Cr(CO)(6) and Mo(CO)(6) have been used as precursors to obtain grafted (eta(6)-arene) M(CO)(3) species inside the CPO-27-Ni material. The presence of open Ni(II) sites in the MOF scaffold promotes distinctive reactivities with respect to that observed previously on other MOFs (MOF-5 and UiO-66). The formation of two organometallic M(CO)(3)(eta(6)-arene) conformers (staggered and eclipsed) has been considered, also taking into account data obtained by a recent theoretical work. IR spectroscopy shows how open metal sites in a MOF structure can destabilize metal carbonyl molecules, favoring CO elimination and acting as CO scavenger, which fastens the decomposition and frustrate the reverse reaction. The work can open new studies on precursors of catalytic species stabilized inside MOFs cages. (C) 2012 Elsevier Inc. All rights reserved.

Functionalization of CPO-27-Ni through metal hexacarbonyls: The role of open Ni2+ sites

CHAVAN, SACHIN MARUTI;VITILLO, Jenny Grazia;BORDIGA, Silvia
2012

Abstract

Cr(CO)(6) and Mo(CO)(6) have been used as precursors to obtain grafted (eta(6)-arene) M(CO)(3) species inside the CPO-27-Ni material. The presence of open Ni(II) sites in the MOF scaffold promotes distinctive reactivities with respect to that observed previously on other MOFs (MOF-5 and UiO-66). The formation of two organometallic M(CO)(3)(eta(6)-arene) conformers (staggered and eclipsed) has been considered, also taking into account data obtained by a recent theoretical work. IR spectroscopy shows how open metal sites in a MOF structure can destabilize metal carbonyl molecules, favoring CO elimination and acting as CO scavenger, which fastens the decomposition and frustrate the reverse reaction. The work can open new studies on precursors of catalytic species stabilized inside MOFs cages. (C) 2012 Elsevier Inc. All rights reserved.
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http://www.sciencedirect.com/science/article/pii/S1387181111006469
GAUSSIAN-BASIS SETS; ORGANIC FRAMEWORK; COORDINATION POLYMER; ADSORPTION; CR(CO)6; DENSITY; DEHYDRATION; REACTIVITY; STABILITY; COMPLEXES
S. Chavan; J. G. Vitillo; C. Larabi; E. A. Quadrelli; P. D. C. Dietzel; S. Bordiga
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Utilizza questo identificativo per citare o creare un link a questo documento: http://hdl.handle.net/2318/122540
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