Synthesis and characterisation of 1-(diphenylphosphino)-1′-(methylsulfanyl)ferrocene and a series of metal (CuI, AgI)–ferrocenylene complexes

Long, Nicholas J.; Martin, Jeff; Opromolla, Giuliana; White, Andrew J. P.; Williams, David J.; Zanello, Piero

doi:10.1039/a903539g

Cited by 33 publications

(30 citation statements)

References 23 publications

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“…The analytical data were identical to those described in the literature. 26 [Cu 2 (Bphen) 2 (µ-dppm) 2 ](BF 4 ) 2 . This compound was thus obtained in 48% yield as a yellow crystalline solid.…”

Section: Methodsmentioning

confidence: 99%

“…Figure 10 The homoleptic Cu(I) complex prepared from dppFc has been characterized in solution by Long and co-workers but no X-ray crystal structure has been published for this compound. 26 We decided to prepare this compound from dppFc and Cu(CH 3 CN) 4 BF 4 . As reported by Long and co-workers, the resulting complex displays broadened 1 H and 31 P NMR features at room temperature suggesting dissociative processes in solution.…”

Section: 9-mentioning

confidence: 99%

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Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands

et al. 2013

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Preparation of [Cu(NN)(PP)](+) derivatives has been systematically investigated starting from two libraries of phenanthroline (NN) derivatives and bis-phosphine (PP) ligands, namely, (A) 1,10-phenanthroline (phen), neocuproine (2,9-dimethyl-1,10-phenanthroline, dmp), bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, Bphen), 2,9-diphenethyl-1,10-phenanthroline (dpep), and 2,9-diphenyl-1,10-phenanthroline (dpp); (B) bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), 1,1'-bis(diphenylphosphino)ferrocene (dppFc), and bis[(2-diphenylphosphino)phenyl] ether (POP). Whatever the bis-phosphine ligand, stable heteroleptic [Cu(NN)(PP)](+) complexes are obtained from the 2,9-unsubstituted-1,10-phenanthroline ligands (phen and Bphen). By contrast, heteroleptic complexes obtained from dmp and dpep are stable in the solid state, but a dynamic ligand exchange reaction is systematically observed in solution, and the homoleptic/heteroleptic ratio is highly dependent on the bis-phosphine ligand. Detailed analysis revealed that the dynamic equilibrium resulting from ligand exchange reactions is mainly influenced by the relative thermodynamic stability of the different possible complexes. Finally, in the case of dpp, only homoleptic complexes were obtained whatever the bis-phosphine ligand. Obviously, steric effects resulting from the presence of the bulky phenyl rings on the dpp ligand destabilize the heteroleptic [Cu(NN)(PP)](+) complexes. In addition to the remarkable thermodynamic stability of [Cu(dpp)2]BF4, this negative steric effect drives the dynamic complexation scenario toward almost exclusive formation of homoleptic [Cu(NN)2](+) and [Cu(PP)2](+) complexes. This work provides the definitive rationalization of the stability of [Cu(NN)(PP)](+) complexes, marking the way for future developments in this field.

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Section: Methodsmentioning

confidence: 99%

Section: 9-mentioning

confidence: 99%

Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands

et al. 2013

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“…The coordination chemistry of these ligands towards several metals such as nickel, palladium or rhodium has been studied. [23][24][25] As part of our studies of ferrocene derivatives as ligands, 26 we report here on the synthesis of the first unsymmetrical ferrocenyl ligand having both P and Se as donor atoms and on the reactivity of the Fc(SPh)PPh 2 and Fc(SePh)PPh 2 ligands with group 11 metal complexes. The reactivity of the three metals is different; gold predominantly coordinates through the phosphorus donor ligand, silver can coordinate either through the phosphorus only or through both donor atoms (phosphorus and chalcogen), and copper coordinates to both donor atoms.…”

