Ethynyl[2.2]paracyclophanes and 4-isocyano[2.2]paracyclophane as ligands in organometallic chemistry

Reinvestigation of the Pd-catalyzed 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}]

“…We have also prepared 1,1,2,2-tetramethyl-1,2-bis(phenylthiomethyl)disilane (1) and coordinated 1 via its dithioether functions as chelate or bridging ligand to a range of transition metals such as Pt, Re and Ru [27]. Furthermore we have demonstrated that the catalytic cleavage of the SieSi bond by Ito's Pd(OAc) 2 /CNR catalyst allows addition across the triple bond of phenylacetylene, p-tolylacetylene and (AE)-4-ethynyl [2.2] paracyclophane to afford the corresponding bis(silylated) olefins, whose Z-stereochemistry has been confirmed by an X-ray diffraction study on Z-(PhSCH 2 )Me 2 SiC(H)]C(Ph)SiMe 2 (CH 2 SPh) [27,28]. In this work, we have extended our investigation on the palladiumcatalyzed double silylation of 1 across ethynylferrocene, since the presence of an electrochemically active ferrocenyl moiety appeared attractive for further studies.…”

“…The bis(silylation) reaction was performed under the same conditions as reported in our previous work [27,28]. A toluene solution of 1 was reacted with ethynylferrocene in presence of a catalytic amount of 1,1,3,3-tetramethylbutylisocyanide and palladium acetate (Scheme 1).…”

Crystal structure of dicarbonyl[μ2-methylenebis(diphenylphosphane)-κ2P:P′][μ2-2-(2,4,5-trimethylphenyl)-3-oxoprop-1-ene-1,3-diyl](triphenylphosphane-κP)ironplatinum(Fe—Pt)–dichloromethane–toluene (1/1/2), [(OC)2Fe(μ-dppm)(μ-C(=O)C(2,4,5-C6H2Me3)=CH)Pt(PPh3)]

“…The coordination and transformation of alkynes on homobimetallic transition-metal complexes, in which the two metal centres are in close contact via a metal-metal bond, has been investigated intensively (Liddle, 2015). For example, during the course of a Pauson-Khand reaction, an acetylenic triple bond is added across [Co 2 (CO) 8 )], yielding a dimetallatetrahedrane [Co 2 (CO) 6 (-C 2 RR 0 )] (Bennett et al, 1992;Clé ment et al, 2007).…”

Synthesis, crystallographic and electrochemical study of ethynyl[2.2]paracyclophane-derived cobalt metallatetrahedranes

“…4-ethynylPCP, 4,16-diethynylPCP, [Co 2 (CO) 6 (m-h 2 -PCPeCCH)] (2) [26], [Co 2 (CO) 6 (m-dppm)], [Co 2 (CO) 6 (m-dppa)] [6b], and Co 2 (CO) 6 - …”