Bidentate Phosphanyl‐ and Arsanylboranes

Abstract

An ew class of neutral bidentate ligands with pnictogenyl-functionals ites has been obtained. The reaction of tmeda·(BH 2 I) 2 (1,t meda = tetramethylethylendiamine) with different phosphanidesy ields the corresponding bidentate phosphanylboranes tmeda·(BH 2 PH 2 ) 2 (2a), tmeda·(BH 2 PPh 2 ) 2 (2b), and tmeda·(BH 2 tBuPH) 2 (2c). This reactions trategy couldb ef urthere xtended to synthesize the first bidentate arsanylborane tmeda·(BH 2 AsPh 2 ) 2 (3). Depending on the substituents on the phosphorus, these compounds form different Au I complexes, to build either polymeric tmeda·(BH 2 PH 2 AuCl) 2 (4a), or monomeric tme-da·(BH 2 PPh 2 AuCl) 2 (4b)p roducts.T hese compounds form also neutral oligomeric group 13/15 chain-likem olecules by coordination to ab oron moiety such as tme-da·(BH 2 PH 2 BH 3 ) 2 (5a)a nd tmeda·(BH 2 AsPh 2 BH 3 ) 2 (5b). DFT calculations provide insighti nto the differencesb etween the syntheses of mono-and bidentate pnictogenylboranes.[b] Prof.

Small Chains of Main Group Elements by BH3 Adduct Formation of tBu2E‐N(H)‐EtBu2 (E = P, As)

“…[9] Bis(di-tert-butylarsino)amine (1b) was synthesized following the procedure published by Janssen and Scherer. [10] 1 H, 7 Li, 13 C, 11 B and 31 P NMR spectra were recorded using Bruker Avance HD 250, 300 A, DRX 400, DRX 500 and Avance 500 NMR spectrometers at 300 K. 1 H and 13 C{ 1 H}, 13 C-APT (attached proton test) NMR chemical shifts are reported in ppm downfield from tetramethylsilane. The resonance of the residual protons in the deuterated solvent was used as internal standard for 1 H NMR spectra.…”

“…for certain substituents an equilibrium with a tautomer (1a 1 ) is observed. [9] For the heavier homologue arsenic, a number of arsines including tBu 2 As-N(H)-AstBu 2 are well-known, [10] but their corresponding BH 3 adducts [11][12][13] as well as adducts with haloboranes are in contrast exceedingly rare. [14,15] Oligomers and polymers, in which the main chain is based on elements other than carbon, gained increasing attention in recent years.…”

“…For the heavier homologue arsenic, a number of arsines including t Bu 2 As‐N(H)‐As t Bu 2 are well‐known, but their corresponding BH 3 adducts as well as adducts with haloboranes are in contrast exceedingly rare , …”

Coordination chemistry of pnictogenylboranes towards group 6 transition metal Lewis acids

“…Considering the recently reported bidentate phosphanyl‐ and arsanylboranes [15] as well as the increasing interest in longer or mixed‐element chain pnictogenylboranes, [16] a further investigation of the coordination behavior of pnictogenylboranes was the next step, especially focusing on the less frequently investigated earlier transition metals.…”