Inverse Isotope Effects in Single-Crystal to Single-Crystal Reactivity and the Isolation of a Rhodium Cyclooctane σ-Alkane Complex.

The sequential solid/gas single-crystal to single-crystal reaction of [Rh(Cy2P(CH2)3PCy2)(COD)][BArF 4] (COD = cyclooctadiene) with H2 or D2 was followed in situ by solid-state 31P{1H} NMR spectroscopy (SSNMR) and ex situ by solution quenching and GC-MS. This was quantified using a two-step Johnson-Mehl-Avrami-Kologoromov (JMAK) model that revealed an inverse isotope effect for the second addition of H2, that forms a σ-alkane complex [Rh(Cy2P(CH2)3PCy2)(COA)][BArF 4]. Using D2, a temporal window is determined in which a structural solution for this σ-alkane complex is possible, which reveals an η2,η2-binding mode to the Rh(I) center, as supported by periodic density functional theory (DFT) calculations. Extensive H/D exchange occurs during the addition of D2, as promoted by the solid-state microenvironment.

MicroED characterization of a robust cationic σ-alkane complex stabilized by the [B(3,5-(SF5)2C6H3)4]- anion, via on-grid solid/gas single-crystal to single-crystal reactivity.

Microcrystalline (∼1 µm) [Rh(Cy2PCH2CH2PCy2)(norbornadiene)][S-BArF4], [S-BArF4] = [B(3,5-(SF5)2C6H3)4]-, reacts with H2 in a single-crystal to single-crystal transformation to form the σ-alkane complex [Rh(Cy2PCH2CH2PCy2)(norbornane)][S-BArF4], for which the structure was determined by microcrystal Electron Diffraction (microED), to 0.95 Å resolution, via an on-grid hydrogenation, and a complementary single-crystal X-ray diffraction study on larger, but challenging to isolate, crystals. Comparison with the [BArF4]- analogue [ArF = 3,5-(CF3)2(C6H3)] shows that the [S-BArF4]- anion makes the σ-alkane complex robust towards decomposition both thermally and when suspended in pentane. Subsequent reactivity with dissolved ethene in a pentane slurry, forms [Rh(Cy2PCH2CH2PCy2)(ethene)2][S-BArF4], and the catalytic dimerisation/isomerisation of ethene to 2-butenes. The increased stability of [S-BArF4]- salts is identified as being due to increased non-covalent interactions in the lattice, resulting in a solid-state molecular organometallic material with desirable stability characteristics.

Selectivity of Rh⋠⋠⋠H-C Binding in a σ-Alkane Complex Controlled by the Secondary Microenvironment in the Solid State.

Single-crystal to single-crystal solid-state molecular organometallic (SMOM) techniques are used for the synthesis and structural characterization of the σ-alkane complex [Rh(tBu2 PCH2 CH2 CH2 PtBu2 )(η2 ,η2 -C7 H12 )][BArF 4 ] (ArF =3,5-(CF3 )2 C6 H3 ), in which the alkane (norbornane) binds through two exo-C-H⋅⋅⋅Rh interactions. In contrast, the bis-cyclohexyl phosphine analogue shows endo-alkane binding. A comparison of the two systems, supported by periodic DFT calculations, NCI plots and Hirshfeld surface analyses, traces this different regioselectivity to subtle changes in the local microenvironment surrounding the alkane ligand. A tertiary periodic structure supporting a secondary microenvironment that controls binding at the metal site has parallels with enzymes. The new σ-alkane complex is also a catalyst for solid/gas 1-butene isomerization, and catalyst resting states are identified for this.

The ditungsten decacarbonyl dianion.

