Cationic copper complexes

Scheme 61).22 149 150 152 229 230 The methylene-bridged bis(oxazoline)s (70) can afford either neutral copper complexes of the semicorrin type (72) or cationic copper complexes (73). Cyclopro-panation with copper complexes of type (70) shows similar stereochemistry to that with the corresponding copper semicorrin complexes.229-231 Alternatively, bis(oxazoline) ligand (71), bearing... 

A cationic copper complex with (K)-tol-BINAP as chiral auxiliary catalyzes asymmetric addition of allenyltin and propargyltin compounds to a-iminoesters to produce, preferentially, propargyl and allenyl adducts, respectively, in moderate to high enantioselectivity (Scheme 12.32) [83]. 

In 2006, Diez-Gonzalez et al. synthesized air- and moisture-stable cationic copper complexes bearing two NHC ligands. These complexes were found highly active toward the hydrosilylation of different ketones, aldehydes and esters with Et3SiH, and generally, starting substrates were transformed into the... 

Fonnation of a complex with a copper cation only further stimulates this behaviour. As a result, S.lg is almost completely bound to the micelles, even at low concentrations of Cu(DS)2. By contrast, the reaction of 5.1 f still benefits from an increasing surfactant concentration at 10 mM of Cu(DS)2. In fact, it is surprising that the reaction of this anionic compound is catalysed at all by an anionic surfactant. Probably it is the copper complex of 5.If, being overall cationic, that binds to the micelle. Not surprisingly, the neutral substrate S.lc shows intermediate behaviour. 

Despite the weak basicity of isoxazoles, complexes of the parent methyl and phenyl derivatives with numerous metal ions such as copper, zinc, cobalt, etc. have been described (79AHC(25) 147). Many transition metal cations form complexes with Imidazoles the coordination number is four to six (70AHC(12)103). The chemistry of pyrazole complexes has been especially well studied and coordination compounds are known with thlazoles and 1,2,4-triazoles. Tetrazole anions also form good ligands for heavy metals (77AHC(21)323). 

The cationic aqua complexes prepared from traws-chelating tridentate ligand, R,R-DBFOX/Ph, and various transition metal(II) perchlorates induce absolute enantio-selectivity in the Diels-Alder reactions of cyclopentadiene with 3-alkenoyl-2-oxazoli-dinone dienophiles. Unlike other bisoxazoline type complex catalysts [38, 43-54], the J ,J -DBFOX/Ph complex of Ni(C104)2-6H20, which has an octahedral structure with three aqua ligands, is isolable and can be stored in air for months without loss of catalytic activity. Iron(II), cobalt(II), copper(II), and zinc(II) complexes are similarly active. 

Jorgensen et al. [84] studied how solvent effects could influence the course of Diels-Alder reactions catalyzed by copper(II)-bisoxazoline. They assumed that the use of polar solvents (generally nitroalkanes) improved the activity and selectivity of the cationic copper-Lewis acid used in the hetero Diels-Alder reaction of alkylglyoxylates with dienes (Scheme 31, reaction 1). The explanation, close to that given by Evans regarding the crucial role of the counterion, is a stabilization of the dissociated ion, leading to a more defined complex conformation. They also used this reaction for the synthesis of a precursor for highly valuable sesquiterpene lactones with an enantiomeric excess superior to 99%. 

The neutral 3 dx metallocenes are thus known for x = 3 — 8, but the d9 copper complex has thus far resisted preparation, and the d2 titanocene has been found (54) to be both diamagnetic and dimeric, and is therefore excluded from consideration here. A number of cationic species, corresponding formally to Ti(Cp)2+, and V(Cp)2+, systems are however well known, but it seems very probable that these do not possess pseudo-axial symmetry (see (41) for further discussion), and very recently it has been demonstrated (55) that stable V(Cp)2+ complexes cannot be isolated without the coordination of an additional ligand to the metal. The parent systems are therefore limited to V(Cp)2, Cr(Cp)2, Mn(Cp)2, Fe(Cp)2, Co(Cp)2, and Ni(Cp)2 and the cationic species to Cr(Cp)2+, Fe(Cp)2+, Co(Cp)2+, and Ni (Cp)2+> and the d-d spectra of these systems are now considered individually. 

Despite numerous studies involving copper catalysts, only a few isolated copper complexes have been examined, including complexes (155)-(157). Bipyridine,397 phenanthroline,398 and pyridyli-mine cationic complexes399 all exhibit tetrahedral geometries, in which the copper center is bound to two ligands. 

Furthermore, the first direct amination of benzene has been achieved and has generated the aniline derivative in an acceptable yield (Equation (103)). Recently, a cationic copper(i) complex 132-catalyzed nitrene transformation to the C-H bonds of the electron-rich arene was reported by Sadighi and co-workers (Equation (104)).285... 

The analogous cationic pyridylbis(oxazoline)-copper complexes exhibit square pyramidal geometries in the solid state. As in the bis(oxazoline) series, the triflate is closer to the metal than the SbF6 counterion (2.36 and 2.49 A vs 2.90 A). A single molecule of water is bound to the copper center in the triflate complex 267b, whereas the SbF6 complex 268b accommodates two water molecules in the coordination sphere, Fig. 24 (197). 

The cationic aqua complexes of the C2-symmetric trans-chelating tridentate ligand 447 proved also highly effective chiral catalysts. The complexes involving the metal(II) perchlorates of iron, cobalt, nickel, copper and zinc produced the main endo adduct of cyclopentadiene and N - aery loy 1-1,3 -oxazo I i din -2 -one with very high ee values281. 

Scheme 2.38. Reactions between copper-zinc reagents and cationic metal complexes.

Oxygenic photosynthetic organisms, [2Fe-2S] ferredoxins, 38 224-233 Oxygenyl ion, preparation of, 9 229 Oxyhalides, of berkelium, 28 49, 51-53 Oxyhalogeno cations, 9 276-279 Oxyhemerythrin, 40 373-374, 45 84 XAS, 36 325 Oxyhemocyanin, 40 363 m-peroxo dinuclear copper complexes as models for, 39 41-52 physicochemical properties, 39 47-48 Oxyhemocyanins, XAS, 36 326-327 Oxyhemoglobin, 21 135 Oxyiodonium cations, 9 277 Oxymanganese phthalocyanine, strucmre of, 7 31-35... 

SCHEME 84. Addition of functionalized zinc-copper reagents to cationic chromium complexes and subsequent cyclization... 

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