Author: Fabrice Guyon

Effect of t-BuS vs. n-BuS on the topology, Cu⋯Cu distances and luminescence properties of 2D Cu4I4/RS(CH2)4SR metal–organic frameworks

CuI reacts with RS(CH2)4SR (R = n-Bu (L1); t-Bu (L2)) to afford the 2D coordination polymers [Cu4I4{μ-RS(CH2)4SR}2]n (R = n-Bu (1); t-Bu (2)). Their grid networks exhibit nodal Cu4(μ3-I)4 clusters interconnected by dithioethers with mean Cu⋯Cu distances of 2.7265(10) and 2.911(2) A for 1 and 2, respectively. This difference translates in a blue shift of the solid state emission bands and a decrease in emission lifetimes when trading R = n-Bu to the bulky t-Bu.

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Reinvestigation of the Pd-catalysed bis(silylation) of alkynes with 1,1,2,2-tetramethyl-1,2-bis(phenylthiomethyl)disilane: Unexpected formation of the eight-membered siloxane-chelate complex cis-[PdCl2{(PhSCH2SiMe2)2O}].

International audience; The bis(silylated) alkenes Z-(PhSCH2)Me2SiC(H)=C(Fc)SiMe2(CH2SPh) (2) and Z-(PhSCH2)Me2SiC(H)=C(bipheny)SiMe2(CH2SPh) (3) have been prepared by Pd-catalysed double silylation of ethynylferrocene and 4-ethynyl-1,1'-biphenyl in the presence of 1,1,2,2-tetramethyl-1,2-bis(phenylthiomethyl)disilane (1). A reinvestigation on the interaction of 1 with [PdCl2(PhCN)2] in technical-grade CH2Cl2 as solvent revealed competition between reduction to elemental palladium (due to oxidative addition of the Si-Si bond across Pd(II) and subsequent reductive elimination) and formation of an unusual eight-membered chelate complex cis-[PdCl2{(PhSCH2SiMe2)2O}] (4), which is fluxional in s…

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Synthesis of μ-C2S44− Cobalt Complexes by Activation of the 1,3,4,6-tetrathiapentalene-2,5-dione, and Electrochemical Study of [(Cp*Co)2(μ-C2S4)]

The bimetallic complex [Cp(*)Co)2(μ-C2S4)] in which the two metal centres are linked by an ethylenetetrathiolate C2S44− unit, was synthesized in high yield by oxidative addition of 1,3,4,6 tetrathiapentalene-2,5-dione to [Cp(*)Co(CO)2]. The X-ray crystal structure of the intermediate product Cp*Co(dmid) (dmid2− = 4,5-disulfanyl-1,3-dithiol-2-onate) is presented. The electrochemical behaviour of the [(Cp*Co)2(μ-C2S4)] complex was studied in detail in the oxidative range. This study has shown that the nature of the product obtained after oxidation depends on the presence of complexing agent in the solution. The mechanism has been elucidated in a CH2Cl2 solution in the presence of P(OMe)3. In …

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1,4-Bis(arylthio)but-2-enes as Assembling Ligands for (Cu2X2)n (X = I, Br; n = 1, 2) Coordination Polymers: Aryl Substitution, Olefin Configuration, and Halide Effects on the Dimensionality, Cluster Size, and Luminescence Properties

CuI reacts with E-PhS(CH2CH═CHCH2)SPh, L1, to afford the coordination polymer (CP) [Cu2I2{μ-E-PhS(CH2CH═CHCH2)SPh}2]n (1a). The unprecedented square-grid network of 1 is built upon alternating two-dimensional (2D) layers with an ABAB sequence and contains rhomboid Cu2(μ2-I)2 clusters as secondary building units (SBUs). Notably, layer A, interconnected by bridging L1 ligands, contains exclusively dinuclear units with short Cu···Cu separations [2.6485(7) A; 115 K]. In contrast, layer B exhibits Cu···Cu distances of 2.8133(8) A. The same network is observed when CuBr reacts with L1. In the 2D network of [Cu2Br2{μ-E-PhS(CH2CH═CHCH2)SPh}2]n (1b), isotype to 1a, one square-grid-type layer contain…

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