Synthesis and structures of gold(I) phosphine complexes containing monoanionic selenocarbamate ester ligands

Article abstract of DOI:10.1016/j.jorganchem.2009.03.032

A series of mono- and dinuclear gold(I) phosphine complexes of the type [Au{SeC(OMe){double bond, long}NPh}(P)] [P = PPh₃, PTA, P(o-tolyl)₃, P(p-MeOC₆H₄)₃] and [Au₂{SeC(OMe){double bond, lo

Full text of DOI:10.1016/j.jorganchem.2009.03.032

Journal of Organometallic Chemistry 694 (2009) 2380–2385
Contents lists available at ScienceDirect
Journal of Organometallic Chemistry
journal homepage: www.elsevier.com/locate/jorganchem
Synthesis and structures of gold(I) phosphine complexes containing monoanionic
selenocarbamate ester ligands
Daniel Gallenkamp a, Timo Porsch a, Anja Molter a, Edward R.T. Tiekink b, Fabian Mohr a,
*
a Fachbereich C – Anorganische Chemie, Bergische Universität Wuppertal, 42119 Wuppertal, Germany
b Department of Chemistry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, TX, USA
a r t i c l e i n f o
a b s t r a c t
Article history:
A series of mono- and dinuclear gold(I) phosphine complexes of the type [Au{SeC(OMe)@NPh}(P)]
[P = PPh3, PTA, P(o-tolyl)3, P(p-MeOC6H4)3] and [Au2{SeC(OMe)@NPh}2(l-PP)] (PP = dppm, dppe, dppp,
Received 18 February 2009
Accepted 17 March 2009
Available online 27 March 2009
dppf, dppee) were prepared from the reaction of the appropriate chlorogold(I) phosphine complexes with
N-phenyl-O-methylselenocarbamide in the presence of base. These new complexes were fully character-
ised by spectroscopic techniques and, in several cases, by X-ray crystallography. The differences in the
solid-state structures of these selenium complexes were compared with those of some sulfur analogues.
Ó 2009 Elsevier B.V. All rights reserved.
Keywords:
Gold
Selenium
Binuclear complex
X-ray structure
Aurophilicity
1. Introduction
selenocarbamate ligands are known. Given that gold(I) phosphine
complexes containing ArNHC(S)OMe (Ar = Ph, 4-NO2C6H4) form a
The chemistry of gold(I) phosphine complexes with sulfur li-
gands is today a well-established field. A vast number of such com-
pounds have been prepared and some interesting applications
have emerged from their supramolecular structures, luminescence
properties and their biological activity [1]. Particularly in medicinal
applications, gold thiolate complexes have shown much promise;
in fact the gold(I) compounds Auranofin, Myocrisin and Solgonal
(Fig. 1) have been in clinical use against rheumatoid arthritis for
more than 30 years [2].
variety of supramolecular structures and are also strongly lumines-
cent [16–19], we were interested in exploring the so far unknown
chemistry of their selenium counterparts, in particular focusing on
N-phenyl-O-methylselenocarbamate. The results of this investiga-
tion are presented herein [20].
