Dinitrogen silylation and cleavage with a hafnocene complex

Scott P. Semproni; Emil Lobkovsky; Paul J. Chirik

doi:10.1021/ja2042595

Dinitrogen silylation and cleavage with a hafnocene complex

Scott P. Semproni, Emil Lobkovsky, Paul J. Chirik

Chemistry

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

62 Scopus citations

Abstract

Silylation of a hafnocene complex containing a strongly activated dinitrogen ligand, [(η⁵-C₅H₂-1,2,4-Me ₃)₂Hf]₂(μ₂,η², η²-N₂), by addition of CySiH₃ resulted in N-Si and Hf-H bond formation and a compound poised for subsequent N₂ cleavage. Warming the silane addition product to 75 ° triggered N-N scission, for which the requisite electrons were provided by silyl migration. Dinitrogen cleavage coupled to N-C bond formation was also accomplished by carbonylation of the silylated product, yielding an unprecedented μ-formamidide ([NC(H)O]^2-) ligand. Subsequent treatment with HCl yielded free formamide, demonstrating that an important organic molecule can be synthesized from N₂, CO, an organosilane, and protons.

Original language	English (US)
Pages (from-to)	10406-10409
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	133
Issue number	27
DOIs	https://doi.org/10.1021/ja2042595
State	Published - Jul 13 2011

All Science Journal Classification (ASJC) codes

General Chemistry
Biochemistry
Catalysis
Colloid and Surface Chemistry

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title = "Dinitrogen silylation and cleavage with a hafnocene complex",

abstract = "Silylation of a hafnocene complex containing a strongly activated dinitrogen ligand, [(η5-C5H2-1,2,4-Me 3)2Hf]2(μ2,η2, η2-N2), by addition of CySiH3 resulted in N-Si and Hf-H bond formation and a compound poised for subsequent N2 cleavage. Warming the silane addition product to 75 ° triggered N-N scission, for which the requisite electrons were provided by silyl migration. Dinitrogen cleavage coupled to N-C bond formation was also accomplished by carbonylation of the silylated product, yielding an unprecedented μ-formamidide ([NC(H)O]2-) ligand. Subsequent treatment with HCl yielded free formamide, demonstrating that an important organic molecule can be synthesized from N2, CO, an organosilane, and protons.",

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T1 - Dinitrogen silylation and cleavage with a hafnocene complex

AU - Semproni, Scott P.

AU - Lobkovsky, Emil

AU - Chirik, Paul J.

PY - 2011/7/13

Y1 - 2011/7/13

N2 - Silylation of a hafnocene complex containing a strongly activated dinitrogen ligand, [(η5-C5H2-1,2,4-Me 3)2Hf]2(μ2,η2, η2-N2), by addition of CySiH3 resulted in N-Si and Hf-H bond formation and a compound poised for subsequent N2 cleavage. Warming the silane addition product to 75 ° triggered N-N scission, for which the requisite electrons were provided by silyl migration. Dinitrogen cleavage coupled to N-C bond formation was also accomplished by carbonylation of the silylated product, yielding an unprecedented μ-formamidide ([NC(H)O]2-) ligand. Subsequent treatment with HCl yielded free formamide, demonstrating that an important organic molecule can be synthesized from N2, CO, an organosilane, and protons.

AB - Silylation of a hafnocene complex containing a strongly activated dinitrogen ligand, [(η5-C5H2-1,2,4-Me 3)2Hf]2(μ2,η2, η2-N2), by addition of CySiH3 resulted in N-Si and Hf-H bond formation and a compound poised for subsequent N2 cleavage. Warming the silane addition product to 75 ° triggered N-N scission, for which the requisite electrons were provided by silyl migration. Dinitrogen cleavage coupled to N-C bond formation was also accomplished by carbonylation of the silylated product, yielding an unprecedented μ-formamidide ([NC(H)O]2-) ligand. Subsequent treatment with HCl yielded free formamide, demonstrating that an important organic molecule can be synthesized from N2, CO, an organosilane, and protons.

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Dinitrogen silylation and cleavage with a hafnocene complex

Abstract

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