Single Electron Transfer to Diazomethane-Borane Adducts Prompts C-H Bond Activations

被引：21

作者：

Cao, Levy L. ^{[1
]}

Zhou, Jiliang ^{[1
]}

Qu, Zheng-Wang ^{[2
]}

Stephan, Douglas W. ^{[1
]}

机构：

[1] Univ Toronto, Dept Chem, 80 St George St, Toronto, ON M5S 3H6, Canada

[2] Rheinische Friedrich Wilhelms Univ Bonn, Inst Phys & Theoret Chem, Mulliken Ctr Theoret Chem, Beringstr 4, D-53115 Bonn, Germany

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2019年 / 58卷 / 51期

基金：

加拿大自然科学与工程研究理事会;

关键词：

borane; DFT; diazomethane; one-electron reduction; radical anions; FRUSTRATED LEWIS PAIRS; ZETA-VALENCE QUALITY; AUXILIARY BASIS-SETS; CATALYTIC-REDUCTION; DINITROGEN FIXATION; NITROUS-OXIDE; MOLYBDENUM; CHEMISTRY; AMMONIA; BINDING;

D O I：

10.1002/anie.201912338

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

While (Ph2CN2)B(C6F5)(3) is unstable, single electron transfer from Cp*Co-2 affords the isolation of stable products [Cp*Co-2][Ph2CNNHB(C6F5)(3)] 1 and [Cp*Co(C5Me4CH2B(C6F5)(3))] 2. The analogous combination of Ph2CN2 and BPh3 showed no evidence of adduct formation and yet single electron transfer from Cp*Cr-2 affords the species [Cp*Cr-2][PhC(C6H4)NNBPh3] 3 and [Cp*Cr-2][Ph2CNNHBPh3] 4. Computations showed both reactions proceed via transient radical anions of the diphenyldiazomethane-borane adducts to effect C-H bond activations.

引用

页码：18487 / 18491

页数：5

共 91 条

[1] NITROGENOPENTAMMINERUTHENIUM(2) COMPLEXES [J].

ALLEN, AD ;

SENOFF, CV .

CHEMICAL COMMUNICATIONS, 1965, (24) :621-&

[2] Catalytic conversion of nitrogen to ammonia by an iron model complex [J].

Anderson, John S. ;

Rittle, Jonathan ;

Peters, Jonas C. .

NATURE, 2013, 501 (7465) :84-+

[3]

[Anonymous], 2004, ANGEW CHE

[4]

[Anonymous], 2013, ANGEW CHEM

[5]

[Anonymous], 2017, Angew. Chem

[6]

[Anonymous], 2017, Angew. Chem., Int. Ed

[7]

[Anonymous], 2018, TURBOMOLE VERSION 7

[8]

[Anonymous], 2018, ANGEW CHEM INT EDIT

[9]

[Anonymous], 2015, ANGEW CHEM

[10] TRIPHENYLPHOSPHINEAZINE PH3P=N-N=PPH3 [J].

APPEL, R ;

SCHOLLHORN, R .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 1964, 3 (12) :805-+

← 1 2 3 4 5 6 7 8 9 10 →