Group 11 complexes with the bidentate (SePPh2) 2CH2 and tridentate [(SePPh2) 2CH]- ligands

Article abstract of DOI:10.1515/znb-2007-0314

The reaction of (SePPh₂)₂CH₂ with group 11 metal complexes such as [Au(C₆F₅)₃(tht)] (tht = tetrahydrothiophene) affords the complex [Au(C₆F₅) ₃(SePPh₂CH2PPh2Se)] in which the ligand coordinates to the gold(III) center only through one selenium atom. The treatment of the ligand with Ag(OTf) or [Cu(NCMe)₄]PF₆ leads, depending on the molar ratio, to the complexes [Ag₂{(SePPh₂) ₂CH₂}₂](OTf)₂ or [M{(SePPh ₂)₂CH₂}₂]X (M = Ag, X = OTf; M = Cu, X = PF₆; OTf = CF₃SO₃) in which the phosphine selenide ligand coordinates as a bidentate bridging or chelating ligand through the Se,Se atoms. The reaction of (SePPh₂)₂CH₂ with [Au(C₆F₅)₂(acac)] (acac = acetylacetonate) occurs with deprotonation of the methylene group, and the methanide complex, [Au(C₆F₅)₂(SePPh₂CHPPh ₂Se)], is obtained, with a bidentate chelate Se,C coordination to the gold(III) center. The selenium atom can react further with other metal complexes such as [Au(C₆F₅)₃(tht)] to give the dinuclear species [Au(C₆F₅)₂{SePPh ₂CHPPh₂SeAu(C₆F₅)₃}], in which the ligand coordinates in a tridentate Se,C,Se form. The crystal structure of [Au(C₆F₅)₂{SePPh₂CHPPh ₂SeAu(C₆F₅)₃}] has been established by X-ray diffraction.

Full text of DOI:10.1515/znb-2007-0314

Group 11 Complexes with the Bidentate (SePPh2)2CH2 and Tridentate
[(SePPh2)2CH]– Ligands
Silvia Canalesa, Olga Crespoa, M. Concepcio´n Gimenoa, Peter G. Jonesb, and
Antonio Lagunaa
a Departamento de Qu´ımica Inorga´nica, Instituto de Ciencia de Materiales de Arago´n,
Universidad de Zaragoza-C.S.I.C., E-50009 Zaragoza, Spain
b Institut fu¨r Anorganische und Analytische Chemie der Technischen Universita¨t,
Postfach 3329, D-38023 Braunschweig, Germany
Reprint requests to Prof. A. Laguna. E-mail: alaguna@unizar.es
Z. Naturforsch. 2007, 62b, 407 – 412; received December 4, 2006
Dedicated to Prof. Helgard G. Raubenheimer on the occasion of his 65th birthday
The reaction of (SePPh2)2CH2 with group 11 metal complexes such as [Au(C6F5)3(tht)] (tht =
tetrahydrothiophene) affords the complex [Au(C6F5)3(SePPh2CH2PPh2Se)] in which the ligand
coordinates to the gold(III) center only through one selenium atom. The treatment of the lig-
and with Ag(OTf) or [Cu(NCMe)4]PF6 leads, depending on the molar ratio, to the complexes
[Ag2{(SePPh2)2CH2}2](OTf)2 or [M{(SePPh2)2CH2}2]X (M = Ag, X = OTf; M = Cu, X = PF6;
OTf = CF3SO3) in which the phosphine selenide ligand coordinates as a bidentate bridging or
chelating ligand through the Se,Se atoms. The reaction of (SePPh2)2CH2 with [Au(C6F5)2(acac)]
(acac = acetylacetonate) occurs with deprotonation of the methylene group, and the methanide
complex, [Au(C6F5)2(SePPh2CHPPh2Se)], is obtained, with a bidentate chelate Se,C coordina-
tion to the gold(III) center. The selenium atom can react further with other metal complexes
such as [Au(C6F5)3(tht)] to give the dinuclear species [Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}],
in which the ligand coordinates in a tridentate Se,C,Se form. The crystal structure of
[Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}] has been established by X-ray diffraction.
