Reactions of dicarbonyltitanocenes with 2-diazo-1,3-diketones: O-,N- versus O-,O- chelation and self-assembly of a novel heteroleptic Ti5O6-cage compound

Reaction of 2-diazo-1,3-diketones with titanocene precursors can produce five-, six- or seven-membered 1-titana-2,n-diheterocyclic complexes with different coordination modes: whereas reaction with dicarbonyltitanocene is fast and furnishes either five-membered titanaoxazacycles or CC coupled seven-membered dioxochelates, decamethyltitanocene dicarbonyl reacts sluggishly to give a novel heteroleptic, trigonal-bipyramidal oxygen bridged Ti5O6-cluster containing six unsymmetric six-membered titanadioxacyclic ligands.