Metal-involved C⋯d_z²-Pt^IItetrel bonding as a principal component of the stacking interaction between arenes and the platinum(ii) square-plane

Abstract

The half-lantern PtII2 complexes [Pt(CN)(μ-SN)]2 (HCN = 2-phenylbenzothiazolate 1; 2-naphtylbenzothiazolate 2; HSN = 2-thiopyridine) were crystallized with such electron-deficient arenes as hexafluorobenzene (C6F6) and octafluoroanthraquinone (OFA) to give cocrystals 1·C6F6,...

Dichotomy of π-stacking-directing noncovalent forces in organic–inorganic planar assemblies: the case of halo-substituted benzoquinones π-stacked with a platinum(ii) square-plane

“…The ρ b and ∇ 2 ρ b values of the C⋯Pt contact decrease along the row of halogens from F to I which may suggest a weakening of this interaction from [ 1 ·QF] to [ 1 ·QI]. The C⋯Pt interaction exhibits a high value of bond ellipticity in all structures ( ε = 1.4–8.8); this effect has been previously observed 56 for the C⋯Pt contacts in the cocrystals of [Pt( pbt )(μ-S ∩ N)] 2 (S ∩ N = 2-thiopyridine, pbt = 2-phenylbenzothiazole) with electron-deficient arenes.…”

“…We previously reported that CT plays a crucial role in the noncovalent tetrel π-hole C⋯Pt interactions in the complexes [Pt( pbt )(μ-N ∩ S)] 2 ·Ar F (N ∩ S = 2-μ-mercaptopyridine, Ar F = perfluoroarene). 32 The total NBO/AIM atomic charges of QF in [ 1 ·QF] are −45/–88 me, which corresponds to the total CT from 1 to QX upon the generation of [ 1 ·QX]. In the cases of [ 1 ·QCl] and [ 1 ·QBr], these atomic charges are close to −14/–30 me, while for QI there are no more than −10/–8 me.…”

“…We previously investigated cocrystals of binuclear platinum complexes with electron-deficient arenes and found that their structure is determined by π-stacking, which includes metal-involving tetrel bonds 42,43 C⋯Pt as one of the dominant structure-directing forces. 32 All these theoretical studies clearly demonstrated that a metal site significantly affects the organic–inorganic stacking, at least in terms of the increased energy of the interaction and the geometry of the formed stacks.…”

“…Other studies focused on organic–inorganic planar integrations considered noncovalent interactions with a nucleophilic d-orbital of a positively charged metal ion. 28–40 In particular, it has been demonstrated that square-planar platinum( ii ) complexes can act as integrated nucleophiles and function as π-hole acceptors via their filled d z 2 [Pt II ] orbital and interact with π-hole donating electron-poor aromatics forming reverse sandwich systems. 29–31,33,34 In addition, we reported that electron-deficient aromatics easily sandwiched with the integrated d 8 [Pd]O 4 10 or d 8 [M]S 4 (M = Ni, Pd, Pt) 34 nucleophilic planes.…”

Solid-Phase Synthesis of 2-Benzothiazolyl and 2-(Aminophenyl)benzothiazolyl Amino Acids and Peptides

“…2-phenylbenzothiazoles have also shown interesting metal-involved noncovalent interactions [ 27 , 28 , 29 , 30 ] with broad applications in materials science, while in the diagnostic area, many metal-radiolabeled 2-phenylbenzothiazole derivatives are continuing to be explored as amyloid imaging agents [ 23 , 31 , 32 , 33 ]. Non-metal-based positron emission tomography (PET) imaging of Aβ plaques is also possible through the use of radiolabeled benzothiazoles such as the 18 F-labeled derivative of 2-(4-aminophenyl)benzothiazole [ 18 F] Flutemetamol, which gained approval in 2013 for clinical use [ 34 , 35 ].…”