Synthesis of aryl-substituted bis(imino) pyridine iron dinitrogen complexes

Sarah K. Russell; Jonathan M. Darmon; Emil Lobkovsky; Paul J. Chirik

doi:10.1021/ic902162z

Synthesis of aryl-substituted bis(imino) pyridine iron dinitrogen complexes

Sarah K. Russell, Jonathan M. Darmon, Emil Lobkovsky, Paul J. Chirik

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Abstract

The synthesis and characterization of dimeric, aryl-substituted bis(imino)pyridine iron dinitrogen complexes is described. In contrast to reduction with sodium amalgam where bis(chelate) iron compounds were isolated, stirring (^ArPDI)FeBr₂ or (^MeBPDI)FeBr ₂ (PDI = 2,6-(ArN=CMe)₂C₅H₃N; Ar = 2,6-Et₂-C₆H₃N (^EtPDI), 2,6-Me ₂-C₆H₃N (^MePDI), 2- ⁱPr,6-Me-C₆H₃N (^Me,iPrPDI); ^MeBPDI = 2,6-(2,6-Me₂-C₆H₃N=CPh) ₂C₅H₃N) with sodium naphthalenide resulted in isolation of the desired iron dinitrogen compounds as diamagnetic solids. Two examples, [(^EtPDI)Fe(N₂)]₂(μ₂- N₂) and [(^MeBPDI)Fe(N₂)] ₂(μ₂-N₂), were characterized by X-ray diffraction. The solid state metrical parameters, in combination with infrared and Mössbauer spectroscopic data, establish ferrous compounds with doubly reduced chelates. Each new bis(imino)pyridine iron dinitrogen compound was screened for the catalytic hydrogenation of ethyl-3-methylbut-2-enoate, and the compound bearing the smallest aryl substituent, [(^MePDI)Fe(N ₂)]₂(μ₂-N₂), offers significant improvement over the original (^iPrPDI)Fe(N₂)₂ pre-catalyst and is one of the most active iron pre-catalysts known.

Original language	English (US)
Pages (from-to)	2782-2792
Number of pages	11
Journal	Inorganic Chemistry
Volume	49
Issue number	6
DOIs	https://doi.org/10.1021/ic902162z
State	Published - Mar 15 2010
Externally published	Yes

All Science Journal Classification (ASJC) codes

Inorganic Chemistry
Physical and Theoretical Chemistry

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10.1021/ic902162z

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@article{651b2bc166004f8ba5c0b8b228d05455,

title = "Synthesis of aryl-substituted bis(imino) pyridine iron dinitrogen complexes",

abstract = "The synthesis and characterization of dimeric, aryl-substituted bis(imino)pyridine iron dinitrogen complexes is described. In contrast to reduction with sodium amalgam where bis(chelate) iron compounds were isolated, stirring (ArPDI)FeBr2 or (MeBPDI)FeBr 2 (PDI = 2,6-(ArN=CMe)2C5H3N; Ar = 2,6-Et2-C6H3N (EtPDI), 2,6-Me 2-C6H3N (MePDI), 2- iPr,6-Me-C6H3N (Me,iPrPDI); MeBPDI = 2,6-(2,6-Me2-C6H3N=CPh) 2C5H3N) with sodium naphthalenide resulted in isolation of the desired iron dinitrogen compounds as diamagnetic solids. Two examples, [(EtPDI)Fe(N2)]2(μ2- N2) and [(MeBPDI)Fe(N2)] 2(μ2-N2), were characterized by X-ray diffraction. The solid state metrical parameters, in combination with infrared and M{\"o}ssbauer spectroscopic data, establish ferrous compounds with doubly reduced chelates. Each new bis(imino)pyridine iron dinitrogen compound was screened for the catalytic hydrogenation of ethyl-3-methylbut-2-enoate, and the compound bearing the smallest aryl substituent, [(MePDI)Fe(N 2)]2(μ2-N2), offers significant improvement over the original (iPrPDI)Fe(N2)2 pre-catalyst and is one of the most active iron pre-catalysts known.",

author = "Russell, {Sarah K.} and Darmon, {Jonathan M.} and Emil Lobkovsky and Chirik, {Paul J.}",

year = "2010",

month = mar,

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doi = "10.1021/ic902162z",

language = "English (US)",

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journal = "Inorganic Chemistry",

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TY - JOUR

T1 - Synthesis of aryl-substituted bis(imino) pyridine iron dinitrogen complexes

AU - Russell, Sarah K.

AU - Darmon, Jonathan M.

AU - Lobkovsky, Emil

AU - Chirik, Paul J.

PY - 2010/3/15

Y1 - 2010/3/15

N2 - The synthesis and characterization of dimeric, aryl-substituted bis(imino)pyridine iron dinitrogen complexes is described. In contrast to reduction with sodium amalgam where bis(chelate) iron compounds were isolated, stirring (ArPDI)FeBr2 or (MeBPDI)FeBr 2 (PDI = 2,6-(ArN=CMe)2C5H3N; Ar = 2,6-Et2-C6H3N (EtPDI), 2,6-Me 2-C6H3N (MePDI), 2- iPr,6-Me-C6H3N (Me,iPrPDI); MeBPDI = 2,6-(2,6-Me2-C6H3N=CPh) 2C5H3N) with sodium naphthalenide resulted in isolation of the desired iron dinitrogen compounds as diamagnetic solids. Two examples, [(EtPDI)Fe(N2)]2(μ2- N2) and [(MeBPDI)Fe(N2)] 2(μ2-N2), were characterized by X-ray diffraction. The solid state metrical parameters, in combination with infrared and Mössbauer spectroscopic data, establish ferrous compounds with doubly reduced chelates. Each new bis(imino)pyridine iron dinitrogen compound was screened for the catalytic hydrogenation of ethyl-3-methylbut-2-enoate, and the compound bearing the smallest aryl substituent, [(MePDI)Fe(N 2)]2(μ2-N2), offers significant improvement over the original (iPrPDI)Fe(N2)2 pre-catalyst and is one of the most active iron pre-catalysts known.

AB - The synthesis and characterization of dimeric, aryl-substituted bis(imino)pyridine iron dinitrogen complexes is described. In contrast to reduction with sodium amalgam where bis(chelate) iron compounds were isolated, stirring (ArPDI)FeBr2 or (MeBPDI)FeBr 2 (PDI = 2,6-(ArN=CMe)2C5H3N; Ar = 2,6-Et2-C6H3N (EtPDI), 2,6-Me 2-C6H3N (MePDI), 2- iPr,6-Me-C6H3N (Me,iPrPDI); MeBPDI = 2,6-(2,6-Me2-C6H3N=CPh) 2C5H3N) with sodium naphthalenide resulted in isolation of the desired iron dinitrogen compounds as diamagnetic solids. Two examples, [(EtPDI)Fe(N2)]2(μ2- N2) and [(MeBPDI)Fe(N2)] 2(μ2-N2), were characterized by X-ray diffraction. The solid state metrical parameters, in combination with infrared and Mössbauer spectroscopic data, establish ferrous compounds with doubly reduced chelates. Each new bis(imino)pyridine iron dinitrogen compound was screened for the catalytic hydrogenation of ethyl-3-methylbut-2-enoate, and the compound bearing the smallest aryl substituent, [(MePDI)Fe(N 2)]2(μ2-N2), offers significant improvement over the original (iPrPDI)Fe(N2)2 pre-catalyst and is one of the most active iron pre-catalysts known.

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DO - 10.1021/ic902162z

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EP - 2792

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 6

ER -

Synthesis of aryl-substituted bis(imino) pyridine iron dinitrogen complexes

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