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Synthesis and Reactivity of Manganese(II) Dialkylamido Complexes. Crystal and Molecular Structure of 2>*C7H16 (thf = tetrahydrofuran) and i2)2(NPri2)2>

DOI: 10.1039/DT9910002419

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2419 - 2428 (1991)

Update date:2022-08-28

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Authors:

Belforte, AntonioBelforte, Antonio

Calderazzo, FaustoCalderazzo, Fausto

Englert, UlliEnglert, Ulli

Straehle, JoachimStraehle, Joachim

Wurst, KlausWurst, Klaus

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Article abstract of DOI:10.1039/DT9910002419

By reaction of MnCl2 with LiNR2 (R = Me, Et or Pri) the corresponding dialkylamido complexes were prepared.The compounds 2> 1 (thf = tetrahydrofuran), i2)2(NPri2)2> 2 and 3 were isolated, and the molcular and crystal structures of 1 and 2 determined by single-crystal X-ray diffraction methods.Crystal data: 1, monoclinic, space group C2/c, a = 18.81(1), b = 20.45(2), c = 18.15(2) Angstroem, β = 113.31(8) deg, R = 0.063; 2, monoclinic, space group P21/c, a = 9.361(2), b = 9.724(2), c = 16.883(2) Angstroem, β = 100.91(1) deg, R = 0.046.The pentanuclear compound 1 consists of a trinuclear Mn3(NEt2)6Cl2 core, built up by edge-sharing of the three co-ordination tetrahedra, which are connected by four bridging diethylamido ligands, and terminally bonded to the Li(thf)2 moieties via chloride and amido bridges.The homoleptic compound 2 contains two three-co-ordinated manganese atoms, joined by two bridging dialkylamido groups, with an overall planar arrangement of the Mn2N4 skeleton.Both 1 and 2 react with CO2 to give the expected dialkylcarbamato complexes.The reactions of 1-3 with CO result in reductive carbonylation to -.The compounds also catalyse the selective carbonylation of secondary amines to dialkylformamides, a 87percent yield of Et2NC(O)H being obtained from NHEt2 and CO at atmospheric pressure, in 24 h, in the presence of 1, at room temperature.

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