2. Results and discussion
N-phenyl-O-methylselenocarbamide is accessible in good yield
by treatment of PhNCSe with MeOH as reported by Barton in
1994 [21]. The X-ray crystal structure of the compound was re-
cently reported by us [22]. The reaction of N-phenyl-O-methylsel-
enocarbamide with appropriate amounts of either mononuclear or
binuclear chlorogold(I) phosphine complexes in the presence of
base affords the colourless or pale-yellow gold(I) complexes
[Au{SeC(OMe)@NPh}(P)] [P = PPh3 (1), PTA (2), P(o-tolyl)3 (3),
In marked contrast, the chemistry of gold(I) complexes contain-
ing organic selenium ligands is a relatively unexplored field. The
comparatively small number of known gold–selenium compounds
are generally derived from selenium derivatives which are either
commercially available or easily accessible including NCSeꢀ,
H2NC(Se)NH2,
PhSeꢀ,
Ph3PSe,
[Ph2P(Se)NP(Se)Ph2]ꢀ
and
Ph2P(Se)CH2P(Se)PPh2 [3–12]. More recently, some highly lumi-
nescent clusters containing the Au3Se core have also been reported
[13,14]. Selenocarbamate esters, specifically N-phenyl-O-alkylsele-
nocarbamides, have been known for more than 35 years but have
so far been completely neglected as ligands in coordination
chemistry [15]. There exists only one report of a metal complex
containing N-phenyl-O-methylselenocarbamide acting as a neutral
Se-donor ligand to a cobalt(II) centre [15]. However, to date no
complexes containing deprotonated, monoanionic N-aryl-O-akyl-
P(p-MeOC6H4)3 (4)] and [Au2{SeC(OMe)@NPh}2(l-PP)] (PP = dppm
(5), dppe (6), dppp (7), dppee (8), dppf (9)], respectively (Scheme
1).
The new gold complexes were fully characterised by various
spectroscopic methods, including 1H and 31P NMR spectroscopy,
IR spectroscopy and mass spectrometry. The combination of the
relatively poor solubility and stability of the compounds in solu-
tion combined with the low sensitivity of the 77Se nucleus (7.63%
natural abundance) did not allow us to obtain any 77Se NMR spec-
tra. The chemical shifts of the singlet resonances in the 31P NMR
spectra of complexes 1–9 are in the range typically observed for
* Corresponding author.
E-mail address: fmohr@uni-wuppertal.de (F. Mohr).
0022-328X/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2009.03.032

D. Gallenkamp et al. / Journal of Organometallic Chemistry 694 (2009) 2380–2385
2381
N-phenyl-O-methylselenocarbamate. Whilst we were unable to
obtain X-ray quality crystals of the mononuclear derivatives 1–5,
we were able to determine the solid-state structures of the binu-
clear complexes 6, 7 and 9. The molecular structures of these com-
pounds are shown in Figs. 2–4 and selected geometric parameters
are collected in Table 1.
The two independent gold atoms in 6 each exist in a distorted
linear geometry defined by the selenium and phosphorus atoms.
Key differences in geometric parameters describing the N-phe-
nyl-O-methylselenocarbamate ligand compared with the neutral
N-phenyl-O-methylselenocarbamide molecule are evident. Most
noteworthy is the elongation of the C–Se bond to 1.921(14) and
1.902(15) Å in the anion compared with 1.8322(19) Å in the
neutral molecule [22]. This difference is associated with con-
comitant shortening of the C1–N1 and C35–N2 bond distances to
1.289(17) and 1.277(18) Å, respectively, compared with
1.328(2) Å [22], consistent with significant double bond character
in the C1–N1 and C35–N2 bonds. In terms of angles, the Se–C–N
Fig. 1. Gold thiolate complexes used in medicine.
phosphine gold(I) complexes. Deprotonation of the N-phenyl-O-
methylselenocarbamide is confirmed in both the 1H and IR spectra
by the absence of signals due to the NH group. In addition, the C–N
stretching frequencies in the IR spectra of complexes 1–9 are
shifted to higher wavenumbers (by ca. 100 cmꢀ1) compared to that
of the (protonated) free ligand, consistent with an increase in the
C–N bond order. These selenium complexes thus represent the
very first examples of metal complexes containing deprotonated
Scheme 1.
Fig. 2. Molecular structure of complex 6. Displacement ellipsoids are shown at the 50% probability level. Hydrogen atoms and the solvent CH2Cl2 molecule have been omitted
for reasons of clarity.

2382
D. Gallenkamp et al. / Journal of Organometallic Chemistry 694 (2009) 2380–2385
Fig. 3. Molecular structure of complex 7. Displacement ellipsoids are shown at the 50% probability level. Hydrogen atoms have been omitted for reasons of clarity.
