Dinitrosyl Iron Complexes (DNICs) Bearing O-Bound Nitrito Ligand: Reversible Transformation between the Six-Coordinate {Fe(NO)₂}⁹ [(1-MeIm)₂(η²-ONO)Fe(NO)₂] (<i>g</i> = 2.013) and Four-Coordinate {Fe(NO)₂}⁹ [(1-MeIm)(ONO)Fe(NO)₂] (<i>g</i> = 2.03)

Dinitrosyl Iron Complexes (DNICs) Bearing O-Bound Nitrito Ligand: Reversible Transformation between the Six-Coordinate {Fe(NO)2}9 [(1-MeIm)2(η2-ONO)Fe(NO)2] (g = 2.013) and Four-Coordinate {Fe(NO)2}9 [(1-MeIm)(ONO)Fe(NO)2] (g = 2.03

Dinitrosyl Iron Complexes (DNICs) Bearing O-Bound Nitrito Ligand: Reversible Transformation between the Six-Coordinate {Fe(NO)₂}⁹ [(1-MeIm)₂(η²-ONO)Fe(NO)₂] (<i>g</i> = 2.013) and Four-Coordinate {Fe(NO)₂}⁹ [(1-MeIm)(ONO)Fe(NO)₂] (<i>g</i> = 2.03)

Dinitrosyl Iron Complexes (DNICs) Bearing O-Bound Nitrito Ligand: Reversible Transformation between the Six-Coordinate {Fe(NO)2}9 [(1-MeIm)2(η2-ONO)Fe(NO)2] (g = 2.013) and Four-Coordinate {Fe(NO)2}9 [(1-MeIm)(ONO)Fe(NO)2] (g = 2.03

Dinitrosyl Iron Complexes (DNICs) Bearing O-Bound Nitrito Ligand: Reversible Transformation between the Six-Coordinate {Fe(NO)₂}⁹ [(1-MeIm)₂(η²-ONO)Fe(NO)₂] (<i>g</i> = 2.013) and Four-Coordinate {Fe(NO)₂}⁹ [(1-MeIm)(ONO)Fe(NO)₂] (<i>g</i> = 2.03)

Dinitrosyl Iron Complexes (DNICs) Bearing O-Bound Nitrito Ligand: Reversible Transformation between the Six-Coordinate {Fe(NO)2}9 [(1-MeIm)2(η2-ONO)Fe(NO)2] (g = 2.013) and Four-Coordinate {Fe(NO)2}9 [(1-MeIm)(ONO)Fe(NO)2] (g = 2.03

Directed Assembly of Chiral Oxidovanadium(V) Methoxides into <i>C</i>₄-Symmetric Metal(I) Vanadate-Centered Quadruplexes: Synergistic K⁺- and Ag⁺-specific Transport

Directed Assembly of Chiral Oxidovanadium(V) Methoxides into C4-Symmetric Metal(I) Vanadate-Centered Quadruplexes: Synergistic K+- and Ag+-specific Transpor

Directed Assembly of Chiral Oxidovanadium(V) Methoxides into <i>C</i>₄-Symmetric Metal(I) Vanadate-Centered Quadruplexes: Synergistic K⁺- and Ag⁺-specific Transport

Directed Assembly of Chiral Oxidovanadium(V) Methoxides into C4-Symmetric Metal(I) Vanadate-Centered Quadruplexes: Synergistic K+- and Ag+-specific Transpor

Dinitrosyl Iron Complexes (DNICs) Bearing O-Bound Nitrito Ligand: Reversible Transformation between the Six-Coordinate {Fe(NO)₂}⁹ [(1-MeIm)₂(η²-ONO)Fe(NO)₂] (<i>g</i> = 2.013) and Four-Coordinate {Fe(NO)₂}⁹ [(1-MeIm)(ONO)Fe(NO)₂] (<i>g</i> = 2.03)

Dinitrosyl Iron Complexes (DNICs) Bearing O-Bound Nitrito Ligand: Reversible Transformation between the Six-Coordinate {Fe(NO)2}9 [(1-MeIm)2(η2-ONO)Fe(NO)2] (g = 2.013) and Four-Coordinate {Fe(NO)2}9 [(1-MeIm)(ONO)Fe(NO)2] (g = 2.03

