Metal-Metal Interactions in C3-Symmetric Diiron Imido Complexes Linked by Phosphinoamide Ligands

被引：50
|
作者：
Kuppuswamy, Subramaniam [1 ]
Powers, Tamara M. [2 ]
Johnson, Bruce M. [3 ]
Bezpalko, Mark W. [1 ]
Brozek, Carl K. [4 ]
Foxman, Bruce M. [1 ]
Berben, Louise A. [3 ]
Thomas, Christine M. [1 ]
机构：
[1] Brandeis Univ, Dept Chem, Waltham, MA 02454 USA
[2] Harvard Univ, Dept Chem & Chem Biol, Cambridge, MA 02139 USA
[3] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
[4] MIT, Dept Chem, Cambridge, MA 02139 USA
来源：
INORGANIC CHEMISTRY | 2013年 / 52卷 / 09期
关键词：
ELECTRONIC-STRUCTURE; BASIS-SETS; ATOM-TRANSFER; IRON; FE; SUSCEPTIBILITY; APPROXIMATION; ENVIRONMENTS; AMINATION; ENERGY;
D O I：
10.1021/ic302108k
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
The tris(phosphinoamide)-bridged (FeFeII)-Fe-II diiron complex Fe(mu-PrNPPh2)(3)Fe(eta(2)-(PrNPPh2)-Pr-i) (1) can be reduced in the absence or presence of PMe3 to generate the mixed valence (FeFeI)-Fe-II complexes Fe(mu-(PrNPPh2)-Pr-i)(3)Fe((PPh2NHPr)-Pr-i) (2) or Fe(mu-(PrNPPh2)-Pr-i)(3)Fe(PMe3) (3), respectively. Following a typical oxidative group transfer procedure, treatment of 2 or 3 with organic azides generates the mixed-valent (FeFeIII)-Fe-II imido complexes Fe((PrNPPh2)-Pr-i)(3)Fe NR (R = Bu-t (4), Ad (5), 2,4,6-trimethylphenyl (6)). These complexes represent the first examples of first-row bimetallic complexes featuring both metal-ligand multiple bonds and metal-metal bonds. The reduced complexes 2 and 3 and imido complexes 4-6 have been characterized via X-ray crystallography, Mossbauer spectroscopy, cyclic voltammetry, and SQUID magnetometry, and a theoretical description of the bonding within these diiron complexes has been obtained using computational methods. The effect of the metal-metal interaction on the electronic structure and bonding in diiron imido complexes 4-6 is discussed in the context of similar monometallic iron imido complexes.
引用
收藏
页码：4802 / 4811
页数：10
相关论文
共 50 条
  • [1] Metal-metal interactions in phosphinoamide-linked early/late heterobimetallic complexes
    Thomas, Christine M.
    Kuppuswamy, Subramaniam
    Napoline, J. Wesley
    Krogman, Jeremy
    Wu, Bing
    Evers-McGregor, Deirdra
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2013, 245
  • [2] Metal-metal multiple bonding in C3-symmetric bimetallic complexes of the first row transition metals
    Krogman, Jeremy P.
    Thomas, Christine M.
    CHEMICAL COMMUNICATIONS, 2014, 50 (40) : 5115 - 5127
  • [3] Metal-Metal Bonding in Low-Coordinate Dicobalt Complexes Supported by Phosphinoamide Ligands
    Mathialagan, Ramyaa
    Kuppuswamy, Subramaniam
    De Denko, Alexandra T.
    Bezpalko, Mark W.
    Foxman, Bruce M.
    Thomas, Christine M.
    INORGANIC CHEMISTRY, 2013, 52 (02) : 701 - 706
  • [4] Metal complexes incorporating C3-symmetric, phenol-based ligands.
    Gdula, RL
    Johnson, MJA
    ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2003, 225 : U152 - U152
  • [5] Multielectron Redox Activity Facilitated by Metal-Metal Interactions in Early/Late Heterobimetallics: Co/Zr Complexes Supported by Phosphinoamide Ligands
    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
  • [6] Utilization of Phosphinoamide Ligands in Homobimetallic Fe and Mn Complexes: The Effect of Disparate Coordination Environments on Metal-Metal Interactions and Magnetic and Redox Properties
    Kuppuswamy, Subramaniam
    Bezpalko, Mark W.
    Powers, Tamara M.
    Turnbull, Mark M.
    Foxman, Bruce M.
    Thomas, Christine M.
    INORGANIC CHEMISTRY, 2012, 51 (15) : 8225 - 8240
  • [7] Metal-metal interactions in linked metallocenes
    Barlow, S
    OHare, D
    CHEMICAL REVIEWS, 1997, 97 (03) : 637 - 669
  • [8] Oxazole cyclopeptides for chirality transfer in C3-symmetric octahedral metal complexes
    Pinter, Aron
    Haberhauer, Gebhard
    EUROPEAN JOURNAL OF ORGANIC CHEMISTRY, 2008, 2008 (14) : 2375 - 2387
  • [9] Metal-Metal Interactions in Heterobimetallic Complexes with Dinucleating Redox-Active Ligands
    Broere, Daniel L. J.
    Modder, Dieuwertje K.
    Blokker, Eva
    Siegler, Maxime A.
    van der Vlugt, Jarl Ivar
    ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2016, 55 (07) : 2406 - 2410
  • [10] C3-symmetric ligands for catalysis
    Ruck-Braun, K
    NACHRICHTEN AUS CHEMIE TECHNIK UND LABORATORIUM, 1998, 46 (06): : 646 - 650
12345