Oxidative Coupling of Terminal Rhenium Pnictide Complexes

The isolation of rhenium(V) complexes with terminal phosphide and arsenide ligands was achieved upon decarbonylation of rhenium(III) pnictaethynolates. One‐electron oxidation of the pnictide complexes yielded Pn?Pn (Pn=P, As) coupling products, which were spectroscopically and crystallographically characterized. Computational bond analysis suggests that these complexes are best described as {Pn₂}⁰ complexes that are stabilized by donor–acceptor interactions with the metal and a pyrazole ligand.     

Triamidoamine–Uranium(IV)‐Stabilized Terminal Parent Phosphide and Phosphinidene Complexes

Reaction of [U(Tren^TIPS)(THF)][BPh₄] ( 1 ; Tren^TIPS=N{CH₂CH₂NSi(iPr)₃}₃) with NaPH₂ afforded the novel f‐block terminal parent phosphide complex [U(Tren^TIPS)(PH₂)] ( 2 ; U–P=2.883(2) Å). Treatment of 2 with one equivalent of KCH₂C₆H₅ and two equivalents of benzo‐15‐crown‐5 ether (B15C5) afforded the unprecedented metal‐stabilized terminal parent phosphinidene complex [U(Tren^TIPS)(PH)][K(B15C5)₂] ( 4 ; U?P=2.613(2) Å). DFT calculations reveal a polarized‐covalent U?P bond with a Mayer bond order of 1.92.     

Ni2P Interlayer and Mn Doping Synergistically Expedite the Hydrogen Evolution Reaction Kinetics of Co2P

Transition metal phosphide is regarded as one of the most promising candidates to replace noble-metal hydrogen evolution reaction (HER) electrocatalysts. Nevertheless, the controllable design and synthesis of transition metal phosphide electrocatalysts with efficient and stable electrochemical performance are still very challenging. Herein, a novel hierarchical HER electrocatalyst consisting of three-dimensional (3D) coral-like Mn-doped Co₂P@an intermediate layer of Ni₂P generated in situ by phosphorization on Ni foam (MnCoP/NiP/NF) is reported. Notably, both the incorporation of Mn and introduction of the Ni₂P interlayer promote Co atoms to carry more electrons, which is beneficial to reduce the force of the Co−H bond and optimize the adsorption energy of hydrogen intermediate (|ΔG_H*|), thereby making MnCoP/NiP/NF exhibit outstanding HER performance with onset overpotential and Tafel slope as low as 31.2 mV and 61 mV dec⁻¹, respectively, in 1 m KOH electrolyte.     

A Low‐Valent Molybdenum Nitride Complex: Reduction Promotes Carbonylation Chemistry

Toward nitrogen functionalization, reactive terminal transition metal nitrides with high d‐electron counts are of interest. A series of terminal Mo^IV nitride complexes were prepared within the context of exploring nitride/carbonyl coupling to cyanate. Reduction affords the first Mo^II nitrido complex, an early metal nitride with four valence d‐electrons. The binding mode of the para‐terphenyl diphosphine ancillary ligand changes to stabilize an electronic configuration with a high electron count and a formal M?N bond order of three. Even with an intact Mo≡N bond, this low‐valent nitrido complex proves to be highly reactive, readily undergoing N‐atom transfer upon addition of CO, releasing cyanate anion.     

Metal–Organic Frameworks (MOFs) of a Cubic Metal Cluster with Multicentered MnIMnI Bonds

MOFs with both multicentered metal–metal bonds and low‐oxidation‐state (LOS) metal ions have been underexplored hitherto. Here we report the first cubic [Mn^I₈] cluster‐based MOF ( 1 ) with multicentered Mn^I? Mn^I bonds and +1 oxidation state of manganese (Mn^I or Mn(I)), as is supported by single‐crystal structure determination, XPS analyses, and quantum chemical studies. Compound 1 possesses the shortest Mn^I? Mn^I bond of 2.372 Å. Theoretical studies with density functional theory (DFT) reveal extensive electron delocalization over the [Mn^I₈] cube. The 48 electrons in the [Mn^I₈] cube fully occupy half of the 3d‐based and the lowest 4s‐based bonding orbitals, with six electrons lying at the nonbonding 3d‐orbitals. This bonding feature renders so‐called cubic aromaticity. Magnetic properties measurements show that 1 is an antiferromagnet. This work is expected to inspire further investigation of cubic metal–metal bonding, MOF materials with LOS metals, and metalloaromatic theory.     

