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Synthesis and Reactivity of the Paramagnetic Nitrosyl Complexes 2+ (M = Cr or Mo), and the Crystal Structures of and

DOI: 10.1039/DT9800002162

Source and publish data:

Journal of the Chemical Society, Dalton Transactions p. 2162 - 2169 (1980)

Update date:2022-08-11

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Authors:

Clamp, SaraClamp, Sara

Connelly, Neil G.Connelly, Neil G.

Taylor, Graham E.Taylor, Graham E.

Louttit, Thomas S.Louttit, Thomas S.

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Article abstract of DOI:10.1039/DT9800002162

Excess of Y (Y = BF4 or PF6) and in acetonitrile afford paramagnetic Y2.At room temperature (1; M = Cr) and (1-) yield (2; R = Me or ET) which affords cis- in refluxing toluene; only cis-(2-) is isolable from the reaction between (1; M = Cr) and Na2.A crystal-structure determination of (2; R = Et) has revealed the geometry about chromium to be pentagonal bipyramidal with the nitrosyl ligand in an axial position; crystals are triclinic, space group PI, with Z = 2, in a unit cell of dimensions a = 9.525(3), b = 9.903(5), c = 14.649(7) Angstroem, α = 103.8(4), β = 74.5(3), and γ = 107.4(3) degree.The structure has been solved from diffractometer data by the heavy-atom method, and refined to R = 0.040 for 3.033 observed reflections.With 1,2-bis(diphenylphosphino)ethane (dppe) in acetonitrile (1; M = Cr or Mo) affords Y2 (3; M = Cr) and Y (4; M = Mo) which is oxidised to (3; M = Mo) by Y.Dppe and (1; M = Cr) also give Y (5; X = F) which is reduced, as is (3; M = Cr), by Na in tetrahydrofuran to (6; X = F).The crystal structure of (6; X = F) has verified the trans disposition of the NO and F ligands; crystals are monoclinic, space group P21/n, with Z = 2, in a unit cell of dimensions a = 11.080(6), b = 16.352(6), c = 13.129(7) Angstroem, and β = 109.17(4) deg.The structure has been solved from diffractometer data by the heavy-atom method, and refined to R = 0.047 for 2633 observed reflections.Complexes (3) and (4) react with chloride ion to give Y (5; M = Cr or Mo, X = Cl) and (6; M = Mo, X = Cl) respectively, which are interconvertible by Y oxidation <(6) to (5) or Na reduction <(5) to (6)>.The redox properties of complexes (1)-(6) have also been studied, by cyclic voltammetry, and the retention during electron transfer of the mutually trans disposition of the dppe ligands of (3)-(6) verified by 31P NMR and e.s.r. spectroscopy.

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