Molecular qubits based on potentially nuclear-spin-free nickel ions.

Molecular qubits with the longest coherence times thus far are based on nuclear-spin-carrying central ions. These nuclear spins can cause quantum state leakage, which is detrimental to quantum algorithm performance. We present two novel molecular qubits based on potentially nuclear spin-free Ni in the formal oxidation state 3+. (d20-PPh4)[Ni(mnt)2] (Ni-mnt, mnt2- = maleonitrile-1,2-dithiolate) possesses a coherence time of up to 38.7 µs at 7 K. Functionalization of the dithiolate ligand decreases the coherence time by a factor of only four in (HNEt3)[Ni(dip)2] (Ni-dip, dip2- = 3-(diphenylphosphoryl)-methylbenzene-1,2-dithiolate), indicating that monoanionic Ni-dithiolene complexes are promising and robust building blocks for polynuclear molecular qubit gates.

Isolable N-heterocyclic carbene adducts of the elusive diiodophosphine.

Reactions of PH-substituted phosphinidene-imidazolylidenes with I2 afford isolable NHC-adducts of the transient diiodophosphine PHI2. The products, which show a surprising structural diversity, are according to DFT studies best formulated as charge-transfer complexes of onio-substituted cationic phosphines with I- and are capable of reaction under formal transfer of an NHC-P+ unit.

Synthesis, spectroscopic characterisation and transmetalation of lithium and potassium diaminophosphanide-boranes.

A secondary diaminophosphane-borane (Et2N)2PH(BH3) was prepared from a chlorophosphane precursor and LiBH4 and metalated by reaction with anion bases (n-BuLi, KN(SiMe3)2) to yield the corresponding metal diaminophosphanide-boranes [(Et2N)2P(BH3)]M (M = Li, K). Multinuclear NMR studies permitted the first spectroscopic characterisation of the metalation products and revealed the presence of monomeric (for M = Li) contact ion pairs in solution. NMR spectroscopic evidence that the ions in each pair interact via LiP- rather than LiH3B-interactions as had been inferred for a Ph-substituted analogue was confirmed by DFT studies, which revealed also that the borane coordination plays a decisive role in boosting the PH-acidity of the original secondary diaminophosphane precursor. Transmetalation of the potassium and lithium diaminophosphanide-boranes with Cu(i) and Zn(ii) chlorides afforded the first functional transition metal complexes of a P-heteroatom-functionalised phosphanide-borane ligand. Both products were fully characterised. Thermolysis of the Cu-complex induced a reaction which involved transfer of an NHC ligand from the metal to the phosphorus atom and yielded a phosphaalkene NHC[double bond, length as m-dash]PH (NHC = N-heterocyclic carbene) as the major phosphorus-containing product.

A very peculiar family of N-heterocyclic phosphines: unusual structures and the unique reactivity of 1,3,2-diazaphospholenes.

This Perspective gives an account of the peculiar electronic and molecular structures of N-heterocyclic phosphines featuring either a single 1,3,2-diazaphospholene (DAP) ring with an exocyclic P-substituent X or two DAP rings linked by a P-P bond (bis-diazaphospholenyls), respectively, and their impact on the chemical properties of these molecules. The bonding situation in simple DAPs is epitomized by strong hyperconjugation between endocyclic π-type electrons and the exocyclic P-X bond. This interaction may induce a perceptible ionic polarization of the P-X bond which can persist even in the limit of a vanishing electronegativity gradient between P and X, and becomes visible in unusual geometric distortions of molecular structures and a unique chemical behaviour. Structural distortions are particularly evident in bond lengthening effects in P-halogen and P-phosphino derivatives R2P-DAP (with R2P ≠ DAP) which span the whole range from covalent molecules to contact ion pairs with a close relation to frustrated Lewis-pairs. The most significant impact on the chemical properties is found for P-phosphino- and P-hydrogen derivatives where reactions at substantially accelerated rates or totally new reaction modes can be observed, and new stoichiometric and first catalytic processes exploiting these features are currently emerging. The recently discovered bis-diazaphospholenyls differ from the simple derivatives as their central bond remains unpolarised as a consequence of the symmetric molecular structure. The occurrence of low-energy P-P bond homolysis that was nonetheless observed in one case is according to the results of thermochemical studies of P-P bond fission reactions attributable to the effects of steric congestion and induces chemical reactivity that can be considered complementary to that of the simple R2P-DAPs. Some concluding remarks will pay attention to a facet of DAP reactivity that has so far been widely neglected but is currently receiving increasing attention, namely well-defined ring-opening processes.

