Molecular Structure of Nickel Octamethylporphyrin—Rare Experimental Evidence of a Ruffling Effect in Gas Phase

The structure of a free nickel (II) octamethylporphyrin (NiOMP) molecule was determined for the first time through a combined gas-phase electron diffraction (GED) and mass spectrometry (MS) experiment, as well as through quantum chemical (QC) calculations. Density functional theory (DFT) calculations do not provide an unambiguous answer about the planarity or non-planar distortion of the NiOMP skeleton. The GED refinement in such cases is non-trivial. Several approaches to the inverse problem solution were used. The obtained results allow us to argue that the ruffling effect is manifested in the NiOMP molecule. The minimal critical distance between the central atom of the metal and nitrogen atoms of the coordination cavity that provokes ruffling distortion in metal porphyrins is about 1.96 Å

Crystal structure of μ-carbonyl-1:2κ2C:C-carbonyl-1κC-(1η5-cyclopentadienyl)iodido-2κI-[μ-2-(pyridin-2-yl)ethene-1,1-diyl-1κC1:2κ2N,C1]ironpalladium(Fe—Pd) benzene monosolvate

The reaction of Cp(CO)2FeI with 2-ethynylpyridine under Sonogashira conditions [5% PdCl2(PPh3)2, 10% CuI, THF–NEt3 (2:1)] afforded the title binuclear μ-pyridylvinylidene FePd complex (FePd1) as a benzene solvate, [FePd(C5H5)(C7H5N)I(CO)2]·C6H6, in a very low yield rather than the expected iron o-pyridylethynyl complex Cp(CO)2Fe—C[triple-bond]C-(2-C5H4N). The Fe and Pd atoms in FePd1 are bridged by carbonyl and pyridylvinylidene ligands, the pyridyl N atom being bonded to the palladium atom. The use of equimolar amounts of PdCl2 increases the yield of FePd1 to 12%. The reaction pathway leading to FePd1 is proposed

Chemistry of Vinylidene Complexes. XVII. The First μ-vinylidene Complex with the Re-Pt Bond: Synthesis, Spectroscopic Study and Structure of (η5-C5H5)(CO)2RePt(μ-C=CHPh)(PPh3)2

При взаимодействии Cp(CO)2Re=C=CHPh (1) с Pt(PPh3)4 получен μ-винилиденовый комплекс Cp(CO)2RePt(μ-C=CHPh)(PPh3)2 (2). Исследованы спектры ИК и ЯМР 1Н, 13С и 31P соединения 2. Кристаллическая и молекулярная структура комплекса 2 установлена методом РСА [длины связей Re—Pt 2.7360(3), Re—C1 2.083(5), Pt—C1 2.008(4), C1=C2 1.351(6) Å; валентные углы Pt-C1-C2 133.5(4), Re-C1-C2 141.6(4)°]. Обсуждается влияние природы атома металла M = Re, Mn на структурные и спектральные характеристики комплексов Cp(CO)2MPt(μ-C=CHPh)(PPh3)2.The interaction between Cp(CO)2Re=C=CHPh (1) and Pt(PPh3)4 afforded the μ-vinylidene complex Cp(CO)2RePt(μ-C=CHPh)(PPh3)2 (2). The IR and 1H, 13C and 31P NMR spectra of complex 2 were studied. Crystal and molecular structure of complex 2 has been determined by an X-ray single crystal analysis. The bond distances and angles are Re—Pt 2.7360(3), Re—C1 2.083(5), Pt—C1 2.008(4), C1=C2 1.351(6) Å; Pt-C1-C2 133.5(4), Re-C1-C2 141.6(4)°. The influence of the nature of the M = Re, Mn atoms on structural and spectroscopic characteristics of complexes Cp(CO)2MPt(μ-C=CHPh)-(PPh3)2 has been considered

Chemistry of Vinylidene Complexes. XVII. The First μ-vinylidene Complex with the Re-Pt Bond: Synthesis, Spectroscopic Study and Structure of (η5-C5H5)(CO)2RePt(μ-C=CHPh)(PPh3)2

При взаимодействии Cp(CO)2Re=C=CHPh (1) с Pt(PPh3)4 получен μ-винилиденовый комплекс Cp(CO)2RePt(μ-C=CHPh)(PPh3)2 (2). Исследованы спектры ИК и ЯМР 1Н, 13С и 31P соединения 2. Кристаллическая и молекулярная структура комплекса 2 установлена методом РСА [длины связей Re—Pt 2.7360(3), Re—C1 2.083(5), Pt—C1 2.008(4), C1=C2 1.351(6) Å; валентные углы Pt-C1-C2 133.5(4), Re-C1-C2 141.6(4)°]. Обсуждается влияние природы атома металла M = Re, Mn на структурные и спектральные характеристики комплексов Cp(CO)2MPt(μ-C=CHPh)(PPh3)2.The interaction between Cp(CO)2Re=C=CHPh (1) and Pt(PPh3)4 afforded the μ-vinylidene complex Cp(CO)2RePt(μ-C=CHPh)(PPh3)2 (2). The IR and 1H, 13C and 31P NMR spectra of complex 2 were studied. Crystal and molecular structure of complex 2 has been determined by an X-ray single crystal analysis. The bond distances and angles are Re—Pt 2.7360(3), Re—C1 2.083(5), Pt—C1 2.008(4), C1=C2 1.351(6) Å; Pt-C1-C2 133.5(4), Re-C1-C2 141.6(4)°. The influence of the nature of the M = Re, Mn atoms on structural and spectroscopic characteristics of complexes Cp(CO)2MPt(μ-C=CHPh)-(PPh3)2 has been considered