An experimental and theoretical study of a heptacoordinated tungsten(VI) complex of a noninnocent phenylenediamine bis(phenolate) ligand

被引：8

作者：

Hossain, Md Kamal ^{[1
,2
]}

Haukka, Matti ^{[3
]}

Hanninen, Mikko M. ^{[3
]}

Lisensky, George C. ^{[4
]}

Paturi, Petriina ^{[5
]}

Nordlander, Ebbe ^{[1
]}

Lehtonen, Ari ^{[6
]}

机构：

[1] Lund Univ, Dept Chem, Chem Phys, Inorgan Chem Res Grp, Box 124, SE-22100 Lund, Sweden

[2] Jahangirnagar Univ, Dept Chem, Dhaka 1342, Bangladesh

[3] Univ Jyvaskyla, Dept Chem, Jyvaskyla, Finland

[4] Beloit Coll, Dept Chem, Beloit, WI 53511 USA

[5] Univ Turku, Dept Phys & Astron, Turku 20014, Finland

[6] Univ Turku, Dept Chem, Lab Mat Chem & Chem Anal, Inorgan Mat Chem Res Grp, Turku 20014, Finland

来源：

INORGANIC CHEMISTRY COMMUNICATIONS | 2018年 / 93卷

关键词：

Tungsten; Oxidation states; Noninnocent ligand; Amidophenoxide radical; DFT calculations; Electronic structure; ZETA VALENCE QUALITY; GAUSSIAN-BASIS SETS; OXIDATION-STATES; EPR SPECTROSCOPY; ATOMS LI; CHEMISTRY; KR;

D O I：

10.1016/j.inoche.2018.05.023

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

W(N2O2)(HN2O2)] (H4N2O2 = N,N'-bis(3,5-di-tert-butyl-2-hydroxyphenyl)-1,2-phenylenediamine) with a noninnocent ligand was formed by reaction of the alkoxide precursor [W(eg)(3)] (eg = the 1,2-ethanediolate dianion) with two equivalents of ligand. The phenol groups on one of the ligands are completely deprotonated and the ligand coordinates in a tetradentate fashion, whereas the other ligand is tridentate with one phenol having an intact OH group. The molecular structure, magnetic measurements, EPR spectroscopy, and density functional theory calculations indicate that the complex is a stable radical with the odd electron situated on the tridentate amidophenoxide ligand. The formal oxidation state of the metal center is W(VI), with the paramagnetic properties being due to the unpaired electron on the ligand.

引用

页码：149 / 152

页数：4

共 23 条

[1] The bioinorganic chemistry of tungsten [J].

Bevers, Loes E. ;

Hagedoorn, Peter-Leon ;

Hagen, Wilfred R. .

COORDINATION CHEMISTRY REVIEWS, 2009, 253 (3-4) :269-290

[2] Catalytic reactivity of a zirconium(IV) redox-active ligand complex with 1,2-diphenylhydrazine [J].

Blackmore, Karen J. ;

Lal, Neetu ;

Ziller, Joseph W. ;

Heyduk, Alan F. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (09) :2728-+

[3] Group IV Coordination Chemistry of a Tetradentate Redox-Active Ligand in Two Oxidation States [J].

Blackmore, Karen J. ;

Lal, Neetu ;

Ziller, Joseph W. ;

Heyduk, Alan F. .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2009, (06) :735-743

[4] Metrical Oxidation States of 2-Amidophenoxide and Catecholate Ligands: Structural Signatures of Metal-Ligand π Bonding in Potentially Noninnocent Ligands [J].

Brown, Seth N. .

INORGANIC CHEMISTRY, 2012, 51 (03) :1251-1260

[5] Aerobic oxidation of primary alcohols (including methanol) by copper(II)- and zinc(II)-phenoxyl radical catalysts [J].

Chaudhuri, P ;

Hess, M ;

Müller, J ;

Hildenbrand, K ;

Bill, E ;

Weyhermüller, T ;

Wieghardt, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (41) :9599-9610

[6] Electronic structure of bis(o-iminobenzosemiquinonato)metal complexes (Cu, Ni, Pd).: The art of establishing physical oxidation states in transition-metal complexes containing radical ligands [J].

Chaudhuri, P ;

Verani, CN ;

Bill, E ;

Bothe, E ;

Weyhermüller, T ;

Wieghardt, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (10) :2213-2223

[7] A new octacoordinated tin complex with tetradentate redox-active ligands [J].

Cherkasov, V. K. ;

Piskunov, A. V. ;

Trofimova, O. Yu ;

Smolyaninov, I. V. ;

Fukin, G. K. .

DOKLADY CHEMISTRY, 2013, 448 :61-65

[8] EPR Spectroscopy as a Tool in Homogeneous Catalysis Research [J].

Goswami, Monalisa ;

Chirila, Andrei ;

Rebreyend, Christophe ;

de Bruin, Bas .

TOPICS IN CATALYSIS, 2015, 58 (12-13) :719-750

[9] Heptacoordinated Molybdenum(VI) Complexes of Phenylenediamine Bis(phenolate): A Stable Molybdenum Amidophenoxide Radical [J].

Hanninen, Mikko M. ;

Paturi, Petriina ;

Tuononen, Heikki M. ;

Sillanpaa, Reijo ;

Lehtonen, Ari .

INORGANIC CHEMISTRY, 2013, 52 (10) :5714-5721

[10] Manifestations of Noninnocent Ligand Behavior [J].

Kaim, Wolfgang .

INORGANIC CHEMISTRY, 2011, 50 (20) :9752-9765

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