This thesis describes the synthesis, structure/bonding studies and reactivity of cationic terminal borylene complexes. Reactions of the cationic terminal borylene complexes, [CpFe(CO)₂(BNR₂)]⁺[BArf₄]⁻ (R = Cy, ⁱPr) with heteroallenes have been investigated and shown to proceed by initial coordination of the substrate at the electrophilic boron centre. Reaction with isocyanate ultimately forms [CpFe(CO)₂(CNPh)]⁺[BArf₄]⁻ by a net metathesis process. Dicyclohexylcarbodiimide, however, reacts by insertion into the Fe=B bond of the aminoborylene to form [CpFe(CO)₂C(NCy)₂BNR₂]⁺[BArf₄]⁻. An excess of the substrate yields the spirocyclic complex, [CpFe(CO)₂C(NCy)₂B(NCy)₂BNR₂]⁺[BArf₄]⁻ via a second insertion into the B=N bond. Computational studies investigating insertion and metathesis reaction pathways of these aminoborylene complexes are also reported. Reactions of dicyclohexylcarbodiimide with three-coordinate aminoborane and aminoboryl complexes are described. Formation of the first boron guanidinate complexes featuring dihalide substituents, Cy₂NC(NCy)₂BCl₂ and ⁱPr₂NC(NCy)₂BCl₂ by both salt metathesis and carbodiimide insertion routes are reported. The aminoboryl complexes, CpFe(CO)₂B(NPh₂)Cl and CpFe(CO)₂B(NBz₂)Cl have also been synthesized and their reactions with carbodiimides probed. A novel cationic terminal borylene complex, [Cp'Fe(CO)₂(BNⁱPr₂)]⁺ [BArf₄]⁻ featuring a methyl-substituted Cp ring is reported and represents the first structurally characterized isopropyl substituted aminoborylene complex. Substitution of the ancillary carbonyl ligands of cationic terminal borylene complexes has been investigated. Irradiation of the aminoboryl precursor complex, CpFe(CO)₂B(NCy₂)Cl in the presence of trialkylphosphines, PR₃ (PR₃ = PMe₃, PPh₃, P(OMe)₃) yield the mono(phosphine) complexes, CpFe(CO)(PR₃)B(NCy₂)Cl. The mono(substituted) dimer [{CpFe(CO)(BNCy₂)}₂(μ-dmpe)] was also formed from the reaction with the chelating ligand, dmpe. Replacement of the second carbonyl is prevented by the steric bulk of the dicyclohexylamino substituent, and instead [CpFe(CO)(PR₃)₂]⁺Cl⁻ is formed by extrusion of the borylene fragment. The mono(phosphine) ligated cationic terminal borylene complexes, [CpFe(CO)(PR₃)(BNCy₂)]⁺[BArf₄]⁻ were subsequently formed by halide abstraction. Both [CpFe(CO)(PMe₃)(BNCy)₂]⁺[BArf₄]⁻ and the bridging dication [{CpFe(CO)(BNCy₂)}₂(μ-dmpe)]₂⁺[BArf₄]⁻₂ were structurally authenticated. Replacing the bulky cyclohexyl groups of the aminoboryl precursor for methyl groups allowed synthesis of the bis(substituted) complexes, CpFe(PMe₃)₂B(NMe₂)Cl and CpFe(dmpe)B(NMe₂)Cl. Extraction of these complexes into dichloromethane resulted in formation of the borylene, [CpFe(PMe₃)₂(BNMe₂)]⁺Cl⁻ and [CpFe(dmpe)(BNMe₂)]⁺Cl⁻ by spontaneous halide ejection.

