Polar covalent apex-base bonding in borapyramidanes probed by solid-state NMR and DFT calculations.

Pyramidane molecules have attracted chemists for many decades due to their regular shape, high symmetry and their correspondence in the macroscopic world. Recently, experimental access to a number of examples has been reported, in particular the rarely reported square pyramidal bora[4]pyramidanes. To describe the bonding situation of the nonclassical structure of pyramidanes, we present solid-state Nuclear Magnetic Resonance (NMR) as a versatile tool for deciphering such bonding properties for three now accessible bora[4]pyramidane and dibora[5]pyramidane molecules. 11 B solid-state NMR spectra indicate that the apical boron nuclei in these compounds are strongly shielded (around -50 ppm vs. BF3 -Et2 O complex) and possess quadrupolar coupling constants of less than 0.9 MHz pointing to a rather high local symmetry. 13 C-11 B spin-spin coupling constants have been explored as a measure of the bond covalency in the borapyramidanes. While the carbon-boron bond to the -B(C6 F5 )2 substituents of the base serves as an example for a classical covalent 2-center-2-electron (2c-2e) sp2 -carbon-sp2 -boron σ-bond with 1 J(13 C-11 B) coupling constants in the order of 75 Hz, those of the boron(apical)-carbon(basal) bonds in the pyramid are too small to measure. These results suggest that these bonds have a strongly ionic character, which is also supported by quantum-chemical calculations.

Structure of diopside, enstatite, and magnesium aluminosilicate glasses: A joint approach using neutron and x-ray diffraction and solid-state NMR.

Neutron diffraction with magnesium isotope substitution, high energy x-ray diffraction, and 29Si, 27Al, and 25Mg solid-state nuclear magnetic resonance (NMR) spectroscopy were used to measure the structure of glassy diopside (CaMgSi2O6), enstatite (MgSiO3), and four (MgO)x(Al2O3)y(SiO2)1-x-y glasses, with x = 0.375 or 0.25 along the 50 mol. % silica tie-line (1 - x - y = 0.5) or with x = 0.3 or 0.2 along the 60 mol. % silica tie-line (1 - x - y = 0.6). The bound coherent neutron scattering length of the isotope 25Mg was remeasured, and the value of 3.720(12) fm was obtained from a Rietveld refinement of the powder diffraction patterns measured for crystalline 25MgO. The diffraction results for the glasses show a broad asymmetric distribution of Mg-O nearest-neighbors with a coordination number of 4.40(4) and 4.46(4) for the diopside and enstatite glasses, respectively. As magnesia is replaced by alumina along a tie-line with 50 or 60 mol. % silica, the Mg-O coordination number increases with the weighted bond distance as less Mg2+ ions adopt a network-modifying role and more of these ions adopt a predominantly charge-compensating role. 25Mg magic angle spinning (MAS) NMR results could not resolve the different coordination environments of Mg2+ under the employed field strength (14.1 T) and spinning rate (20 kHz). The results emphasize the power of neutron diffraction with isotope substitution to provide unambiguous site-specific information on the coordination environment of magnesium in disordered materials.

Oxy-Borylenes as Photoreductants: Synthesis and Application in Dehalogenation and Detosylation Reactions.

While the range of accessible borylenes has significantly broadened over the last decade, applications remain limited. Herein, we present tricoordinate oxy-borylenes as potent photoreductants that can be readily activated by visible light. Facile oxidation of CAAC stabilized oxy-borylenes (CAAC)(IPr2 Me2 )BOR (R=TMS, CH2 CH2 C6 H5 , CH2 CH2 (4-F)C6 H4 ) to their corresponding radical cations is achieved with mildly oxidizing ferrocenium ion. Cyclovoltammetric studies reveal ground-state redox potentials of up to -1.90 V vs. Fc+/0 for such oxy-borylenes placing them among the strongest organic super electron donors. Their ability as photoreductants is further supported by theoretical studies and showcased by the application as stoichiometric reagents for the photochemical hydrodehalogenation of aryl chlorides, aryl bromides and unactivated alkyl bromides as well as the detosylation of anilines.

Solid-State Nuclear Magnetic Resonance Techniques for the Structural Characterization of Geminal Alane-Phosphane Frustrated Lewis Pairs and Secondary Adducts.

