Organotin compounds as reagents for the synthesis of lanthanoid complexes by redox transmetallation reactions

Article abstract of DOI:10.1002/ejic.200600045

Redox transmetallation reactions between trimethyltin compounds, SnMe ₃L [L = 3,5-diphenylpyrazolate (Ph₂pz), 2,6-di-tert-butyl-4-methylphenolate (OAr), or C₆F₅] and lanthanoid metals have yielded [Ln(Ph₂

Full text of DOI:10.1002/ejic.200600045

FULL PAPER
DOI: 10.1002/ejic.200600045
Organotin Compounds as Reagents for the Synthesis of Lanthanoid Complexes
by Redox Transmetallation Reactions
Samar Beaini,[a] Glen B. Deacon,*[a] Matthias Hilder,[a] Peter C. Junk,[a] and
David R. Turner[a]
Keywords: Redox transmetallation / Lanthanoid / Trimethyltin reagents / Pyrazolate / Aryl oxide / Ytterbium / Europium
Redox transmetallation reactions between trimethyltin com-
pounds, SnMe3L [L = 3,5-diphenylpyrazolate (Ph2pz), 2,6-di-
tert-butyl-4-methylphenolate (OAr), or C6F5] and lanthanoid
metals have yielded [Ln(Ph2pz)2(DME)2] (Ln = Eu, Yb),
[Ln(Ph2pz)3(DME)2] (Ln = Y, La, Nd, Eu), [Ln(Ph2pz)3(THF)3]
(Ln = Nd, Sm), [Ln(Ph2pz)3(THF)2] (Ln = Y, Yb), [Sm(OAr)3-
(THF)], [Yb(OAr)2(THF)3], and [Yb(C6F5)2(THF)4] complexes
in yields generally competitive with those from other
methods, and hexamethylditin. The crystal structures of
[Nd(Ph2pz)3(DME)2]·DME, [Eu(Ph2pz)3(DME)2]·2DME, and
[Sm(Ph2pz)3(THF)3]·3THF were determined. All have nine-
coordination of the lanthanoid atom and three η2-Ph2pz li-
gands, the first two also having an η1- and an η2-DME ligand
and the last having three THF ligands.
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2006)
6 [Sm(η5-C5H4tBu)2(THF)2] + 6 SnMe3F Ǟ
2 [Sm(η5-C5H4tBu)2F]3 + 3 Sn2Me6 (4)
Introduction
Redox transmetallation reactions between lanthanoid
metals and mercury or thallium compounds [Equations (1)
and (2); n = 2, 3] have become an important route to rare
earth organometallic compounds, organoamides, aryl ox-
ides,[1] and thiolates.[2]
However, the reduction of hexaphenylditin and tri-
phenyltin halide by ytterbium giving [Yb(SnPh3)2][6] sends
a note of warning especially if excess Ln metal is used, de-
spite the high E0 value (–2.9 V) for reduction of
Ph3SnSnPh3.[7]
Ln + n/2 HgL2 Ǟ Ln(L)n + n/2 Hg
(1)
Lead(II) compounds have also been used as oxidants,[8]
and an attempted use in redox transmetallation unexpec-
tedly gave a Pb/La dimetallic compound.[9] We now report
proof of concept of reaction according to Equation (3) by
syntheses of a range of lanthanoid pyrazolates and aryl ox-
ides generally in good yield from appropriate trimethyltin
reagents. In addition, in situ formation of Yb(C6F5)2 from
SnMe3(C6F5) has been demonstrated.
Ln + n TlL Ǟ Ln(L)n + n Tl
(2)
On the other hand, there has been only one example of
redox transmetallation between a tin reagent and a lan-
thanoid metal; viz formation of an ytterbium(II) organo-
amide from an SnII precursor,[3] despite the widespread use
of tin reagents in non-redox transmetallations.[4] Trialkyltin
compounds can be envisaged as potential redox transmetal-
lation reagents for the preparation of lanthanoid complexes
[Equation (3)].
Results and Discussion
Ln + n SnR3L Ǟ Ln(L)n + n/2 Sn2R6
(3)
The outcomes of the reactions of trimethyltin 3,5-di-
Encouragement that such syntheses may be possible phenylpyrazolate [SnMe3(Ph2pz)],[10] trimethyltin 2,6-di-
comes from the oxidation of bis(tert-butylcyclopentadienyl)- tert-butyl-4-methylphenolate [SnMe3(OAr)] and trimethyl-
samarium(II) by trimethyltin fluoride to give the corre- (pentafluorophenyl)tin with lanthanoid metals in 1,2-di-
sponding organosamarium(III) fluoride [Equation (4)].[5]
methoxyethane and tetrahydrofuran are summarised in
Scheme 1. Reactions with SnMe3(Ph2pz) gave both trivalent
[Ln(Ph2pz)3(DME)2] (Ln = Y, La, Nd, Eu), [Ln(Ph2pz)3-
(THF)3] (Ln = Nd, Sm), [Ln(Ph2pz)3(THF)2] (Ln = Y, Yb)
and divalent [Ln(Ph2pz)2(DME)2] (Ln = Eu, Yb) pyrazolate
complexes [Equations (5) and (6); L = Ph2pz; S = DME or
THF].
[a] School of Chemistry, Monash University,
P. O. Box 23, Clayton, Victoria 3800, Australia
Fax: +61-3-9905-4597
E-mail: glen.deacon@sci.monash.edu.au
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Lanthanoid Complexes by Redox Transmetallation Reactions
FULL PAPER
(THF)3], and [Sm(Ph2pz)3(THF)3] are obtained in higher
yield by the present method, but [Ln(Ph2pz)3(THF)2] (Ln
= Y, Yb) in lower yield. In addition, [Ln(Ph2pz)3(DME)2]
(Ln = Y, Eu), and [Sm(Ph2pz)3(THF)3] are new complexes,
while [Nd(Ph2pz)3(DME)2]·DME is a new solvate. The last
complex has previously been isolated as an unsolvated pow-
(5)
(6) der[14] and as a C6D6 solvate.[15] Of special interest is the
formation of [Yb(Ph2pz)3(THF)2] by reaction according to
Equation (5), as attempts to prepare this complex from Yb
metal, Hg(C6F5)2 and Ph2pzH led to gross decomposi-
tion,[16a] and the corresponding reaction using HgPh2, and
redox transmetallation between Yb metal and Tl(Ph2pz)
both yielded YbII complexes.[16b] Thus, previous access to
[Yb(Ph2pz)3(THF)2] required
a
two-step synthesis[17]
(Table 1). Attempted reaction of Yb metal with
SnMe3(C6F5) in tetrahydrofuran at room temperature for
2 d failed, but, after 1 d of ultrasonication, incomplete for-
mation of Yb(C6F5)2 [Equation (6); Ln = Yb; L = C6F5]
was detected. By contrast, redox transmetallation between
Yb and Hg(C6F5)2 in tetrahydrofuran requires only a few
minutes induction and is complete in 4 h.[1c]
Scheme 1. Redox transmetallation reactions between SnMe3L and
Ln metals.
