Monomeric complexes of palladium(II) and platinum(II) with a series of open-chain tetrathioether ligands prepared from complexes of weak donor ligands

First- and second-generation dendrimers with an isocyanide group as the focal functional point (CN-G(n); n: 1,2) and their corresponding organometallic complexes [MCl(CN-G(n))] (M: Au, Cu), [{CuCl(CN-G(n))2}2], and trans-[MI2(CN-G(n))2] (M: Pd, Pt) have been synthesized. The free ligands and the first-generation complexes do not show mesogenic behavior, but all of the second-generation complexes display a thermotropic micellar cubic mesophase, over a large temperature range, and some of them directly at room temperature. The structure of the mesophase consists of the packing of two, discrete polyhedral micellar aggregates in a three-dimensional cubic Im$\bar 3$m lattice.

Section: Methodsmentioning

confidence: 99%

“…Experimental conditions for the analytical, spectroscopic, and XRD studies were as reported elsewhere 19. 25 Literature methods were used to prepare [AuCl(tht)] (tht=tetrahydrothiophene),33 [MCl 2 (NCCH 3 ) 2 ] (M=Pd, Pt),34 and CuCl 35…”

Section: Methodsmentioning

confidence: 99%

Self‐Organization of Dendritic Supermolecules, Based on Isocyanide–Gold(I), –Copper(I), –Palladium(II), and –Platinum(II) Complexes, into Micellar Cubic Mesophases

Coco

Cordovilla

Donnio

et al. 2008

“…Each crystallographicallyi ndependent part contains one type (2) )a re slightly longer than those in the relevant aryl palladium-isocyanide species trans-[PdBr 2 (CNR) 2 ]( R = Cy:1 .955(9)-1.964(9) ;R = Xyl: 1.963 (3) ). [12] In each structure, the bond lengths of the two coordinated CN groups fall in the intervalo f1 .144-1.155 , which is the typical range for CN triple bonds in the related isocyanide complexes, for example, [PdX 2 (CNXyl) 2 ]( 1.145-1.156 ;X= Cl, Br). [12] Hirshfeld surface analysis…”

Section: Generalconsiderationofthe Structuresmentioning

confidence: 99%

“…[12] In each structure, the bond lengths of the two coordinated CN groups fall in the intervalo f1 .144-1.155 , which is the typical range for CN triple bonds in the related isocyanide complexes, for example, [PdX 2 (CNXyl) 2 ]( 1.145-1.156 ;X= Cl, Br). [12] Hirshfeld surface analysis…”

Section: Generalconsiderationofthe Structuresmentioning

confidence: 99%

(Isocyano Group π‐Hole)⋅⋅⋅[d‐M^II] Interactions of (Isocyanide)[M^II] Complexes, in which Positively Charged Metal Centers (d⁸‐M=Pt, Pd) Act as Nucleophiles

Katkova

Mikherdov

Kinzhalov

et al. 2019

Inspection of the X‐ray structures of the newly prepared trans‐[MII(CNXyl)2(DAPT)2]Cl(BF4) (M=Pd, Pt; Xyl=2,6‐Me2C6H3; DAPT=4,6‐diaminopyrimidine‐2(1H)‐thione) complexes and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unknown π‐hole⋅⋅⋅metal interactions between a ligated isocyano group (acting as a π‐hole donor) and the positively charged d8‐PtII and d8‐PdII metal centers (acting as nucleophiles); this is the first identification of π‐hole⋅⋅⋅metal interactions with triple‐bond species. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of Bader's theory (quantum theory of atoms in molecules, QTAIM) confirmed the presence of these contacts. The electrostatic surface potential calculations indicated that π‐hole⋅⋅⋅metal contacts are formed upon interaction between the electrophilic isocyano C atom (π‐hole donor) and the nucleophilic dz2 orbital of the metal centers, which act as π‐hole acceptors. Available CCDC data were processed from the perspective of the π‐hole⋅⋅⋅metal interactions with isocyanide ligands, and their analysis disclosed the role of metal nucleophilicity in the corresponding π‐hole acceptor ability.

“…Unless otherwise stated, all other reagents were used as obtained from commercial suppliers. The compounds (3‐hydroxybenzyl)di‐ tert ‐butyl phosphine,12a bis(pentafluorophenyl)bromophosphine,38 [PdCl 2 (NCMe) 2 ],39 [PtCl(N(SiMe 3 ) 2 )(COD)],26 [PtCl 2 (COD)],40 [PtCl 2 (hex)],41 [PtCl 2 (SEt 2 ) 2 ],42 and [Pt(nb) 3 ]43 were synthesised according to literature procedures. NMR spectra were obtained using a Varian Unity Inova 300 (300 MHz for 1 H, 121 MHz for 31 P, and 282 MHz for 19 F), a Varian Unity Inova 500 (500 MHz for 1 H and 125 MHz for 13 C), or a Varian DirectDrive 600 (600 MHz for 1 H and 150 MHz for 13 C).…”

Section: Methodsmentioning

confidence: 99%

The Coordination Chemistry of Pentafluorophenylphosphino Pincer Ligands to Platinum and Palladium

Anderson

Spencer

2014

The synthesis of electron-poor PCP pincer ligands 1,3-((C6F5)2PO)2C6H4, 1,3-((C6F5)2PCH2)2C6H4, and 1-((C6F5)2PO)-3-(tBu2PCH2)C6H4, and their coordination chemistry to platinum and palladium is described. The most electron-poor ligand 1,3-((C6F5)2PO)2C6H4 (POCOPH) reacts with Group 10 metal chloride precursors to form a range of unusual cis, trans-dimers of the type κ(2)-P,P-[(POCOPH)MCl(L)]2 (M = Pt, Pd; L = Cl, Me), which undergo metallation to form [(POCOP)MCl] pincer complexes only under prolonged thermolysis. The formation of such cis,trans-dimers during pincer complex formation can be mitigated through the use of starting materials with more strongly binding ancillary ligands, improving the overall rate of ligand metallation. Carbonyl complexes of the type [(PCP)M(CO)](+) were synthesised from the pincer chloride complexes by halide abstraction, and displayed large ν(C-O) values, from 2170-2111 cm(-1), confirming the electron-poor nature of the compounds. The [(PCP)Pd(CO)](+) complexes also demonstrated the ability to reversibly bind carbon monoxide both in solution and the solid state, with the rate of decarbonylation increasing with increasing wavenumber for the C-O stretch.