Zintl Ions and Phases Promote the Catalytic Hydrophosphination of Alkynes, Alkenes, and Imines.

Although Zintl ions and phases have been known for more than a century, their application as tools to build organic molecules is underdeveloped. Here, a range of Zintl ions and phases were surveyed in the hydrophosphination of alkynes, alkenes, and imines with diphenylphosphine to afford useful organophosphine products. Further investigations with diphenylphosphine in the absence of the unsaturated organic substrates revealed the formation of the diphenylphosphide anion, allowing for the conclusion that the role of the Zintl species is as an initiator in these transformations.

Comparison of group 4 and thorium M(IV) substituted cyclopentadienyl silanide complexes.

We report the synthesis and characterisation of a series of M(IV) substituted cyclopentadienyl hypersilanide complexes of the general formula [M(CpR)2{Si(SiMe3)3}(X)] (M = Hf, Th; CpR = Cp', {C5H4(SiMe3)} or Cp'', {C5H3(SiMe3)2-1,3}; X = Cl, C3H5). The separate salt metathesis reactions of [M(CpR)2(Cl)2] (M = Zr or Hf, CpR = Cp'; M = Hf or Th, CpR = Cp'') with equimolar K{Si(SiMe3)3} gave the respective mono-silanide complexes [M(Cp')2{Si(SiMe3)3}(Cl)] (M = Zr, 1; Hf, 2), [Hf(Cp'')(Cp'){Si(SiMe3)3}(Cl)] (3) and [Th(Cp'')2{Si(SiMe3)3}(Cl)] (4), with only a trace amount of 3 presumably formed via silatropic and sigmatropic shifts; the synthesis of 1 from [Zr(Cp')2(Cl)2] and Li{Si(SiMe3)3} has been reported previously. The salt elimination reaction of 2 with one equivalent of allylmagnesium chloride gave [Hf(Cp')2{Si(SiMe3)3}(η3-C3H5)] (5), whilst the corresponding reaction of 2 with equimolar benzyl potassium yielded [Hf(Cp')2(CH2Ph)2] (6) together with a mixture of other products, with elimination of both KCl and K{Si(SiMe3)3}. Attempts to prepare isolated [M(CpR)2{Si(SiMe3)3}]+ cations from 4 or 5 by standard abstraction methodologies were unsuccessful. The reduction of 4 with KC8 gave the known Th(III) complex, [Th(Cp'')3]. Complexes 2-6 were characterised by single crystal XRD, whilst 2, 4 and 5 were additionally characterised by 1H, 13C{1H} and 29Si{1H} NMR spectroscopy, ATR-IR spectroscopy and elemental analysis. In order to probe differences in M(IV)-Si bonds for d- and f-block metals we studied the electronic structures of 1-5 by density functional theory calculations, showing M-Si bonds of similar covalency for Zr(IV) and Hf(IV), and less covalent M-Si bonds for Th(IV).

Electronic structure comparisons of isostructural early d- and f-block metal(iii) bis(cyclopentadienyl) silanide complexes.

We report the synthesis of the U(iii) bis(cyclopentadienyl) hypersilanide complex [U(Cp'')2{Si(SiMe3)3}] (Cp'' = {C5H3(SiMe3)2-1,3}), together with isostructural lanthanide and group 4 M(iii) homologues, in order to meaningfully compare metal-silicon bonding between early d- and f-block metals. All complexes were characterised by a combination of NMR, EPR, UV-vis-NIR and ATR-IR spectroscopies, single crystal X-ray diffraction, SQUID magnetometry, elemental analysis and ab initio calculations. We find that for the [M(Cp'')2{Si(SiMe3)3}] (M = Ti, Zr, La, Ce, Nd, U) series the unique anisotropy axis is conserved tangential to ; this is governed by the hypersilanide ligand for the d-block complexes to give easy plane anisotropy, whereas the easy axis is fixed by the two Cp'' ligands in f-block congeners. This divergence is attributed to hypersilanide acting as a strong σ-donor and weak π-acceptor with the d-block metals, whilst f-block metals show predominantly electrostatic bonding with weaker π-components. We make qualitative comparisons on the strength of covalency to derive the ordering Zr > Ti ≫ U > Nd ≈ Ce ≈ La in these complexes, using a combination of analytical techniques. The greater covalency of 5f3 U(iii) vs. 4f3 Nd(iii) is found by comparison of their EPR and electronic absorption spectra and magnetic measurements, with calculations indicating that uranium 5f orbitals have weak π-bonding interactions with both the silanide and Cp'' ligands, in addition to weak δ-antibonding with Cp''.

Synthesis and Characterization of Yttrium Methanediide Silanide Complexes.