Metal–Organic Frameworks (MOFs) of a Cubic Metal Cluster with Multicentered MnI?MnI Bonds

MOFs with both multicentered metal–metal bonds and low‐oxidation‐state (LOS) metal ions have been underexplored hitherto. Here we report the first cubic [Mn^I₈] cluster‐based MOF ( 1 ) with multicentered Mn^I Mn^I bonds and +1 oxidation state of manganese (Mn^I or Mn(I)), as is supported by single‐crystal structure determination, XPS analyses, and quantum chemical studies. Compound 1 possesses the shortest Mn^I Mn^I bond of 2.372 Å. Theoretical studies with density functional theory (DFT) reveal extensive electron delocalization over the [Mn^I₈] cube. The 48 electrons in the [Mn^I₈] cube fully occupy half of the 3d‐based and the lowest 4s‐based bonding orbitals, with six electrons lying at the nonbonding 3d‐orbitals. This bonding feature renders so‐called cubic aromaticity. Magnetic properties measurements show that 1 is an antiferromagnet. This work is expected to inspire further investigation of cubic metal–metal bonding, MOF materials with LOS metals, and metalloaromatic theory.     

Oligo-m-phenyleneoxalamide copper(II) mesocates as electro-switchable ferromagnetic metal-organic wires

Double‐stranded copper(II) string complexes of varying nuclearity, from di‐ to tetranuclear species, have been prepared by the Cu^II‐mediated self‐assembly of a novel family of linear homo‐ and heteropolytopic ligands that contain two outer oxamato and either zero ( 1 b ), one ( 2 b ), or two ( 3 b ) inner oxamidato donor groups separated by rigid 2‐methyl‐1,3‐phenylene spacers. The X‐ray crystal structures of these Cu^II_n complexes (n=2 ( 1 d ), 3 ( 2 d ), and 4 ( 3 d )) show a linear array of metal atoms with an overall twisted coordination geometry for both the outer CuN₂O₂ and inner CuN₄ chromophores. Two such nonplanar all‐syn bridging ligands 1 b – 3 b in an anti arrangement clamp around the metal centers with alternating M and P helical chiralities to afford an overall double meso‐helicate‐type architecture for 1 d – 3 d . Variable‐temperature (2.0–300 K) magnetic susceptibility and variable‐field (0–5.0 T) magnetization measurements for 1 d – 3 d show the occurrence of S=nS_Cu (n=2–4) high‐spin ground states that arise from the moderate ferromagnetic coupling between the unpaired electrons of the linearly disposed Cu^II ions (S_Cu=1/2) through the two anti m‐phenylenediamidate‐type bridges (J values in the range of +15.0 to 16.8 cm^?1). Density functional theory (DFT) calculations for 1 d – 3 d evidence a sign alternation of the spin density in the meta‐substituted phenylene spacers in agreement with a spin polarization exchange mechanism along the linear metal array with overall intermetallic distances between terminal metal centers in the range of 0.7–2.2 nm. Cyclic voltammetry (CV) and rotating‐disk electrode (RDE) electrochemical measurements for 1 d – 3 d show several reversible or quasireversible one‐ or two‐electron steps that involve the consecutive metal‐centered oxidation of the inner and outer Cu^II ions (S_Cu=1/2) to diamagnetic Cu^III ones (S_Cu=0) at relatively low formal potentials (E values in the range of +0.14 to 0.25 V and of +0.43 to 0.67 V vs. SCE, respectively). Further developments may be envisaged for this family of oligo‐m‐phenyleneoxalamide copper(II) double mesocates as electroswitchable ferromagnetic ‘metal–organic wires’ (MOWs) on the basis of their unique ferromagnetic and multicenter redox behaviors.     

磷叶立德CH2PH3和类磷叶立德自由基∙CHPH3优势构型和C—P键结构的研究

采用MP4/6-311++G(d,p)和B3LYP/6-311++G(d,p)对磷叶立德CH₂PH₃和类磷叶立德自由基∙CHPH₃进行构型优化，从电子密度拓扑分析的角度对C—P键的键结构进行了探讨。得到如下结论：类磷叶立德自由基和磷叶立德的C—P键性质类似，但磷叶立德中π键由两个电子形成，类磷叶立德自由基中π键由一个电子形成，所以前者的π性明显，而后者的π性不明显。类磷叶立德自由基中的这个单电子在碳原子附近，垂直于对称面的方向上运动，有p_(C→P)配键的特征，所以类磷叶立德自由基∙CHPH₃中的C—P键比相应的产物∙CH₂PH₂中的C—P键要弱一些。     