Table 1. Comparison of yields of Ln(L)n complexes of the current
study with literature methods.
Ln(Ph2pz)n(S)m
Ln + Reported
SnMe3L
Method
Similarly, [Sm(OAr)3(THF)] and [Yb(OAr)2(THF)3] were
obtained from analogous reactions of lanthanoid metals
with SnMe3(OAr) in tetrahydrofuran [reactions according
to Equations (5) and (6); Ln = Sm, Yb; L = OAr; S =
THF]. Formation of hexamethylditin in all reactions was
[Y(Ph2pz)3(DME)2]·DME
[La(Ph2pz)3(DME)2]
[Nd(Ph2pz)3(DME)2]·DME
[Eu(Ph2pz)2(DME)2]
[Eu(Ph2pz)3(DME)2]·2DME
[Yb(Ph2pz)2(DME)2]
80
82
79
88
70
80
54
97
96
51
–
–
77[a]
17[a]
90[b]
–
La/Ph2pzH/Hg(C6F5)2
[a]
[a]
Nd/Ph2pzH/Hg(C6F5)2
Eu/Tl(Ph2pz)[b]
1
established by H NMR spectroscopy[11] and in one case
–
66[c]
76[d]
69[e]
72[f]
64[g]
several[c]
also by 119Sn NMR spectroscopy.[12] Thus, the 119Sn NMR
spectrum of the filtrate after isolation of [Yb(OAr)2-
(THF)3]·THF showed the presence of a resonance attribut-
able to Sn2Me6.[12] There was no resonance near δ =
–95 ppm where the signal of the Yb–Sn-bonded species
[Yb{Sn(CH2tBu)3}2(THF)2] is observed,[13] suggesting sig-
nificant amounts of Yb(SnMe3)2 are not formed despite the
use of a large excess of Yb metal. Reactions were carried
out with activation of the lanthanoid metal by Hg metal.
Without activation, reactions occurred, but were slower.
Initiation of reactions was faster in DME than in THF.
Variation of the excess of europium metal in the reactions
of SnMe3(Ph2pz) in DME enabled either the EuII or EuIII
product to be obtained (Scheme 1) in good yield. On the
other hand, the corresponding reaction of Yb metal has a
solvent-dependent outcome, yielding a YbII complex in
DME but a YbIII complex in THF (Scheme 1), even though
a greater excess of Yb metal was utilised for the latter. In
THF, a deep orange-red colour suggestive of some YbII was
observed after sonication, but the solution turned yellow
after removal from the excess of Yb due to oxidation by
SnMe3(Ph2pz) [Equation (7)].
[d]
[Y(Ph2pz)3(THF)2]
Y/Ph2pzH/Hg(C6F5)2
Nd/Ph2pzH/Hg(C6F5)2
[e]
[f]
[Nd(Ph2pz)3(THF)3]·THF
[Sm(Ph2pz)3(THF)3]·3THF
[Yb(Ph2pz)3(THF)2]
Sm/Ph2pzH/Hg(C6F5)2
Yb/Tl(Ph2pz) + oxid. with
Tl(Ph2pz)[g]
[Sm(OAr)3(THF)]·THF
[Yb(OAr)2(THF)3]·THF
45
87
49[h]
76[i]
metathesis[h]
several[i]
[a] Ref.[14] [b] Ref.[16a] [c] Ref.[16b] [d] Ref.[18] [e] Ref.[19] [f] This work.
[g] Ref.[17] [h] Ref.[20] [i] Ref.[21]
Known complexes (Table 1) were characterised by lan-
thanoid metal analyses, IR spectroscopy and 1H NMR
spectroscopy, which confirmed the DME or THF/Ph2pz or
OAr ratio. However, 4-H(pz) and o-H(Ph) resonances of
[Nd(Ph2pz)3(THF)3]·THF were too broad for satisfactory
integrations. Furthermore, single crystals of [Nd(Ph2pz)3-
(THF)3]·THF, [Yb(Ph2pz)2(DME)2] and [Yb(OAr)2-
(THF)3]·THF were grown, and their unit cells are in agree-
ment with the reported data.[16,19,20] In the case of the
known[16a] [Eu(Ph2pz)2(DME)2], fifteen of sixteen single
crystals examined had unit cell data corresponding to that
reported for trans-[Eu(Ph2pz)2(DME)2],[16a] the product of
redox transmetallation between Eu metal and
Tl(Ph2pz).[16a] However, the values for one crystal were
close to those for cis-[Yb(Ph2pz)2(DME)2],[16b] and can be
2 Yb(Ph2pz)2 + 2 SnMe3(Ph2pz) Ǟ 2 Yb(Ph2pz)3 + Sn2Me6 (7)
Reactions according to Equations (5) and (6) generally attributed to cis-[Eu(Ph2pz)2(DME)2]. It previously seemed
give yields comparable with those of alternative routes surprising that [Eu(Ph2pz)2(DME)2] crystallised with the
(Table 1). However, [Nd(Ph2pz)3(DME)2], [Nd(Ph2pz)3- Ph2pz ligands mutually transoid when the complex of the
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S. Beaini, G. B. Deacon, M. Hilder, P. C. Junk, D. R. Turner
FULL PAPER
adjacent Sm was isolated cisoid[16a] as was cis-[Yb(Ph2pz)2- in the erbium complex (4.62 Å/122°) and the neodymium
(DME)2].[16b] Although only one crystal of cis-[Eu(Ph2pz)2- C6D6 solvate (4.92 Å/129°). Plausibly, packing effects asso-
(DME)2] was identified from the reaction according to ciated with differing solvation in the crystals [2 DME (Eu),
Equation (6), its existence is established.
