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SM ISO690:2012 BĂLAN, Iolanta, GORINCIOI, Natalia. Ab initio study of chemical activation and hydrogenation of white phosphorus in reaction with rhodium trihydride complex
. In: Chemistry Journal of Moldova, 2011, nr. 2(6), pp. 84-90. ISSN 1857-1727. |
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Chemistry Journal of Moldova | ||||||
Numărul 2(6) / 2011 / ISSN 1857-1727 /ISSNe 2345-1688 | ||||||
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Pag. 84-90 | ||||||
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The four-stage mechanism of reaction of the rhodium trihydride complex [(triphos)RhH3] (triphos=1,1,1-
tris(diphenylphosphanylmethyl)ethane) with the white phosphorus molecule resulting in the phosphane and the
cyclo-P3 complex [(triphos)M(η3-P3] is analyzed on the basis of ab initio calculations of reactants, products, and
intermediate complexes of reaction. It is shown that generation of the transient complex [(triphos)RhH(η1:η1-P4)]
followed by intramolecular hydrogen atom migration from the metal to one of the phosphorus atoms is the energetically
favourable process. Calculations also show that P4 molecule is activated by coordination to the above complex: the
metal-bonded P-P edge is broken, and the tetrahedron P4 is opened to form the butterfly geometry. This activation is
realized mainly due to the one-orbital back donation of 4d-electron density from the atom of Rh to the unoccupied
antibonding triple degenerate t1*-MO of P4.
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Cuvinte-cheie white phosphorus, ab initio calculations, triphos, rhodium trihydride complex |
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