Triazolide Complexes of Sodium and Potassium in the Gas Phase DOI
Arthur E. Lee, Cailum M. K. Stienstra, Terrance B. McMahon

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 23, 2024

Aromatic organometallic complexes, such as ferrocene and the "inverse sandwich complex" [Na2Cp]+, are stabilized via charge-transfer (C-T) interactions cation-π (i.e., charge-induced dipole charge-quadrupole interactions). Much effort has gone into investigating systems that contain organic moieties, benzene or cyclopentadienyl ligands, but less attention been paid to aromatic heteroatoms (e.g., N), possibly owing complexity arising from a lowering of symmetry introduction electron lone pair density moments. Here we investigate sodiated potassiated clusters 1,2,3-triazolide, [Mx (123T)x−1]+ (x = 3, 4; M Na, K), 1,2,4-triazolide, (124T)x−1]+ using combination infrared ion spectroscopy (IRIS) DFT calculations. Cluster structures strongly influenced by charge-dipole C-T N pairs metal cations. IRIS spectra indicated geometries triazolide moieties essentially unperturbed interaction with ions. Additional spectral features, not predicted calculations, observed in 1500–1800 cm–1 region seem be associated bands involving C–H wagging ring torsion motions.

Language: Английский

Synthesis and Alkyne Metathesis Activity of Rhenium Carbyne Complexes with PS‐Chelating Ligands DOI Creative Commons
Long Yiu Tsang, Lam Cheung Kong, Herman H. Y. Sung

et al.

European Journal of Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 26, 2025

Abstract Inspired by the catalytic alkyne metathesis activity of Re(V) carbyne complexes supported phosphinophenolate (PO) ligands, new with analogous phoshorus‐sulfur hybrid chelating ligands were synthesized. Treatment Re(≡CR)Cl 2 (PMePh ) 3 (R = CH Ph, Ph) (2‐thiophenyl)diphenylphosphine (Ph P‐ o ‐C 6 H 4 SH, PSH) in presence NEt produced six‐coordinated PS Re(≡CR)(PMePh )(PS) (PS Ph S), which reacted [(η ‐cymene)RuCl ] to give five‐coordinated trigonal bipyramidal Re(≡CR)(PS) and (η ). The complex Re(≡CCH Ph)(PS) can be oxidized sulfinate Ph)(H O)(PS O SO thiophenolate showed marginal at 100 °C, whereas is unreactive toward reactions under similar condition. DFT calculations reveal that lower compared PO related thermochemistry coordination species Re(≡CR)(PX) (X O, S, S an alkyne‐alkylidyne thermodynamically favored for Re(≡CR)(PO) , but unfavored Re(≡CR)(PS 2, resulting a higher barrier systems.

Language: Английский

Citations

0
Synthesis and Alkyne Metathesis Activity of Pincer Rhenium Carbyne Complexes DOI
Long Yiu Tsang, Wei Bai, Lam Cheung Kong

et al.

Organometallics, Journal Year: 2024, Volume and Issue: 43(8), P. 849 - 858

Published: April 10, 2024

While alkyne metathesis reactions involving d0 carbynes (alkylidynes) are well documented, those well-defined non-d0 still rare. This work reports the synthesis and activity of d2 Re(V) carbyne complexes supported by a [LXL]-type monoanionic [PNP]-pincer ligand, [LLX]-type [PNO]-pincer [ONOH]-bidentate ligand derived from Schiff base 2-[(2-hydroxyphenyl)iminomethyl]phenol. Treatment Re(≡CCH2Ph)Cl2(PMePh2)3 (1) with bis(2-diphenylphosphino-4-tolyl)amine (PNHP) 2-{(2-diphenylphosphino-phenyl)iminomethyl}phenol (PNOH) in presence NEt3 produced pincer Re(≡CCH2Ph)Cl(PMePh2)(PNP) (2) Re(≡CCH2Ph)Cl(PMePh2)(PNO) (3), respectively. The 2-[(2-hydroxyphenyl)iminomethyl]phenol (HONOH) reacted to give complex Re(≡CCH2Ph)Cl(PMePh2)(ONOH) (4) (ONOH = o-O-C6H4–CH═N-(o-C6H4OH)) bearing ligand. [PNP]- catalytically active for homometathesis neat 1-methoxy-4-(1-propyn-1-yl)benzene at 150 °C, while is inactive under similar conditions. energy profiles model rhenium alkyne-carbyne have been calculated DFT methods.

