Gold(i) complexes of tetra-tert-butylcyclotetraphosphane

Abstract

The reaction of tetra-tert-butylcyclotetraphosphane cyclo-(PtBu)4 (L) with one to four equivalents [AuCl(tht)] (tht = tetrahydrothiophene) leads to the gold(I) complexes [(AuCl)nL] (n = 1–4, 1–4) in which the ligand coordinates...

Coordination chemistry of hepta-tert-butylnonaphosphane

“…Different isomers could indeed be observed for platinum( ii ) complexes of the octaphosphane { cyclo -(P 4 t Bu 3 )} 2 as well as for the respective gold( i ) complexes, which moreover showed a rapid interconversion. 29,51 To investigate this possibility for complex 4 , DFT calculations of different conceivable configurational isomers were conducted to access their relative energies (Scheme S2, ESI†). Fig.…”

“…The activation energy for the transformations between the different isomers was not calculated, but it is reasonable to assume that they are low enough to proceed at room temperature considering the transformation reactions of oligophosphane complexes observed for similar systems. 29,34,51…”

“…showed a rapid interconversion. 29,51 To investigate this possibility for complex 4, DFT calculations of different conceivable configurational isomers were conducted to access their relative energies (Scheme S2, ESI †). Fig.…”

“…The activation energy for the transformations between the different isomers was not calculated, but it is reasonable to assume that they are low enough to proceed at room temperature considering the transformation reactions of oligophosphane complexes observed for similar systems. 29,34,51 Further complexation reactions Attempts to prepare the corresponding complexes of nickel(0), palladium(II) or platinum(II) failed as either no complexation with L occurred ([Ni(COD) 2 ], COD = cycloocta-1,5-diene), the resulting complex decomposed ([PdCl 2 (COD)]) or the ligand was degraded ([PtCl 2 (COD)]). Apparently, the exocyclic P-P bonds between the cyclo-(P Bu 3 )} 2 P t Bu-κ 2 P 6 ,P 9 )] (5) could be obtained, due to decomposition it was not possible to reproduce this compound in larger quantities for further characterisation.…”

Phosphorus makes inroads

“…As mentioned in the article, oxidation is a possible explanation; however, it is also possible that rearrangement reactions occur in solution. 10,11 Further investigations are required to establish the origin of the additional signals observed in the 31 P{ 1 H} NMR spectra.…”