Chemical, Electrochemical, and Theoretical Investigations of [(Cp)Ru(CO)₃]⁺and [(Ind)Ru(CO)₃]⁺

Abstract

The complexes [(Cp)Ru(CO)3]+ and [(Ind)Ru(CO)3]+ were subjected to chemical, electrochemical, and spectroelectrochemical investigations in an attempt to gauge their similarity to [(Cp)Fe(CO)3]+ and [(Ind)Fe(CO)3]+. While the Fe complexes exhibited reversible electrochemical behaviorthe indene analogue exhibiting a so-called “inverse indenyl effect”the Ru complexes exhibited limited electrochemical reversibility, even at −30 °C and higher scan rates. The formation of the hydride complexes [(Cp)Ru(CO)2H] and [(Ind)Ru(CO)2H] was observed via 1H NMR and IR. The X-ray crystal structure of [(Ind)Ru(CO)3]+ is presented here for the first time.

A Commercially Available Ruthenium Compound for Catalytic Hydrophosphination

“…[16] To test the first proposal, a stoichiometric reaction of 2 with diphenylphosphine, both Cp(CO) 2 RuPPh 2 and Cp(CO) 2 RuH are observed by 1 H and 31 P NMR spectroscopy (benezene-d 6 , Eq 3). [17] To test the latter supposition, 2 was treated with two equivalents of diphenylphosphine and monitored by NMR spectroscopy over the course of 24 hours. In that reaction, the relative concentration of Cp(CO) 2 RuH rises and then falls with an increase in Cp(CO) 2 RuPPh 2 .…”

“…Thus, it is reasonable to suspect that Cp(CO) 2 RuH could also react with phosphine to also form Cp(CO) 2 RuPRR’ derivatives, which are known . To test the first proposal, a stoichiometric reaction of 2 with diphenylphosphine, both Cp(CO) 2 RuPPh 2 and Cp(CO) 2 RuH are observed by 1 H and 31 P NMR spectroscopy (benezene‐ d 6 , Eq 3) . To test the latter supposition, 2 was treated with two equivalents of diphenylphosphine and monitored by NMR spectroscopy over the course of 24 hours.…”

A Commercially Available Ruthenium Compound for Catalytic Hydrophosphination

“…[16] To test the first proposal, a stoichiometric reaction of 2 with diphenylphosphine, both Cp(CO)2RuPPh2 and Cp(CO)2RuH are observed by 1 H and 31 P NMR spectroscopy (benezene-d6, Eq 3). [17] To test the latter supposition, 2 was treated with two equivalents of diphenylphosphine and monitored by NMR spectroscopy over the course of 24 hours. In that reaction, the relative concentration of Cp(CO)2RuH rises and then falls with an increase in Cp(CO)2RuPPh2.…”

Electrochemical analysis of cyclopentadienylmetal carbonyl dimer complexes: Insight into the design of hydrogen-producing electrocatalysts

“…This not only leads to a poorer basic nature of the central ruthenium, but also allows for greater nucleophilic attack upon the ruthenium (a suspected degradation pathway when conjugate base of the weak acid proton source is present) [48]. Studies on the DFT-computed LUMO of the related cationic species Fp þ and Rp þ (equivalent to HOMO-1 for the anion) also showed a large discrepancy in the orbital density on the central metal (53% iron vs. 20% ruthenium) [49].…”