The first comprehensive solid-state nuclear magnetic resonance (NMR) characterization of geminal alane-phosphane frustrated Lewis pairs (Al/P FLPs) is reported. Their relevant NMR parameters (isotropic chemical shifts, direct and indirect 27 Al-31 P spin-spin coupling constants, and 27 Al nuclear electric quadrupole coupling tensor components) have been determined by numerical analysis of the experimental NMR line shapes and compared with values computed from the known crystal structures by using density functional theory (DFT) methods. Our work demonstrates that the 31 P NMR chemical shifts for the studied Al/P FLPs are very sensitive to slight structural inequivalences. The 27 Al NMR central transition signals are spread out over a broad frequency range (>200 kHz), owing to the presence of strong nuclear electric quadrupolar interactions that can be well-reproduced by the static 27 Al wideband uniform rate smooth truncation (WURST) Carr-Purcell-Meiboom-Gill (WCPMG) NMR experiment. 27 Al chemical shifts and quadrupole tensor components offer a facile and clear distinction between three- and four-coordinate aluminum environments. For measuring internuclear Al⋅⋅⋅P distances a new resonance-echo saturation-pulse double-resonance (RESPDOR) experiment was developed by using efficient saturation via frequency-swept WURST pulses. The successful implementation of this widely applicable technique indicates that internuclear Al⋅⋅⋅P distances in these compounds can be measured within a precision of ±0.1 Å.

Electronic effects in profluorescent benzotriazinyl radicals: a combined experimental and theoretical study.

The synthesis, photophysical characterization, and quantum chemical calculations of a series of benzotriazinyl radicals and their styryl radical trapping products are presented. The benzotriazinyl radicals are non-luminescent but surprisingly the corresponding styryl radical trapping products exhibit high fluorescence quantum yields (up to 60% in some cases), making them highly valuable probes or labels. Additionally, the influence of the substitution pattern on the optical properties of the radical trapping products was observed experimentally and interpreted by means of quantum chemical calculations. Specific substitution patterns showed a bathochromic shift compared to the unsubstituted compound. Computationally, it was shown that this substitution pattern leads to a stronger energetic stabilization of the lowest unoccupied molecular orbital than the highest occupied molecular orbital. Analysis of the influence of the substitution pattern on the optical properties showed a bathochromic shift in several examples, which was interpreted by means of quantum chemical calculations.

Structure of crystalline and amorphous materials in the NASICON system Na1+xAlxGe2-x(PO4)3.

The structure of crystalline and amorphous materials in the sodium (Na) super-ionic conductor system Na1+xAlxGe2-x(PO4)3 with x = 0, 0.4, and 0.8 was investigated by combining (i) neutron and x-ray powder diffraction and pair-distribution function analysis with (ii) 27Al and 31P magic angle spinning (MAS) and 31P/23Na double-resonance nuclear magnetic resonance (NMR) spectroscopy. A Rietveld analysis of the powder diffraction patterns shows that the x = 0 and x = 0.4 compositions crystallize into space group-type R3̄, whereas the x = 0.8 composition crystallizes into space group-type R3̄c. For the as-prepared glass, the pair-distribution functions and 27Al MAS NMR spectra show the formation of sub-octahedral Ge and Al centered units, which leads to the creation of non-bridging oxygen (NBO) atoms. The influence of these atoms on the ion mobility is discussed. When the as-prepared glass is relaxed by thermal annealing, there is an increase in the Ge and Al coordination numbers that leads to a decrease in the fraction of NBO atoms. A model is proposed for the x = 0 glass in which super-structural units containing octahedral Ge(6) and tetrahedral P(3) motifs are embedded in a matrix of tetrahedral Ge(4) units, where superscripts denote the number of bridging oxygen atoms. The super-structural units can grow in size by a reaction in which NBO atoms on the P(3) motifs are used to convert Ge(4) to Ge(6) units. The resultant P(4) motifs thereby provide the nucleation sites for crystal growth via a homogeneous nucleation mechanism.

The Bis(η6 -benzene)lithium Cation: A Fundamental Main-Group Organometallic Species.

The synthesis and characterization of the bis(η6 -benzene)lithium cation, the benzene metallocene of the lightest metal, is reported. The boron compound FmesBCl2 [Fmes: 2,4,6-tris(trifluoromethyl)phenyl] reacted with three molar equivalents of the lithio-acetylene reagent Li-C≡C-Fmxyl [Fmxyl: 3,5-bis(trifluoromethyl)phenyl]. Subsequent crystallization from benzene gave the [bis(η6 -benzene)Li]+ cation with the [{FmesB(-C≡C-Fmxyl)3 }2 Li]- anion. This parent [(arene)2 Li]+ cation shows an eclipsed arrangement of the pair of benzene ligands at the central lithium cation with uniform carbon-lithium bond lengths. The corresponding [(η6 -toluene)2 Li]+ and [(η6 -durene)2 Li]+ containing salts were similarly prepared. The bis(arene)lithium cations were characterized by X-ray diffraction, by solid-state 7 Li MAS NMR spectroscopy and their bonding features were analyzed by DFT calculations.

