Tetranuclear Rh4 chains supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) capturing H2 to afford Rh4H3 hydride complexes

Neutral [X‐{Ir2}‐{Ir2}‐X] (X = Cl, Br, SCN, I) and dicationic [L‐{Ir2}‐{Ir2}‐L]2+ (L = MeCN, Me2CO) tetrametallic iridium chains made by connecting two dinuclear {Ir2} units ({Ir2} = [Ir2(μ‐OPy)2(CO)4], OPy = 2‐pyridonate) by an iridium‐iridium bond are described. The complexes exhibit fractional averaged oxidation states of +1.5 and electronic delocalization along the metallic chain. While the axial ligands do not significantly affect the metal‐metal bond lengths, the metallic chain has a significant impact on the iridium‐L/X bond distances. The complexes show free rotation around the unsupported iridium‐iridium bond in solution, with a low‐energy transition state for the chloride chain. The absorption spectra of these complexes show characteristic bands at 438‐504 nm, which can be fine‐tuned by varying the terminal capping ligands.

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Mixed‐Valence Tetrametallic Iridium Chains

Rı́o

Villarroya

López

et al. 2023

Chemistry A European J

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Fine tunable metal assemblies constrained by multidentate phosphine ligands

Tanase

Nakamae

Ura

et al. 2022

Coordination Chemistry Reviews

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Tetranuclear Rh4 chains supported by meso-Ph2PCH2P(Ph)CH2P(Ph)CH2PPh2 (meso-dpmppm) capturing H2 to afford Rh4H3 hydride complexes

Cited by 2 publications

References 27 publications

Mixed‐Valence Tetrametallic Iridium Chains

Mixed‐Valence Tetrametallic Iridium Chains

Fine tunable metal assemblies constrained by multidentate phosphine ligands

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