Cooperative reactivity of halomethanes and -silanes at an A-frame complex: transannular addition versus bridging tetrylenes

Max Passargus; Celine Nieuwland; Merle Arrowsmith; F. Matthias Bickelhaupt; Holger Braunschweig

doi:10.1039/d6sc00337k

Cooperative reactivity of halomethanes and -silanes at an A-frame complex: transannular addition versus bridging tetrylenes

Max Passargus
, Celine Nieuwland
, Merle Arrowsmith
, F. Matthias Bickelhaupt^*
, Holger Braunschweig^*

^*Corresponding author for this work

Research output: Contribution to Journal › Article › Academic › peer-review

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 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 H, Cl). In contrast, reactions with Me_4−nSiX_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(SiMe_4−nX_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.

Original language	English
Pages (from-to)	10547-10558
Number of pages	12
Journal	Chemical Science
Volume	17
Issue number	21
Early online date	15 Apr 2026
DOIs	https://doi.org/10.1039/d6sc00337k
Publication status	Published - 3 Jun 2026

Bibliographical note

Publisher Copyright:
This journal is © The Royal Society of Chemistry, 2026

Funding

The authors thank Mr Christoph Maler for mass-spectroscopic and Dr Rüdiger Bertermann for NMR-spectroscopic analyses. Financial support from the Julius-Maximilians-Universität Würzburg, as well as funding from the Deutsche Forschungsgemeinschaft (DFG project number 466754611) is gratefully acknowledged. C. N. and F. M. B. thank the Dutch Research Council (NWO) for financial support and SURF Cooperative and VU ADA for the computational resources.

Funders	Funder number
Julius-Maximilians-Universität Würzburg
Nederlandse Organisatie voor Wetenschappelijk Onderzoek
SURF
Deutsche Forschungsgemeinschaft	466754611

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title = "Cooperative reactivity of halomethanes and -silanes at an A-frame complex: transannular addition versus bridging tetrylenes",

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 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 H, Cl). In contrast, reactions with Me4−nSiXn (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−nXn−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.",

author = "Max Passargus and Celine Nieuwland and Merle Arrowsmith and Bickelhaupt, \{F. Matthias\} and Holger Braunschweig",

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T1 - Cooperative reactivity of halomethanes and -silanes at an A-frame complex: transannular addition versus bridging tetrylenes

AU - Passargus, Max

AU - Nieuwland, Celine

AU - Arrowsmith, Merle

AU - Bickelhaupt, F. Matthias

AU - Braunschweig, Holger

PY - 2026/6/3

Y1 - 2026/6/3

N2 - 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 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 H, Cl). In contrast, reactions with Me4−nSiXn (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−nXn−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.

AB - 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 00000000 00000000 00000000 00000000 11111111 00000000 11111111 00000000 00000000 00000000 H, Cl). In contrast, reactions with Me4−nSiXn (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−nXn−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.

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Cooperative reactivity of halomethanes and -silanes at an A-frame complex: transannular addition versus bridging tetrylenes

Abstract

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