A new class of neutral bidentate ligands with pnictogenyl-functional sites has been obtained. The reaction of tmeda⋅(BH 2I) 2 (1, tmeda=tetramethylethylendiamine) with different phosphanides yields the corresponding bidentate phosphanylboranes tmeda⋅(BH 2PH 2) 2 (2 a), tmeda⋅(BH 2PPh 2) 2 (2 b), and tmeda⋅(BH 2tBuPH) 2 (2 c). This reaction strategy could be further extended to synthesize the first bidentate arsanylborane tmeda⋅(BH 2AsPh 2) 2 (3). Depending on the substituents on the phosphorus, these compounds form different Au I complexes, to build either polymeric tmeda⋅(BH 2PH 2AuCl) 2 (4 a), or monomeric tmeda⋅(BH 2PPh 2AuCl) 2 (4 b) products. These compounds form also neutral oligomeric group 13/15 chain-like molecules by coordination to a boron moiety such as tmeda⋅(BH 2PH 2BH 3) 2 (5 a) and tmeda⋅(BH 2AsPh 2BH 3) 2 (5 b). DFT calculations provide insight into the differences between the syntheses of mono- and bidentate pnictogenylboranes.
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