TY - JOUR
T1 - Coordination chemistry of 3-mercapto-2-(mercaptomethyl)propanoic acid (dihydroasparagusic acid) with iron and nickel
AU - Volkers, Phillip I.
AU - Rauchfuss, Thomas B.
AU - Wilson, Scott R.
PY - 2006/12/4
Y1 - 2006/12/4
N2 - The first transition-metal complexes bearing the natural product dihydroasparagusic acid, (HSCH2)2CHCO2H, as a ligand are reported. Various coordination modes and nuclearities are demonstrated for the chelating ligand by a series of iron and nickel complexes. Fe2[(SCH2)2CHCO2H](CO)6 retains carbonyl substitution reactivity typical of Fe2(SR) 2(CO)6 complexes, yet carboxy coordination to Fe I was unobserved. Coupling of the carboxylic acid with amines yields the corresponding amides Fe2[(SCH2)2CHC(O)NHR] (CO)6 (R = Et, gly-O-tBu). Fe2[(SCH2) 2CHCO2H](CO)4(PMe3)2 catalyzes H2 production, but no better than unfunctionalized alkyl dithiolate analogs. Reactions of the ligand with NiCl2(dppe) afforded mono-, di-, and trinuclear complexes. Noteworthy is Ni3[(SCH 2)2CHCO2]2(dppe)2, which features an octahedrally coordinated NiII center linked to a pair of square-planar NiII centers.
AB - The first transition-metal complexes bearing the natural product dihydroasparagusic acid, (HSCH2)2CHCO2H, as a ligand are reported. Various coordination modes and nuclearities are demonstrated for the chelating ligand by a series of iron and nickel complexes. Fe2[(SCH2)2CHCO2H](CO)6 retains carbonyl substitution reactivity typical of Fe2(SR) 2(CO)6 complexes, yet carboxy coordination to Fe I was unobserved. Coupling of the carboxylic acid with amines yields the corresponding amides Fe2[(SCH2)2CHC(O)NHR] (CO)6 (R = Et, gly-O-tBu). Fe2[(SCH2) 2CHCO2H](CO)4(PMe3)2 catalyzes H2 production, but no better than unfunctionalized alkyl dithiolate analogs. Reactions of the ligand with NiCl2(dppe) afforded mono-, di-, and trinuclear complexes. Noteworthy is Ni3[(SCH 2)2CHCO2]2(dppe)2, which features an octahedrally coordinated NiII center linked to a pair of square-planar NiII centers.
KW - Bridging ligands
KW - Coordination modes
KW - Iron
KW - Nickel
KW - S ligands
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U2 - 10.1002/ejic.200600636
DO - 10.1002/ejic.200600636
M3 - Article
AN - SCOPUS:33845638728
SN - 1434-1948
SP - 4793
EP - 4799
JO - European Journal of Inorganic Chemistry
JF - European Journal of Inorganic Chemistry
IS - 23
ER -