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Synthesis and Characterization of a Terminal Iron(II)-PH₂ Complex and a Series of Iron(II)-PH₃ Complexes.

ABSTRACT: Reported is the reaction of a series of iron(II) bisphosphine complexes with PH₃ in the presence of NaBAr^F₄ [where BAr^F₄ = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate]. The iron(II) bisphosphine reagents bear two chlorides or a hydride and a chloride motif. We have isolated six different cationic terminal-bound PH₃ complexes and undertaken rigorous characterization by NMR spectroscopy, single crystal X-ray diffraction, and mass spectrometry, where the PH₃ often remains intact during the ionization process. Unusual bis- and tris-PH₃ complexes are among the compounds isolated. Changing the monophosphine from PH₃ to PMe₃ results in the formation of an unusual Fe₇ cluster, but with no PMe₃ being ligated. Finally, by using an iron(0) source, we have provided a rare example of a terminally bound iron-PH₂ complex.

SUBMITTER: Lau S

PROVIDER: S-EPMC11022175 | biostudies-literature | 2024 Apr

REPOSITORIES: biostudies-literature

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Synthesis and Characterization of a Terminal Iron(II)-PH2 Complex and a Series of Iron(II)-PH3 Complexes.

Lau Samantha S Mahon Mary F MF Webster Ruth L RL

Inorganic chemistry 20240402 15

Reported is the reaction of a series of iron(II) bisphosphine complexes with PH3 in the presence of NaBArF4 [where BArF4 = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate]. The iron(II) bisphosphine reagents bear two chlorides or a hydride and a chloride motif. We have isolated six different cationic terminal-bound PH3 complexes and undertaken rigorous characterization by NMR spectroscopy, single crystal X-ray diffraction, and mass ...[more]

PMID: 38563561

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Project description:Interest in O2-dependent aliphatic carbon-carbon (C-C) bond cleavage reactions of first row divalent metal diketonate complexes stems from the desire to further understand the reaction pathways of enzymes such as DKE1 and to extract information to develop applications in organic synthesis. A recent report of O2-dependent aliphatic C-C bond cleavage at ambient temperature in Ni(ii) diketonate complexes supported by a tridentate nitrogen donor ligand [(MBBP)Ni(PhC(O)CHC(O)Ph)]Cl (7-Cl; MBBP = 2,6-bis(1-methylbenzimidazol-2-yl)pyridine) in the presence of NEt3 spurred our interest in further examining the chemistry of such complexes. A series of new TERPY-ligated Ni(ii) diketonate complexes of the general formula [(TERPY)Ni(R2-1,3-diketonate)]ClO4 (1: R = CH3; 2: R = C(CH3)3; 3: R = Ph) was prepared under air and characterized using single crystal X-ray crystallography, elemental analysis, 1H NMR, ESI-MS, FTIR, and UV-vis. Analysis of the reaction mixtures in which these complexes were generated using 1H NMR and ESI-MS revealed the presence of both the desired diketonate complex and the bis-TERPY derivative [(TERPY)2Ni](ClO4)2 (4). Through selective crystallization 1-3 were isolated in analytically pure form. Analysis of reaction mixtures leading to the formation of the MBBP analogs [(MBBP)Ni(R2-1,3-diketonate)]X (X = ClO4: 5: R = CH3; 6: R = C(CH3)3; 7-ClO4: R = Ph; X = Cl: 7-Cl: R = Ph) using 1H NMR and ESI-MS revealed the presence of [(MBBP)2Ni](ClO4)2 (8). Analysis of aerobic acetonitrile solutions of analytically pure 1-3, 5 and 6 containing NEt3 and in some cases H2O using 1H NMR and UV-vis revealed evidence for the formation of additional bis-ligand complexes (4 and 8) but suggested no oxidative diketonate cleavage reactivity. Analysis of the organic products generated from 3, 7-ClO4 and 7-Cl revealed unaltered dibenzoylmethane. Our results therefore indicate that N3-ligated Ni(ii) complexes of unsubstituted diketonate ligands do not exhibit O2-dependent aliphatic C-C bond clevage at room temperature, including in the presence of NEt3 and/or H2O.

Dataset Information

Synthesis and Characterization of a Terminal Iron(II)-PH₂ Complex and a Series of Iron(II)-PH₃ Complexes.

Publications

Synthesis and Characterization of a Terminal Iron(II)-PH<sub>2</sub> Complex and a Series of Iron(II)-PH<sub>3</sub> Complexes.

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