The Coordination Chemistry of the Phosphanylborane (C₆H₅)₂PBH₂·N(CH₃)₃ towards Copper(I) Salts

Abstract

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.

Organo Chalcogenone-Triggered Luminescent Copper(I) Clusters for Light Emitting Applications

“…Figure shows the crystal structure of 1 . The copper­(I) bromide cluster 1 has a rare structural motif that differs from the reported pentanuclear clusters [({Cu 5 (μ 3 -Br)­(μ 3 -Br) 2 (μ 3 -Br) 2 } 5 (μ 2 -SMePr) 3 ) ∞ and Cu 5 Br 5 (Ph 2 PBH 2 NMe 3 ) 4 ]. , Unlike reported clusters, Cu 5 Br 5 forms discrete cyclic clusters and each copper­(I) atom depicts two Cu···Cu interactions. The four copper­(I) atoms are arranged in a distorted planar geometry, while the other copper­(I) atom is in a nonplanar arrangement.…”

“…The five Cu···Cu distances are 2.763(17) Å (Cu1–Cu2 and Cu1A-Cu2A), 2.876(15) Å (Cu1–Cu3 and Cu1A-Cu3A), and 2.709(2) Å (Cu2–Cu2A). The cuprophilic interactions of Cu2–Cu2A is shorter than the reported pentanuclear complexes, Cu 5 Br 5 (Ph 2 PBH 2 NMe 3 ) 4 [2.722(10) Å] and ({Cu 5 (μ 3 -Br)­(μ 3 -Br) 2 (μ 3 -Br) 2 } 5 (μ 2 -SMePr) 3 ) ∞ (2.777–2.91 Å) . The three copper­(I) atoms (Cu1, Cu3, and Cu1A) adopted a distorted tetrahedral geometry, while the remaining two copper­(I) atoms (Cu2 and Cu2A) are in the distorted trigonal planar geometry.…”

Coordination chemistry of pnictogenylboranes towards group 6 transition metal Lewis acids

“…For the reaction of the parent phosphanylborane Ia towards the early transition metal complex Cp 2 Ti(btmsa) (btmsa=bis(trimethylsilyl)acetylene), adduct formation at low temperature as well as at room temperature by using several equivalents of Ia the formation of coordination oligomers incorporating multiple metal centers was observed [9] . For late transition metal complexes, the coordination towards Cu I centers was reported for the parent compound Ia [10] as well as for the diphenyl‐substituted derivative IIIa [11] . In a similar manner, the reaction of IIIa with Ag I salts has been investigated [12] .…”

Coordination of Pnictogenylboranes Towards Tl(I) Salts and a Tl‐ Mediated P−P Coupling

“…Our group has an interest in the synthesis and reactivity of only LB‐stabilized 13/15 monomers such as pnictogenylboranes EH 2 BH 2 ⋅ NMe 3 (E=P, As), [14,15] which are excellent building blocks for the formation of group 13/15 oligomeric and polymeric compounds [16] . In addition, pnictogenylboranes turned out to be excellent donors for transition metal and main group Lewis‐acids [14,15,17–20] . While cluster formation was observed for reactions with Cu(I) complexes, [18,20] coordination towards Au(I) centers afforded complexes with aurophilic interactions acting as blue‐green light emitters [19] .…”

“…[16] In addition, pnictogenylboranes turned out to be excellent donors for transition metal and main group Lewis‐acids. [ 14 , 15 , 17 , 18 , 19 , 20 ] While cluster formation was observed for reactions with Cu(I) complexes,[ 18 , 20 ] coordination towards Au(I) centers afforded complexes with aurophilic interactions acting as blue‐green light emitters. [19] The reaction of phosphanylborane with the early transition metal compound [Cp 2 Ti(btmsa)] (btmsa=bis(trimethylsilyl)acetylene) results in dehydrocoupling leading to oligomeric chains stabilized in the coordination sphere of titanium.…”