NHC-Stabilized Mixed Group 13/14/15 Element Hydrides.

The syntheses of novel N-heterocyclic carbene (NHC) adducts of group 13, 14 and 15 element hydrides are reported. Salt metathesis reactions between NaPH2 and IDipp ⋅ GeH2 BH2 OTf (1) (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene) led to mixtures of the two isomers IDipp ⋅ GeH2 BH2 PH2 (2 a) and IDipp ⋅ BH2 GeH2 PH2 (2 b); by altering the reaction conditions an almost exclusive formation of 2 b was achieved. Attempts to purify mixtures of 2 a and 2 b by re-crystallization from THF afforded a salt [IDipp ⋅ GeH2 BH2 ⋅ IDipp][PHGeH2 BH2 PH2 BH2 GeH2 ] (4) that contains the novel anionic cyclohexyl-like inorganic heterocycle [PHGeH2 BH2 PH2 BH2 GeH2 ]- . In addition, the borane adducts IDipp ⋅ GeH2 BH2 PH2 BH3 (3 a) and IDipp ⋅ BH2 GeH2 PH2 BH3 (3 b) as even longer chain compounds were obtained from reactions of 2 a/2 b with H3 B ⋅ SMe2 and were studied by NMR spectroscopy. Accompanying DFT computations give insight into the mechanism and energetics associated with 2 a/2 b isomerization as well as their decomposition pathways.

A convenient route to mixed cationic group 13/14/15 compounds.

The formation of novel cationic mixed main group compounds is reported revealing a chain composed of different elements of group 13, 14, and 15. Reactions of different pnictogenylboranes R2EBH2·NMe3 (E = P, R = Ph, H; E = As, R = Ph, H) with the NHC-stabilized compound IDipp·GeH2BH2OTf (1) (IDipp = 1,3-bis(2,6-diisopropylphenyl)imidazole-2-ylidene) were carried out, yielding the novel cationic, mixed group 13/14/15 compounds [IDipp·GeH2BH2ER2BH2·NMe3]+ (2a E = P; R = Ph; 2b E = As; R = Ph; 3a E = P; R = H; 3b E = As; R = H) by the nucleophilic substitution of the triflate (OTf) group. The products were analysed by NMR spectroscopy and mass spectrometry and for 2a and 2b also by X-ray structure analysis. Further reactions of 1 with H2EBH2·IDipp (E = P, As) resulted in the unprecedented parent complexes [IDipp·GeH2BH2EH2BH2·IDipp][OTf] (5a E = P; 5b E = As), which were studied by X-ray structure analysis, NMR spectroscopy and mass spectrometry. Accompanying DFT computations give insight into the stability of the formed products with respect to their decomposition.

Coordination of Pnictogenylboranes Towards Tl(I) Salts and a Tl- Mediated P-P Coupling.

The coordination chemistry of only Lewis-base (LB)-stabilized pnictogenylboranes EH2 BH2 ⋅NMe3 (E=P, As) towards Tl(I) salts has been studied. The reaction of Tl[BArCl ] (BArCl =[B(3,5-C6 H3 Cl2 )4 ]- ) with the corresponding pnictogenylborane results in the formation of [Tl(EH2 BH2 ⋅NMe3 )][BArCl ] (1 a: E=P; 1 b: E=As). Whereas the Tl ion in 1 a/b is monocoordinated, the exchange of the weakly coordinating anion (WCA) in the Tl(I) salt leads to the formation of a trigonal pyramidal coordination mode at the Tl atom by coordination of three equivalents of EH2 BH2 ⋅ NMe3 in [Tl(EH2 BH2 ⋅ NMe3 )3 ][WCA] (2 a: E=P, WCA=TEFCl ; 2 b: E=As, WCA=TEF) (TEF=[Al{OC(CF3 )3 }4 ]- , TEFCl =[Al{(OC(CF3 )2 (CCl3 )}4 ]- ). Furthermore, by using two equivalents of PH2 BH2 ⋅NMe3 , a Tl(I)-mediated P-P coupling takes place in CH2 Cl2 as solvent resulting in [Me3 N⋅BH2 PH2 PHBH2 ⋅NMe3 ][WCA] (WCA=TEF, 3 a; BArCl , 3 b; TEFCl , 3 c). In contrast, for the arsenic derivatives 1 b and 2 b, no coupling reaction is observed. The underlying chemical processes are elucidated by quantum chemical computations.

