Synthesis and Crystal Structures of Copper Zinc Phenylthiolate and the First Copper Zinc Selenolate and Tellurolate Complexes

Abstract

Five copper zinc phenylchalcogenolate complexes [(iPr 3 PCu) 3 (ZnMe 2 ) 2 (SPh) 3 ] (1), [(iPr 3 PCu) 2 (ZnPh) 4 (SPh) 6 ] (2), [(iPr 3 PCu) 2 (ZnEt) 4 (SPh) 6 ] (3), [(iPr 3 PCu) 3 (ZnEt)(SePh) 4 ] (4), and [(iPr 3 PCu) 3 Cu(iPr 3 PZn)(TePh) 6 ] (5) were synthesized by the reaction of phosphine stabilized copper phenylchalcogenolate complexes with ARTICLE Scheme 1. Reactions starting from [iPr 3 PCuSPh] 3 , [(iPr 3 P) 4 (CuSePh) 6 ] or [(iPr 3 P) 3 (CuTePh) 4 ] with ZnR 2 (R = Me, Et, Ph) with and without additional chalcogenol.

Adamantane-type clusters: compounds with a ubiquitous architecture but a wide variety of compositions and unexpected materials properties

“… 516 The Zn congener [(μ 3 -Cu)(ZnP i Pr 3 )(CuP i Pr 3 ) 3 (TePh) 3 (μ 3 -TePh) 3 ] (905) was later isolated by a more complex synthetic route starting from a tetranuclear cluster precursor [(P i Pr 3 ) 3 (CuTePh) 4 ] which was reacted in a stepwise manner with ZnEt 2 , P i Pr 3 and PhTeSiMe 3 . 517 The same motif could also be stabilized for compounds with the main group metal Ga, [μ 3 -Cu{Cu(PR 3 ) 3 } 3 (GaMe)(EPh) 6 ] (906–909, E = Se, R = Me, Et, Et 2 i Pr; E = Te, R = Et). 174 They are obtained after reacting the complexes [(PR 3 ) 5 (CuEPh) 6 ] with chalcogenidolates and a GaMe source.…”

“…516 The Zn congener [(m 3 -Cu)(ZnP i Pr 3 )(CuP i Pr 3 ) 3 (TePh) 3 (m 3 -TePh) 3 ] (905) was later isolated by a more complex synthetic route starting from a tetranuclear cluster precursor [(P i Pr 3 ) 3 (-CuTePh) 4 ] which was reacted in a stepwise manner with ZnEt 2 , P i Pr 3 and PhTeSiMe 3 . 517 The same motif could also be stabilized for compounds with the main group metal Ga, [m 3 -Cu {Cu(PR 3 ) 3 } 3 (GaMe)(EPh There are also examples of mixed adamantanes accessible directly from the elements and simple binary compounds if the correct additives and conditions are used. [H 3 TAEA] 2 [InGe 4 -S 11 (SH) 2 (OH)] (911, TAEA = tris(2-aminoethyl)amine, Fig.…”

Ultra-mild synthesis of nanometric metal chalcogenides using organyl chalcogenide precursors

“…These silylated chalcogenides (R 3 Si) 2 E react readily with a metal reagent MX n (X = alkyl, halide, amide, carboxylate, oxide), where facile and homogeneous delivery of chalcogenide (E 2-) to the metal center is promoted by the affinity of silicon(IV) for oxygen and halides as well as volatility of the formed byproduct R 3 SiX (Scheme 2). [71][72][73][74][75][76] When the reaction is performed in the presence of an ancillary ligand L (e.g., PR 3 ), it often leads to the formation of high nuclear nanoclusters [M x E y (L) z ]. [28][29][30][31] The reaction is supposed to proceed through the formation of chalcogenolate intermediates, although the high thermal instability of the M-ESiR 3 bonds makes it difficult to isolate these intermediates before they afford E 2-.…”

“…These silylated chalcogenides (R 3 Si) 2 E react readily with a metal reagent MX n (X = alkyl, halide, amide, carboxylate, oxide), where facile and homogeneous delivery of the chalcogenide (E 2− ) to the metal center is promoted by the affinity of silicon( iv ) for oxygen and halides as well as the volatility of the formed byproduct R 3 SiX (Scheme 2). 71–76 When the reaction is performed in the presence of an ancillary ligand L ( e.g. , PR 3 ), it often leads to the formation of high nuclear nanoclusters [M x E y (L) z ].…”