Fig. 4. Molecular structure of complex 9. Displacement ellipsoids are shown at the 50% probability level. The Fe atom is located on a crystallographic centre of inversion;
unlabelled atoms are related by the symmetry operation 1 ꢀ x, 1 ꢀ y, ꢀz. Hydrogen atoms and the solvent CH2Cl2 molecule have been omitted for clarity.
Table 1
Selected bond distances (Å) and angles (°) for complexes 6, 7 and 9.
6
7
9a
Au1–P1, Au2–P2
2.267(3), 2.261(3)
2.262(3), 2.265(3)
2.270(2)
Au1–Se1, Au2–Se2
C–Se1, C–Se2
C–N1, C–N2
Se1–Au1–P1, Se2–Au2–P2
Au1–Se1–C, Au2–Se2–C
2.4172(13), 2.4162(13)
1.921(14), 1.902(15)
1.289(17), 1.277(18)
172.05(8), 172.86(8)
104.5(4), 103.6(5)
2.4072(12), 2.3991(14)
1.924(10), 1.895(13)
1.273(14), 1.259(16)
177.57(8), 168.21(8)
98.6(3), 109.3(3)
2.4048(12)
1.935(10)
1.239(13)
176.36(6)
98.8(3)
a
Molecule is disposed about a crystallographic centre of inversion.
angles open up by over 10° to 132.9(10) and 134.1(11)° compared
with 122.07(14)° in the neutral molecule and the remaining angles
about the quaternary carbon atom each contracting about 5° [22].
Similar observations were made when comparing geometric
parameters of the related thiocarbamate phosphine gold(I) com-
plexes [16–19] and their neutral precursors [23–25] whereupon
it was concluded that the anion was functioning as a thiolate li-
gand. Similar trends are found in the molecular structures of each

D. Gallenkamp et al. / Journal of Organometallic Chemistry 694 (2009) 2380–2385
2383
of 7 and 9; the latter molecule is centrosymmetric with the iron
atom located on a crystallographic centre of inversion.
Bruker MicroTOF spectrometer in positive ion mode. IR spectra
were run as KBr pellets on a Bruker Tensor 27 instrument. Elemen-
tal analyses were performed by staff of the microanalytical labora-
tory of the University of Wuppertal. Although the products were
air-stable, all reactions were routinely carried out under dried dini-
trogen. N-Phenyl-O-methylselenocarbamate was prepared as de-
scribed previously [21,22]. The chlorogold(I) phosphine
complexes were prepared by the reaction of [AuCl(tht)] [28]
(tht = tetrahydrothiophene) with appropriate amounts of the phos-
phines. All other chemicals and solvents (anhydrous grade) were
sourced commercially and used as received.
An interesting observation in the structures is the relative ori-
entations of the selenocarbamate anions. In 6, the anions are orien-
tated so as to place the aromatic ring in close proximity of the gold
centre. The Au1, 2ꢁ ꢁ ꢁCg separations are 3.304(3) and 3.289(4) Å,
respectively where Cg is the ring centroid of the C2–C7 and C36–
C41 aromatic rings, respectively. In 7, the Au1 atom forms a more
conventional intramolecular Auꢁ ꢁ ꢁO interaction of 3.091(7) Å
whereby a Auꢁ ꢁ ꢁ
p interaction persists for the Au2 atom, with
Au2ꢁ ꢁ ꢁCg(C25–C30) = 3.646(5) Å. In centrosymmetric 9, a Auꢁ ꢁ ꢁO1
interaction of 3.146(9) Å is noted. The appearance of both orienta-
tions of the selenocarbamate anion in 7 suggests that each confor-
mation is of comparable energy. A recent systematic study of
related phosphinegold thiocarbamate structures demonstrated
3.2. Preparation of the gold(I) complexes
To a solution of PhNHC(Se)OMe (0.1 mmol) in 5 mL MeOH was
added NaOMe (0.007 g, 0.13 mmol) followed by appropriate quan-
tities of the chlorogold(I) phosphine complexes (1 equiv. of the
mononuclear and 0.5 equiv. of the dinuclear compounds, respec-
tively). The mixture was allowed to stir at room temperature for
ca. 18 h. After this time the mixture was evaporated to dryness
and the resulting solid residue was extracted into CH2Cl2
(2 ꢂ 5 mL) and passed through Celite. Addition of Et2O precipitated
the products, which were isolated by filtration, washed with Et2O
and dried. Using this procedure the following complexes were
prepared.
