The Synthesis and Structure of the Two Hexafluorophosphate Salts {Cu[P(C7H7)3](CH3CN)2}PF6 and {Cu[P(C7H7)3]2}PF6 Containing the Ligand Tri(1-cyclohepta-2,4,6-trienyl)phosphane

Herberhold, Max; Akkus, Nilgün; Milius, Wolfgang

doi:10.1515/znb-2003-0607

Cited by 5 publications

(1 citation statement)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…27 Notably, coordination of the ligand alkene functions is absent, in contrast to Herberhold's closely related complex bearing the tropilidene P-alkene ligand shown in Chart 1. 28 Possible explanations for this difference are: (i) the π–π stacking interactions in 18 stabilize the complex more than a metal-alkene coordination would, 27 (ii) sterics of the dibenzazepine moiety is unfavorbale, (iii) rehybridization of the azepine N atom form sp 2 to sp 3 in ligand 9 to attain a favorable bite angle is energetically uphill, and (iv) the lower Lewis basicity of ligand 9 when compared to Herberhold's tropilidene ligand may not give sufficient electron density to copper for alkene coordination.…”

Section: Resultsmentioning

confidence: 99%

Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons

et al. 2023

View full text Add to dashboard Cite

show abstract

Section: Resultsmentioning

confidence: 99%

Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons

et al. 2023

View full text Add to dashboard Cite

show abstract

Tris(dibenzo[a,d]cycloheptenyl)phosphane: A Bulky Monodentate or Tetrapodal Ligand

Fischbach

Rüegger

2007

Eur J Inorg Chem

View full text Add to dashboard Cite

The tetradendate phosphane tris(5H‐dibenzo[a,d]cyclohepten‐5‐yl)phosphane (trop3P, 1) was synthesized from tris(trimethylsilyl)phosphane and 5‐chloro‐5H‐dibenzo[a,d]cycloheptene. Sulfurization of 1 with elemental sulfur led to trop3P=S. Complexes of 1 with AgI, AuI, RhI, IrI, and PdII were prepared. The structures of trop3P (1), trop3P=S (2), [AgCl(trop3P)] (3), [Au(trop3P)(MeCN)]PF6 (5), [RhCl(trop3P)] (6) and [Pd(trop3P)(H2O)](OTf)2 (9) were determined by X‐ray diffraction studies. In the coinage metal complexes, 1 serves as monodentate extremely bulky κ1‐phosphane ligand (cone angle ca. 250°). In the RhI, IrI, and PdII complexes, 1 acts as tetradendate ligand. CP MAS NMR spectroscopy shows that the span of the chemical shift tensor increases in 7, 6, and 9 in this order (Ω = 310 ppm, 410 ppm, 465 ppm) and contains two strongly deshielded components, which are responsible for the unusual high frequency isotropic shift of the 31P resonances. This property correlates inversely with the metal to olefin backbonding (M→C=Ctrop) and δ(31P) decreases with increasing M→C=Ctrop in the order 9 (δ = 260 ppm) > 7 (δ = 196 ppm) > 6 (δ = 135 ppm) > 3 (δ = –30.9 ppm). (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

show abstract

1:1 Adducts of Copper(I) and Silver(I) Halides with the Olefinic Phosphane Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane. Molecular Structures of CuX[P(C₇H₇)₃] (X = Cl, Br), AgCl[P(C₇H₇)₃] and {Cu(μ₃‐I)[P(C₇H₇)₃]}₄

