(C5Me4H)1--based reduction of dinitrogen by the mixed ligand tris(polyalkylcyclopentadienyl) lutetium and yttrium complexes, (C5Me5)3-x(C5Me 4H)xLn

Thomas J. Mueller; Megan E. Fieser; Joseph W. Ziller; William J. Evans

doi:10.1039/c1sc00139f

(C₅Me₄H)^1--based reduction of dinitrogen by the mixed ligand tris(polyalkylcyclopentadienyl) lutetium and yttrium complexes, (C₅Me₅)_3-x(C₅Me ₄H)_xLn

Thomas J. Mueller, Megan E. Fieser, Joseph W. Ziller, William J. Evans

Chemistry (Twin Cities)

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Abstract

Synthesis of the mixed ligand complexes (C₅Me ₅)(C₅Me₄H)₂Ln (Ln = Lu, Y) for comparison with (C₅Me₅)₂(C₅Me ₄H)Ln to evaluate details of steric effects on reductive reactivity has revealed that (C₅Me₅)_3-x(C ₅Me₄H)_xLn complexes can reduce dinitrogen to (NN)^2-. (C₅Me₅)(C₅Me ₄H)₂Lu reacts with N₂ to form [(C ₅Me₅)(C₅Me₄H)Lu]₂(μ- η²:η²-N₂), (C₅Me ₅)₂(C₅Me₄H)Y reduces N₂ to [(C₅Me₅)₂Y]₂(μ- η²:η²-N₂), and (C₅Me ₄H)₃Sc converts N₂ to [(C₅Me ₄H)₂Sc]₂(μ-η²: η²-N₂). Exclusive (C₅Me₄H) ^1- loss occurs in each case with formation of (C₅Me ₄H)₂ as the byproduct. (C₅Me₅) ₂, the signature byproduct of sterically induced reduction reactions, is not observed. Since these complexes do not exhibit unusual steric parameters and since the more crowded (C₅Me₅)₂(C ₅Me₄H)Lu and (C₅Me₅)₃Y do not display analogous reactivity, these reactions do not appear to be sterically induced reductions and suggest a new type of ligand-based reduction pathway involving (C₅Me₄H)^1-.

Original language	English (US)
Pages (from-to)	1992-1996
Number of pages	5
Journal	Chemical Science
Volume	2
Issue number	10
DOIs	https://doi.org/10.1039/c1sc00139f
State	Published - Oct 2011

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title = "(C5Me4H)1--based reduction of dinitrogen by the mixed ligand tris(polyalkylcyclopentadienyl) lutetium and yttrium complexes, (C5Me5)3-x(C5Me 4H)xLn",

abstract = "Synthesis of the mixed ligand complexes (C5Me 5)(C5Me4H)2Ln (Ln = Lu, Y) for comparison with (C5Me5)2(C5Me 4H)Ln to evaluate details of steric effects on reductive reactivity has revealed that (C5Me5)3-x(C 5Me4H)xLn complexes can reduce dinitrogen to (NN)2-. (C5Me5)(C5Me 4H)2Lu reacts with N2 to form [(C 5Me5)(C5Me4H)Lu]2(μ- η2:η2-N2), (C5Me 5)2(C5Me4H)Y reduces N2 to [(C5Me5)2Y]2(μ- η2:η2-N2), and (C5Me 4H)3Sc converts N2 to [(C5Me 4H)2Sc]2(μ-η2: η2-N2). Exclusive (C5Me4H) 1- loss occurs in each case with formation of (C5Me 4H)2 as the byproduct. (C5Me5) 2, the signature byproduct of sterically induced reduction reactions, is not observed. Since these complexes do not exhibit unusual steric parameters and since the more crowded (C5Me5)2(C 5Me4H)Lu and (C5Me5)3Y do not display analogous reactivity, these reactions do not appear to be sterically induced reductions and suggest a new type of ligand-based reduction pathway involving (C5Me4H)1-.",

author = "Mueller, {Thomas J.} and Fieser, {Megan E.} and Ziller, {Joseph W.} and Evans, {William J.}",

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AU - Mueller, Thomas J.

AU - Fieser, Megan E.

AU - Ziller, Joseph W.

AU - Evans, William J.

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N2 - Synthesis of the mixed ligand complexes (C5Me 5)(C5Me4H)2Ln (Ln = Lu, Y) for comparison with (C5Me5)2(C5Me 4H)Ln to evaluate details of steric effects on reductive reactivity has revealed that (C5Me5)3-x(C 5Me4H)xLn complexes can reduce dinitrogen to (NN)2-. (C5Me5)(C5Me 4H)2Lu reacts with N2 to form [(C 5Me5)(C5Me4H)Lu]2(μ- η2:η2-N2), (C5Me 5)2(C5Me4H)Y reduces N2 to [(C5Me5)2Y]2(μ- η2:η2-N2), and (C5Me 4H)3Sc converts N2 to [(C5Me 4H)2Sc]2(μ-η2: η2-N2). Exclusive (C5Me4H) 1- loss occurs in each case with formation of (C5Me 4H)2 as the byproduct. (C5Me5) 2, the signature byproduct of sterically induced reduction reactions, is not observed. Since these complexes do not exhibit unusual steric parameters and since the more crowded (C5Me5)2(C 5Me4H)Lu and (C5Me5)3Y do not display analogous reactivity, these reactions do not appear to be sterically induced reductions and suggest a new type of ligand-based reduction pathway involving (C5Me4H)1-.

AB - Synthesis of the mixed ligand complexes (C5Me 5)(C5Me4H)2Ln (Ln = Lu, Y) for comparison with (C5Me5)2(C5Me 4H)Ln to evaluate details of steric effects on reductive reactivity has revealed that (C5Me5)3-x(C 5Me4H)xLn complexes can reduce dinitrogen to (NN)2-. (C5Me5)(C5Me 4H)2Lu reacts with N2 to form [(C 5Me5)(C5Me4H)Lu]2(μ- η2:η2-N2), (C5Me 5)2(C5Me4H)Y reduces N2 to [(C5Me5)2Y]2(μ- η2:η2-N2), and (C5Me 4H)3Sc converts N2 to [(C5Me 4H)2Sc]2(μ-η2: η2-N2). Exclusive (C5Me4H) 1- loss occurs in each case with formation of (C5Me 4H)2 as the byproduct. (C5Me5) 2, the signature byproduct of sterically induced reduction reactions, is not observed. Since these complexes do not exhibit unusual steric parameters and since the more crowded (C5Me5)2(C 5Me4H)Lu and (C5Me5)3Y do not display analogous reactivity, these reactions do not appear to be sterically induced reductions and suggest a new type of ligand-based reduction pathway involving (C5Me4H)1-.

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(C₅Me₄H)^1--based reduction of dinitrogen by the mixed ligand tris(polyalkylcyclopentadienyl) lutetium and yttrium complexes, (C₅Me₅)_3-x(C₅Me ₄H)_xLn

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