Zirconium-Nitrogen Intermolecular Frustrated Lewis Pairs

被引：17

作者：

Hamilton, Hugh B. ^{[1
]}

King, Ashley M. ^{[1
]}

Sparkes, Hazel A. ^{[1
]}

Pridmore, Natalie E. ^{[1
]}

Wass, Duncan F. ^{[2
]}

机构：

[1] Univ Bristol, Sch Chem, Cantocks Close, Bristol BS8 1TS, Avon, England

[2] Cardiff Univ, Sch Chem, Cardiff Catalysis Inst, Main Bldg,Pk Pl, Cardiff CF10 3AT, S Glam, Wales

来源：

INORGANIC CHEMISTRY | 2019年 / 58卷 / 09期

基金：

英国工程与自然科学研究理事会;

关键词：

HYDROGEN ACTIVATION; CHEMISTRY; REACTIVITY; POLYMERIZATION; BEHAVIOR; BASE; ACID; CO2;

D O I：

10.1021/acs.inorgchem.9b00569

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A series of intermolecular transition metal frustrated Lewis pairs (FLPs) based on zirconocene alkoxide complexes ([Cp2Zr(OMes)](+) 1 or ([Cp*Zr-2(OMes)](+)2) with nitrogen Lewis bases (NEt3, (NEtPr2)-Pr-i, pyridine, 2-methylpyridine, 2,6-lutidine) are reported. The interaction between Zr and N depends on the specific derivatives used, in general more sterically encumbered pairs leading to a more frustrated interaction; however, DOSY NMR spectroscopy reveals these interactions to be dynamic in nature. The pairs with various amine bases undergo typical FLP-type reactivity with D-2, CO2, THF, and PhCCD. The catalytic dehydrocoupling of Me2NH center dot BH3 is also reported. Comparisons can be made with previous work employing phosphines as Lewis bases suggesting that hard-hard or hard-soft acid-base considerations are of little importance compared to the more prominent roles of steric bulk and basicity.

引用

页码：6399 / 6409

页数：11

共 42 条

[1] Heterolytic activation of hydrogen using frustrated Lewis pairs containing tris(2,2′,2"-perfluorobiphenyl)borane [J].

Binding, Samantha C. ;

Zaher, Hasna ;

Chadwick, F. Mark ;

O'Hare, Dermot .

DALTON TRANSACTIONS, 2012, 41 (30) :9061-9066

[2] PHOSPHINE BASICITIES AS DETERMINED BY ENTHALPIES OF PROTONATION [J].

BUSH, RC ;

ANGELICI, RJ .

INORGANIC CHEMISTRY, 1988, 27 (04) :681-686

[3] Cationic Group 4 Metallocene-(o-Phosphanylaryl)oxido Complexes: Synthetic Routes to Transition-Metal Frustrated Lewis Pairs [J].

Chapman, Andy M. ;

Haddow, Mairi F. ;

Wass, Duncan F. .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2012, (09) :1546-1554

[4] Frustrated Lewis Pairs beyond the Main Group: Synthesis, Reactivity, and Small Molecule Activation with Cationic Zirconocene-Phosphinoaryloxide Complexes [J].

Chapman, Andy M. ;

Haddow, Mairi F. ;

Wass, Duncan F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (45) :18463-18478

[5] Frustrated Lewis Pairs beyond the Main Group: Cationic Zirconocene-Phosphinoaryloxide Complexes and Their Application in Catalytic Dehydrogenation of Amine Boranes [J].

Chapman, Andy M. ;

Haddow, Maki F. ;

Wass, Duncan F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2011, 133 (23) :8826-8829

[6] Metal-Free sp2-C-H Borylation as a Common Reactivity Pattern of Frustrated 2-Aminophenylboranes [J].

Chernichenko, Konstantin ;

Lindqvist, Markus ;

Kotai, Bianka ;

Nieger, Martin ;

Sorochkina, Kristina ;

Papai, Imre ;

Repo, Timo .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2016, 138 (14) :4860-4868

[7] Intramolecular Frustrated Lewis Pair with the Smallest Boryl Site: Reversible H2 Addition and Kinetic Analysis [J].

Chernichenko, Konstantin ;

Kotai, Bianka ;

Papai, Imre ;

Zhivonitko, Vladimir ;

Nieger, Martin ;

Leskela, Markku ;

Repo, Timo .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (06) :1749-1753

[8] Hydrogen activation by 2-boryl-N,N-dialkylanilines: a revision of Piers' ansa-aminoborane [J].

Chernichenko, Konstantin ;

Nieger, Martin ;

Leskela, Markku ;

Repo, Timo .

DALTON TRANSACTIONS, 2012, 41 (30) :9029-9032

[9] N-Methylacridinium Salts: Carbon Lewis Acids in Frustrated Lewis Pairs for σ-Bond Activation and Catalytic Reductions [J].

Clark, Ewan R. ;

Ingleson, Michael J. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2014, 53 (42) :11306-11309

[10]

Clarke K., 1960, J. Chem. Soc., P1885

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