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

J. G. Vitillo;S. Bordiga
2012-01-01

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.
2012
http://www.sciencedirect.com/science/article/pii/S1387181111006469
GAUSSIAN-BASIS SETS; ORGANIC FRAMEWORK; COORDINATION POLYMER; ADSORPTION; CR(CO)6; DENSITY; DEHYDRATION; REACTIVITY; STABILITY; COMPLEXES
Chavan, S.; Vitillo, J. G.; Larabi, C.; Quadrelli, E. A.; Dietzel, P. D. C.; Bordiga, S.
File in questo prodotto:
Non ci sono file associati a questo prodotto.

I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.

Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11383/2076403
 Attenzione

L'Ateneo sottopone a validazione solo i file PDF allegati

Citazioni
  • ???jsp.display-item.citation.pmc??? ND
  • Scopus 14
  • ???jsp.display-item.citation.isi??? 12
social impact