Bivalent and monovalent rhodium porphyrin complexes

Stable mononuclear rhodium(II) polypyridyl complexes: synthesis, spectroscopic and structural characterisation

“…7, 13 It has also been reported that the reaction between rhodium trichloride hydrate and bulky phosphine resulted in a mixture of rhodium() and rhodium() complexes. 12, 30 Our observations, therefore, are similar to some earlier reports with different types of ligands. 12,30…”

The synthesis, X-ray structure, and substitution lability of chloro(2,3,7,8,12,13,17,18-octaethylporphinato)(triphenylphosphine)rhodium(III)

“…Complex 1 in benzene, THF, or MeCN, however, is photochromic in the presence of 1 atm CO, and reacts according to reactions [8] and [9]. Exposure to laboratory light or sunlight yields within minutes an in situ carbonyl (vco = 2087 em-' in THF) with concomitant release of PPh3, and the nmr data (Table 1) Table 9.…”

“…Isoelectronic with 3, the neutral, isolated Ru(OEP)(PPh,) species reacts more readily with CO ( 3 , 6 , 17), presumably because the better T-acceptor properties of CO (vs. PPh3) are more compatible with the lower oxidation state of Ru(I1). The lack of reaction with CO also indicates negligible dissociation of PPh3 under these conditions to form Rh(OEP)Cl, which is known to react with CO to form Rh(OEP)(CO)Cl (27, and see below), reactions [8] and [9] :…”

Novel rhodium(I)-porphyrin complexes and organorhodium(III)-porphyrin complexes. IV

“…3 The synthesis of a Rh(I)-porphyrin complex formulated as H[Rh1 (porphyrin)] •2 20 has been reported by James and Stynes. 4 We have also prepared new Rh(I)-porphyrin complexes during the incorporation of Rh by porphyrin and (V-alkylporphyrin.5 '6 The alkylrhodium(III) porphyrins were obtainable from the reaction of chlororhodium(III) porphyrin with alkyllithium. 5 The formation of a Rh-C bond in the case of rhodium(III)-a,/3,y,5-tetraphenylporphine complexes has been recently reported by two different groups.7•8 In view of the paucity of information concerned with the reaction of the low valent Rh porphyrin complex in relation to cobalamins, this present report deals with the formation of the Rh(III)-C bond by means of various new synthetic pathways.…”