Abstract:Ditelluraporphodimethene, a nonaromatic porphyrinoid containing two tellurophene rings, reacted with palladium(II), platinum(II), and rhodium(I) following two different paths. Palladium(II) formed bonds to two tellurium donors of the macrocycle, yielding a side-on coordination compound, with a square planar (Te 2 Cl 2 ) metal ion environment. An alternative reaction path has been observed for ditelluraporphodimethene with platinum(II) or rhodium(I) in high boiling solvents. These conditions led to the profound… Show more
“…The synthesis avoided unlikely four-fold activation of C–H bonds of the formal ligand, 2 , and followed the tellurium-to-metal substitution protocol, employed in our former studies. 15,20–22 The synthetic path, starting with tetrakis(4-methoxyphenyl)-21,23-ditelluraporphyrin 3 , 16 takes advantage of a significant difference in the reactivity of a tellurophene unit towards platinum( ii ) and rhodium( i ) salts, which determines the order of steps. Thus, a single tellurium-to-metal replacement proceeded with platinum( ii ), yielding the known 21-platina-23-telluraporphyrin 4 , 21 which served as a starting material for the second substitution with the more reactive rhodium( i ), as shown in Scheme 1.…”
mentioning
confidence: 99%
“…23,24 Generally, it can be considered as a rule, that the tellurium-to-metal substitution in metallaporphyrin synthesis is preceded by the formation of a side-on coordination compound. 15,[20][21][22] The heterobimetallic 5, reacts with chlorine through an oxidative addition at the platinum(II) centre yielding quantitatively the platinum(IV) analogue, 5-Cl 2 . The reaction can be readily reversed with zinc amalgam.…”
The incorporation of two metal atoms, platinum and rhodium, in place of NH groups in the porphyrin macrocycle brings them into close proximity. The weak metal–metal bond is switched on and off depending on the oxidation state of the platinum ion.
“…The synthesis avoided unlikely four-fold activation of C–H bonds of the formal ligand, 2 , and followed the tellurium-to-metal substitution protocol, employed in our former studies. 15,20–22 The synthetic path, starting with tetrakis(4-methoxyphenyl)-21,23-ditelluraporphyrin 3 , 16 takes advantage of a significant difference in the reactivity of a tellurophene unit towards platinum( ii ) and rhodium( i ) salts, which determines the order of steps. Thus, a single tellurium-to-metal replacement proceeded with platinum( ii ), yielding the known 21-platina-23-telluraporphyrin 4 , 21 which served as a starting material for the second substitution with the more reactive rhodium( i ), as shown in Scheme 1.…”
mentioning
confidence: 99%
“…23,24 Generally, it can be considered as a rule, that the tellurium-to-metal substitution in metallaporphyrin synthesis is preceded by the formation of a side-on coordination compound. 15,[20][21][22] The heterobimetallic 5, reacts with chlorine through an oxidative addition at the platinum(II) centre yielding quantitatively the platinum(IV) analogue, 5-Cl 2 . The reaction can be readily reversed with zinc amalgam.…”
The incorporation of two metal atoms, platinum and rhodium, in place of NH groups in the porphyrin macrocycle brings them into close proximity. The weak metal–metal bond is switched on and off depending on the oxidation state of the platinum ion.
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