Key words: Group 11 Metals, Selenium Ligands, Methanide Ligands
Introduction
plexes reported include the ligands SedppfSe or
Sedppf (dppf = 1,1ꢀ-bis(diphenylphosphino)ferrocene)
[10, 11], SePR3 [12 – 16] or SePPh2CH2PPh2 [17 –
19]. The ligand (SePPh2)2CH2 has been very rarely
used in coordination chemistry [20, 21] including
group 11 metal chemistry, and to date only the cop-
per complex [CuBr(SedppmSe)]n [22] has been struc-
turally characterized. For the deprotonated ligand
[(SePPh2)2CH]− only the rhodium derivative [RhCp
{(SePPh2)2CH}]ClO4 has thus been characterized,
and no group 11 compound has been prepared [23].
Here we report on the synthesis of several group
11 complexes with the ligands (SePPh2)2CH2 and
[(SePPh2)2CH]−, in which the coordination to the
metal centers occurs via monodentate Se, biden-
tate bridging or chelating Se,Se or the tridentate
Se,C,Se modes. The latter coordination mode has been
structurally characterized in the complex [Au(C6F5)2
{SePPh2CHPPh2SeAu(C6F5)3}].
Gold and the other metals in group 11 have a
remarkably affinity for chalcogen elements. How-
ever, complexes with sulfur ligands have been much
more thoroughly investigated than the correspond-
ing selenium and tellurium derivatives, among which
the selenide and selenolate derivatives have been
the most studied [1]. Phosphine selenide ligands
have been known for a long time but their chem-
istry has not been widely explored [2, 3]. In par-
ticular, few complexes have been described in the
chemistry of group 11 metals with this type of
ligands. The most studied ligands are the dise-
lenoiminodiphosphinate[Ph2P(Se)NP(Se)Ph2]− or the
protonated species, bis(diphenylselenophosphoranyl)
amine [Ph2P(Se)NHP(Se)Ph2], for which several cop-
per(I) [4, 5] silver(I) [6, 7] and gold(I) and gold(III)
[6, 8, 9] complexes have been described. Other com-
0932–0776 / 07 / 0300–0407 $ 06.00 © 2007 Verlag der Zeitschrift fu¨r Naturforschung, Tu¨bingen · http://znaturforsch.com
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408
S. Canales et al. · Group 11 Complexes with Bidentate and Tridentate Selenium Ligands
C6F5
Au
Ph2P
Ph2P
Se
Se
Ag
Se
Se
PPh2
PPh2
C6F5
Se
Se
PPh2
H2C
CH2
(CF3SO3)2
CH2
C6F5
Ag
PPh2
ii)
1
2
i)
Ph2P
Se
Se
Se
PPh2
Se
Se
PPh2
iii)
H2C
CH2
M
X
CH2
Ph2P
Se
PPh2
PPh2
Scheme 1. i) [Au(C6F5)3(tht)];
ii) Ag(OTf); iii) 1/2 Ag(OTf) or
[Cu(NCMe)4]PF6.
M = Ag, X = CF3SO3 (3); M = Cu, X = PF6 (4)
Results and Discussion
The treatment of (SePPh2)CH2 with Ag(OTf) in
a 1 : 1 molar ratio gives the species [Ag2{(SePPh2)2
CH2}2](OTf)2 (2). We assume a dinuclear structure
with the ligand bridging both silver atoms, rather than a
mononuclear structure with a chelating ligand, because
the IR spectrum shows the typical absorptions for ionic
(non-coordinated) triflate; for a chelated structure, the
trifluoromethanesulfonate anion would probably coor-
The bis(diphenylselenophosphoryl)methane ligand
is easily obtained from the reaction of elemental se-
lenium with bis(diphenylphosphino)methane. In prin-
ciple, this ligand can coordinate metal centers only
through the selenium donor atoms in a monoden-
tate Se or bidentate Se,Se mode but, after depro-
tonation of the methylene group, it can also co-
ordinate through the methanide carbon atom as
a tridentate Se,C,Se donor ligand. We have pre-
pared various group 11 complexes with this lig-
and in several coordination modes. Thus, the reac-
tion of (SePPh2)CH2 with [Au(C6F5)3(tht)] leads to
the complex [Au(C6F5)3(SePPh2CH2PPh2Se)] (1) (see
Scheme 1), in which the ligand is monodentate, with
coordination through one Se atom. The IR spectrum
1
dinate to the metal center. The 31P{ H} NMR spec-
trum shows only one singlet for the equivalent phos-
phorus atoms coupled to the selenium nuclei (J(PSe) =
615 Hz). In the 1H spectrum multiplets for the methy-
lene and the phenyl protons appear. In the mass spec-
trum (LSIMS+) the peak at m/z = 615 (100%) appears,
which corresponds to the fragment [Ag{(SePPh2)2-
CH2}]+.