Redox Non‐Innocent Behavior of a Terminal Iridium Hydrazido(2−) Triple Bond

The synthesis of the first terminal Group 9 hydrazido(2‐) complex, Cp*IrN(TMP) ( 6 ) (TMP=2,2,6,6‐tetramethylpiperidine) is reported. Electronic structure and X‐ray diffraction analysis indicate that this complex contains an Ir?N triple bond, similar to Bergman's seminal Cp*Ir(N^tBu) imido complex. However, in sharp contrast to Bergman's imido, 6 displays remarkable redox non‐innocent reactivity owing to the presence of the N_β lone pair. Treatment of 6 with MeI results in electron transfer from N_β to Ir prior to oxidative addition of MeI to the iridium center. This behavior opens the possibility of carrying out facile oxidative reactions at a formally Ir^III metal center through a hydrazido(2?)/isodiazene valence tautomerization.     

Observation of Transition‐Metal–Boron Triple Bonds in IrB2O− and ReB2O−

Multiple bonds between boron and transition metals are known in many borylene (:BR) complexes via metal d_π→BR back‐donation, despite the electron deficiency of boron. An electron‐precise metal–boron triple bond was first observed in BiB₂O^? [Bi≡B?B≡O]^? in which both boron atoms can be viewed as sp‐hybridized and the [B?BO]^? fragment is isoelectronic to a carbyne (CR). To search for the first electron‐precise transition‐metal‐boron triple‐bond species, we have produced IrB₂O^? and ReB₂O^? and investigated them by photoelectron spectroscopy and quantum‐chemical calculations. The results allow to elucidate the structures and bonding in the two clusters. We find IrB₂O^? has a closed‐shell bent structure (C_s, ¹A′) with BO^? coordinated to an Ir≡B unit, (^?OB)Ir≡B, whereas ReB₂O^? is linear (C_∞v, ³Σ^?) with an electron‐precise Re≡B triple bond, [Re≡B?B≡O]^?. The results suggest the intriguing possibility of synthesizing compounds with electron‐precise M≡B triple bonds analogous to classical carbyne systems.     

Can Cyclen Bind Alkali Metal Azides? A DFT Study as a Precursor to Synthesis

Can cyclen (1,4,7,10‐tetraazacyclododecane) bind alkali metal azides? This question is addressed by studying the geometric and electronic structures of the alkali metal azide‐cyclen [M(cyclen)N₃] complexes using density functional theory (DFT). The effects of adding a second cyclen ring to form the sandwich alkali metal azide‐cyclen [M(cyclen)₂N₃] complexes are also investigated. N₃^? is found to bind to a M⁺(cyclen) template to give both end‐on and side‐on structures. In the end‐on structures, the terminal nitrogen atom of the azide group (N1) bonds to the metal as well as to a hydrogen atom of the cyclen ring through a hydrogen bond in an end‐on configuration to the cyclen ring. In the side‐on structures, the N₃ unit is bonded (in a side‐on configuration to the cyclen ring) to the metal through the terminal nitrogen atom of the azide group (N1), and through the other terminal nitrogen atom (N3) of the azide group by a hydrogen bond to a hydrogen atom of the cyclen ring. For all the alkali metals, the N₃‐side‐on structure is lowest in energy. Addition of a second cyclen unit to [M(cyclen)N₃] to form the sandwich compounds [M(cyclen)₂N₃] causes the bond strength between the metal and the N₃ unit to decrease. It is hoped that this computational study will be a precursor to the synthesis and experimental study of these new macrocyclic compounds; structural parameters and infrared spectra were computed, which will assist future experimental work.     

Maximum Spin Polarization in Chromium Dimer Cations as Demonstrated by X‐ray Magnetic Circular Dichroism Spectroscopy

X‐ray magnetic circular dichroism spectroscopy has been used to characterize the electronic structure and magnetic moment of Cr₂⁺. Our results indicate that the removal of a single electron from the 4sσ_g bonding orbital of Cr₂ drastically changes the preferred coupling of the 3d electronic spins. While the neutral molecule has a zero‐spin ground state with a very short bond length, the molecular cation exhibits a ferromagnetically coupled ground state with the highest possible spin of S=11/2, and almost twice the bond length of the neutral molecule. This spin configuration can be interpreted as a result of indirect exchange coupling between the 3d electrons of the two atoms that is mediated by the single 4s electron through a strong intraatomic 3d‐4s exchange interaction. Our finding allows an estimate of the relative energies of two states that are often discussed as ground‐state candidates, the ferromagnetically coupled ¹²Σ and the low‐spin ²Σ state.     