The salt metathesis reactions of the yttrium methanediide iodide complex [Y(BIPM)(I)(THF)2] (BIPM = {C(PPh2NSiMe3)2}) with the group 1 silanide ligand-transfer reagents MSiR3 (M = Na, R3 = tBu2Me or tBu3; M = K, R3 = (SiMe3)3) gave the yttrium methanediide silanide complexes [Y(BIPM)(SitBu2Me)(THF)] (1), [Y(BIPM)(SitBu3)(THF)] (2), and [Y(BIPM){Si(SiMe3)3}(THF)] (3). Complexes 1-3 provide rare examples of structurally authenticated rare earth metal-silicon bonds and were characterized by single-crystal X-ray diffraction, multinuclear NMR and ATR-IR spectroscopies, and elemental analysis. Density functional theory calculations were performed on 1-3 to probe their electronic structures further, revealing predominantly ionic Y-Si bonding. The computed Y-Si bonds show lower covalency than Y═C bonds, which are in turn best represented by Y+-C- dipolar forms due to the strong σ-donor properties of the silanide ligands investigated; these observations are in accord with experimentally obtained 13C{1H} and 29Si{1H} NMR data for 1-3 and related Y(III) BIPM alkyl complexes in the literature. Preliminary reactivity studies were performed, with complex 1 treated separately with benzophenone, azobenzene, and N,N'-dicyclohexyl-carbodiimide. 29Si{1H} and 31P{1H} NMR spectra of these reaction mixtures indicated that 1,2-migratory insertion of the unsaturated substrate into the Y-Si bond is favored, while for the latter substrate, a [2 + 2]-cycloaddition reaction also occurs at the Y═C bond to afford [Y{C(PPh2NSiMe3)2[C(NCy)2]-κ4C,N,N',N'}{C(NCy)2(SitBu2Me)-κ2N,N'}] (4); these reactivity profiles complement and contrast with those of Y(III) BIPM alkyl complexes.

Mapping boron catalysis onto a phosphorus cluster platform.

Clusters of main group elements, such as phosphorus, arsenic, germanium, and tin - called Zintl clusters - have been known for more than a century. However, their application in main group catalysis is largely unknown. Here, we tether boranes to a seven-atom phosphorus cluster ({C8H14}BCH2CH2SiMe2)3P7 (2) and we demonstrate Lewis acid catalysis as proof-of-principle that boron chemistry can be mapped onto clusters using this method. Catalyst 2 was employed to mediate key organic transformations, including the hydroboration of carbodiimides, isocyanates, ketones, alkenes, alkynes, and nitriles. To the best of our knowledge, this is the first application of Zintl-based clusters as an innocent platform in metal-free catalysis. By chaining boron, its treasure chest of chemistry can be unlocked at these clusters. Hence, beyond catalysis this method could find applications for main group clusters in neutron capture therapy, stimuli responsive materials, and cross-coupling, and frustrated Lewis pair and functional polymer chemistries.

29Si NMR Spectroscopy as a Probe of s- and f-Block Metal(II)-Silanide Bond Covalency.

We report the use of 29Si NMR spectroscopy and DFT calculations combined to benchmark the covalency in the chemical bonding of s- and f-block metal-silicon bonds. The complexes [M(SitBu3)2(THF)2(THF)x] (1-M: M = Mg, Ca, Yb, x = 0; M = Sm, Eu, x = 1) and [M(SitBu2Me)2(THF)2(THF)x] (2-M: M = Mg, x = 0; M = Ca, Sm, Eu, Yb, x = 1) have been synthesized and characterized. DFT calculations and 29Si NMR spectroscopic analyses of 1-M and 2-M (M = Mg, Ca, Yb, No, the last in silico due to experimental unavailability) together with known {Si(SiMe3)3}--, {Si(SiMe2H)3}--, and {SiPh3}--substituted analogues provide 20 representative examples spanning five silanide ligands and four divalent metals, revealing that the metal-bound 29Si NMR isotropic chemical shifts, δSi, span a wide (∼225 ppm) range when the metal is kept constant, and direct, linear correlations are found between δSi and computed delocalization indices and quantum chemical topology interatomic exchange-correlation energies that are measures of bond covalency. The calculations reveal dominant s- and d-orbital character in the bonding of these silanide complexes, with no significant f-orbital contributions. The δSi is determined, relatively, by paramagnetic shielding for a given metal when the silanide is varied but by the spin-orbit shielding term when the metal is varied for a given ligand. The calculations suggest a covalency ordering of No(II) > Yb(II) > Ca(II) ≈ Mg(II), challenging the traditional view of late actinide chemical bonding being equivalent to that of the late lanthanides.

Polarised covalent thorium(IV)- and uranium(IV)-silicon bonds.

