1
31
1
in the H and Ɋ spectra manifesting direct spin-spin coupling ( J 433.5 Hz), unambiguously prove (within the limits of
NMR sensitivity) that bis(2-phenylethyl)phosphine selenide occurs in the selenone form in solution. The IR spectrum of this
–1
–1
compound has P=Se and P–H stretching vibrations near 443 cm and 2365 cm in accordance with the literature data [21].
Near 250-280 nm, the UV spectrum of bis(2-phenylethyl)phosphine selenide displays a characteristic absorption band of the
phenyl ring with poorly resolved vibrational structure and with maxima at 248 nm, 252 nm, 258 nm, 264 nm, and 268 nm.
Moreover, there is an absorption shoulder around 200-230 nm with maxima at 206 nm, 210 nm, and 218 nm, which may be
attributed to an overlap of the bands that are due to the S–S* transitions in the phenyl ring and the Ɋ=Se group.
The structure of bis(2-phenylethyl)phosphine selenide in the crystalline state was confirmed by XRD data. The
P(1)=Se(1) distance of 2.108(1) Å agrees with the P=Se distances known from the literature [22, 23].
Single crystal data for bis(2-phenylethyl)phosphine selenide evidence that in the crystal phase the phosphorus atom
in the molecule has tetrahedral coordination; i.e., as in solution, the tautomeric equilibrium is entirely shifted toward the
selenone form.
CONCLUSIONS
Thus the four-coordinated environment of the phosphorous atom found in the bis(2-phenylethyl)phosphine selenide
molecule makes it possible to predict the reactivity of this compound; in nucleophilic or radical addition reactions, phosphine
selenides should behave like phosphorous-centered radicals of nucleophiles.
This work was supported by RFBR grant Nos. 03-02-17733 and 04-03-32045 and Siberian Division of Russian
Academy of Sciences integration project No. 153.
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