Language: Английский

Citations

2
Reshaping aromatic frameworks: expansion of aromatic system drives metallabenzenoids to metallapentalenes DOI Creative Commons
Qian Li, Jiawei Fei,

Kaidong Ruan

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(21), P. 5672 - 5680

Published: Jan. 1, 2023

The first skeletal rearrangement from one metallaaromatic framework to another.

Language: Английский

Citations

5
Aromaticity of Osmaacenes in Their Lowest-Lying Singlet and Triplet States DOI
Slavko Radenković, Miquel Solà

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(24), P. 9578 - 9588

Published: June 4, 2023

The aromatic character of a series osmaacenes in their lowest-lying singlet and triplet states was thoroughly examined by means the magnetically induced current densities multicentre delocalization indices (MCIs). Both employed approaches agree that osmabenzene molecule (OsB) S0 state exhibits dominant π-Hückel-type character, with small but nonnegligible amount π-Craig–Möbius aromaticity. Contrary to benzene, which is antiaromatic T1 state, OsB preserves some its aromaticity state. In higher members osmaacene states, central Os-containing ring becomes nonaromatic, acting as barrier between two side polyacenic units which, on other hand, exhibit significant extent π-electron delocalization.

Language: Английский

Citations

3
Preparation, Aromaticity, and Bromination of Spiro Iridafurans DOI
Miguel A. Esteruelas, Félix León,

Sonia Moreno-Blázquez

et al.

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(41), P. 16810 - 16824

Published: Oct. 2, 2023

Iridium centers of [Ir(μ-Cl)(C8H14)2]2 (1) activate the Cβ(sp2)-H bond benzylideneacetone to give [Ir(μ-Cl){κ2-C,O-[C(Ph)CHC(Me)O]}2]2 (2), which is starting point for preparation spiro iridafurans IrCl{κ2-C,O-[C(Ph)CHC(Me)O]}2(PiPr3) (3), [Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2(MeCN)2]BF4 (4), [Ir(μ-OH){κ2-C,O-[C(Ph)CHC(Me)O]}2]2 (5), Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2{κ2-C,N-[C6MeH3-py]} (6), and Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2{κ2-O,O-[acac]} (7). The five-membered rings are orthogonally arranged with oxygen atoms in trans an octahedral environment iridium atom. Spiro aromatic. degree aromaticity negative charge CH-carbon depend on ligand carbon directly attached metal. Aromaticity has been experimentally confirmed by bromination N-bromosuccinimide (NBS). Reactions sensitive ring attacked CH-carbon. Iridafurans can be selectively brominated, when different ligands lie metalated carbons. Bromination 3 occurs chloride, whereas 6 takes place pyridyl. first gives IrCl{κ2-C,O-[C(Ph)CBrC(Me)O]}{κ2-C,O-[C(Ph)CHC(Me)O]}(PiPr3) (8), reacts more NBS form IrCl{κ2-C,O-[C(Ph)CBrC(Me)O]}2(PiPr3) (9). second yields Ir{κ2-C,O-[C(Ph)CBrC(Me)O]}{κ2-C,O-[C(Ph)CHC(Me)O]}{κ2-C,N-[C6MeH3-py]} (10). origin selectivity kinetic, rate-determining step reaction being attack. activation energy depends atom; a higher allows lower energy. Accordingly, complex 7 undergoes acetylacetonate ligand, giving Ir{κ2-C,O-[C(Ph)CHC(Me)O]}2{κ2-O,O-[acacBr]} (11).

Language: Английский

Citations

1
Unequivocal Characterization of an Osmium Complex with a Terminal Sulfide Ligand and Its Transformation into Hydrosulfide and Methylsulfide DOI
Marı́a L. Buil, Miguel A. Esteruelas, Enrique Oñate

et al.

