Capping calixarenes with metallodiphosphine fragments: towards intracavity reactions

Abstract

The co-ordinative properties of four disubstituted 5,11,17,23-tetra-tert-butyl-25,27-di-RCH₂O-26,28- bis(diphenylphosphinomethoxy)calix[4]arenes [R = C(O)NEt₂ L¹, C(O)OEt L², (R)-C(O)NHCH(Me)Ph L³ or CH₂OMe L⁴] have been investigated. Compound L¹ reacted with [Au(thf )(SC₄H₈)]BF₄ (thf = tetrahydrofuran, SC₄H₈ = tetrahydrothiophene) and AgBF₄ to yield the chelate complexes [AuL¹]BF₄ 1 and [AgL¹]BF₄ 2, respectively. Reaction of L¹ with trans-[PtH(Cl)(PPh₃)₂] resulted in quantitative formation of trans-[PtH(Cl)L¹] 3 in which the platinum hydrogen bond is partially encapsulated within the calixarene cavity. The structurally related cationic complexes [PtH(PPh₃)Lⁱ ]BF₄ (Lⁱ = L¹ 4, L³ 5 or L⁴ 6), having a PPh₃ ligand trans to the hydrido ligand, were obtained in high yield by treating trans-[PtH(thf )(PPh₃)₂]BF₄ with diphosphine Lⁱ. Abstraction of the chloride ion from 3 with AgBF₄ gave [PtH(L¹)]BF₄ 7, a complex in which the calixarene behaves as a tridentate P₂O_amide ligand and in which the metal plane caps one end of the calixarene tunnel. Reaction of 7 with PPh₃ resulted in substitution of the co-ordinated amide to form 4, while reaction with 4,4′-bipyridine gave the binuclear complex [(L¹)HPt(4,4′-bipy)PtH(L¹)][BF₄] ₂ 8. Reaction of trans-[PtH(Cl)(PPh₃)₂] with Lⁱ resulted in a mixture of complexes of general formula [PtH(PPh₃)Lⁱ ]Cl (type A) and [PtH(Cl)Lⁱ] (type B). The A∶B ratio depends on the co-ordinating ability of the R groups, since these act as internal solvent molecules in promoting PPh₃ substitution. For R groups containing strong donors, e.g. as in L¹ and L², complexes of type B are favoured; with L⁴ the reaction leads selectively to [PtH(PPh₃)L⁴]Cl, no B-type complex being formed. In at least one case (L³) it was shown that complexes of type A may be converted into the B type. Reaction of 7 with dimethyl acetylenedicarboxylate gave the insertion product trans-P,P′-[Pt(MeO₂CC=CHCO ₂Me)L¹]BF₄ where the two amides compete for co-ordination. Complex 7 reacted instantaneously with tetracyanoethylene (tcne) to yield the platinum(0) complex [Pt(tcne)L¹] for which NMR spectra suggest fast flipping of the co-ordination plane between amides. In contrast to [Pt(MeO₂CC=CHCO₂Me)L¹]BF₄ , strong tridentate P₂O co-ordination abounds in the rhodium carbonyl complexes [Rh(CO)Lⁱ]BF₄ (Lⁱ = L¹ or L³) obtained from [Rh(CO)₂(thf )₂]BF₄ and the corresponding diphosphines.

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