On the energetics of P-P bond dissociation of sterically strained tetraamino-diphosphanes.

The homolytic P-P bond fission in a series of sterically congested tetraaminodiphosphanes (R2N)2P-P(NR2)2 ({4}2-{9}2, two of which were newly synthesized and fully characterized) into diaminophosphanyl radicals (R2N)2P˙ (4-9) was monitored by VT EPR spectroscopy. Determination of the radical concentration from the EPR spectra permitted to calculate free dissociation energies ΔGDiss(295) as well as dissociation enthalpies ΔHDiss and entropies ΔSDiss, respectively. Large positive values of ΔGDiss(295) indicate that the degree of dissociation is in most cases low, and the concentration of persistent radicals--even if they are spectroscopically observable at ambient temperature--remains small. Appreciable dissociation was established only for the sterically highly congested acyclic derivative {9}2. Analysis of the trends in experimental data in connection with DFT studies indicate that radical formation is favoured by large entropy contributions and the energetic effect of structural relaxation (geometrical distortions and conformational changes in acyclic derivatives) in the radicals, and disfavoured by attractive dispersion forces. Comparison of the energetics of formation for CC-saturated N-heterocyclic diphosphanes and the 7π-radical 3c indicates that the effect of energetic stabilization by π-electron delocalization in the latter is visible, but stands back behind those of steric and entropic contributions. Evaluation of spectroscopic and computational data indicates that diaminophosphanyl radicals exhibit, in contrast to aminophosphenium cations, no strong energetic preference for a planar arrangement of the (R2N)2P unit.

An anionic phosphenium complex as an ambident nucleophile.

A unique anionic phosphenium complex was prepared from reaction of an N-heterocyclic chlorophosphine with Collman's reagent or K[HFe(CO)4]/NaH and characterized by spectral and XRD data. The complex behaves as an ambident nucleophile. Reactions with acetic acid, ClSnPh3, and a further equivalent of an N-heterocyclic chlorophosphine proceed via electrophilic functionalization at the metal site to yield appropriate mono- or bis-phosphenium complexes. Reaction with MeI at -70 °C produces a P-alkylation product as the first spectroscopically detectable intermediate, which decays at a higher temperature to give a mixture of free P-methylated N-heterocyclic phosphine and its Fe(CO)4 complex. The different reaction products were characterized by spectral and XRD data. Computational studies indicate that the NHP units in all complexes display π-acceptor behaviour but show no disposition to adopt phosphide-like character or formally oxidize the metal centre.

Reversible Tautomeric Transformation between a Bis(amino)cyclodiphosph(V)azene and a Bis(imino)cyclodiphosph(V)azane.

The tautomeric four-membered-ring P-N heterocycles 1, 2, and 3 can be interconverted; the formation of the cyclodiphosph(V)azene 1 is enthalpically and entropically favored. The crystal structures of the tautomers 1 and 3 have been determined and indications are given regarding the mechanism of the interconversion.