Cycloaddition Reactions of an Active Cyclic Phosphane/Borane Pair with Alkenes, Alkynes, and Carbon Dioxide.

The active six-membered cyclo-FLP 6 undergoes a rapid P/B addition reaction to carbon dioxide. At elevated temperature, the resulting heterobicyclo[2.2.2]octane derived product 7 undergoes ring opening and equilibrates with the cyclotetramer (7)4 . In the large macrocyclic structure, four monomeric six-membered cyclo-FLP units are connected by four CO2 molecules to form the supramolecular ring system. The P/B cyclo-FLP 6 undergoes a variety of additional cycloaddition reactions.

Solid-State NMR Techniques for the Structural Characterization of Cyclic Aggregates Based on Borane-Phosphane Frustrated Lewis Pairs.

Modern solid-state NMR techniques offer a wide range of opportunities for the structural characterization of frustrated Lewis pairs (FLPs), their aggregates, and the products of cooperative addition reactions at their two Lewis centers. This information is extremely valuable for materials that elude structural characterization by X-ray diffraction because of their nanocrystalline or amorphous character, (pseudo-)polymorphism, or other types of disordering phenomena inherent in the solid state. Aside from simple chemical shift measurements using single-pulse or cross-polarization/magic-angle spinning NMR detection techniques, the availability of advanced multidimensional and double-resonance NMR methods greatly deepened the informational content of these experiments. In particular, methods quantifying the magnetic dipole-dipole interaction strengths and indirect spin-spin interactions prove useful for the measurement of intermolecular association, connectivity, assessment of FLP-ligand distributions, and the stereochemistry of adducts. The present review illustrates several important solid-state NMR methods with some insightful applications to open questions in FLP chemistry, with a particular focus on supramolecular associates.

From 3D to 2D: Structural, Spectroscopic and Theoretical Investigations of the Dimensionality Reduction in the [PtAl2 ]δ- Polyanions of the Isotypic MPtAl2 Series (M=Ca-Ba, Eu).

Four new MPtAl2 (M=Ca, Sr, Ba, Eu) compounds, adopting the orthorhombic MgCuAl2 -type structure, have been synthesized from the elements using tantalum ampoules. All compounds are obtained as platelet-shaped crystallites and exhibit an increasing moisture sensitivity with increasing size of the formal M cation. Structural investigations indicate a pronounced elongation of the crystallographic b-axis, which results in a significant distortion of the [PtAl2 ]δ- polyanion. Within the polyanion, layer-like arrangements can be found with bonding Pt-Al interactions within the slab; the increase of the b-axis can be attributed to increasing Al-Al distances and therefore decreasing interactions between the slabs, caused by the differently-sized formal M cations. While the alkaline earth (M=Ca, Sr) representatives exhibit Pauli paramagnetism, BaPtAl2 shows diamagnetic behavior, finally EuPtAl2 is ferromagnetic with TC =54.0(5) K. The effective magnetic moment indicates that the Eu atoms are in a divalent oxidation state, which is confirmed by 151 Eu Mössbauer spectroscopic investigations. Measurements below the Curie-temperature show a full magnetic hyperfine field splitting with Bhf =21.7(1) T. 27 Al and 195 Pt magic-angle spinning NMR spectroscopy corroborates the presence of single crystallographic sites for the Pt and Al atoms. The large 27 Al nuclear electric quadrupolar coupling constants confirm unusually strong electric field gradients, in agreement with the structural distortions and the respective theoretical calculations. X-ray photoelectron spectroscopy has been utilized to investigate the charge transfer within the polyanion. The Pt 4f binding energy decreases with decreasing electronegativity / ionization energy of the alkaline earth elements, suggesting an increasing electron density at the Pt atoms. Theoretical investigations underline the platinide character of the investigated compounds by Bader charge calculations. The analysis of the integrated crystal orbital Hamilton population (ICOHP) values, electron localization function (ELF) and isosurface analyses lead to a consistent structural picture, indicating stable layer-like arrangements of the [PtAl2 ]δ- polyanion.