The reactions of (SePPh2)CH2 with Ag(OTf) or
of 1 shows the absorptions of the pentafluorophenyl [Cu(NCMe)4]PF6 in a 2 : 1 molar ratio give the com-
groups bonded to a gold(III) center at 1505 (s), 996 (s), plexes [M{(SePPh2)2CH2}2]X [M = Ag, X = OTf
805 (s) and 795 (s) cm−1 and the vibration ν(P=Se) (3); M = Cu, X = PF6 (4)], in which the geometry
1
at 565 cm−1. The H NMR spectrum shows the pro- at the metal centers is probably tetrahedral. The IR
tons of the methylene group as a pseudo triplet, which spectra of these complexes show the absorptions of
indicates that the coupling with the phosphorus atoms counterions OTf− or PF6 (846 cm−1). The 31P{ H}
−
1
is different, and multiplets for the phenyl protons. NMR spectra in each case show one singlet for the
1
The 31P{ H} NMR spectrum shows an AB system, phosphorus atoms, also with coupling to the sele-
which proves that the coordination of the ligand takes nium atoms. In the 1H NMR spectra the methy-
places through only one of the selenium atoms. In lene protons appear as triplets by coupling to both
the 19F NMR spectrum six resonances appear for phosphorus atoms. In the mass spectra the molec-
the Au(C6F5)3 unit, which corresponds to two types ular cation at m/z = 1193 (10 %) is observed for
of pentafluorophenyl moieties (ratio 2 : 1); each type complex 3, whereas for compound 4 only the frag-
presents two multiplets for the meta and ortho fluorine ment [Cu{(SePPh2)CH2}]+ at m/z = 606 (55%) is de-
and a triplet for the para fluorine atoms.
tected.
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S. Canales et al. · Group 11 Complexes with Bidentate and Tridentate Selenium Ligands
409
˚
Se
Table 1. Selected bond lengths (A) and angles (deg) for com-
Se
PPh2
C6F5
C6F5
plex 6.
i)
CH2
Au
PPh2
Au(1)–C(51)
Au(1)–C(61)
Au(1)–C(1)
Au(1)–Se(1)
Au(1)···P(1)
Au(2)–C(71)
Au(2)–C(91)
2.048(3)
2.054(3)
2.153(3)
Au(2)–C(81)
Au(2)–Se(2)
Se(2)–P(2)
2.077(3)
2.4940(4)
2.1814(8)
2.1716(10)
1.808(3)
1.813(3)
Se
PPh2
CH
Ph2P
2.4639(4) Se(1)–P(1)
2.9364(9) P(2)–C(1)
Se
2.048(3)
2.061(3)
P(1)–C(1)
ii)
5
C(51)–Au(1)–C(61) 86.76(12) C(71)–Au(2)–Se(2) 175.43(9)
C(51)–Au(1)–C(1) 97.57(12) C(91)–Au(2)–Se(2) 93.81(8)
C(61)–Au(1)–C(1) 175.28(12) C(81)–Au(2)–Se(2) 87.54(9)
C(51)–Au(1)–Se(1) 174.77(10) P(2)–Se(2)–Au(2) 107.53(3)
Se
C6F5
C6F5
Au
PPh2
C(61)–Au(1)–Se(1) 93.83(8)
C(1)–Au(1)–Se(1) 81.69(8)
P(1)–Se(1)–Au(1) 78.33(3)
P(2)–C(1)–P(1)
120.86(18)
117.93(16)
95.16(14)
CH
P
C6F5
Au
C(71)–Au(2)–C(91) 90.76(12) P(2)–C(1)–Au(1)
C(71)–Au(2)–C(81) 87.93(12) P(1)–C(1)–Au(1)
C(91)–Au(2)–C(81) 173.75(12)
Ph2
Se
C6F5
C6F5
6
Scheme 2. i) [Au(C6F5)2(acac)]; ii) [Au(C6F5)3(tht)].
