Dragoslav Vidovic

A Stable Two-Coordinate Acyclic Silylene

Simple two-coordinate acyclic silylenes, SiR(2), have hitherto been identified only as transient intermediates or thermally labile species. By making use of the strong σ-donor properties and high steric loading of the B(NDippCH)(2) substituent (Dipp = 2,6-(i)Pr(2)C(6)H(3)), an isolable monomeric species, Si{B(NDippCH)(2)}{N(SiMe(3))Dipp}, can be synthesized which is stable in the solid state up to 130 °C. This silylene species undergoes facile oxidative addition reactions with dihydrogen (at sub-ambient temperatures) and with alkyl C-H bonds, consistent with a low singlet-triplet gap (103.9 kJ mol(-1)), thus demonstrating fundamental modes of reactivity more characteristic of transition metal systems.

Transition metal borylene complexes: boron analogues of classical organometallic systems

In the ten years since the first examples of terminal borylene complexes were reported, rapid advances in the chemistry of this ligand class have been made, and parallels emerged with classical organometallic ligand systems (such as carbenes, vinylidenes and even CO) as well as with other subvalent main group ligand systems. This article reviews key developments in synthetic, structural and reaction chemistry, with particular attention focusing on recent discoveries in the field.

Isolation of a Bis(oxazol‐2‐ylidene)–Phenylborylene Adduct and its Reactivity as a Boron‐Centered Nucleophile

An isolable phenylborylene species supported by two oxazol-2-ylidene ligands was synthesized and structurally characterized. Computational studies revealed the presence of lone-pair electrons on the boron atom in this molecule; therefore, there are eight electrons around the three-coordinate boron center. The nucleophilic property was confirmed by the reactions with trifluoromethanesulfonic acid and [(thf)Cr(CO)5], which gave the corresponding conjugate acid and a chromium-borylene complex, respectively.

Coordination and Activation of the BF Molecule

No CO: Fluoroborylene (BF), isoelectronic with CO and N(2), can be trapped by a transition metal. The structurally characterized complex [{CpRu(CO)(2)}(2)(mu-BF)] contains an unsupported bridging BF ligand, which is unprecedented in the structural chemistry of CO. With AlCl(3) , metal-bound CO coordinates through the O atom without bond rupture, while the more polar and less pi-bonded BF ligand is heterolytically cleaved (see picture).

Amine elimination synthesis of a titanium(IV) N-heterocyclic carbene complex with short intramolecular Cl⋯Ccarbene contacts

The reaction of 1,3-dimesitylimidazolium chloride with Ti(NMe(2))(4) results in the 1,3-dimesitylimadazol-2-ylidene complex of Ti(NMe(2))(2)Cl(2)(3); the X-ray crystal structure of 3 evidences short intramolecular Cl...C(carbene) contacts.

Facile syntheses of dissymmetric ferrocene-functionalized Lewis acids and acid–base pairs

A facile synthetic approach is reported for the synthesis of dissymmetric 1,2-ferrocenediyl Lewis acids and mixed acid-base pairs including the first example of a 1-phosphino-2-borylferrocene; the use of non-racemic electrophiles allows for the isolation of single diastereomer products.

An N,N′-chelated phosphenium cation supported by a β-diketiminate ligand

The first example of a phosphenium cation supported by N,N′-chelation of a β-diketiminate ligand has been prepared and structurally characterized.

Generation of cationic two-coordinate group-13 ligand systems by spontaneous halide ejection: remarkably nucleophile-resistant (dimethylamino)borylene complexes.

Spontaneous ejection of chloride from a three-coordinate boron Lewis acid can be effected by employing very electron rich metal substituents and leads to the formation of a sterically unprotected terminal (dimethylamino)borylene complex that has a short metal-boron bond and remarkable resistance to attack by nucleophilic and protic reagents.

Tuning main group redox chemistry through steric loading: subvalent Group 13 metal complexes of carbazolyl ligands.

The ability of substituted carbazol-9-yl systems to ligate in σ fashion through the amido N-donor, or to adopt alternative coordination modes through the π system of the central five-membered ring, can be tuned by systematic variation in the steric demands of substituents in the 1- and 8-positions. The differing affinities of the two modes of coordination for hard and soft metal centres can be shown to influence not only cation selectivity, but also the redox properties of the metal centre. Thus, the highly sterically sterically demanding 1,3,6,8-tetra-tert-butylcarbazolyl ligand can be used to generate the structurally characterised amido-indium(I) complex, [{(tBu(4)carb)In}(n)], (together with its isostructural thallium counterpart) in which the metal centre interacts with the central pyrrolyl ring in η(3) fashion [d(In-N)=2.679(3) Å; d(In-C)=2.819(3), 2.899(3) Å]. By contrast, the smaller 3,6-di-tert-butylcarbazolyl system is less able to restrict the metal centre from binding at the anionic nitrogen donor in the plane of the carbazolyl ligand (i.e. in σ fashion). Analogous chemistry with In(I) precursors therefore leads to disproportionation to the much harder In(II) [and In(0)], and the formation of the mixed-valence product, [In(2){In(2)(tBu(2)carb)(6)}], a homoleptic molecular [In(4)(NR(2))(6)] system. This chemistry reveals a flexibility of ligation for carbazolyl systems that contrasts markedly with that of the similarly sterically encumbered terphenyl ligand family.

Oxidative addition of water and methanol to a dicationic trivalent phosphorus centre.

Our recently synthesised phosphorus dication is observed to activate water (and methanol) under reactions conditions atypical for other systems containing a non-metal centre. This particular activation described as oxidative addition is quite rare and has been reserved exclusively for a couple of metal-based compounds.