Dihydrogen Splitting by Intramolecular Borane-Phosphane Frustrated Lewis Pairs: A Comprehensive Characterization Strategy Using Solid State NMR and DFT Calculations.

Four hydrogenated intramolecular phosphane-borane frustrated Lewis pair (B/P FLP) compounds bearing unsaturated cyclic or aromatic carbon backbones have been synthesized and structurally characterized using 11 B, 31 P, 1 H and 2 H solid-state NMR spectroscopy. A comparison of the spectra with those of the corresponding free B/P FLPs shows that both 11 B isotropic chemical shifts as well as nuclear electric quadrupolar coupling constants decrease significantly upon FLP hydrogenation, revealing the breakage of the partial B-P bond present in the starting materials. Likewise, the 31 P isotropic chemical shift, the chemical shift anisotropy, and the asymmetry parameter decrease significantly upon FLP hydrogenation, reflecting the formation of a more symmetric, C3v -like local environment. 11 B{31 P} rotational echo double resonance (REDOR) experiments can be used to measure the B-P internuclear distance (about 3.2 Å) of these compounds. Observation of the hydrogen atoms bound to the Lewis centers is best accomplished via 31 P{1 H} and 11 B{1 H} cross-polarization-heteronuclear correlation experiments or by direct observation of the 2 H MAS NMR signals on especially prepared FLP-D2 adducts. For accurately measuring the phosphorus-deuterium distance via 31 P{2 H} rotational echo adiabatic passage double resonance (REAPDOR), it is essential to take the secondary dipolar coupling of 31 P with the boron-bonded 2 H nuclei explicitly into consideration, by simulating a 2 HP -31 P-2 HB three-spin system based on structural input. All of the experimental NMR interaction parameters are found in excellent agreement with values calculated by DFT methods, using the geometries obtained either by energy optimization or from single-crystal structures.

Correlations of Crystal and Electronic Structure via NMR and X-ray Photoelectron Spectroscopies in the RETMAl2 (RE = Sc, Y, La-Nd, Sm, Gd-Tm, Lu; TM = Ni, Pd, Pt) Series.

A total of 35 intermetallic aluminum compounds have been synthesized from the elements via arc melting and characterized by powder X-ray diffraction. A total of 15 of them have been previously reported; however, detailed property investigations were missing. Compounds of the RETMAl2 (rare earth metal RE = Sc, Y, La-Nd, Sm, Gd-Tm, Lu) series with transition metal TM = Ni, Pd, and Pt crystallize isostructurally in the orthorhombic MgCuAl2 type structure ( Cmcm, oC16, fc2). Single-crystal X-ray diffraction investigations were conducted on YNiAl2, LaNiAl2, YPdAl2, ScPtAl2, and YPtAl2. The TM and Al atoms form a [TMAl2]δ- polyanion, the RE atoms reside in cavities within the framework. While the Sc, Y, La, and Lu compounds exhibit Pauli-paramagnetic behavior, consistent with all atoms being closed shell, the other RETMAl2 compounds show paramagnetism along with magnetic ordering at low temperatures, in line with an open-shell trivalent oxidation state for the RE atoms. Solid-state 27Al NMR investigations were carried out on the Pauli-paramagnetic samples, all showing only a single central transition, in line with one crystallographic site for the respective atoms. The observed quadrupolar coupling constants and electric-field-gradient asymmetry parameters were found to be in good agreement with the density-functional-theory-calculated values. Isotropic resonance shifts are dominated by the Fermi-contact interactions with s-conduction electron densities at the Fermi edge (Knight shifts). The bonding characteristics mirror the electronic density of states and crystal chemistry of the family of intermetallic compounds under consideration. Both the Knight shifts and quadrupolar coupling constants can be predicted based on element-specific increments.

Photophysical Properties of Ir(III) Complexes Immobilized in MCM-41 via Templated Synthesis.

In the search for understanding and improving the luminescence of optical materials based on Ir(III) complexes, three [Ir(C∧N)2(dnbp)]+ (dnbp = 4,4'-dinonyl-2,2'-bipyridine) emitters were immobilized in MCM-41 mesoporous nanoparticles. By taking advantage of the amphiphilic nature of [Ir(C∧N)2(dnbp)]+, the complexes were mixed with an appropriate surfactant and the resulting micelles served as templates for the synthesis of mesoporous silica host materials in a one-step sol-gel route. The MCM-encapsulated [Ir(C∧N)2(dnbp)]+ complexes present intense emissions with prominent rigidochromic spectral changes that are substantially less affected by O2 as compared to methanolic solutions, with a thousand-fold decrease in quenching rate constants. These photophysical results points to a possible suitability of Ir(III)-complex-MCM-41 host-guest systems for possible future optoelectronic devices, rigidity optical sensors, or biological markers in different colors.