New Members of a Class of Dinitrosyliron Complexes (DNICs): Interconversion and Spectroscopic Discrimination of the Anionic {Fe(NO)₂}⁹ [(NO)₂Fe(C₃H₃N₂)₂]⁻ and [(NO)₂Fe(C₃H₃N₂)(SR)]⁻ (C₃H₃N₂ = Deprotonated Imidazole; R = <i>^t</i>Bu, Et, Ph)

The anionic {Fe(NO)2}9 DNIC [(NO)2Fe(C3H3N2)2]− (2) (C3H3N2 = deprotonated imidazole) containing the deprotonated imidazole-coordinated ligands and DNICs [(NO)2Fe(C3H3N2)(SR)]− (R = tBu (3), Et (4), Ph (5)) containing the mixed deprotonated imidazole−thiolate coordinated ligands, respectively, were synthesized by thiol protonation or thiolate(s) ligand-exchange reaction. The anionic {Fe(NO)2}9 DNICs 2−5 were characterized by IR, UV–vis, EPR, and single-crystal X-ray diffraction. The facile transformation among the anionic {Fe(NO)2}9 DNICs 2−5 and [(NO)2Fe(StBu)2]−/[(NO)2Fe(SEt)2]−/[(NO)2Fe(SPh)2]− was demonstrated in this systematic study. Of importance, the distinct electron-donating ability of thiolates serve to regulate the stability of the anionic {Fe(NO)2}9 DNICs and the ligand-substitution reactions of DNICs. At 298 K, DNIC 2 exhibits the nine-line EPR signal with g = 2.027 (aN(NO) = 2.20 and aN(Im-H) = 3.15 G; Im-H = deprotonated imidazole) and DNIC 3 displays the nine-line signals with g = 2.027 (aN(NO) = 2.35 and aN(Im-H) = 4.10 G). Interestingly, the EPR spectrum of complex 4 exhibits a well-resolved 11-line pattern with g = 2.027 (aN(NO) = 2.50, aN(Im-H) = 4.10 G, and aH = 1.55 G) at 298 K. The EPR spectra (the pattern of hyperfine splitting) in combination with IR νNO spectra (ΔνNO = the separation of NO stretching frequencies, ΔνNO = ∼62 cm−1 for 2 vs ∼50 cm−1 for 3−5 vs ∼43 cm−1 for [(NO)2Fe(StBu)2]−/[(NO)2Fe(SEt)2]−/[(NO)2Fe(SPh)2]−) may serve as an efficient tool for the discrimination of the existence of the anionic {Fe(NO)2}9 DNICs containing the different ligations [N,N]/[N,S]/[S,S]

New Members of a Class of Dinitrosyliron Complexes (DNICs): Interconversion and Spectroscopic Discrimination of the Anionic {Fe(NO)₂}⁹ [(NO)₂Fe(C₃H₃N₂)₂]⁻ and [(NO)₂Fe(C₃H₃N₂)(SR)]⁻ (C₃H₃N₂ = Deprotonated Imidazole; R = <i>^t</i>Bu, Et, Ph)

The anionic {Fe(NO)2}9 DNIC [(NO)2Fe(C3H3N2)2]− (2) (C3H3N2 = deprotonated imidazole) containing the deprotonated imidazole-coordinated ligands and DNICs [(NO)2Fe(C3H3N2)(SR)]− (R = tBu (3), Et (4), Ph (5)) containing the mixed deprotonated imidazole−thiolate coordinated ligands, respectively, were synthesized by thiol protonation or thiolate(s) ligand-exchange reaction. The anionic {Fe(NO)2}9 DNICs 2−5 were characterized by IR, UV–vis, EPR, and single-crystal X-ray diffraction. The facile transformation among the anionic {Fe(NO)2}9 DNICs 2−5 and [(NO)2Fe(StBu)2]−/[(NO)2Fe(SEt)2]−/[(NO)2Fe(SPh)2]− was demonstrated in this systematic study. Of importance, the distinct electron-donating ability of thiolates serve to regulate the stability of the anionic {Fe(NO)2}9 DNICs and the ligand-substitution reactions of DNICs. At 298 K, DNIC 2 exhibits the nine-line EPR signal with g = 2.027 (aN(NO) = 2.20 and aN(Im-H) = 3.15 G; Im-H = deprotonated imidazole) and DNIC 3 displays the nine-line signals with g = 2.027 (aN(NO) = 2.35 and aN(Im-H) = 4.10 G). Interestingly, the EPR spectrum of complex 4 exhibits a well-resolved 11-line pattern with g = 2.027 (aN(NO) = 2.50, aN(Im-H) = 4.10 G, and aH = 1.55 G) at 298 K. The EPR spectra (the pattern of hyperfine splitting) in combination with IR νNO spectra (ΔνNO = the separation of NO stretching frequencies, ΔνNO = ∼62 cm−1 for 2 vs ∼50 cm−1 for 3−5 vs ∼43 cm−1 for [(NO)2Fe(StBu)2]−/[(NO)2Fe(SEt)2]−/[(NO)2Fe(SPh)2]−) may serve as an efficient tool for the discrimination of the existence of the anionic {Fe(NO)2}9 DNICs containing the different ligations [N,N]/[N,S]/[S,S]

