Aqueous transformation of a metal diformate to a metal dihydride carbonyl complex accompanied by H2 evolution from the formato ligands

Seiji Ogo; Hiromi Nishida; Hideki Hayashi; Yusuke Murata; Shunichi Fukuzumi

doi:10.1021/om0504147

Aqueous transformation of a metal diformate to a metal dihydride carbonyl complex accompanied by H₂ evolution from the formato ligands

Seiji Ogo, Hiromi Nishida, Hideki Hayashi, Yusuke Murata, Shunichi Fukuzumi

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20 Citations (Scopus)

Abstract

The rhodium diformate complex [Rh^III(tacn)(HCOO) ₂](OTf) (2, tacn = 1,4,7-triazacy-clononane, OTf^- = CF₃SO₃^-) reacts with HCOONa at pH 6-7 at 80°C in water to form a rhodium dihydride CO complex, [Rh ^III(tacn)(H)₂(CO)](OTf) (5), with H₂ evolution from the formato ligands of 2. This is the first example of H₂ evolution from hydrogen atoms of formato ligands of a metal diformate complex. Complex 2 was synthesized from the reaction of a rhodium aqua complex, [Rh ^III(tacn)(H₂O)₃](OTf)₃ (1), with HCOONa in water. Recrystallization of 2 with HCOONa in water gave crystals of a rhodium triformate complex, [Rh^III-(tacn)(HCOO)₃] (3), whose structure was unequivocally determined by X-ray analysis. The key intermediate in the transformation from 2 to 5 is a rhodium hydride formate complex, [Rh^III(tacn)H(HCOO)](OTf) (4), which was obtained by heating of an aqueous solution of the rhodium diformate complex 2 with 10 equiv of dimethyl sulfoxide (DMSO) at pH 6-7 in water. Complex 4 was well characterized by isotopic labeling measurements of ¹H NMR, electrospray ionization mass spectrometry (ESI-MS), and GC.

Original language	English
Pages (from-to)	4816-4823
Number of pages	8
Journal	Organometallics
Volume	24
Issue number	20
DOIs	https://doi.org/10.1021/om0504147
Publication status	Published - Sep 26 2005
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Aqueous transformation of a metal diformate to a metal dihydride carbonyl complex accompanied by H2 evolution from the formato ligands",

abstract = "The rhodium diformate complex [RhIII(tacn)(HCOO) 2](OTf) (2, tacn = 1,4,7-triazacy-clononane, OTf- = CF3SO3-) reacts with HCOONa at pH 6-7 at 80°C in water to form a rhodium dihydride CO complex, [Rh III(tacn)(H)2(CO)](OTf) (5), with H2 evolution from the formato ligands of 2. This is the first example of H2 evolution from hydrogen atoms of formato ligands of a metal diformate complex. Complex 2 was synthesized from the reaction of a rhodium aqua complex, [Rh III(tacn)(H2O)3](OTf)3 (1), with HCOONa in water. Recrystallization of 2 with HCOONa in water gave crystals of a rhodium triformate complex, [RhIII-(tacn)(HCOO)3] (3), whose structure was unequivocally determined by X-ray analysis. The key intermediate in the transformation from 2 to 5 is a rhodium hydride formate complex, [RhIII(tacn)H(HCOO)](OTf) (4), which was obtained by heating of an aqueous solution of the rhodium diformate complex 2 with 10 equiv of dimethyl sulfoxide (DMSO) at pH 6-7 in water. Complex 4 was well characterized by isotopic labeling measurements of 1H NMR, electrospray ionization mass spectrometry (ESI-MS), and GC.",

author = "Seiji Ogo and Hiromi Nishida and Hideki Hayashi and Yusuke Murata and Shunichi Fukuzumi",

year = "2005",

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doi = "10.1021/om0504147",

language = "English",

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journal = "Organometallics",

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T1 - Aqueous transformation of a metal diformate to a metal dihydride carbonyl complex accompanied by H2 evolution from the formato ligands

AU - Ogo, Seiji

AU - Nishida, Hiromi

AU - Hayashi, Hideki

AU - Murata, Yusuke

AU - Fukuzumi, Shunichi

PY - 2005/9/26

Y1 - 2005/9/26

N2 - The rhodium diformate complex [RhIII(tacn)(HCOO) 2](OTf) (2, tacn = 1,4,7-triazacy-clononane, OTf- = CF3SO3-) reacts with HCOONa at pH 6-7 at 80°C in water to form a rhodium dihydride CO complex, [Rh III(tacn)(H)2(CO)](OTf) (5), with H2 evolution from the formato ligands of 2. This is the first example of H2 evolution from hydrogen atoms of formato ligands of a metal diformate complex. Complex 2 was synthesized from the reaction of a rhodium aqua complex, [Rh III(tacn)(H2O)3](OTf)3 (1), with HCOONa in water. Recrystallization of 2 with HCOONa in water gave crystals of a rhodium triformate complex, [RhIII-(tacn)(HCOO)3] (3), whose structure was unequivocally determined by X-ray analysis. The key intermediate in the transformation from 2 to 5 is a rhodium hydride formate complex, [RhIII(tacn)H(HCOO)](OTf) (4), which was obtained by heating of an aqueous solution of the rhodium diformate complex 2 with 10 equiv of dimethyl sulfoxide (DMSO) at pH 6-7 in water. Complex 4 was well characterized by isotopic labeling measurements of 1H NMR, electrospray ionization mass spectrometry (ESI-MS), and GC.

AB - The rhodium diformate complex [RhIII(tacn)(HCOO) 2](OTf) (2, tacn = 1,4,7-triazacy-clononane, OTf- = CF3SO3-) reacts with HCOONa at pH 6-7 at 80°C in water to form a rhodium dihydride CO complex, [Rh III(tacn)(H)2(CO)](OTf) (5), with H2 evolution from the formato ligands of 2. This is the first example of H2 evolution from hydrogen atoms of formato ligands of a metal diformate complex. Complex 2 was synthesized from the reaction of a rhodium aqua complex, [Rh III(tacn)(H2O)3](OTf)3 (1), with HCOONa in water. Recrystallization of 2 with HCOONa in water gave crystals of a rhodium triformate complex, [RhIII-(tacn)(HCOO)3] (3), whose structure was unequivocally determined by X-ray analysis. The key intermediate in the transformation from 2 to 5 is a rhodium hydride formate complex, [RhIII(tacn)H(HCOO)](OTf) (4), which was obtained by heating of an aqueous solution of the rhodium diformate complex 2 with 10 equiv of dimethyl sulfoxide (DMSO) at pH 6-7 in water. Complex 4 was well characterized by isotopic labeling measurements of 1H NMR, electrospray ionization mass spectrometry (ESI-MS), and GC.

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Aqueous transformation of a metal diformate to a metal dihydride carbonyl complex accompanied by H₂ evolution from the formato ligands

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