Coordination Polymers Based on [Cp*Fe(η⁵‐P₅)]: Solid‐State Structure and MAS NMR Studies

Abstract

Slow diffusion reactions of the pentaphosphaferrocene [Cp*Fe(η(5)-P(5))] (Cp*=η(5)-C(5)Me(5) (1)) with CuX (X=Cl, Br, I) in different stoichiometric ratios and solvent mixtures result in the formation of one- and two-dimensional polymeric compounds 2-6 with molecular formula [{Cu(μ-X)}{Cp*Fe(μ(3),η(5):η(1):η(1)-P(5))}](n) (X=Cl (2a), I (2'c)), [{Cu(μ-I)}{Cp*Fe(μ(3),η(5):η(1):η(1)-P(5))}](n) (3), [{CuX}{Cp*Fe(μ(4),η(5):η(1):η(1):η(1)-P(5))}](n) (X=Cl (4a), Br (4b), I (4c), Br (4'b), I (4'c)), [{Cu(3)(μ-I)(2)(μ(3)-I)}{Cp*Fe(μ(5),η(5):η(1):η(1):η(1):η(1)-P(5))}](n) (5) and [{Cu(4)(μ-X)(4)(CH(3)CN)}{Cp*Fe(μ(7),η(5):η(2):η(1):η(1):η(1):η(1):η(1)-P(5))}](n) (X=Cl (6a), Br (6b)), respectively. The polymeric compounds have been characterised by single-crystal X-ray diffraction analyses and, for selected examples, by magic angle spinning (MAS) NMR spectroscopy. The solid-state structures demonstrate the versatile coordination modes of the cyclo-P(5) ligand of 1, extending from two to five coordinating phosphorus atoms in either σ or σ-and-π fashion. In compounds 2a, 2'c and 3, two phosphorus atoms of 1 coordinate to copper atoms in a 1,2 coordination mode (2a, 2'c) and an unprecedented 1,3 coordination mode (3) to form one-dimensional polymers. Compounds 4a-c, 4'b, 4'c and 5 represent two-dimensional coordination polymers. In compounds 4, three phosphorus atoms coordinate to copper atoms in a 1,2,4 coordination mode, whereas in 5 the cyclo-P(5) ligand binds in an unprecedented 1,2,3,4 coordination mode. The crystal structures of 6a,b display a tilted tube, in which all P atoms of the cyclo-P(5) ligand are coordinated to copper atoms in σ- and π-bonding modes.

Remarkable Structural and Electronic Features of the Complex Formed by Trimeric Copper Pyrazolate with Pentaphosphaferrocene

“…2.111(4) Å)6b and similar to those in the starting compound 2 3a. To our knowledge, only two examples have been reported of copper coordinating to PP bonds in a π‐fashion among various one‐ and two‐dimensional polymeric compounds formed by the interaction of [Cp*Fe(η 5 ‐P 5 )] with simple copper halides CuX (X=Cl, Br, I) 3c. 11 Our study in the solid and solution states shows an astonishingly strong π‐interaction of pentaphosphaferrocene 2 with the copper pyrazolate macrocycle 1 , which entails substantial structural changes in both reactants.…”

Stabilization of Tetrahedral P4 and As4 Molecules as Guests in Polymeric and Spherical Environments

“…Therefore a Raman spectrum of 2 was compared to those of the original polymer [Cu 2 Cl 2 {Cp*Fe(η 5 ‐P 5 )} 2 ] ∞ ⋅CH 2 Cl 2 (cf. Supporting Information) 11b. The Raman bands for the embedded As 4 molecules at $\tilde \nu $ =202 (broad), 259, and 347 cm −1 agree well with those calculated for As 4 in the gas phase at $\tilde \nu $ =203 (two‐fold degenerate), 259 (three‐fold degenerate), and 349 cm −1 .…”

Ein nanoskaliges Supramolekül jenseits der Fulleren‐Topologie

“…Einkristalle von 3 werden aus CH 2 Cl 2 /MeCN‐Mischungen als Solvat erhalten, mit einem Molekül CH 2 Cl 2 pro Wiederholungseinheit. Die Struktur von 3 wird aus planaren Schichten von 1 gebildet, welches in einem eher ungewöhnlichen 1,2,3,4‐Koordinationsmodus an Cu 6 I 6 ‐Einheiten bindet 12. Das Gerüst besteht daher aus cyclo ‐P 5 ‐Liganden der Pentaphosphaferrocene, viergliedrigen Cu 2 I 2 ‐Ringen der Leiter, fünfgliedrigen Cu 2 P 2 I‐Ringen und sechsgliedrigen Cu 2 P 4 ‐Ringen (Abbildung 3).…”

“…Folglich sind die Schichten mit den Phenylringen der Cp Bn ‐Einheiten belegt. Ein Koordinationspolymer mit 1 a als Baustein und der gleichen elementaren Zusammensetzung wurde bereits früher erhalten 12. Jedoch sind in diesem die Cu 6 I 6 ‐Einheiten nicht in Leiterform angeordnet, sondern in Form von sechsgliedrigen Ringen.…”