Developments in the chemistry of the hard early metals (Groups 1–6) with thioether, selenoether and telluroether ligands

Abstract

The coordination chemistry of neutral thio-, seleno-and telluroether ligands towards the hard s-block, f-block and higher oxidation state early d-block metals has developed significantly over the 15 or so years. This has revealed several hitherto unknown classes of complexes and new insights into the chemistries of these hard-soft metal-ligand combinations. This Perspective describes the synthetic routes used to access such complexes and draws out their key structural features and spectroscopic properties. Where appropriate, applications of these species are also highlighted, including their use as single source precursors for the chemical vapour deposition of semiconducting metal chalcogenide thin films and as pre-catalysts for olefin polymerisation reactions. IntroductionThioether and selenoether ligands, which are neutral sulfur and selenium donors respectively, were for many years viewed as modest σ-donor ligands that formed complexes with the softer later d-block elements in low or medium oxidation states, or with post transition metals such as silver or mercury.1,2Complexes of the early d-block metals were mostly limited to low valent organometallics or carbonyls. The chemistry of telluroethers was very little explored, in major part a reflection of their limited availability and, for the alkyl telluroethers in particular, their extremely malodorous nature. 2,3The R2Te ligands are also oxygen sensitive (in contrast to the air stable R2S or R2Se), modest reducing agents and prone to cleavage of the CTe bond upon reaction with some metal centres. Even today, their chemistry remains much less extensive than that of their lighter analogues. 4 Major developments in the syntheses and coordination chemistry of macrocyclic thioethers considerably extended the range and stability of complexes containing metal centres across the d-block. More recent work has resulted in complexes of chalcogenoethers with many of the p-block elements,

Synthesis and properties of MoCl4complexes with thio- and seleno-ethers and their use for chemical vapour deposition of MoSe2and MoS2films

“…13 Chalcogenoether complexes of the early d-block metal halides can function as single source CVD precursors for some ME 2 (for example, M = Ti, V or Nb; E = S or Se). 14,15 Chemical vapour deposition from molybdenum halide complexes has rarely been used to form molybdenum dichalcogenides, although MoSe 2 films were produced by dual source atmospheric pressure chemical vapour deposition (CVD) using MoCl 5 and either Et 2 Se or n Bu 2 Se. 16 The tetrathiolate complex, [Mo(S t Bu) 4 ], has also been used to deposit MoS 2 films by CVD.…”

1,3-Dithianes as Assembling Ligands for the Construction of Copper(I) Coordination Polymers. Investigation of the Impact of the RC(H)S2C3H6 Substituent and Reaction Conditions on the Architecture of the 0D–3D Networks

“…They have also been used as assembling ligands to construct 1D and 2D coordination polymers and 3D MOFs. [1][2][3][4][5][6][7][8][9][10] The less flexible six-membered dithiaheterocycle 1,3-dithiane L1 (also named 1,3-dithiacyclohexane) has also been used in the past as mono-and bidentate ligand to coordinate to a series of early and late transition metal complexes. Crystallographically characterized examples include mono-and dinuclear compounds [(C 6 H 6 )Cr(CO) 2 ( 1 -L1)], 11 [Fe(CO) 4 (( 1 -L1)], 12 [(C 5 H 5 )Ru(PPh 3 ) 2 (( 1 -L1)][CF 3 SO 3 ], 13 [(C 5 Me 5 )IrCl 2 (( 1 -L1)] and [{(C 5 Me 5 )IrCl 2 } 2 ( 2 -L1)], 14 as well as polynuclear clusters such as [( 2 -H) 2 Ru 3 (CO) 8 Cl( 3 - 3 -L1)] and [H 4 Ru 4 (CO) 10 ( 2 -L1)].…”

Selenium Substitution-Induced Hydration Changes of Crown Ethers As Tools for Probing Water Interactions with Supramolecular Macrocycles in Aqueous Solutions

“…To the best of our knowledge, the investigation of aqueous behaviors of selenacrown ethers is belittled in the literature and remains a challenging task. 50 The oxacrown C7CN was synthesized following the wellestablished synthetic protocol in our group. 51 To substitute Se over O, we prepared the Se-substituted hexaethylene glycol and followed the ring closure method, affording C7SeCN with a satisfied yield (Scheme S1).…”