In order to obtain complexes with the ligand
coordinated additionally through the carbon atom,
we have carried out the reaction of the ligand
with [Au(C6F5)2(acac)], in which the acetylaceto-
nate ligand deprotonates the methylene group, form-
ing acetylacetone and the methanide compound
[Au(C6F5)2(SePPh2CHPPh2Se)] (5) (see Scheme 2).
Compound 5 is a yellow air- and moisture-stable solid.
The IR spectrum shows the absorptions arising from
pentafluorophenyl rings in a cis disposition and the vi-
1
bration ν(P=Se). The 31P{ H} NMR spectrum shows
Fig. 1. Molecular structure of complex 6 in the crystal show-
ing the atom labelling scheme (atoms with arbitrary radii;
hydrogen atoms omitted for clarity with the exception of the
methanide C–H).
the presence of two inequivalent phosphorus atoms at
56.1 and 33.5 ppm, suggesting that one of the sele-
nium atoms is coordinated to the gold(III) center. In
1
the H NMR spectrum the methanide proton appears
atoms, the methanide proton appears as a doublet of
doublets, and all the pentafluorophenyl rings are in-
as a pseudo triplet. In the 19F NMR spectrum, not only
the two pentafluorophenyl rings but in fact all the flu- equivalent, including the mutually trans rings of the
orine atoms are inequivalent, probably owing to hin- Au(C6F5)3 unit, probably because of hindered rotation
dered rotation of the pentafluorophenyl moieties. In
the mass spectrum (LSIMS+) the molecular ion [M]+
with m/z = 1075 (20 %) and the fragment [M–C6F5]+
(30%) appear.
about the Au–Se bond.
The crystal structure of complex 6 has been es-
tablished by X-ray diffraction and the molecule is
shown in Fig. 1. A selection of bond lengths and
Although the structure of compound 5 has not been angles are collected in Table 1. The two gold(III)
confirmed by X-ray diffraction, the NMR data indicate centers are coordinated to the ligand in a different
a coordination of one selenium and the methanide car- manner, one being chelated (Se,C for Au1) and the
bon atoms to the gold(III) center. This coordination other monodentate (Se at Au2). Both gold centers are
is confirmed by reaction of 5 with [Au(C6F5)3(tht)], in a square planar geometry (r.m.s. deviations of gold
˚
whereby the coordination of this gold fragment to and four donor atoms 0.04, 0.06 A); the (C6F5)3Au–
the uncoordinated selenium atom gives the com- Se unit is more regular with angles ranging from
plex [Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}] (6). 87.54(9)– 93.81(8)◦ but the other has a narrow bite
The NMR data indicate two inequivalent phosphorus angle of the chelating ligand, 81.69(8)◦. The distances
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410
S. Canales et al. · Group 11 Complexes with Bidentate and Tridentate Selenium Ligands
˚
Au1–Se1 2.4639(4) and Au2–Se2 2.4940(4) A are alyzer. Mass spectra were recorded on a VG Autospec,
with the liquid secondary-ion mass spectrometry (LSIMS)
technique, using nitrobenzyl alcohol as matrix. NMR spec-
tra were recorded on a Varian Unity 300 spectrometer
or a Bruker ARX 300 spectrometer in CD2Cl2. Chemi-
cal shifts are cited relative to SiMe4 (1H, external), 85 %
significantly different, more so than those found in
the only other structurally characterized complex
with Au(III)–Se–P bonds, [Au(C6F5)2{(SePPh2)2N}]
˚
(2.4808(3) and 2.4832(3) A) [10]. The Au–C bond
lengths to the pentafluorophenyl units are very similar
H3PO4 ( (
31P, external), or CFCl3 19F, external). The start-
˚
and lie in the range 2.048(3)– 2.077(3) A; the longest
ing materials (SePPh2)2CH2 [25], [Au(C6F5)3(tht)] [26],
[Cu(NCMe)4]PF6 [27] and [Au(C6F5)2(acac)] [28] were
prepared by published procedures.
