Volumes of activation for kinetically labile organometallic complexes: solvent displacement from cis-[(C₆H₅Cl)(PPh₂R)W(CO)₄][R = Ph, (CH₂)₄CHCH₂] in chlorobenzene solution

Abstract

Large, positive, and similar volumes of activation, indicative of dissociative desolvation mechanisms, have been observed for chlorobenzene displacement by pyridine and through chelate ring closure, respectively, f r o m c~s-[(C~H,CI)(PP~~R)W(CO)~] complexes [R = Ph, (CHJ4C=CH2] produced via pulsed laser flash photolysis.

Synthesis and structure of hydridobis(ethylene) and hydrido dinitrogen complexes of rhenium(I) having dimethylphenylphosphine ligands

“…Preparation of mer -Hy dridobis (ethylene) tris (dimethyphenylphosphine)rhenium(I) (1). Treatment of mer-trichlorotris(dimethylphenylphosphine)rhenium(III)6…”

“…R=Pr with ethyllithium (8 mol/Re) in dry ether at room temperature gave yellow crystals of mer-hydridobis (ethylene)tris(dimethylphenylphosphine)rhenium(I) (1) in 54% yield (eq 1). 1 is moderately stable thermally but slowly decomposes under air.…”

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mer-Hydridobis(ethylene)tris(dimethylphenylphosphine)rhenium(I) (1) and cis-hydrido(dinitrogen)tetrakis(dimethylphenylphosphine)rhenium(I) (2) have been prepared by the reaction of mer-trichlorotris(dimethylphenylphosphine)rhenium(I) with ethyllithium and n-propyllithium, respectively. X-ray structure analysis reveals that both complexes are octahedral, and in the former complex the two coordinated ethylenes occupy sites perpendicular to each other in cis positions and in the latter complex hydrido and dinitrogen ligands in cis positions.

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