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 H2 derived from subtle ligand modifications have also been investigated. importance balance between bimetallic adduct formation and complete frustration has interrogated, providing for first time evidence genuine FLP reactivity in solution. origin strong inverse kinetic isotopic effect...

Bimetallic motifs mediate the selective activation and functionalization of CO

Introducing transition metals into frustrated Lewis pair systems has attracted considerable attention in recent years. Here we report a selection of three metal-only based on Au(I)/Pt(0) combinations and their reactivity toward alkynes. We have inspected the activation acetylene phenylacetylene. The gold(I) fragments are stabilized by bulky phosphines bearing terphenyl groups. observed that subtle modifications substituents these ligands proved critical controlling regioselectivity product...

More than four decades ago, a complex identified as the planar homoleptic lithium nickelate "Li3NiPh3(solv)3" was reported by Taube and co-workers. This subsequent reports involving this have lain dormant since; however, absence of an X-ray diffraction structure leaves questions to nature Ni-PhLi bonding coordination geometry at Ni. By systematically evaluating reactivity Ni(COD)2 with PhLi under different conditions, we found that classical molecule is instead unique octanuclear complex,...

Abstract Invited for the cover of this issue is group Joaquín López‐Serrano and Jesús Campos at Consejo Superior de Investigaciones Científicas University Sevilla. The image depicts importance balancing degree frustration/interaction in splitting H 2 by Au I /Pt 0 . Read full text article 10.1002/chem.201905793

Reaction of a molecular zinc–hydride [{(ArNCMe)2CH}ZnH] (Ar = 2,6-di-isopropylphenyl) with 0.5 equiv. [Ni(CO)Cp]2 led to the isolation nickel–zinc hydride complex containing bridging 3-centre,2-electron Ni–H–Zn interaction. This species has been characterized in solid-state by single crystal X-ray diffraction. DFT calculations are consistent its formulation as -complex derived from coordination paramagnetic nickel(I) fragment. Continuous wave and pulse EPR experiments suggest that this is...

Reaction of a molecular zinc-hydride [{(ArNCMe)

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 bis(hydrocarbyl) derivatives of the Mo[quadruple m-dash]Mo bond. Reversible migratory insertion β-hydrogen elimination, well reductive elimination other reactions, have been uncovered. PhC[triple m-dash]CH behaves instead a Brönsted-Lowry acid towards strongly basic Mo-H bonds 1·THF.

LiCH3 and LiCH2 CH3 react with the complex [Mo2 (H)2 (μ-AdDipp2 )2 (thf)2 ] (1⋅thf) coordination of two molecules R (R=H, ) formation complexes {μ-HLi(thf)CH2 R}2 (AdDipp2 ], 5⋅LiCH3 5⋅LiCH2 , respectively =HC(NDipp)2 ; Dipp=2,6-i Pr2 C6 H3 thf=C4 H8 O). Due to steric hindrance, only one molecule LiC6 H5 adds 1⋅thf generating (H){μ-HLi(thf)C6 }(μ-AdDipp2 (4⋅LiC6 ). Computational studies disclose existence five-center six-electron bonding within H-Mo≣Mo-C-Li metallacycles, a mostly covalent...

Abstract This contribution focuses on complex [Mo 2 (H) (μ‐Ad Dipp2 ) ] ( 1 and tetrahydrofuran pyridine adducts (L) 1⋅thf 1⋅py ), which contain a trans ‐(H)Mo≣Mo(H) core (Ad =HC(NDipp ; Dipp=2,6‐ i Pr C 6 H 3 ). Computational studies provide insights into the coordination electronic characteristics of central ‐Mo unit , with four‐coordinate, fourteen‐electron Mo atoms ϵ ‐agostic interactions Dipp methyl groups. Small size C‐ N‐donors give rise to related complexes 1⋅L but only one molecule...

The reactions of LiAlH4 as the source LiH with complexes that contain (H)Mo≣Mo and (H)Mo≣Mo(H) cores stabilized by coordination bulky AdDipp2 ligands result in respective one two molecules (thf)LiH, generation exhibiting HLi(thf)H extending across Mo≣Mo bond (AdDipp2 = HC(NDipp)2; Dipp 2,6-iPr2C6H3; thf tetrahydrofuran, C4H8O). A theoretical study reveals formation Mo–H–Li three-center–two-electron bonds, supplemented to Li ion. Attempts construct a [Mo2{HLi(thf)H}3(AdDipp2)] molecular...

