The First Triple-Decker Complex with a Carbenium Center, [CpCo(μ-C3B2Me5)RuC5Me4CH2]+: Synthesis, Reactivity, X-Ray Structure, and Bonding

The first derivative of the methylium cation with the triple-decker substituent, [CpCo(C3B2Me5)RuC5Me4CH2]PF6 ( 2 PF6), was synthesized from the reaction of the triple-decker complex CpCo(C3B2Me5)RuCp* ( 1 ) with the salt of the trityl cation [CPh3]+. The X-ray crystal structure of 2 PF6 reveals that the methylium carbon is bound to the ruthenium with Ru−C bond length of 2.259 Å and corresponds to the description of its structure as η6-fulvene-ruthenium. Reactions of 2 PF6 with nucleophiles OH−, Ph3P, Et3N led to the corresponding derivatives of 1 in high yields. Aromatic amines PhNEt2 and 4-MeC6H4NH2 react with 2 PF6 to give the electrophilic aromatic substitution products quantitatively. Chemical reduction of 2 PF6 with Zn powder in tetrahydrofuran leads to the formation of the bis(triple-decker) derivative (CpCo(C3B2Me5)RuC5Me4CH2)2 ( 10 ) with a CH2CH2-bridge. The structures of complexes 4 , 7 – 10 were determined by X-ray diffraction. Density functional calculations support the crystallographically determined geometry of 2 and allow rationalization of some characteristics of its structure, spectroscopy, and reactivity

Dual catalytic decarboxylative allylations of α-amino acids and their divergent mechanisms

This is the peer reviewed version of the following article: Lang, S. B., O'Nele, K. M., Douglas, J. T. and Tunge, J. A. (2015), Dual Catalytic Decarboxylative Allylations of α-Amino Acids and Their Divergent Mechanisms. Chem. Eur. J., 21: 18589–18593. doi:10.1002/chem.201503644, which has been published in final form at http://doi.org/10.1002/chem.201503644. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.The room temperature radical decarboxylative allylation of N-protected α-amino acids and esters has been accomplished via a combination of palladium and photoredox catalysis to provide homoallylic amines. Mechanistic investigations revealed that the stability of the α-amino radical, which is formed by decarboxylation, dictates the predominant reaction pathway between competing mechanisms

A Selective, Efficient and Environmentally Friendly Method for the Oxidative Cleavage of Glycols

A catalytic methodology for the oxidative cleavage of vicinal diols is described as an advantageous alternative in terms of the environmental impact on classical methods involving toxic oxidants. The novel strategy is based on the use of dioxomolybdenum(VI) complexes as catalysts and dimethyl sulfoxide (DMSO) as an oxidant and displays high selectivity and a broad scope for glycol cleavage. In addition, the developed system is also useful for the oxidation of acyloins to diketones.Ministerio de Economía y Competitividad (MINECO) and FEDER (CTQ2013-48937-C2-1-P) and Junta de Castilla y León (BU237U13