electronic and steric control of intramolecular Auꢁ ꢁ ꢁ
p interactions
contacts as a supramolecu-
[19]; a review of intermolecular Auꢁꢁꢁ
p
lar synthon has also appeared recently [26].
An important difference between the structures of 6, 7, and 9 on
the one hand and the thiolate counterparts on the other is noted.
Thus, whereas aurophilic interactions are absent in 6, 7, and 9,
these are present in each of the thiolate derivatives [17]. This
observation is correlated with the electronegativity differences be-
tween the sulfur and selenium donor atoms. Despite the absence of
aurophilic interactions in 6, 7, and 9, other intermolecular contacts
serve to consolidate the respective crystal structures.
In 6, intermolecular Auꢁ ꢁ ꢁSe and C–Hꢁ ꢁ ꢁSe contacts link mole-
cules into supramolecular chains, as illustrated in Fig. 5a. The
Au1ꢁ ꢁ ꢁSe2i and Au2ꢁ ꢁ ꢁSe1ii separations of 3.7423(15) and
3.7356(17) Å, respectively, are well within the sum of the van
der Waals radii of gold and selenium, being 4.4 Å [27]; symmetry
operations i: x, ꢀ1 + y, z and ii: x, 1 + y, z. The AuꢁꢁꢁSe interactions
are supported by C–Hꢁ ꢁ ꢁSe contacts [C22–Hꢁ ꢁ ꢁSe2i = 2.89 Å,
C22ꢁ ꢁ ꢁSe2i = 3.821(6) Å with angle at H22 = 167°; C24–
3.2.1. [Au{SeC(OMe)@NPh}(PPh3)] (1)
0.059 g, 88%, colourless solid. 1H NMR (CD2Cl2): d = 7.49 (m,
15H, Ph3P), 7.04 (t, J = 7.6 Hz, 2H, meta-PhN), 6.74 (m, 3H, ortho/
para-PhN), 3.87 (s, 3H, OCH3). 31P{1H} NMR (CD2Cl2): d = 39.83. IR
(KBr disk): 1625 cmꢀ1
m(C–N). Anal. Calc. for C26H23AuN-
1
OPSe ꢁ 4CH2Cl2 (693.60): C, 45.46; H, 3.42; N, 2.02. Found: C,
45.58; H, 3.48; N, 1.86%.
Hꢁ ꢁ ꢁSe1ii = 2.91 Å,
C24ꢁ ꢁ ꢁSe1ii = 3.842(6) Å
with
angle
at
3.2.2. [Au{SeC(OMe)@NPh}(PTA)] (2)
H24 = 168°]. Globally, the chains pack in the ab-plane with layers
stacked in the c-direction being interspersed by the dichlorometh-
ane molecules of crystallisation. Similar Auꢁ ꢁ ꢁSe interactions are
found in the structure of 7 but involve only the Au1 and Se2i atoms
with a distance of 3.873(2) Å; symmetry operation i: x, ꢀy, ꢀ½ + z.