We report the synthesis and structural authentication of the ditungsten decarbonyl dianion in [(OC)5W-W(CO)5][K(18-crown-6)(THF)2]2 (1), completing the group 6 dianion triad over half a century since the area began. The W-W bond is long [3.2419(8) Å] and, surprisingly, in the solid-state the dianion adopts a D4h eclipsed rather than D4d staggered geometry, the latter of which dominates the structural chemistry of binary homobimetallic carbonyls. Computational studies at levels of theory from DFT to CCSD(T) confirm that the D4d geometry is energetically preferred in the gas-phase, being ∼18 kJ mol-1 more stable than the D4h form, since slight destabilisation of the degenerate W-CO π 5dxz and 5dyz orbitals is outweighed by greater stabilisation of the W-W σ-bond orbital. The gas-phase D4h structure displays a single imaginary vibrational mode, intrinsic reaction coordinate analysis of which links the D4h isomer directly to the D4d forms, which are produced by rotation around the W-W bond by ±45°. It is therefore concluded that the gas-phase transition state becomes a minimum on the potential energy surface when subjected to crystal packing in the solid-state.

f-Element Half-Sandwich Complexes: A Tetrasilylcyclobutadienyl-Uranium(IV)-Tris(tetrahydroborate) Anion Pianostool Complex.

Despite there being numerous examples of f-element compounds supported by cyclopentadienyl, arene, cycloheptatrienyl, and cyclooctatetraenyl ligands (C5-8 ), cyclobutadienyl (C4 ) complexes remain exceedingly rare. Here, we report that reaction of [Li2 {C4 (SiMe3 )4 }(THF)2 ] (1) with [U(BH4 )3 (THF)2 ] (2) gives the pianostool complex [U{C4 (SiMe3 )4 }(BH4 )3 ][Li(THF)4 ] (3), where use of a borohydride and preformed C4 -unit circumvents difficulties in product isolation and closing a C4 -ring at uranium. Complex 3 is an unprecedented example of an f-element half-sandwich cyclobutadienyl complex, and it is only the second example of an actinide-cyclobutadienyl complex, the other being an inverse-sandwich. The U-C distances are short (av. 2.513 Å), reflecting the formal 2- charge of the C4 -unit, and the SiMe3 groups are displaced from the C4 -plane, which we propose maximises U-C4 orbital overlap. DFT calculations identify two quasi-degenerate U-C4 π-bonds utilising the ψ2 and ψ3 molecular orbitals of the C4 -unit, but the potential δ-bond using the ψ4 orbital is vacant.

Back-bonding between an electron-poor, high-oxidation-state metal and poor π-acceptor ligand in a uranium(V)-dinitrogen complex.

A fundamental bonding model in coordination and organometallic chemistry is the synergic, donor-acceptor interaction between a metal and a neutral π-acceptor ligand, in which the ligand σ donates to the metal, which π back-bonds to the ligand. This interaction typically involves a metal with an electron-rich, mid-, low- or even negative oxidation state and a ligand with a π* orbital. Here, we report that treatment of a uranium-carbene complex with an organoazide produces a uranium(V)-bis(imido)-dinitrogen complex, stabilized by a lithium counterion. This complex, which was isolated in a crystalline form, involves an electron-poor, high-oxidation-state uranium(V) 5f1 ion that is π back-bonded to the poor π-acceptor ligand dinitrogen. We propose that this is made possible by a combination of cooperative heterobimetallic uranium-lithium effects and the presence of suitable ancillary ligands that render the uranium ion unusually electron rich. This electron-poor back-bonding could have implications for the field of dinitrogen activation.

Bimetallic Cooperative Cleavage of Dinitrogen to Nitride and Tandem Frustrated Lewis Pair Hydrogenation to Ammonia.

Although reductive cleavage of dinitrogen (N2 ) to nitride (N3- ) and hydrogenation with dihydrogen (H2 ) to yield ammonia (NH3 ) is accomplished in heterogeneous Haber-Bosch industrial processes on a vast scale, sequentially coupling these elementary reactions together with a single metal complex remains a major challenge for homogeneous molecular complexes. Herein, we report that the reaction of a chloro titanium triamidoamine complex with magnesium effects complete reductive cleavage of N2 to give a dinitride dititanium dimagnesium ditriamidoamine complex. Tandem H2 splitting by a phosphine-borane frustrated Lewis pair (FLP) shuttles H atoms to the N3- , evolving NH3 . Isotope labelling experiments confirmed N2 and H2 fixation. Though not yet catalytic, these results give unprecedented insight into coupling N2 and H2 cleavage and N-H bond formation steps together, highlight the importance of heterobimetallic cooperativity in N2 activation, and establish FLPs in NH3 synthesis.