1 DME (Nd) (this study); 0 DME (Er);[14] 2 C6D6 (Nd)[15]
]
The composition of the new complex Y(Ph2pz)3(DME)3 affect the arrangements of the η1-DME ligand. All Ph2pz
was established by microanalysis, metal analysis, and the and η2-DME ligands are nearly symmetrically chelating
DME/Ph2pz ratio by 1H NMR spectroscopy. Single crystals with only a small divergence in Ln–N (0.01–0.05 Å) and
could not be obtained, but as Y3+ has a similar size to Er3+
,
Ln–O (η2-DME) (0.01–0.03 Å) bond lengths (Table 2).
which gives a nine-coordinate [Er(Ph2pz)3(η2-DME)(η1- Nevertheless, the differences between Nd–N bond lengths
DME)][14] complex, it is likely the yttrium complex is a of each chelating pair in the DME solvate (0.018, 0.054,
nine-coordinate mono-DME solvate [Y(Ph2pz)3(DME)2]· 0.012 Å) (Table 2) are slightly larger than in the C6D6 solv-
DME. Besides characterisation by IR and NMR spec- ate (0.008, 0.026, 0.005 Å).[15] For [Eu(Ph2pz)3(DME)2]·
troscopy, and lanthanoid metal analyses, the new complexes 2DME (Table 2) and [Nd(Ph2pz)3(DME)2]·2C6D6,[15] the
[Eu(Ph2pz)3(DME)2]·2DME, [Sm(Ph2pz)3(THF)3]·3THF Ln–O (η1-DME) distance lies between the values for Ln–O
and the new solvate [Nd(Ph2pz)3(DME)2]·DME were char- (η2-DME), whereas for [Nd(Ph2pz)3(DME)2]·DME
acterised by single-crystal X-ray structure determinations (Table 2) and the Er complex[14] Ln–O (η1-DME) is the
(below). For the Nd complex, both 4-H(pz) and o-H(Ph) shortest Ln–O distance. Moreover, the pairings here do not
resonances were severely broadened. The DME of solvation conform to the η1-DME conformational pairings. Whilst
was readily lost from crystals of the Eu complex and the the ϽLn–N(O)Ͼ distances decline in the sequence Nd, Eu,
%Eu value for the dried complex corresponded to the com- Er as expected from the lanthanoid contraction, ϽEu-NϾ
1
position [Eu(Ph2pz)3(DME)2], whilst the H NMR spectra
from two separate preparations showed a DME/Ph2pz ratio
of 4:3, as in single crystals, and 3:3. Similarly, the dried
product from one preparation of the samarium complex
showed a THF/Ph2pz ratio of 6:3 as in the single crystals,
and the product from another a THF/Ph2pz ratio of 5:3.
No other products showed a similar loss of lattice solvent
of crystallisation.
The structures of [Eu(Ph2pz)3(DME)2]·2DME (Figure 1)
and the new solvate [Nd(Ph2pz)3(DME)2]·DME have nine-
coordinate lanthanoid atoms with three η2-Ph2pz ligands,
one chelating DME and one (less usual[22]) unidentate
DME. Selected bond lengths and angles are given in
Table 2. The complexes have similar connectivity to unsol-
vated [Er(Ph2pz)3(DME)2][14] and [Nd(Ph2pz)3(DME)2]·
2C6D6,[15] but there are differences in the structural details.
Notably, the uncoordinated end of the unidentate DME
Figure 1. Molecular structure of [Eu(Ph2pz)3(DME)2]·2DME. Se-
points away from the metal atom in the present complexes
lected bond lengths [Å] and angles [°] for this structure and the near
[Eu···O(2)nonbonding 5.47 Å, Nd···O(2)nonbonding 5.41 Å; Eu–
isostructural Nd complex are given in Table 2. Only one disordered
O(1)···O(2) 162°, Nd–O(1)···O(2) 153°] more markedly than position of η2-DME shown for clarity.
Table 2. Selected bond lengths [Å] and angles [°] for the new Ln(Ph2pz)n complexes.
[Nd(Ph2pz)3(DME)2]·DME [Eu(Ph2pz)3(DME)2]·2DME
[Sm(Ph2pz)3(THF)3]·3THF
Molecule 1 Molecule 2
Sm(1)–N(1) Sm(2)–N(7)
Bond lengths
Ln(1)–N(1)
Ln(1)–N(2)
Ln(1)–N(3)
Ln(1)–N(4)
Ln(1)–N(5)
Ln(1)–N(6)
Ln(1)–O(1)
Ln(1)–O(3)
Ln(1)–O(4)
2.452(3)
2.470(3)
2.485(3)
2.430(3)
2.451(2)
2.462(2)
2.526(2)
2.558(2)
2.576(2)
2.411(3)
2.424(3)
2.454(3)
2.418(3)
2.436(3)
2.423(3)
2.505(2)
2.532(3)
2.504(2)
2.428(4)
2.463(4)
2.435(4)
2.418(4)
2.415(4)
2.460(4)
2.507(3)
2.588(3)
2.517(3)
2.439(4)
2.423(4)
2.450(4)
2.425(4)
2.467(4)
2.428(4)
2.627(3)
2.520(3)
2.498(3)
Sm(1)–N(2)
Sm(1)–N(3)
Sm(1)–N(4)
Sm(1)–N(5)
Sm(1)–N(6)
Sm(1)–O(1)
Sm(1)–O(2)
Sm(1)–O(3)
Sm(2)–N(8)
Sm(2)–N(9)
Sm(2)–N(10)
Sm(2)–N(11)
Sm(2)–N(12)
Sm(2)–O(4)
Sm(2)–O(5)
Sm(2)–O(6)
Bond angles
O(1)–Ln(1)–O(3)
O(1)–Ln(1)–O(4)
O(3)–Ln(1)–O(4)
140.87(7)
156.04(7)
63.05(7)
134.91(8)
160.42(8)
64.14(8)
O(1)–Sm(1)–O(2) 76.25(11) O(4)–Sm(2)–O(5) 74.47(11)
O(1)- Sm(1)–O(3) 159.00(12) O(4)–Sm(2)–O(6) 131.23(11)
O(2)–Sm(1)–O(3) 124.48(11) O(5)–Sm(2)–O(6) 153.80(11)
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Lanthanoid Complexes by Redox Transmetallation Reactions
FULL PAPER
exceeds ϽEr-NϾ by more (0.09 Å) than than expected is 0.02 Å shorter than ϽNd–NϾ, near ionic radius expecta-
(0.06 Å) from ionic radii,[23] whereas the corresponding tions.[23]
ϽLn–OϾ difference is less (0.03 Å) than expected.
