This third review in a series involving reactions of hydrosilanes and transition metal complexes and characterization of the products covers the period 2009 thru 2013. After a brief discussion of other synthetic methods used for the formation of Si-TM complexes, Section 3 provides an extended discussion of the types of ligands and metal complexes used as reactants with hydrosilanes. The increase in use of pincer ligands in forming stable, isolable complexes is featured. Three tables list the complexes reported for primary, secondary, and tertiary silanes. Many reactions leading to SiTM complexes are initiated by loss of a ligand prior to oxidative addition of the hydrosilane or by a metathesis reaction. Structural data are tabulated for the isolated complexes and provide the Si-TM bond ranges for the elements in the “d” block. A major section on nonclassical (σ or agostic) complexes includes two general groupings with Si–H···TM and M–H···Si interactions. A section on solution processes identified by NMR s...

Reactions of Hydrosilanes with Transition Metal Complexes.

Aromatic C–H σ-Bond Activation by Ni0, Pd0, and Pt0 Alkene Complexes: Concerted Oxidative Addition to Metal vs Ligand-to-Ligand H Transfer Mechanism

Reaction of the donor-stabilized silylene 1 with [Cr(CO)6], [Mo(CO)6], [W(CO)6], or [Fe(CO)5] leads to the formation of the transition-metal silylene complexes 2–5, which contain five-coordinate silicon(II) moieties with Si–M bonds (M = Cr, Mo, W, Fe). These compounds were characterized by NMR spectroscopic studies in the solid state and in solution and by crystal structure analyses. These experimental investigations were complemented by computational studies to gain insight into the bonding situation of 2–5. The nature of the Si–M bonds is best described as a single bond.

Five-coordinate silicon(II) compounds with Si-M bonds (M = Cr, Mo, W, Fe): Bis[N,N'-diisopropylbenzamidinato(-)]silicon(II) as a ligand in transition-metal complexes.

The donor-stabilized silylene 2 (the first bis(guanidinato)silicon(II) complex) reacts with the transition-metal carbonyl complexes [M(CO)6] (M=Cr, Mo, W) to form the respective silylene complexes 7–10. In the reactions with [M(CO)6] (M=Cr, Mo, W), the bis(guanidinato)silicon(II) complex 2 behaves totally different compared with the analogous bis(amidinato)silicon(II) complex 1, which reacts with [M(CO)6] as a nucleophile to replace only one of the six carbonyl groups. In contrast, the reaction of 2 leads to the novel spirocyclic compounds 7–9 that contain a four-membered SiN2C ring and a five-membered MSiN2C ring with a MSi and MN bond (nucleophilic substitution of two carbonyl groups). Compounds 7–10 were characterized by elemental analyses (C, H, N), crystal structure analyses, and NMR spectroscopic studies in the solid state and in solution.

Novel Transition-Metal (M=Cr, Mo, W, Fe) Carbonyl Complexes with Bis(guanidinato)silicon(II) Ligands

The chemistry of the carbon-transition metal double and triple bond: Annual survey covering the year 2011

Synthesis, Structure, and Bonding Nature of Ethynediyl-Bridged Bis(silylene) Dinuclear Complexes of Tungsten and Molybdenum

Reactions of tungsten acetylide-silylene complexes with pyridines: Direct observation of silylene/silyl migration in tungsten acetylide and carbyne/vinylidene frameworks

Hiroyuki Oike

Papers

Synthesis, Structure, and Bonding Nature of Ethynediyl-Bridged Bis(silylene) Dinuclear Complexes of Tungsten and Molybdenum

Reactions of tungsten acetylide-silylene complexes with pyridines: Direct observation of silylene/silyl migration in tungsten acetylide and carbyne/vinylidene frameworks

Conversion of an Acetylide−Silylene Complex to an Alkenylcarbyne Complex by Consecutive Ketone Addition and Base-Induced Silanone Elimination