Incorporation of thiolate donation using 2,2'-dithiodibenzaldehyde: complexes of a pentadentate N2S3 ligand with relevance to the active site of Co nitrile hydratase.
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.
Smucker
Bradley W
BW
Department of Chemistry, Wichita State University, Wichita, KS 67260-0051, United States.
Vanstipdonk
Michael J
MJ
Eichhorn
David M
DM
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*
C525678:2,2'-dithiodibenzaldehyde; D001547:Benzaldehydes; D008024:Ligands; D013438:Sulfhydryl Compounds; D003035:Cobalt; D006836:Hydro-Lyases; C048831:nitrile hydratase
Biochem Biophys Res Commun. 1982 Sep 30;108(2):658-63
6293499
Eur J Biochem. 1987 Feb 2;162(3):691-8
3830164
Biochem Biophys Res Commun. 1983 Sep 15;115(2):658-65
6312988
J Am Chem Soc. 2001 Jan 24;123(3):463-8
11456548
Nat Struct Biol. 1998 May;5(5):347-51
9586994
Acta Crystallogr B. 2002 Jun;58(Pt 3 Pt 1):380-8
12037359
J Biol Chem. 1991 Nov 5;266(31):20687-93
1657934
Biochem Biophys Res Commun. 2001 Nov 16;288(5):1169-74
11700034
Trends Biotechnol. 1992 Nov;10(11):402-8
1368882
Eur J Biochem. 1991 Mar 28;196(3):581-9
2013281
Structure. 1997 May 15;5(5):691-9
9195885
J Org Chem. 2002 Sep 6;67(18):6542-5
12201779
Chem Rev. 2004 Feb;104(2):825-48
14871143
Biochemistry. 1991 Jan 15;30(2):431-5
1846295
Inorg Chem. 2003 Sep 8;42(18):5751-61
12950226
Biochem Biophys Res Commun. 1988 Sep 15;155(2):1008-16
3421954
Biochemistry. 1997 May 6;36(18):5447-54
9154927
Science. 2002 Oct 18;298(5593):567-72
12386327
Science. 1994 May 6;264(5160):817-9
8171334
Biochem Biophys Res Commun. 1986 Sep 30;139(3):1305-12
3768004
Biochem Biophys Res Commun. 1996 Apr 5;221(1):146-50
8660325
Nat Struct Biol. 2003 Apr;10(4):271-9
12627225
Inorg Chem. 2000 Oct 30;39(22):4998-9
11233193
J Am Chem Soc. 2001 Apr 11;123(14):3247-59
11457060
Chem Rev. 1996 Nov 7;96(7):2515-2540
11848835
Acc Chem Res. 2004 Apr;37(4):253-60
15096062
J Biol Chem. 1990 Mar 5;265(7):3873-9
2154491
Science. 1995 Oct 27;270(5236):628-30
7570019