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 (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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