Three- and Five-Membered Anionic Chains of Pnictogenylboranes.

An unprecedented family of three- and five-membered substituted anionic derivatives of parent pnictogenylboranes is herein reported. Reacting various combinations of the pnictogenylboranes H2 E'-BH2 -NMe3 (E'=P, As) with pnictogen-based nucleophiles MER1R2 (E=P, As; R1=H, R2=t Bu; R1=R2=Ph; M=Na, K) allows for the isolation of the unsymmetrical products [Na(18-crown-6)][H2 E'-BH2 -EHt Bu] (3: E=E'=P; 4: E=E'=As; 5: E=As, E'=P) and [M(C)][H2 E'-BH2 -EPh2 ] (7: E=E'=P, M=Na, C=18-crown-6; 8: E=E'=As; M=K, C=[2.2.2]cryptand; 9: E=P, E'=As, M=Na, C=[2.2.2]cryptand; 10: E=As, E'=P, M=K, C=[2.2.2]cryptand). [Na(18-crown-6)][H2 As-BH2 -t BuPH-BH3 ] (6) is only accessible by a different pathway, using t BuPH2 , BH3 ⋅ SMe2 and NaNH2 as starting materials. Additionally, the synthesis of symmetrical diphenyl-substituted compounds [M(18-crown-6)][Ph2 E-BH2 -EPh2 ] (11: E=P, M=Na; 12: E=As, M=K) is reported which can be regarded as isostructural inorganic, negatively charged analogs of dppm (1,1-bis(diphenylphosphino)methane) and dpam (1,1-bis(diphenylarsino)methane). Furthermore, an elongation of the pnictogen boron backbone in compounds 3, 7 and 9' (similar compound to 9, stabilized however by 18-crown-6), is attainable by reacting them with the pnictogenylboranes H2 E'-BH2 -NMe3 leading to corresponding five-membered chain-like compounds [Na(18-crown-6)][H2 E-BH2 -R1R2P-BH2 -E'H2 ] (E=E'=P, R1=H, R2=t Bu (13); E=E'=P, R1=R2=Ph (14); E=E'=As, R1=R2=Ph (15); E=P, E'=As, R1=R2=Ph (16)). Finally, the thermodynamics of the reaction pathways were evaluated by quantum chemical computations.

An NHC-Stabilized H2 GeBH2 Precursor for the Preparation of Cationic Group 13/14/15 Hydride Chains.

The synthesis, characterization and reactivity studies of the NHC-stabilized complex IDipp ⋅ GeH2 BH2 OTf (1) (IDipp=1,3-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene) are reported. Nucleophilic substitution of the triflate (OTf) group in 1 by phosphine or arsine donors provides access to the cationic group 13/14/15 chains [IDipp ⋅ GeH2 BH2 ERR1 R2 ]+ (2 E=P; R, R1 =H; R2 =t Bu; 3 E=P; R=H; R1 , R2 =Ph; 4 a E=P; R, R1 , R2 =Ph; 4 b E=As; R, R1 , R2 =Ph). These novel cationic chains were characterized by X-ray crystallography, NMR spectroscopy and mass spectrometry. Moreover, the formation of the parent complexes [IDipp ⋅ GeH2 BH2 PH3 ][OTf] (5) and [IDipp ⋅ GeH3 ][OTf] (6) were achieved by reaction of 1 with PH3 . Accompanying DFT computations give insight into the stability of the formed chains with respect to their decomposition.