Synthesis and crystal structures of octahedral metal complexes containing the new dianion [PhP(Se,O)Se-Se(O,Se)PPh]2-

Article abstract of DOI:10.1002/zaac.200600297

The synthesis and structures of three new compounds are reported. [Mg ₂{PhP(Se,O)Se-Se(O,Se)PPh}₂(thf)₇(H ₂O)₃] (1), [Mg{PhP(Se,O)Se-Se(O,Se)PPh}(thf) ₃(H₂O)] (2), and [Mn{PhP(Se

Full text of DOI:10.1002/zaac.200600297

DOI: 10.1002/zaac.200600297
Synthesis and Crystal Structures of Octahedral Metal Complexes containing the
New Dianion [PhP(Se,O)Se-Se(O,Se)PPh]2؊
Weifeng Shia, Le Zhanga, Maryam Shafaei-Fallaha, and Alexander Rothenbergera,b,
*
a
Karlsruhe, Institut für Anorganische Chemie der Universität und b Institut für Nanotechnologie, Forschungszentrum Karlsruhe GmbH
Received November 4th, 2006.
Dedicated to Professor Michael Binnewies on the Occasion of his 60th Birthday
Abstract. The synthesis and structures of three new compounds
are reported. [Mg2{PhP(Se,O)Se-Se(O,Se)PPh}2(thf)7(H2O)3] (1),
treatment of Woollins’ reagent [PhP(Se)(µ-Se)]2 with the correspon-
ding hydrated metal acetates.
[Mg{PhP(Se,O)Se-Se(O,Se)PPh}(thf)3(H2O)]
[Mn{PhP(Se,O)Se-Se(O,Se)PPh}(thf)3(H2O)] (3) were prepared by
(2),
and
Keywords: Magnesium; Manganese; Phosphorus; Selenium;
Crystal structure
Introduction
were reacted with W. R. and herein synthesis and crystal
structures of the first examples of metal complexes contain-
ing the new dianion [PhP(Se,O)Se-Se(O,Se)PPh]2Ϫ are
reported. Out of a number of first-row transition metal and
main group metal carboxylates so far only those of mag-
nesium and manganese have led to products which could
be characterized unequivocally (Scheme 1).
The chemistry of metal complexes containing anionic phos-
phorus/selenium-ligands is currently intensively studied
[1Ϫ6]. In addition to the great structural diversity observed
in this class of compounds, the potential applications of
new phosphorus-containing metal selenides in semicond-
ucting devices is of interest [7].
For the revival of this area which was pioneered by
Kuchen et al. [8], the availability of PϪSe-containing start-
ing materials was a key issue. For the present investigations,
the synthesis of Woollins’ reagent (W. R.) [PhP(Se)(µ-Se)]2
[9, 10] (which is commercially available) and its conversion
to metal complexes containing PϪSe ligands was the start-
ing point for the development of a general route to coordi-
nation oligomers, polymers and clusters based on neutral
P/Se precursors [11, 12]. The present work follows up re-
sults obtained earlier from reactions of neutral P/S and
As/S precursors with metal salts [13Ϫ17] and describes the
first solid-state structures of a new P/Se-anion with divalent
metal ions.
Scheme 1 Synthesis of 1-3.
1 crystallizes in the orthorhombic space group Pca21
with two differently-coordinated Mg atoms in the asym-
metric unit. The constituting magnesium complexes
[Mg{PhP(Se,O)Se-Se(O,Se)PPh}(thf)3(H2O)]
and
[Mg{PhP(Se,O)Se-Se(O,Se)PPh}(thf)4(H2O)2] in 1 exhibit
an octahedral metal coordination environment (Fig. 1).
The new generated ligand [PhP(Se,O)Se-Se(O,Se)PPh]2Ϫ
chelates the magnesium atoms and coordinates in a similar
fashion like the neutral related ligand 1,2-Bis-diphenylphos-
phineoxide [18, 19]. The two isolated units are connected
by a weak hydrogen bond between Se(5) and O(6) (distance
Results and Discussion
The reaction of [PhPSe(µ-Se)]2 (W. R.) with the hydrated
metal carboxylate [NaOAc·3H2O] has recently been re-
ported and it was shown that the presence of water played
a crucial role in the formation of the resulting coordination
polymer 2/ϱ[Na2(PhPSe2O)(H2O)4(thf)]ϱ [11]. As an exten-
sion of this initial report, a number of metal carboxylates
˚
Se5···O6 ca. 3.35 A) [20]. Other hydrogen bonds present in-
clude the strongly bound THF at O(12) and a weak
H-bond between Se(1) and O(6). 2 is very similar to 1. Slightly
modified experimental conditions, however have led to a slight
change in the substitution pattern of the magnesium atom in
[Mg{PhP(Se,O)Se-Se(O,Se)PPh}(thf)3(H2O)] (2) (Fig. 2).
