A theoretical study of the spin-forbidden reaction Fe(CO)(4) + CO -> Fe(CO)(5)

• The spin-forbidden reaction of Fe(CO)(4)+CO -> Fe(CO)(5) has been investigated with multiconfigurational quantum chemical methods (CASSCF/CASPT2). The structure of the minimum energy crossing point ( MECP) between the singlet and triplet energy surfaces as well as the equilibrium structures of Fe(CO)(5) ( a singlet state) and Fe(CO)(4) ( a triplet state) has been determined. The partition rational function (RF) method has been used for the geometry optimization together with approximate numerical gradient vectors and Hessian matrices. The Fe-CO bond angles of the MECP are between those of the equilibrium structures of the ground states of Fe(CO)(5) and Fe(CO)(4), while a considerable extension of the Fe-CO bonds have been shown to occur at the MECP when transferring from the triplet ( reactant) PES to the singlet ( product) PES. It has also been shown that the MECP prefers to have a Cs symmetry structure with the incoming CO tilted rather than a C-2v structure with Fe and the incoming CO on a straight line.

Ämnesord

NATURVETENSKAP  -- Kemi -- Teoretisk kemi (hsv//swe)

NATURAL SCIENCES  -- Chemical Sciences -- Theoretical Chemistry (hsv//eng)

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