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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, ...

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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 ...

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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 ...

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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, ...

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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 ...

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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. ...

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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 = ...

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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 ...

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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 ...

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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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