Acid-induced demetalation

The rate of acid-induced demetalation depends only slightly on the nature of the head substituents X (Table I). In contrast, the tail-R groups dramatically affect k and, for the most part, k3, suggesting that tail amide O-atoms are sites of peripheral protonation. Thus, the acid tolerant Fem-TAML catalysts with tail electron-withdrawing groups should be more acid resistant and replacement of R = Me with R = F results in a remarkable stabilization. The rate constants (Table I) show that under weakly acidic conditions (pH 2-3), when the k pathway dominates over k3, fluorinated lk is 105-fold more H +-tolerant than la. 

Five years later, Gust s group [34] developed another triad incorporating a porphyrin (P) linked to a dithienylethene (DTE) and a fulgimide (FG) (Scheme 6). The main synthetic approach was still the Sonogashira coupling of dithienylethene and fulgimide-appended zinc porphyrin (FG-PZn-DTE). Trifluoroacetic acid-induced demetalation of FG-PZn-DTE produced FG-P-DTE in 57% yield. 

An approach to isobacteriochlorins1 ln-e makes use of Pd(II) or metal-free bilatrienes 1 as starting materials. Cyclization of the corresponding bilatriene derivatives is induced by base in the presence of palladium(II) or zinc(II) which exercise a template effect. Zinc can be readily removed from the cyclized macrotetracycles by acid whereas palladium forms very stable complexes which cannot be demetalated. Prior to the cyclization reaction, an enamine is formed by elimination of hydrogen cyanide from the 1-position. The nucleophilic enamine then attacks the electrophilic 19-position with loss of the leaving group present at the terminal pyrrole ring. 

Elimination to yield alkenes can be induced thermally or by treatment with acids or bases (for one possible mechanism, see Figure 3.39) [138,206]. Less common thermal demetallations include the thermolysis of arylmethyloxy(phenyl)carbene complexes, which can lead to the formation of aryl-substituted acetophenones [276]. Further, (difluoroboroxy)carbene complexes of molybdenum, which can be prepared by treating molybdenum hexacarbonyl with an organolithium compound and then with boron trifluoride etherate at -60 °C, decompose at room temperature to yield acyl radicals [277]. 

The acid demetallation mechanism is simpler than the metallation mechanism.18 In general, the rate law is expressed as d[H4Por2+]/df = k[M(Por)][H+]" [n = 1-3 depending on the stability of M(Por)] where aggregation is negligible, and N protonation induces the metal dissociation. 

Ferritin induced nanoparticle synthesis was adapted from a number of different synthetic strategies reliant upon the physical nature of ferritin. For instance, ferritin can readily exist in two stable forms (native ferritin with an intact iron oxide core or apo-ferritin lacking a mineral core) owing to the enhanced structural integrity of the protein shell. As a result, two general reaction schemes were adopted. The first route utilized the iron oxide core of native or reconstituted ferritin as a precursor to different mineral phases and types of iron nanoparticles, while the second invokes mineralization within the empty cavity of apo-ferritin. In the latter approach, the native protein must be demetallated by reductive dissolution with thioglycolic acid to yield apo-ferritin. Ultimately, apo-ferritin provides a widely applicable means to the synthesis of various nanoparticle compositions under many conditions. 

Figure 11 Fast demetallation in acidic solution of [M"(dioxocyclamato(2 )] complexes (M = Cu, Ni). Two protons attack the very accessible and partially negative oxygen atoms of the carbonyl groups, which induces a drastic reduction of the coordinating tendencies of the adjacent nitrogen atoms and promotes metal extrusion.

A catalytic addition of acidic alcohols or phenols to hexafluoropropene is induced by the complex Pd(PPh3)4 [110]. Catalytic activity is increased in the presence of cocatalytic l,4-bis-(diphenylphosphino)butane (dppb) (Scheme 19). The authors propose a mechanism involving external protonation of a Pd(0)-coordinated olefin and reductive elimination to the ether product, but both steps appear improbable. There is literature precedence for insertion of tetrafluoroethylene into the Pt-O bond of (dppe)PtMe(OMe) to give (dppe)PtMe(CF2CF20Me), but proto-demetallation of the resulting complex has not been reported [111, 112]. 

---