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Intramolecular Hydride Transfer Reactions in (Formazanate)Boron Dihydride Complexes

05-Feb-2016 | Mu-Chieh Chang; Edwin Otten, Organometallics, 2016

The solution-phase thermolysis of (formazanate)boron dihydrides (LBH2; 2) results in the formation of aminoborane compounds (4) via a series of boron-to-ligand intramolecular hydride transfer reactions. Monitoring the reactions by NMR spectroscopy allowed identification of several intermediates, ...


Reactions of Terphenyl-Substituted Digallene AriPr4GaGaAriPr4 (AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2) with Transition Metal Carbonyls and Theoretical Investigation of the Mechanism of Addition

29-Jan-2016 | Madison L. McCrea-Hendrick; Christine A. Caputo; Christopher J. Roberts; James C. Fettinger; Heikki M. Tuononen; Phi ..., Organometallics, 2016

The neutral digallene AriPr4GaGaAriPr4 (AriPr4 = C6H3-2,6-(C6H3-2,6-iPr2)2) was shown to react at ca. 25 °C in pentane solution with group 6 transition metal carbonyl complexes M(CO)6 (M = Cr, Mo, W) under UV irradiation to afford compounds of the general formula trans-[M(GaAriPr4)2(CO)4] in ...


A Frustrated Lewis Pair Based on a Cationic Aluminum Complex and Triphenylphosphine

08-Jan-2016 | Tom E. Stennett; Jürgen Pahl; Harmen S. Zijlstra; Falk W. Seidel; Sjoerd Harder, Organometallics, 2016

The highly Lewis acidic, cationic aluminum species [DIPP-nacnacAlMe]+[B(C6F5)4]− (1, DIPP-nacnac = [HC{C(Me)N(2,6-iPr2C6H3)}2]−) has been shown to undergo reactions with a wide variety of small molecules, in both the presence and absence of an external weak phosphine base, PPh3. Cycloaddition ...


Discrete Ionic Complexes of Highly Isoselective Zirconocenes. Solution Dynamics, Trimethylaluminum Adducts, and Implications in Propylene Polymerization

05-Jan-2016 | Gabriel Theurkauff; Manuela Bader; Nicolas Marquet; Arnaud Bondon; Thierry Roisnel; Jean-Paul Guegan; Anissa Amar; A ..., Organometallics, 2016

Discrete ionic complexes belonging to two main families of highly isoselective polymerization zirconocene systems, C1-symmetric {Cp/Flu} (a,b) and C2-symmetric {SBI} (c) systems, have been scrutinized. The ion pair reorganization processes for inner-sphere ion pairs (ISIPs) 3a,b-MeB(C6F5)3, ...


Mono- and Bis-Cyclometalated Palladium Complexes: Synthesis, Characterization, and Catalytic Activity

31-Dec-2015 | Sebastian Molitor; Christopher Schwarz; Viktoria H. Gessner, Organometallics, 2015

Cyclometalated palladium complexes have found a variety of applications, above all in homogeneous catalysis. Most complexes include mono-cyclometalated ligands, particularly systems with P- or N-donors. Herein, we report the preparation of a series of mono- and bis-cyclometalated palladium ...


Base-Free and Bisphosphine Ligand Dialkylmanganese(II) Complexes as Precursors for Manganese Metal Deposition

30-Dec-2015 | Jeffrey S. Price; Preeti Chadha; David J. H. Emslie, Organometallics, 2015

The solid-state structures and the physical, solution magnetic, solid-state magnetic, and spectroscopic (NMR and UV/vis) properties of a range of oxygen- and nitrogen-free dialkylmanganese(II) complexes are reported, and the solution reactivity of these complexes toward H2 and ZnEt2 is described. ...


Synthesis, Isomerization, and Catalytic Transfer Hydrogenation Activity of Rhodium(III) Complexes Containing Both Chelating Dicarbenes and Diphosphine Ligands

16-Dec-2015 | Kevin Farrell; Helge Müller-Bunz; Martin Albrecht, Organometallics, 2015

Different rhodium(III) complexes [Rh(C,C)(P,P)X2]+ bearing both a cis-chelating dicarbene and a diphosphine ligand were synthesized (C,C = methylene(4,4′-diimidazolylidene); P,P = 1,2-bis(diphenylphosphino)ethane (dppe), (R)-(+)-2,2′-bis(diphenylphosphino)-1,1′-binaphthalene (R-BINAP); X = ...


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 ...


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