Weak Pnictogen Bond with Bismuth: Experimental Evidence Based on Bi−P Through‐Space Coupling

Mokrai, Réka; Barrett, Jamie; Apperley, David C.; Batsanov, Andrei S.; Benkő, Zoltán; Heift, Dominikus

doi:10.1002/chem.201900266

Cited by 41 publications

(52 citation statements)

References 72 publications

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“…The central Sb atom of SbCl 3 engages in three Sb···O contacts short enough to be characterized as ZBs 92 or in three Sb···S bonds with trithiane; 93 three Bi···S bonds with BiX 3 have also been observed quite recently. 94 Radha et al 95 have shown that a Sb atom can engage in three Sb···S ZBs, that complement its three covalent Sb–S bonds. Their analysis also concluded that a bulky alkyl substituent can inhibit the formation of this number of noncovalent interactions.…”

Section: Discussionmentioning

confidence: 99%

How Many Pnicogen Bonds can be Formed to a Central Atom Simultaneously?

et al. 2020

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A central ZF 3 molecule (Z = P, As, Sb, Bi) is allowed to interact with a number of nucleophiles exemplified by NCH, NH 3 , and NC – anion. The Z···N pnicogen bond (ZB) to a single base grows stronger for heavier Z atom: P < A < Sb < Bi and follows the NCH < NH 3 < NC – order for the three bases. The maximum number of ZBs depends on both the nature of the base and pnicogen atom. PF 3 and AsF 3 can pnicogen bond with only a single CN – ; SbF 3 and BiF 3 can interact with two anions but only weakly. The weak NCH nucleophile can engage in a maximum of two ZBs, while three ZBs occur for NH 3 . The latter NH 3 maximum can be extended to four ZBs but only for BiF 3 . The fourth ZB is somewhat longer and weaker than the others, and the entire (H 3 N) 4 ···BiF 3 complex relies partially on secondary interactions for its stability.

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Section: Discussionmentioning

confidence: 99%

How Many Pnicogen Bonds can be Formed to a Central Atom Simultaneously?

et al. 2020

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“…In the following we only discuss the results obtained at the ωB97XD/(aug-)cc-pVDZ(-PP) level, which has been used successfully for similar systems before. 56 The solvent effects were simulated using the polarizable continuum model (PCM) with dichloromethane as solvent.…”

Section: Results and Discussionmentioning

confidence: 99%

“…Altogether, the phosphorus and the three sulfur donor atoms endow the PS 3 ligand with versatile coordination ability, complementing the previously reported tridentate and tetradentate coordination modes. 56 The UV–vis absorption bands connected to excitations from the dibismuthate core into the π* system of the phosphonium units can be tuned by varying the halogen substitutions at the bismuth centers in the bis-zwitterions.…”

Section: Discussionmentioning

confidence: 99%

“…In the starting materials PS 3 BiX 3 of these reactions the bismuth center is stabilized by the cooperation of three dative S→Bi bonds and a further P···Bi pnictogen interaction, which altogether endow these complexes with significant stabilization energies of 25.9–28.3 kcal/mol. 56 In this paper we also aim to shed light on the energy requirements for the breakdown of these stabilizing interactions, leading to the formation of dibismuthate units.…”

Section: Introductionmentioning

confidence: 99%

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Dibismuthates as Linking Units for Bis-Zwitterions and Coordination Polymers

et al. 2020

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Adducts of bismuth trihalides BiX 3 (X = Cl, Br, I) and the PS 3 ligand ( PS 3 = P(C 6 H 4 - o -CH 2 SCH 3 ) 3 ) react with HCl to form inorganic/organic hybrids with the general formula [H PS 3 BiX 4 ] 2 . On the basis of their solid-state structures determined by single-crystal X-ray diffraction, these compounds exhibit discrete bis-zwitterionic assemblies consisting of two phosphonium units [H PS 3 ] + linked to a central dibismuthate core [Bi 2 X 8 ] 2– via S→Bi dative interactions. Remarkably, the phosphorus center of the PS 3 ligand undergoes protonation with hydrochloric acid. This is in stark contrast to the protonation of phosphines commonly observed with hydrogen halides resulting in equilibrium. To understand the important factors in this protonation reaction, 31 P NMR experiments and DFT computations have been performed. Furthermore, the dibismuthate linker was utilized to obtain the coordination polymer {[Ag PS 3 BiCl 3 (OTf)] 2 (CH 3 CN) 2 } ∞ , in which dicationic [Ag( PS 3 )] 2 2+ macrocycles containing five-coordinate silver centers connect the dianionic [Bi 2 Cl 6 (OTf) 2 ] 2– dibismuthate fragments. The bonding situation in these dibismuthates has been investigated by single-crystal X-ray diffraction and DFT calculations (NBO analysis, AIM analysis, charge distribution).

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“…The vast majority of these ligands possess Ndonors, [2][3][4][5][6][7][8] whereas as P-donors are only occasionally encountered. [9][10][11][12][13][14][15] As part of our research programme on peri-substituted scaffolds, we recently prepared the monoarylbismuth dichloride RBiCl 2 (1a, R = 6-diphenylphosphinoacenaphth-5-yl), the analogous arylantimony dichloride RSbCl 2 (1b) 16 as well as the diarylantimony chloride R 2 SbCl (2b) and the triarylantimony R 3 Sb (3b). 17 The latter two compounds were also used as (coordination noninnocent) ligands towards late transitions metals.…”

Section: Introduction *mentioning

confidence: 99%