Catalytic Silylation of Dinitrogen with a Dicobalt Complex

被引：150

作者：

Siedschlag, Randall B. ^{[1
]}

Bernales, Varinia ^{[1
,2
,3
]}

Vogiatzis, Konstantinos D. ^{[1
,2
,3
]}

Planas, Nora ^{[1
,2
,3
]}

Clouston, Laura J. ^{[1
]}

Bill, Eckhard ^{[4
]}

Gagliardi, Laura ^{[1
,2
,3
]}

Lu, Connie C. ^{[1
]}

机构：

[1] Univ Minnesota, Dept Chem, Minneapolis, MN 55455 USA

[2] Univ Minnesota, Inst Supercomp, Minneapolis, MN 55455 USA

[3] Univ Minnesota, Chem Theory Ctr, Minneapolis, MN 55455 USA

[4] Max Planck Inst Chem Energiekonvers, D-45470 Mulheim, Germany

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2015年 / 137卷 / 14期

基金：

美国国家科学基金会;

关键词：

MOLECULAR NITROGEN; MOLYBDENUM CENTER; IRON; COBALT; REDUCTION; AMMONIA; ACTIVATION; CONVERSION; FIXATION;

D O I：

10.1021/jacs.5b01445

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A dicobalt complex catalyzes N-2 silylation with Me3SiCl and KC8 under 1 atm N-2 at ambient temperature. Tris(trimethylsilyl)amine is formed with an initial turnover rate of 1 N(TMS)3/min, ultimately reaching a turnover number of similar to 200. The dicobalt species features a metal-metal interaction, which we postulate is important to its function. Although N-2 functionalization occurs at a single cobalt site, the second cobalt center modifies the electronics at the active site. Density functional calculations reveal that the Co-Co interaction evolves during the catalytic cycle: weakening upon N-2 binding, breaking with silylation of the metal-bound N-2 and reforming with expulsion of [N-2(SiMe3)(3)](-).

引用

页码：4638 / 4641

页数：4

共 33 条

[1]

AMATORE C, 1978, J ELECTROANAL CHEM, V86, P227, DOI 10.1016/0368-1874(78)87021-X

[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] A molybdenum complex bearing PNP-type pincer ligands leads to the catalytic reduction of dinitrogen into ammonia [J].

Arashiba, Kazuya ;

Miyake, Yoshihiro ;

Nishibayashi, Yoshiaki .

NATURE CHEMISTRY, 2011, 3 (02) :120-125

[4]

Belyi V. I., 1998, SILICON NITRIDE IN E

[5] Dinitrogen chemistry from trigonally coordinated iron and cobalt platforms [J].

Betley, TA ;

Peters, JC .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (36) :10782-10783

[6] Systematic Variation of Metal-Metal Bond Order in Metal-Chromium Complexes [J].

Clouston, Laura J. ;

Siedschlag, Randall B. ;

Rudd, P. Alex ;

Planas, Nora ;

Hu, Shuxian ;

Miller, Adam D. ;

Gagliardi, Laura ;

Lu, Connie C. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2013, 135 (35) :13142-13148

[7] Resolving Heterogeneity Problems and Impurity Artifacts in Operationally Homogeneous Transition Metal Catalysts [J].

Crabtree, Robert H. .

CHEMICAL REVIEWS, 2012, 112 (03) :1536-1554

[8] Cobalt-Dinitrogen Complexes with Weakened N-N Bonds [J].

Ding, Keying ;

Pierpont, Aaron W. ;

Brennessel, William W. ;

Lukat-Rodgers, Gudrun ;

Rodgers, Kenton R. ;

Cundari, Thomas R. ;

Bill, Eckhard ;

Holland, Patrick L. .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2009, 131 (27) :9471-+

[9] Multielectron Redox Activity Facilitated by Metal-Metal Interactions in Early/Late Heterobimetallics: Co/Zr Complexes Supported by Phosphinoamide Ligands [J].

Greenwood, Bennett P. ;

Forman, Scott I. ;

Rowe, Gerard T. ;

Chen, Chun-Hsing ;

Foxman, Bruce M. ;

Thomas, Christine M. .

INORGANIC CHEMISTRY, 2009, 48 (13) :6251-6260

[10] Homogeneous iron complexes for the conversion of dinitrogen into ammonia and hydrazine [J].

Hazari, Nilay .

CHEMICAL SOCIETY REVIEWS, 2010, 39 (11) :4044-4056

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