期刊
ORGANOMETALLICS
卷 30, 期 16, 页码 4315-4319出版社
AMER CHEMICAL SOC
DOI: 10.1021/om2003859
关键词
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资金
- Harvard University
- NSF [CHE-0955885]
- Direct For Mathematical & Physical Scien
- Division Of Chemistry [0955885] Funding Source: National Science Foundation
The reactivity of the high-spin (S = 2) [((Mes)tpe)Fe(THF)][Li(THF)(4)] (1) complex ((Mes)tpe = tris-(mesitylpyrrolide)ethane) with isocyanide and CO substrates is explored. Reaction of 1 with excess (BuNC)-Bu-t forms a low-spin (S = 0), six-coordinate iron(H) species with three (BuNC)-Bu-t ligands bound to iron, producing a notable tautomerization of one of the pyrrolide units from N- to C-ligation to iron. Reaction of 1 with an atmosphere of CO also produces a new diamagnetic complex, wherein two molecules of CO are consecutively reductively coupled, driven by the two-electron oxidation and fragmentation of the tris(pyrrolide)ethane ligand. The product features a six-coordinate Fe(II) species bound to a dipyrromethene ligand (resulting from oxidative fragmentation of the (Mes)tpe ligand), an oxalylimino pyrrole fragment from pyrrole coupling to two molecules of CO. The reactions of 1 with (BuNC)-Bu-t and CO provide insight into how tautomerization of the tris(pyrrolide) ligand upon substrate binding initiates the contiguous reductive coupling of CO.
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