Addition complexes of tetrakis(isopropylisocyanide)cobalt(II) perchlorate with nitrogen bases

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Author list: Becker CAL, Odisitse S

Place: NEW YORK

Publication year: 2000

Journal: SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY (0094-5714)

Journal acronym: SYN REACT INORG MET

Volume number: 30

Issue number: 8

Start page: 1547

End page: 1560

Number of pages: 14

ISSN: 0094-5714

Languages: English-Great Britain (EN-GB)

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Abstract

Complexes of the form [Co(CNCHMe2)(4)L-2](ClO4)(2), L = C5H5N, 4-MeC5H4N, H2NC(S)NH2, have been synthesized by short-term digestion of [Co-2(CNCHMe2)(10)](ClO4)(4). 5H(2)O in excess amine or an ethanolic solution of excess thiourea. A trans-MA(4)B(2) composition is achieved through substitution of one CNCHMe2 ligand by the nitrogen base, rather than a MA(5)B composition that would result from simple ligand addition. This does not imply that the nitrogen bases are stronger ligands than alkylisocyanides, but that tetragonal coordination of four CNR ligands and two strongly a-bonding ligands is preferable to square-pyramidal coordination of five CNR ligands and one a-donating ligand. Stability of the [Co(CNCHMe2)(4)L-2](ClO4)(2) complexes in the solid state follows the order: L = H2NC(S)NH2 > C5H5N > 4-MeC5H4N much greater than C5H10NH; the complexes decompose in solution. The complexes show similar v(N=C) IR patterns, but transmission electronic spectra for the amine complexes are significantly different from that of the thiourea complex. The complexes with C5H5N and 4-Me5H4N are magnetically low-spin (mu(eff) = 2.24 and 3.08 BM, respectively), while the H2NC(S)NH2 complex is high-spin (mu(eff) = 4.92 BM).

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