These contacts are reinforced by C–Hꢁ ꢁ ꢁO [C4–Hꢁ ꢁ ꢁO2ii = 2.47 Å,
C4ꢁ ꢁ ꢁO2ii = 3.373(16) Å with angle at H4 = 160° for ii: x, y, ꢀ1 + z]
and C–Hꢁ ꢁ ꢁSe [C33–Hꢁ ꢁ ꢁSe2i = 2.85 Å, C33ꢁ ꢁ ꢁSe2i = 3.632(11) Å with
angle at H33 = 141°] contacts to form a supramolecular chain along
the c-direction. The most prominent intermolecular interactions
operating in the crystal structure of 9 are of the type C–Hꢁ ꢁ ꢁSe
and involve the complex and solvent dichloromethane molecules
of crystallisation. The weak nature of these interactions accounts
for the disorder observed for the dichloromethane molecules, see
Experimental, whereby these are disposed about a centre of inver-
sion and occupy two positions of equal weight. Nevertheless, a rec-
ognisable supramolecular aggregation pattern, namely a chain, is
evident, Fig. 5c. The parameters defining this interaction are
C26–Hꢁ ꢁ ꢁSe1 = 2.97 Å, C26–Hꢁ ꢁ ꢁSe1 = 3.75(4) Å with an angle at
H26a = 137°. Globally, the chains superimpose upon each other
so that in a sense channels along the a-direction are formed in
which reside the dichloromethane molecules.
0.040 g, 70%, colourless solid. 1H NMR (CD2Cl2): d = 7.38 (t,
J = 7.6 Hz, 2H, meta-PhN), 7.04 (t, J = 7.6 Hz, 1H, para-PhN), 6.71
(d, J = 7.6 Hz, 2H, ortho-PhN), 4.35 (AB quart., J = 13.2 Hz, 6H,
NCH2N), 4.10 (s, 6H, PCH2N), 3.83 (s, 3H, OCH3). 31P{1H} NMR
(CD2Cl2): d = ꢀ48.05. IR (KBr disk): 1612 cmꢀ1
m(C–N). Anal. Calc.
for C14H20AuN4OPSe ꢁ 2CH2Cl2 (737.09): C, 26.07; H, 3.28; N, 7.60.
Found: C, 25.79; H, 3.16; N, 7.97%.
3.2.3. [Au{SeC(OMe)@NPh}{P(o-tolyl)3}] (3)
0.048 g, 67%, colourless solid. 1H NMR (CD2Cl2): d = 7.48 (t,
J = 7.6 Hz, 3H, H4 o-tol3P), 7.38 (t, J = 7.1 Hz, 3H, H3 o-tol3P), 7.21
(t, J = 7.6 Hz, 3H, H5 o-tol3P), 7.13 (t, J = 7.6 Hz, 2H, meta-PhN),
6.99 (dd, J = 7.6 Hz, 3H, H6 o-tol3P), 6.88 (t, J = 7.1 Hz, 1H, para-
PhN), 6.77 (d, J = 7.6 Hz, 2H, ortho-PhN), 3.79 (s, 3H, OCH3,), 2.64
(s, 9H, o-tol3P). 31P{1H} NMR (CD2Cl2): d = 21.25. IR (KBr disk):
1628 cmꢀ1
m(C–N). Anal. Calc. for C29H29AuNOPSe (714.45): C,
48.75; H, 4.09; N, 1.96. Found: C, 48.61; H, 4.02; N, 1.96%.
3.2.4. [Au{SeC(OMe)@NPh}{P(p-MeOC6H4)3}] (4)
0.034 g, 44%, colourless solid. 1H NMR (CD2Cl2): d = 7.37 (d,
J = 8.1 Hz, 6H, P{p-MeOC6H4}3), 7.06 (t, J = 7.6 Hz, 2H, meta-PhN),
6.94 (d, J = 8.1 Hz, 6H, P{p-MeOC6H4}3), 6.83 (d, J = 8.2 Hz, 2H,
ortho-PhN), 6.76 (t, J = 7.6 Hz, 1H, para-PhN), 3.92 (s, 3H, OCH3),
3.83 (s, 9H, P{p-MeOC6H4}3). 31P{1H} NMR (CD2Cl2): d = 36.45. IR
3. Experimental
(KBr disk): 1619 cmꢀ1
m(C–N). Anal. Calc. for C29H29AuNO4P-
1
3.1. General
Se ꢁ 4CH2Cl2 (783.68): C, 44.83; H, 3.79; N, 1.79. Found: C, 45.00;
H, 3.65; N, 1.69%.