2 crystallizes in the monoclinic space group P21/c with
two crystallographically independent molecules in the
asymmetric unit. Attempts to characterize the new anion
spectroscopically were also made and indicated that 2
slowly decomposes in [D6]DMSO. It was, however, possible
to dissolve 2 by stirring crystals in [D8]THF during 12
hours. In the 31P{1H}NMR a singlet resonance for the
* Dr. A. Rothenberger
Institut für Anorganische Chemie
der Universität Karlsruhe
Engesserstraße 15
76131 Karlsruhe
FAX: 0721-6088440
E-mail: ar252@chemie.uni-karlsruhe.de
440
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Z. Anorg. Allg. Chem. 2007, 633, 440Ϫ442

Octahedral Metal Complexes containing the New Dianion [PhP(Se,O)Se-Se(O,Se)PPh]2Ϫ
Figure 1 Molecular structure of 1 in the solid state [carbon atoms
of THF at O(3, 4, 5, 9, 11, 13, 14) have been omitted for clarity].
˚
Selected bond lengths /A and angles /°:
Figure 2 Molecular structure of one of the two complexes present
Se(1)-P(1) 2.113(2), Se(2)-P(1) 2.261(2), Se(3)-P(2) 2.249(2), Se(4)-P(2)
2.124(2), Se(5)-P(3) 2.131(2), Se(6)-P(3) 2.250(2), Se(7)-P(4) 2.252(2), Se(8)-
P(4) 2.121(2), Se(2)-Se(3) 2.3302(12), Se(6)-Se(7) 2.3360(12), P(1)-O(1)
1.503(5), P(2)-O(2) 1.499(5), P(3)-O(7) 1.493(6), P(4)-O(8) 1.485(6), Mg(1)-
O(1) 2.008(6), Mg(1)-O(2) 1.986(6), Mg(2)-O(8) 2.025(6), Mg(2)-O(7)
2.036(6), Mg-O(3, 4, 5, 9, 11; thf) 2.089(6)-2.151(6), Mg-O(H2O) 2.057(6)-
2.091(6), Se(5)···O(6) ca. 3.35, Se(1)···O(6) ca. 3.43, O(12)···O(13) ca. 2.68,
O(12)···O(14) ca. 2.69, P(1)-Se(2)-Se(3) 99.35(6), P(2)-Se(3)-Se(2) 99.62(6),
P(3)-Se(6)-Se(7) 103.44(6), P(4)-Se(7)-Se(6) 100.38(6), O(1)-P(1)-Se(1)
118.2(2), O(1)-P(1)-Se(2) 110.3(2), Se(1)-P(1)-Se(2) 101.40(8), O(2)-P(2)-
Se(4) 119.3(2), O(2)-P(2)-Se(3) 110.4(2), Se(4)-P(2)-Se(3) 102.20(8), O(7)-
P(3)-Se(5) 120.3(2), O(7)-P(3)-Se(6) 113.0(2), Se(5)-P(3)-Se(6) 98.27(8), O(8)-
P(4)-Se(8) 118.3(2), O(8)-P(4)-Se(7) 111.1(2), Se(8)-P(4)-Se(7) 100.99(9),
O(2)-Mg(1)-O(1) 93.7(2), O(8)-Mg(2)-O(7) 91.5(2).
in the asymetric unit of 2 (disordered components of THF ligands
are omitted). Selected bond lengths /A and angles /°:
˚
Se(1)-P(1) 2.127(4), Se(2)-P(1) 2.247(4), Se(2)-Se(3) 2.329(2), Se(3)-P(2)
2.241(4), Se(4)-P(2) 2.134(4), P(1)-O(1) 1.496(10), P(2)-O(2) 1.519(8), Mg(1)-
O(1) 1.996(11), Mg(1)-O(2) 2.016(9), Mg(1)-O(3, 4, 5; thf) 2.02(2)-2.190(16),
Mg(1)-O(6) 2.090(9), P(1)-Se(2)-Se(3) 98.54(11), P(2)-Se(3)-Se(2) 100.11(11),
O(1)-P(1)-Se(1) 118.6(4), O(1)-P(1)-Se(2) 111.0(4), Se(1)-P(1)-Se(2)
102.48(16), O(2)-P(2)-Se(4) 117.8(4), O(2)-P(2)-Se(3) 111.1(4), Se(4)-P(2)-
Se(3) 99.73(14), O(1)-Mg(1)-O(2) 93.1(4).