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 63(13), P. 5779 - 5782

Published: March 15, 2024

Deprotonation of the thioamidate group [OsH{κ2-N,S-[NHC(CH3)S]}(≡CPh)(IPr)(PiPr3)]OTf [1; IPr = 1,3-bis(2,6-diisopropylphenyl)imidazolylidene; OTf CF3SO3] results in release acetonitrile and formation terminal sulfide complex OsH(S)(≡CPh)(IPr)(PiPr3) (2), which has been transformed into hydrosulfide [OsH(SH)(≡CPh)(IPr)(PiPr3)]OTf (3) methylsulfide [OsH(SMe)(≡CPh)(IPr)(PiPr3)]OTf (4) through protonation methylation reactions, respectively. The structure, spectroscopic characteristics, reactivity these compounds are compared. Reactions 3 4 with 2-hydroxypyridine 2-mercaptopyridine afford [OsH{κ2-X,N-[X-py]}(≡CPh)(IPr)(PiPr3)]OTf [X O (5), S(6)].

Language: Английский

Citations

0
Unpredictable Dynamic Behaviour of Ruthenium Chelate Pyrrole Derivatives DOI Creative Commons
Giacomo Drius, Riccardo Tarroni,

Matteo Birchmeier

et al.

Molecules, Journal Year: 2024, Volume and Issue: 29(13), P. 3068 - 3068

Published: June 27, 2024

Reaction of [Ru(H)2(CO)(PPh3)3] 1 with an equimolar amount pyrrole-2-carboxylic acid (H2L1) leads to the homoleptic chelate derivative k2(O,O)-[RuH(CO)(HL1)(PPh3)2] 2. Prolonged acetonitrile refluxing promotes unusual k2(O,O)- → k2(N,O)- dynamic conversion, forming a neutral, stable, air- and moisture- insensitive, solvento-species k2(N,O)-[Ru(MeCN)(CO)(L1)(PPh3)2] 3. Analogously, reaction pyrrole-2-carboxyaldehyde (HL2) affords k2(N,O)-[RuH(CO)(HL2)(PPh3)2] 4, 5, as couple functional isomers. Optimized conditions such temperature solvent polarity allow isolation dominant configurations. Structure 5 is pyrrolide Ru-carbaldehyde, obtained from cyclization pendant CHO function, whereas species 4 can be viewed ethanoyl-conjugated Ru-pyrrole. Derivatives 3–5 were characterized by single crystal X-ray diffraction, ESI-Ms, IR, NMR spectroscopy, indicating distinct features for Ru-bonded pyrrolyl groups. DFT computational results, coplanarity, bond equalization, electron delocalization along fused five-membered rings support aromatic features. In accordance antisymbiotic trans-influence, both isolated isomers disclose CO ligands opposite N- or O-anionic The quantitative Mayer order evidences stabilizing backbonding effect. Antibacterial antifungal trials on Gram-positive (Staphylococcus aureus), Gram-negative (Escherichia coli), Candida albicans further carried out.

Language: Английский

Citations

0
Triazolide Complexes of Sodium and Potassium in the Gas Phase DOI
Arthur E. Lee, Cailum M. K. Stienstra, Terrance B. McMahon

et al.

The Journal of Physical Chemistry A, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 23, 2024

Aromatic organometallic complexes, such as ferrocene and the "inverse sandwich complex" [Na2Cp]+, are stabilized via charge-transfer (C-T) interactions cation-π (i.e., charge-induced dipole charge-quadrupole interactions). Much effort has gone into investigating systems that contain organic moieties, benzene or cyclopentadienyl ligands, but less attention been paid to aromatic heteroatoms (e.g., N), possibly owing complexity arising from a lowering of symmetry introduction electron lone pair density moments. Here we investigate sodiated potassiated clusters 1,2,3-triazolide, [Mx (123T)x−1]+ (x = 3, 4; M Na, K), 1,2,4-triazolide, (124T)x−1]+ using combination infrared ion spectroscopy (IRIS) DFT calculations. Cluster structures strongly influenced by charge-dipole C-T N pairs metal cations. IRIS spectra indicated geometries triazolide moieties essentially unperturbed interaction with ions. Additional spectral features, not predicted calculations, observed in 1500–1800 cm–1 region seem be associated bands involving C–H wagging ring torsion motions.

Language: Английский

Citations

0