178743-32-3Relevant academic research and scientific papers
Sodium oximates as starting materials for the synthesis of half-sandwich-type arene( oximato) and arene( azavinylidene) osmium complexes
Werner,Daniel,Mueller,Mahr
, p. 197 - 205 (2007/10/03)
The reaction of [C6H6OsI2(PiPr3)] (1) with Na[ON=CR2] (R2 = Ph2, Me2, C(CH2)5) in the presence of KPF6 leads to the formation of the oximato osmium(II) complexes [C6H6Os(η2-ON=CR2)(PiPr3)]PF6 (6, 7, 8b) in almost quantitative yield. The mesitylene compounds [(mes)Os(η2-ON=CR′R″)(PR3)]PF6 (9-14) have been prepared similarly using [(mes)OsCl2(PR3)] (3-5) as starting materials. The synthesis of [C6H6Os(η2-ON=CMetBu)(PiPr3)]PF6 (17) has been achieved from [C6H6OsCl2(PiPr3)] (16) which in turn is prepared from [C6H6Os(η2-O2C=O)(PiPr3)] (15) and excess Me3SiCl. Reaction of 1, [C6H6OsI2(PMetBu2)] (2) and 3 (PR3 = PiPr3) with Na[ON = CMetBu] in the presence of KPF6, in methanol as solvent, unexpectedly yields the azavinylidene complexes [(arene)Os(=N=CMetBu)(PR3)]PF6 (18b, 19, 20). The X-ray structural analysis of 18b reveals the presence of a nearly linear Os-N-C fragment with an Os-N distance that is in agreement with typical osmium-nitrogen double bond lengths. Related azavinylideneosmium compounds [(arene)Os(=N=CR′R″)(PR3)]PF6 (21-26) have been obtained on treatment of the corresponding oximato complexes 7, 10 or 14 with either HN=CR′R″ or, for R′ = H and R″ = Ph, the trimethylsilyl derivative.
