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Reactivity of a Tp–Iridacyclopentene Complex

12-Nov-2015 | Ángela Vivancos; Nuria Rendón; Margarita Paneque; Manuel L. Poveda; Eleuterio Álvarez, Organometallics, 2015

The known iridacyclopentene [TpIr{κ2(C,C)-CH2CH2C(R)═C(R)}(THF)] (1; R = CO2Me) is unstable in C6H6 solution (t1/2 ≈ 4 h at 25 °C), evolving, following dissociation of THF, to the Ir(I) diene [TpIr{η4-CH2═CHC(R)═CH(R)}] (3) as a ca. 9:1 mixture of trans and cis isomers. However, studies carried ...


Preparation, Structural Analysis, and Reactivity Studies of Phosphenium Dications

06-Nov-2015 | Madelyn Qin Yi Tay; Gordana Ilić; Ulrike Werner-Zwanziger; Yunpeng Lu; Rakesh Ganguly; Louis Ricard; Gilles Frison; ..., Organometallics, 2015

This work expands on the recent synthesis and reactivity of the two-coordinate P(III)-containing dication [((Ph3P)2C)P(NiPr2)]2+ (3a2+). Two additional dications of general formula [((RPh2P)2C)P(NR′2)]2+ (3b2+, R = 1/2 (CH2)3, R′ = iPr; 3c2+, R = Ph, R′ = Cy) have been prepared. Solution and ...


η5–η1 Switch in Divalent Phosphaytterbocene Complexes with Neutral Iminophosphoranyl Pincer Ligands: Solid-State Structures and Solution NMR 1JYb–P Coupling Constants

03-Nov-2015 | Thibault Cheisson; Audrey Auffrant; Grégory Nocton, Organometallics, 2015

This paper reports the synthesis of a series of complexes based on the bis(pentamethylcyclopentadienyl)ytterbium(II) (1; Cp*2Yb) and bis(tetramethylphospholyl)ytterbium(II) (2; Tmp2Yb) fragments bearing an additional neutral bis(methyliminophosphoranyl)pyridine ligand (L) on which the steric ...


The Unusual Redox Properties of Fluoroferrocenes Revealed through a Comprehensive Study of the Haloferrocenes

02-Nov-2015 | Michael S. Inkpen; Shuoren Du; Mariana Hildebrand; Andrew J. P. White; Nicholas M. Harrison; Tim Albrecht; Nicholas ..., Organometallics, 2015

We report the synthesis and full characterization of the entire haloferrocene (FcX) and 1,1′-dihaloferrocene (fcX2) series (X = I, Br, Cl, F; Fc = ferrocenyl, fc = ferrocene-1,1′-diyl). Finalization of this simple, yet intriguing set of compounds has been delayed by synthetic challenges ...


Stable Germenolates and Germenes with Exocyclic Structures

27-Oct-2015 | Michael Haas; Mario Leypold; Dominik Schnalzer; Ana Torvisco; Harald Stueger, Organometallics, 2015

The first germenolates with exocyclic structures [(Me3Si)2Ge(Si2Me4)2GeC(R)O]−K+ (5a: R = Mes; 5b: o-Tol; 5c: 1-Ad) were synthesized by the reaction of the corresponding cyclic acylgermanes with KOtBu. 5a–c could be isolated by crystallization. The remarkable thermal stability of 5a–c even at ...


Reactivity of an Acyclic Silylsilylene toward Ethylene: Migratory Insertion into the Si–Si Bond

13-Oct-2015 | Daniel Wendel; Wolfgang Eisenreich; Christian Jandl; Alexander Pöthig; Bernhard Rieger, Organometallics, 2015

The reaction of the only known room-temperature-stable, acyclic silylsilylene, Si{NDipp(SiMe3)}{Si(SiMe3)3}, toward ethylene was investigated. A full conversion to the silirane product Si{CH2–CH2}{NDipp(SiMe3)}{Si(SiMe3)3} (1) was observed at ambient temperature. However, heating of the benzene ...


Unusual Benzyl Migration Reactivity in NHC-Bearing Group 4 Metal Chelates: Synthesis, Characterization, and Mechanistic Investigations

29-Sep-2015 | Charles Romain; David Specklin; Karinne Miqueu; Jean-Marc Sotiropoulos; Christophe Fliedel; Stéphane Bellemin-Laponn ..., Organometallics, 2015

The reaction of 1 equiv of [M(CH2Ph)4] (M = Zr, Hf) and 1,3-bis(3,5-di-tert-butyl-2-hydroxyphenyl)imidazolinium chloride [tBu(OCO)H3, 1] cleanly yielded the corresponding M-NHC chloro benzyl derivatives [[tBu(OCO)]M(Cl)(CH2Ph)] (2Zr and 2Hf) along with 3 equiv of toluene. For both metal ...


Synthesis and Reactivity of Manganese(II) Complexes Containing N-Heterocyclic Carbene Ligands

24-Sep-2015 | Malik H. Al-Afyouni; V. Mahesh Krishnan; Hadi D. Arman; Zachary J. Tonzetich, Organometallics, 2015

A series of manganese(II) complexes containing aryl-substituted N-heterocyclic carbene (NHC) ligands have been synthesized and characterized. Chloride complexes of Mn(II) containing the NHC ligands 1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene (IPr) and 1,3-dimesitylimidazol-2-ylidene (IMes) ...


Direct Detection, Dimerization, and Chemical Trapping of Dimethyl- and Diphenylstannylene from Photolysis of Stannacyclopent-3-enes in Solution

22-Sep-2015 | Ian R. Duffy; William J. Leigh, Organometallics, 2015

Dimethyl- and diphenylstannylene (SnMe2 and SnPh2, respectively) have been successfully detected and characterized in solution. The stannylenes were generated by photolysis of 1,1,3-trimethyl-4-phenyl- (2) and 3,4-dimethyl-1,1-diphenylstannacyclopent-3-ene (3), respectively, which have been shown ...


Metal Effects on the Asymmetric Cycloaddition Reaction between 3,4-Dimethyl-1-phenylphosphole and Sulfoxide

22-Sep-2015 | Mengtao Ma; Na Zhang; Yongxin Li; Sumod A. Pullarkat; Pak-Hing Leung, Organometallics, 2015

The orthometalated [1-(dimethylamino)ethyl]naphthalene platinum(II) complex has been used successfully to promote the asymmetric cycloaddition reaction between 3,4-dimethyl-1-phenylphosphole and sulfoxide in high selectivity. The exo-cycloadduct coordinated to the platinum template as bidentate ...


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