[PhP(Se,O)Se-Se(O,Se)PPh]2Ϫ dianion was observed to-
gether with two satellite sets, which can be ascribed to
1JP-Se coupling to chemically inequivalent terminal and ‘in-
ner’ Se atoms [2, 12]. In the 77Se NMR spectra of 1 and 2,
however, one weak resonance at ca. 40 ppm was detected,
whilst at 131 ppm a further resonance could be ascribed
to the different Se environments present. Generally, NMR
investigations are complicated by low solubility of 1 and 2.
The incorporation of paramagnetic metal ions into the
new ligand framework was finally exemplified by treating
W. R. with [Mn(OAc)2(H2O)4] and X-ray analysis of crys-
tals of 3 (Figure 3).
Figure 3 Molecular structure of 3 (connections to adjacent com-
plexes in the 1D polymeric arrangement of complexes are indicated
by dashed bonds; symmetry operation (A) x, yϩ1, z) [carbon atoms
of THF at O(3, 4, 5, 9, 10, 11) have been omitted for clarity]. Se-
3 crystallizes in the monoclinic space group P21/c with
two crystallographically independent, but chemically equiv-
alent [Mn{PhP(Se,O)Se-Se(O,Se)PPh}(thf)3(H2O)] (3) com-
plexes in the asymmetric unit. In the extended solid-state
structure 3 forms a 1D polymeric arrangement held to-
˚
lected bond lengths /A and angles /°:
Mn(1)-O(1) 2.078(6), Mn(1)-O(2) 2.124(6), Mn(2)-O(7) 2.138(6), Mn(2)-O(8)
2.096(6), Mn-O(3, 4, 5, 9, 10, 11; thf) 2.188(6)-2.284(6), Mn(1)-O(6) 2.206(6),
Mn(2)-O(12) 2.186(7), Se(1)-P(1) 2.124(2), Se(2)-P(1) 2.264(2), Se(2)-Se(3)
2.3353(12), Se(3)-P(2) 2.249(2), Se(4)-P(2) 2.118(2), Se(5)-P(3) 2.125(2),
Se(6)-P(3) 2.247(2), Se(6)-Se(7) 2.3306(14), Se(7)-P(4) 2.261(2), Se(8)-P(4)
2.120(2), P(1)-O(1) 1.497(6), P(2)-O(2) 1.517(6), P(3)-O(7) 1.505(6), P(4)-
O(8) 1.502(6), Se(1)···O(12A) ca. 3.36, O(1)-Mn(1)-O(2) 95.9(2), O(8)-Mn(2)-
O(7) 94.6(2), P(1)-Se(2)-Se(3) 98.71(7), P(2)-Se(3)-Se(2) 102.02(6), P(3)-
Se(6)-Se(7) 101.71(7), P(4)-Se(7)-Se(6) 98.46(7), O(1)-P(1)-Se(1) 118.0(3),
O(1)-P(1)-Se(2) 110.2(3), Se(1)-P(1)-Se(2) 102.23(9), O(2)-P(2)-Se(4)
118.6(3), O(2)-P(2)-Se(3) 111.4(3), Se(4)-P(2)-Se(3) 99.55(9), O(7)-P(3)-Se(5)
120.8(3), O(7)-P(3)-Se(6) 113.2(3), Se(5)-P(3)-Se(6) 98.13(9), O(8)-P(4)-Se(8)
119.6(3), O(8)-P(4)-Se(7) 109.2(3), Se(8)-P(4)-Se(7) 101.45(9).
˚
gether by weak hydrogen bonds (Se1···O12A ca. 3.36 A).
The formation of the [PhP(Se,O)Se-Se(O,Se)PPh]2Ϫ in 1-3
represents a new development in P-Se chemistry. The new
ligand can be regarded as the product of an oxidation of
the recently reported [PhP(O)Se2]2Ϫ anion [11]. Future
work will both attempt to clarify the mechanisms, involved
in nucleophilic addition/hydrolysis reactions of neutral
P-chalcogen precursors and use the formation of novel li-
gands for the synthesis of novel coordination polymers.
Z. Anorg. Allg. Chem. 2007, 440Ϫ442
 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
www.zaac.wiley-vch.de
441

W. Shi, L. Zhang, M. Shafaei-Fallah, A. Rothenberger
Experimental Part
Table 1 Details of the X-ray data collection and refinements.
All operations were carried out in an atmosphere of purified dini-
trogen. Solvents were dried over appropriate drying agents and
freshly distilled.
