title: Incorporation of thiolate donation using 2,2'-dithiodibenzaldehyde: complexes of a pentadentate N2S3 ligand with relevance to the active site of Co nitrile hydratase.
abstract: The use of 2,2'-dithiodibenzaldehyde (DTDB) as a reactant for incorporating thiolate donors into the coordination sphere of a transition metal complex without the need for protecting groups is expanded to include the synthesis of complexes with pentadentate ligands. The ligand N,N'-bis(thiosalicylideneimine)-2,2'-thiobis(ethylamine) (tsaltp) is synthesized at a cobalt center by the reaction of DTDB with a Co complex of thiobis(ethylamine). The resulting Co complexes are thus coordinated by the N(2)S(3) pentadentate ligand through two imine N atoms, two thiolate S atoms, and one thioether S atom. A dimeric, bis-thiolate-bridged complex (1) is isolated and converted to a monomeric CN adduct (2) by treatment with KCN. The N(2)S(3) coordination environment provided by the tsaltp ligand is similar to that provided by the protein donors at the active site of the nitrile hydratase enzymes, with 2 being the first octahedral Co complex reported with such a coordination sphere.
authors: Department of Chemistry, Wichita State University, Wichita, KS 67260-0051, United States.
authors: Bradley W
authors: BW
authors: Smucker
authors: Michael J
authors: MJ
authors: Vanstipdonk
authors: David M
authors: DM
authors: Eichhorn
mesh_terms: D001547:Benzaldehydes / Q000737:chemistry*; D001665:Binding Sites; D003035:Cobalt / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006836:Hydro-Lyases / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D021241:Spectrometry, Mass, Electrospray Ionization; D017550:Spectroscopy, Fourier Transform Infrared; D013438:Sulfhydryl Compounds / Q000737:chemistry*
chemical_list: C525678:2,2'-dithiodibenzaldehyde; D001547:Benzaldehydes; D008024:Ligands; D013438:Sulfhydryl Compounds; D003035:Cobalt; D006836:Hydro-Lyases; C048831:nitrile hydratase
references: Biochem Biophys Res Commun. 1982 Sep 30;108(2):658-63
references: 6293499
references: Eur J Biochem. 1987 Feb 2;162(3):691-8
references: 3830164
references: Biochem Biophys Res Commun. 1983 Sep 15;115(2):658-65
references: 6312988
references: J Am Chem Soc. 2001 Jan 24;123(3):463-8
references: 11456548
references: Nat Struct Biol. 1998 May;5(5):347-51
references: 9586994
references: Acta Crystallogr B. 2002 Jun;58(Pt 3 Pt 1):380-8
references: 12037359
references: J Biol Chem. 1991 Nov 5;266(31):20687-93
references: 1657934
references: Biochem Biophys Res Commun. 2001 Nov 16;288(5):1169-74
references: 11700034
references: Trends Biotechnol. 1992 Nov;10(11):402-8
references: 1368882
references: Eur J Biochem. 1991 Mar 28;196(3):581-9
references: 2013281
references: Structure. 1997 May 15;5(5):691-9
references: 9195885
references: J Org Chem. 2002 Sep 6;67(18):6542-5
references: 12201779
references: Chem Rev. 2004 Feb;104(2):825-48
references: 14871143
references: Biochemistry. 1991 Jan 15;30(2):431-5
references: 1846295
references: Inorg Chem. 2003 Sep 8;42(18):5751-61
references: 12950226
references: Biochem Biophys Res Commun. 1988 Sep 15;155(2):1008-16
references: 3421954
references: Biochemistry. 1997 May 6;36(18):5447-54
references: 9154927
references: Science. 2002 Oct 18;298(5593):567-72
references: 12386327
references: Science. 1994 May 6;264(5160):817-9
references: 8171334
references: Biochem Biophys Res Commun. 1986 Sep 30;139(3):1305-12
references: 3768004
references: Biochem Biophys Res Commun. 1996 Apr 5;221(1):146-50
references: 8660325
references: Nat Struct Biol. 2003 Apr;10(4):271-9
references: 12627225
references: Inorg Chem. 2000 Oct 30;39(22):4998-9
references: 11233193
references: J Am Chem Soc. 2001 Apr 11;123(14):3247-59
references: 11457060
references: Chem Rev. 1996 Nov 7;96(7):2515-2540
references: 11848835
references: Acc Chem Res. 2004 Apr;37(4):253-60
references: 15096062
references: J Biol Chem. 1990 Mar 5;265(7):3873-9
references: 2154491
references: Science. 1995 Oct 27;270(5236):628-30
references: 7570019