. We are grateful to Cytec Canada
Inc. for the kind donation of the secondary cage phosphane used
in this work and to Johnson-Matthey for their loan of precious
metals. The EPSRC Mass Spectrometry Service centre at Swansea
are also acknowledged. The EPSRC X-ray service at Southampton
are gratefully acknowledged for the data collection for compounds
6, 7 and 9. Finally we thank Dr Mark Edgar for acquiring the
variable-temperature NMR spectra for compound 10.
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Received: December 18, 2006
Published Online: February 23, 2007
1414
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