Syntheses, Structures and Magnetic Properties of New Chalcogen‐Bridged Heterodimetallic Cluster Compounds with Heterocubane Structure

Abstract

Abstract The reaction of nickel, iron and cobalt complexes with MCl 5 (M = Nb, Ta) and silylated chalcogen compounds in the presence of phosphane ligands yield the cluster compounds [Nb 2 Ni 2 S 4 Cl 4 (PPh 3 ) 2 (CH 3 CN) 2 ] ( 1 ), [Nb 2 Ni 2 Se 4 Cl 4 (PPh 3 ) 2 (CH 3 CN) 2 ] ( 2 ), [Ta 2 Ni 2 S 4 Br 4 (PPh 3 ) 2 (CH 3 CN) 2 ] ( 3 ), [Ta 2 Ni 2 Se 4 Br 4 (PPh 3 ) 2 (CH 3 CN) 2 ] ( 4 ), [Ni 3 S 2 (PMe 3 ) 6 ][Ta 3 NiS 4 (PMe 3 ) 4 Cl 6 ] 2 ( 5 ), [Fe(dppm) 2 (CH 3 CN) 2 ][NbFe 3 S 4 Cl 3 (dppm)(CH 3 CN)] 2 ( 6 ) [dppm = (diphenylphosphanyl)methane], [Fe(dppm) 2 (CH 3 CN) 2 ][TaFe 3 S 4 Cl 3 (dppm)(CH 3 CN)] 2 ( 7 ), [FeCl(dppmSe) 2 ][TaFe 3 Se 4 Cl 3 (dppm)(CH 3 CN)] ( 8 ) and [NbCo 3 Se 4 (PPh 3 ) 3 (CH 3 CN) 3 ][CoCl 3 (PPh 3 )] ( 9 ). The compounds (Et 4 N) 3 [NbFe 2 S 4 (SPh) 4 ] ( 10 ) and (Et 4 N) 3 [NbFe 2 Se 4 (SPh) 4 ] ( 11 ) were obtained by treating (Et 4 N) 2 [Fe(SPh) 4 ] with Li 3 NbE 4 (E = S, Se). (Et 4 N) 3 [Nb 2 Fe 6 S 8 (SPh) 9 ] ( 12 ) was synthesized by adding FeCl 2 to compound 10 used as starting material. (Et 4 N) 3 [Nb 2 Fe 6 Se 8 (SePh) 9 ] ( 13 ) (which is isostructural to 12 ) was synthesized by treating FeCl 2 with NaSe t Bu, NbCl 5 and PhSeSiMe 3 . (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2008)