We report the synthesis and characterisation of isostructural thorium(iv)- and uranium(iv)-silanide actinide (An) complexes, providing an opportunity to directly compare Th-Si and U-Si chemical bonds. Quantum chemical calculations show significant and surprisingly similar An%:Si%, 7s-, 6d-, and 5f-orbital contributions from both elements in polarised covalent An-Si bonds, and marginally greater covalency in the U-Si vs. Th-Si linkages.

Heteroleptic Samarium(III) Chalcogenide Complexes: Opportunities for Giant Exchange Coupling in Bridging σ- and π-Radical Lanthanide Dichalcogenides.

The introduction of (N2)3-• radicals into multinuclear lanthanide molecular magnets raised hysteresis temperatures by stimulating strong exchange coupling between spin centers. Radical ligands with larger donor atoms could promote more efficient magnetic coupling between lanthanides to provide superior magnetic properties. Here, we show that heavy chalcogens (S, Se, Te) are primed to fulfill these criteria. The moderately reducing Sm(II) complex, [Sm(N††)2], where N†† is the bulky bis(triisopropylsilyl)amide ligand, can be oxidized (i) by diphenyldichalcogenides E2Ph2 (E = S, Se, Te) to form the mononuclear series [Sm(N††)2(EPh)] (E = S, 1-S; Se, 1-Se, Te, 1-Te); (ii) S8 or Se8 to give dinuclear [{Sm(N††)2}2(µ-η2:η2-E2)] (E = S, 2-S2; Se, 2-Se2); or (iii) with Te═PEt3 to yield [{Sm(N††)2}(µ-Te)] (3). These complexes have been characterized by single crystal X-ray diffraction, multinuclear NMR, FTIR, and electronic spectroscopy; the steric bulk of N†† dictates the formation of mononuclear complexes with chalcogenate ligands and dinuclear species with the chalcogenides. The Lα1 fluorescence-detected X-ray absorption spectra at the Sm L3-edge yielded resolved pre-edge and white-line peaks for 1-S and 2-E2, which served to calibrate our computational protocol in the successful reproduction of the spectral features. This method was employed to elucidate the ground state electronic structures for proposed oxidized and reduced variants of 2-E2. Reactivity is ligand-based, forming species with bridging superchalcogenide (E2)-• and subchalcogenide (E2)3-• radical ligands. The extraordinarily large exchange couplings provided by these dichalcogenide radicals reveal their suitability as potential successors to the benchmark (N2)3-• complexes in molecular magnets.

f-Element silicon and heavy tetrel chemistry.

The last three decades have seen a significant increase in the number of reports of f-element carbon chemistry, whilst the f-element chemistry of silicon, germanium, tin, and lead remain underdeveloped in comparison. Here, in this perspective we review complexes that contain chemical bonds between f-elements and silicon or the heavier tetrels since the birth of this field in 1985 to present day, with the intention of inspiring researchers to contribute to its development and explore the opportunities that it presents. For the purposes of this perspective, f-elements include lanthanides, actinides and group 3 metals. We focus on complexes that have been structurally authenticated by single-crystal X-ray diffraction, and horizon-scan for future opportunities and targets in the area.

Heteroleptic samarium(iii) halide complexes probed by fluorescence-detected L3-edge X-ray absorption spectroscopy.

The addition of various oxidants to the near-linear Sm(ii) complex [Sm(N††)2] (1), where N†† is the bulky bis(triisopropylsilyl)amide ligand {N(SiiPr3)2}, afforded a family of heteroleptic three-coordinate Sm(iii) halide complexes, [Sm(N††)2(X)] (X = F, 2-F; Cl, 2-Cl; Br, 2-Br; I, 2-I). In addition, the trinuclear cluster [{Sm(N††)}3(µ2-I)3(µ3-I)2] (3), which formally contains one Sm(ii) and two Sm(iii) centres, was isolated during the synthesis of 2-I. Complexes 2-X are remarkably stable towards ligand redistribution, which is often a facile process for heteroleptic complexes of smaller monodentate ligands in lanthanide chemistry, including the related bis(trimethylsilyl)amide {N(SiMe3)2} (N''). Complexes 2-X and 3 have been characterised by single crystal X-ray diffraction, elemental analysis, multinuclear NMR, FTIR and electronic spectroscopy. The Lα1 fluorescence-detected X-ray absorption spectra recorded at the Sm L3-edge for 2-X exhibited a resolved pre-edge peak defined as an envelope of quadrupole-allowed 2p → 4f transitions. The X-ray absorption spectral features were successfully reproduced using time-dependent density functional theoretical (TD-DFT) calculations that synergistically support the experimental observations as well as the theoretical model upon which the electronic structure and bonding in these lanthanide complexes is derived.