Compound
1
2
3
Formula
C52H82Mg2O14P4Se8 C24H36MgO6P2Se4 C24H36MnO6P2Se4
Formula weight 1735.36
T/K 170(2)
Crystal system orthorhombic
822.62
150(2)
monoclinic
P21/c
15.527(3)
41.777(8)
9.782(2)
91.38(3)
6343(2)
8
853.25
105(2)
monoclinic
P21/c
9.6810(19)
15.539(3)
42.003(8)
95.33(3)
6291(2)
8
1: A mixture of 266 mg (0.5 mmol) Woollins’ reagent and 107 mg
(0.5 mmol) [Mg(OAc)2(H2O)4] was dissolved in 8 mL THF. The
yellow solution was heated to 50 °C for 5 hours and then stirred
12 h at room temperature. The reaction was filtered and the filtrate
layered with 50 mL hexane. Storage of the solution at room tem-
perature for 4 weeks produced yellow crystals. 0.26 g, yield 60 %
(based on [Mg(OAc)2(H2O)4] supplied). mp 130 °C (decompo-
sition); Found: C, 32.79; H, 4.17. C44H66Mg2O12P4Se8 requires C,
33.21; H, 4.18 %.
Space group
Pca21
42.900(9)
15.650(3)
10.115(2)
90
6791(2)
4
4.474
3448
45508
˚
a/A
˚
b/A
˚
c/A
β/°
3
˚
V/A
Z
µ/mmϪ1
F(000)
4.782
3248
19615
5.185
3352
38688
Reflections
collected
Unique data
Rint
Parameters
wR2 (all data) 0.1928
R1 [I>2σ(I)] 0.0661
IR (Nujol, NaCl): ν(H2O) 3321 br, 1608 m, ν(P-C) 1430 s, 1036 m, 880 m,
692 m cmϪ1; 1H NMR (400 MHz, [D6]DMSO, 25 °C) δ ϭ 8.1 (4H, m, ArH),
7.4 (4H, m, ArH), 3.6 (10H, m, OCH2CH2), 3.3 (s, H2O), 1.8 (10H, m,
OCH2CH2); 13C NMR (100 MHz, [D6]DMSO, 25 °C) δ ϭ 130.9, 130.8,
129.8, 126.8, 126.7, 67.0, 25.2; 31P NMR (162 MHz, [D6]DMSO, 25 °C, 65 %
H3PO4) δ ϭ 32.9 (s ϩ 2 d satellites, 1JP-Se ϭ Ϫ396 Hz, Ϫ698 Hz); 77Se NMR
15777
0.0843
739
10383
0.0684
651
0.2967
0.0997
12175
0.0968
673
0.1901
0.0660
1
(76 MHz, [D6]DMSO, 25 °C, Me2Se) δ ϭ 40.5 (d, JP-Se ϭ Ϫ698 Hz).
2: Synthesis of 1 performed at room temperature. 0.25 g, yield
60 %. mp 125-128 °C (decomposition); Found: C, 35.94; H, 4.41.
C24H36MgO6P2Se4 requires C, 35.04; H, 4.41 %.
Acknowledgment. The work was funded by the DFG Center for
Functional Nanostructures (fellowship W. S.) and the Forschungsz-
entrum Karlsruhe. A. R. thanks Prof. Dieter Fenske for his support.
IR (KBr): ν(H2O) 3306 br , 2970 m, 1610 s, ν(P-C) 1436 s, 1036 s, 888 br s,
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690 s cmϪ1 1H NMR (400 MHz, [D6]DMSO, 25 °C) δ ϭ 8.1-6.9 (10H, 6 x
.
m, ArH), 3.6 (10H, m, OCH2CH2), 3.3 (s, H2O), 1.7 (10H, m, OCH2CH2);
13C NMR (100 MHz, [D6]DMSO, 25 °C) δ ϭ 126.2 Ϫ130.9 (8C, ar. C), 67.0,
25.2; 31P NMR (162 MHz, [D6]DMSO, 25 °C, 65 % H3PO4) δ ϭ 32.9
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1
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1
1
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yellow cloudy solution was stirred overnight at room temperature,
and filtered. The filtrate was layered with 60 mL hexane. Storage
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33.25; H, 4.18. C24H36MnO6P2Se4 requires C, 33.78; H, 4.25 %.
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charge at www.ccdc.cam.ac.uk/conts/retrieving.html [or from the
Cambridge Crystallographic Data Centre, 12, Union Road, Cam-
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442
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Z. Anorg. Allg. Chem. 2007, 440Ϫ442