are found for the mutually trans pentafluorophen-
yl units and the shortest trans to selenium. The
˚
Au1–C1 distance of 2.153(3) A is longer than the
bonds to the pentafluorophenyl rings, but similar
to those found in methanide complexes such as
[Au(C6F5)3{SPPh2CH(AuC6F5)PPh2CHCOOMe}]
Preparations
Bis(diphenylselenophosphoryl)methane-tris(pentafluoro-
phenyl)gold(III) (1)
˚
(2.119(21) A) [24]. The folding angle of the four-
membered ring about the Se···C axis is 27.1(2)◦ and
To a solution of (SePPh2)2CH2 (0.054 g, 0.1 mmol)
in dichloromethane (20 mL) was added [Au(C6F5)3(tht)]
(0.078 g, 0.1 mmol) and the mixture was stirred for 30 min.
Evaporation of the solvent to a volume of ca. 5 mL and addi-
tion of hexane gave complex 1 as a white solid. Yield: 0.078 g
(65 %). – ΛM = 3.5 Ω−1 cm2 mol−1. – C43H22AuF15P2Se2
(1240.445): calcd. C 41.63, H 1.78; found C 41.74, H 1.78. –
1H NMR: δ = 4.63 (t, 2H, 2J(PH) = 13 Hz, CH2), 7.17 –
˚
the Au···P distance across the ring is 2.9364(9) A.
The Au–C–P–Se–Au backbone displays an extended
conformation, with torsion angles 177.7(1)◦ and
−169.4(1)◦ about C1—P2 and P2—Se2, respectively.
The rings at C51, C31 and C91 thereby attain an
intramolecular stacking geometry, with interplanar an-
gles C5x/C3x 3◦, C9x/C3x 6◦, intercentroid distances
8.02 (m, 20H, Ph). – 31P{ H} NMR: δ = 24.5 (AB system,
1
˚
˚
C5x/C3x 3.51 A, C9x/C3x 3.48 A, and ring offsets
PA), 28.8 (AB system, PB, J(AB) = 17 Hz). – 19F NMR:
2
˚
˚
C5x/C3x 0.8 A, C9x/C3x 0.9 A.
δ = −120.2 (m, 4F, o-F), −123.0 (m, 2F, o-F), −157.0 (t,
J(FF) = 19 Hz, 1F, p-F), −157.4 (t, J(FF) = 19 Hz, 2F, p-F),
−161.0 (m, 4F, m-F), −161.5 (m, 2F, m-F).
Conclusions
In this work, the hitherto poorly explored coordina-
tion chemistry of the ligand bis(diphenylselenophos-
phoryl)methanetowards group 11 metal complexes has
been investigated. The first examples of complexes
with silver(I) and gold(III) are described. Further-
more several complexes of group 11 metals have been
synthesized with the ligand in various coordination
modes, monodentate to gold(III) through the selenium
atom in [Au(C6F5)3(SePPh2CH2PPh2Se)], bidentate
Se,Se bridging or chelating in the silver(I) or copper(I)
derivatives, and the unprecedented coordination modes
bidentately chelating Se,C or tridentate Se,C,Se in the
gold(III) derivatives [Au(C6F5)2(SePPh2CHPPh2Se)]
and [Au(C6F5)2{SePPh2CHPPh2SeAu(C6F5)3}].
Bis[bis(diphenylselenophosphoryl)methane-silver(I)
(trifluoromethanesulfonate)] (2)
To a solution of (SePPh2)2CH2 (0.054 g, 0.1 mmol) in
dichloromethane (20 mL) was added Ag(OTf) (0.026 g,
0.1 mmol) and the mixture was stirred for 1 h. Evap-
oration of the solvent to a volume of ca. 5 mL and
addition of diethyl ether gave complex 2 as a white
solid. Yield: 0.099 g (63 %). – ΛM = 138 Ω−1 cm2
mol−1
. – C52H44Ag2F6O6P4S2Se4 (1598.496): calcd.
