This work describes a thorough investigation of the mechanism of a highly selective hydrosilylation of CO2 to the formaldehyde level catalyzed by a bis(phosphino)boryl (PBP)Ni(II) complex in the presence of B(C6F5)3. CO2 activation by insertion into the Ni–H bond of the catalyst precursor 2 is shown to occur very easily, because of the trans...
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June 22, 2018 (v1)PublicationUploaded on: March 25, 2023
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April 28, 2021 (v1)Publication
A seemingly simple combination of [Zn(quin)2(H2O)] (quin− = quinaldinate) and a selected secondary cyclic amine, piperidine (pipe), pyrrolidine (pyro) or morpholine (morph), afforded in acetonitrile a number of products: anionic homoleptic quinaldinate, neutral heteroleptic quinaldinate/amine and quinaldinate/amidine complexes. The piperidine...
Uploaded on: March 25, 2023 -
July 17, 2018 (v1)Publication
Selective reduction of CO2 to the formaldehyde level remains an important challenge and to date only a few catalysts have been developed for this reaction. Herein, we report an efficient catalyst that consists of a bis(phosphino)boryl nickel hydride complex in combination with B(C6F5)3, for the highly selective hydrosilation of CO2 to...
Uploaded on: March 25, 2023 -
May 29, 2018 (v1)Publication
Organometallic chemistry can be considered as a wide area of knowledge that combines concepts of classic organic chemistry, that is, based essentially on carbon, with molecular inorganic chemistry, especially with coordination compounds. Transition-metal methyl complexes probably represent the simplest and most fundamental way to view how these...
Uploaded on: March 27, 2023 -
July 1, 2022 (v1)Publication
Transition metal tetrylene complexes offer great opportunities for molecular cooperation due to the ambiphilic character of the group 14 element. Here we focus on the coordination of germylene [(ArMes2)2Ge :] (ArMes=C6H3-2,6-(C6H2-2,4,6-Me3)2) to [RhCl(COD)]2 (COD=1,5-cyclooctadiene), which yields a neutral germyl complex in which the rhodium...
Uploaded on: March 25, 2023 -
September 12, 2022 (v1)Publication
Heavier group 14 element cations exhibit a remarkable reactivity that has typically hampered their isolation. For the few available examples, the role of π-arene interactions is crucial to provide kinetic stabilization, but dynamic and structural information on those contacts is yet limited. In this study we have accessed the metalogermylenium...
Uploaded on: March 24, 2023 -
October 6, 2022 (v1)Publication
Pd(OTf)2(bcope) is shown to react in methanol solution with diphenylacetylene, carbon monoxide and hydrogen to produce the methoxy-carbonylation product methyl 2,3 diphenyl acrylate alongside cis- and trans-stilbene. In situ NMR studies harnessing the parahydrogen induced polarization effect reveal substantially enhanced 1H NMR signals in both...
Uploaded on: March 24, 2023 -
May 8, 2023 (v1)Publication
Two phosphonite ligands bearing the highly sterically demanding 2,6-bis (2,6-dimethylphenyl)phenyl group (ArXyl2), PArXyl2(OPhNO2)2 and PArXyl2(OPhNO2)2, were prepared from the parent dihalophosphines PArXyl2X2 (X = Cl, Br) and the corresponding phenols, 4-nitrophenol and 4-nitro-2,6-dimethylphenol, respectively. DFT methods were used to...
Uploaded on: May 10, 2023 -
August 16, 2019 (v1)Publication
Complex [Mo2(H)2{μ-HC(NDipp)2}2(THF)2], (1·THF), reacts with C2H4 and PhCH[double bond, length as m-dash]CH2 to afford hydrido-hydrocarbyl and bis(hydrocarbyl) derivatives of the Mo[quadruple bond, length as m-dash]Mo bond. Reversible migratory insertion and β-hydrogen elimination, as well as reductive elimination and other reactions, have been...
Uploaded on: December 5, 2022 -
June 22, 2018 (v1)Publication
The low-electron-count cationic platinum complex [Pt(ItBu')(ItBu)][BAr], 1, interacts with primary and secondary silanes to form the corresponding σ-SiH complexes. According to DFT calculations, the most stable coordination mode is the uncommon η-SiH. The reaction of 1 with EtSiH leads to the X-ray structurally characterized 14-electron Pt...
Uploaded on: December 4, 2022 -
November 20, 2017 (v1)Publication
The TpMe2Ir(III) complex 1-OH2 (TpMe2 = hydrotris(3,5-dimethylpyrazolyl)borate), which contains a labile molecule of water and an iridium-bonded alkenyl moiety (−C(R)═C(R)–(R=CO2Me)) as part of a benzo-annulated five-membered iridacycle, reacts readily with the conjugated dienes butadiene and 2,3-dimethylbutadiene to afford the corresponding...