1H and 31P{1H} NMR spectra were recorded on a 400 MHz
Bruker ARX spectrometer. Chemical shifts are quoted relative to
external TMS (1H) and 85% H3PO4 (31P); coupling constants are re-
ported in Hertz. Electrospray mass spectra were measured on a
3.2.5. [Au2{SeC(OMe)@NPh}2{l-Ph2PCH2PPh2}] (5)
0.036 g, 51%, pale yellow solid. 1H NMR (CD2Cl2): d = 7.27–7.66
(m, 20H, Ph2P), 7.07 (t, J = 7.6 Hz, 4H, meta-PhN), 6.79 (m, 6H,

2384
D. Gallenkamp et al. / Journal of Organometallic Chemistry 694 (2009) 2380–2385
Fig. 5. Supramolecular chains in the crystal structures of 6, 7 and 9. (a) Complex 6: mediated by AuꢁꢁꢁSe (orange dashed lines) and C–Hꢁ ꢁ ꢁSe (green dashed lines) contacts; (b)
Complex 7: mediated by Au???Se (orange dashed lines), C–HꢁꢁꢁO (red dashed lines) and C–HꢁꢁꢁSe (green dashed lines) contacts; and (c) 9: mediated by C–Hꢁ ꢁ ꢁSe (green dashed
lines) contacts. Note that the dichloromethane molecules of crystallisation are disordered about a crystallographic centre of inversion and that both orientations for each are
shown in this figure. Hydrogen atoms not participating in intermolecular contacts leading to chains are omitted for clarity. Colour code: gold, orange; selenium, olive; iron,
purple; phosphorus, pink; chloride, cyan; oxygen, red; nitrogen, blue; carbon, grey; and hydrogen, green.
ortho/para-PhN), 3.80 (s, 6H, OCH3), 1.91 (m, 2H, PCH2P). 31P{1H}
NMR (CD2Cl2): d = 31.22. IR (KBr disk): 1617 cmꢀ1
(C–N). Anal.
PCH2CH2CH2P), 1.74 (m, 2H, PCH2CH2CH2P). 31P{1H} NMR (CD2Cl2):
d = 33.31. IR (KBr disk): 1613 cmꢀ1
(C–N). Anal. Calc. for
m
m
Calc. for C42H40Au2N2O2P2Se2 (1204.55): C, 40.88; H, 3.18; N,
2.33. Found: C, 40.97; H, 3.07; N, 2.14%.
C43H42Au2N2O2P2Se2 (1232.61): C, 41.90; H, 3.43; N, 2.27. Found:
C, 42.13; H, 5.76; N, 2.10%. Crystals suitable for X-ray diffraction
were grown by slow diffusion of Et2O into a CH2Cl2 solution of
the complex.
3.2.6. [Au2{SeC(OMe)@NPh}2{l-Ph2P(CH2)2PPh2}] (6)
0.040 g, 65%, colourless solid. 1H NMR (CD2Cl2): d = 7.65–7.44
(m, 20H, Ph2P), 7.04 (t, J = 7.6 Hz, 4H, meta-PhN), 6.74 (m, 6H,
ortho/para-PhN), 3.82 (s, 6H, OCH3), 2.53 (m, 4H, PCH2CH2P).
31P{1H} NMR (CD2Cl2): d = 37.28. IR (KBr disk): 1616 cmꢀ1
3.2.8. cis-[Au2{SeC(OMe)@NPh}2{l-Ph2PHC=CHPPh2}] (8)
0.040 g, 56%, colourless solid. 1H NMR (CD2Cl2): d = 6.74–7.88
(m, 32H, Ph2P, Ph, HC@CH), 3.75 (s, 6H, OCH3). 31P{1H} NMR
m(C–N). Anal. Calc. for C42H40Au2N2O2P2Se2 (1218.58): C, 41.40;
(CD2Cl2): d = 19.80. IR (KBr disk): 1612 cmꢀ1
m(C–N). Anal. Calc.
