NHC-ligated nickel(II) cyanoborate complexes and salts.

A comprehensive study on the synthesis and characterization of NHC-ligated nickel(II) cyanoborates (CBs) is presented (NHC = N-heterocyclic carbene). Nickel(II) cyanoborates Ni[BH2(CN)2]2·H2O (Ib·H2O), Ni[BH(CN)3]2·0.5H2O (Ic·0.5H2O), Ni[B(CN)4]2·H2O (Id·H2O) were reacted with selected NHCs of different steric size. The reaction of the nickel cyanoborates with small to medium-sized NHCs Me2ImMe and iPr2Im (R2Im = 1,3-di-organyl-imidazolin-2-ylidene; R2ImMe = 1,3-di-organyl-4,5-dimethyl-imidazolin-2-ylidene) afforded cyanoborate salts containing the rare homoleptic fourfold NHC-ligated nickel(II) cations [Ni(NHC)4]2+ (NHC = Me2ImMe (1c-d), iPr2Im (2c-d)) and cyanoborate counter-anions. Bulkier NHCs such as Mes2Im and Dipp2Im afforded complexes trans-[Ni(NHC)2(CB)2] (trans-4b, trans-5c). For the combination of the cyanoborate anion [BH2(CN)2]- and iPr2ImMe the salt of the tris-NHC complex [Ni(iPr2ImMe)3(NC-BH2CN)][BH2(CN)2] (3b) was isolated. Salt metathesis of NHC-ligated nickel(II) halides (Ni(NHC)2X2) (X = Cl, Br) with silver(I) and alkali metal cyanoborates were used to synthesize mono- and disubstituted coordination compounds of the type cis- or trans-[Ni(NHC)2(CB)X] (cis-10c, cis-11c, trans-12b) and cis- or trans-[Ni(NHC)2(CB)2] (cis-13b, cis-14a-c, trans-14a-b, trans-15b, trans-5b). Further investigations reveal that NHC-ligated cyanoborate complexes can act as building blocks for coordination polymers, as observed for structurally characterized 1∞{trans-[Ni(Mes2Im)2(µ2-[NC-BH2-CN])2]·2Ag(µ2-[BH2(CN)2])} (trans-5b·Ag). This study demonstrates the diverse character of cyanoborates in coordination chemistry as both, non-coordinating counter-anions, and weakly to medium coordinating anions forming novel transition metal complexes and salts. It provides evidence that a proper choice of cyanoborate and a proper choice of co-ligand can lead to a rich coordination chemistry of cyanoborate anions.

Nickel(II) Cyanoborates and Cyanoborate-Ligated Nickel(II) Complexes.

Nickel(II) cyanoborates Ni[BH2(CN)2]2·H2O (1b·H2O), Ni[BH(CN)3]2·0.5H2O (1c·0.5H2O), and Ni[B(CN)4]2·0.5H2O (1d·0.5H2O) were synthesized, and their reactivity with respect to dppeO2 (=1,2-bis-(diphenylphosphinoethane dioxide)), pyNO (=pyridine-N-oxide), dppe (=1,2-bis-(diphenylphosphinoethane), and DMSO (=dimethyl sulfoxide) was examined. Using these ligands, either cyanoborate (CB) complex salts of [Ni(dppe)2]2+ (2b-d) and [Ni(pyNO)6]2+ (3c-d) were isolated or complexes [Ni(DMSO)4{NC-B(CN)3}2] (1dDMSO) and [Ni(dppeO2)2{NC-B(CN)3}2] (1ddppeO2) were formed. Salt metathesis of [Ni(dppe)Cl2] with alkali metal cyanoborates resulted in mono- and disubstituted coordination compounds [Ni(dppe){NC-BH(CN)2}Cl] (5c) and [Ni(dppe){NC-BH2CN)2}] (4b), which decomposed to salts 2b-d. The synthetical pathways explored offer convenient routes to nickel(II) cyanoborates, nickel(II) complexes ligated with cyanoborates, and nickel(II) complex salts of cyanoborates. Further, our studies demonstrate the diverse character of cyanoborates in coordination chemistry as noncoordinating counteranions and also as medium coordinating anions forming novel transition-metal complexes and salts.

N-Heterocyclic carbene and cyclic (alkyl)(amino)carbene ligated half-sandwich complexes of chromium(II) and chromium(I).

The synthesis and characterization of a series of Cr(II) N-Heterocyclic Carbene (NHC) complexes of the type [{Cr(NHC)Cl(µ-Cl)}2] and [(Cyp)Cr(NHC)X] (Cyp = η5-C5H5, cyclopentadienyl; η5-C5Me5, pentamethylcyclopentadienyl; X = Cl, η3-C3H5; NHC = IMeMe, IiPrMe, IMes, IDipp) as well as the cyclic (alkyl)(amino)carbene cAACMe ligated complexes [(η5-C5H5)Cr(cAACMe)X] (X = Cl, NPh2), [(η5-C9H7)Cr(cAACMe)Cl] (C9H7 = Ind, indenyl) and [(η5-C13H9)Cr(cAACMe)Cl] (C13H9 = Fl, fluorenyl) are reported. The reduction of [(η5-C5Me5)Cr(IMeMe)Cl] with KC8 in the presence of CO afforded the NHC ligated Cr(I) metallo-radical [(η5-C5Me5)Cr(IMeMe)(CO)2]. Quantum chemical calculations performed on [(η5-C5Me5)Cr(IMeMe)(CO)2] confirm for this complex a predominantly chromium centered radical.

Stable Actinide π Complexes of a Neutral 1,4-Diborabenzene.

The π coordination of arene and anionic heteroarene ligands is a ubiquitous bonding motif in the organometallic chemistry of d-block and f-block elements. By contrast, related π interactions of neutral heteroarenes including neutral bora-π-aromatics are less prevalent particularly for the f-block, due to less effective metal-to-ligand backbonding. In fact, π complexes with neutral heteroarene ligands are essentially unknown for the actinides. We have now overcome these limitations by exploiting the exceptionally strong π donor capabilities of a neutral 1,4-diborabenzene. A series of remarkably robust, π-coordinated thorium(IV) and uranium(IV) half-sandwich complexes were synthesized by simply combining the bora-π-aromatic with ThCl4 (dme)2 or UCl4 , representing the first examples of actinide complexes with a neutral boracycle as sandwich-type ligand. Experimental and computational studies showed that the strong actinide-heteroarene interactions are predominately electrostatic in nature with distinct ligand-to-metal π donation and without significant π/δ backbonding contributions.