The reaction of [Cp*RuCl]4 (1; Cp* = η5-C5Me5) with the carbene ligand 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes) affords a coordinatively unsaturated Cp*Ru(IMes)Cl (3) complex in 86% isolated yield. Solution calorimetric results this system provide information concerning electron donor properties ligand, which are very similar to those PCy3. Structural from single-crystal X-ray studies for 3 allows determination steric parameters associated ligand. thermochemical is used...

Clear experimental evidence from X-ray photoelectron spectroscopy and (31)P NMR has been obtained for the first time to confirm that combination of Ag(+) cation with [L-Au](+) results in formation different complexes solution. Re-evaluation literature-reported gold-catalyzed reactions revealed a significant difference reactivities without silver. In extreme cases (more than "rare"), conventional catalysts could not promote reaction presence This investigation therefore long-overlooked...

Combined solution calorimetric and quantum mechanics studies of reactions involving saturated unsaturated N-heterocyclic carbene (NHC) ligands show that the difference in their relative bond dissociation energies is very small (1 kcal·mol-1). Structural computational reveal metric parameter differences. These observations conjunction with reactivity profiles NHC-modified ruthenium-based olefin metathesis catalysts suggest changes donor properties NHC can translate into significant...

A series of 1,2,3-triazole-bound cationic Au(I) catalysts have been synthesized, and their structures characterized by X-ray crystallography. Variable-temperature NMR studies revealed dynamic triazole-Au cation coordination in solution. Reaction profiles clearly indicated that these new possess much better thermal stability than literature-reported Au catalysts, including IPrAu x NTf(2). By application challenging intermolecular hydroaminations were achieved with less-reactive internal...

Selective cyclization and substitution was achieved with designated 1,2,3-triazole acid auxiliary groups under Pd catalyzed C–H activation conditions. Both sp2 sp3 bonds were effectively activated, giving the desired products in good yields. This result revealed first successful example of exclusive using ligands, while another triazole-containing directing group dominantly gave identical

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTA new class of highly conductive molecular solids: the partially oxidized phthalocyaninesJ. L. Petersen, C. S. Schramm, D. R. Stojakovic, B. M. Hoffman, and T. J. MarksCite this: Am. Chem. Soc. 1977, 99, 1, 286–288Publication Date (Print):January 1977Publication History Published online1 May 2002Published inissue 1 January 1977https://pubs.acs.org/doi/10.1021/ja00443a070https://doi.org/10.1021/ja00443a070research-articleACS PublicationsRequest...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTN-Pyrrolyl Phosphines: An Unexploited Class of Phosphine Ligands with Exceptional .pi.-Acceptor CharacterKenneth G. Moloy and Jeffrey L. PetersenCite this: J. Am. Chem. Soc. 1995, 117, 29, 7696–7710Publication Date (Print):July 1, 1995Publication History Published online1 May 2002Published inissue 1 July 1995https://pubs.acs.org/doi/10.1021/ja00134a014https://doi.org/10.1021/ja00134a014research-articleACS PublicationsRequest reuse...

The homologous series of ansa-monocyclopentadienyl amido complexes [(C5H4)SiMe2(N-t-Bu)]M(NMe2)2 (M = Ti (2), Zr (3), Hf (4)) and [(C5Me4)SiMe2(N-t-Bu)]Zr(NMe2)2 (8) are prepared in 70−85% isolated yields by heating the neat 1:1 reaction mixture (C5R4H)SiMe2(N(H)-t-Bu), where R H, Me, M(NMe2)4, at 110−120 °C for 24−48 h under a N2 purge. Whereas reactions 2 with equiv [NEt3H]Cl or HCl produce [(C5H4)SiMe2(N-t-Bu)]TiCl2 (5) [(C5H4)SiMe2Cl]TiCl2(NMe2)(NMe2H) (6), SiMe3Cl toluene provides...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis, Structures, and Reactivity of (R6-acen)ZrR'2 (R6-acen)Zr(R')+ Complexes (R = H, F; R' CH2CMe3, CH2Ph)Erik B. Tjaden, Dale C. Swenson, Richard F. Jordan, Jeffrey L. PetersenCite this: Organometallics 1995, 14, 1, 371–386Publication Date (Print):January 1995Publication History Published online1 May 2002Published inissue 1 January 1995https://pubs.acs.org/doi/10.1021/om00001a053https://doi.org/10.1021/om00001a053research-articleACS...

