Synthesis and Characterization of a Family of Air-Stable Ferrocene- and Ruthenocene-Containing Primary, Secondary, and Tertiary Phosphines

Authors

Amir Rabiee Kenaree
Tyler J. Cuthbert
Stephanie M. Barbon
Paul D. Boyle
Elizabeth R. GilliesFollow
Paul J. Ragogna
Joe GilroyFollow

Document Type

Article

Publication Date

Summer 8-28-2015

Journal

Organometallics

Volume

34

First Page

4272

Last Page

4280

URL with Digital Object Identifier

DOI: 10.1021/acs.organomet.5b00496

Abstract

The synthesis and characterization of a family of air-stable primary, secondary, and tertiary phosphines containing all possible combinations of ethylferrocene and ethylruthenocene substituents are reported. Each phosphine was characterized by ¹H, ¹³C, and ³¹P NMR spectroscopy, IR and UV-vis absorption spectroscopy, mass spectrometry, and elemental analysis. With the exception of primary ethylruthenocene phosphine 8a, all of the title compounds have been studied by single crystal X-ray crystallography. Ferrocene-containing phosphines showed maximum absorption at wavelengths of ca. 440 nm and qualitatively reversible oxidation waves in their cyclic voltammograms with intensities scaling to the number of ferrocene units present. The average metal-cyclopentadienyl centroid distances observed for ferrocene-containing phosphines were shorter than those of ruthenocene-containing phosphines, which also had maximum absorption wavelengths of ca. 320 nm and underwent irreversible electrochemical oxidation. Phosphines containing both ethylferrocene and ethylruthenocene substituents displayed properties consistent with the presence of both metallocene types.