Synthesis and Structures of Zinc(II) and Cadmium(II) Complexes with (η⁶‐Benzenecarboxylate) Chromium Tricarbonyl and Pyrazole Derivatives

Abstract

Reaction of zinc acetate with four different substituted pyrazoles (3,5-dimethyl pyrazole (3,5-Me 2 PzH), 3,5-di-tert-butyl pyrazole (3,5-tBu 2 PzH), 3,5-diphenyl pyrazole (3,5-Ph 2 PzH), and 5-methyl-3phenyl pyrazole (3-Ph-5-Me-PzH)) followed by treatment with (η 6 -benzenecarboxylic acid) chromium tricarbonyl afforded the bimetallic zinc-chromium complexes [Zn{(η 6 -C 6 H 5 COO)Cr(CO) 3 } 2 -(3,5-Me 2 PzH) 2 ], [Zn{(η 6 -C 6 H 5 COO)Cr(CO) 3 } 2 (3,5-tBu 2 PzH) 2 ], [Zn{(η 6 -C 6 H 5 COO)Cr(CO) 3 } 2 (3,5-Ph 2 PzH) 2 ], and [Zn{η 6 -C 6 H 5 COO)

Metal–Organic Frameworks Containing (Alkynyl)Gold Functionalities: A Comparative Evaluation of Solvent-Assisted Linker Exchange, de Novo Synthesis, and Post-synthesis Modification

“…Over the past decade, as the number of published metal–organic framework (MOF) structures exponentially increased, MOFs containing organometallic functionalities also began to appear in high numbers. Interestingly, the majority of these functionalities have been stable metal–carbonyl species, − ferrocene derivatives, − and late metal- N -heterocyclic carbene moieties. , Given the relatively high temperature and acidic reaction media often used for MOF syntheses, it is not surprising that MOFs containing less-stable metal-hydrocarbyl moieties have been relatively rare. − While post-synthesis modification (PSM) strategies can potentially be used to prepare metal-hydrocarbyl-containing MOFs, − they are hampered by the low accessibility of the reactive sites in the parent MOF and/or the need to use multiple reactions to arrive at the desirable organometallic-functionalized framework. As such, we were interested in the possible application of solvent-assisted linker exchange (SALE)a concept that was originated by Choe, − and expanded by Cohen, − us, − and others, − to synthesize MOFs containing non-carbonyl organometallic functionalities.…”