A series of (NHC)AuICl (1, NHC = N,N'-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr); 2, N,N'-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene (IMes); 3, N,N'-bis(2,6-diisopropylphenyl)imidazolin-2-ylidene (SIPr); 4, N,N'-bis(2,4,6-trimethylphenyl)imidazolin-2-ylidene (SIMes); 5, N,N'-dicyclohexylimidazol-2-ylidene (ICy); 6, N,N'-diadamantylimidazol-2-ylidene (IAd); 7, N,N'-di-tert-butylimidazol-2-ylidene (ItBu)) complexes were reacted with LiBr to generate [(IPr)AuBr] (8), [(IMes)AuBr] (9),...

N-Heterocyclic carbene complexes of platinum(II) have been synthesized, notably monocarbene cis-[(IPr)Pt(dmso)(Cl)2], 6, cis-[(IMes)Pt(dmso)(Cl)2], 7, cis-[(SIPr)Pt(dmso)(Cl)2], 8, cis-[(SIMes)Pt(dmso)(Cl)2], 9, and cis-[(TTP)Pt(dmso)(Cl)2], 10. All fully characterized by multinuclear NMR spectroscopy. Complex 10 X-ray crystallography. The data obtained allowed for the differentiation between electronic contributions (σ π) present in Pt−NHC bond. Supported computational analyses, percentage...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis, structural characterization, and electrochemistry of [1]metallocenophane complexes, [Si(alkyl)2(C5H4)2]MCl2, M = Ti, ZrChandrasekhar S. Bajgur, Wayne Tikkanen, Jeffrey L. PetersenCite this: Inorg. Chem. 1985, 24, 16, 2539–2546Publication Date (Print):July 1, 1985Publication History Published online1 May 2002Published inissue 1 July 1985https://pubs.acs.org/doi/10.1021/ic00210a015https://doi.org/10.1021/ic00210a015research-articleACS...

The amine elimination reaction of Zr(NMe2)4 (2) and (EBI)H2 (1,2-bis(3-indenyl)ethane, 3) in toluene at 100 °C affords pure rac-(EBI)Zr(NMe2)2 (rac-4, EBI = ethylene-1,2-bis(1-indenyl)) 68% isolated yield. This proceeds via the rapidly formed mono-indenyl intermediate (η5-C9H6CH2CH2C9H7)Zr(NMe2)3 (6) which undergoes reversible intermolecular with a second equivalent 2 to give binuclear species (μ-η5,η5-EBI){Zr(NMe2)3}2 (5, rac meso isomers) or intramolecular either rac-4 meso-4. kinetic...

Efficient post-triazole regioselective N-2 arylation was developed from C-4, C-5 disubstituted-1,2,3-NH-triazoles. Three different approaches had been investigated, including SNAr, Cu(I) catalyzed aryl amidation and Cu(II) mediated boronic acid coupling. The N-2-aryl triazoles were successfully synthesized with excellent yields. structures characterized by X-ray crystallography some N-2-triazole products gave strong fluorescence various emission controlled the groups.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and structural characterization by x-ray diffraction EPR single-crystal techniques of (dichloro)bis(.eta.5-methylcyclopentadienyl)vanadium (dichloro)bis(.eta.5-methylcyclopentadienyl)titanium. Spatial distribution the unpaired electron in a V(.eta.5-C5H5)2L2-type complexJeffrey L. Petersen Lawrence F. DahlCite this: J. Am. Chem. Soc. 1975, 97, 22, 6422–6433Publication Date (Print):October 1, 1975Publication History Published online1 May...

