Hans-Peter Neuner

Transition metal complexes with sulfur ligands Part LXXIX. Crown thioether complexes of iron, cobalt, nickel and copper with bzo2-18S6. X-ray structure analysis of [Ni(bzo2-18S6)][B(C6H5)4]2 (bzo2-18S6 = 2,3,11,12-dibenzo-1,4,7,10,13,16-hexathiacyclooctadeca-2,11-diene)

Abstract Reaction of bzo2-18S6 (2,3,11,12-dibenzo-1,4,7,10,13,16-hexathiacyclooctadeca-2,11-diene) with Fe, Co, Ni and Cu salts yields the corresponding metal complexes [M(bzo2-18S6)]n+. Their trifluoromethanesulfonate salts were characterized by spectroscopic and electrochemical methods and the structure of [Ni(bzo2-18S6)][B(C6H5)4]2 was elucidated by X-ray structure determination. It crystallizes in space group P21/n with a = 1497.8(4), b = 1096.5(4), c = 1772.5(5) pm, β = 104.26(2)°, Z = 2 and Dcalc = 1.36 g/cm3; R = 0.061, Rw = 0.041. The nickel centre is surrounded by the six sulfur atoms of the ligand in a slightly distorted octahedron. The NiS distances indicate a ligand compression effect of bzo2-18S6. The different electrochemical behaviour of the [M(bzo2-18S6)]n+ complexes is discussed.

Transition metal complexes with sulfur ligands Part LVI. First metal complexes of the crown thioether bzo2-18S6 and its tertiarybutyl derivative bubzo2-18S6 with Ru, Ag, Cr, Mo, W and Fe. X-ray structure analysis of [Ru(bzo218S6)](PF6)2·2CH3NO2

Abstract In order to investigate the coordination behaviour of the macrocyclic crown thioether bzo 2 -18S6 (2,3,11,12-dibenzo-1,4,7,10,13,16-hexathiacyclooctadecane) and the properties of its metal compounds, the ruthenium and silver complexes [Ru(bzo 2 18S6)] 2+ and [Ag(bzo 2 18S6)] + were synthesized. [Ru(bzo 2  18S6)](PF 6 2 ·2CH 3 NO 2 crystallizes in space group P 2 1 / c with a =1151.7(4), b =554.1(2), c =2695.8(13) pm, β=100.00(4)°, Z =2 and D calc =1.90 g/cm 3 ; R =0.072, R w =0.052. The ruthenium center is surrounded by the six sulfur atoms of the ligand in almost ideal octahedral geometry. Reaction of bzo 2 18S6 with [M(CO) 3 L 3 ] (MCr, Mo, W; LCH 3 CN, EtCN) yields the corresponding complexes [M(CO) 3 (bzo 2  18S6)], indicating that the crown thioether will not act as a hexadentate ligand, if the metal center carries strongly bound coligands. The tertiarybutyl derivative of bzo 2 18S6, bu bzo 2 18S6 (2,3,11,12- bis(2′,4′-di-tertiarybutyl-benzo)-1,4,7,10,13,16-hexathiacyclooctadecane), is obtained by template alkylation of [Fe(CO)‘ bu S 5 ’] (‘ bu S 5 ’ 2− = 2,2′-bis(2-mercapto-3,5-di-tertiarybutyl-phenylthio)diethylsulfide(20−)) with bis(β-bromoethyl sulfide, followed by acidic hydrolysis of the primary product [Fe( bu bzo 2 18S6)]Br 2 . As the structure of [Fe( bu bzo 2 18S6)]Br 2 remained uncertain, free bu bzo 2 18S6 was reacted with Fe(CF 3 SO 3 ) 2 to give [Fe bu bzo 2 18S6)](CF 3 SO 3 ) 2 which was characterized by NMR spectroscopy.