Herberhold

Akkus

Milius

2003

Zeitschrift anorg allge chemie

View full text Add to dashboard Cite

A suspension of CuX (X ϭ Cl, Br) or AgCl in organic solvents (such as CH 2 Cl 2 ) reacts with P(C 7 H 7 ) 3 (1) in a molar ratio 1:1 to give the mononuclear adducts CuX[P(C 7 H 7 ) 3 ] (X ϭ Cl (2a), Br (2b)) and AgCl[P(C 7 H 7 ) 3 ] (3a) which crystallize as isotypic compounds in the orthorhombic space group Pnma (Z ϭ 4). In the crystal, two (of the three) cyclohepta-2,4,6-trienyl substituents are present in the boat conformation, thus establishing a loose longdistance interaction between the central double bond and the metal atom. A distorted pseudo-tetrahedral coordination sphere is assumed to exist around the metal atom, with large P-M-X angles of 165.49 (8)°(2a), 162.07(7)°(2b) and 168.54(3)°(3a), respectively. The tetrameric 1:1 adduct {Cu(µ 3 -I)[P(C 7 H 7 ) 3 ]} 4 (2c) which was obtained from CuI and 1 in boiling ethanol, has also been charac-1:1 Addukte von Kupfer(I)-und Silber(I)-Halogeniden mit dem Olefinischen Phosphan Tri(1-cyclohepta-2,4,6-trienyl)phosphan. Molkülstrukturen von CuX[P(C 7 H 7 ) 3 ] (X ‫؍‬ Cl, Br), AgCl[P(C 7 H 7 ) 3 ] und {Cu(µ 3 -I)[P(C 7 H 7 ) 3 ]} 4Inhaltsübersicht. Eine Suspension von CuX (X ϭ Cl, Br) oder AgCl in organischen Solvenzien (wie CH 2 Cl 2 ) reagiert mit P(C 7 H 7 ) 3 (1) im Molverhältnis 1:1 unter Bildung der einkernigen Addukte CuX[P(C 7 H 7 ) 3 ] (X ϭ Cl (2a), Br (2b)) und AgCl[P(C 7 H 7 ) 3 ] (3a), die als isotype Verbindungen in der orthorhombischen Raumgruppe Pnma kristallisieren (Z ϭ 4). Im Kristall liegen zwei (der drei) Cyclohepta-2,4,6-trienyl-Substituenten in der Wannenform vor und bilden so eine lockere Wechselwirkung zwischen der zentralen Doppelbindung und dem Metall-Atom aus. Es wird eine verzerrt pseudo-tetraedrische Koordinationssphäre um das Metall-Atom angenommen, in der große P-M-X Winkel von 165.49(8)°( 2a), 162.07(7)°(2b) bzw. 168.54(3)°(3a) auftreten. Das tetramere terized by X-ray crystallography (monoclinic space group P2(1)/n, Z ϭ 4); it contains all 12 cyclohepta-2,4,6-trienyl substituents in the chair conformation. The NMR spectra ( 1 H, 13 C, 31 P) of the new complexes 2a-c and 3a indicate non-rigid structures in solution. At room temperature, the 31 P NMR signal of 3a appears as a doublet with an averaged coupling constant, 1 J(Ag,P), of 700.1 Hz, whereas at Ϫ45°C the two expected doublets are clearly discernible with coupling constants 1 J( 107 Ag, 31 P) ϭ 671.0 Hz and 1 J( 109 Ag, 31 P) ϭ 774.4 Hz, respectively.

show abstract

The Synthesis and Structure of the Two Hexafluorophosphate Salts {Cu[P(C₇H₇)₃](CH₃CN)₂}PF₆ and {Cu[P(C₇H₇)₃]₂}PF₆ Containing the Ligand Tri(1-cyclohepta-2,4,6-trienyl)phosphane

Cited by 5 publications

References 0 publications

Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons

Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons

Tris(dibenzo[a,d]cycloheptenyl)phosphane: A Bulky Monodentate or Tetrapodal Ligand

1:1 Adducts of Copper(I) and Silver(I) Halides with the Olefinic Phosphane Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane. Molecular Structures of CuX[P(C₇H₇)₃] (X = Cl, Br), AgCl[P(C₇H₇)₃] and {Cu(μ₃‐I)[P(C₇H₇)₃]}₄

Contact Info

Product

Resources

About

The Synthesis and Structure of the Two Hexafluorophosphate Salts {Cu[P(C7H7)3](CH3CN)2}PF6 and {Cu[P(C7H7)3]2}PF6 Containing the Ligand Tri(1-cyclohepta-2,4,6-trienyl)phosphane

Cited by 5 publications

References 0 publications

Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons

Developing bulky P-alkene ligands: stabilization of copper complexes with 14 valence electrons

Tris(dibenzo[a,d]cycloheptenyl)phosphane: A Bulky Monodentate or Tetrapodal Ligand

1:1 Adducts of Copper(I) and Silver(I) Halides with the Olefinic Phosphane Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane. Molecular Structures of CuX[P(C7H7)3] (X = Cl, Br), AgCl[P(C7H7)3] and {Cu(μ3‐I)[P(C7H7)3]}4

Contact Info

Product

Resources

About

The Synthesis and Structure of the Two Hexafluorophosphate Salts {Cu[P(C₇H₇)₃](CH₃CN)₂}PF₆ and {Cu[P(C₇H₇)₃]₂}PF₆ Containing the Ligand Tri(1-cyclohepta-2,4,6-trienyl)phosphane

1:1 Adducts of Copper(I) and Silver(I) Halides with the Olefinic Phosphane Tri(1‐cyclohepta‐2, 4, 6‐trienyl)phosphane. Molecular Structures of CuX[P(C₇H₇)₃] (X = Cl, Br), AgCl[P(C₇H₇)₃] and {Cu(μ₃‐I)[P(C₇H₇)₃]}₄