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Updated: Jun 11, 2025

Line Shape Analysis of Dynamic NMR Spectra for Characterizing Coordination Sphere Rearrangements at a Chiral Rhenium Polyhydride Complex
Published on: July 27, 2022
Unsymmetric Ir2 and RhIr Dinuclear Complexes Supported by a Linear Tetraphosphine meso-dpmppp, Showing High
Takayuki Nakajima1, Momoko Kotani1, Yuki Maeda1
1Department of Chemistry, Faculty of Science, Nara Women's University, Kitauoya-nishi-machi, Nara 630-8506, Japan.
Abstract:
Unsymmetric dinuclear Ir(I) complexes, [Ir2Cl2(L)(meso-dpmppp)] (L = XylNC (1aIr), BuNC (1bIr), CO (1cIr)), were synthesized using meso-Ph2PCH2P(Ph)(CH2)3P(Ph)CH2PPh2 (meso-dpmppp), which supports cis-P,P (M1) and trans-P,P (M2) metal sites, and exhibited high reactivity for O2, H2, and HCl. The IrRh heterodinuclear complexes, [M1M2Cl2(L)(meso-dpmppp)] (1MM) (M1M2 = IrRh, RhIr; L = XylNC, CO ( = a, c)), were also synthesized and used together with the Rh2 complexes (1a,cRh) to elucidate the role of each metal site. For the reactions of O2, 1aIr and 1aRhIr showed higher reactivity than those of 1aIrRh and 1aRh, giving η2-peroxide complexes [{M1Cl2}{M2(η2-O2)(XylNC)}(meso-dpmppp)] (2aIr, 2aRhIr), from which O2 would not dissociate. All the CO complexes 1cMM (M1, M2 = Ir or Rh) showed no reactivity for O2. In the reactions with H2, 1aIr reacted with H2 to give the dihydride complex, [{IrCl2}{Ir(H)2L}(meso-dpmppp)] (11aIr) and the tetrahydride complex, [{Ir(H)Cl2}(μ-H){Ir(H)2L}(meso-dpmppp)] (12aIr), while 1aRhIr gave the dihydride complex, and 1aIrRh and 1aRh gave no hydride complexes. Reactions of 1a,cMM with HCl afforded the dihydride complexes, [{IrCl3}(μ-H){Ir(H)Cl(XylNC)}(meso-dpmppp)] (14aIr), [{Ir(H)Cl2}(μ-H){M2Cl2(L)}(meso-dpmppp)] (M2 = Ir, L = CO (15cIr); M2 = Rh, L = XylNC (15aIrRh), CO (15cIrRh)), and [{Rh(H)Cl2}(μ-Cl){Ir(H)Cl(XylNC)}(meso-dpmppp)] (18aRhIr), the structures varying depending on M1 and M2 as well as L.
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