Probing Donor–Acceptor Interactions in peri-Substituted Diphenylphosphinoacenaphthyl–Element Dichlorides of Group 13 and 15 Elements

Abstract

Transmetalation reactions of ArLi with ECl 3 (E = Al, P, In, Bi) and ArSnBu 3 with ECl 3 (E = B, Ga, Tl, As, Sb) gave rise to the formation of peri-substituted diphenylphosphinoacenaphthyl−element dichlorides ArECl 2 (Ar = 6-Ph 2 PAce-5-), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. DFT calculations were performed on the compounds at relaxed gas-phase molecular geometries. For the series ArECl 2 containing group 13 elements one structure type featuring regular Lewis pairs with short E−P peri distances (E = B, Al, Ga, In, Tl) was observed. For the series ArECl 2 containing group 15 elements two structural types with very different peri distances (E = P, As, Sb, Bi) were found. The computed electron and pair densities were topologically analyzed according to the atoms-in-molecules (AIM) and electron localizability indicator (ELI-D) spacepartitioning schemes, which facilitates the characterization of the peri interactions and also allows for monitoring minute electronic effects induced by different substituents and/or spatial arrangements. ■ INTRODUCTIONDonor−acceptor interactions between phosphines and maingroup elements have received tremendous interest, 1 which has been recently fueled by the discovery that bulky phosphines and boranes may form frustrated Lewis pairs (FLPs) that are able to activate small molecules, such as dihydrogen and carbon dioxide, without the aid of a transition metal. 2 Peri-substituted (ace)naphthylphosphinoboranes comprise regular Lewis pairs or FLPs depending on the nature of the substituents attached to the B and P atoms in 1,8-and 5,6-positions (Chart 1). Sasamori and Tokitoh et al. 3 communicated two 1-dichlorophosphino-8-naphthyl-diarylboranes 1-(Cl 2 P)-8-(R 2 B)-Nap (Ia, R = 3,5-t-Bu 2 C 6 H 3 ; Ib, R = Mes) and later disclosed structural data. 4 Reduction of Ia,b with Mg proceeded with aryl group migration and gave rise to the formation of unique phosphaboranes. 3 Miqueu and Bourissou et al. 5 reported on the three 1-diisopropylphosphino-8-naphthyl-diorganoboranes 1-(iPr 2 P)-8-(R 2 B)-Nap (IIa, R = Mes; IIb, R = Cy; IIc, R 2 = Flu; Flu = 2,2′-biphenylene), which were structurally elucidated. The different P−B peri distances (Å) of 2.108(2) (Ia), 2.892(2) (Ib), 2.173(3) (IIa), 2.076(2) (IIb), and 2.011(2) (IIc) demonstrate that the bulk and electronic effect of the substituents attached to the B and P atoms determines the nature of the peri interaction: namely, if it is dominated by attractive or repulsive forces.Our group described 1-diphenylphosphino-8-naphthyl-dimesitylborane (1-(Ph 2 P)-8-(Mes 2 B)-Nap, IIIa) and the closely related 5-diphenylphosphino-6-acenaphthyl-dimesitylborane (5-(Ph 2 P)-6-(Mes 2 B)-Ace, IIIb), possessing the same substituents at the B and P atoms with albeit quite different B−P peri distances of 2.162(2) and 3.050(3) Å, which is due to the fact that the naphthyl framework accommodates a higher degree of conformational flexibility in comparison to the rigid acenaphthyl framework. 6 Wang et al. also conducted an ...

Sterically Congested 5-Diphenylphosphinoacenaphth-6-yl-silanes and -silanols

“…8,9,11 In contrast to 5-Ph 2 P(O)-Ace-6-SiMe 2 OH (3O), the silanols 5-Ph 2 P(S)-Ace-6-SiMe 2 OH (3S) and 5-Ph 2 P(Se)-Ace-6-SiMe 2 OH (3Se) comprise a moderate P/Si out-of-plane displacement comparable to those of the silanes 5- (7) 115.03 (9) 115.51(9) E−P(1)−C(20) 109.57 (5) 109.1(2) 108.73 (7) 108.17 (9) 108.13(9) E−P(1)−C (30) 114.90 (5) 115.0(2) 112.10 (7) 115.03 (9) 115.04(9) C(18)−P(1)−C(20)…”

“…2(2) C(18)−P(1)−C (30) 104.06 (7) 107.22 (7) 107.4 (2) 104.57 (7) 107.4 (2) 107. 3(2) C(20)−P(1)−C (30) 102.18 (7) 103.73 (7) 103.7 (2) 104.00 (7) 103.…”

“…2(2) C(18)−P(1)−C (30) 104.06 (7) 107.22 (7) 107.4 (2) 104.57 (7) 107.4 (2) 107. 3(2) C(20)−P(1)−C (30) 102.18 (7) 103.73 (7) 103.7 (2) 104.00 (7) 103. 8(2) 103.7(2) Peri Region Distances P(1)···Si (1) 3.1835 (7) 3.6905 (6) peri-contacts.…”

Structural, Spectroscopic and Computational Examination of the Dative Interaction in Constrained Phosphine–Stibines and Phosphine–Stiboranes

“…Very recently, Beckmann reported a comprehensive series of phosphine–pnictine species shown in Figure 1 13. All species show a strong attractive P–E interaction.…”

Understanding the structure of salicyl hydrazone metallocomplexes: crystal structure, AIM and Hirshfeld surface analysis of trichloro-(N-salicylidenebenzoylhydrazinato-N,O,O′)-tin(IV)

“…Until now, the results of topological analysis of tincontaining compounds are limited to two hypothetical stannatranes [22], the complex [Sn(C 7 H 8 ) 3 ] 2+ dication [23], the low-coordinated tin Sn 2 (OCH 2 CH 2 NMe 2 )(OPh) dimer [20], hexacoordinated tin(IV) [24] and phenyl (triphenylstannyl)telluride [25,26]. According to the AIM theory, information on chemical bonding can be obtained analyzing the local minima, maxima, and saddle points of the electron density ρ(r) function.…”