A Bonding Quandary-or-A Demonstration of the Fact That Scientists Are Not Born With Logic

被引:68
作者
Alvarez, Santiago [1 ,2 ]
Hoffmann, Roald [3 ]
Mealli, Carlo [4 ]
机构
[1] Univ Barcelona, Dept Quim Inorgan, E-08028 Barcelona, Spain
[2] Univ Barcelona, IQTC, E-08028 Barcelona, Spain
[3] Cornell Univ, Dept Chem & Chem Biol, Ithaca, NY 14853 USA
[4] ICCOM CNR, Ist Chim Composti Organomet, I-50019 Florence, Italy
关键词
bond lengths; chemical bonding; cluster compounds; S-S bonding; sulfides; CRYSTAL-STRUCTURES; ELECTRONIC-STRUCTURE; TRANSITION-METALS; OXIDATION-STATE; COMPLEXES; SULFUR; CLUSTERS; REACTIVITY; NICKEL; LIGAND;
D O I
10.1002/chem.200900239
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
We document here a spirited debate among three colleagues and friends who have strong opinions on a specific bonding problem, the presence or absence of a cross-ring sulfur-sulfur bond in a trinuclear Cu3S2 cluster. The example may seem esoteric, but through their struggles with this specific bond (and with each other) the authors approach the more general problematic of chemistry, the chemical bond. The discussion focuses on bond lengths and the population of bonding and antibonding orbitals, and on oxidation states, electron counting, and associated geometries. It expands to encompass other bonding criteria, and introduces examples ranging far across organic and inorganic chemistry. The authors suggest molecules that might test their ideas. An Appendix to the paper discusses a mat er rarely broached in the chemical literature-should one review for publication a paper which criticizes one of your own contributions.
引用
收藏
页码:8358 / 8373
页数:16
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