C 39.07, H 2.77, S 4.01; found C 38.69, H 2.50, S 4.02. –
1H NMR: δ = 4.83 (m, 4H, CH2), 7.25 – 7.63 (m, 40H, Ph). –
1
31P{ H} NMR: δ = 24.7 (s, J(PSe) = 615 Hz, 4P).
Bis[bis(diphenylselenophosphoryl)methane]silver(I)
trifluoromethanesulfonate (3)
Experimental Section
General procedure
To a solution of (SePPh2)2CH2 (0.054 g, 0.1 mmol) in
dichloromethane (20 mL) was added Ag(OTf) (0.013 g,
Infrared spectra were recorded in the range 4000 – 0.05 mmol) and the mixture was stirred for 1 h. Evapo-
200 cm−1 on a Perkin-Elmer 883 spectrophotometer us- ration of the solvent to leave a volume of ca. 5 mL and
ing Nujol mulls between polyethylene sheets. Conductiv- addition of diethyl ether gave complex 3 as a white solid.
ities were measured in ca. 5 × 10−4 M solutions with Yield: 0.099 g (72 %). – ΛM = 110 Ω−1 cm2 mol−1. –
a Philips 9509 conductimeter. C, H, N and S analy- C51H44AgF3O3P4SSe4 (1341.557): calcd. C 45.66, H 3.30,
ses were carried out with a Perkin-Elmer 2400 microan- S 2.39; found C 45.39, H 3.05, S 2.14. – 1H NMR: δ = 4.56
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S. Canales et al. · Group 11 Complexes with Bidentate and Tridentate Selenium Ligands
411
2
(t, J(PH) = 13 Hz, 4H, CH2), 7.26 – 7.77 (m, 40H, Ph). – mol−1. – C55H21Au2F25P2Se2 (1770.515): calcd. C 37.31,
1
31P{ H} NMR: δ = 26.2 (s, J(PSe) = 615 Hz, 4P).
H 1.19; found C 37.43, H 1.41. – 1H NMR: δ = 3.60 (dd,
2J(PH) = 15 and 10 Hz, 1H, CH), 7.0 – 8.1 (m, 20H, Ph). –
1
31P{ H} NMR: δ = 34.1 (d, 2J(PP) = 13 Hz, J(PSe) =
Bis[bis(diphenylselenophosphoryl)methane]copper(I)
hexafluorophosphate (4)
566 Hz, 1P, PPh2Se), 34.1 (d, 2J(PP) = 13 Hz, J(PSe) =
428 Hz, 1P, PPh2Se). – 19F NMR: δ = −119.4 (m, 2F, o-F),
−120.2 (m, 2F o-F), −120.7 (m, 1F, o-F), −121.4 (m, 2F,
o-F), −122.8 (m, 2F, o-F), −123.4 (m, 1F, o-F), −124.4
(m, 1F, o-F), −156.4 (t, J(FF) = 19 Hz, 2F, p-F), −156.7 (t,
J(FF) = 20 Hz, 1F, p-F), −157.8 (t, J(FF) = 19 Hz, 1F, p-F),
−157.9 (t, J(FF) = 23 Hz, 3F, p-F), −159.8 (m, 1F, m-F),
−161.0 (m, 4F, m-F), −161.5 (m, 1F, m-F), −161.8 (m, 4F,
m-F).
To a solution of (SePPh2)2CH2 (0.054 g, 0.1 mmol)
in tetrahydrofuran (20 mL) was added [Cu(NCMe)4]PF6
(0.018 g, 0.05 mmol) and the mixture was stirred for 1 h.