Titanium and zirconium complexes carrying two 2,6-bis(pyrrolyl)pyridine ligands have been synthesized characterized. The neutral Ti(MePDP)2 Zr(MePDP)2 (MePDP = 2,6-bis(5-methyl-3-phenyl-1H-pyrrol-2-yl)pyridine) show intense ligand-to-metal charge-transfer bands in the visible region undergo multiple reversible redox events under highly reducing conditions. exhibits photoluminescent behavior its excited state can be quenched by mild reductants to generate a powerful electron transfer reagent...

The preparation of two series [Cu(NHC)2]X complexes (NHC=N-heterocyclic carbene, X=PF6 or BF4) in high yields from readily available materials is reported. These have been spectroscopically and structurally characterized. activity these cationic bis-NHC the hydrosilylation ketones was examined, both ligand counterion showed a significant influence on catalytic performance. Moreover, when compared with related [Cu(NHC)]-based systems, proved to be more efficient under similar reaction...

The intramolecular cyclohexylene-bridged P/B frustrated Lewis pair [Mes(2)P-C(6)H(10)-B(C(6)F(5))(2)] 1b reacts rapidly with NO to give the persistent FLP-NO aminoxyl radical 2b formed by addition nitrogen atom of NO. This species was fully characterized X-ray diffraction, EPR and UV/vis spectroscopies, C,H,N elemental analysis, DFT calculations. reactive oxygen-centered undergoes a H-atom abstraction (HAA) reaction 1,4-cyclohexadiene diamagnetic FLP-NOH product 3b. toluene at 70 °C in an...

Gold-catalyzed C(sp)-C(sp(2)) and C(sp(2))-C(sp(2)) cross-coupling reactions are accomplished with aryldiazonium salts as the coupling partner. With assistance of bpy ligand, gold(I) species were oxidized to gold(III) by diazonium without any external oxidants. Monitoring reaction NMR ESI-MS provided strong evidence for nitrogen extrusion followed Au(III) reductive elimination key step.

A general method for the synthesis of α-substituted vinyl sulfones makes use a combination triazole gold complex and gallium triflate. This efficient CS bond formation between simple terminal alkynes sulfinic acids provides access to various sulfones.

Directed sulfenylation of both sp² and sp³ C–H bonds was achieved through nickel catalyzed directed C–S bond formation, giving the desired product in good to excellent yield (up 90%).

'Lene' and mean: The strong Lewis acid B(C6F5)3 efficiently converts some bis(arylethynyl)benzenes into dibenzopentalenes through a series of induced cyclization reactions at room temperature. Thus the reaction has potential to be useful in synthesis substituted dibenzopentalene derivatives which are difficult make by conventional means.

Time-resolved emission spectroscopy for the luminescent zirconium complex Zr(MePDP)2 (MePDP = 2,6-bis(5-methyl-3-phenyl-1H-pyrrol-2-yl)pyridine) revealed a long-lived excited state with lifetime τ 325 ± 10 μs. Computational studies using time-dependent density functional theory were conducted to identify nature of as mixed triplet intraligand/ligand-to-metal charge-transfer state. Stern–Volmer experiments showed strong dependence quenching rate on redox potential quencher indicating...

Regioselective copper-catalyzed boracarboxylation of vinyl arenes with bis(pinacolato)diboron and carbon dioxide has been achieved. New boron-functionalized α-aryl carboxylic acids, including nonsteroidal anti-inflammatory drugs (NSAIDs), are obtained in moderate to excellent yields. The synthetic utility the transformation was shown through subsequent derivatization carbon-boron bond yielding formal hydroxy- fluorocarboxylation products as well anionic difluoroboralactones.