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

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.

Synthesis and characterization of metal–rich phosphonium polyelectrolytes and their use as precursors to nanomaterials

“…The electrochemical properties of the phosphonium triflate monomers 7a-d and the corresponding polyelectrolytes 8a-d were examined by cyclic voltammetry (CV) in a CH 2 Cl 2 /CH 3 CN (2/1) solvent mixture containing 0.1 M [n-Bu 4 N][OTf ] as supporting electrolyte. Consistent with the electrochemical properties of the parent phosphines, 13 the ferrocene units of the monomers and polyelectrolytes were oxidized reversibly, Scheme 1 Synthetic pathway for the preparation of polyelectrolytes 8a-d. 2, and C36-P1-C37 109.6(3).…”

“…1 H NMR (DMSO-d 6 ): δ 7.62 (d, 3 J HH = 8 Hz, 2H, aryl CH), 7.48 (dd, 3 J HH = 7 Hz, 5 J HP = 2 Hz, 2H, aryl CH), 6.78 (dd, 3 J HH,cis = 11 Hz, 3 J HH,trans = 18 Hz, 1H, ArCHvCH 2 ), 5.90 (d, 3 J HH,trans = 18 Hz, 1H, ArCHvCH 2 ), 5.30 (d, 3 and C 5 H 4 CH 2 CH 2 , overlaps with residual CD 3 CD 2 HSO signal). 13 Phosphonium chloride salt 6c (1 × Fc, 2 × Rc). From tertiary phosphine 5c (1.00 g, 1.32 mmol) and 4-vinylbenzyl chloride (204 µL, 1.45 mmol, 1.1 equiv.).…”

Mechanochemical Synthesis of Phosphinecarboxamides by Reaction of 2‐Phosphaethynolate Anion and Amines under Acid‐Free Conditions: A Combined Scope and Mechanism Investigation

“…In the last decade, many strategies have been reported for the synthesis of air‐stable primary phosphines by introducing a bulky substituent, a heteroatom, or a ferrocenyl backbone to the phosphine structure. These species have been adapted successfully to the needs and expectations of modern organic chemistry . The preparation of N ‐substituted carbamoylphosphines from the reaction of an aryl isocyanate with a phosphine having a P–H bond has been reported; however, only tertiary phosphines were prepared in this report .…”

Synthesis and properties of alternating metallopolymers

“…图 1 交替序列金属有机聚合物的合成路线 [5,[26][27][28] Figure 1 Synthetic approach toward alternating metallopolymers. [41] [39] , 450 nm 处的吸收峰是二茂铁典型的 d-d* 跃迁, 350 nm 处的肩峰归属于环戊二烯上酯键取代 基的贡献 [40] . 6 UV-vis spectra of four alternating metallopolymers in dichloromethane.…”