Rare-earth solid-state NMR spectroscopy of intermetallic compounds: The case of the 175Lu isotope.

The feasibility of high-resolution 175Lu solid-state NMR spectroscopy in intermetallic compounds crystallizing with cubic crystal structures is explored by magic-angle spinning NMR at different magnetic flux densities. The large quadrupole moment of this isotope (3.49 × 10-28 m2) restricts observation of the NMR signal to nearly perfectly ordered crystalline samples. Signals are successfully detected and analyzed in the binary pnictides LuPn (NaCl-type structure; Pn = P, As, Sb) and the intermetallic compounds LuPtSb and LuAuSn, both crystallizing with the MgAgAs-type structure. Sources of line broadening are discussed based on field-dependent static and MAS-NMR spectra, providing guidance with respect to measurement conditions resulting in reliable results. The results highlight the importance of ionic/covalent bonding effects for the detectability of the signal, which reduce the probability of real structure effects commonly observed in intermetallic compounds. No 175Lu NMR signals can be observed in various cubic Heusler compounds. This is attributed to mixed site occupancies and other structural defects producing electric field gradients whose interaction with the 175Lu quadrupole moments broadens the signal beyond detection.

Aggregation Behavior of a Six-Membered Cyclic Frustrated Phosphane/Borane Lewis Pair: Formation of a Supramolecular Cyclooctameric Macrocyclic Ring System.

A new six-membered cyclic frustrated phosphane/borane Lewis pair was liberated from its HB(C6 F5 )2 adduct by treatment with vinylcyclohexane. The system is an active frustrated Lewis pair that undergoes cycloaddition reactions with suitable π reagents and it splits dihydrogen. At room temperature in solution the new compound is a monomer, however, in the crystal and in solution at low temperature it aggregates to a thermodynamically favoured supramolecular macrocyclic cyclooctamer.

Structural Characterization of Intermetallic Compounds by 27Al Solid State NMR Spectroscopy.

Intermetallic compounds are of broad interest for solid state chemists, condensed matter physicists, and material scientists due to their intriguing crystal chemistry, their physical properties, and their potential applications, ranging from lab curiosities to everyday objects. To characterize and understand the properties of new compounds and novel materials, the availability of structural information, particularly single-crystal X-ray diffraction data, is a mandatory prerequisite. Especially when it comes to the formation of compounds with deficient or mixed site occupancies, superstructures, or representatives crystallizing in other, thus far unknown structure types, a complementary method for structural analysis is of great value. Solid state nuclear magnetic resonance spectroscopy has been a valuable tool in many areas of chemistry, being an element-selective, site-specific, and inherently quantitative tool for detailed structural characterization. Magic-angle spinning conditions eliminate or reduce the effect of anisotropic interactions in the solid state, producing high-resolution spectra. Until recently, 27Al NMR studies of intermetallic aluminum compounds have been relatively sparse and mostly limited to binary systems. In this Account, we will summarize the current state of the art of high-resolution 27Al NMR in intermetallic compounds focusing on recent research efforts in our laboratories and the interpretation of NMR parameters in terms of the structural details of the compounds investigated. Besides theoretical aspects of 27Al NMR spectroscopy, short paragraphs on experimental details and the crystal chemistry of the discussed compounds are given. In the main part of this Account, we focus on three key aspects: (i) crystal structure validation, (ii) structural disorder and mixed site occupancies, and (iii) the electronic structure, all of which can be investigated by spectroscopic means. For the first part, we have chosen the ternary equiatomic compounds CaAuAl (TiNiSi type), BaAuAl (LaIrSi type), and Ba3Pt4Al4 (own type). Structural disorder and mixed site occupancies have been probed in the ScTAl series (T = Cr, Ru, Ag, Re) crystallizing in the TiNiSi, HfRhSn, and MgZn2-type structures. Also Na2Au3Al and the Heusler compounds, Sc(T0.5T'0.5)2Al (T = T' = Ni, Pd, Pt, Cu, Ag, Au), have been used for structure validation purposes, based on the number and signal area ratios of the resonances observed and on the comparison between experimental and theoretically calculated nuclear electric quadrupolar interaction parameters. Electronic structure information available from 27Al magnetic shielding will be discussed based on experimental data obtained for the RET5Al2 series (RE = Y, Lu; T = Pd, Pt), the extended RE10TAl3 series (RE = Y, Lu; T = Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt), and the ordered Heusler compounds ScT2Al (T = Ni, Pd, Pt, Cu, Ag, Au).