An X-ray crystal structure was also obtained for the
[Sm(Ph2pz)3(THF)3]·3THF has nine-coordination for sa- [SnMe3(OAr)] reagent (Figure 3). The compound is essen-
marium with three η2-Ph2pz and three THF ligands (Fig- tially isostructural with the known [SiMe3(OAr)].[24] The
ure 2). It is isostructural with [Nd(Ph2pz)3(THF)3]·THF, coordination environment around the tin atom is distorted
which was isolated as a mono-THF solvate,[19] whereas the tetrahedral. However, the C–O–Sn angle is significantly
present complex has two closely related independent mole- smaller than the C–O–Si angle within the silicon ana-
cules and six THF solvent molecules in the asymmetric logue,[24] presumably owing to reduced steric crowding by
unit. The Sm–O bond lengths are very similar to the Nd– the tert-butyl groups due to the increased ionic radius of
O bond lengths,[23] despite the expectation of a 0.03 Å dif- tin.
ference based on ionic radii.[23] Molecule 2 has almost iden-
tical O–Ln–O angles to those of the Nd complex, but mole-
cule 1 shows some deviation. More symmetrical η2-Ph2pz
bonding is observed in the present complex, and ϽSm–NϾ
Conclusions
This study shows that organotin(IV) compounds can be
used in redox transmetallation reactions with lanthanoid el-
ements to provide metal–organic lanthanoid complexes
[Equations (5) and (6)]. Although their initial reactivity is
somewhat lower than that of the analogous TlI reagents or
redox transmetallation with HgR2 and LH, comparable or
in some cases better yields have been obtained with the tin
reagents (Table 1). Moreover, the different reactivity has en-
abled both EuII and EuIII complexes to be isolated and a
different Yb oxidation state outcome than with previous
redox transmetallation methods. Besides variation of the
alkyl groups, there is opportunity for considerable modula-
tion of the tin reagents, e.g. (i) use of SnMe3Ar reagents
with lanthanoid metals and protic reagents such as pyr-
azoles, phenols, and amines in redox transmetallation/li-
gand exchange, and (ii) exploration of SnVI Ǟ SnII re-
duction with the potentially more transfer efficient
SnMe2L2 reagents. Evidence that Yb metal reacts with
SnMe3(C6F5) to give Yb(C6F5)2 in solution provides en-
couragement for the use of this compound in redox trans-
metallation/ligand exchange.
Figure 2. Molecular structure of [Sm(Ph2pz)3(THF)3]·3THF. One
of the two independent but closely related molecules is displayed.
Experimental Section
General Remarks: All reactions were carried out under dry nitrogen
using standard Schlenk and dry-box equipment. THF was freshly
distilled from sodium/benzophenone, while DME was distilled
from sodium. Infrared spectra (4000–650 cm–1) were recorded as
Nujol mulls with a Perkin–Elmer 1600 FTIR spectrophotometer.
1H NMR spectra were recorded with a Bruker DPX 300 MHz
spectrometer using dry degassed deuteriobenzene or deuteriote-
trahydrofuran solvents at 25 °C; resonances were referenced to re-
sidual hydrogen from the solvent. 119Sn NMR spectra were ob-
tained with a Bruker DRX 400 spectrometer and were referenced
to tetramethyltin. 19F NMR spectra were recorded with a Bruker
1
DPX 300 spectrometer and were referenced to external CFCl3. H
NMR spectra of all solutions following reactions of lanthanoid
metals with SnMe3L reagents showed the presence of Sn2Me6 (δ
117Sn–CH3
= 0.20 ppm; J
= 46.4 Hz, J
= 48.4 Hz).[11] Metal
119Sn–CH3
Figure 3. Molecular structure of [SnMe3(OAr)]. Selected bond
lengths [Å] and angles [°]: Sn(1)–O(3) 2.0082(15), O(3)–C(1)
1.363(3), Sn(1)–C(7) 2.127(2), Sn(1)–C(8) 2.139(3), Sn(1)–C(9)
2.127(3); C(1)–O(3)–Sn(1) 133.77(14), O(3)–Sn(1)–C(7) 105.56(9),
O(3)–Sn(1)–C(8) 104.31(9), O(3)–Sn(1)–C(9) 106.44(9), C(7)–
Sn(1)–C(8) 113.92(11), C(7)–Sn(1)–C(9) 117.10(11), C(8)–Sn(1)–
C(9) 108.42(11).
analyses of the lanthanoid complexes were performed by EDTA
titration with xylenol orange indicator following digestion in con-
centrated nitric and sulfuric acids and buffering with hexamine.[16a]
Microanalysis samples were sealed in glass ampoules under puri-
fied N2 and were determined by the Campbell Microanalytical ser-
vice, University of Otago, New Zealand. 3,5-Diphenylpyrazole and
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FULL PAPER
SnMe3(Ph2pz) were prepared as reported.[25,10] A modification
(LiC6F5 instead of MgC6F5Br) of the reported method[26] was used
to obtain SnMe3(C6F5), which was distilled under reduced pressure
and had IR and 19F NMR spectra as reported.[26] Bis(pentafluoro-
phenyl)mercury Hg(C6F5)2 was prepared by a literature method.[27]
[Nd(Ph2pz)3(DME)2]·DME: Nd metal powder (0.94 g; 6.55 mmol)
and SnMe3(Ph2pz) (0.52 g; 1.36 mmol) in DME, stirred for 5 d,
gave lavender-blue crystals; 0.38 g, 79%. The IR spectrum is in
agreement with that of [Nd(Ph2pz)3(DME)2].[15] 1H NMR (C6D6):
δ = –3.41 (br. s, 12 H, CH2-DME), 0.29 (s, 18 H, CH3-DME), 8.08-
8.22 (m, 18 H, m-H, p-H), 12.4 (v. br. s, o-H), 17.8 (v. br. s, 4-H)
ppm. C57H63N6NdO6 (1072.39): calcd. Nd 13.45; found Nd 13.71.
X-ray crystallography established the composition [Nd(Ph2pz)3-
(DME)2]·DME.
(2,6-Di-tert-butyl-4-methylphenolato)trimethyltin(IV). Method (a):
n-Butyllithium (11.2 mL, 1.6  in hexanes, 18.0 mmol) was added
dropwise to pre-dried 2,6-di-tert-butyl-4-methylphenol (3.30 g,
15.0 mmol) in Et2O (50 mL), and the mixture was stirred for 1 h.