The synthesis and characterisation of a series of novel borane, boryl and borylene complexes of electron rich group 8 and 9 metal centres are described in this thesis. Chapter 3 reports on the properties of a highly nucleophile tolerant borylene system, [CpFe(dmpe)(BNMe₂)]⁺, together with its surprising formation via an unprecedented spontaneous halide ejection process. The incorporation of strongly electron releasing ancillary phosphine ligands is reflected by an Fe-B distance (ca. 1.80 Å) which is more akin to alkyl/aryl substituted borylene complexes, and perhaps more strikingly, by the very low exothermicity associated with the binding of pyridine to the two-coordinate boron centre (∆H = -7.4 kcal mol⁻¹ cf. -40.7 kcal mol⁻¹ for BCl₃). Despite the strong π electron release from the metal fragment implied by this suppressed reactivity and short Fe-B bond, the barrier to rotation about the Fe=B bond in the asymmetric variant [CpFe(dmpe){BN(C₆H₄OMe-4)Me}]⁺ is very small (ca. 2.9 kcal mol⁻¹). This apparent contradiction is rationalised by the orthogonal orientations of the HOMO and HOMO-2 orbitals of the [CpML2]⁺ fragment, which mean that the M-B π interaction does not fall to zero even in the highest energy conformation. The reactivities of the aminoboryl complexes, CpFe(CO)₂B(NR₂)Cl (R = Me, Cy), towards electrophiles (H⁺, Me⁺) are discussed in Chapter 4, with a view to probing potential modification of the boryl ligand substituents. The reaction of CpFe(CO)₂B(NCy₂)Cl with [Me₃O][BF₄] leads to the formation of CpFe(CO)₂B(NCy₂)F. Subsequent reactivity with Brookhart’s acid results in the formation of the known difluoroboryl system CpFe(CO)₂BF₂. Reaction of the dimethylaminoboryl complex CpFe(CO)₂B(NMe₂)Cl with [Me₃O][BF₄] generates CpFe(CO)₂BF₂ directly; however, reaction of CpFe(dmpe)B(NMe₂)Cl with [Me₃O][BF₄] is limited to the formation of CpFe(dmpe)B(NMe₂)F, presumably on steric grounds. Additionally, given the enhanced stability of the bis(phosphine) ligated systems, [CpM(PR₃)₂(BNR2)]⁺ compared to related dicarbonyl ligated complexes, it has also proved possible to synthesise other borylene complexes e.g. [CpFe(dmpe)(BOMes)]⁺ which are otherwise unstable under ambient conditions. Chapter 5 reports the coordination and B-H bond activation of aminoboranes at ruthenium and iridium metal centres. Reaction of aminoboranes, H₂BNR₂, with 14-electron fragments of the type [Cp*RuL]⁺, leads to κ² coordination. The interaction with 16- electron fragments, [CpRu(PR₃)₂]⁺, has also been probed. In contrast to side on-binding of isoelectronic alkene donors, an alternative κ¹-(σ-BH) mode of aminoborane ligation has been established, albeit with binding energies only ~ 8 kcal mol⁻¹ greater than for those for analogous dinitrogen complexes. Variations in ground-state structure and exchange dynamics as a function of the phosphine ancillary ligand set are consistent with chemically significant back-bonding into an orbital of B-H σ* character. By contrast, simple borane coordination compounds prove difficult to isolate on addition of aminoboranes, H₂BNR₂, to <m>in situ</m> generated sources of [(p-cymene)Ru(PR₃)Cl]⁺; spontaneous loss of HCl to generate a rare class of primary hydridoboryl complexes is witnessed instead. Attempts to synthesise boryl complexes via simple oxidative addition of monomeric aminoboranes have also proved successful, through the use of electron rich iridium precursors containing the [Ir(PMe₃)₃] fragment. This step results in the synthesis of novel amino(hydrido)boryl complexes, Ln(H)M{B(H)NR₂}; subsequent conversion (on loss of an ancillary ligand) to a borylene dihydride system proceeds via a novel B-to-M α hydride migration. The latter step is unprecedented for group 13 ligand systems and is remarkable in offering α-substituent migration from a Lewis acidic centre as a route to a two-coordinate ligand system.

Im Rahmen dieser Arbeit wurden Gruppe 6 Aminoborylenkomplexe zum Borylentransfer auf Alkine verwendet. Die Bor–Übergangsmetallmehrfachbindung wird gespalten, und die Boryleneinheit (BR) auf die C-C-Dreifachbindung übertragen. Diese formale [2+1]-Cycloaddition macht Borirene (Boracyclopropene) in sehr guten Ausbeuten zugänglich. In früheren Arbeiten ist die Borirensynthese entweder auf geringe Ausbeuten oder auf wenige Beispiele mit schwer zugänglichen Edukten beschränkt. Die entwickelte Methode des Borylentranfers, macht die nach Hückel kleinsten, aromatischen Systeme im Sinne einer „Eintopfreaktion“ darstellbar. Die Verbindungen konnten vollständig spektroskopisch und strukturell charakterisiert werden. Die photophysikalischen Eigenschaften der Borirene wurden mit UV/Vis-Spektroskopie untersucht, mit dem Ergebnis, dass diese im nicht sichtbaren Bereich des Spektrums absorbieren.Die allgemeine Anwendbarkeit des Borylentransfers konnte durch eine doppelte Borylenübertragung auf Diine belegt werden. Es konnte gezeigt werden, dass zwei Aminoboryleneinheiten