Insertion of Unsaturated Organic Electrophiles into MolybdenumAlkoxide and RheniumAlkoxide Bonds of Neutral, Stable Carbonyl Complexes

Regioselective Carbon–Carbon Bond Formation Reactions between TCNE or TCNQ and a Quinonoid Ring

“…Tetracyanoethylene (TCNE) and 7,7′,8,8′‐tetracyanoquinodimethane (TCNQ) are strong organic, one‐electron acceptors, and as such are much used as precursors to electron‐transfer salts and superconducting or magnetic materials 1. The coordination chemistry of TCNE and TCNQ has been much investigated,2 and their reactions with organometallic compounds include: 1) insertion into MH,3a,b MC,3c–f or MOR bonds;3g 2) [2+2], [4+2], or [3+2] additions on the ligand;4 3) α,β‐additions to an acetylide group;5 4) cycloadditions;6 and 5) insertions into an aromatic CH bond 7. Although numerous reactions of TCNE and TCNQ with organic compounds have been reported,8 only insertion reactions into a CC bond of a spiroanellated bicyclopropyl system9 or a CH bond of 4‐hydroxycoumarins,10 cyclic enol ethers,11 phenols,12 or a mesoionic thiazolium system13 have been observed.…”

Synthesis, structures and in vitro cytotoxicity of some platinum(II) complexes containing thiocarbamate esters

“…For example, the mercury(II) complex [Hg{PhN@C(S)OMe} 2 ] was prepared from [Hg(OMe) 2 ] and PhNCS [1]; the subsequent X-ray structure determination showed that the ligand was coordinated to the mercury only via the sulfur atom and also confirmed the presence of a C@N double bond [2]. Similarly, in the rhenium, molybdenum and zinc complexes [Re(CO) 3 , which were all prepared by reactions of aryl isothiocyanates with the corresponding metal-alkoxides, the thiocarbamate ester ligands coordinate only via the sulfur atom [3,4]. In contrast, the ligand adopts a chelating mode via the N and S atoms in the rhenium complexes [ReOCl 2 {RC 6 H 4 N@C(S)OR 0 }(PPh 3 )] (R = Me, H; R 0 = Me, Et) [5].…”

Reactivity of ortho‐Substituted Aryl–Palladium Complexes towards Carbodiimides, Isothiocyanates, Nitriles, and Cyanamides

“…Isothiocyanates insert into MÀO (M= Re, [44,45] Ni, [46] Cu, [47] Zn [48] ), MÀN (M= Mg, [34] Yb, [39] Ln, [38,49] Re, [50] Fe, [51] Ni, [46] Pd, [52] ), MÀH (M= Zr, [53] Nb, Ta, [54] Ru, Os, Ir, [55] Rh [56] ), M À S (M= Nd [57] ), and M À C (M= Mg, [34,58] Al, [59] Zr, [60] Nb, Ta, [61] Re, [62] Fe, [63] Co, [64] Ni, [65] Pd [10] ) bonds in the same way as carbodiimides. We have recently reported the first example of insertion of an isothiocyanate into a Pd À C bond followed by formation of PdS.…”