The structural and photophysical properties of a series of new Au I compounds have been studied. The reactionso fA uCl(tht) with the phosphanyl-and arsanylboranes RR ' EBH 2 NMe 3 (E = P, As;R = H, Ph;R ' = H, Ph, tBu) afford the complexes [AuCl(RR ' EBH 2 NMe 3 )].I nt he solid state, [AuCl(H 2 PBH 2 NMe 3 )] 2 (2a)i sad imer showingu nsupported intermolecular aurophilic interactionsw ith short Au···Au distances. In contrast,[ AuCl(H 2 AsBH 2 NMe 3 )] n (2b) aggregates to form 1D chains. Organic substituentso n the pnictogen atomsl ead to discrete moleculesi n [AuCl(RR ' PBH 2 NMe 3 )] (2c:R = H, R' = tBu; 2d:R = R' = Ph). To increase the aurophilicity,t he ionic homoleptic complexes [Au(RR ' EBH 2 NMe 3 ) 2 ][AlCl 4 ]( 3a-d)h ave been synthesized, for which 3a,b form chains in the solid state and exhibit luminescence. The emissions show ad rastic redshift with temperature decrease, correlating with decreasing Au···Au distances.D FT calculations provide insight into the bondings ituation of the products. [a] J. Braese, Dr.M.B odensteiner,Prof. Dr.M .
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.
The reactions of the phosphinoborane Ph2PBH2·NMe3 with Cu(I) halides [CuCl, CuBr, CuI] and [Cu(CH3CN)4BF4], respectively, were studied. Depending on the ratio of the reactants used, the former reaction allowed for the synthesis of eight neutral coordination compounds with the general formula [CunXn(Ph2PBH2·NMe3)m] (X = Cl, Br, I; n = 1, 2, 4, 5; m = 2, 4) (4–11). The latter reaction, however, led to the formation of the homoleptic complex [Cu(Ph2PBH2·NMe3)3][BF4] (13). The structures of the products 4–11 and 13 were compared to related complexes possessing the well‐known Ph3P ligand. All compounds were characterized by single crystal X‐ray structure analysis, multinuclear NMR spectroscopy, IR spectroscopy and mass spectrometry.
The reaction of the Lewis base‐stabilized phosphinoborane monomer tBuHPBH2NMe3 (2a) with catalytic amounts of bis(η5:η1‐adamantylidenepentafulvene)titanium (1) provides a convenient new route to the polyphosphinoborane [tBuPH‐BH2]n (3a). This method offers access to high molar mass materials under mild conditions and with short reaction times (20 °C, 1 h in toluene). It represents an unprecedented example of a transition metal‐mediated polymerization of a Lewis base‐stabilized Group 13/15 compound. Preliminary studies of the substrate scope and a potential mechanism are reported.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.