具有刚性非芳香间隔基的双核乙炔桥连钌（II）配合物

Dinuclear acetylide-bridged ruthenium(ii) complexes with rigid non-aromatic spacers.

作者信息

Naik Surabhi, Scottwell Synøve Ø, Li Hsiu L, Leong Chanel F, D'Alessandro Deanna M, Field Leslie D

机构信息

School of Chemistry, UNSW Sydney, NSW 2052, Australia.

School of Chemistry, University of Sydney, Sydney, NSW 2006, Australia.

出版信息

Dalton Trans. 2020 Feb 25;49(8):2687-2695. doi: 10.1039/c9dt04856a.

DOI:10.1039/c9dt04856a

PMID:32048664

Abstract

Rigid dinuclear ruthenium complexes containing non-aromatic caged and polycyclic spacer groups were synthesised and characterised. The complexes, [trans,trans-{Ru(dmpe)2(C[triple bond, length as m-dash]CtBu)}2(μ-C[triple bond, length as m-dash]C-X-C[triple bond, length as m-dash]C)], where X = 1,4-bicyclo[2.2.2]octane (C8H12) or 1,12-p-carborane (p-C2B10H10), were formed via the metathesis of terminal organic bisacetylenes with the methylruthenium complex, [trans-Ru(dmpe)2(CH3)(C[triple bond, length as m-dash]CtBu)], under mild conditions. Electrochemical studies demonstrated electronic interactions across the non-aromatic caged and polycyclic spacers was less than in the analogous complex with an aromatic spacer group, [trans,trans-{Ru(dmpe)2(C[triple bond, length as m-dash]CtBu)}2(μ-C[triple bond, length as m-dash]C-p-C6H4-C[triple bond, length as m-dash]C)]. Mononuclear complexes, [trans-Ru(dmpe)2(C[triple bond, length as m-dash]CtBu)(C[triple bond, length as m-dash]C-X-C[triple bond, length as m-dash]CH)], were also synthesised. [trans-Ru(dmpe)2(C[triple bond, length as m-dash]CtBu)(C[triple bond, length as m-dash]C-C8H12-C[triple bond, length as m-dash]CH)] and [trans,trans-{Ru(dmpe)2(C[triple bond, length as m-dash]CtBu)}2(μ-C[triple bond, length as m-dash]C-p-C2B10H10-C[triple bond, length as m-dash]C)] were structurally characterised by X-ray crystallography.

摘要

合成并表征了含有非芳香族笼状和多环间隔基团的刚性双核钌配合物。通过末端有机双乙炔与甲基钌配合物[trans-Ru(dmpe)2(CH3)(C≡CtBu)]在温和条件下的复分解反应，形成了配合物[trans,trans-{Ru(dmpe)2(C≡CtBu)}2(μ-C≡C-X-C≡C)]，其中X = 1,4-双环[2.2.2]辛烷（C8H12）或1,12-对-碳硼烷（p-C2B10H10）。电化学研究表明，与具有芳香族间隔基团的类似配合物[trans,trans-{Ru(dmpe)2(C≡CtBu)}2(μ-C≡C-p-C6H4-C≡C)]相比，非芳香族笼状和多环间隔基团之间的电子相互作用较小。还合成了单核配合物[trans-Ru(dmpe)2(C≡CtBu)(C≡C-X-C≡CH)]。通过X射线晶体学对[trans-Ru(dmpe)2(C≡CtBu)(C≡C-C8H12-C≡CH)]和[trans,trans-{Ru(dmpe)2(C≡CtBu)}2(μ-C≡C-p-C2B10H10-C≡C)]进行了结构表征。