Evaporation of the solvent to leave a volume of ca. 5 mL
and addition of diethyl ether gave complex 4 as a white
solid. Yield: 0.097 g (75 %). – ΛM = 92 Ω−1 cm2 mol−1. –
C50H44CuF6P5Se4 (1293.129): calcd. C 46.44, H 3.43;
found C 46.15, H 3.40. – 1H NMR: δ = 4.15 (t, 2J(PH) =
13 Hz, 4H, CH2), 7.28 – 7.78 (m, 40H, Ph). – 31P{ H} NMR:
1
X-Ray structure determination
δ = 21.8 (s, J(PSe) = 673 Hz, 4P).
A suitable single crystal of 6 (0.40 × 0.20 × 0.14 mm3)
was mounted in inert oil on a glass fibre. Data were
[Bis(diphenylselenophosphoryl)methanido]bis(pentafluoro-
phenyl)gold(III) (5)
˚
measured using MoKα radiation (λ = 0.71073 A) on a
Bruker SMART 1000 CCD diffractometer. Crystal data:
To a solution of (SePPh2)2CH2 (0.054 g, 0.1 mmol) C55H21Au2F25P2Se2, M = 1770.51, monoclinic, space
in dichloromethane (20 mL) was added [Au(C6F5)2(acac)] group P21/n, a = 16.5513(16), b = 18.7736(18), c =
3
(0.063 g, 0.1 mmol) and the mixture was stirred for 1 h. 17.9090(18) A, β = 100.160(3)◦, V = 5477.6(9) A ,
Evaporation of the solvent to leave a volume of ca. 5 mL Z = 4, T = −130 ◦C, Dc = 2.147 Mg m−3, µ =
and addition of hexane gave complex 5 as a white solid. 6.862 mm−1, F(000) = 3328, 117460 reflections mea-
˚
˚
Yield: 0.078 g (60 %). – ΛM = 2.1 Ω−1 cm2 mol−1. – sured (2θmax 60.08◦, ω scans), 16036 unique (Rint
=
C37H21AuF10P2Se2 (1072.380): calcd. C 41.44, H 1.97; 0.0570), absorption corrections based on multiple scans
found C 41.63, H 2.16. – 1H NMR: δ = 3.77 (“t”, 2J(PH) = (SADABS [29]). The structure was solved by heavy-atom
11.3 Hz, 1H, CH), 7.0 – 8.3 (m, 20H, Ph). – 31P{ H} methods, and subjected to full-matrix least-squares refine-
1
NMR: δ = 35.1 (s, 1P, PPh2Se), 56.1 (s, 1P, AuSePPh2). – ment on F2 (SHELXL-97 [30]). All non-hydrogen atoms
19F NMR: δ = −120.5 (m, 1F, o-F), −123.5 (m, 1F o-F), were refined anisotropically. H atoms were included using
−124.4 (m, 1F, o-F), −125.3 (m, 1F, o-F), −158.6 (t, J(FF) = a riding model, except for the methanide hydrogen at C1,
19 Hz, 1F, p-F), −159.1 (t, J(FF) = 19 Hz, 1F, p-F), −161.9 which was refined freely. Refinement proceeded to wR(F2)
(m, 2F, m-F), −161.7 (m, 2F, m-F).
0.0557, conventional R(F) 0.0260 for 779 parameters and
132 restraints (to local−r3ing symmetry), S(F2) = 0.951, max-
CCDC 629514 contains the supplementary crystallo-
graphic 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.
˚
imum ∆ρ = 1.557 e A
.
{[Se-Tris(pentafluorophenyl)gold(III)]-C,N-bis(diphenyl-
selenophosphoryl)methanido-bis(pentafluorophenyl)-
gold(III)}(6)
To
a
solution of [Au(C6F5)2(SePPh2CHPPh2Se)]
(0.107 g, 0.1 mmol) in dichloromethane (20 mL) was added
[Au(C6F5)3(tht)] (0.078 g, 0.1 mmol) and the mixture was
stirred for 1 h. Evaporation of the solvent to leave a volume
of ca. 5 mL and addition of hexane gave complex 6 as a
Acknowledgement
We thank the Direccio´n General de Investigacio´n
Cient´ıfica y Te´cnica (BQU2004-05495-C02-01) for financial
white solid. Yield: 0.120 g (68 %). – ΛM = 3.2 Ω−1 cm2 support.
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