TY - JOUR
T1 - Functionalization of CPO-27-Ni through metal hexacarbonyls
T2 - The role of open Ni 2+ sites
AU - Chavan, Sachin
AU - Vitillo, Jenny G.
AU - Larabi, Cherif
AU - Quadrelli, E. Alessandra
AU - Dietzel, Pascal D.C.
AU - Bordiga, Silvia
PY - 2012/7/15
Y1 - 2012/7/15
N2 - Cr(CO) 6 and Mo(CO) 6 have been used as precursors to obtain grafted (η 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(η 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.
AB - Cr(CO) 6 and Mo(CO) 6 have been used as precursors to obtain grafted (η 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(η 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.
KW - IR spectroscopy
KW - MOF post-functionalization
KW - Metal carbonyls
UR - http://www.scopus.com/inward/record.url?scp=84861197219&partnerID=8YFLogxK
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U2 - 10.1016/j.micromeso.2011.07.025
DO - 10.1016/j.micromeso.2011.07.025
M3 - Article
AN - SCOPUS:84861197219
SN - 1387-1811
VL - 157
SP - 56
EP - 61
JO - Microporous and Mesoporous Materials
JF - Microporous and Mesoporous Materials
ER -