The synthesis of a novel class of alcohol- and ether-functionalized indenyl ligands, focusing on the haptotropic rearrangements of the hybrid O-indenyl rhenium species, is herein described. η1- Indx OMeRe(CO)5 (12x) and η3-IndxOMeRe(CO)4 (13x, x=a, d) [IndaOMe=C9H6CH2CH(Me)OMe, 1a; Indd OMe=C9H6CH(CH2)3CHOMe, 1da] are examples of σ and allylic intermediates in the Cp substitution. The tuning of stereoelectronic effects of the functionalized alkyl chain or the coordinating solvent (MeCN, THF) allows the study of the relative stabilities of the intercepted solvento species η5-Indb OMeRe(CO)2(NCMe), 14b, η5-Indc OMeRe(CO)2(THF), 15c, or the chelate [η5:k1-OIndb, c ORe(CO)2], 16b,c {Indb OMe=[C9H6CH2CH(Ph)OMe]-, 4b; Indc OMe=[C9H6CH(Ph)CH2OMe]-, 4c}. DFT calculations reported on some of the IndO systems have been compared with those of smaller (CpO) 5a or larger (Flua O) 10a congeners, confirming the experimental findings. As peculiar examples of the underrepresented low-valent rhenium alkoxy species, the isolation of k1-O-HIndxORe(CO)5 [x=a, b] is also reported

Ligand Control in Multihaptotropic O-Indenyl Rhenium Systems. Experimental and Theoretical Study

S. Bordoni;S. Cerini;R. Tarroni;S. Zacchini;
2009

Abstract

The synthesis of a novel class of alcohol- and ether-functionalized indenyl ligands, focusing on the haptotropic rearrangements of the hybrid O-indenyl rhenium species, is herein described. η1- Indx OMeRe(CO)5 (12x) and η3-IndxOMeRe(CO)4 (13x, x=a, d) [IndaOMe=C9H6CH2CH(Me)OMe, 1a; Indd OMe=C9H6CH(CH2)3CHOMe, 1da] are examples of σ and allylic intermediates in the Cp substitution. The tuning of stereoelectronic effects of the functionalized alkyl chain or the coordinating solvent (MeCN, THF) allows the study of the relative stabilities of the intercepted solvento species η5-Indb OMeRe(CO)2(NCMe), 14b, η5-Indc OMeRe(CO)2(THF), 15c, or the chelate [η5:k1-OIndb, c ORe(CO)2], 16b,c {Indb OMe=[C9H6CH2CH(Ph)OMe]-, 4b; Indc OMe=[C9H6CH(Ph)CH2OMe]-, 4c}. DFT calculations reported on some of the IndO systems have been compared with those of smaller (CpO) 5a or larger (Flua O) 10a congeners, confirming the experimental findings. As peculiar examples of the underrepresented low-valent rhenium alkoxy species, the isolation of k1-O-HIndxORe(CO)5 [x=a, b] is also reported
2009
S. Bordoni; S. Cerini; R.Tarroni; S. Zacchini; L. Busetto
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/77617
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