N-H cleavage: Vs. Werner complex formation: Reactivity of cationic group 14 tetrelenes towards amines

Dinh Cao Huan Do; Andrey V. Protchenko; M. Ángeles Fuentes; Jamie Hicks; Petra Vasko; Simon Aldridge

doi:10.1039/d0cc00875c

N-H cleavage: Vs. Werner complex formation: Reactivity of cationic group 14 tetrelenes towards amines

Dinh Cao Huan Do, Andrey V. Protchenko, M. Ángeles Fuentes, Jamie Hicks, Petra Vasko, Simon Aldridge^*

^*Corresponding author for this work

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

32 Citations (Scopus)

Abstract

β-Diketiminate ligands featuring backbone NMe₂ groups have been exploited to access a series of two-coordinate cations of the type [(N-nacnac)E]⁺ (E = Si, Ge, Sn), whose reactivity towards N-H bonds has been investigated. While the heavier group 14 systems react via simple adduct formation, N-H oxidative addition occurs for E = Si consistent with differences in E^II/E^IV redox potentials. The structurally characterized Ge/Sn adducts can be viewed as models for the corresponding (transient) Si systems [(N-nacnac)Si·(NH₂R)]⁺ (R = H, ^tBu)-which are potential intermediates in the formation of [(N-nacnac)Si(H)(NHR)]⁺via a proton-shuttling mechanism.

Original language	English
Pages (from-to)	4684-4687
Number of pages	4
Journal	Chemical Communications
Volume	56
Issue number	34
DOIs	https://doi.org/10.1039/d0cc00875c
Publication status	Published - 30 Apr 2020
Externally published	Yes

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title = "N-H cleavage: Vs. Werner complex formation: Reactivity of cationic group 14 tetrelenes towards amines",

abstract = "β-Diketiminate ligands featuring backbone NMe2 groups have been exploited to access a series of two-coordinate cations of the type [(N-nacnac)E]+ (E = Si, Ge, Sn), whose reactivity towards N-H bonds has been investigated. While the heavier group 14 systems react via simple adduct formation, N-H oxidative addition occurs for E = Si consistent with differences in EII/EIV redox potentials. The structurally characterized Ge/Sn adducts can be viewed as models for the corresponding (transient) Si systems [(N-nacnac)Si·(NH2R)]+ (R = H, tBu)-which are potential intermediates in the formation of [(N-nacnac)Si(H)(NHR)]+via a proton-shuttling mechanism.",

author = "Do, {Dinh Cao Huan} and Protchenko, {Andrey V.} and Fuentes, {M. {\'A}ngeles} and Jamie Hicks and Petra Vasko and Simon Aldridge",

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year = "2020",

month = apr,

day = "30",

doi = "10.1039/d0cc00875c",

language = "English",

volume = "56",

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journal = "Chemical Communications",

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T1 - N-H cleavage

T2 - Vs. Werner complex formation: Reactivity of cationic group 14 tetrelenes towards amines

AU - Do, Dinh Cao Huan

AU - Protchenko, Andrey V.

AU - Fuentes, M. Ángeles

AU - Hicks, Jamie

AU - Vasko, Petra

AU - Aldridge, Simon

PY - 2020/4/30

Y1 - 2020/4/30

N2 - β-Diketiminate ligands featuring backbone NMe2 groups have been exploited to access a series of two-coordinate cations of the type [(N-nacnac)E]+ (E = Si, Ge, Sn), whose reactivity towards N-H bonds has been investigated. While the heavier group 14 systems react via simple adduct formation, N-H oxidative addition occurs for E = Si consistent with differences in EII/EIV redox potentials. The structurally characterized Ge/Sn adducts can be viewed as models for the corresponding (transient) Si systems [(N-nacnac)Si·(NH2R)]+ (R = H, tBu)-which are potential intermediates in the formation of [(N-nacnac)Si(H)(NHR)]+via a proton-shuttling mechanism.

AB - β-Diketiminate ligands featuring backbone NMe2 groups have been exploited to access a series of two-coordinate cations of the type [(N-nacnac)E]+ (E = Si, Ge, Sn), whose reactivity towards N-H bonds has been investigated. While the heavier group 14 systems react via simple adduct formation, N-H oxidative addition occurs for E = Si consistent with differences in EII/EIV redox potentials. The structurally characterized Ge/Sn adducts can be viewed as models for the corresponding (transient) Si systems [(N-nacnac)Si·(NH2R)]+ (R = H, tBu)-which are potential intermediates in the formation of [(N-nacnac)Si(H)(NHR)]+via a proton-shuttling mechanism.

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U2 - 10.1039/d0cc00875c

DO - 10.1039/d0cc00875c

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SP - 4684

EP - 4687

JO - Chemical Communications

JF - Chemical Communications

IS - 34

ER -

N-H cleavage: Vs. Werner complex formation: Reactivity of cationic group 14 tetrelenes towards amines

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