Electron Transfer and Multi‐Electron Accumulation in ExBox4+

Molecules capable of accepting and storing multiple electrons are crucial components of artificial photosynthetic systems designed to drive catalysts, such as those used to reduce protons to hydrogen. ExBox⁴⁺, a boxlike cyclophane comprising two π‐electron‐poor extended viologen units tethered at both ends by two p‐xylylene linkers, has been shown previously to accept an electron through space from a photoexcited guest. Herein is an investigation of an alternate, through‐bond intramolecular electron‐transfer pathway involving ExBox⁴⁺ using a combination of transient absorption and femtosecond stimulated Raman spectroscopy (FSRS). Upon photoexcitation of ExBox⁴⁺, an electron is transferred from one of the p‐xylylene linkers to one of the extended viologen units in ca. 240 ps and recombines in ca. 4 ns. A crystal structure of the doubly reduced species ExBox²⁺ was obtained.     

Terminal Parent Phosphanide and Phosphinidene Complexes of Zirconium(IV)

The reaction of [Zr(Tren^DMBS)(Cl)] [ Zr1 ; Tren^DMBS=N(CH₂CH₂NSiMe₂Bu^t )₃] with NaPH₂ gave the terminal parent phosphanide complex [Zr(Tren^DMBS)(PH₂)] [ Zr2 ; Zr−P=2.690(2) Å]. Treatment of Zr2 with one equivalent of KCH₂C₆H₅ and two equivalents of benzo‐15‐crown‐5 ether (B15C5) afforded an unprecedented example (outside of matrix isolation) of a structurally authenticated transition‐metal terminal parent phosphinidene complex [Zr(Tren^DMBS)(PH)][K(B15C5)₂] [ Zr3 ; Zr=P=2.472(2) Å]. DFT calculations reveal a polarized‐covalent Zr=P double bond, with a Mayer bond order of 1.48, and together with IR spectroscopic data also suggest an agostic‐type Zr⋅⋅⋅HP interaction [∡_ZrPH=66.7°] which is unexpectedly similar to that found in cryogenic, spectroscopically observed phosphinidene species. Surprisingly, computational data suggest that the Zr=P linkage is similarly polarized, and thus as covalent, as essentially isostructural U=P and Th=P analogues.     

Computational studies on azaphosphiridines, or how to effect ring-opening processes through selective bond activation

The relative energies of azaphosphiridine and its isomers, the ring stability towards valence isomerization, and the ring strain, as well as the kinetics and thermodynamics of possible ring‐opening reactions of P^III derivatives ( 1 – 5 ) and P^V chalcogenides ( 6 – 9 ; O to Te), were studied at high levels of theory (up to CCSD(T)). The barrier to inversion at the nitrogen atom in the trimethyl‐substituted P^III derivative 5 increases from 12.11 to 15.25 kcal mol^?1 in the P‐oxide derivative 6 (P^V); the relatively high barrier to inversion at the phosphorus in 5 (75.38 kcal mol^?1) points to a configurationally stable center (MP2/def2‐TZVPP//BP86/def2‐TZVP). The ring strain for azaphosphiridine 5 (av. 22.6 kcal mol^?1) was found to increase upon P‐oxidation ( 6 ) (30.8 kcal mol^?1; same level of theory). Various ring‐bond‐activation processes were studied: N‐protonation of P^III ( 5 ) and P^V ( 6 , 7 ) derivatives leads to highly activated species that readily undergo P? N bond cleavage. In contrast, metal chlorides such as LiCl, CuCl, CuCl₂, BeCl₂, BCl₃, AlCl₃, TiCl₃, and TiCl₄ show little P? N bond activation in 5 and 7 . Remarkably, TiCl₃ selectively activates the C? N bond, and induces stronger bond activation for P^V ( 6, 7 ) than for P^III azaphosphiridines ( 5 ). The ring‐expanding rearrangement of P^V azaphosphiridines 6 – 9 to yield P^III 1,3,2‐chalcogena‐azaphosphetidines 32 a – d is predicted to be preferred for the heavier chalcogenides 7 – 9 , but not for the P‐oxide 6 . The first comparative analysis of three bond strength parameters is presented: 1) the electron density at bond critical points, 2) Wiberg’s bond index, and 3) the relaxed force constant. This reveals the usefulness of these parameters in assessing the degree of ring bond activation.     

