Structural and electronic elucidation of a N-heterocyclic silylene vanadocene adduct.

The solid and solution state structure of the vanadium(ii) N-heterocyclic silylene (NHSi) complex, [(SiIPr)V(Cp)2] (1) is reported (SiIPr: 1,3-bis(2,6-diisopropylphenyl)-1,3-diaza-2-silacyclopent-4-en-2-ylidene). The electronic structure of 1 is probed using a combination of magnetic measurements, EPR spectroscopy and computational studies. The V-Si bond strength and complex forming mechanism between vanadocene and an NHSi ligand is elucidated using computational methods.

[1]  P. Power,et al.  London dispersion forces in sterically crowded inorganic and organometallic molecules , 2017 .

[2]  Marc D. Walter,et al.  N‐Heterocyclic Carbene (NHC) Adducts of [(C5H5)2Mn] Revisited: Nothing More, Nothing Less than High‐Spin (S = 5/2) Molecules! , 2016 .

[3]  M. Hänninen,et al.  A three-coordinate iron-silylene complex stabilized by ligand-ligand dispersion forces. , 2016, Dalton transactions.

[4]  R. Beckhaus,et al.  Flexible Structural Features of Pentafulvene Titanium Derivatives: Isolation and Characterization of NHC Complexes. , 2016, Chemistry.

[5]  P. Menezes,et al.  Alkaline-Earth-Metal-Induced Liberation of Rare Allotropes of Elemental Silicon and Germanium from N-Heterocyclic Metallylenes. , 2015, Inorganic chemistry.

[6]  M. Driess,et al.  Unprecedented silicon(II)→calcium complexes with N-heterocyclic silylenes. , 2015, Dalton transactions.

[7]  Tanya K. Ronson,et al.  Reactions of Cp2M (M = Ni, V) with dilithium diamido-aryl reagents; retention and oxidation of the transition metal ions. , 2013, Dalton transactions.

[8]  Keith S. Murray,et al.  PHI: A powerful new program for the analysis of anisotropic monomeric and exchange‐coupled polynuclear d‐ and f‐block complexes , 2013, J. Comput. Chem..

[9]  M. Driess,et al.  New vistas in N-heterocyclic silylene (NHSi) transition-metal coordination chemistry: syntheses, structures and reactivity towards activation of small molecules. , 2013, Chemistry.

[10]  Timothy A. Jackson,et al.  Vanadocene de Novo: Spectroscopic and Computational Analysis of Bis(η5-cyclopentadienyl)vanadium(II) , 2012 .

[11]  D. Wright,et al.  The redox effect of the [1,2-(NH)2C6H4]2- ligand in the formation of transition metal compounds. , 2012, Chemical communications.

[12]  V. Cherkasov,et al.  Vanadocene complexes with asymmetric alkyne ligands, [Cp2V(1-2η-R1C=CR2)] , 2012, Russian Chemical Bulletin.

[13]  R. Beckhaus,et al.  Bridging Azines in the Coordination Sphere of Low-Valent Vanadocene Derivatives† , 2010 .

[14]  Artur Michalak,et al.  A Combined Charge and Energy Decomposition Scheme for Bond Analysis. , 2009, Journal of chemical theory and computation.

[15]  M. Mcpartlin,et al.  Trapping of Oligomeric Cyclopentadienyllithium Cationic and Anionic Fragments by a VV‐Bonded Ligand , 2007 .

[16]  R. Choukroun,et al.  Adventures in Vanadocene Chemistry , 2005 .

[17]  Richard A. Jones,et al.  Reactions of Transition-Metal Metallocenes with Stable Carbenes , 1999 .

[18]  Jennifer C. Green,et al.  Bent metallocenes revisited , 1998 .

[19]  M. Che,et al.  EPR as a Tool To Investigate the Transition Metal Chemistry on Oxide Surfaces. , 1997, Chemical reviews.

[20]  M. Denk,et al.  Synthesis and Structure of a Stable Silylene , 1994 .

[21]  F. Köhler,et al.  Origin of NMR temperature shift and electronic structure of vanadocene , 1987 .

[22]  C. Floriani,et al.  Decamethylvanadocene chemistry: synthesis, structure, and reactions of vanadium(II) and vanadium(III) derivatives with carbon monoxide and isocyanides , 1984 .

[23]  L. Griffith,et al.  Electron paramagnetic resonance and structural studies of small-ring metallacycles. Bonding in a metallacyclopropene formed by the oxidative addition of an acetylene to vanadocene , 1980 .

[24]  C. Floriani,et al.  Vanadium-olefin and -acetylene complexes: structural studies on (.eta.2-diethyl fumarato-C,C)- and (.eta.2-dimethyl acetylenedicarboxylato-C,C)bis(.eta.-cyclopentadienyl)vanadium , 1979 .

[25]  J. Morton,et al.  Atomic parameters for paramagnetic resonance data , 1978 .

[26]  R. Hoffmann,et al.  Structure and chemistry of bis(cyclopentadienyl)-MLn complexes , 1976 .

[27]  Z. Benedek,et al.  Can low-valent silicon compounds be better transition metal ligands than phosphines and NHCs? , 2015 .

[28]  M. Denk,et al.  Electronic structure of a stable silylene: photoelectron spectra and theoretical calculations of Si(NRCHCHNR), Si(NRCH2CH2NR) and SiH2(NRCHCHNR) , 1994 .