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Computational study of bridge splitting, aryl halide oxidative addition to PtII, and reductive elimination from PtIV: route to pincer-PtII reagents with chemical and biological applications

Citation

Canty, AJ and Ariafard, A and van Koten, G, Computational study of bridge splitting, aryl halide oxidative addition to PtII, and reductive elimination from PtIV: route to pincer-PtII reagents with chemical and biological applications, Chemistry - A European Journal, 27, (62) pp. 15426-15433. ISSN 0947-6539 (2021) [Refereed Article]

DOI: doi:10.1002/chem.202102687

Abstract

Density functional theory computation indicates that bridge splitting of [PtIIR2(μ-SEt2)]2 proceeds by partial dissociation to form R2Pta(μ-SEt2)PtbR2(SEt2), followed by coordination of N-donor bromoarenes (L-Br) at Pta leading to release of PtbR2(SEt2), which reacts with a second molecule of L-Br, providing two molecules of PtR2(SEt2)(L-Br-N). For R=4-tolyl (Tol), L-Br=2,6-(pzCH2)2C6H3Br (pz=pyrazol-1-yl) and 2,6-(Me2NCH2)2C6H3Br, subsequent oxidative addition assisted by intramolecular N-donor coordination via PtIITol2(L-N,Br) and reductive elimination from PtIV intermediates gives mer-PtII(L-N,C,N)Br and Tol2. The strong σ-donor influence of Tol groups results in subtle differences in oxidative addition mechanisms when compared with related aryl halide oxidative addition to palladium(II) centres. For R=Me and L-Br=2,6-(pzCH2)2C6H3Br, a stable PtIV product, fac-PtIVMe2{2,6-(pzCH2)2C6H3-N,C,N)Br is predicted, as reported experimentally, acting as a model for undetected and unstable PtIVTol2{L-N,C,N}Br undergoing facile Tol2 reductive elimination. The mechanisms reported herein enable the synthesis of PtII pincer reagents with applications in materials and bio-organometallic chemistry.

Item Details

Item Type:Refereed Article
Keywords:aryl halides, bridge splitting, coordination modes, oxidative addition, pincer complexes, platinum, reductive elimination, organometallic mechanisms, density functional theory, DFT
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Transition metal chemistry
Objective Division:Expanding Knowledge
Objective Group:Expanding knowledge
Objective Field:Expanding knowledge in the physical sciences
UTAS Author:Canty, AJ (Professor Allan Canty)
UTAS Author:Ariafard, A (Associate Professor Alireza Ariafard)
ID Code:147690
Year Published:2021
Deposited By:Chemistry
Deposited On:2021-11-11
Last Modified:2021-12-13
Downloads:0

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