By Buchler J.W.
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Additional info for Metal Complexes with Tetrapyrrole Ligands III
Example text
The bidentate bis(diphenylphosphino) alkane ligands (entries 8 and 42) are not capable of forcing the porphyrin ligand to leave the equatorial position of noble metal porphyrins. Either two bidentates are bound in a monodentate fashion, or a bidentate bridges two metalloporphyrin entities. Synthesis and Coordination Chemistry of Noble Metal Porphyrins Table 2. Representative precious metal porphyrins as studied by X-ray crystallography Entry Complex Ref. W. Buchler et al. 22 Table 2. Continued e) Palladium and platinum porphyrins 44 45 46 47 48 Pd(TPP) Pd(OEP), Pd(H2OEP) Pd(TDBOHPP) = Pd(SDPDTP)" Pt(TPP) [183] [183] [185] [186] [187] f) Silver and gold porphyrins 49 50 Ag(TPP) AuCI(TPP) • CHCI3 [188] [189] "dpm: Bis(diphenylphosphino)methane b H2 (PBP): "picnic-basket" porphyrin ¢ H(NPhOEP): N-Phenyloctaethylporphyrin d StOx: styrene oxide.
G. (TPP)RhMn(CO)s, [path c, X = Mn(CO)5] was formulated as starting from RhCI(TPP) [63], but the work referred to [264] clearly stated that hexacoordinate species, namely RhCI(TPP)H20, RhCI(TPP)(EtOH), or RhCI(TPP)CO were involved. On the other hand, the heterobimetallic species appear to be pentacoordinate about the rhodium, in accord with many metal-metal-bonded porphyrin complexes [222] (see also below). Bubbling carbon monoxide through a solution of RhCI(TPP)H20 (path d) yields the photolabile (path - d) carbonylrhodium(III) complex in which the rather high CO frequency (2100 cm-1) suggested the possibility of a nucleophilic attack to this ligand which was indeed achieved (path f), yielding an ethoxycarbonylrhodium(III) moiety; this reaction could be reversed with hydrogen chloride (path - f).
Buchler et al. g. T H F or MeCN, an inner-sphere process is operative, ultimately leading to dioxometal(VI) porphyrins (paths - k , - j ) . These reactions are similar to those of the "bare" ruthenium(II) or osmium(II) porphyrins (see below). If L is a strong donor (L = Py, 1-Meim), the osmochromes are substitutionally inert. The inner-sphere attack of dioxygen is precluded. Nevertheless, an outer-sphere autoxidation occurs which is acid-induced. It proceeds more rapidly in the presence of Bronsted acids and stops at the Os(III) level (path v); the stoichiometry of Eqs.