3 years ago

Influence of highly basic phosphine ligand on the reactivity and hydrolysis of P4 and P4S3 supported by ruthenium fragments

Influence of highly basic phosphine ligand on the reactivity and hydrolysis of P4 and P4S3 supported by ruthenium fragments
Substitution of PPh3 in [RuCp(PPh3)2Cl] with highly basic PMe3 gave a remarkable change in the reactivity towards P4 and unexpectedly only the bimetallic complex cation [{RuCp(PMe3)2}2(μ,η1:1-P4)]2+ (3) was formed which was characterized by NMR spectroscopy and single crystal X-ray diffraction analysis. The equimolar reaction between the synthon [RuCp(PMe3)2]+ and the mixed cage P4S3 is highly selective quantitatively yielding only the product with η1-Pbasal coordination to ruthenium. On the other hand, the related [RuCp(PPh3)2]+ cation gave a 2:1 mixture of mono-η1-Pbasal and bimetallic complex. The solid state structure of [RuCp(PMe3)21-Pbasal-P4S3)]+ (4) was solved by X-ray diffraction and represents the first example of X-ray structure of intact P4S3 coordinated to a mononuclear ruthenium organometallic fragment. Hydrolysis of the P4 ligand in 3 resulted mainly in two products, i.e. free H3PO3 and the diphosphane complex cation [{RuCp(PMe3)2}2(μ,η1:1-P2H4)]2+ (9), while in the presence of methanol two mononuclear complexes [RuCp(PMe3)2{P(OH)3}]+ (8) and [RuCp(PMe3)2{P(OCH3)3}]+ (10) in (2:1) ratio were selectively formed.

Publisher URL: www.sciencedirect.com/science

DOI: S0022328X18300056

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