Trimethyltin chloride (14.97 mL, 1.0  in hexanes, 14.97 mmol) was
then added dropwise. After stirring the reaction mixture overnight,
the diethyl ether solution was filtered and the filtrate concentrated
to crystallisation. Data of the crude product, which contained
[Eu(Ph2pz)2(DME)2]: Eu metal filings (2.52 g, 16.6 mmol) and
SnMe3(Ph2pz) (0.60 g, 1.57 mmol) in DME, sonicated for 5 d, gave
deep yellow crystals; 1.06 g, 88%. The IR spectrum is identical with
that reported.[16a] 1H NMR (C6D6): δ = 0.43 (br. s, 8 H, CH2-
DME), 0.92 (br. s, 12 H, CH3-DME), 1.32–2.09 (br. m, 22 H, 4-H,
traces of lithium phenolate (NMR identification): IR: ν = 2726 w,
˜
1603 w, 1418 vs, 1346 s, 1263 s, 1233 s, 1216 m, 1194 m, 1118 w, p-, m-, o-H) ppm. C38H42EuN4O4 (770.73): calcd. Eu 19.73; found
1023 w, 918 w, 886 s, 861 m, 822 m, 772 m, 722 m cm–1. 1H NMR
Eu 19.26. X-ray crystallographic examination of the yellow crystals
(C6D6): δ = 0.34 (s, JH,117 = 53 Hz, JH,119 = 57 Hz, 9 H, gave one crystal: monoclinic, space group P21/a, a = 7.8740, b =
2
2
Sn
Sn
Me3Sn), 1.51 (s, 18 H, tBu), 2.32 (s, 3 H, Me), 7.20 (s, 2 H, 3,5-H)
ppm. Extraction with hexane and concentration of the solvent
yielded pure SnMe3OAr as colourless crystals (1.99 g, 35%), iden-
tified by X-ray crystallography (below). 119Sn{1H} NMR
(149 MHz, C6D6, 25 °C): δ = 131.5 ppm. Method (b): Excess of
SnMe3Cl (1.80 g; 9.05 mmol) was added to a solution of lithium
2,6-di-tert-butyl-4-methylphenolate (LiOAr) (1.33 g; 5.90 mmol) in
Et2O (50 mL), and the resulting solution was stirred at room tem-
perature overnight. After filtration through a filter cannula, the
Et2O was removed under vacuum yielding a very fine crystalline
material, which was washed with 3×10 mL of hexane to remove
SnMe3Cl. M.p. 138–140 °C;1.35 g, 55%. The 1H NMR spectrum
(C6D6) as above, was void of LiOAr resonances. C18H32OSn
(383.16): calcd. C 56.42, H 8.41; found C 56.56, H 8.22.
18.8715, c = 23.9260 Å; β = 91.042°, V = 3554.67 Å3; isomorphous
with cis-[Yb(Ph2pz)2(DME)2][16b] [monoclinic, space group P21/a,
a = 7.882(4), b = 18.959(3), c = 24.080(14) Å; β = 91.03(2)°, V =
3598(3) Å3] and fifteen crystals of trans-[Eu(Ph2pz)2(DME)2], mo-
noclinic, space group P2/c, a = 14.9771, b = 12.5269, c =
19.6728 Å; β = 109.398°, V = 3481.40 Å3, in agreement with re-
ported data[16a] [monoclinic, space group P2/c, a = 19.746(3), b =
12.635(2), c = 15.396(2) Å; β = 110.12(1)°, V = 3607 Å3].
[Eu(Ph2pz)3(DME)2]·2DME: Eu metal chunks (0.73 g, 4.80 mmol)
and SnMe3(Ph2pz) (0.53 g, 1.38 mmol) in DME, stirred for 3 d,
gave golden yellow crystals; 0.38 g, 70%. IR: ν = 1604 m, 1246 w,
˜
1192 m, 1124 m, 1107 m, 1057 s, 1026 m, 971 s, 916 w, 865 m, 800
1
w, 758 vs, 724 w, 696 s, 684 s, 666 w cm–1. H NMR (C6D6): δ =
0.23 (s, 3 H, 4-H), 2.09-3.68 (br. s, 40 H, CH3 and CH2-DME),
7.01-8.56 (m, 30 H, o-, m-, p-H) ppm. Metal analysis on dried crys-
tals for C53H53EuN6O4 (loss of DME of solvation) (989.99): calcd.
Eu 15.35; found Eu 15.36. Single crystals were obtained from an-
other preparation that involved sonication of the DME mixture of
Eu metal chunks and SnMe3(Ph2pz) for 3 d (yield Ͻ5%). X-ray
crystallographic examination revealed the composition [Eu-
(Ph2pz)3(DME)2]·2DME. The 1H NMR spectrum in [D8]THF
showed loss of 1DME of solvation (C4D8O): δ = 3.47–3.59 (m, 30
H, CH3-, CH2-DME), 5.16 (s, 3 H, 4-H), 7.35 (br. t, 18 H, m- and
p-H), 7.84 (d, 12 H, o-H) ppm.
Redox Transmetallation Reactions
Preparation of Bis(3,5-diphenylpyrazolato)lanthanoid(II) and
Tris(3,5-diphenylpyrazolato)lanthanoid(III) Complexes: DME or
THF (50 mL) was added to excess lanthanoid metal (powder or
filings), SnMe3(Ph2pz) and 1–2 drops of mercury. The resulting
mixture was stirred or sonicated at room temperature usually for
5 d. A colour change was observed for most reactions within 4 h
(Yb: 1 h). The filtrate was collected by a filter cannula, and the
solvent volume reduced to 15 mL. Crystalline or powdered
Ln(Ph2pz)n (n = 2,3) compounds were obtained by cooling of the
1
concentrated solutions to –20 °C. In all cases, the H NMR spec-
[Yb(Ph2pz)2(DME)2]: Yb metal filings (1.20 g, 6.96 mmol) and
SnMe3(Ph2pz) (0.66 g, 1.72 mmol) in DME, sonicated for 5 d, gave
deep red crystals; 0.54 g, 80%. The IR spectrum is in agreement
with that reported.[16b] 1H NMR (C6D6): δ = 3.12 (br. s, 20 H, CH3,
CH2-DME), 7.22 (br. s, 6 H, p-H, 4-H), 7.33 (br. s, 8 H, m-H), 8.10
(br. s, 8 H, o-H) ppm (reasonable agreement with data for a solu-
tion in C4D8O).[16b] C38H42N4O4Yb (791.80): calcd. Yb 21.85;
found Yb 20.32. A unit cell, monoclinic, space group P21/a, a =
7.7214, b = 18.7327, c = 23.8207 Å; β = 91.03°, V = 3445.20 Å3 is
in agreement with that of cis-[Yb(Ph2pz)2(DME)2][16b] [monoclinic,
space group P21/a, a = 7.882(4), b = 18.959(3), c = 24.080(14) Å;
β = 91.03(2)°, V = 3598(3) Å3].
trum of the crude product was obtained to verify Sn2Me6 forma-
tion.[11] The product was then washed with hexane to remove
Sn2Me6, and dried briefly under vacuum.
