Coordination Behavior of the 1,2,3-Triphosphaferrocene [Cp′′′Fe(η⁵-P₃C₂(H)Ph)] with Organometallic Moieties

Abstract

The reaction of the 1,2,3-triphosphaferrocene [Cp′′′Fe(η 5 -P 3 C 2 (H)Ph)] (1) with the Lewis acidic complex [PtCl 2 (PEt 3 )] 2 yields the monosubstituted derivative [Cp′′′Fe(η 5 -P 3 C 2 (H)Ph){PtCl 2 (PEt 3 )}] (2), in which the Pt moiety is located at the P atom adjacent to the C(H) group of the cyclo-P 3 C 2 ring. Using an excess of the Pt complex no multiple substitution occurs. In contrast, using [W(CO) 5 ] units as Lewis acids results in mono-, di-, and tricoordination at the cyclo-P 3 C 2 ring. The products, [Cp′′′Fe(η 5 -P 3 C 2 (H)Ph){W(CO) 5 } n ] (n ) 1 (3), 2 (4), 3 (5)), have all been spectroscopically characterized, and the substitution patterns of the experimentally found (mono-and disubstituted) isomers are found to be in accordance with the energetically favored derivatives calculated by DFT methods. For these structures the energetically favored rotational conformers have also been calculated. The energetically favored 2,3coordinated isomer 4b could be crystallized, and its structure and that of the tricoordinated derivative 5 were determined by X-ray diffraction methods.

Coordination Behavior of [Cp′′2Zr(η1:1‐P4)] towards Different Lewis Acids

“…Consequently, the central P 4 unit is slightly distorted compared to 1 , but all bonds are in the range of P−P single bonds . The P−W distance (2.5966(8) Å) is in agreement with the calculated value (2.633 Å) and similar to [(CO) 4 W(η 4 ‐P 4 {W(CO) 5 } 4 ], but elongated compared to complexes such as [{Cp′′′Fe(μ,η 5:1:1 ‐P 3 C 2 (H)Ph)}{W(CO) 5 } 2 ], [{W(CO) 5 }(P 3 C 2 t Bu 2 ){Cu(PPh 3 }], or [(CO) 5 WPH 3 ] . This can be attributed to the steric repulsion.…”

Synthesis and Characterization of Free and Coordinated 1,2,3-Tripnictolide Anions

“…This anion was previously reported by Mathey and co-workers but has never been crystallographically authenticated as a free ligand . Metal complexes of the triphospholide have been isolated by the research groups of Scherer, Scheer, and Nixon . Extension of this synthetic methodology allowed for the isolation of the novel arsenic analogue 4,5-diphenyl-1,2,3-triarsolide, [As 3 C 2 (C 6 H 5 ) 2 ] − ( 4 ), staring from the K 3 As 7 Zintl phase.…”

“…The number of known [P n (CR) 5– n ] − phospholide ligands (and their respective metal complexes) varies dramatically depending on the isomer in question . Thus, while the synthesis of monophospholide ligands is relatively straightforward (following a method first reported by Braye and co-workers involving the reduction of phospholes), other isomers are far more elusive. , 1,3-Diphospholide and 1,2,4-triphospholide anions can be obtained by chemical reduction of phospha-alkynes, and their coordination chemistry has been extensively investigated. , In contrast, the related isomers 1,2-diphospholides and 1,2,3-triphospholides are much rarer, due to the lack of versatile synthetic methods for their synthesis. − The tetraphospholide anion is similarly uncommon, while the pentaphospholide species, which has been observed in solution but has yet to be isolated as a free ligand, has been isolated in a number of transition-metal complexes typically as a result of the metal-mediated activation of white phosphorus. ,, …”

1,2,4-Triphospholyl anions – versatile building blocks for the formation of 1D, 2D and 3D assemblies

“…Three-dimensional networks (2,8,9) Surprisingly, from the reaction of 1a with CuCl as a second product also the 3D polymer 2 can be isolated, despite the sterically demanding Mes group. Since they differ significantly in their Cu content, a directed synthesis is enabled by using different stoichiometries.…”

“…1 . In particular, phosphaferrocenes and CuX (X = Cl, Br, I) turned out to be a great combination for the construction of monomeric, 2 oligomeric, 3 polymeric 3 , 4 and even spherical 5 coordination compounds. This vast abundance of results can be partially traced back to the variability and flexibility of the coordination behaviour of Cu halides.…”