Use of 1,2,3-Selenadiazoles in the synthesis of 1,1'- bis(diphenylselenophosphoryl)ferrocene

Article abstract of DOI:10.1007/s10593-012-1129-5

A method has been developed for obtaining 1,1'- bis(diphenylselenophosphoryl)ferrocene based on utilization of 1,2,3-selenadiazoles as the source of selenium. The molecular structure was confirmed by X-ray analysis.

Full text of DOI:10.1007/s10593-012-1129-5

Chemistry of Heterocyclic Compounds, Vol. 48, No. 8, November, 2012 (Russian Original Vol. 48, No. 8, August, 2012)
USE OF 1,2,3-SELENADIAZOLES IN THE SYNTHESIS OF
1,1'-BIS(DIPHENYLSELENOPHOSPHORYL)FERROCENE
P. Arsenyan1*, A. Petrenko1, K. Oberte1, and S. Belyakov1
A method has been developed for obtaining 1,1'-bis(diphenylselenophosphoryl)ferrocene based on
utilization of 1,2,3-selenadiazoles as the source of selenium. The molecular structure was confirmed by
X-ray analysis.
Keywords: 1,1'-bis(diphenylphosphino)ferrocene, 1,1'-bis(diphenylselenophosphoryl)ferrocene,
1,2,3-selenadiazole, selenium.
1,2,3-Selenadiazole derivatives play an important role in solving many theoretical and practical
problems of organic chemistry [1]. Their interesting property is the ability to eliminate molecules of nitrogen
and selenium with the formation of acyclic derivatives and new heterocyclic systems [2]. In turn, the synthesis
of 1,1'-bis(phosphino)ferrocene selanes is of interest, since these compounds act as promising complex-forming
ligands with salts of copper [2], silver [3, 4], and gold [4]. Previously we described a reaction of 1,2,3-selena-
diazoles with tributyl- and triphenylphosphines [5]. In the present work, a method is given for obtaining the 1,1'-bis-
(diphenylphosphino)ferrocene diselane, and its molecular structure has been investigated.
Substituted 1,2,3-selenadiazoles 2-5 react with 1,1'-bis(diphenylphosphino)ferrocene (dppf) (1) upon
heating in toluene.
Ph
Ph
PPh2
P
PhMe
80°C, 30 min
R
R
Se
N
Fe
Fe
+
+
R1
N
–N2
Se
2–5
R1
Se
PPh2
P
1
Ph
Ph
6
2 R = i-Pr, R1 = H; 3 R = Ph, R1 = H; 4 R = 2-thienyl; R1 = H; 5 R = Me, R1 = COOEt
According to the experimental data obtained, the nature of the initial 1,2,3-selenadiazoles 2-5 had
practically no influence on the yield of 1,1'-bis(diphenylselenophosphoryl)ferrocene (6). The desired compound
was formed in 93-98% yield. The derivative 6 was previously obtained in 95% yield by heating compound 1
with elemental selenium [6].
_______
*To whom correspondence should be addressed, e-mail: pavel@osi.lv.
1Latvian Institute of Organic Synthesis, 21 Aizkraukles St., Riga LV-1006, Latvia.
_________________________________________________________________________________________
Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1356-1359, August, 2012.
Original article submitted March 12, 2012.
0009-3122/12/4808-1263©2012 Springer Science+Business Media New York
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An X-ray structural investigation was carried out on crystals of compound 6 grown in a mixture of ethyl
acetate–petroleum ether. There are data in the literature on the crystal structure of a diselane 6 solvate with
dichloromethane [6]. Results are given in the present work of the X-ray structural analysis of the pure derivative
6 crystal structure (Fig. 1). As in the case of the solvate with CH2Cl2 [6], the molecule of the obtained
compound 6 is in a particular position (center of inversion), consequently numbering is given only for the atoms
found in the independent part of the unit cell.
Fig. 1. Spatial model of the compound 6 molecule with atoms denoted by ellipsoids of thermal
vibrations of 50% probability.
The ferrocene system has a characteristic symmetry D5d; the values of the bond lengths, valence, and
dihedral angles in the compound 6 molecule are close to those given in [6]. However, the crystal structure of the
investigated compound 6 was significantly different from the structure described in [6]. A projection is shown in
Fig. 2 of the crystal structure of compound 6 along the crystallographic direction [1 0 0]. A characteristic feature
of this structure is the shortened intermolecular contacts Se…Se, the length of which is 3.491(1) Å, significantly
lower than the sum of the van der Waals radii for Se at 3.80 Å [7-9]. As a result of these contacts the molecules
are combined in chains stretched along the [0 0 1] direction. It should be noted that similar contacts also occur
in the structure of the CH2Cl2 solvate, but in the latter case their length is equal to 3.528(1) Å [6]. According to
the literature data of [7, 9] shortened intra- and intermolecular Se…Se contacts are fairly common.
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Fig. 2. Projection of the crystal structure of compound 6 along the crystallographic a axis.
We have thus developed a new method for the synthesis of 1,1'-bis(diphenylselenophosphoryl)-
ferrocene, using 1,2,3-selenadiazoles. The molecular and crystal structure of the obtained compound has been
investigated by X-ray analysis.
EXPERIMENTAL
1
The H and 13C NMR spectra were recorded on a Varian Mercury 400 instrument (400 and 100 MHz,
respectively) in CDCl3, internal standard was HMDS (δ 0.05 ppm). Monitoring of the reaction progress was
performed by TLC on Merck Kieselgel plates (eluent CH2Cl2) with visualization in UV light.
1,1'-Bis(diphenylselenophosphoryl)ferrocene (6). A mixture of 1,2,3-selenadiazole 2-5 [10-13]
(2.1 mmol) and 1,1'-bis(diphenylphosphino)ferrocene (1) (0.554 g, 1.0 mmol) was dissolved in toluene (10 ml)
and heated to 80oC for 30 min. The solvent was then evaporated and the residue recrystallized from a mixture of
EtOAc–petroleum ether. The data of 1H and 13C NMR spectra for 1,1'-bis(diphenylselenophosphoryl)-ferrocene
(6) agreed with the literature data of [6].
X-Ray Structural Investigation of 1,1'-Bis(diphenylselenophosphoryl)ferrocene (6). Monocrystals
of compound 6 obtained by crystallization from an EtOAc–petroleum mixture belonged to the monoclinic
system. The parameters of the crystal lattice were: a 8.8821(4), b 16.1458(7), c 10.9639(5) Å; β 104.987(2)o;
V 1518.8(1) Å3; F(000) 712; μ 3.021 mm-1; dcalc 1.557 g·cm-1; Z 2; space group P21/n. The intensities of 3381
independent reflections were measured on a Bruker-Nonius KappaCCD automatic diffractometer (MoKα-
radiation, λ 0.71073 Å, graphite monochromator) to 2θmax 55o at room temperature. The structure was solved on
2611 reflections with I > 2σ(I) using the SIR97 set of programs [14]. Refinement was carried out by the least-
squares method in a full-matrix anisotropic approximation with the aid of the SHELXL97 set of programs [15].
The final value of the probability factor R was 0.0687. Full crystallographic information has been deposited at
the Cambridge Crystallographic Data Center (deposit CCDC 870663).
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The work was carried out with the assistance of the European Social Fund (2009/0197/1DP/ 1.1.1.2.0/09/
APIA/VIAA/014), and also a grant from the Latvian Council of Science (No 09.1588).
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