X-ray Crystal Structure and Homonuclear 31P-31P δ/J-Resolved NMR Spectroscopic Studies of [AgIr2(dimen)4(PPh3)2](PF6)3. Observation of a Statistical Mixture of “Head/Tail” Isomers

Andrew G. Sykes; Kent R. Mann

doi:10.1021/ic00347a023

X-ray Crystal Structure and Homonuclear ³¹P-³¹P δ/J-Resolved NMR Spectroscopic Studies of [AgIr₂(dimen)₄(PPh₃)₂](PF₆)3. Observation of a Statistical Mixture of “Head/Tail” Isomers

Andrew G. Sykes, Kent R. Mann

Chemistry (Twin Cities)

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Abstract

The reaction of [AgIr₂(dimen)₄(PF₆)₃(dimen = 1,8-diisocyanomenthane) with 2 equiv of triphenylphosphine results in the coordination of triphenylphosphine to the iridium atoms and forms a linear P-Ir-Ag-Ir-P unit. Recrystallization of the compound from acetone/hexane solutions afforded crystals of [AgIr₂(dimen)₄(PPh₃)₂](PF₆)₃(AgIr₂C₈₄H₁₀₂F_l8N₈P₅) that were the subject of X-ray structural characterization. The complex crystallizes in the monoclinic space group C2/c (No. 15) with Z = 4, a = 26.6 (1) Å, b = 4.67 (1) Å, c = 27.49 (6) Å, β = 117.8 (3)°, and V= 9496 Å³. At convergence, R = 0.108 and R_w= 0.123 for 1251observed reflections. The structure features an encapsulated two-coordinate Ag⁺ion with Ir⁺−Ag⁺distances of 2.642 (1) Å. The dimen ligands are disordered in a “head to tail” fashion about the iridium metal centers. Homonuclear ³¹P{¹H) δ/J-resolved NMR data for solutions of the [AgIr₂(dimen)₄(PPh₃)₂]³⁺cation show that a statistical distribution of four different geometrical isomers with different “head to tail” orientations of the dimen ligand occurs in the complex.

Original language	English (US)
Pages (from-to)	4449-4453
Number of pages	5
Journal	Inorganic chemistry
Volume	29
Issue number	22
DOIs	https://doi.org/10.1021/ic00347a023
State	Published - 1990

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@article{1795bfc6154244bda5731a002224bec5,

title = "X-ray Crystal Structure and Homonuclear 31P-31P δ/J-Resolved NMR Spectroscopic Studies of [AgIr2(dimen)4(PPh3)2](PF6)3. Observation of a Statistical Mixture of “Head/Tail” Isomers",

abstract = "The reaction of [AgIr2(dimen)4(PF6)3(dimen = 1,8-diisocyanomenthane) with 2 equiv of triphenylphosphine results in the coordination of triphenylphosphine to the iridium atoms and forms a linear P-Ir-Ag-Ir-P unit. Recrystallization of the compound from acetone/hexane solutions afforded crystals of [AgIr2(dimen)4(PPh3)2](PF6)3(AgIr2C84H102Fl8N8P5) that were the subject of X-ray structural characterization. The complex crystallizes in the monoclinic space group C2/c (No. 15) with Z = 4, a = 26.6 (1) {\AA}, b = 4.67 (1) {\AA}, c = 27.49 (6) {\AA}, β = 117.8 (3)°, and V= 9496 {\AA}3. At convergence, R = 0.108 and Rw= 0.123 for 1251observed reflections. The structure features an encapsulated two-coordinate Ag+ion with Ir+−Ag+distances of 2.642 (1) {\AA}. The dimen ligands are disordered in a “head to tail” fashion about the iridium metal centers. Homonuclear 31P{1H) δ/J-resolved NMR data for solutions of the [AgIr2(dimen)4(PPh3)2]3+cation show that a statistical distribution of four different geometrical isomers with different “head to tail” orientations of the dimen ligand occurs in the complex.",

author = "Sykes, {Andrew G.} and Mann, {Kent R.}",

year = "1990",

doi = "10.1021/ic00347a023",

language = "English (US)",

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pages = "4449--4453",

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publisher = "American Chemical Society",

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T1 - X-ray Crystal Structure and Homonuclear 31P-31P δ/J-Resolved NMR Spectroscopic Studies of [AgIr2(dimen)4(PPh3)2](PF6)3. Observation of a Statistical Mixture of “Head/Tail” Isomers

AU - Sykes, Andrew G.

AU - Mann, Kent R.

PY - 1990

Y1 - 1990

N2 - The reaction of [AgIr2(dimen)4(PF6)3(dimen = 1,8-diisocyanomenthane) with 2 equiv of triphenylphosphine results in the coordination of triphenylphosphine to the iridium atoms and forms a linear P-Ir-Ag-Ir-P unit. Recrystallization of the compound from acetone/hexane solutions afforded crystals of [AgIr2(dimen)4(PPh3)2](PF6)3(AgIr2C84H102Fl8N8P5) that were the subject of X-ray structural characterization. The complex crystallizes in the monoclinic space group C2/c (No. 15) with Z = 4, a = 26.6 (1) Å, b = 4.67 (1) Å, c = 27.49 (6) Å, β = 117.8 (3)°, and V= 9496 Å3. At convergence, R = 0.108 and Rw= 0.123 for 1251observed reflections. The structure features an encapsulated two-coordinate Ag+ion with Ir+−Ag+distances of 2.642 (1) Å. The dimen ligands are disordered in a “head to tail” fashion about the iridium metal centers. Homonuclear 31P{1H) δ/J-resolved NMR data for solutions of the [AgIr2(dimen)4(PPh3)2]3+cation show that a statistical distribution of four different geometrical isomers with different “head to tail” orientations of the dimen ligand occurs in the complex.

AB - The reaction of [AgIr2(dimen)4(PF6)3(dimen = 1,8-diisocyanomenthane) with 2 equiv of triphenylphosphine results in the coordination of triphenylphosphine to the iridium atoms and forms a linear P-Ir-Ag-Ir-P unit. Recrystallization of the compound from acetone/hexane solutions afforded crystals of [AgIr2(dimen)4(PPh3)2](PF6)3(AgIr2C84H102Fl8N8P5) that were the subject of X-ray structural characterization. The complex crystallizes in the monoclinic space group C2/c (No. 15) with Z = 4, a = 26.6 (1) Å, b = 4.67 (1) Å, c = 27.49 (6) Å, β = 117.8 (3)°, and V= 9496 Å3. At convergence, R = 0.108 and Rw= 0.123 for 1251observed reflections. The structure features an encapsulated two-coordinate Ag+ion with Ir+−Ag+distances of 2.642 (1) Å. The dimen ligands are disordered in a “head to tail” fashion about the iridium metal centers. Homonuclear 31P{1H) δ/J-resolved NMR data for solutions of the [AgIr2(dimen)4(PPh3)2]3+cation show that a statistical distribution of four different geometrical isomers with different “head to tail” orientations of the dimen ligand occurs in the complex.

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X-ray Crystal Structure and Homonuclear ³¹P-³¹P δ/J-Resolved NMR Spectroscopic Studies of [AgIr₂(dimen)₄(PPh₃)₂](PF₆)3. Observation of a Statistical Mixture of “Head/Tail” Isomers

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