Synthesis, Structure, and Hydrogenolysis of Pyridine Dicarbene Iron Dialkyl Complexes

Two methods for the synthesis of bis(imidazol-2-ylidene)pyridine iron dialkyl complexes, (CNC)Fe(CH2SiMe3)2, have been developed. The first route consists of addition of two equivalents of LiCH2SiMe3 to the iron dihalide complex, (CNC)FeBr2, while the second relies on addition of the free CNC ligand...

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Veröffentlicht in:Organometallics. - 1998. - 38(2019), 16 vom: 26. Aug., Seite 3159-3168
1. Verfasser: Rummelt, Stephan M (VerfasserIn)
Weitere Verfasser: Darmon, Jonathan M, Yu, Renyuan Pony, Viereck, Peter, Pabst, Tyler P, Turner, Zoë R, Margulieux, Grant W, Gu, Shunlin, Chirik, Paul J
Format: Online-Aufsatz
Sprache:English
Veröffentlicht: 2019
Zugriff auf das übergeordnete Werk:Organometallics
Schlagworte:Journal Article
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520 |a Two methods for the synthesis of bis(imidazol-2-ylidene)pyridine iron dialkyl complexes, (CNC)Fe(CH2SiMe3)2, have been developed. The first route consists of addition of two equivalents of LiCH2SiMe3 to the iron dihalide complex, (CNC)FeBr2, while the second relies on addition of the free CNC ligand to readily-prepared (py)2Fe(CH2SiMe3)2 (py = pyridine). With aryl-substituted CNC ligands, octahedral complexes of the type ( Ar CNC)Fe(CH2SiMe3)2(N2) ( Ar CNC = bis(arylimidazol-2-ylidene)pyridine) were isolated, where the dinitrogen ligand occupies the site trans to the pyridine of the CNC-chelate. In contrast, the alkyl-substituted variant, (tBuACNC)Fe(CH2SiMe3)2 (tBuACNC = 2,6-(tBu-imidazol-2-ylidene)2pyridine) was isolated as the five-coordinate compound lacking dinitrogen. Exposure of the ( Ar CNC)Fe(CH2SiMe3)2(N2) derivatives to an H2 atmosphere resulted in formation of the corresponding iron hydride complexes ( Ar CNC)FeH4. These compounds catalyzed hydrogen isotope exchange between the deuterated benzene solvent and H2, generating isotopologues and isotopomers of ( Ar CNC)Fe(H n )(D4-n ) (n = 0-4). When (3,5-Me2 MesCNC)Fe(CH2SiMe3)2(N2) (3,5-Me2 MesCNC = 2,6-(2,4,6-Me3-C6H2-imidazol-2-ylidene)2-3,5-Me2-pyridine) was treated successively with H2 and then N2, the corresponding reduced dinitrogen complex (3,5-Me2 MesCNC)Fe(N2)2 was isolated. The same product was also obtained following addition of pinacolborane to (3,5-Me2 MesCNC)Fe(CH2SiMe3)2(N2) 
650 4 |a Journal Article 
700 1 |a Darmon, Jonathan M  |e verfasserin  |4 aut 
700 1 |a Yu, Renyuan Pony  |e verfasserin  |4 aut 
700 1 |a Viereck, Peter  |e verfasserin  |4 aut 
700 1 |a Pabst, Tyler P  |e verfasserin  |4 aut 
700 1 |a Turner, Zoë R  |e verfasserin  |4 aut 
700 1 |a Margulieux, Grant W  |e verfasserin  |4 aut 
700 1 |a Gu, Shunlin  |e verfasserin  |4 aut 
700 1 |a Chirik, Paul J  |e verfasserin  |4 aut 
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773 1 8 |g volume:38  |g year:2019  |g number:16  |g day:26  |g month:08  |g pages:3159-3168 
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