Structural models for the active site of acetyl-CoA synthase: synthesis of dinuclear nickel complexes having thiolate, isocyanide, and thiourea on the Ni(p) site.
The trinuclear nickel complex [{Ni(dadt(Et))}(2)Ni](NiBr(4)) (dadt(Et) = N,N'-diethyl-3,7-diazanonane-1,9-dithiolate) (1a), prepared by the reaction of Ni(dadt(Et)) and Ni(EtOH)(4)Br(2), was found to serve as a useful synthetic precursor of various dinuclear nickel complexes modeling the active site of acetyl-CoA synthase (ACS). The reactions of 1a with 4 equiv of the potassium salts of arenethiolates in ethanol produced a series of dinuclear nickel thiolate complexes Ni(dadt(Et))Ni(SAr)(2) (Ar = Ph (2a), p-Tol (2b), 2,4,6-triisopropylphenyl (Tip) (2c)) in good yields. The analogous reactions of 1a with Ag(OTf) in the presence of (t)BuNC and (NMe(2))(2)CS (tmtu) generated the dicationic dinuclear nickel complexes [Ni(dadt(Et))Ni((t)BuNC)(2)](OTf)(2) (3) and [Ni(dadt(Et))Ni(tmtu)(2)](OTf)(2) (4), respectively. The molecular structures of 1a, 2a-c, 3, and 4 determined by X-ray analysis compare well with that of A-cluster in ACS.
Ito
Mikinao
M
Research Center for Materials Science, and Department of Chemistry, Graduate School of Science, Nagoya University, Furo-cho, Chikusa-ku, Nagoya 464-8602, Japan.
Kotera
Mai
M
Song
Yumei
Y
Matsumoto
Tsuyoshi
T
Tatsumi
Kazuyuki
K
D000445:Aldehyde Oxidoreductases / Q000737:chemistry* / Q000378:metabolism*; D020134:Catalytic Domain; D002412:Cations / Q000737:chemistry; D018360:Crystallography, X-Ray; D003486:Cyanides / Q000737:chemistry*; D008024:Ligands; D008958:Models, Molecular; D008961:Models, Structural; D009532:Nickel / Q000737:chemistry*; D013438:Sulfhydryl Compounds / Q000737:chemistry*; D013890:Thiourea / Q000737:chemistry*
D002412:Cations; D003486:Cyanides; D008024:Ligands; D013438:Sulfhydryl Compounds; D009532:Nickel; D000445:Aldehyde Oxidoreductases; D013890:Thiourea