Towards reliable references for electron paramagnetic resonance parameters based on quantum chemistry: the case of verdazyl radicals.

We present an efficient and accurate computational procedure to calculate properties measurable by EPR spectroscopy. We simulate a molecular dynamics (MD) trajectory by employing the quantum mechanically derived force field (QMDFF) [S. Grimme, J. Chem. Theory Comput., 2014, 10, 4497] and sample the trajectory at different time steps. For each snapshot EPR properties are calculated with a hybrid density functional theory (DFT) method. EPR spectra are simulated based on the averaged results. We applied the strategy to a number of previously published and novel verdazyl radicals, for which we recorded EPR spectra. The resulting simulated spectra are compatible with experiment already before employing an additional fitting step, in contrast to those from single point electronic-structure calculations. After the refinement, the experimental data are excellently reproduced, and the fitted EPR parameters do not deviate much from the calculated ones. This provides confidence in ascribing a direct physical meaning to the refined data in terms of experimental EPR parameters rather than merely considering them as mathematical fit parameters. We also find that couplings to hydrogen nuclei have a significant influence on the spectra of verdazyl radicals.

Ferro- or antiferromagnetism? Heisenberg chains in the crystal structures of verdazyl radicals.

In this study, we address the question of the origin of ferromagnetic or antiferromagnetic interactions in alkynyl-substituted 1,5-diphenyl-6-oxo verdazyl radicals. While a TMS-alkynyl derivative (3) shows antiferromagnetic ordering at low temperatures, the corresponding deprotected alkynyl verdazyl (4) shows ferromagnetic interactions. For both compounds, magnetic Heisenberg chains are characteristic, which were studied systematically by means of X-ray crystallography and quantum chemical calculations. Ferromagnetic interactions are rarely found in such radicals. Therefore, uncovering such structure-property relationships is of crucial importance in order to understand and design promising ferromagnetic networks. Using this knowledge, we were able to design and crystallize diyne derivatives showing comparable solid state characteristics and therefore antiferro- and ferromagnetic Heisenberg chain structures. We show that the understanding of such property-structure relationships is adequate for the design of organic-magnetic materials with defined cooperative effects within the class of verdazyl radicals.

Antiferromagnetic ordering based on intermolecular London dispersion interactions in amphiphilic TEMPO ammonium salts.

Antiferromagnetic coupling in TEMPO-based radicals can be enhanced via self-assembly through London dispersion interactions in amphiphilic solids. The synthesis, magnetic characterization, and three crystal structures of the solid radical ion salts (R-DMAT-n)X with various counterions X and alkyl chain lengths n are reported. Magnetic susceptibility and absolute EPR signal intensity measurements show singlet-triplet transitions in a number of cases, which is discussed in relation to the crystal structures. Antiferromagnetic ordering effects are sensitive to both the length of the alkyl chain and the counter anion.

CO-Reduction Chemistry: Reaction of a CO-Derived Formylhydridoborate with Carbon Monoxide, with Carbon Dioxide, and with Dihydrogen.

Treatment of the bulky metallocene hydride Cp*2Zr(H)OMes (Cp* = pentamethylcyclopentadienyl, Mes = mesityl) with Piers' borane [HB(C6F5)2] and carbon monoxide (CO) gave the formylhydridoborate complex [Zr]-O═CH-BH(C6F5)2 ([Zr] = Cp*2Zr-OMes). From the dynamic NMR behavior, its endergonic equilibration with the [Zr]-O-CH2-B(C6F5)2 isomer was deduced, which showed typical reactions of an oxygen/boron frustrated Lewis pair. It was trapped with CO to give an O-[Zr] bonded borata-ß-lactone. Trapping with carbon dioxide (CO2) gave the respective O-[Zr] bonded cyclic boratacarbonate product. These reaction pathways were analyzed by density functional theory calculation. The formylhydridoborate complex was further reduced by dihydrogen via two steps; it reacted rapidly with H2 to give Cp*2Zr(OH)OMes and H3C-B(C6F5)2, which then slowly reacted further with H2 to eventually give [Zr]-O(H)-B(H)(C6F5)2 and methane (CH4). Most complexes were characterized by X-ray diffraction.