Related Experiment Video
Updated: Apr 21, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
Cooperative reactivity of halomethanes and -silanes at an A-frame complex: transannular addition versus bridging
Max Passargus1,2, Celine Nieuwland3, Merle Arrowsmith1,2
1Institute for Inorganic Chemistry, Julius-Maximilians-Universität Würzburg Am Hubland 97074 Würzburg Germany.
Abstract:
With CH2X2 (X = Cl, Br, I) and CCl4 the diplatinum(0) complex [(µ-dmpm)2Pt2(nbe)2] (dmpm = bis(dimethylphosphino)methane, nbe = norbornene) undergoes facile cooperative addition of one C-X bond at each Pt centre to yield the methylene-bridged diplatinum(ii) A-frame complexes [(µ-dmpm)2Pt2X2(µ-CY2)] (Y[double bond, length as m-dash]H, Cl). In contrast, reactions with Me4-n SiX n (X = Cl, n = 1-3; X = I, n = 1) lead preferentially to transannular oxidative additions of a single Si-X bond over the two metal centres, yielding the complexes [(µ-dmpm)2{PtX}{Pt(SiMe4-n X n-1)}]. In CH2Cl2 [(µ-dmpm)2{PtCl}{Pt(SiCl3)}] undergoes rearrangement to the silylene-bridged [(µ-dmpm)2Pt2Cl2(µ-SiCl2)], while in CH2Br2 oxidation of the platinum centres to Pt(ii), Cl-Br exchange, and the insertion of a CH2Br2-derived methylene unit into the Pt-Si bond are observed. Quantum-chemical calculations provide insights into the differences in reactivity between the halomethanes and -silanes.
More Related Videos
Related Concept Videos
Preparation and Reactions of Sulfides
Electrophilic Addition to Alkynes: Halogenation
Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
Multiple Halogenation of Methyl Ketones: Haloform Reaction
Alkyl Halides
Alkyl halides are halogen-substituted alkanes wherein one or more hydrogen atoms of an alkane is replaced by a halogen atom such as fluorine, chlorine, bromine, or iodine. The carbon atom in an alkyl halide is bonded to the halogen atom, which is sp3-hybridized and exhibits a tetrahedral shape.
Unlike alkyl halides, compounds in which a halogen atom is bonded to an sp2 -hybridized carbon atom of a carbon-carbon double bond (C=C) are called vinyl halides. Whereas aryl...
Formation of Halohydrin from Alkenes
Diazonium Group Substitution with Halogens and Cyanide: Sandmeyer and Schiemann Reactions

![The Synthesis of [Sn10SiSiMe334]2- Using a Metastable SnI Halide Solution Synthesized via a Co-condensation Technique](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F54498.jpg&w=3840&q=50)