title: NMR Spectroscopic Characterization of Methylcobalt(III) Compounds with Classical Ligands. Crystal Structures of [Co(NH(3))(5)(CH(3))]S(2)O(6), trans-[Co(en)(2)(NH(3))(CH(3))]S(2)O(6) (en = 1,2-Ethanediamine), and [Co(NH(3))(6)]-mer,trans-[Co(NO(2))(3)(NH(3))(2)(CH(3))](2)-trans- [Co(NO(2))(4)(NH(3))(2)].
abstract: A series of methylcobalt(III) compounds with solely classical ligands such as NH(3), H(2)O, NO(2)(-), CN(-), and 1,2-ethanediamine (en) has been prepared by ligand substitution of the pentaamminemethylcobalt(III) cation. The new compounds have been characterized by (1)H, (13)C, and (59)Co nuclear magnetic resonance spectroscopy and by absorption spectroscopy. Single-crystal X-ray structure determinations at 122.0(5) K were performed on [Co(NH(3))(5)(CH(3))]S(2)O(6) (1), trans-[Co(en)(2)(NH(3))(CH(3))]S(2)O(6) (2), and [Co(NH(3))(6)]-mer,trans-[Co(NO(2))(3)(NH(3))(2)(CH(3))](2)-trans-[Co(NO(2))(4)(NH(3))(2)] (3). Compound 1 is monoclinic, P2(1)/n, with cell dimensions a = 6.4856(9) Å, b = 18.0720(11) Å, c = 9.7854(14) Å, and beta = 98.280(13) degrees. Compound 2 is orthorhombic, P2(1)2(1)2, with cell dimensions a = 12.211(3) Å, b = 10.107(3) Å, and c = 11.514(3) Å. Compound 3 is monoclinic, P2(1)/n, with cell dimensions a = 8.390(2) Å, b = 8.970(3) Å, c = 20.650(9) Å, and beta = 91.29(2) degrees. Virtually identical Co-C distances in the range 1.980-1.984 Å are found in the three compounds. The methyl group exerts a strong trans influence. The largest relative elongation of the bond to the trans ligand is 0.170 Å in the trans-[Co(en)(2)(NH(3))(CH(3))](2+) cation. The structural trans influence appears to decrease with the overall charge of the coordination compound. Estimates of the scalar one-bond cobalt-carbon coupling constants, (1)J(Co)(-)(C), in the pentacyanomethylcobalt(III) anion was obtained by line shape analysis, yielding values of 127, 95, and 62 Hz for the cis cyano groups, the trans cyano group, and the methyl group, respectively.
authors.affiliation: Chemistry Department, The Royal Veterinary and Agricultural University, Thorvaldsensvej 40, DK-1871 Frederiksberg, Denmark, and Centre for Crystallographic Studies, Department of Chemistry, University of Copenhagen, Universitetsparken 5, DK-2100 Copenhagen, Denmark.
authors.forename: Pauli
authors.initials: P
authors.lastname: Kofod
authors.forename: Pernille
authors.initials: P
authors.lastname: Harris
authors.forename: Sine
authors.initials: S
authors.lastname: Larsen