N,N′-Diarylformamidine Dithiocarbamate Ag(I) Cluster and Coordination Polymer

Abstract

An Ag(I)formamidine cluster Ag6L16 (1) and an Ag(I)formamidine coordination polymer Ag7(L2)2 2 (L1 = N,N′-bis(2,6-disopropylphenyl) formamidine dithiocarbamate and L2 = N,N′-mesityl formamidine dithiocarbamate) have been synthesized from the reactions of L1 and L2 with AgNO3 respectively. The complexes were characterized using spectroscopic and analytical methods, including single-crystal X-ray diffraction. In the structure of 1, a six vertex distorted square bi-pyramidal octahedron is formed from an Ag6 core. The N,N′-bis(2,6-disopropylphenyl) formamidine dithiocarbamate ligands stabilize this core through two main –CS2 bridging modes giving a propeller like structure. In the structure of 2, each of the two Ag(I) centers are bridged by two N,N′-mesityl formamidine dithiocarbamate ligands forming 8-member Ag2(CS2)2 metallacycles with an inversion center in the middle of the Ag—Ag argentophilic bond. The metallacycles are connected through Ag—S bonds forming ribbons in the crystallographic a-axis. The Ag(I) centers are coordinated to two N,N′-mesitylformamidine dithiocarbamates through the dithiocarbamate S atoms. The thermal decomposition of complexes 1 and 2 had similar thermograms with one major weight loss activity and the formation of elemental silver particles thereafter.

Supramolecular assembly and structural transformation of d10-metal complexes containing (aza-15-crown-5)dithiocarbamate

“…Unlike the 2-coordinate Au( i ) ion and the μ 2 -bridging mode for the dithiocarbamate ligand in Au( i ) dithiocarbamates, 11–14 the rich structural features of Cu( i ) and Ag( i ) clusters and coordination polymers with μ 3 -, 16 μ 4 -, 17 and μ 3 /μ 4 -bridging 18 modes for the dithiocarbamate ligand have been widely observed. The reaction of Cu( i ) salts with Na(S 2 C(aza-15-crown-5)) (the same as NaO 4 NCS 2 ) and (Bu 4 N)BH 4 in CH 3 CN solution at room temperature gave the monocationic hydride-centered octanuclear Cu( i ) cluster as reported by Liu and coworkers, 18 a and such a hydrido Cu( i ) cluster can be supported by the μ 3 /μ 4 -bridging dithiocarbamate.…”