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Crystal engineering is the planning and construction of the structure and properties of crystalline materials by designing molecular building blocks.1 In this regard, tropolone (2-hydroxy-2,4,6-cycloheptatrienone) have been utilized as building blocks for the construction of liquid crystals and organogels.2 The growing application of rhodium(I tropolonato tertiary aryl phosphine complexes toward oxidative addition as relevant to the Monsanto process, has also gained significant interest since the work done by Steyl et al. in the early 2000’s.3,4 The small bite (OM-O) angle in tropolonato rhodium(I) complexes make them suitable to accommodate two phosphine/arsine ligands in the rhodium coordination sphere, hence forming a trigonalbipyramidal geometry.5

The solid and solution states mysteries of rhodium(I) functionalized tropolonato complexes