10.1002/ejic.200600939
The research aimed on the preparation, structure, and reactivity of polynuclear gold(I) phosphanyl alkane thiolates. The purpose of the study was to synthesize, characterize, and investigate the redox behavior of a series of gold(I) thiolate complexes derived from simple sterically demanding alkanethiols, including tert-butyl, sec-butyl, neopentyl, and trityl groups. The researchers converted homoleptic gold(I) thiolates into their phosphane derivatives and examined their electrochemical behavior and chemical oxidation, ultimately revealing that the aliphatic thiols form neutral gold thiolates without Au–Au bonding interactions in the solid state. However, upon oxidation, these complexes form cationic derivatives that dimerize to dicationic tetranuclear species with aurophilic interactions in the solid state. The study also observed an unusual zigzag organization in the case of complexes with a chelating phosphane. The chemicals used in this process included various gold(I) thiolates, phosphanes like PMe3, PMe2Ph, PMePh2, PPh3, and dppe, as well as oxidizing agents like [FeCp2]BF4, and nucleophiles such as thiolate anions and lithium alkyls. The conclusions highlight the structural diversity and reactivity of these gold(I) complexes, which are influenced by the nature of the ligands and can lead to different polynuclear structures.
10.1021/om700305e
The research discusses the reaction of cyclopentadienyl ruthenium complexes with a carborane anion, aiming to understand the impact of spectator ligands on the substitution site. The study explores how the steric and electronic properties of different ligands influence the nucleophilic attack site, leading to the formation of two types of complexes: [Ru(H)(C5H4-carb)L1L2] or [Ru(carb)(Cp)L1L2]. The researchers used a variety of ruthenium cyclopentadienyl complexes with different neutral ligands such as PPh3, PMe2Ph, PMePh2, dppe, COD, CO, and PPh3, along with the carborane anion derived from 2-Me-1,2-dicarba-closo-dodecaborane (HCC(Me)B10H10). The results indicated that electronic effects play a predominant role in determining the site of nucleophilic attack, with complexes containing poorer electron-donor ligands favoring nucleophilic attack at the Cp ring. The study concluded that the reactivity trend is related to the electron density on the metal center, which is influenced by the basicity of the ligands, and proposed a possible mechanism for the observed reactivity involving nucleophilic substitution, reductive elimination, exo-1,5-shift, and oxidative addition.
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