Lewis Acid Mediated Vinyl‐Transfer Reaction of Alkynes to N‐Alkylimines by Using the N‐Alkyl Residue as a Sacrificial Hydrogen Donor

A variety of N‐alkyl‐α,α‐dichloroaldimines were vinylated by terminal acetylenes in the presence of Lewis acids such as In(OTf)₃ or BF₃ ? OEt₂ and hexafluoroisopropanol (HFIP) as an additive. The reaction proceeds at ambient temperature and leads to geometrically pure allylic β,β‐dichloroamines. This approach is complementary to previously reported transition‐metal‐catalyzed vinyl‐transfer methods, which are not applicable to aliphatic imines and are restricted to imines that contain an electron‐withdrawing nitrogen substituent. In the present approach, terminal alkynes were used as a source of the vinyl residue, and the N‐alkyl moiety of the imine acts as a sacrificial hydrogen donor. The additional advantage of this methodology is the fact that no external toxic or hazardous reducing agents or molecular hydrogen has to be used. This new methodology nicely combines a C(sp²)? C(sp) bond formation, hydride transfer, and an unusual cleavage of an unactivated C? N bond, thereby giving rise to functionalized primary allylic amines. A detailed experimental study supported by DFT calculations of the mechanism has been done.     

Synthesis of Triangular Tripalladium Cations as Noble‐Metal Analogues of the Cyclopropenyl Cation

The first C₃‐symmetric 44‐core‐valence‐electron triangular palladium clusters, [{(SAr′)(PAr₃)Pd}₃]⁺, have been synthesized by activation of the C? S bond of isothioureas. Owing to delocalized metal–metal bonding, these stable complexes are the first noble‐metal analogues of the π‐aromatic cyclopropenyl cation [C₃H₃]⁺, with their all‐metal aromaticity involving d‐type atomic orbitals.     

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3 (M=Sr,Ba)

We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)₃ (M=Sr, Ba) in low‐temperature Ne matrix. Both complexes are characterized by a D₃ symmetric structure involving three equivalent η⁶‐bound benzene ligands and a closed‐shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n?1)d AOs of M and strong backdonation from the occupied (n?1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20‐electron complexes have 18 effective valence electrons, and, thus, fulfill the 18‐electron rule if only the metal–ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.     

Transition‐Metal Chemistry of Alkaline‐Earth Elements: The Trisbenzene Complexes M(Bz)3 (M=Sr,Ba)

We report the synthesis and spectroscopic identification of the trisbenzene complexes of strontium and barium M(Bz)₃ (M=Sr, Ba) in low‐temperature Ne matrix. Both complexes are characterized by a D₃ symmetric structure involving three equivalent η⁶‐bound benzene ligands and a closed‐shell singlet electronic ground state. The analysis of the electronic structure shows that the complexes exhibit metal–ligand bonds that are typical for transition metal compounds. The chemical bonds can be explained in terms of weak donation from the π MOs of benzene ligands into the vacant (n?1)d AOs of M and strong backdonation from the occupied (n?1)d AO of M into vacant π* MOs of benzene ligands. The metals in these 20‐electron complexes have 18 effective valence electrons, and, thus, fulfill the 18‐electron rule if only the metal–ligand bonding electrons are counted. The results suggest that the heavier alkaline earth atoms exhibit the full bonding scenario of transition metals.     

Mechanisms investigation of the WGSR catalyzed by single noble metal atoms supported on vanadium oxide clusters

The redox and carbonyl mechanisms of the water gas shift reaction (WGSR) catalyzed by the single noble metal (NM) atoms of Ru, Rh, Pd, Ag (from the 4d row) and Os, Ir, Pt, Au (from the 5d row) supported on vanadium oxide cluster ion V₂O₆⁺ have been firstly investigated through the density functional theory (DFT) calculations. Natural population analysis (NPA) shows NMs possess positive charges in the model systems and usually act as reactant molecule trapper and an effective electron store to accept or release electrons. The carbonyl mechanism avoiding the oxygen vacancy (O_v) formation and directing NM‐H bond cleavage is strongly preferred over the redox mechanism. Our computations identified single‐atom catalysts (SAC), especially RhV₂O₆⁺ and PdV₂O₆⁺ exhibit improved overall catalytic performance because of the lower rate‐control step activation barriers via the associate carbonyl mechanism. This work aims to provide some detailed insights into the effects of NM in bimetallic oxide clusters for WGSR at a molecular level, and serves as a starting point for further theoretical studies on the mechanisms of related SAC catalytic reactions.