Chemo-selective Stille-type coupling of acyl-chlorides upon phosphine-borane Au(i) catalysis.

Phosphine-boranes do not promote oxidative addition of acyl chlorides to gold, but the phosphine-borane gold triflimide complex [PrP(-CH)BCy]AuNTf was found to catalyze the coupling of acyl chlorides and aryl stannanes. The reaction involves aryl/chloride-bridged dinuclear gold(i) complexes as key intermediates, as substantiated by spectroscopic and crystallographic analyses. Similar to Pd(0)/Pd(ii)-catalyzed Stille coupling with phosphine-borane ligands, the gold-catalyzed variant shows complete chemoselectivity for acyl chlorides over aryl iodides and bromides, enabling straightforward access to halogenated aryl ketones.

A highly constrained -dihydride platinum complex trapped by cooperative gold/platinum dihydrogen activation.

A series of Au(I)/Pt(0) combinations that behave as bimetallic frustrated Lewis pairs activates dihydrogen in a cooperative manner. The steric bulk of the terphenyl phosphines that stabilize both fragments allows for the isolation of a rather unique and highly distorted -type dihydride platinum(II) structure.

Enhanced Dihydrogen Activation by Mononuclear Iridium(II) Compounds: A Mechanistic Study.

The organometallic chemistry of 4d and 5d transition metals has been vastly dominated by closed-shell states. The reactivity of their metalloradical species is though remarkable, albeit yet poorly understood and with limited mechanistic investigations available. In this work we report the synthesis and characterization of two mononuclear Ir species, including the first dinitrogen adduct.

Metal-Free Phosphorus-Directed Borylation of C(sp )-H Bonds.

Spectacular progress has recently been achieved in transition metal-catalyzed C-H borylation of phosphines as well as directed electrophilic C-H borylation. As shown here, P-directed electrophilic borylation provides a new, straightforward, and efficient access to phosphine-boranes. It operates under metal-free conditions and leverages simple, readily available substrates.

Reactivity of [Pt(P Bu)] with Zinc(I/II) Compounds: Bimetallic Adducts, Zn-Zn Bond Cleavage, and Cooperative Reactivity.

Metal-only Lewis pairs (MOLPs) based on zinc electrophiles are particularly interesting due to their relevance to Negishi cross-coupling reactions. Zinc-based ligands in bimetallic complexes also render unique reactivity to the transition metals at which they are bound. Here we explore the use of sterically hindered [Pt(P Bu)] () to access Pt/Zn bimetallic complexes.

Reversible Hydride Migration from CMe to Rh Revealed by a Cooperative Bimetallic Approach.

The use of cyclopentadienyl ligands in organometallic chemistry and catalysis is ubiquitous, mostly due to their robust spectator role. Nonetheless, increasing examples of non-innocent behaviour are being documented. Here, we provide evidence for reversible intramolecular C-H activation at one methyl terminus of CMe in [(η-CMe)Rh(PMe)] to form a new Rh-H bond, a process so far restricted to early transition metals.

Tuning Activity and Selectivity during Alkyne Activation by Gold(I)/Platinum(0) Frustrated Lewis Pairs.

Introducing transition metals into frustrated Lewis pair systems has attracted considerable attention in recent years. Here we report a selection of three metal-only frustrated systems based on Au(I)/Pt(0) combinations and their reactivity toward alkynes. We have inspected the activation of acetylene and phenylacetylene.

Evidence for Genuine Bimetallic Frustrated Lewis Pair Activation of Dihydrogen with Gold(I)/Platinum(0) Systems.

Invited for the cover of this issue is the group of Joaquín López-Serrano and Jesús Campos at the Consejo Superior de Investigaciones Científicas and the University of Sevilla. The image depicts the importance of balancing the degree of frustration/interaction in the splitting of H by Au /Pt . Read the full text of the article at 10.

Evidence for Genuine Bimetallic Frustrated Lewis Pair Activation of Dihydrogen with Gold(I)/Platinum(0) Systems.

A joint experimental/computational effort to elucidate the mechanism of dihydrogen activation by a gold(I)/platinum(0) metal-only frustrated Lewis pair (FLP) is described herein. The drastic effects on H activation derived from subtle ligand modifications have also been investigated. The importance of the balance between bimetallic adduct formation and complete frustration has been interrogated, providing for the first time evidence for genuine metal-only FLP reactivity in solution.

Reactivity of a gold(i)/platinum(0) frustrated Lewis pair with germanium and tin dihalides.

The reactivity of germanium and tin dichlorides with a transition metal-only frustrated Lewis pair based on Au(i) and Pt(0) compounds bearing bulky phosphine ligands is described in this work. We have examined both the reactivity of tetrylene dihalides towards the individual components of the metallic pair, as well as under metal/metal cooperative conditions. These studies allowed us to isolate several uncommon homo- and heterometallic structures.

Cooperative activation of X-H (X = H, C, O, N) bonds by a Pt(0)/Ag(i) metal-only Lewis pair.

Metal-only Lewis pairs made of Pt(0)/Ag(i) combinations have been previously reported, but their cooperative reactivity remains unexplored. Here we demonstrate that these systems are capable of synergistically activating a wide variety of X-H (X = H, C, O, N) bonds, including those in dihydrogen, alkynes, water and ammonia.