[Y(Ph2pz)3(DME)2]·DME: Y metal powder (0.59 g; 6.62 mmol) and
SnMe3(Ph2pz) (0.50 g; 1.32 mmol) in DME, stirred for 5 d, gave
colourless crystals;0.36 g, 80%. IR: ν = 1603 m, 1512 w, 1420 w,
˜
1260 m, 1225 w, 1192 w, 1154 w, 1130 w, 1107 m, 1072 m, 1057 s,
1026 m, 1000 w, 972 vs, 912 m, 872 s, 804 m, 794 m, 758 vs, 704 s,
1
696 vs, 688 s cm–1. H NMR (C6D6): δ = 2.98 (br. s, 18 H, CH3-
DME), 3.10 (br. s, 12 H, CH2-DME), 7.04–7.07 (br. t, 6 H, p-H),
7.08 (s, 3 H, 4-H), 7.14 (br. s, 12 H, m-H), 7.90–7.93 (br. d, 12 H,
o-H) ppm. C57H63N6O6Y (1017.05): calcd. C 67.31, H 6.24, N 8.26,
Y 8.74; found C 66.73, H 6.60, N 8.22, Y 8.91.
[Y(Ph2pz)3(THF)2]: Y metal powder (1.01 g; 11.36 mmol) and
SnMe3(Ph2pz) (0.61 g; 1.60 mmol) in DME, sonicated for 5 d, gave
a white powder; 0.26 g, 54%. The IR spectrum is identical with
that reported.[18] 1H NMR (C6D6): δ = 1.36 (s, 8 H, CH2-THF),
3.43 (br. s, 8 H, CH2-THF), 6.91 (br. s, 6 H, p-H), 7.02 (br. t,
12 H, m-H), 7.17 (br. s, 3 H, 4-H), 7.71 (br. s, 12 H, o-H) ppm.
C53H49N6O2Y (890.90): calcd. Y 9.98; found Y 9.28.
[La(Ph2pz)3(DME)2]: La powder (1.03 g; 7.44 mmol) and
SnMe3(Ph2pz) (0.50 g; 1.31 mmol) in DME, stirred for 5 d, gave
a white powder; 0.35 g, 82%. The IR spectrum is similar to that
reported.[14] 1H NMR (C6D6): δ = 3.02 (br. s, 12 H, CH3-DME),
3.17 (br. s, 8 H, CH2-DME), 7.01–7.12 (m, 21 H, m-H, p-H, 4-H),
7.86 (br. s, 12 H, o-H) ppm. C53H53LaN6O4 (976.93): calcd. La
14.22; found La 14.51.
[Nd(Ph2pz)3(THF)3]·THF: Nd metal powder (0.95 g; 6.57 mmol)
and SnMe3(Ph2pz) (0.57 g; 1.49 mmol) in THF, stirred for 5 d, gave
3438
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Eur. J. Inorg. Chem. 2006, 3434–3441

Lanthanoid Complexes by Redox Transmetallation Reactions
FULL PAPER
lavender-blue crystals; 0.51 g, 97%. The IR spectrum is identical
25 mL, resulting in golden-yellow crystalline [Yb(OAr)2(THF)3]·
THF; 1.12 g, 87%. The IR spectrum corresponds to that report-
with that reported.[19] 1H NMR (C6D6): δ = –5.59 (br. s, 16 H,
CH2-THF), –2.78 (br. s, 16 H, CH2-THF), 7.90–8.01 (br. s, 18 H, ed.[21b] C46H78O6Yb (900.15): calcd. Yb 19.22; found Yb 19.92. The
m-H, p-H), 12.37–12.62 (v. br. s, o-H), 17.95–17.98 (v. br. s, 4-H) unit cell, monoclinic, space group P21, a = 9.7489, b = 15.2423, c
ppm. C61H65N6NdO4 (1090.45): calcd. Nd 13.22; found Nd 13.58.
A unit cell on the lavender blue crystals, orthorhombic, space
group P212121, a = 14.18(2), b = 16.26(1), c = 22.78(2) Å; V =
5254(8) Å3 is identical with that of [Nd(Ph2pz)3(THF)3]·THF[19]
[orthorhombic, space group P212121, a = 14.009(9), b = 16.280(8),
c = 22.640(16) Å; V = 5163(5) Å3].
= 15.3858 Å; β = 95.62°, V = 2277.68 Å3, is in agreement with
that reported[21a] [monoclinic, space group P21, a = 15.393(4), b =
15.619(5), c = 9.859(2) Å; β = 95.62(2)°, V = 2359 Å3]. A 119Sn{1H}
NMR (149 MHz, C6D6, 25 °C) spectrum of the filtrate shows the
presence of Sn2Me6: δ = –109.0 ppm (reported: δ = –108.7 ppm)[12]
1
but no SnMe3(OAr) signal. The H NMR spectrum (C6D6) of the
concentrated solution shows phenolate resonances: δ = 2.18 (s, 6
H, Me), 7.42 (s, 4 H, 3,5-H) ppm (tBu methyl resonances hidden
by the residual THF solvent resonances).
[Sm(Ph2pz)3(THF)3]·3THF. Method (a). SnMe3(Ph2pz) with Sm
Metal in THF: Sm metal powder (1.59 g; 10.6 mmol) and
SnMe3(Ph2pz) (0.52 g; 1.36 mmol) in THF, stirred for 5 d, then
sonicated for 1 d, gave a brownish/yellow precipitate; 0.54 g, 96%.
