A Nitrido Salt Reagent of Titanium

Deprotonation of the parent titanium imido (^tBunacnac)­TiNH­(Ntolyl₂) (^tBunacnac^– = [ArNC^tBu]₂CH; Ar = 2,6-ⁱPr₂C₆H₃) with KCH₂Ph forms a rare example of a molecular titanium nitride as a dimer, {[K]­[(^tBunacnac)­TiN­(Ntolyl₂)]}₂. From the parent imido or nitride salt, the corresponding aluminylimido–etherate adduct, (^tBunacnac)­TiN­[AlMe₂(OEt₂)]­(Ntolyl₂), can be isolated and structurally characterized. The parent imido is also a source for the related borylimido, (^tBunacnac)­TiNBEt₂(Ntolyl₂)

Structural Elucidation of the Illustrious Tebbe Reagent

The Tebbe reagent, [Cp₂Ti­(μ₂-Cl)­(μ₂-CH₂)­AlMe₂] (<b>1</b>), has finally been structurally characterized due to the fortuitous formation of cocrystals of <b>1</b> and [Cp₂Ti­(μ₂-Cl)₂AlMe₂] (<b>2</b>). Single crystals of <b>1</b> and <b>2</b>, despite being extremely reactive and forming an amorphous white coat, can be mounted and data collected to high resolution, thereby providing for the first time a solid-state representation of a titanium methylidene adduct with diphilic AlClMe₂

Structural Elucidation of the Illustrious Tebbe Reagent

The Tebbe reagent, [Cp₂Ti­(μ₂-Cl)­(μ₂-CH₂)­AlMe₂] (<b>1</b>), has finally been structurally characterized due to the fortuitous formation of cocrystals of <b>1</b> and [Cp₂Ti­(μ₂-Cl)₂AlMe₂] (<b>2</b>). Single crystals of <b>1</b> and <b>2</b>, despite being extremely reactive and forming an amorphous white coat, can be mounted and data collected to high resolution, thereby providing for the first time a solid-state representation of a titanium methylidene adduct with diphilic AlClMe₂

Addition of Si–H and B–H Bonds and Redox Reactivity Involving Low-Coordinate Nitrido–Vanadium Complexes

In this study we enumerate the reactivity for two molecular vanadium nitrido complexes of [(nacnac)­VN­(X)] formulation [nacnac = (Ar)­NC­(Me)­CHC­(Me)­(Ar)⁻, Ar = 2,6-(CHMe₂)₂C₆H₃); X^– = OAr (<b>1</b>) and N­(4-Me-C₆H₄)₂ (Ntolyl₂) (<b>2</b>)]. Density functional theory calculations and reactivity studies indicate the nitride motif to have nucleophilic character, but where the nitrogen atom can serve as a conduit for electron transfer, thus allowing the reduction of the vanadium­(V) metal ion with concurrent oxidation of the incoming substrate. Silane, H₂SiPh₂, readily converts the nitride ligand in <b>1</b> into a primary silyl–amide functionality with concomitant two-electron reduction at the vanadium center to form the complex [(nacnac)­V­{N­(H)­SiHPh₂}­(OAr)] (<b>3</b>). Likewise, addition of the B–H bond in pinacolborane to the nitride moiety in <b>2</b> results in formation of the boryl–amide complex [(nacnac)­V­{N­(H)­B­(pinacol)}­(Ntolyl₂)] (<b>4</b>). In addition to spectroscopic data, complexes <b>3</b> and <b>4</b> were also elucidated structurally by single-crystal X-ray diffraction analysis. One-electron reduction of <b>1</b> with 0.5% Na/Hg on a preparative scale allowed for the isolation and structural determination of an asymmetric bimolecular nitride radical anion complex having formula [Na]₂[(nacnac)­V­(N)­(OAr)]₂ (<b>5</b>), in addition to room-temperature solution X-band electron paramagnetic resonance spectroscopic studies

A Planar Three-Coordinate Vanadium(II) Complex and the Study of Terminal Vanadium Nitrides from N₂: A Kinetic or Thermodynamic Impediment to N–N Bond Cleavage?

We report the first mononuclear three-coordinate vanadium­(II) complex [(nacnac)­V­(ODiiP)] and its activation of N₂ to form an end-on bridging dinitrogen complex with a topologically linear V­(III)­N₂V­(III) core and where each vanadium center antiferromagnetically couples to give a ground state singlet with an accessible triplet state as inferred by HFEPR spectroscopy. In addition to investigating the conversion of N₂ to the terminal nitride (as well as the microscopic reverse process), we discuss its similarities and contrasts to the isovalent <i>d</i>³ system, [Mo­(N­[^<i>t</i>Bu]­Ar)₃], and the <i>S</i> = 1 system [(Ar­[^<i>t</i>Bu]­N)₃Mo]₂(μ₂-η¹:η¹-N₂)

A Planar Three-Coordinate Vanadium(II) Complex and the Study of Terminal Vanadium Nitrides from N₂: A Kinetic or Thermodynamic Impediment to N–N Bond Cleavage?

We report the first mononuclear three-coordinate vanadium­(II) complex [(nacnac)­V­(ODiiP)] and its activation of N₂ to form an end-on bridging dinitrogen complex with a topologically linear V­(III)­N₂V­(III) core and where each vanadium center antiferromagnetically couples to give a ground state singlet with an accessible triplet state as inferred by HFEPR spectroscopy. In addition to investigating the conversion of N₂ to the terminal nitride (as well as the microscopic reverse process), we discuss its similarities and contrasts to the isovalent <i>d</i>³ system, [Mo­(N­[^<i>t</i>Bu]­Ar)₃], and the <i>S</i> = 1 system [(Ar­[^<i>t</i>Bu]­N)₃Mo]₂(μ₂-η¹:η¹-N₂)

A Planar Three-Coordinate Vanadium(II) Complex and the Study of Terminal Vanadium Nitrides from N₂: A Kinetic or Thermodynamic Impediment to N–N Bond Cleavage?

We report the first mononuclear three-coordinate vanadium­(II) complex [(nacnac)­V­(ODiiP)] and its activation of N₂ to form an end-on bridging dinitrogen complex with a topologically linear V­(III)­N₂V­(III) core and where each vanadium center antiferromagnetically couples to give a ground state singlet with an accessible triplet state as inferred by HFEPR spectroscopy. In addition to investigating the conversion of N₂ to the terminal nitride (as well as the microscopic reverse process), we discuss its similarities and contrasts to the isovalent <i>d</i>³ system, [Mo­(N­[^<i>t</i>Bu]­Ar)₃], and the <i>S</i> = 1 system [(Ar­[^<i>t</i>Bu]­N)₃Mo]₂(μ₂-η¹:η¹-N₂)