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Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium.

ABSTRACT: The reversible reaction of H₂ with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H₂ and yields a spectroscopically detectable phosphenium-stabilized (σ-H₂)-complex, readily showing exchange with gaseous H₂ and D₂. Further reaction of this complex affords a phosphine-functionalized metal hydride, representing a unique example of reversible H₂ cleavage across a 3d M[double bond, length as m-dash]P bond. The same species is also accessible via stepwise H⁺/H^- transfer to the bis-phosphenium complex, and releases H₂ upon heating or irradiation. Dihydrogen transfer from the H₂-complex to styrene is exploited to demonstrate the first example of promoting hydrogenation with a phosphenium complex.

SUBMITTER: Birchall N

PROVIDER: S-EPMC8161683 | biostudies-literature | 2020 Aug

REPOSITORIES: biostudies-literature

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Reversible cooperative dihydrogen binding and transfer with a bis-phosphenium complex of chromium.

Birchall Nicholas N Feil Christoph M CM Gediga Michael M Nieger Martin M Gudat Dietrich D

Chemical science 20200821 35

The reversible reaction of H2 with a bis-phosphenium complex of chromium provides a rare example of 3d transition metal/phosphenium cooperativity. Photolysis induces the activation of H2 and yields a spectroscopically detectable phosphenium-stabilized (σ-H2)-complex, readily showing exchange with gaseous H2 and D2. Further reaction of this complex affords a phosphine-functionalized metal hydride, representing a unique example of reversible H ...[more]

PMID: 34094222

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