SnMe3(C6F5) with Yb Metal in THF: SnMe3(C6F5) (1 mL,
8.03 mmol) was added under N2 to a stirred mixture of Yb filings
(1.14 g, 6.60 mmol) and 2 drops of Hg metal in THF (50 mL). Af-
ter 2 d, no colour change was observed. The reaction mixture was
ultrasonicated for 1 d resulting in a deep-coloured solution. A 19F
NMR spectrum (282 MHz, 25 °C) of the solution showed
[Yb(C6F5)2(THF)4][28] and SnMe3(C6F5)[26] in a 2:1 ratio: δ =
–108.3 (br. m, 8 F, o-F, [Yb(C6F5)2(THF)4]), –121.5 [m, 2 F, o-F,
SnMe3(C6F5)], –154.0 [m, 1 F, p-F, SnMe3(C6F5)], –161.5 (m, 14 F,
m-F, SnMe3(C6F5) and m-, p-F, [Yb(C6F5)2(THF)4]) ppm (in agree-
IR ν = 1602 m, 1562 w, 1424 w, 1298 w, 1225 w, 1154 w, 1071 m,
˜
1050 (sh), 1026 m, 970 s, 915 m, 869 m, 803 w, 757 s, 697 m, 669
w cm–1. 1H NMR (C6D6): δ = 0.91 (m, 24 H, CH2-THF), 2.66 (m,
24 H, CH2-THF), 7.29 (t, 6 H, p-H), 7.60 (t, 12 H, m-H), 7.83 (s,
3 H, 4-H), 9.48 (d, 12 H, o-H) ppm. C69H81N6O6Sm (1240.78):
calcd. Sm 12.12; found Sm 11.98. In a similar reaction, sonicating
the same amounts of Sm and SnMe3(Ph2pz) for 6 d, the filtrate,
after isolation of the bulk product as a powder, was allowed to
stand for a few months and deposited single crystals of [Sm(Ph2pz)3-
(THF)3]·3THF (0.16 g, 30%). The IR spectrum and 1H NMR
chemical shifts agree with those of the above preparation, but the
solid had lost 1THF of solvation. An X-ray structure determi-
nation of the colourless crystals found two [Sm(Ph2pz)3(THF)3]·
3THF molecules in the unit cell (see below). Method (b): Sm pow-
der (0.22 g; 1.50 mmol), bis(pentafluorophenyl)mercury (0.80 g;
1.50 mmol) and 3,5-diphenylpyrazole (0.66 g; 3.00 mmol) were
stirred in THF (30 mL) at room temperature for 5 d. After fil-
tration through a diatomaceous earth pad, the pale yellow filtrate
was concentrated to 2 mL. Petroleum spirit (20 mL) was added
causing formation of a white precipitate, which was dried under
vacuum for 3.5 h; 0.89 g, 0.72 mmol, 72%. The IR spectrum is as
above. C69H81N6O6Sm (1240.78): calcd. Sm 12.12; found Sm 12.30.
ment with the respective reported data {[Yb(C6F5)2(THF)4]:[28]
δ
= –108.3 (o-F) and –161.4 (m-, p-F) ppm; SnMe3C6F5:[26] δ =
–122.2 (o-F), –153.9 (p-F), –161.4 (m-F) ppm}.
X-ray Crystallography: Crystalline samples of SnMe3(OAr),
[Nd(Ph2pz)3(DME)2]·DME, [Nd(Ph2pz)3(THF)3]·THF, [Eu(Ph2pz)2-
(DME)2], [Eu(Ph2pz)3(DME)2]·2DME, [Yb(Ph2pz)2(DME)2],
[Sm(Ph2pz)3(THF)3]·3THF, and [Yb(OAr)2(THF)3]·THF were
mounted on glass fibres in viscous hydrocarbon oil. Crystal data
were collected using an Enraf–Nonius Kappa CCD instrument (Sn,
Sm, Eu, Yb) or Bruker ApexII diffractometer (Nd) both equipped
with monochromated Mo-Kα radiation, λ = 0.71073 Å. All data
were collected at 123 K, maintained using an open flow of nitrogen
from an Oxford Cryostreams cryostat. X-ray data were processed
using the DENZO program (Nonius)[29] or SAINT package
(Bruker).[30] Structural solution and refinement was carried out
using SHELXL-97[31] and SHELXS-97[32] utilising the graphical
interface X-Seed.[33] For [Eu(Ph2pz)3(DME)2]·2DME there was one
disordered DME molecule in the lattice which was modelled over
two sites. The η2-DME contains two disordered positions of the
C2 backbone, also successfully modelled. For [Sm(Ph2pz)3(THF)3]·
3THF there were three THF molecules in the lattice with varying
degrees of disorder. These were refined isotropically and no hydro-
gen atoms were attached. For [Nd(Ph2pz)3(DME)2]·DME, one
Ph2pz phenyl group was successfully modelled as being disordered
over two positions. The corresponding phenyl group of the same
Ph2pz ligand also showed signs of disorder but this could not be
satisfactorily modelled. The µ2-DME showed signs of being disor-
dered in an analogous manner to that in the Eu complex but could
not be modelled adequately. Crystal data and refinement param-
eters for all complexes are compiled below. CCDC-288000 to
-288002 and -607830 contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge
from The Cambridge Crystallographic Data Centre via
www.ccdc.cam.ac.uk/data_request/cif.
[Yb(Ph2pz)3(THF)2]: Yb metal filings (1.36 g; 7.89 mmol) and
SnMe3(Ph2pz) (0.55 g; 1.44 mmol) in THF were sonicated for 5 d.
The initial deep orange-red solution lightened to a yellow colour
after filtration and concentration. A white powder was obtained
after evaporation of THF; 0.24 g, 51%. The IR spectrum is similar
to that reported.[17] C53H49N6O2Yb (975.03): calcd. Yb 17.75;
found Yb 18.34.
Preparation of (2,6-Di-tert-butyl-4-methylphenolato)lanthanoid(II)
and 2,6-Di-tert-butyl-4-(methylphenolato)lanthanoid(III) Complexes
[Sm(OAr)3(THF)]·THF: THF (50 mL) was added to a mixture of
Sm metal powder (1.52 g; 10.1 mmol), SnMe3(OAr) (0.89 g;
2.33 mmol) and 2 drops of Hg metal, and the resulting solution
was sonicated for 5 d. The deep-coloured solution was filtered
through a filter cannula, and THF was removed under vacuum.
The precipitate was washed with hexane to remove Sn2Me6, giving
a yellow powder; 0.33 g, 45%. IR ν = 1602 w, 1550 w, 1420 m, 1272
˜
s, 1217 w, 1196 w, 1040 s, 918 m, 888 m, 862 m, 818 s, 802 s. 789
1
s, 722 w, 668 w cm–1. H NMR (C6D6): δ = 1.24 (br. s, 8 H, CH2-
THF), 1.71 (s, 54 H, tBu), 2.43 (s, 9 H, Me), 3.19 (br. s, 8 H, CH2-
THF), 7.42 (s, 6 H, 3,5-H) ppm. C53H85O5Sm (952.60): calcd. Sm
15.78; found Sm 16.08.
