Department of Chemistry, University of Oxford, Chemistry Research Laboratory, 12 Mansfield Road, Oxford, OX1 3TA, UK.
Department of Chemistry, Indiana University-Bloomington, 800 E. Kirkwood Ave., Bloomington, IN-47405-7102, USA.
Angew Chem Int Ed Engl. 2023 Mar 6;62(11):e202218047. doi: 10.1002/anie.202218047. Epub 2023 Feb 1.
The cyaphide anion, CP , is shown to undergo three distinct oligomerization reactions in the coordination sphere of metals. Reductive coupling of Au(IDipp)(CP) (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) by Sm(Cp*) (OEt ) (Cp*=1,2,3,4,5-pentamethylcyclopentadienyl), was found to afford a tetra-metallic complex containing a 2,3-diphosphabutadiene-1,1,4,4-tetraide fragment. By contrast, non-reductive dimerization of Ni(SIDipp)(Cp)(CP) (SIDipp=1,3-bis(2,6-diisopropylphenyl)-imidazolidin-2-ylidene; Cp=cyclopentadienyl), gives rise to an asymmetric bimetallic complex containing a 1,3-diphosphacyclobutadiene-2,4-diide moiety. Spontaneous trimerization of Sc(Cp*) (CP) results in the formation of a trimetallic complex containing a 1,3,5-triphosphabenzene-2,4,6-triide fragment. These transformations show that while cyaphido transition metal complexes can be readily accessed using metathesis reactions, many such species are unstable to further oligomerization processes.
氰阴离子 CP 在金属配位球中被证明会经历三种不同的齐聚反应。通过 Sm(Cp*) (OEt )（Cp*=1,2,3,4,5-五甲基环戊二烯基）还原偶联 Au(IDipp)(CP)（IDipp=1,3-双(2,6-二异丙基苯基)咪唑-2-亚基），得到了一种含有 2,3-二膦丁二烯-1,1,4,4-四炔片段的四金属配合物。相比之下，Ni(SIDipp)(Cp)(CP)（SIDipp=1,3-双(2,6-二异丙基苯基)-咪唑烷-2-亚基；Cp=环戊二烯基）的非还原二聚化导致了一种不对称双金属配合物，其中含有 1,3-二膦环丁二烯-2,4-二亚基部分。Sc(Cp*)（CP）的自发三聚化导致形成了一种含有 1,3,5-三膦苯-2,4,6-三炔片段的三金属配合物。这些转化表明，虽然氰桥过渡金属配合物可以通过复分解反应轻易获得，但许多这样的物种对进一步的齐聚反应过程不稳定。
