Hydrolytic Reactivity of a Samarium(II) Organometallic Complex:  Synthesis and Structure of a Hexametallic Organosamarium Oxide Hydroxide, [(C₅Me₅)Sm]₆O₉H₆

Abstract

Controlled hydrolysis of the divalent organosamarium complex (C5Me5)2Sm(THF)2 in THF forms [(C5Me5)Sm]6O9H6, 1, which has a solid-state structure consisting of a distorted octahedral array of six [(C5Me5)Sm]2+ units connected by eight triply bridging oxygens and a central oxygen.

Samarium(III) Pentalene Sandwich Compounds [Sm(η8-C8H4{SiiPr3-1,4}2)(Cp*)] and [Sm(η8-C8H4{SiiPr3-1,4}2)(η5-C8H5{SiiPr3-1,4}2)] and a Mixed-Valence Hexasamarium Cluster Derived from Sm(II)-Based Solvent Activation

“…The cluster is remarkably similar to the hydroxide/Cp* samarium cluster, obtained by Evans et al via controlled hydrolysis of Sm(Cp*) 2 (THF) 2 (Figure ) . This has been formulated as a neutral compound [Cp*Sm] 6 (OH) 6 (O) 3 , and although the H atoms could not be located by crystallographic methods, the six OH − anions give a fully trivalent complex.…”

Organometallic Hydroxides of Transition Elements

“…The complex formation is thought to proceed via an oxidative addition of the OH radicals to the metallocene complexes. A different samarium hydroxy compound, [SmCp*] 6 O 9 H 6 , was obtained from the reaction of water vapor with a solution of Cp* 2 Sm(THF) 2 . The structure consists of six Cp*Sm groups arranged around a central oxygen atom in a roughly octahedral fashion, with triply bridging oxygens on each face.…”

Synthesis and controlled hydrolysis of organolanthanide complexes with mono- and dianionic benzimidazole-2-thiolate ligands

“…On the other hand, although hydrolysis is one of the most common reactions that can occur during the manipulation of organolanthanides, little is known about the structures and reactivities of initially formed reactive intermediates in these courses, [25][26][27][28][29][30][31][32][33][34] due to the difficulty in the control of product distribution and the isolation of the products. To the best of our knowledge, no example of selective hydrolysis of thiolate ligands has been reported in organolanthanide chemistry so far.…”