Reversible carbon-boron bond formation at platinum centers through σ-BH complexes
Ríos, Pablo (Universidad de Sevilla)
Martín-de la Calle, Rocío (Universidad de Sevilla)
Vidossich, Pietro (Istituto Italiano di Tecnologia)
Fernández de Córdova Martín, Francisco José (Universidad de Sevilla)
Lledós, Agustí (Lledós i Falcó) (Universitat Autònoma de Barcelona. Departament de Química)
Conejero, Salvador (Universidad de Sevilla)

Data:	2020
Resum:	A reversible carbon-boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt() complex [Pt(I t Bu i Pr')(I t Bu i Pr)][BAr F ], 1, with tricoordinated boranes HBR. X-ray diffraction studies provided structural snapshots of the sequence of reactions involved in the process. At low temperature, we observed the initial formation of the unprecedented σ-BH complexes [Pt(HBR)(I t Bu i Pr')(I t Bu i Pr)][BAr F ], one of which has been isolated. From −15 to +10 °C, the σ-BH species undergo a carbon-boron coupling process leading to the platinum hydride derivative [Pt(H)(I t Bu i Pr-BR)(I t Bu i Pr)][BAr F ], 4. Surprisingly, these compounds are thermally unstable undergoing carbon-boron bond cleavage at room temperature that results in the 14-electron Pt() boryl species [Pt(BR)(I t Bu i Pr)][BAr F ], 2. This unusual reaction process has been corroborated by computational methods, which indicate that the carbon-boron coupling products 4 are formed under kinetic control whereas the platinum boryl species 2, arising from competitive C-H bond coupling, are thermodynamically more stable. These findings provide valuable information about the factors governing productive carbon-boron coupling reactions at transition metal centers. A reversible carbon-boron bond formation has been observed in the reaction of the coordinatively unsaturated, cyclometalated, Pt() complex [Pt(I t Bu i Pr')(I t Bu i Pr)][BAr F ], 1, with tricoordinated boranes HBR.
Ajuts:	Ministerio de Economía, Industria y Competitividad CTQ2016-76267-P Agencia Estatal de Investigación CTQ2017-87889-P Agencia Estatal de Investigación PID2019-109312GB-I00 Agencia Estatal de Investigación RED2018-102387-T
Drets:	Aquest document està subjecte a una llicència d'ús Creative Commons. Es permet la reproducció total o parcial, la distribució, la comunicació pública de l'obra i la creació d'obres derivades, sempre que no sigui amb finalitats comercials, i sempre que es reconegui l'autoria de l'obra original.
Llengua:	Anglès
Document:	Article ; recerca ; Versió publicada
Publicat a:	Chemical science, Vol. 12, Issue 5 (February 2021) , p. 1647-1655, ISSN 2041-6539

DOI: 10.1039/d0sc05522k
PMID: 34163924

10 p, 1.5 MB

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