Heterobimetallic complexes containing M–C–E linkages (M = transition metal atom; E main group metal) have been postulated as relevant intermediates in cross-coupling reactions. Despite this, structural data for these species are scarce. In this contribution, we explore the coordination of E–C bonds (E Zn, Mg, Al) to Mo atoms dimolybdenum quadruple Mo–Mo bonds. addition, reactivity bis(hydride) [Mo2(H)2(μ-AdDipp2)2(thf)2] complex (AdDipp2 HC[N(2,6-iPr2C6H3)]2) with zincocenes Zn(C5Me5)2 and...

Abstract Bimetallic motifs mediate the selective activation and functionalization of CO 2 in metalloenzymes some recent synthetic systems. In this work, we build on nascent concept bimetallic frustrated Lewis pairs (FLPs) to investigate reduction . Using Fe 0 fragment [(depe) Fe] (depe=1,2‐bis(diethylphosphino)ethane) as base, modify nature partner acid accomplish a divergent highly chemoselective reactivity towards [Au(PMe Ar)] + irreversibly dissociates , Zn(C 6 F 5 ) B(C 3 yield different...

Addition of H2 to a Zn–Fe heterometallic complex was observed occur under photochemical conditions (390 or 428 nm LED) and leads the formation corresponding metal dihydride. The reaction does not thermal DFT calculations suggest this is an endergonic, light driven process. Through combined experimental computational approach, plausible mechanisms for activation were investigated. Inhibition experiments, double-label cross-over radical trapping EPR spectroscopy used gain insight into system....

Addition of H

Abstract Reaction of a molecular zinc–hydride [{(ArNCMe) 2 CH}ZnH] (Ar=2,6‐di‐isopropylphenyl) with 0.5 equiv. [Ni(CO)Cp] led to the isolation nickel–zinc hydride complex containing bridging 3‐centre,2‐electron Ni−H−Zn interaction. This species has been characterized in solid‐state by single crystal X‐ray diffraction. DFT calculations are consistent its formulation as σ‐complex derived from coordination paramagnetic nickel(I) fragment. Continuous‐wave and pulse EPR experiments suggest that...

The oxidation selectivity of the η6-arene ligand in a series [(η5-C5Me5)Ir(η6-arene)](OTf)2 complexes to corresponding [(η5-C5Me5)Ir(η5-phenoxo)](OTf) derivatives was studied as complementary protocol metal-catalyzed borylation-oxidation. A representative compounds prepared with mono-, di-, and trisubstituted arenes well two examples biphenyls rationally explore site C(sp2)–H oxidation. isolated organometallic arene were treated NaClO2 formed desired iridium η5-phenoxo products. While...

Starting with the first σ-H2 complex reported by Kubas in 1984, 3-center 2-electron bonding between σ-E–H bonds of main group elements and transition metals has become a common topic fundamental importance organometallic chemistry. In many cases, E atom is metal series, as Mg, Al, or Zn. However, despite ubiquity reagents metal-carbon (i.e. MgR2, AlR3 ZnR2) that are commonly used conjunction metals, related σ-E–C complexes (E = metal) have not been described such. Those would involve...

Addition of H2 to a Zn–Fe heterometallic complex was observed occur under photochemical conditions (390 or 428 nm LED) and leads the formation corresponding metal dihydride. The reaction does not thermal DFT calculations suggest this is an endergonic, light driven process. Through combined experimental computational approach, plausible mechanisms for activation were investigated. Inhibition experiments, double-label cross-over radical trapping EPR spectroscopy used gain insight into system....

Introducing transition metals into frustrated Lewis pair systems has attracted considerable attention in recent years. Here we report a selection of three metal-only based on Au(I)/Pt(0) combinations and their reactivity towards alkynes. We have inspected the activation simplest alkyne, namely acetylene, as well other internal terminal triply bonded hydrocarbons. The gold(I) fragments are stabilized by bulky phosphines bearing terphenyl groups. observed that subtle modifications substituents...