Coordination chemistry of 3-mercapto-2-(mercaptomethyl)propanoic acid (dihydroasparagusic acid) with iron and nickel

Phillip I. Volkers; Thomas Rauchfuss; Scott R. Wilson

doi:10.1002/ejic.200600636

Coordination chemistry of 3-mercapto-2-(mercaptomethyl)propanoic acid (dihydroasparagusic acid) with iron and nickel

Phillip I. Volkers, Thomas Rauchfuss, Scott R. Wilson

Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

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 Ni^II center linked to a pair of square-planar Ni^II centers.

Original language	English (US)
Pages (from-to)	4793-4799
Number of pages	7
Journal	European Journal of Inorganic Chemistry
Issue number	23
DOIs	https://doi.org/10.1002/ejic.200600636
State	Published - Dec 4 2006

Keywords

Bridging ligands
Coordination modes
Iron
Nickel
S ligands

ASJC Scopus subject areas

Inorganic Chemistry

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title = "Coordination chemistry of 3-mercapto-2-(mercaptomethyl)propanoic acid (dihydroasparagusic acid) with iron and nickel",

abstract = "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.",

keywords = "Bridging ligands, Coordination modes, Iron, Nickel, S ligands",

author = "Volkers, {Phillip I.} and Thomas Rauchfuss and Wilson, {Scott R.}",

year = "2006",

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AU - Volkers, Phillip I.

AU - Rauchfuss, Thomas

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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