alexa Synthesis, Characterization And Reactivity Of Metal Carbonyl Complexes Containing Hemilabile Phosphines As Ligands | 62314
ISSN: 2161-0444

Medicinal Chemistry
Open Access

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International Conference on Stereochemistry

Yomaira Otero
Instituto Venezolano de Investigaciones Científicas (IVIC), Venezuela
Posters & Accepted Abstracts: Med chem
DOI: 10.4172/2161-0444.C1.022
Abstract
The hemilability of polydentated hybrid ligands has become an attractive area of study due to their high potential in homogeneous catalytic systems to enhance selectivity or stabilize reactive intermediates. The lability of π-coordinated substituents to metal centers has been taken as an advantage to design potentially hemilabile phosphine ligands. Thus, it has been shown that functionalized phosphines with alkenyl substituents behave as hemilabile ligands in transition metal clusters. We have found that diallylphosphine ligands RP(CH2CH=CH2)2, where R=iPr2N, p–MeOC6H4 and o–MeOC6H4, coordinate to dirhenium and triosmium metal carbonyl, preferably by the phosphorus atom, but also through the allyl fragment. We have observed that complexes with metal–allyl π–bond exit as a mixture of two conformational isomers, and such isomerization can be described as a reorientation of the coordinated double bond with respect to dirhenium or triosmium metal complex. These complexes also display hemilability properties, which are evidenced by reaction with nucleophiles (such as: CO, PPh3 and allene), leading to cleavage of the allyl π-coordination and its substitution through the corresponding nucleophile. Additionally, these results suggest that the metal–allyl π–interaction is stronger for diallyldiisopropylaminophosphine than diallyl (p-methoxyphenyl) phosphine ligand.
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