Section: Introductionmentioning

confidence: 99%

Group 11 complexes with unsymmetrical P,S and P,Se disubstituted ferrocene ligands

et al. 2005

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The reaction of the unsymmetrical ligands 1-diphenylphosphino-1'-(phenylsulfanyl)ferrocene and 1-diphenylphosphino-1'-(phenylselenyl)ferrocene, Fc(EPh)PPh2(E = S, Se), with several group 11 metal derivatives leads to the synthesis of complexes of the type [MX{Fc(EPh)PPh2}](M = Au, X = Cl, C6F5; M = Ag, X = OTf), (OTf = trifluoromethanesulfonate), [M{Fc(EPh)PPh2}2]X (M = Au, X = ClO4; M = Ag, X = OTf), [M(PPh3){Fc(EPh)PPh2}]OTf (M = Au, Ag), [Au2{Fc(SPh)PPh2}2](ClO4)2, [Au(C6F5)2{Fc(SePh)PPh2}]ClO4, [Au(C6F5)3{Fc(EPh)PPh2}], [Au2(C6F5)6{Fc(SePh)PPh2}] or [Cu{Fc(EPh)PPh2}2]PF6(E = S, Se). In these complexes coordination depends upon the metal centre; with gold it takes place predominantly to the phosphorus atom and with silver and copper to both phosphorus and chalcogen atoms. The treatment of some of the gold complexes with other metal centres affords heterometallic derivatives that in some cases are in equilibrium with the homometallic derivatives. Several compounds have been characterized by X-ray diffraction, four pairs of homologous compounds, yet not a single pair is isotypic. In many of them a three dimensional network is formed through secondary bonds such as hydrogen bonds, Au...Cl or Au...Se interactions. The complex [Ag(OTf){Fc(SePh)PPh2}] forms one-dimensional chains through trifluoromethanesulfonate bridging ligands.

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“…In addition to a downfield shift of the signal of the methylsulfanyl group in the 1 H and 13 C NMR spectra, the value of which to some extent reflects the strength of the sulfur-metal bond, the most characteristic is a strong narrowing of the signal of the substituted boron atom in the 11 B NMR spectra together with the broadening of the signals of unsubstituted boron atoms. The last one makes it possible to observe the metal coordination in the reaction mixture, while the shift of the SMe group signal in the case of weakly bound complexes can be insignificant [23][24][25][26], and the signal itself can be "masked" by the signals of the solvent, ligand, or accidental water.…”

Section: Resultsmentioning

confidence: 99%

Bis(dicarbollide) Complexes of Transition Metals as a Platform for Molecular Switches. Study of Complexation of 8,8′-Bis(methylsulfanyl) Derivatives of Cobalt and Iron Bis(dicarbollides)

et al. 2020

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Complexation of the 8,8′-bis(methylsulfanyl) derivatives of cobalt and iron bis(dicarbollides) [8,8′-(MeS)2-3,3′-M(1,2-C2B9H10)2]− (M = Co, Fe) with copper, silver, palladium and rhodium leads to the formation of the corresponding chelate complexes, which is accompanied by a transition from the transoid to the cisoid conformation of the bis(dicarbollide) complex. This transition is reversible and can be used in design of coordination-driven molecular switches based on transition metal bis(dicarbollide) complexes. The solid-state structures of {(Ph3P)ClPd[8,8′- (MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} and {(COD)Rh[8,8′-(MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} were determined by single crystal X-ray diffraction.

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Synthesis and characterisation of 1-(diphenylphosphino)-1′-(methylsulfanyl)ferrocene and a series of metal (CuI, AgI)–ferrocenylene complexes

Cited by 33 publications

References 23 publications

Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands

Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands

Group 11 complexes with unsymmetrical P,S and P,Se disubstituted ferrocene ligands

Bis(dicarbollide) Complexes of Transition Metals as a Platform for Molecular Switches. Study of Complexation of 8,8′-Bis(methylsulfanyl) Derivatives of Cobalt and Iron Bis(dicarbollides)

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