Uploaded on: December 4, 2022 -
February 7, 2018 (v1)Publication
A stable Nickel(II) methyl complex containing a diphosphinoboryl (PBP) pincer ligand is described. Mechanistic studies on the hydrogenolysis of the Ni-Me bond suggest a metal ligand cooperation mechanism that involves the intermediacy of a - B‒H Ni(0) species that further undergoes B‒H oxidative addition to form a Ni(II) hydride complex.
Uploaded on: December 5, 2022 -
September 26, 2022 (v1)Publication
The reactions between [Cu(quin)2(H2O)] (quin− = the anionic form of quinoline-2-carboxylic acid) and a series of aliphatic amino alcohols have yielded structurally very diverse copper(II) complexes, labelled a–g. Single-crystal X-ray structure analysis has revealed either intact amino alcohol molecules or amino alcoholate ions serving as...
Uploaded on: December 4, 2022 -
September 9, 2022 (v1)Publication
Metal-only Lewis pairs (MOLPs) in which the two metal fragments are solely connected by a dative M→M bond represent privileged architectures to acquire fundamental understanding of bimetallic bonding. This has important implications in many catalytic processes or supramolecular systems that rely on synergistic effects between two metals....
Uploaded on: March 24, 2023 -
January 30, 2024 (v1)Publication
Among phenol-derived electrophiles, aryl sulfamates are attractive substrates since they can be employed as directing groups for C–H functionalization prior to catalysis. However, their use in C–N coupling is limited only to Ni catalysis. Here, we describe a Pd-based catalyst with a broad scope for the amination of aryl sulfamates. We show that...
Uploaded on: February 4, 2024 -
July 5, 2019 (v1)Publication
We report the synthesis and structural characterization of five-coordinate complexes of rhodium and iridium of the type [(η5-C5Me5)M(N^N)]+ (3-M+), where N^N represents the aminopyridinate ligand derived from 2-NH(Ph)-6-(Xyl)C5H3N (Xyl = 2,6-Me2C6H3). The two complexes were isolated as salts of the BArF anion (BArF = B[3,5-(CF3)2C6H3]4). The...
Uploaded on: March 27, 2023 -
October 7, 2022 (v1)Publication
The synthesis and double asymmetric hydrogenation of (Z,Z)-1,3- diene-1,4-diyl diacetates is described. In this reaction C2/meso ratios up to 85 : 15 and enantioselectivities up to 97% ee have been achieved. As the hydrogenation products can be converted into chiral 1,4-diols, key starting materials for the preparation of the best catalysts...
Uploaded on: December 5, 2022 -
October 2, 2018 (v1)Publication
The fully CO2Me substituted aquo-iridacyclopentadiene 1 reacts with a variety of aromatic aldehydes, at 90–120 °C, with the formation of bicyclic Fischer-type carbenes, generated by the transfer of the aldehydic H atom to an α carbon of the metallacycle and concomitant bonding of the O atom to the adjacent β carbon. These carbenes have a...
Uploaded on: December 4, 2022 -
January 27, 2023 (v1)Publication
Cationic rhodium(I) complexes containing picolyl-NHC (NHC = N-heterocyclic carbene) ligands that differ in the substitution at the 6-position of the pyridine donor serve as efficient E-selective alkyne hydrosilylation catalyst precursors. Particularly, when the steric hindrance of the picolyl fragment is increased, a catalyst...
Uploaded on: March 1, 2023 -
October 5, 2022 (v1)Publication
Platinum(II) complex [Pt(It Bu0 )(It Bu)][BArF 4] (1a) is a highly active and selective catalyst in the dehydrocoupling of amines and silanes at part-per-million catalyst loadings (up to 10 ppm, 0.001 mol%), achieving the highest TON and TOF numbers reported in the literature (up to 1 mmol scale). NMR studies suggest a process taking place...
Uploaded on: March 24, 2023 -
September 21, 2018 (v1)Publication
Cationic five-coordinate Pt(IV) alkyl complexes stabilized by bulky N-heterocyclic carbenes have been isolated and fully characterized. Related species have been postulated as key intermediates in carbon–heteroatom coupling reactions and most particularly in Shilov-type chemistry. The alkyl groups exhibit a pronounced electrophilic character...
Uploaded on: March 27, 2023 -
April 13, 2018 (v1)Publication
We describe the synthesis of a series of cationic rhodium(I) and iridium(I) compounds stabilized by sterically demanding phosphines that contain a terphenyl substituent, PMe 2 Ar' (Ar' = 2,6-diarylphenyl radical). Salt metathesis of metal precursors [MCl(COD)(PMe 2 Ar')] (M = Rh, Ir; COD = cyclooctadiene) with...
Uploaded on: March 27, 2023