H, 3.31; N, 2.30. Found: C, 41.21; H, 3.36; N, 2.16%. Crystals suitable
for X-ray diffraction were grown by slow diffusion of Et2O into a
CH2Cl2 solution of the complex.
for C42H38Au2N2O2P2Se2 (1216.56): C, 41.47; H, 3.15; N, 2.30.
Found: C, 41.83; H, 3.05; N, 2.24%.
3.2.9. [Au2{SeC(OMe)@NPh}2{l-Ph2P{(C5H4)2Fe}PPh2}] (9)
3.2.7. [Au2{SeC(OMe)@NPh}2{
l
-Ph2P(CH2)3PPh2}] (7)
0.046 g, 67%, yellow solid. 1H NMR (CD2Cl2): d = 7.67–7.38 (m,
20H, Ph2P), 7.14 (t, J = 7.6 Hz, 4H, meta-PhN), 6.87 (t, J = 7.63 Hz,
2H, para-PhN), 6.75 (d, J = 7.6 Hz, 4H, ortho-PhN), 4.46 (br. s, 8H,
PC5H4), 3.83 (s, 6H, OCH3). 31P{1H} NMR (CD2Cl2): d = 31.90. IR
0.020 g, 32%, colourless solid 1H NMR (CD2Cl2): d = 7.42–7.61
(m, 20H, Ph2P), 7.01 (t, J = 7.6 Hz, 4H, meta-PhN), 6.76–6.71 (m,
6H, ortho, para-PhN), 3.89 (s, 6H, OCH3), 2.63 (m, 4H,

D. Gallenkamp et al. / Journal of Organometallic Chemistry 694 (2009) 2380–2385
2385
Table 2
Crystallographic and refinement details of complexes 6, 7 and 9.
Compound
6
7
9
Formula
C85H82Au4Cl2N4O4P4Se4
2522.05
Orthorhombic
Pca21
17.421(3)
9.8508(15)
26.095(5)
90
C43H42Au2N2O2P2Se2
1232.59
Monoclinic
Cc
11.106(4)
22.558(7)
16.510(6)
90
95.165(11)
90
4119(2)
4
C51H46Au2Cl2FeN2O2P2Se2
1459.44
Formula weight
Crystal system
Space group
a (Å)
b (Å)
c (Å)
Triclinic
ꢀ
P1
8.2671(8)
13.3552(9)
13.6061(10)
61.989(19)
77.22(2)
69.87(2)
1242.0(3)
1
b (°)
90
90
V (Å3)
Z
4478.2(13)
2
T (K)
153
1.870
2396
8.337
98
1.987
2344
8.998
153
1.951
698
7.859
Dc (g cmꢀ3
F(000)
)
l
(Mo K
a
) (mmꢀ1
)
Measured data
49317
21986
14502
h Range (°)
Unique data
2.5–26.5
9059
2.2–26.5
8049
2.6–26.5
4956
Observed data (I P 2
r
(I))
8748
7875
4609
R, observed data; all data
a, b in weighting scheme
Rw, observed data; all data
0.049; 0.051
0.052, 40.534
0.122; 0.123
0.044; 0.046
0.070, 46.207
0.113; 0.119
0.064; 0.070
0.092, 5.544
0.169; 0.178
(KBr disk): 1612 cmꢀ1
N2O2P2Se2 (1374.54): C, 43.69; H, 3.23; N, 2.04. Found: C, 44.23;
H, 3.28; N, 1.99%. Crystals suitable for X-ray diffraction were grown
by slow diffusion of Et2O into a CH2Cl2 solution of the complex.
m
(C–N). Anal. Calc. for C50H44Au2Fe-
www.ccdc.cam.ac.uk/data_request/cif. Supplementary data associ-
ated with this article can be found, in the online version, at
doi:10.1016/j.jorganchem.2009.03.032.
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F.M. gratefully acknowledges generous support from the Fonds
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Appendix A. Supplementary material
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