Complexes of rhenium and osmium with o-phenylenediamine and o-aminobenzenethiol. X-Ray crystal structures of [Re{o-(HN)2C6H4}3][ReO4], Re[o-(HN)2C6H4]3, Re[o-(HN)2C6H4]2[o-(HN)NC6H4], K[Re{o-(HN)2C6H4}-{o-(HN)NC6H4}2], and M[o-(HN)SC6H4]3(M = Re or Os)
Abstract
The interaction of trimethylsilyl perrhenate, ReO3(OSiMe3), or Re2O7, with o-phenylenediamine gives the homoleptic amido complex cation of rhenium(VII), [Re{o-(HN)2C6H4}3]+, as its perrhenate salt. The cation can be reduced by sodium to the neutral rhenium(VI) species Re[o-(HN)2C6H4]3′ which can be reoxidised by AgPF6 to the cation as its hexafluorophosphate salt. Interaction of [Re{o-(HN)2C6H4}3]+ with KOH leads to the singly and doubly deprotonated species, Re[o-(HN)2C6H4]2[o-(HN)NC6H4] and K[Re{o-(HN)2C6H4}{o-(HN)NC6H4}2]. An improved preparation of the known amido thiolate Re[(HN)SC6H4]3′i.e. interaction of o-(H2N)(HS)C6H4 with ReO3-(OSiMe3), is described; the osmium analogue, Os[(HN)SC6H4]3′ is synthesised by interaction of the aminothiol with OsO4. Interaction of OsO4 with o-(H2N)2C6H4 gives the complex trans-OsO2[(HN)2C6H4]2. Infrared, 1H n.m.r., e.s.r., and electronic absorption and cyclic voltammetric data are given. The X-ray crystal structure of the cation [Re{o-(HN)2C6H4}3]+ as the acetone solvate of the perrhenate shows a trigonal prismatic geometry, which is also confirmed for Re[o-(HN)2C6H4]3, Re[o-(HN)2C6H4][o-(HN)NC6H4], K[Re{o-(HN)2C6H4}{o-(HN)NC6H4}2], and Re[(HN)SC6H4]3. The structure of Os[o-(HN)SC6H4]3 shows it to have a slightly distorted octahedral geometry.