Tetrahedral Coordination in the First Structurally Characterized Dichlorooxovanadium(V) Alkoxide

Abstract

Reaction of VOCl 3 with 2-phenoxyethanol in n-hexane in a 1:1 fashion gives dichlorooxo(2-phenoxyethanolato)vanadium(V). HCl elimination yields the orange vanadium(V) complex, which is the first structurally characterized dichlorooxovanadium(V) alkoxide. The structure analysis reveals an unexpected tetrahedral coordination around the vanadium atom in the monomeric Tetraedrische Koordination im ersten strukturell charakterisierten Dichlorooxovanadium(V)-alkoxidInhaltsübersicht. Die Reaktion von VOCl 3 mit 2-Phenoxyethanol in n-Hexan im Verhältnis 1:1 ergibt Dichlorooxo(2-phenoxyethanolato)vanadium(V). HCl-Eliminierung führt zu dem orangefarbenen Vanadium(V)-Komplex, bei dem es sich um das erste strukturell charakterisierte Dichlorooxovanadium(V)-alkoxid handelt. Die Röntgenstrukturanalyse zeigt eine unerwartete tetraedrische Koor-

A novel oxovanadium(V) complex of 2-(2-butoxyethoxy)ethanolate with high catalytic activities for polymerisation and epoxidation

“…This class of vanadates has attracted extensive current research interests in modelling the coordination environment of vanadium-dependent haloperoxidases or nitrogenases [10]. In the context of developing vanadium catalysts for olefin polymerisation and oxidation our research group has reported a class of novel chloro vanadate complexes with aryloxyalkoxide [11] or alkoxyalkoxide ligands [12]. The aryloxyalkoxide derivative [VOCl 2 (OCH 2 CH 2 OPh)] is monomeric in the solid state.…”

“…The aryloxyalkoxide derivative [VOCl 2 (OCH 2 CH 2 OPh)] is monomeric in the solid state. Neither ether donor coordination nor alkoxide bridging is found in this complex [11]. In sharp contrast, the alkoxyalkoxide complexes are dimeric and contain a pair of chloride bridging groups instead of alkoxide ones [12].…”

Fifteen Years of Dancing with Vanadium

“…The versatility of these compounds in organic syntheses continues to be explored. As recently reported by the Rosenthal group, vanadium(V)-alkoxide chemistry now shows potential utility in polymer catalysis [91,92]. These studies demonstrated coordination chemistry of mixed vanadium(V) chloro-alkoxides with four-, five-, and six-coordinate vanadium(V) complexes with bridging chloro groups [92].…”

“…The Rosenthal group [91,92] has recently reported an interesting example of this type of chemistry. The mixed vanadium(V) chloroalkoxides investigated are of interest for their application as catalysts, and their coordination chemistry is showing a wide range of geometries with four-, five-, and six-coordinate vanadium(V) in mono and dinuclear complexes with bridged chloro groups [91,92]. As more structures with bridging chlorides such as shown in 7, and their reactivity become available, a better understanding of the structural preferences in these systems will be forthcoming.…”

“…Calculations probing these geometries revealed that the coordination preference could not be attributed to the electrostatic properties of the vanadium, but rather to the subtle ligand effect often referred to as the gem-dimethyl effect [76]. Upon substitution of a second alkoxide group with a chloro group, a monomeric four-coordinate vanadium(V) dichloro-alkoxide complex forms [91] suggesting that the addition of the second chloro group shifted the favored geometry. Substituting the 1,2-diol with a 1,3-diol increases the distance between the ligand oxygen atoms and affects the ligand arrangements around the vanadium atom.…”