stöchiometrisch auf ein Substrat übertragen werden. Auf diese Weise konnten erstmalig Bisborirene spektroskopisch und strukturell charakterisiert werden. Die Röntgenstrukturanalysen der Bisborirene 82 und 86 haben ergeben, dass aufgrund der sperrigen Bis(trimethylsilyl)aminosubstituenten eine starke Verdrillung der beiden Boracyclopropeneinheiten zueinander vorliegt. Im Falle von 82 sind beide Ebenen der dreigliedrigen Ringsysteme nahezu senkrecht zueinander angeordnet. Die in guten Ausbeuten synthetisierten Borirene konnten wiederum für deren Reaktivitätsuntersuchungen eingesetzt werden. Interessanterweise war es möglich, das Boriren 58e zu hydroborieren. In Gegenwart von 9-BBN erfolgte eine selektive B–C-Bindungsspaltung von 58e, unter Bildung einer B–H-Bindung. Ein weiterer Aspekt dieser Arbeit sind die Reaktivitätsstudien der Borylenkomplexe 32 und 33, gegenüber C=O-Doppelbindungen sowie C–N-Mehrfachbindungen. Es wurden durch die photochemischen Umsetzungen von 32 bzw. 33 mit Aceton, Benzophenon und tert-Butylcyanid, andere borhaltige Verbindungen erhalten, deren Konstitution aber nicht geklärt werden konnte. Die Reaktivitätsuntersuchungen von 32 und 33 gegenüber Alkenen, hat ergeben, dass eine formale Insertion des Borylenliganden in eine olefinische C–H-Bindung stattfindet. C–H-Aktivierungen durch Borylene wurden vorher nur in der Matrix beobachtet oder postuliert, ohne die erhaltenen Reaktionsprodukte zu charakterisieren. Durch die photochemische Umsetzung von 32 mit 3,3-Dimethyl-1-buten sind die Verbindungen 104 und 105 zugänglich (Abb. 78). Das Vinylaminoboran 104 wurde als farblose Flüssigkeit in 31% Ausbeute erhalten, und das Tieftemperatur 1H-NMR-Spektrum zeigte deutlich ein Signal des borgebundenen H-Atoms bei = 5.47ppm. Die Struktur des Olefinkomplexes 105 konnte durch Röntgenstrukturanalyse geklärt werden und in Übereinstimmung mit der NMR-Spektroskopie, lassen sich die Bindungsverhältnisse der B–H-Bindung als sigma-Koordination zum Chromzentrum erklären. / In this thesis group 6 aminoborylene complexes were used as borylene sources in presence of main group element multiple bond systems. The reactivity of the complexes 32 and 33 with several alkynes was studied extensively. In Fig. 79 the formal [2+1]-cycloaddition is outlined, the transition metal–boron multiple bond is cleaved, and the borylene moiety (BR) transferred to the C-C-triple bond. The borylene transfer allows access to borirenes (boracyclopropenes) by a high yielding, straightforward route (Fig. 80). Earlier reported preparations of borirenes were low yielding or restricted in scope. The obtained compounds, which are aromatic and isoelectronic to the cyclopropenylium cation, were completely spectroscopically characterized and a few of their structures could be determined by X-Ray diffraction. Their photophysical properties were investigated by UV/Vis absorption, and their maximum absorption was found in the non- visible region. The versatility of the synthetic method was proved by borylene transfer to diynes, ultimately resulting in two aminoborylene moieties being transferred stochiometrically to one substrate (Fig. 81). The bisborirenes were obtained in good yields and were completely spectroscopically characterised and their structures were determined by X-Ray structure analysis. The X-Ray structure of 82 (Fig. 81) and 86 (Fig. 82) showed that the two boracyclopropene units were strongly non-co-planar. In case of 82 the planes of the three-membered rings were nearly perpendicular to each other. The borirenes were also used for reactivity studies. Interestingly it was possible to hydroborate the borirene 58e (Fig. 83). In presence of 9-BBN one B–C bond is cleaved from 58e, with the formation of a B–H bond. Further reactivity studies of the aminoborylene complexes 32 and 33 were made with C=O double bonds and C–N multiple bonds. By photochemical activation of 32 and 33 with acetone, benzophenone and tbutylcyanide, other boron containing compounds were obtained, but their constitution could not be determined. In contrast to the addition of the borylene moiety to alkynes, the investigation of the reactivity profile of 32 with olefins uncovered a formal insertion of the borylene ligand into the vinylic C–H bond. C–H activations by borylenes have been previously observed in a matrix or postulated without the characterization of the reaction products. The irradiation of 32 with 3,3-dimethyl-1-butene led to the compounds 104 and 105 (Fig. 85). The vinylaminoborane 104 was isolated as a colorless liquid in 31% yield, and its low temperature 1H-NMR-spectra showed clearly the boron bound proton at 5.47ppm. The structure of the olefin complex 105 was determined by X-Ray diffraction and is in agreement with the NMR-spectroscopical examination, the B–H bond is sigma-coordinated to the chromium center resulting in a three-center-two-electron bonding situation.

No description available.