Cooperative transition metal/Lewis acid bond-activation reactions by a bidentate (boryl)iminomethane complex: a significant metal-borane interaction promoted by a small bite-angle LZ chelate.

The synthesis of a three-coordinate Pt-borane complex featuring a bidentate "LZ" (boryl)iminomethane (BIM) ligand is reported. Unlike other LZ-type borane ligands featuring a single-donor buttress, the small bite angle enforced by the BIM ligand is shown to promote a significant metal-borane reverse-dative σ-interaction akin to multiply strapped metalloboratranes. The steric accessibility of the reactive Pt → B bond fostered by the BIM ligand allows for a rich reactivity profile toward small molecules that exploit metal-borane cooperative effects. The unligated (boryl)iminomethane BIM is also synthetically accessible and functions as a Frustrated Lewis Pair (FLP). The ability of the free BIM to effect bond activation reactions is contrasted with the behavior seen in the corresponding platinum-bound complexes.

[1]  Wei Wang,et al.  Linear neutral platinum-acetylide moiety: beyond the links. , 2014, Chemical communications.

[2]  J. Peters,et al.  Catalytic conversion of nitrogen to ammonia by a molecular Fe model complex , 2013, Nature.

[3]  J. Peters,et al.  A CO-derived iron dicarbyne that releases olefin upon hydrogenation. , 2013, Journal of the American Chemical Society.

[4]  Rian D. Dewhurst,et al.  Reactivity of Lewis basic platinum complexes towards fluoroboranes. , 2013, Chemistry.

[5]  Yunho Lee,et al.  Heterolytic H2 Cleavage and Catalytic Hydrogenation by an Iron Metallaboratrane. , 2013, Organometallics.

[6]  Gareth R. Owen.  Hydrogen atom storage upon Z-class borane ligand functions: an alternative approach to ligand cooperation. , 2012, Chemical Society reviews.

[7]  W. Harman,et al.  Reversible H2 addition across a nickel-borane unit as a promising strategy for catalysis. , 2012, Journal of the American Chemical Society.

[8]  T. Kupfer,et al.  Unexpected bonding mode of the diboran(4)yl ligand: combining the boryl motif with a dative Pt-B interaction. , 2011, Angewandte Chemie.

[9]  T. Braun,et al.  Facile oxidative addition of water at iridium: reactivity of trans-[Ir(4-C5NF4)(H)(OH)(PiPr3)2] towards CO2 and NH3. , 2011, Dalton transactions.

[10]  J. Peters,et al.  Terminal iron dinitrogen and iron imide complexes supported by a tris(phosphino)borane ligand. , 2011, Angewandte Chemie.

[11]  D. Bourissou,et al.  σ-Acceptor, Z-type ligands for transition metals. , 2011, Chemical communications.

[12]  Rian D. Dewhurst,et al.  Transition metals as Lewis bases: "Z-type" boron ligands and metal-to-boron dative bonding. , 2011, Dalton transactions.

[13]  Gareth R. Owen,et al.  Double addition of H2 to transition metal-borane complexes: a 'hydride shuttle' process between boron and transition metal centres. , 2011, Chemical communications.

[14]  Joshua S. Figueroa,et al.  Four-coordinate iridium(I) monohydrides: reversible dinitrogen binding, bond activations, and deprotonations. , 2010, Journal of the American Chemical Society.

[15]  Rian D. Dewhurst,et al.  Electron-precise coordination modes of boron-centered ligands. , 2010, Chemical reviews.

[16]  Joshua S. Figueroa,et al.  Bond activation, substrate addition and catalysis by an isolable two-coordinate Pd(0) bis-isocyanide monomer. , 2009, Journal of the American Chemical Society.

[17]  Frédéric-Georges Fontaine,et al.  Coordination Chemistry of Neutral (Ln)–Z Amphoteric and Ambiphilic Ligands , 2008 .

[18]  J. Meyer,et al.  Multidentate ligand systems featuring dual functionality. , 2008, Dalton transactions.

[19]  Preston A. Chase,et al.  Lewis acid-catalyzed hydrogenation: B(C6F5)3-mediated reduction of imines and nitriles with H2. , 2008, Chemical communications.

[20]  D. Bourissou,et al.  Metallaboratranes derived from a triphosphanyl-borane: intrinsic C3 symmetry supported by a Z-type ligand. , 2008, Angewandte Chemie.

[21]  H. Braunschweig,et al.  Experimental studies on the trans-influence of boryl ligands in square-planar platinum(II) complexes. , 2007, Chemistry.

[22]  L. Zakharov,et al.  Bifunctional Imidazolylphosphine Ligands as Hydrogen Bond Donors Promote N−H and O−H Activation on Platinum , 2006 .

[23]  D. Bourissou,et al.  On the versatile and unusual coordination behavior of ambiphilic ligands o-R2P(Ph)BR'2. , 2006, Journal of the American Chemical Society.

[24]  G. Parkin.  A simple description of the bonding in transition-metal borane complexes , 2006 .

[25]  H. Braunschweig,et al.  Transition-metal complexes of boron-new insights and novel coordination modes. , 2006, Angewandte Chemie.

[26]  Emily Y. Tsui,et al.  Catalytic diboration of aldehydes via insertion into the copper-boron bond. , 2006, Journal of the American Chemical Society.

[27]  F. Castellano,et al.  Photophysics in bipyridyl and terpyridyl platinum(II) acetylides , 2006 .

[28]  G. Parkin,et al.  Synthesis and Structural Characterization of [κ3-B,S,S-B(mimR)3]Ir(CO)(PPh3)H (R = But, Ph) and [κ4-B(mimBut)3]M(PPh3)Cl (M = Rh, Ir): Analysis of the Bonding in Metal Borane Compounds , 2006 .

[29]  P. Müller,et al.  Efficient homogeneous catalysis in the reduction of CO2 to CO. , 2005, Journal of the American Chemical Society.

[30]  Hill,et al.  The Sting of the Scorpion: A Metallaboratrane. , 1999, Angewandte Chemie.

[31]  N. C. Norman,et al.  Transition Metal−Boryl Compounds: Synthesis, Reactivity, and Structure , 1998 .

[32]  S. Heřmánek.  Boron-11 NMR spectra of boranes, main-group heteroboranes, and substituted derivatives. Factors influencing chemical shifts of skeletal atoms , 1992 .

[33]  H. Nöth,et al.  Catalytic Hydroboration with Rhodium Complexes , 1985 .

[34]  O. Ozerov.  Oxidative addition of water to transition metal complexes. , 2009, Chemical Society reviews.