Stability and electrophilicity of phosphorus analogues of arduengo carbenes--an experimental and computational study

A variety of differently substituted 1,3,2-diazaphospholenium salts and P-halogeno-1,3,2-diazaphospholenes (X = F, Cl, Br) were synthesized, and their molecular structures, bonding situation, and Lewis acid properties were characterized by experimental (single-crystal X-ray diffraction, NMR and IR/Raman spectroscopy, MS, conductometry, titrations with Lewis bases) and computational methods. Both experimental and computational investigations confirmed that the structure and bonding in the diazaphospholenium cations of OTf and BF4 salts resembles that of neutral Arduengo carbenes and that the cations should not be described as genuinely aromatic. P-Halogenodiazaphospholenes are, in contrast to earlier assumptions, molecular species with covalent P-X bonds whose bonding situation can be expressed in terms of hyperconjugation between the six pi electrons in the C2N2 unit and the sigma*(P-X) orbital. This interaction induces a weakening of the P-X bonds, whose extent depends subtly on substituent influences and contributes fundamentally to the amazing structural similarity of ionic and covalent diazaphospholene compounds. A further consequence of this effect is the unique polarizability of the P-Cl bonds in P-chlorodiazaphospholenes, which is documented in a considerable spread of P-X distances and bond orders. Measurement of the stability constants for complexes of diazaphospholene compounds with Lewis bases confirmed the lower Lewis acidities and higher stabilities of diazaphospholenium ions as compared with nonconjugated phosphenium ions; this had been inferred from computed energies of isodesmotic halide-transfer reactions, and permitted also to determine equilibrium constants for P-Cl bond dissociation reactions. The results suggest, in accord with conductance measurements, that P-chlorodiazaphospholenes dissociate in solution only to a small extent. On the basis of these findings, the unique solvatochromatic behavior of NMR chemical shifts of these compounds was attributed to solvent-dependent P-Cl bond polarization rather than to shifts in dissociation equilibria.

Heterobimetallic catechol-phosphine complexes with palladium and a group-13 element: structural flexibility and dynamics.

Group-13 metal acetylacetonates [M(acac)3] (M = Al, Ga, In) or Al(OiPr)3 react with a complex [Pd(catphosH)2] that may act as chelating ligand towards a second metal, or with a mixture of catechol phosphine (catphosH2) and [PdCl2(cod)], to give heterometallic complexes featuring either dinuclear M(catphos)2Pd or trinuclear M{(catphos)2Pd}2 motifs. Characterisation of the products by crystallographic and solution NMR studies gives insight into the structural diversity and flexibility of the coordination environments of the group-13 elements and their impact on the stability of the multinuclear complexes. The results indicate that gallium and indium are the most suitable elements for the stabilisation of di- and trinuclear assemblies, respectively. Dynamic NMR spectroscopy allowed to follow the dynamic averaging of the coordination environments of the four distinguishable catechol phosphines in the indium complex [M{(catphos)2Pd}2]H. The results revealed that the isomerisation follows a complicated pathway involving several distinguishable proton transfer steps, and allowed to propose a mechanistic explanation for the observed isomerisation.

Phosphines with N-heterocyclic boranyl substituents.

A lithio-diazaborole reacted with diamino-chlorophosphines via metathesis to yield previously unavailable phosphinoboranes bearing amino substituents at both the phosphorus and boron atoms, and with Ph2PCl and Mes*PCl2via chloride transfer and reductive PP coupling to give a chloro-diazaborole and the corresponding diphosphine or diphosphene, respectively. Diazaboroles with phenylphosphino- and PH2-substituents were nonetheless accessible via inverse metathesis upon treatment of a bromoborane precursor with phosphides PhnPH2-nM (n = 0-2, M = Li, K). The products were characterised by spectroscopic data and in most cases by single-crystal X-ray diffraction studies which show the molecules to exhibit strongly pyramidal coordination at the phosphorus atom and long BP bonds of 1.93-1.95 Å. The insensitivity of the BP distance towards substituent effects and the tolerance of large sterically induced torsional twists along the BP bond axis suggest the presence of pure single bonds without any contribution from P→B dative π-interactions. This view was confirmed by DFT studies which indicate further that the molecules lack a significant electrophilic character at boron but may act as potential σ-donor/π-acceptor ligands through the phosphorus atom.