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Synthesis, Structures, and Reactivity of Single and Double Cyclometalated Complexes Formed by Reactions of [Cp*MCl₂]₂ (M = Ir and Rh) with Dinaphthyl Phosphines.

ABSTRACT: Reactions of two dinaphthyl phosphines with [Cp*IrCl₂]₂ have been carried out. In the case of di(?-naphthyl)phenylphosphine (1a), a simple P-coordinated neutral adduct 2a is obtained. However, tert-butyldi(?-naphthyl)phenylphosphine (1b) is cyclometalated to form [Cp*IrCl(P^C)] (3b). Complexes 2a and 3a undergo further cyclometalation to give the corresponding double cyclometalated complexes [Cp*Ir(C^P^C)] (4a,b) upon heating. In the presence of sodium acetate, reactions of 1a,b with [Cp*IrCl₂]₂ directly afford the final double cyclometalated complexes (4a,b). In the absence of acetate, [Cp*RhCl₂]₂ shows no reaction with 1a,b, whereas with acetate the reactions form the corresponding single cyclometalated complexes [Cp*RhCl(P^C)] (5a,b), which react with ^t BuOK to form the corresponding rhodium hydride complexes (6a,b). Treatment of 4a with CuCl₂ or I₂ leads to opening of two Ir-C ? bonds to yield the corresponding P-coordinated iridium dihalide (7 or 8) by means of an intramolecular C-C coupling reaction. A new chiral phosphine (11) is formed by the ligand-exchange reaction of 8 with PMe₃. Reactions of the single cycloiridated complex 3b with terminal aromatic alkynes result in the corresponding five- and six-membered doubly cycloiridated complex 12 and/or ?²-alkene coordinated complexes 13-15; the latter discloses that the electronic effect of terminal alkynes affects the regioselectivity. While the single cyclorhodated complex 5b reacts with terminal aromatic alkynes to form the corresponding six-membered cyclometalated complexes 16a-c by vinylidene rearrangement/1,1-insertion. Plausible pathways for formation of insertion products 13-16 were proposed. Molecular structures of twelve new complexes were determined by X-ray diffraction.

SUBMITTER: Zhang S

PROVIDER: S-EPMC6641399 | biostudies-literature | 2018 Apr

REPOSITORIES: biostudies-literature

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Synthesis, Structures, and Reactivity of Single and Double Cyclometalated Complexes Formed by Reactions of [Cp*MCl2]2 (M = Ir and Rh) with Dinaphthyl Phosphines.

Zhang Shaowei S Chu Xiaodan X Li Tongyu T Wang Zhuo Z Zhu Bolin B

ACS omega 20180425 4

Reactions of two dinaphthyl phosphines with [Cp*IrCl2]2 have been carried out. In the case of di(α-naphthyl)phenylphosphine (1a), a simple P-coordinated neutral adduct 2a is obtained. However, tert-butyldi(α-naphthyl)phenylphosphine (1b) is cyclometalated to form [Cp*IrCl(P^C)] (3b). Complexes 2a and 3a undergo further cyclometalation to give the corresponding double cyclometalated complexes [Cp*Ir(C^P^C)] (4a,b ...[more]

PMID: 31458676

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Project description:We have combined results from several spectroscopic techniques to investigate the aerobic reactions of Rh2(AcO)4 (AcO- = CH3COO-) with l-cysteine (H2Cys) and its derivatives d-penicillamine (3,3'-dimethylcysteine, H2Pen), with steric hindrance at the thiol group, and N-acetyl-l-cysteine (H2NAC), with its amino group blocked. Previous investigations have shown that antitumor active dirhodium(II) carboxylates may irreversibly inhibit enzymes containing a thiol group at or near their active sites. Also, cysteine, the only thiol-containing proteinogenic amino acid, interacts in vivo with this class of antitumor compounds, but structural information on the products of such reactions is lacking. In the present study, the reactions of Rh2(AcO)4 and H2L were carried out in aqueous solutions at the pH of mixing (acidic) and at physiological pH, using the different mole ratios 1:2, 1:4, and 1:6, which resulted in the same products in increasing yields. Electrospray ionization mass spectrometry (ESI-MS) indicates formation of dimeric [RhIII 2Pen4]2- or oligomeric {RhIII 2L4} n (L = Cys, NAC) complexes with bridging thiolate groups. Analyses of Rh K edge extended X-ray absorption fine structure (EXAFS) data reveal 3-4 Rh-S and 2-3 Rh-(N/O) bonds around six-coordinated Rh(III) ions at mean distances of 2.33 ± 0.02 and 2.09 ± 0.02 Å, respectively. In the N-acetyl-l-cysteine compound, the RhIII···RhIII distance 3.10 ± 0.02 Å obtained from the EXAFS spectrum supports trithiolate bridges between the Rh(III) ions, as was also found when using glutathione as ligand. In the cysteine and penicillamine complexes, double thiolate bridges join the Rh(III) ions, with the nonbridging Cys2- and Pen2- ligands in tridentate chelating (S,N,O) mode, which is consistent with the ΔδC = 7.3-8.4 ppm shift of the COO- signal in their carbon-13 cross polarization magic angle spinning (CPMAS) NMR spectra. For the penicillamine complex, the 2475.6 eV peak in its S K edge X-ray absorption near edge structure (XANES) spectrum shows partial oxidation, probably caused by peroxide generated from reduction of dissolved O2, of thiolato to sulfenato (S=O) groups, which were also identified by ESI-MS for all three {RhIII 2L4} n compounds.

Dataset Information

Synthesis, Structures, and Reactivity of Single and Double Cyclometalated Complexes Formed by Reactions of [Cp*MCl₂]₂ (M = Ir and Rh) with Dinaphthyl Phosphines.

Publications

Synthesis, Structures, and Reactivity of Single and Double Cyclometalated Complexes Formed by Reactions of [Cp*MCl<sub>2</sub>]<sub>2</sub> (M = Ir and Rh) with Dinaphthyl Phosphines.

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