Dicarboxylato ligands in osmium carbonyl sawhorse clusters: Chelating vs. bridging

被引:7
作者
Gwini, Nigel [1 ]
Marolf, David M. [1 ]
Yoon, Soo Hun [1 ]
Fikes, Audrey G. [1 ]
Dugan, Amanda C. [1 ]
Powell, Gregory L. [1 ]
Lynch, Vincent M. [2 ]
Nesterov, Vladimir N. [3 ]
McCandless, Gregory T. [4 ]
机构
[1] Abilene Christian Univ, Dept Chem & Biochem, Abilene, TX 79699 USA
[2] Univ Texas Austin, Dept Chem, Austin, TX 78712 USA
[3] Univ North Texas, Dept Chem, Denton, TX 76203 USA
[4] Univ Texas Dallas, Dept Chem & Biochem, Richardson, TX 75080 USA
关键词
Diosmium sawhorse complex; Hexanuclear cluster; Dicarboxylato ligand; Microwave synthesis; X-ray crystal structure; MOLECULAR-STRUCTURE; RUTHENIUM; COMPLEXES;
D O I
10.1016/j.jorganchem.2017.01.026
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Seven new complexes comprising of diosmium(I) tetracarbonyl sawhorse units bound to dicarboxylate anions (DCAs) have been synthesized using microwave heating. Succinic, adipic, pimelic, suberic, tetradecanedioic, and terephthalic acids react with Os-3(CO)(12) at temperatures ranging from 180 to 205 degrees C for 12-20 min to produce the osmium sawhorse complexes, which are subsequently reacted with phosphine ligands to replace the labile axial CO ligands. X-ray crystallographic analysis was used to determine the molecular structures of these complexes. Two complexes, those with suberato and tetradecanedioato ligands, are dinuclear species containing Os-2 sawhorse molecules with chelating DCAs that form intramolecular loops. The succinato, adipato and pimelato complexes are tetranuclear species consisting of two Os-2 sawhorse moieties linked together by two bridging DCAs. Thus the straight-chain hydrocarbon backbone of the DCAs must contain at least six carbon atoms in order for these ligands to prefer to chelate a single Os-2 unit instead of forming bridges between multiple Os-2 units. The terephthalato complex is a triangular hexanuclear species consisting of a trimer of dimers with three bridging dicarboxylato anions. (C) 2017 Elsevier B.V. All rights reserved.
引用
收藏
页码:324 / 331
页数:8
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