Electronic Structure Determination of Pyridine N-Heterocyclic Carbene Iron Dinitrogen Complexes and Neutral Ligand Derivatives

被引：36

作者：

Darmon, Jonathan M. ^{[1
]}

Yu, Renyuan Pony ^{[1
]}

Semproni, Scott P. ^{[1
]}

Turner, Zoe R. ^{[1
]}

Stieber, S. Chantal E. ^{[1
]}

DeBeer, Serena ^{[2
,3
]}

Chirik, Paul J. ^{[1
]}

机构：

[1] Princeton Univ, Dept Chem, Princeton, NJ 08544 USA

[2] Max Planck Inst Chem Energy Convers, D-45470 Mulheim, Germany

[3] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14835 USA

来源：

ORGANOMETALLICS | 2014年 / 33卷 / 19期

基金：

美国国家科学基金会;

关键词：

DENSITY-FUNCTIONAL THEORY; APPROXIMATE COULOMB POTENTIALS; RAY-ABSORPTION-SPECTROSCOPY; TRANSITION-METAL-COMPLEXES; PINCER DICARBENE COMPLEXES; ZETA VALENCE QUALITY; REDOX-ACTIVE LIGANDS; AUXILIARY BASIS-SETS; GAUSSIAN-BASIS SETS; BIS(IMINO)PYRIDINE IRON;

D O I：

10.1021/om500727t

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The electronic structures of pyridine N-heterocyclic dicarbene (iPrCNC) iron complexes have been studied by a combination of spectroscopic and computational methods. The goal of these studies was to determine if this chelate engages in radical chemistry in reduced base metal compounds. The iron dinitrogen example (iPrCNC)Fe(N-2)(2) and the related pyridine derivative (iPrCNC)Fe(DMAP)(N-2) were studied by NMR, Mossbauer, and X-ray absorption spectroscopy and are best described as redox non-innocent compounds with the iPrCNC chelate functioning as a classical ? acceptor and the iron being viewed as a hybrid between low-spin Fe(0) and Fe(II) oxidation states. This electronic description has been supported by spectroscopic data and DFT calculations. Addition of N,N-diallyl-tert-butylamine to (iPrCNC)Fe(N-2)(2) yielded the corresponding iron diene complex. Elucidation of the electronic structure again revealed the CNC chelate acting as a ? acceptor with no evidence for ligand-centered radicals. This ground state is in contrast with the case for the analogous bis(imino)pyridine iron complexes and may account for the lack of catalytic [2 pi + 2 pi] cycloaddition reactivity.

引用

页码：5423 / 5433

页数：11

共 78 条

[1]

[Anonymous], 1986, KAL TOOLS DISC VERS

[2]

[Anonymous], 2009, WMOSS4 MOSSBAUER SPE, P2009

[3] Arene coordination in bis(imino)pyridine iron complexes: Identification of catalyst deactivation pathways in iron-catalyzed hydrogenation and hydrosilation [J].

Archer, Andrew M. ;

Bouwkamp, Marco W. ;

Cortez, Maria-Patricia ;

Lobkovsky, Emil ;

Chirik, Paul J. .

ORGANOMETALLICS, 2006, 25 (18) :4269-4278

[4] High-Selectivity Bis(imino)pyridine Iron Catalysts for the Hydrosilylation of 1,2,4-Trivinylcyclohexane [J].

Atienza, Crisita Carmen Hojilla ;

Tondreau, Aaron M. ;

Weller, Keith J. ;

Lewis, Kenrick M. ;

Cruse, Richard W. ;

Nye, Susan A. ;

Boyer, Julie L. ;

Delis, Johannes G. P. ;

Chirik, Paul J. .

ACS CATALYSIS, 2012, 2 (10) :2169-2172

[5] Preparation and molecular and electronic structures of iron(0) dinitrogen and silane complexes and their application to catalytic hydrogenation and hydrosilation [J].

Bart, SC ;

Lobkovsky, E ;

Chirik, PJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2004, 126 (42) :13794-13807

[6] Neutral-ligand complexes of bis(imino)pyridine iron: Synthesis, structure, and spectroscopy [J].

Bart, Suzanne C. ;

Lobkovsky, Emil ;

Bill, Eckhard ;

Wieghardt, Karl ;

Chirik, Paul J. .

INORGANIC CHEMISTRY, 2007, 46 (17) :7055-7063

[7] Electronic structure of bis(imino)pyridine iron dichloride, monochloride, and neutral ligand complexes: A combined structural, spectroscopic, and computational study [J].

Bart, Suzanne C. ;

Chlopek, Krzysztof ;

Bill, Eckhard ;

Bouwkamp, Marco W. ;

Lobkovsky, Emil ;

Neese, Frank ;

Wieghardt, Karl ;

Chirik, Paul J. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (42) :13901-13912

[8] Recent Advances in Iron Catalysis in Organic Synthesis [J].

Bauer, Eike B. .

CURRENT ORGANIC CHEMISTRY, 2008, 12 (16) :1341-1369

[9] DENSITY FUNCTIONAL CALCULATIONS OF MOLECULAR-BOND ENERGIES [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1986, 84 (08) :4524-4529

[10] DENSITY-FUNCTIONAL THERMOCHEMISTRY .3. THE ROLE OF EXACT EXCHANGE [J].

BECKE, AD .

JOURNAL OF CHEMICAL PHYSICS, 1993, 98 (07) :5648-5652

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