N-N bond cleavage in diazoalkanes by a Bis(imino)pyridine iron complex

Sarah K. Russell; Emil Lobkovsky; Paul J. Chirik

doi:10.1021/ja8075132

N-N bond cleavage in diazoalkanes by a Bis(imino)pyridine iron complex

Sarah K. Russell, Emil Lobkovsky, Paul J. Chirik

Research output: Contribution to journal › Article › peer-review

52 Scopus citations

Abstract

Addition of monosubstituted diazoalkanes, N ₂CHR (R = Ph, p-Tolyl, ^tBu, Cy), to the bis(imino) pyridine iron dinitrogen complex, ( ^iPrPDI)Fe(N ₂)2, at 23 °C in benzene-d ₆ resulted in rapid cleavage of the N-N bond to yield the iron nitrile and imine complexes, ( ^iPrPDI)FeNCR and ( ^iPrPDI) FeHNCHR, respectively. Aryl azines were also cleaved with ( ^iPrPDI) Fe(N ₂) ₂ and yielded the same products. Mechanistic studies support a pathway involving initial formation of an iron alkylidene followed by rapid [4π + 2π] cycloaddition with another equivalent of diazoalkane. Subsequent rate-determining 1,3-hydrogen migration followed by retrocycloaddition yields the observed products.

Original language	English (US)
Pages (from-to)	36-37
Number of pages	2
Journal	Journal of the American Chemical Society
Volume	131
Issue number	1
DOIs	https://doi.org/10.1021/ja8075132
State	Published - Jan 14 2009
Externally published	Yes

All Science Journal Classification (ASJC) codes

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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10.1021/ja8075132

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title = "N-N bond cleavage in diazoalkanes by a Bis(imino)pyridine iron complex",

abstract = "Addition of monosubstituted diazoalkanes, N 2CHR (R = Ph, p-Tolyl, tBu, Cy), to the bis(imino) pyridine iron dinitrogen complex, ( iPrPDI)Fe(N 2)2, at 23 °C in benzene-d 6 resulted in rapid cleavage of the N-N bond to yield the iron nitrile and imine complexes, ( iPrPDI)FeNCR and ( iPrPDI) FeHNCHR, respectively. Aryl azines were also cleaved with ( iPrPDI) Fe(N 2) 2 and yielded the same products. Mechanistic studies support a pathway involving initial formation of an iron alkylidene followed by rapid [4π + 2π] cycloaddition with another equivalent of diazoalkane. Subsequent rate-determining 1,3-hydrogen migration followed by retrocycloaddition yields the observed products.",

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

year = "2009",

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doi = "10.1021/ja8075132",

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journal = "Journal of the American Chemical Society",

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T1 - N-N bond cleavage in diazoalkanes by a Bis(imino)pyridine iron complex

AU - Russell, Sarah K.

AU - Lobkovsky, Emil

AU - Chirik, Paul J.

PY - 2009/1/14

Y1 - 2009/1/14

N2 - Addition of monosubstituted diazoalkanes, N 2CHR (R = Ph, p-Tolyl, tBu, Cy), to the bis(imino) pyridine iron dinitrogen complex, ( iPrPDI)Fe(N 2)2, at 23 °C in benzene-d 6 resulted in rapid cleavage of the N-N bond to yield the iron nitrile and imine complexes, ( iPrPDI)FeNCR and ( iPrPDI) FeHNCHR, respectively. Aryl azines were also cleaved with ( iPrPDI) Fe(N 2) 2 and yielded the same products. Mechanistic studies support a pathway involving initial formation of an iron alkylidene followed by rapid [4π + 2π] cycloaddition with another equivalent of diazoalkane. Subsequent rate-determining 1,3-hydrogen migration followed by retrocycloaddition yields the observed products.

AB - Addition of monosubstituted diazoalkanes, N 2CHR (R = Ph, p-Tolyl, tBu, Cy), to the bis(imino) pyridine iron dinitrogen complex, ( iPrPDI)Fe(N 2)2, at 23 °C in benzene-d 6 resulted in rapid cleavage of the N-N bond to yield the iron nitrile and imine complexes, ( iPrPDI)FeNCR and ( iPrPDI) FeHNCHR, respectively. Aryl azines were also cleaved with ( iPrPDI) Fe(N 2) 2 and yielded the same products. Mechanistic studies support a pathway involving initial formation of an iron alkylidene followed by rapid [4π + 2π] cycloaddition with another equivalent of diazoalkane. Subsequent rate-determining 1,3-hydrogen migration followed by retrocycloaddition yields the observed products.

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N-N bond cleavage in diazoalkanes by a Bis(imino)pyridine iron complex

Abstract

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