Ambiphilic Nature of Dipyrrolylpyridine-Supported Divalent Germanium and Tin Compounds

We describe the synthesis and characterization of a series of divalent Ge and Sn compounds of the dianionic ligand L (2,6-bis­(3,5-diphenylpyrrolyl)­pyridine). Forcing base-stabilized divalent group 14 elements (E) into a planar geometry with a sterically constrained pincer-type L ligand is expected to produce LE species possessing ambiphilic properties, as suggested by theoretical calculations. The reactions of LH2 (the acid form of L) with 1 equiv of M­(HMDS)2 (HMDS = N­(SiMe3)2) yield the dimeric compounds (LE)2 (E = Sn (1) and E = Ge (3)) in benzene or toluene. The dimeric species 1 and 3 react with Lewis bases to yield monomeric LSn­(THF)2 (2) and LE­(dmap)2 (E = Sn (4), Ge (5); dmap = dimethylaminopyridine) and with the Lewis acidic W­(CO)5THF to form LSnW­(CO)5 (6). Finally, compounds 1 and 3 undergo insertion reactions with a Sn­(I) distannyne to give the triple-decker products 7 and 8

New Members of a Class of Dinitrosyliron Complexes (DNICs): Interconversion and Spectroscopic Discrimination of the Anionic {Fe(NO)₂}⁹ [(NO)₂Fe(C₃H₃N₂)₂]⁻ and [(NO)₂Fe(C₃H₃N₂)(SR)]⁻ (C₃H₃N₂ = Deprotonated Imidazole; R = <i>^t</i>Bu, Et, Ph)

The anionic {Fe(NO)2}9 DNIC [(NO)2Fe(C3H3N2)2]− (2) (C3H3N2 = deprotonated imidazole) containing the deprotonated imidazole-coordinated ligands and DNICs [(NO)2Fe(C3H3N2)(SR)]− (R = tBu (3), Et (4), Ph (5)) containing the mixed deprotonated imidazole−thiolate coordinated ligands, respectively, were synthesized by thiol protonation or thiolate(s) ligand-exchange reaction. The anionic {Fe(NO)2}9 DNICs 2−5 were characterized by IR, UV–vis, EPR, and single-crystal X-ray diffraction. The facile transformation among the anionic {Fe(NO)2}9 DNICs 2−5 and [(NO)2Fe(StBu)2]−/[(NO)2Fe(SEt)2]−/[(NO)2Fe(SPh)2]− was demonstrated in this systematic study. Of importance, the distinct electron-donating ability of thiolates serve to regulate the stability of the anionic {Fe(NO)2}9 DNICs and the ligand-substitution reactions of DNICs. At 298 K, DNIC 2 exhibits the nine-line EPR signal with g = 2.027 (aN(NO) = 2.20 and aN(Im-H) = 3.15 G; Im-H = deprotonated imidazole) and DNIC 3 displays the nine-line signals with g = 2.027 (aN(NO) = 2.35 and aN(Im-H) = 4.10 G). Interestingly, the EPR spectrum of complex 4 exhibits a well-resolved 11-line pattern with g = 2.027 (aN(NO) = 2.50, aN(Im-H) = 4.10 G, and aH = 1.55 G) at 298 K. The EPR spectra (the pattern of hyperfine splitting) in combination with IR νNO spectra (ΔνNO = the separation of NO stretching frequencies, ΔνNO = ∼62 cm−1 for 2 vs ∼50 cm−1 for 3−5 vs ∼43 cm−1 for [(NO)2Fe(StBu)2]−/[(NO)2Fe(SEt)2]−/[(NO)2Fe(SPh)2]−) may serve as an efficient tool for the discrimination of the existence of the anionic {Fe(NO)2}9 DNICs containing the different ligations [N,N]/[N,S]/[S,S]