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Chemical and Theoretical Comparison between Phosphido (X = PR2) and Thiolato (X = SR) Bent Niobocenes of the Type . Structure of >

DOI: 10.1039/DT9950003699

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 3699 - 3704 (1995)

Update date:2022-08-11

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Authors:

Kubicki, Marek M.Kubicki, Marek M.

Oudet, PascalOudet, Pascal

Martin, ChristineMartin, Christine

Barre, ChristopheBarre, Christophe

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Article abstract of DOI:10.1039/DT9950003699

The hydrido complexes reacted with MeI to afford the iodo derivatives 1.The reaction of 1 with Na(SEt) led to the terminal thiolato complexes 2.Compounds 2 were used to bind the metal carbonyl fragments Fe(CO)4 and M(CO)5 from and (thf = tetrahydrofuran) respectively.The corresponding monothiolato-bridged complexes n>> 3 (M = Fe, n = 4; M = Mo or W, n = 5) were obtained only in the case of L = CO and no dibridged μ-SEt, μ-Co complex was formed.The new complexes 1-3 were characterized by IR, 1H and 31P NMR spectroscopies.The X-ray analysis of > showed an endo position of the ethyl group with respect to the CO ligand bound to the niobium.The results of extended-Hueckel molecular orbital (EHMO) conformational calculations carried out on the model complexes and are compared, and the importance of electronic and steric effects deduced.An explanation for the non-formation of dibridged μ-SEt, μ-CO complexes is attempted on the basis of EHMO and X-ray results.

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