Novel triosmium cluster complexes with rod-like molecular geometry. Syntheses and crystal structures of [Os3(µ-H)2(CO)9(µ3-CNC5H4CH=NC6H4OC16H33)] and [Os3(µ-H)(CO)10(µ-NC5H3CH=NC6H4OC16H33)]

Abstract

The reaction of [Os3(µ-H)3(CO)9(µ3-CCl)] with 1 equivalent of 1,8-diazabicyclo[5.4.0]undec-7-ene in the presence of a 10-fold excess of NC5H4(CH[double bond, length half m-dash]NC6H4OC16H33-p)-4 in CH2Cl2 at room temperature gave [Os3(µ-H)2(CO)9(µ3-CNC5H4CH[double bond, length half m-dash]NC6H4OC16H33)]1 in 40% yield. The electronic absorption spectra of 1 in a series of organic solvents show significant negative solvatochromic shifts. Treatment of the activated cluster [Os3(CO)10(NCMe)2] with the same Schiff base in CH2Cl2 readily afforded the ortho-metallated cluster complex [Os3(µ-H)(CO)10(µ-NC5H3CH[double bond, length half m-dash]NC6H4OC16H33)]2 in 72% yield. Crystal structure analyses of 1 and 2 revealed that they both exhibit an interesting rod-like molecular geometry.