Heterobimetallic complexes with highly flexible 1,1′-bis(phospholanoalkyl)ferrocene ligands

Abstract

The two highly flexible ligands 1,1'-bis(4-phospholanobutyl)ferrocene (5a) and 1,1'-bis(5-phospholanopentyl)ferrocene (5b) reacted with [PtCl2(cod)] (cod = 1,5-cyclooctadiene), [AuCl(tht)] (tht = tetrahydrothiophene) and [{RhCl(CO)2}2] to give the respective chelate complexes cis-[PtCl2(5a,b-κ(2)P,P')] (7a,b), [AuCl(5a,b-κ(2)P,P')] (8a,b) and trans-[RhCl(CO)(5b-κ(2)P,P')] (9b). Treatment of 5a,b with selenium gave the corresponding selenides 6a,b. All compounds have been fully characterised by NMR ((1)H, (13)C, (31)P) and IR spectroscopy and mass spectrometry. In addition, crystal structures of 6a, 7b, 8a,b and 9b were determined by X-ray crystallography. Furthermore, the rhodium-catalysed hydroformylation of 1-octene has been studied with ligand 5b.

Organophosphorus Compounds in Organic Electronics

“…Recently, developments of phosphinine coordination compounds have greatly expanded that area towards novel catalytic applications, which was recently reviewed by Müller and co‐workers . Similarly, the phospholane core has attracted significant attention as a versatile supramolecular building block . Over the last years an interesting trend has been observed to enhance the acceptor properties of P compounds by modifying the periphery of various P heterocycles.…”

“…[95] Similarly,t he phospholane core has attracted significant attention as av ersatile supramolecular building block. [96] Over the last years an interesting trend has been observed to enhancet he acceptorp roperties of Pc ompounds by modifying the periphery of various Ph eterocycles. Decorating these heterocycles with ketonef unctionalities in some cases had ap rofound impact on the opticaland electronic properties.…”

Selective formation of a supramolecular coordination complex in the nanometre scale with a ferrocene-based phospholane ligand

“…[5][6][7][8][9] Even though phospholane ligands possess unique properties for chiral catalysis and are also referred to as privileged ligands, 10 11 Using a bis-phospholane, in which the central part of the alkylidene spacer had been replaced by a ferrocenylene moiety resulted in formation of macrocyclic 1 : 1 [M : L] complexes. 12 In both complexes, the gold(I) cation is in the usual linear coordination environment but additionally exhibits an interaction with the chloride counterion ([2+1] coordination). When the number of phospholane moieties is increased to three (trisphospholane), a coordination polymer of gold(I) chloride instead of a molecular complex was obtained.…”

“…Both crystallographically independent gold(I) atoms are coordinated by two phosphorus atoms of two different ligands with Au-P bond lengths in the typical range of about 2.30 Å (Table S1, ESI †). 11,12 Fig. 2 shows a detailed view of the Au coordination sphere.…”

“…This is conspicuously long, but was already observed for similar coordination compounds. 11,12 Conversely, the Au-Cl distance of the gold atom with almost perfectly linear P-Au-P bond angle is much longer (Au2Á Á ÁCl2 3.108(3) Å) and can only be considered as an ionic interaction. A similar distance is observed to Cl1 (Au2Á Á ÁCl1 3.309(2) Å) which thus bridges both gold atoms.…”