Application In Synthesis of Cuprous thiocyanate, If you are hungry for even more, make sure to check my other article about Application In Synthesis of Cuprous thiocyanate
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The reaction of Me3SiC<*>CSiMe3 (1), LnMC<*>CSiMe3 (4a, LnM = Cp(CO)2Fe; 4b, LnM = Cp(CO)3Mo> and E(C<*>CR)2 (6, E = Me2Si; 8, E = (eta5-C5H4SiMe3)2Ti; R is a singly bonded organic ligand) with CuX (2) (X is a halide or pseudohalide) is described. 1 and 4 react with CuX (2a, X = Cl; 2b X = Br; 2c, X = I; 2d, X = OSO2CF3) to yield the dimeric compounds <(eta2-Me3SiC<*>CSiMe3)CuX>2 (3a, X = Cl; 3b, X = Br; 3c, X = I; 3d, X = OSO2CF3) or <(eta2-LnMC<*>CSiMe3)CuX>2 (5a, LnM = Cp(CO)2Fe, X = Cl; 5b, LnM = Cp(CO)3Mo, X = Cl) respectively.In these compounds the C2 building block is eta2-coordinated to a CuX moiety and by the formation of copper-X-bridges (Cu2X2) a dimer is formed.However, the reaction of Me2Si(C<*>CSiMe3)(C<*>CR) (6a, R = SiMe3; 6b, R = H) with CuX (2) (X = Cl, Br, OSO2CF3, O2CMe) affords polymeric CSiMe3)(eta2-C<*>CR)Cu2X2>>n (7a, R = SiMe3, X = Cl; 7b, R = SiMe3, X = Br; 7c, R = H, X = Cl; 7d, R = H, X = Br; 7e, R = SiMe3, X = OSO2CF3; 7f, R = SiMe3, X = O2CMe) in high yields.In 7a-7f each alkynyl fragment is eta2-coordinated to a CuX unit.While the reaction of 6a or 6b with CuX yields polymeric 7a-7f, the organometallic, 1,4-diyne RC<*>C--C<*>CR ( = (eta5-C5H4SiMe3)2Ti; 8a, R = Ph; 8b, R = SiMe3) affords with CuX (2a, X = Cl; 2b, X = Br; 2c, X = I; 2e, X = CN; 2f, X = SCN) the dinuclear compounds <(eta5-C5H4SiMe3)2Ti(C<*>CR)2>CuX (9a, R = Ph, X = Cl; 9b, R = SiMe3, X = Cl; 9c, R = SiMe3, X = Br; 9d, R = SiMe3, X = I; 9e, R = SiMe3, X = CN; 9f, R = SiMe3, X = SCN).Compounds 9a-9f feature a monomeric copper(I) halide or copper(I) pseudohalidemoiety, which is stabilized by the chelating effect of the alkynyl ligands on (C<*>CR)2. <(eta5-C5H4SiMe3)2Ti(C<*>CSiMe3)2>CuCl (9b) reacts with AgX (X = CN, SCN, O2CMe, O2CPh) to yield <(eta5-C5H4SiMe3)2Ti(C<*>CSiMe3)2>CuX (9e, X = CN; 9f, X = SCN; 9g, X = OC(O)Me; 9h, X = OC(O)Ph) by precipitation of AgCl.In addition, the bis(alkynyl)-ansa-titanocene <(eta5-C5H4)Me2Si(eta5-C5H3SiMe3)>Ti(C<*>CSiMe3)2 (10) yields with CuCl (2a) the dinuclear species <Ti(C<*>CSiMe3)2>CuCl (11).The identity of compounds 3, 5, 7, 9 and 11 is confirmed by analytical and spectroscopic (IR, MS, 1H, 13C NMR) data, and that of <(eta5-C5H4SiMe3)2Ti(C<*>CPh)2>CuCl (9a) is confirmed by X-ray analysis.Crystals of 9a are monoclinic, space group Pc with cell constant a = 992.6(7), b = 1210(1), c = 1335.5(7) pm, beta = 105.75(5) deg, V = 1543(2)x106 pm3 and Z = 2.Keywords: Alkynes, 1,4-Diynes; Copper(I) halides; Copper(I) pseudohalides
Application In Synthesis of Cuprous thiocyanate, If you are hungry for even more, make sure to check my other article about Application In Synthesis of Cuprous thiocyanate
Reference：
Copper catalysis in organic synthesis – NCBI,
Special Issue “Fundamentals and Applications of Copper-Based Catalysts”