Cooperative metal-ligand reactivity and catalysis in low-spin ferrous alkoxides

Wan Yi Chu; Xiaoyuan Zhou; Thomas B. Rauchfuss

doi:10.1021/om501152h

Cooperative metal-ligand reactivity and catalysis in low-spin ferrous alkoxides

Wan Yi Chu, Xiaoyuan Zhou, Thomas B. Rauchfuss

Chemistry

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Abstract

This report describes examples of combined Fe- and O-centered reactivity of Fe(P₂O₂)(CO)₂ (1), where P₂O₂ is the diphosphinoglycolate (Ph₂PC₆H₄CHO)₂^2-. This 18e low-spin ferrous dialkoxide undergoes substitution of CO to give the labile monosubstituted derivatives Fe(P₂O₂)(CO)(L) (L = PMe₃, pyridine, MeCN). Treatment of Fe(P₂O₂)(CO)₂ with Brønsted acids results in stepwise O-protonation, affording rare examples of low-spin Fe(II) complexes containing alcohol ligands. Substitution reactions with amides (RC(O)NH₂) proceeds with binding of the carbonyl and formation of an intramolecular hydrogen bond between NH and the neighboring alkoxo ligand. This two-site binding was confirmed with crystallographic characterization of the thiourea-substituted derivative. Fe(P₂O₂)(CO)₂ reacts with Ph₂SiH₂ to give the O-silylated hydrido complex, which is inactive for hydrosilylation. The monocarbonyl derivatives Fe(P₂O₂)(CO)(L) (L = NCMe, PMe₃, acetamide) are precursors to catalysts for the hydrosilylation of benzaldehyde, acetophenone, and styrene.

Original language	English (US)
Pages (from-to)	1619-1625
Number of pages	7
Journal	Organometallics
Volume	34
Issue number	9
DOIs	https://doi.org/10.1021/om501152h
State	Published - May 11 2015

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Cooperative metal-ligand reactivity and catalysis in low-spin ferrous alkoxides",

abstract = "This report describes examples of combined Fe- and O-centered reactivity of Fe(P2O2)(CO)2 (1), where P2O2 is the diphosphinoglycolate (Ph2PC6H4CHO)22-. This 18e low-spin ferrous dialkoxide undergoes substitution of CO to give the labile monosubstituted derivatives Fe(P2O2)(CO)(L) (L = PMe3, pyridine, MeCN). Treatment of Fe(P2O2)(CO)2 with Br{\o}nsted acids results in stepwise O-protonation, affording rare examples of low-spin Fe(II) complexes containing alcohol ligands. Substitution reactions with amides (RC(O)NH2) proceeds with binding of the carbonyl and formation of an intramolecular hydrogen bond between NH and the neighboring alkoxo ligand. This two-site binding was confirmed with crystallographic characterization of the thiourea-substituted derivative. Fe(P2O2)(CO)2 reacts with Ph2SiH2 to give the O-silylated hydrido complex, which is inactive for hydrosilylation. The monocarbonyl derivatives Fe(P2O2)(CO)(L) (L = NCMe, PMe3, acetamide) are precursors to catalysts for the hydrosilylation of benzaldehyde, acetophenone, and styrene.",

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Cooperative metal-ligand reactivity and catalysis in low-spin ferrous alkoxides

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