Reversible coordination of N2 and H2 to a homoleptic S = 1/2 Fe(i) diphosphine complex in solution and the solid state.

The synthesis and characterisation of the S = 1/2 Fe(i) complex [Fe(depe)2]+[BArF4]- ([1]+[BArF4]-), and the facile reversible binding of N2 and H2 in both solution and the solid state to form the adducts [1·N2]+ and [1·H2]+, are reported. Coordination of N2 in THF is thermodynamically favourable under ambient conditions (1 atm; ΔG 298 = -4.9(1) kcal mol-1), while heterogenous binding is more favourable for H2 than N2 by a factor of ∼300. [1·H2]+[BArF4]- represents a rare example of a well-defined, open-shell, non-classical dihydrogen complex, as corroborated by ESR spectroscopy. The rapid exchange between N2 and H2 coordination under ambient conditions is unique for a paramagnetic Fe complex.

Catalytic Dinitrogen Reduction to Ammonia at a Triamidoamine-Titanium Complex.

Catalytic reduction of N2 to NH3 by a Ti complex has been achieved, thus now adding an early d-block metal to the small group of mid- and late-d-block metals (Mo, Fe, Ru, Os, Co) that catalytically produce NH3 by N2 reduction and protonolysis under homogeneous, abiological conditions. Reduction of [TiIV (TrenTMS )X] (X=Cl, 1A; I, 1B; TrenTMS =N(CH2 CH2 NSiMe3 )3 ) with KC8 affords [TiIII (TrenTMS )] (2). Addition of N2 affords [{(TrenTMS )TiIII }2 (µ-η1 :η1 -N2 )] (3); further reduction with KC8 gives [{(TrenTMS )TiIV }2 (µ-η1 :η1 :η2 :η2 -N2 K2 )] (4). Addition of benzo-15-crown-5 ether (B15C5) to 4 affords [{(TrenTMS )TiIV }2 (µ-η1 :η1 -N2 )][K(B15C5)2 ]2 (5). Complexes 3-5 treated under N2 with KC8 and [R3 PH][I], (the weakest H+ source yet used in N2 reduction) produce up to 18 equiv of NH3 with only trace N2 H4 . When only acid is present, N2 H4 is the dominant product, suggesting successive protonation produces [{(TrenTMS )TiIV }2 (µ-η1 :η1 -N2 H4 )][I]2 , and that extruded N2 H4 reacts further with [R3 PH][I]/KC8 to form NH3 .

Cationic silyldiazenido complexes of the Fe(diphosphine)2(N2) platform: structural and electronic models for an elusive first intermediate in N2 fixation.

The first cationic Fe silyldiazenido complexes, [Fe(PP)2(NN-SiMe3)]+[BArF4]- (PP = dmpe/depe), have been synthesised and thoroughly characterised. Computational studies show the compounds to be useful structural and electronic surrogates for the more elusive [Fe(PP)2(NN-H)]+, which are postulated intermediates in the H+/e- mediated fixation of N2 by Fe(PP)2(N2) species.

Selective Catalytic Reduction of N2 to N2H4 by a Simple Fe Complex.

