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. 2022 Sep 5;13(38):11382-11387.
doi: 10.1039/d2sc04042e. eCollection 2022 Oct 5.

Synthesis, structure and reactivity of μ3-SnH capped trinuclear nickel cluster

Nicole A Torquato  1 , Joseph M Palasz  1 , Quentin C Bertrand  2 , Felix M Brunner  1 , Thomas Chan  1 , Milan Gembicky  1 , Anthony A Mrse  1 , Clifford P Kubiak  1
Affiliations

Synthesis, structure and reactivity of μ3-SnH capped trinuclear nickel cluster

Nicole A Torquato et al. Chem Sci. .

Abstract

Treatment of the trichlorotin-capped trinuclear nickel cluster, [Ni3(dppm)3(μ3-Cl)(μ3-SnCl3)], 1, with 4 eq. NaHB(Et)3 yields a μ3-SnH capped trinuclear nickel cluster, [Ni3(dppm)3(μ3-H)(μ3-SnH)], 2 [dppm = bis(diphenylphosphino)methane]. Single-crystal X-ray diffraction, nuclear magnetic resonance (NMR) spectroscopy, and computational studies together support that cluster 2 is a divalent tin hydride. Complex 2 displays a wide range of reactivity including oxidative addition of bromoethane across the Sn center. Addition of 1 eq. iodoethane to complex 2 releases H2 (g) and generates an ethyltin-capped nickel cluster with a μ3-iodide, [Ni3(dppm)3(μ3-I)(μ3-Sn(CH2CH3))], 4. Notably, insertion of alkynes into the Sn-H bond of 2 can be achieved via addition of 1 eq. 1-hexyne to generate the 1-hexen-2-yl-tin-capped nickel cluster, [Ni3(dppm)3(μ3H)(μ3-Sn(C6H11))], 5. Addition of H2 (g) to 5 regenerates the starting material, 2, and hexane. The formally 44-electron cluster 2 also displays significant redox chemistry with two reversible one-electron oxidations (E = -1.3 V, -0.8 V vs. Fc0/+) and one-electron reduction process (E = -2.7 V vs. Fc0/+) observed by cyclic voltammetry.

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Conflict of interest statement

There are no conflicts to declare.

Figures

Scheme 1
Scheme 1. Synthesis of [Ni3(dppm)3(μ3-H)(μ3-SnH)], 2.
Fig. 1
Fig. 1. Solid-state structure of 2 as determined by single-crystal X-ray diffraction. Thermal ellipsoids were set at the 50% probability level. A diethyl ether molecule and carbon bound hydrogens were omitted for clarity. The hydride attached to Sn was not precisely located.
Fig. 2
Fig. 2. Computed molecular orbitals of 2, utilizing a B3LYP basis set and LANL2DZ functional showing the two highest energy occupied orbitals (HOMO−1 and HOMO) and the lowest energy unoccupied orbital (LUMO).
Scheme 2
Scheme 2. Synthesis of 3 and 4.
Fig. 3
Fig. 3. Solid-state structure of 3, 4 and 5 as determined by single-crystal X-ray diffraction. Thermal ellipsoids were set at the 50% probability level. A solvent molecule and carbon bound hydrogens were omitted for clarity. The hydride attached to tin was not precisely located in complex 3. Carbons atoms on bis(diphenylphosphino)methane ligands are colored white, while those on Sn are colored grey.
Scheme 3
Scheme 3. Synthesis of [Ni3(dppm)3(μ3-H)(μ3-Sn)(C6H11)], 5, and hydrogenation to [Ni3(dppm)3(μ3-H)(μ3-SnH)], 2.
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