A neutral analogue of a phosphamethine cyanine

Cicač-Hudi, Mario; Kaaz, Manuel; Birchall, Nicholas; Nieger, Martin; Gudat, Dietrich

doi:10.1039/d2dt00837h

Cited by 3 publications

(1 citation statement)

References 34 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…This immediately resulted in multiple resonances in the 31 P{ 1 H} NMR spectrum. Two doublet resonances (180.0 and −58.8 ppm, 1 J P−P =418 Hz) can be assigned as the NHC‐phosphinidene adduct based on the chemical shifts and the P−P coupling constant (e. g. [P]P−IPr: 173.8 and −59.1 ppm, 1 J P−P =410 Hz; [11] IPr=[(HC)(N i Pr)] 2 C); Scheme 2, bottom) [29] . As with the reaction with Ni(PPh 3 ) 2 (CO) 2 , two new doublet resonances were also observed in the 31 P{ 1 H} NMR spectrum (96.0 and −185.6 ppm; 1 J P−P =747 Hz), that in all likelihood correspond to the nickel phosphanyl‐phosphinidene complex, (η 2 ‐[P]=P)Ni(CO)( Me IPr).…”

Section: Resultsmentioning

confidence: 99%

Metal‐mediated decarbonylation of phosphanyl‐phosphaketenes to afford phosphanyl‐phosphinidine complexes

Feld¹,

Goicoechea

2022

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

Dedicated to Professor Cameron Jones on the occasion of his 60 th birthday.The synthesis of group 10 metal complexes bearing a phosphanyl-phosphinidene ligand, [(H 2 C) 2 (NDipp) 2 ]P=P (Dipp = 2,6-di-iso-propylphenyl), is reported. These compounds can be accessed by the decarbonylation of a phosphanyl-phosphaketene with metal nucleophiles including M(P t Bu 3 ) 2 (M = Pt, Pd) and Ni(COD){[C(NMes)(CH) 2 N] 2 CH 2 }.

show abstract

Section: Resultsmentioning

confidence: 99%

Metal‐mediated decarbonylation of phosphanyl‐phosphaketenes to afford phosphanyl‐phosphinidine complexes

Feld¹,

Goicoechea

2022

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

show abstract

Probing Radical Addition to 1‐Phosphabutadienes by Employing Muonium as a “Light Isotope” of Hydrogen

Walsgrove,

Percival,

Gates

2023

Chemistry A European J

View full text Add to dashboard Cite

Understanding free radical addition to multiple bonds is important to elucidating the mechanistic details of addition polymerization reactions, albeit the fleeting radical intermediates are very difficult to detect by conventional methodologies. Muon spin spectroscopy (μSR) is a highly sensitive method that can detect radical species at 106 spins (cf. EPR: 1012 spins, NMR: 1018 spins). Herein, we employ μSR to detect the radical‐addition products from three 1‐phosphabutadiene monomers, P‐analogues of isoprene. We show that muonium (Mu), a “light” H‐atom surrogate, adds predominantly at the C4 position of the P1=C2−C3=C4 moiety to give unprecedented 1‐phosphaallyl radicals as the major products. Our structural assignments are supported by assignment of muon, phosphorus and proton hyperfine coupling constants using DFT‐calculations. A minor radical product is also detected that is tentatively assigned to an PC3‐heterocyclic free radical. On the basis of DFT‐predictions, we speculate that its formation may involve initial addition of Mu+ at the C3 position followed by electron capture. These studies provide rare insights into the prospective radical (or cationic) polymerization of 1‐phosphabutadienes, which have previously been polymerized using anionic initiation.

show abstract

L→S Coordination Complexes Containing Benzothiazol‐2‐ylidene Ligand: Quantum Chemical Analysis and Synthesis

Mukhopadhyay,

Bhagat,

Sahoo

et al. 2024

ChemPlusChem

View full text Add to dashboard Cite

(NHC)→E coordination interactions were known where NHC is an N‐heterocyclic carbene, and E is a main group element (B, C, N, Si, P). Recently, it was suggested that compounds with (NHC)→S coordination chemistry are also possible. This work reports quantum chemical analysis and synthesis of (NHC)→S‐R(+) complexes in which benzothiazol‐2‐ylidene acts as a ligand. Density functional study established that (NHC)→S interaction can best be described as a coordination interaction. Synthetic efforts were made, initially, to generate divalent sulfur compounds containing benzothiazole substituents. N‐alkylation of the heterocyclic ring in these sulfides using methyl triflate led to the generation of the desired products with (NHC)→S coordination chemistry, which involves the in situ generation of NHC ring ligands. The observed changes in the 13C NMR spectra, before and after methylation, confirmed the change in the electronic character of the C‐S bond from a covalent character to a coordination character.

show abstract

A neutral analogue of a phosphamethine cyanine

Abstract: Reaction of an imidazolio-phosphide with a N-heterocyclic bromo-borane and NaH afforded a neutral analogue of a phosphamethine cyanine cation. DFT studies were used to analyse the dative bonding across P–C/B...

Cited by 3 publications

References 34 publications

Metal‐mediated decarbonylation of phosphanyl‐phosphaketenes to afford phosphanyl‐phosphinidine complexes

Metal‐mediated decarbonylation of phosphanyl‐phosphaketenes to afford phosphanyl‐phosphinidine complexes

Probing Radical Addition to 1‐Phosphabutadienes by Employing Muonium as a “Light Isotope” of Hydrogen

L→S Coordination Complexes Containing Benzothiazol‐2‐ylidene Ligand: Quantum Chemical Analysis and Synthesis

Contact Info

Product

Resources

About