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iPr2N–P═Fe(CO)4 in Olefinic Solvents: A Reservoir of a Transient Phosphinidene Complex Capable of Substrate Hopping

06-Apr-2016 | Jan B. M. Wit; G. Bas de Jong; Marius Schakel; Martin Lutz; Andreas W. Ehlers; J. Chris Slootweg; Koop Lammertsma, Organometallics, 2016

The phosphinidene complex iPr2N–P═Fe(CO)4 was prepared as a storable phosphirane solution from Collman’s reagent and iPr2NPCl2 in the olefins 1-pentene and 1-hexene. The carbene-like reagent is able to hop under very mild conditions (>−25 °C) from one olefin to another and to alkynes to give the ...


Aminotroponiminates: Alkali Metal Compounds Reveal Unprecedented Coordination Modes

11-Mar-2016 | Crispin Lichtenberg, Organometallics, 2016

The coordination chemistry of alkalimetal aminotroponiminates (ATIs) was investigated based on (i) a lithium ATI, (ii) the first example of a sodium ATI, and (iii) the first example of a structurally characterized potassium ATI. In the lithium derivative of this series, the ATI ligand adopts a ...


Active O,Npy,N-Titanium(IV) Fluoride Precatalysts for Ethylene Polymerization: Exploring “Fluoride Effects” on Polymer Properties and Catalytic Performance

03-Mar-2016 | Luka A. Wright; Eric G. Hope; Gregory A. Solan; Warren B. Cross; Kuldip Singh, Organometallics, 2016

Three examples of discrete six-coordinate O,Npy,N-bearing titanium(IV) trifluoride complexes, [{2-(C5H4N)-6-(CMe2O)C5H3N}TiF3] (1), [{2-(C6H4-2′-O),6-(CMe═N(2,6-i-Pr2C6H3))C5H3N}TiF3] (2a), and [{2-(3-C12H8-2-O)-6-(CMe═N(2,6-i-Pr2C6H3))C5H3N}TiF3] (3a), were prepared using a one-step HF ...


N-Heterocyclic Carbene Complexes of Three- and Four-Coordinate Fe(I)

02-Mar-2016 | Yasuhiro Ohki; Ryoko Hoshino; Kazuyuki Tatsumi, Organometallics, 2016

N-heterocyclic carbene complexes of three- and four-coordinate Fe(I), [Fe(LR)4][PF6] (LR = 1,3-R2-4,5-dimethylimidazol-2-ylidene, R = Me (2), Et (3), iPr (4)) and [Fe(LMes)2(THF)][PF6] (5) (LMes = 1,3-bis(2,4,6-trimethylphenyl)imidazol-2-ylidene), were synthesized from successive reactions of ...


Synthesis, NMR, and X-ray Studies of Iridium Dihydride C,N and N,P Ligand Complexes

26-Feb-2016 | Stefan Gruber, Organometallics, 2016

The iridium(III) dihydride complexes [Ir(H)2(L1)(6,6′-bi-2-picoline)]BArF (5; L1 = (S)-1-[2-(2-adamantan-2-yl-4,5-dihydrooxazol-4-yl)-ethyl]-3-(2,6-diisopropylphenyl)-1,2-dihydroimidazol-2-ylidene, BArF = tetrakis[3,5-bis(trifluoromethyl)phenyl]borate) and [Ir(H)2(L2)(6,6′-bi-2-picoline)]BArF (6; ...


A Ni0(η2-(Si–H))(η2-H2) Complex That Mediates Facile H Atom Exchange between Two σ-Ligands

22-Feb-2016 | Bridget A. Connor; Jonathan Rittle; David VanderVelde; Jonas C. Peters, Organometallics, 2016

σ-adduct complexes of low-valent, late first-row metal complexes are highly unusual, and this is particularly true of d10 systems. We have discovered a nickel/phosphine/silyl system that undergoes reaction with H2 in solution to generate a species best described as Ni0(η2-(Si–H))(η2-H2) on the ...


Tuning the Oxidation State, Nuclearity, and Chemistry of Uranium Hydrides with Phenylsilane and Temperature: The Case of the Classic Uranium(III) Hydride Complex [(C5Me5)2U(μ-H)]2

18-Feb-2016 | Justin K. Pagano; Jacquelyn M. Dorhout; Kenneth R. Czerwinski; David E. Morris; Brian L. Scott; Rory Waterman; Jaque ..., Organometallics, 2016

This work demonstrates that the oxidation state and chemistry of uranium hydrides can be tuned with temperature and the stoichiometry of phenylsilane. The trivalent uranium hydride [(C5Me5)2U–H]x (5) was found to be comprised of an equilibrium mixture of U(III) hydrides in solution at ambient ...


Magnesiacycloalkanes with Different Ring Sizes

08-Feb-2016 | Reinald Fischer; Helmar Görls; Jens Langer; Marcel Enke; Matthias Westerhausen, Organometallics, 2016

Di-Grignard compounds are prepared via the direct synthesis of magnesium with Br2C{Si(CH3)3}2, α,ω-dihalides of XCH2YCH2X (X: Cl, Br; Y: Si(CH3)2, (CH2)n with n = 4, 5, 6), and with ClC(CH3)2(CH2)n(CH3)2CCl (n = 3, 4) in tetrahydrofuran (THF) or diethyl ether. After removal of the sparingly ...


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 ...


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