Dihalomethanes as Bent Bifunctional XB/XB-Donating Building Blocks

Dihalomethanes as Bent Bifunctional XB/XB-Donating Building Blocks for Construction of Metal-involving Halogen Bonded Hexagons




The dihalomethanes CH2X2 (X = Cl, Br, I) were co-crystallized with the isocyanide complexes trans-[MXM2(CNC6H4-4-XC)2] (M = Pd, Pt; XM = Br, I; XC = F, Cl, Br) to give an extended series comprising of 15 X-ray structures of isostructural adducts featuring 1D metal-involving hexagon-like arrays. In these structures, CH2X2 behave as bent bifunctional XB/XB-donating building blocks, whereas trans-[MXM2(CNC6H4-4-XC)2] act as a linear XB/XB acceptors. Results of DFT calculations indicate that all XCH2–X···XM–M contacts are typical noncovalent interactions with the estimated strengths in the range 1.3–3.2 kcal/mol. CCDC search reveals that hexagon-like arrays are rather common, but previously overlooked structural motives for adducts of trans-bis(halide) complexes and halomethanes.




Popular posts from this blog

Complexes with Acyclic Diaminocarbene Ligands (A Review)

Synthesis and Contemporary Applications of Platinum Group Metals Complexes with Acyclic Diaminocarbene Ligands (A Review) Russ. J. Inorg. Chem. 2022, 67, 48–90 Complexes of platinum group metals with acyclic diaminocarbene ligands have found application as transition metal catalysts, photoluminescent materials, chemosensors, and anticancer drugs. This review systematises the studies published to date, analyses the properties and synthetic routes to complexes of platinum group metals with acyclic diaminocarbene ligands, and discusses the latest advances in the use of these compounds for the development of functional materials.  Free online access to this article https://rdcu.be/cGDRX
Read more

Tuning the Luminescence of Transition Metal Complexes with Acyclic Diaminocarbene Ligands

Image
Organometallics featuring acyclic diaminocarbene (ADC) ligands have recently emerged as powerful emitters for use in OLEDs and other electroluminescent technologies. Owing to strong σ-donor properties and broad synthetic availability, ADCs have successfully challenged the application of other ancillary ligands for fine-tuning of luminescence emission. This review systematises the data reported concerning the preparation of the luminescent metal complexes bearing ADC ligands, uncover their photophysical properties as a function of carbene ligand structure and metal characteristics as well as draw attention to the potential that application of metal-ADCs provides to the family of transition-metal-based phosphors. Inorg. Chem. Front., 2022, Accepted Manuscript
Read more

Cyclometalated Platinum(II) Complexes Simultaneously Catalyze and Function as Luminophores

Image
Cyclometalated Platinum(II) Complexes Simultaneously Catalyze the Cross-Linking of Polysiloxanes and Function as Luminophores Full text: ACS Appl. Polym. Mater., 2021, 3, 857 Write for free PDF A family of the C,N-cyclometalated species [Pt(ppy)Cl(PPh3)], [Pt(ppy)Cl(CNCy)], [Pt(ppy)(CNCy)(PPh3)](OTf), and [Pt(ppy)(CNCy)2](BF4) (ppy = 2-phenylpyridinato-C2,N; Cy = cyclohexyl) was generated from [Pt(ppy)(μ-Cl)]2, CNCy, and PPh3. The obtained platinum(II) complexes were characterized by high-resolution ESI+-MS, IR, and 1D (1H, 13C{1H}, 195Pt{1H}) and 2D (1H,1H-NOESY; 1H,13C-HSQC; 1H,13C-HMBC) NMR spectroscopy, and the latter three complexes were investigated by X-ray diffraction. All four platinum species were examined as hydrosilylation catalysts (c 10–4–10–3 M; 80–120 °C; [Pt(ppy)Cl(PPh3)] exhibited the highest catalytic activity) for the cross-linking of vinyl-terminated polydimethylsiloxane and polymethylhydrosiloxane to achieve luminescent silicone rubbers. Each solid complex and the...
Read more