[Yb(OAr)2(THF)3]·THF: THF (50 mL) was added to a mixture of
SnMe3(OAr) (1.10 g, 2.87 mmol), Yb metal filings (1.70 g,
9.82 mmol) and 2 drops of Hg metal, and the resulting mixture was
ultrasonicated for 5 d. After allowing the suspension to settle, the
deep orange supernatant solution was filtered and concentrated to
Crystal Data for SnMe3(OAr): C18H32OSn, M = 383.16,
0.5×0.5×0.375 mm, monoclinic, space group P21/c (No. 14), a =
13.421(3), b = 15.265(3), c = 9.0962(18) Å, β = 93.34(3)°, V =
1860.5(6) Å3, Z = 4, Dc = 1.368 g/cm3, F(000) = 792, 2θmax = 55.8°,
19949 reflections collected, 4416 unique (Rint = 0.0434). Final GooF
Eur. J. Inorg. Chem. 2006, 3434–3441
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
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3439

S. Beaini, G. B. Deacon, M. Hilder, P. C. Junk, D. R. Turner
FULL PAPER
[5] H. Schumann, M. R. Keitsch, J. Winterfeld, J. Demtschuk, J.
Organomet. Chem. 1996, 525, 279–281.
[6] L. N. Bochkarev, O. V. Grachev, S. F. Ziltsov, L. N. Zakharov,
Y. T. Struchkov, J. Organomet. Chem. 1992, 436, 299–311.
[7] R. E. Dessy, W. Kitching, T. Chivers, J. Am. Chem. Soc. 1966,
88, 453–459.
[8] a) W. J. Evans, C. A. Seibel, J. W. Ziller, J. Am. Chem. Soc.
1998, 120, 6745–6752; b) W. J. Evans, K. J. Forrestal, J. T. Le-
man, J. W. Ziller, Organometallics 1996, 15, 527–531; see also
the related W. J. Evans, G. W. Nyce, M. A. Johnston, J. W.
Ziller, J. Am. Chem. Soc. 2000, 122, 12019–12020.
[9] P. B. Hitchcock, M. F. Lappert, A. V. Protchenko, Main Group
Metal Chemistry, RSC, Dalton Division Meeting, UCL, 9/8/
2005.
[10] G. B. Deacon, E. E. Delbridge, C. M. Forsyth, P. C. Junk,
B. W. Skelton, A. H. White, Aust. J. Chem. 1999, 52, 733–739.
[11] T. L. Brown, G. L. Morgan, Inorg. Chem. 1963, 2, 736–740.
[12] T. N. Mitchell, G. Walter, J. Chem. Soc., Perkin Trans. 2 1977,
1842–1847. .
[13] F. G. N. Cloke, C. I. Dalby, P. B. Hitchcock, H. Karamallakis,
G. A. Lawless, J. Chem. Soc., Chem. Commun. 1991, 11, 779–
781.
[14] J. E. Cosgriff, G. B. Deacon, G. D. Fallon, B. M. Gatehouse,
H. Schumann, R. Weimann, Chem. Ber. 1996, 129, 953–958.
[15] G. B. Deacon, E. E. Delbridge, G. D. Fallon, C. Jones, D. E.
Hibbs, M. B. Hursthouse, B. W. Skelton, A. H. White, Organo-
metallics 2000, 19, 1713–1721.
= 1.103, R1 = 0.0316, wR2 = 0.0851, R indices based on 3616 reflec-
tions with IϾ2σ(I) (refinement on F2), 182 parameters, 0 restraints.
Lp and absorption corrections applied, µ = 1.369 mm–1. The com-
plex is isostructural with SiMe3(OAr).[24]
Crystal Data for [Nd(Ph2pz)3(DME)2]·DME: C57H63N6NdO6, M =
1072.39, blue block, 0.24×0.18×0.10 mm, monoclinic, space
group P21/c (No. 14), a = 12.3824(2), b = 16.0973(4), c =
26.7915(7) Å, β = 97.5260(10)°, V = 5294.2(2) Å3, Z = 4, Dc
=
1.345 g/cm3, F(000) = 2220, 2θmax = 55.0°, 42938 reflections col-
lected, 12144 unique (Rint = 0.0263). Final GooF = 1.076, R1
=
0.0413, wR2 = 0.0963, R indices based on 10980 reflections with
IϾ2σ(I) (refinement on F2), 674 parameters, 9 restraints. Lp and
absorption corrections applied, µ = 1.036 mm–1.
Crystal Data for [Eu(Ph2pz)3(DME)2]·2DME: C61H73EuN6O8, M
= 1170.21, yellow block, 0.35×0.30×0.20 mm, monoclinic, space
group P21/n (No. 14), a = 11.785(2), b = 25.600(5), c = 20.106(4) Å,
β = 106.03(3)°, V = 5830(2) Å3, Z = 4, Dc = 1.333 g/cm3, F(000) =
2432, 2θmax = 55.0°, 23569 reflections collected, 13230 unique (Rint
= 0.0657). Final GooF = 0.951, R1 = 0.0442, wR2 = 0.0748, R
indices based on 8144 reflections with IϾ2σ(I) (refinement on F2),
711 parameters, 0 restraints. Lp and absorption corrections ap-
plied, µ = 1.134 mm–1.
Crystal Data for [Sm(Ph2pz)3(THF)3]·3THF: C69H81N6O6Sm, M =
1240.75, colourless block, 0.20×0.10×0.10 mm, triclinic, space
[16]
a) G. B. Deacon, E. E. Delbridge, B. W. Skelton, A. H. White,
Eur. J. Inorg. Chem. 1999, 751–761; b) G. B. Deacon, E. E. Del-
bridge, B. W. Skelton, A. H. White, Eur. J. Inorg. Chem. 1998,
543–545.
¯
group P1 (No. 2), a = 13.343(3), b = 18.579(4), c = 25.270(5) Å, α
= 76.58(3), β = 85.19(3), γ = 87.35(3)°, V = 6070(2) Å3, Z = 4,
Dc = 1.358 g/cm3, F(000) = 2588, 2θmax = 55.0°, 51382 reflections
collected, 27663 unique (Rint = 0.0737). Final GooF = 1.018, R1 =
0.0598, wR2 = 0.1171, R indices based on 17199 reflections with
IϾ2σ(I) (refinement on F2), 1471 parameters, 280 restraints. Lp
and absorption corrections applied, µ = 1.025 mm–1.
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The authors gratefully acknowledge the continued financial sup-
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© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2006, 3434–3441

Lanthanoid Complexes by Redox Transmetallation Reactions
FULL PAPER
[31] G. M. Sheldrick, SHELXL-97, University of Göttingen, Ger-
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many, 1997.
Received: January 16, 2006
[32] G. M. Sheldrick, SHELXS-97, University of Göttingen, Ger-
many, 1997.
Published Online: July 11, 2006
Eur. J. Inorg. Chem. 2006, 3434–3441
© 2006 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
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