Organoplatinum Building Blocks for One‐Dimensional Hydrogen‐Bonded Polymeric Structures

Abstract

2] Rotananes were first prepared by solid-phase synthesis (I. T. Harrison. S. Harrison. J. Am. C h m . Soc. 1967, 89. 5723-5724) and by directed synthesis (G. Schill. H Zollenkopf, Liehigs Ann. Clium 1969. 721. 53-74). For an early use o f the hydrophobic effect to direct rotaxane synthesis see H. Ogino. J Am. Chmi. Soc. 1981Soc. , 103, 1303Soc. -1304. For some recent rotaxanes see: a) D. B.

Self-assembly of para-OH functionalized ECE-metalated pincer complexes

“…À , E = NMe 2 , PPh 2 and SPh) with a para-functionality (Z) on the aromatic ring of the pincer anion are well known [1][2][3][4][5][6][7][8][9]. Electronic properties of the metal center can be tuned by inductive and mesomeric effects of this substituent [10].…”

“…Self-assembly of functionalized pincer-metal complexes controlled by H-bonding through a H-donor (Z-substituent) and a H-acceptor site (M-X) both in the solid-state and in solution has led to the finding of interesting polymers [25] and supramolecular structures [4,8,[26][27][28][29]. For example, NCN-pincer Pt-complexes [PtCl(NCN-Z)] with Z = OH or C"C-H form one-dimensional polymeric chains via intermolecular hydrogen bonds of the O-HÁ Á ÁCl [8] or C"C-HÁ Á ÁCl [4,29] type, respectively, in the solid-state.…”

“…For example, NCN-pincer Pt-complexes [PtCl(NCN-Z)] with Z = OH or C"C-H form one-dimensional polymeric chains via intermolecular hydrogen bonds of the O-HÁ Á ÁCl [8] or C"C-HÁ Á ÁCl [4,29] type, respectively, in the solid-state. These materials revealed reversible binding of SO 2 in the solidstate with retention of the polymeric structure [27,30].…”

NCN–pincer palladium complexes with multiple anchoring points for functional groups

“…Thus, reactions performed on 8 and products obtained from it should be selective and quantitative. Indeed, the introduction of a trimethylsilyl substituent to C ipso (9), the deprotection of the alcohol (10), the palladation (11), and all subsequent transformations proceeded quantitatively, although loss of material during work-up procedures can lead in certain cases to reduced isolated yields.…”

“…This makes them excellent building blocks for the construction of new (catalytic) organometallic materials [1,9]. Para-hydroxy [10,11] and para-alkynyl NCN-pincer platinum halide complexes [12] form noncovalent linear organometallic main chain polymers. The direct lithiation of para-halo NCN-pincer platinum complexes at −100 • C allows access to para-lithio complexes [6][7][8] which can be further reacted with appropriate electrophiles or lead to the formation of covalent organometallic mainchain polymers.…”