The catalytic fixation of N2 by molecular Fe compounds is a rapidly developing field, yet thus far few complexes can effect this transformation, and none are selective for N2H4 production. Herein we report that the simple Fe(0) complex Fe(Et2PCH2CH2PEt2)2(N2) (1) is an efficient catalyst for the selective conversion of N2 (>25 molecules N2 fixed) into N2H4, attendant with the production of ca. one molecule of NH3. Notably, the reductant (CoCp*2) and acid (Ph2NH2OTf) used are considerably weaker than conventional chemical H+ and e- sources used in previous demonstrations of N2 turnover by synthetic Fe compounds. These results show that the direct catalytic conversion of N2 to the hydrazine oxidation state on molecular Fe complexes is viable and that the mechanism of NH3 formation by such systems may proceed via Fe-N2H4 intermediates.

Teaching old compounds new tricks: efficient N2 fixation by simple Fe(N2)(diphosphine)2 complexes.

The Fe(0) species Fe(N2)(dmpe)2 exists in equilibrium with the previously unreported dimer, [Fe(dmpe2)2(µ-N2)]. For the first time these complexes, alongside Fe(N2)(depe)2, are shown unambiguously to produce N2H4 and/or NH3 upon addition of triflic acid; for Fe(N2)(depe)2 this represents one of the highest electron conversion efficiencies for Fe complexes to date.

Bypassing a highly unstable frustrated Lewis pair: dihydrogen cleavage by a thermally robust silylium-phosphine adduct.

The thermally robust silylium complex [iPr3Si-PtBu3](+)[B(C6F5)4](-) (1) activates H2/D2 at 90 °C (PhCl); no evidence for dissociation into the separated Lewis pair is found. DFT calculations show H2 cleavage proceeds via Si-P bond elongation to form an encounter complex directly from the adduct, thus avoiding the non-isolable iPr3Si(+)-PtBu3 FLP.

A Convenient Synthetic Protocol to 1,2-Bis(dialkylphosphino)ethanes.

1,2-Bis(dialkylphosphino)ethanes are readily prepared from the parent phosphine oxides, via a novel sodium aluminium hydride/sodium hydride reduction protocol of intermediate chlorophosphonium chlorides. This approach is amenable to multi-gram syntheses, utilises readily available and inexpensive reagents, and benefits from a facile non-aqueous work-up in the final reductive step.

A homologous series of first-row transition-metal complexes of 2,2'-bipyridine and their ligand radical derivatives: trends in structure, magnetism, and bonding.

The organometallic first-row transition-metal complexes [M(2,2'-bipy)(mes)2] (M = Cr (1), Mn (2), Co (4), Ni (5); 2,2'-bipy = 2,2'-bipyridine; mes = 2,4,6-Me3C6H2) were reacted with potassium and a suitable alkali-metal sequestering agent to yield salts of the anionic species [M(2,2'-bipy)(mes)2](-). The neutral parent compounds and their corresponding anionic congeners were characterized by single-crystal X-ray diffraction in [Cr(2,2'-bipy)(mes)2]·1.5C6H6, [Mn(2,2'-bipy)(mes)2], [Co(2,2'-bipy)(mes)2]·THF, [Ni(2,2'-bipy)(mes)2], [K(dibenzo-18-crown-6)·THF][Cr(2,2'-bipy)(mes)2]·2THF, [K(18-crown-6)][Mn(2,2'-bipy)(mes)2]·2THF, [K(18-crown-6)][Mn(2,2'-bipy)(mes)2]·0.67py·0.67tol, [K(2,2,2-crypt)][Co(2,2'-bipy)(mes)2], and [K(2,2,2-crypt)][Ni(2,2'-bipy)(mes)2]. These species, along with the previously reported neutral and anionic iron complexes [Fe(2,2'-bipy)(mes)2](0/-) (3/3(-)), form a homologous series of compounds which allow for an in-depth study of the interactions between metals and ligands. Single-crystal X-ray diffraction data, DFT calculations, and various spectroscopic and magnetic measurements indicate that the anionic complexes (1(-)-5(-)) can be best formulated as M(II) complexes of the 2,2'-bipyridyl radical anion. These findings complement recent studies which indicate that bond metric data from single-crystal X-ray diffraction may be employed as an important diagnostic tool in determining the oxidation states of bipyridyl ligands in transition-metal complexes.