Sustainable metal alkynyl chemistry: 3d metals and polyaza macrocyclic ligands

Chemical Communications : Chem Comm
Tong Ren

Abstract

We describe the chemistry of 3d metal alkynyls based on polyaza macrocyclic ligands, an emerging area of alkynyl chemistry that has previously been dominated by 4d and 5d metals with soft ligands. The abundance of 3d metals and low cost of tetraazacyclotetradecane ligands make these compounds more affordable, sustainable alternatives to metal alkynyls based on precious metals. Taking advantage of the rich variety of starting materials available in the literature, trans-[M(cyclam)(C2R)2]X (cyclam = 1,4,8,11-tetraazacyclotetradecane) compounds have been prepared from the reactions between [M(cyclam)X2]X (M = Cr, Fe and Co; X = Cl or OTf) and LiC2R. With [Co(cyclam)Cl2](+), both the {trans-[Co(cyclam)Cl]2(μ-(C≡C)n)}(2+) and trans-[Co(cyclam)(C2R)Cl](+) compounds have been prepared by a dehydrohalogenation reaction. The latter compounds undergo the second alkynylation reaction to afford dissymmetric trans-[Co(cyclam)(C2R)(C2R')](+) compounds. Similar alkynylation chemistry with complexes of the cyclam derivatives TMC (1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane) and HMC (5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) has been demonstrated in studies of [Ni(TMC)(C2R)](+) and trans-/cis-[Cr(HMC)(C2R)2](+). Me...Continue Reading

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Citations

Jul 7, 2016·Chemical Communications : Chem Comm·Di-Chang Zhong, Tong-Bu Lu
Jun 14, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Lucie NorelStéphane Rigaut
Nov 7, 2019·Acta Crystallographica. Section C, Structural Chemistry·Reese A ClendeningTong Ren
May 17, 2018·Acta Crystallographica. Section E, Crystallographic Communications·Benjamin M OxleyTong Ren
Feb 27, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Andrew J CounsellPeter J Rutledge
Apr 21, 2021·Dalton Transactions : an International Journal of Inorganic Chemistry·Ashley J SchumanTong Ren
Aug 10, 2017·Inorganic Chemistry·Sean N NatoliTong Ren

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