Unexpected reactivity of Rh(TPP)I(CO) toward an alkoxide in CH2Cl2: Synthesis and crystal structure of Rh(TPP)(CH2Cl)

Authors
Collman, JP Boulatov, R
Citation
Jp. Collman et R. Boulatov, Unexpected reactivity of Rh(TPP)I(CO) toward an alkoxide in CH2Cl2: Synthesis and crystal structure of Rh(TPP)(CH2Cl), INORG CHEM, 40(3), 2001, pp. 560
Citations number
62
Categorie Soggetti
Inorganic & Nuclear Chemistry
Journal title
INORGANIC CHEMISTRY
ISSN journal
00201669 → ACNP
Volume
40
Issue
3
Year of publication
2001
Database
ISI
SICI code
0020-1669(20010129)40:3<560:URORTA>2.0.ZU;2-A
Abstract
Rh(TPP)I(CO) (TPP = tetraphenylporphyrin dianion) reacts with OR- (R = Me, Et) in CH2Cl2 under CO to yield Rh(TPP)(CH2Cl). The proposed mechanism incl udes displacement of I- by OR-, reductive elimination of aldehyde from Rh(T PP)(OR), and S(N)2 reaction between the resulting Rh(TPP)(-) and CH2Cl2. Th e molecular structure of Rh(TPP)(CH2Cl) reveals the shortest Rh-C bond (2.0 10(4) A) among the reported (chloromethyl)rhodium(III) complexes and an unu sually large "saddle" distortion of the porphin core.