Studies on the condensation pathway to and properties of diiron azadithiolate carbonyls

Jane L. Stanley; Thomas B. Rauchfuss; Scott R. Wilson

doi:10.1021/om0611150

Studies on the condensation pathway to and properties of diiron azadithiolate carbonyls

Jane L. Stanley, Thomas B. Rauchfuss, Scott R. Wilson

Chemistry

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Abstract

Reaction of Fe₂(SH)₂(CO)₆ and HCHO, which gives Fe₂[(SCH₂)₂NH](CO)₆ in the presence of NH₃, affords the possible intermediate Fe ₂(SCH₂OH)₂(CO)₆, which has been characterized crystallographically as its axial-equatorial isomer. Fe ₂(SCH₂OH)₂(CO)₆ was shown to react with ammonia and amines to give Fe₂[(SCH₂) ₂NR](CO)₆ (R = H, alkyl). Related hemithioacetal intermediates were generated by treatment of Fe₂(SH) ₂(CO)₆ with RC(O)C(O)R (R = H, Ph, 4-F-C₆H ₄) to give cycloadducts. The benzil derivative Fe₂[S ₂C₂(OH)₂Ph₂](CO)₆, a C₂-symmetric species, was also characterized crystallographically. The acylated azadithiolate Fe₂[(SCH₂)₂NAc](CO) ₆ was prepared by reaction of Li₂Fe₂S ₂(CO)₆ with (ClCH₂)₂NC(O)Me. DNMR experiments show that the free energies of activation for rotation of the amide bond are the same for Fe₂[(SCH₂)₂NAc](CO) ₆ and Fe₂[(SCH₂)₂NAc](CO) ₄(PMe₃)₂, which implies that the ligands on the iron centers do not strongly affect the basicity of the nitrogen. As a control, we showed that the thioamide Fe₂[(SCH₂) ₂NC(S)Me](CO)₆ does exhibit a significantly higher barrier to rotation, attributable to the increased double-bond character of the N-C(S) bond.

Original language	English (US)
Pages (from-to)	1907-1911
Number of pages	5
Journal	Organometallics
Volume	26
Issue number	8
DOIs	https://doi.org/10.1021/om0611150
State	Published - Apr 9 2007

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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10.1021/om0611150

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title = "Studies on the condensation pathway to and properties of diiron azadithiolate carbonyls",

abstract = "Reaction of Fe2(SH)2(CO)6 and HCHO, which gives Fe2[(SCH2)2NH](CO)6 in the presence of NH3, affords the possible intermediate Fe 2(SCH2OH)2(CO)6, which has been characterized crystallographically as its axial-equatorial isomer. Fe 2(SCH2OH)2(CO)6 was shown to react with ammonia and amines to give Fe2[(SCH2) 2NR](CO)6 (R = H, alkyl). Related hemithioacetal intermediates were generated by treatment of Fe2(SH) 2(CO)6 with RC(O)C(O)R (R = H, Ph, 4-F-C6H 4) to give cycloadducts. The benzil derivative Fe2[S 2C2(OH)2Ph2](CO)6, a C2-symmetric species, was also characterized crystallographically. The acylated azadithiolate Fe2[(SCH2)2NAc](CO) 6 was prepared by reaction of Li2Fe2S 2(CO)6 with (ClCH2)2NC(O)Me. DNMR experiments show that the free energies of activation for rotation of the amide bond are the same for Fe2[(SCH2)2NAc](CO) 6 and Fe2[(SCH2)2NAc](CO) 4(PMe3)2, which implies that the ligands on the iron centers do not strongly affect the basicity of the nitrogen. As a control, we showed that the thioamide Fe2[(SCH2) 2NC(S)Me](CO)6 does exhibit a significantly higher barrier to rotation, attributable to the increased double-bond character of the N-C(S) bond.",

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N2 - Reaction of Fe2(SH)2(CO)6 and HCHO, which gives Fe2[(SCH2)2NH](CO)6 in the presence of NH3, affords the possible intermediate Fe 2(SCH2OH)2(CO)6, which has been characterized crystallographically as its axial-equatorial isomer. Fe 2(SCH2OH)2(CO)6 was shown to react with ammonia and amines to give Fe2[(SCH2) 2NR](CO)6 (R = H, alkyl). Related hemithioacetal intermediates were generated by treatment of Fe2(SH) 2(CO)6 with RC(O)C(O)R (R = H, Ph, 4-F-C6H 4) to give cycloadducts. The benzil derivative Fe2[S 2C2(OH)2Ph2](CO)6, a C2-symmetric species, was also characterized crystallographically. The acylated azadithiolate Fe2[(SCH2)2NAc](CO) 6 was prepared by reaction of Li2Fe2S 2(CO)6 with (ClCH2)2NC(O)Me. DNMR experiments show that the free energies of activation for rotation of the amide bond are the same for Fe2[(SCH2)2NAc](CO) 6 and Fe2[(SCH2)2NAc](CO) 4(PMe3)2, which implies that the ligands on the iron centers do not strongly affect the basicity of the nitrogen. As a control, we showed that the thioamide Fe2[(SCH2) 2NC(S)Me](CO)6 does exhibit a significantly higher barrier to rotation, attributable to the increased double-bond character of the N-C(S) bond.

AB - Reaction of Fe2(SH)2(CO)6 and HCHO, which gives Fe2[(SCH2)2NH](CO)6 in the presence of NH3, affords the possible intermediate Fe 2(SCH2OH)2(CO)6, which has been characterized crystallographically as its axial-equatorial isomer. Fe 2(SCH2OH)2(CO)6 was shown to react with ammonia and amines to give Fe2[(SCH2) 2NR](CO)6 (R = H, alkyl). Related hemithioacetal intermediates were generated by treatment of Fe2(SH) 2(CO)6 with RC(O)C(O)R (R = H, Ph, 4-F-C6H 4) to give cycloadducts. The benzil derivative Fe2[S 2C2(OH)2Ph2](CO)6, a C2-symmetric species, was also characterized crystallographically. The acylated azadithiolate Fe2[(SCH2)2NAc](CO) 6 was prepared by reaction of Li2Fe2S 2(CO)6 with (ClCH2)2NC(O)Me. DNMR experiments show that the free energies of activation for rotation of the amide bond are the same for Fe2[(SCH2)2NAc](CO) 6 and Fe2[(SCH2)2NAc](CO) 4(PMe3)2, which implies that the ligands on the iron centers do not strongly affect the basicity of the nitrogen. As a control, we showed that the thioamide Fe2[(SCH2) 2NC(S)Me](CO)6 does exhibit a significantly higher barrier to rotation, attributable to the increased double-bond character of the N-C(S) bond.

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Studies on the condensation pathway to and properties of diiron azadithiolate carbonyls

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